Sample records for ni2 bis-u-hydroxo dimer

  1. Single-crystalline Ni2Ge/Ge/Ni2Ge nanowire heterostructure transistors. (United States)

    Tang, Jianshi; Wang, Chiu-Yen; Xiu, Faxian; Hong, Augustin J; Chen, Shengyu; Wang, Minsheng; Zeng, Caifu; Yang, Hong-Jie; Tuan, Hsing-Yu; Tsai, Cho-Jen; Chen, Lih Juann; Wang, Kang L


    In this study, we report on the formation of a single-crystalline Ni(2)Ge/Ge/Ni(2)Ge nanowire heterostructure and its field effect characteristics by controlled reaction between a supercritical fluid-liquid-solid (SFLS) synthesized Ge nanowire and Ni metal contacts. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) studies reveal a wide temperature range to convert the Ge nanowire to single-crystalline Ni(2)Ge by a thermal diffusion process. The maximum current density of the fully germanide Ni(2)Ge nanowires exceeds 3.5 × 10(7) A cm(-2), and the resistivity is about 88 μΩ cm. The in situ reaction examined by TEM shows atomically sharp interfaces for the Ni(2)Ge/Ge/Ni(2)Ge heterostructure. The interface epitaxial relationships are determined to be [Formula: see text] and [Formula: see text]. Back-gate field effect transistors (FETs) were also fabricated using this low resistivity Ni(2)Ge as source/drain contacts. Electrical measurements show a good p-type FET behavior with an on/off ratio over 10(3) and a one order of magnitude improvement in hole mobility from that of SFLS-synthesized Ge nanowire.

  2. Magnetic susceptibility, specific heat and magnetic structure of CuNi2(PO4)2

    International Nuclear Information System (INIS)

    Escobal, Jaione; Pizarro, Jose L.; Mesa, Jose L.; Larranaga, Aitor; Fernandez, Jesus Rodriguez; Arriortua, Maria I.; Rojo, Teofilo


    The CuNi 2 (PO 4 ) 2 phosphate has been synthesized by the ceramic method at 800 deg. C in air. The crystal structure consists of a three-dimensional skeleton constructed from MO 4 (M II =Cu and Ni) planar squares and M 2 O 8 dimers with square pyramidal geometry, which are interconnected by (PO 4 ) 3- oxoanions with tetrahedral geometry. The magnetic behavior has been studied on powdered sample by using susceptibility, specific heat and neutron diffraction data. The bimetallic copper(II)-nickel(II) orthophosphate exhibits a three-dimensional magnetic ordering at, approximately, 29.8 K. However, its complex crystal structure hampers any parametrization of the J-exchange parameter. The specific heat measurements exhibit a three-dimensional magnetic ordering (λ-type) peak at 29.5 K. The magnetic structure of this phosphate shows ferromagnetic interactions inside the Ni 2 O 8 dimers, whereas the sublattice of Cu(II) ions presents antiferromagnetic couplings along the y-axis. The change of the sign in the magnetic unit-cell, due to the [1/2, 0, 1/2] propagation vector determines a purely antiferromagnetic structure. - Graphical abstract: Magnetic structure of CuNi2(PO4)2

  3. Ion Ni2+ di Dalam Air; Pembentukan Fungsi Potensial Intermolekul

    Directory of Open Access Journals (Sweden)

    Bambang Setiaji


    Full Text Available Pair potential function of Ni2+-H2O system has been constructed by ab initio method at UHF (Unrestricted Hartre-Fock level. The basis sets used for energy interaction calculation were LANL2 Double-z ECP of Hay and Wadt for Ni2+ and Double-z Polarization of Dunning for H2O. Construction of pair potential function was done by collecting more than 3000 energy points that represent all interactions of Ni2+ ion and water. The pair potential function of Ni2+-H2O resulted of fitting proses by standard deviation of 3,25 kcal/mol is where AiM, BiM, CiM  and DiM are fitting parameter of Ni2+-O or Ni2+-H, riM is distance of i atoms between H2O and Ni2+, q is charge of i atoms of H2O resulted by Mulliken population analysis, and qM is net charge of Ni2+ ion.   Keywords: Ni2+ ion in water, intermoleculer potential function.

  4. Immunoproteomic identification and characterization of Ni2+-regulated proteins implicates Ni2+in the induction of monocyte cell death. (United States)

    Jakob, Annika; Mussotter, Franz; Ohnesorge, Stefanie; Dietz, Lisa; Pardo, Julian; Haidl, Ian D; Thierse, Hermann-Josef


    Nickel allergy is the most common cause of allergic reactions worldwide, with cutaneous and systemic effects potentially affecting multiple organs. Monocytes are precursors of not only macrophages but also dendritic cells, the most potent activators of nickel hypersensitivity. Monocytes are themselves important antigen-presenting cells, capable of nickel-specific T-cell activation in vivo and in vitro, in addition to being important for immediate innate immune inflammation. To elucidate early Ni 2+ -dependent inflammatory molecular mechanisms in human monocytes, a Ni 2+ -specific proteomic approach was applied. Quantitative two-dimensional (2D) differential gel electrophoresis and Delta2D software analyses coupled with matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS) revealed that Ni 2+ significantly regulated 56 protein species, of which 36 were analyzed by MALDI-MS. Bioinformatics analyses of all identified proteins resulted in Ni 2+ -associated functional annotation clusters, such as cell death, metal ion binding, and cytoskeletal remodeling. The involvement of Ni 2+ in the induction of monocyte cell death, but not T-cell death, was observed at Ni 2+ concentrations at or above 250 μM. Examination of caspase activity during Ni 2+ -mediated cell death revealed monocytic cell death independent of caspase-3 and -7 activity. However, confocal microscopy analysis demonstrated Ni 2+ -triggered cytoskeletal remodeling and nuclear condensation, characteristic of cellular apoptosis. Thus, Ni 2+ -specific peripheral blood mononuclear cell stimulation suggests monocytic cell death at Ni 2+ concentrations at or above 250 μM, and monocytic effects on immune regulation at lower Ni 2+ concentrations.

  5. Liquid crystal dimers

    CERN Document Server

    Kumar Pal, Santanu


    This book covers in-depth discussion of design principles, synthesis and thermal behavior of all types of liquid crystal (LC) dimers. The text presents recent advances in the field of LC dimers consisting of different mesogenic units such as calamitic, discotic and bent-core molecules. It starts with a chapter on the introduction of liquid crystal dimers, including their odd-even behavior, basic classification of dimers and common mesophases in dimers. The text shows how the molecular architectures are being used to develop new materials to study a range of interesting phenomena such as the biaxial nematic phase containing rod-like and disc-like mesogenic units. Finally, the text presents perspectives related to technological relevance of these dimers such as dopants in LC display mixtures exhibiting faster relaxation time, strong flexoelectric coupling and others to effect control over the properties of these materials.

  6. Reduction mechanism of Ni2+ into Ni nanoparticles prepared from ...

    Indian Academy of Sciences (India)

    journal of. March 2009 physics pp. 577–586. Reduction mechanism of Ni2+ into Ni nanoparticles prepared from different precursors: Magnetic studies ... 2Department of Chemistry, Indian Institute of Technology, Kanpur 208 016, India ..... this work and Avanti, Analytical Chemistry Division, BARC for her help in cyclic.

  7. Neutron diffraction studies of magnetic ordering in superconducting ErNi2B2C and TmNi2B2C in an applied magnetic field

    DEFF Research Database (Denmark)

    Toft, Katrine Nørgaard

    The field-induced magnetic structures of ErNi2B2C and TmNi2B2C in are especially interesting because the field suppresses the superconducting order parameter and therefore the magnetic properties can be studied while varying the strength ofsuperconductivity. ErNi2B2C: For magnetic fields along al...

  8. 2-Ethynylpyridine dimers

    DEFF Research Database (Denmark)

    Bakarić, Danijela; Spanget-Larsen, Jens


    are used to study possible 2-EP dimer structures as well as their distribution in an inert solvent such as tetrachloroethene. Experimentally, the ≡C–H stretching vibration of the 2-EPmonomer absorbs close to 3300 cm−1, whereas a broad band withmaximum around 3215 cm−1 emerges as the concentration rises...... model with counterpoise correction predict that the two most stable dimers are of the pi-stacked variety, closely followed by dimers with intermolecular ≡C–H···N hydrogen bonding; the predicted red shifts of the ≡C–H stretching wavenumbers due to hydrogen bonding are in the range 54 – 120 cm–1...

  9. Neutron scattering in dimers

    DEFF Research Database (Denmark)

    Gudel, H. U.; Furrer, A.; Kjems, Jørgen


    Insulating compounds containing dimers of transition metal and rare earth ions have been studied by inelastic neutron scattering (INS). Energy splittings can be directly determined, and the corresponding parameters are easily extracted from the experimental data. The intensities of dimer...... excitations are modulated by an interference term reflecting the distance between the magnetic ions within the dimers. The INS technique is particularly powerful for the study of effects like: temperature dependence of exchange, the role of biquadratic exchange, the combination of crystal-field and exchange...

  10. Magnetism in Ni2FeVO6-δ

    International Nuclear Information System (INIS)

    Kolpakowa, L.; Pietrzak, J.; Latosinska, J.N.; Pawlicki, P.


    The temperature dependence of magnetization M(T) of new polycrystalline ilmenite Ni 2 FeVO 6-δ shows remarkable singularities which can be interpreted as a result of coexistence of three magnetic phases in its magnetic structure. A fit of the dependences following four different models, each of which a combination of three functions of chosen type, to the M(T) experimental dependence has been made. ((orig.))

  11. Dimers in nucleating vapors (United States)

    Lushnikov, A. A.; Kulmala, M.


    The dimer stage of nucleation may affect considerably the rate of the nucleation process at high supersaturation of the nucleating vapor. Assuming that the dimer formation limits the nucleation rate, the kinetics of the particle formation-growth process is studied starting with the definition of dimers as bound states of two associating molecules. The partition function of dimer states is calculated by summing the Boltzmann factor over all classical bound states, and the equilibrium population of dimers is found for two types of intermolecular forces: the Lennard-Jones (LJ) and rectangular well+hard core (RW) potentials. The principle of detailed balance is used for calculating the evaporation rate of dimers. The kinetics of the particle formation-growth process is then investigated under the assumption that the trimers are stable with respect to evaporation and that the condensation rate is a power function of the particle mass. If the power exponent λ=n/(n+1) (n is a non-negative integer), the kinetics of the process is described by a finite set of moments of particle mass distribution. When the characteristic time of the particle formation by nucleation is much shorter than that of the condensational growth, n+2 universal functions of a nondimensional time define the kinetic process. These functions are calculated for λ=2/3 (gas-to-particle conversion in the free molecular regime) and λ=1/2 (formation of islands on surfaces).

  12. Synthesis and magnetic characterization of Sr-based Ni2X-type hexaferrite

    Directory of Open Access Journals (Sweden)

    K. Kamishima


    Full Text Available We have investigated the synthesis conditions, and the magnetic properties of the Sr2Ni2X-type hexagonal ferrite, Sr2Ni2Fe28O46. The Sr2Ni2X-type hexaferrite was synthesized at 1240∘C. The spontaneous magnetization at 5 K was 44.2 μB/f.u., suggesting that most of the Ni2+ ions are at the up-spin octahedral sites in the spinel-structure blocks within the model of a Néel-type collinear ferrimagnetic structure. The Curie temperature of the Sr2Ni2X-type hexaferrite was estimated to be TC[Sr2Ni2X] = 472∘C. This is consistent with the difference of the block stacking structures of SrM-type, Sr2Ni2X-type, SrNi2W-type, and nickel spinel ferrites.

  13. Glycine Transporter Dimers (United States)

    Bartholomäus, Ingo; Milan-Lobo, Laura; Nicke, Annette; Dutertre, Sébastien; Hastrup, Hanne; Jha, Alok; Gether, Ulrik; Sitte, Harald H.; Betz, Heinrich; Eulenburg, Volker


    Different Na+/Cl−-dependent neurotransmitter transporters of the SLC6a family have been shown to form dimers or oligomers in both intracellular compartments and at the cell surface. In contrast, the glycine transporters (GlyTs) GlyT1 and -2 have been reported to exist as monomers in the plasma membrane based on hydrodynamic and native gel electrophoretic studies. Here, we used cysteine substitution and oxidative cross-linking to show that of GlyT1 and GlyT2 also form dimeric complexes within the plasma membrane. GlyT oligomerization at the cell surface was confirmed for both GlyT1 and GlyT2 by fluorescence resonance energy transfer microscopy. Endoglycosidase treatment and surface biotinylation further revealed that complex-glycosylated GlyTs form dimers located at the cell surface. Furthermore, substitution of tryptophan 469 of GlyT2 by an arginine generated a transporter deficient in dimerization that was retained intracellulary. Based on these results and GlyT structures modeled by using the crystal structure of the bacterial homolog LeuTAa, as a template, residues located within the extracellular loop 3 and at the beginning of transmembrane domain 6 are proposed to contribute to the dimerization interface of GlyTs. PMID:18252709

  14. Dimeric form of peroxynitrite (United States)

    Simon, K. V.; Tulub, A. V.


    The (ONOO)- anion, known as peroxynitrite, is characterized by a singlet spin state. A new stable dimer form of peroxynitrite [NO-O2]- in the triplet state at distances close to r(O-N) ≈ 2.885 Å between oxygen in the O2 structure and nitrogen has been established within the quantum-chemical CASSCF approximation. The vibrational motion of the dimer is significantly anharmonic; for the 16O and 14N isotopes, the differences in the energies of two neighboring levels correspond to frequencies of about 70-30 cm-1. The triplet dimer structure retains stability in the case of interaction with water molecules. The activation barriers caused by rearrangement of the peroxynitrite structure into the ground state of the NO{3/-} anion with the symmetry D 3 h are found.

  15. Selective amine catalysed steroidal dimerization

    Indian Academy of Sciences (India)

    steroid dimers in which carbon atoms comprise a ben- zene nucleus.6 A standard colour test for the presence of cholesterol is the formation of a green colour in concentrated sulphuric acid, and this was shown to be due to a polyenyl steroidal dimer carbocation.7–9 Many dimeric and oligomeric steroids exhibit interesting.

  16. Superconducting properties of Zr1+xNi2-xGa and Zr1-xNi2+xGa Heusler compounds

    Directory of Open Access Journals (Sweden)

    Saad Alzahrani


    Full Text Available The superconducting properties of a series of Zr1+xNi2-xGa and Zr1-xNi2+xGa compounds have been investigated by x-ray diffraction, electrical resistivity, dc magnetization, and ac susceptibility measurements. While the parent compound, ZrNi2Ga, exhibited the cubic L21 Heusler structure, multiple non-cubic structures formed in the Zr and Ni rich doped materials. For x ≤ 0.3, all Zr1-xNi2+xGa compounds demonstrated superconducting behavior, but no superconductivity was observed in the Zr1+xNi2-xGa alloys for x > 0.2. The magnetization data revealed that all materials in both Zr1+xNi2-xGa and Zr1-xNi2+xGa series exhibited type-II superconductivity. With increasing doping concentration x, the paramagnetic ordering were enhanced in both systems while the superconducting properties were found to weaken. The observations are discussed considering the structural disorders in the systems.

  17. Synthesis of Ni2B nanoparticles by RF thermal plasma for fuel cell catalyst

    International Nuclear Information System (INIS)

    Cheng, Y; Tanaka, M; Watanabe, T; Choi, S Y; Shin, M S; Lee, K H


    The catalyst of Ni 2 B nanoparticles was successfully prepared using nickel and boron as precursors with the quenching gas in radio frequency thermal plasmas. The generating of Ni 2 B needs adequate reaction temperature and boron content in precursors. The quenching gas is beneficial for the synthesis of Ni 2 B in RF thermal plasma. The effect of quenching rate, powder feed rate and boron content in feeding powders on the synthesis of nickel boride nanoparticles was studied in this research. The high mass fraction of 28 % of Ni 2 B nanoparticles can be generated at the fixed initial composition of Ni:B = 2:3. Quenching gas is necessary in the synthesis of Ni 2 B nanoaprticles. In addition, the mass fraction of Ni 2 B increases with the increase of quenching gas flow rate and powder feed rate


    Directory of Open Access Journals (Sweden)

    Tutik Arindah


    Full Text Available Determination of solvation structure of Ni2+ ion in water has been achieved using Monte Carlo method using canonic assemble (NVT constant. Simulation of a Ni2+ ion in 215 H2O molecules has been done under NVT condition (298.15 K. The results showed that number of H2O molecules surround Ni2+ ion were 8 molecules in first shell and 17 molecules in second shell, interaction energy of Ni2+-H2O in first shell was -68.7 kcal/mol and in second shell was -9.8 kcal/mol, and there were two angles of O-Ni2+-O, i.e. 74o and 142o. According to those results, the solvation structure of Ni2+ ion in water was cubic antisymetric.   Keywords: Water simulation, Monte Carlo simulation

  19. An Investigation of Ni2P Single Crystal Surfaces : Structure, Electronic State and Reactivity


    Yuan, Qiuyi; Ariga, Hiroko; Asakura, Kiyotaka


    Ni2P has demonstrated high catalytic activity for hydrodesulfurization and has recently been employed as a catalyst in a variety of other reactions. We have thoroughly reviewed the literature concerning Ni2P single crystal surfaces, with the aim of determining the relationship between surface structure and catalytic properties. Published results to date indicate that Ni2P single crystal surfaces exhibit reconstructed structures, and so the bulk terminated structure may not be stable. We have ...

  20. Alkane dimers interaction

    DEFF Research Database (Denmark)

    Ferrighi, Lara; Madsen, Georg Kent Hellerup; Hammer, Bjørk


    The interaction energies of a series of n-alkane dimers, from methane to decane, have been investigated with Density Functional Theory (DFT), using the MGGA-M06-L density functional. The results are compared both to the available wavefunction-based values as well as to dispersion corrected DFT...... values. The MGGA-M06-L density functional is a semi-local functional designed and has proven to provide accurate estimates of dispersion interactions for several systems at moderate computational cost. In the present application, it reproduces the trends obtained by the more expensive wavefunction...

  1. Neutron diffraction studies of Ho1-xYxNi2B2C compounds

    DEFF Research Database (Denmark)

    Chang, L.J.; Tomy, C.V.; Paul, D.M.K.


    Neutron diffraction measurements have been carried out to investigate the nature of magnetic ordering in Ho(1-x)Y(x)Ni(2)B(2)C (x = 0, 0.1 and 0.2) compounds. HoNi(2)B(2)C shows a complex type of magnetic ordering below the superconducting transition, with a commensurate antiferromagnetic ordering...

  2. Ni 2-uptake in Pseudomonas putida strain S4: a possible role of Mg ...

    Indian Academy of Sciences (India)

    Essential metal ion homeostasis is based on regulated uptake of metal ions, both during its scarcity and abundance. Pseudomonas putida strain S4, a multimetal resistant bacterium, was employed to investigate Ni2+ entry into cells. It was observed that Mg2+ regulates the entry of Ni2+ and by this plays a protective role to ...

  3. Bioaccumulation, distribution and retention of 63Ni2+ in the brown trout (Salmo trutta)

    International Nuclear Information System (INIS)

    Tjaelve, Hans; Gottofrey, James; Borg, Kathleen


    Brown trout, Salmo trutta, were exposed to water containing 0.1 or 10 μgl -1 of 63 Ni 2+ for 1 or 3 weeks. Additional trout were exposed to 0.1 or 10 μgl -1 of 63 Ni 2+ during 3 weeks followed by a 1- or 3-week period without exposure to the metal. At termination of the experimental periods the uptake and distribution of the 63 Ni 2+ in the fishes were determined by whole-body autoradiography and liquid scintillation spectrometry. The average whole-fish concentration of 63 Ni 2+ in the fishes was about 3 times higher than the concentration of 6 Ni 2+ in the water after 1 week's exposure and about 7-8 times higher than in the water after three weeks' exposure. Our results show that there is a moderate bioaccumulation of nickel by fishes from the water. (author)

  4. Selective amine catalysed steroidal dimerization

    Indian Academy of Sciences (India)

    of cholesterol is the formation of a green colour in concentrated sulphuric acid, and this was shown to be due to a polyenyl steroidal dimer carbocation.7–9 Many dimeric and oligomeric steroids exhibit interesting micellular, detergent and liquid crystal behaviour.10,11. Most of the steroidal dimmers are also well-known.

  5. 161Dy Moessbauer spectroscopy of the intermetallic compounds DyNi2Si2, DyNi2Ge2 and DyAg2Si2

    International Nuclear Information System (INIS)

    Onodera, Hideya; Murata, Akifumi; Koizuka, Masaaki; Ohashi, Masayoshi; Yamaguchi, Yasuo


    161 Dy Moessbauer spectroscopic study has been performed on DyNi 2 Si 2 , DyNi 2 Ge 2 and DyAg 2 Si 2 in order to clarify microscopic properties of antiferromagnets with incommensurate and sinusoidally moment-modulated structure. The experiments were done using the standard 161 Tb Moessbauer sources prepared by neutron irradiation at the Japan Material Testing Reactor. The Moessbauer spectra of DyNi 2 Si 2 are analyzed satisfactorily by a single set of hyperfine parameters, and hence the sinusoidal moment-modulation is considered to be realized through a distribution of spin relaxation rate. The broadened spectra of DyNi 2 Ge 2 are fitted tentatively by three subspectra. It seems for DyNi 2 Ge 2 that the incommensurate arrangement of Dy moments differed in magnitude as well as the distribution of spin relaxation rate originates the moment modulation. The fact that the spectrum of DyAg 2 Si 2 at 3 K consists of two distinct subspectra ensures the complicated antiferromagnetic structure where two kinds of Dy moments differed in magnitude are arranged noncollinearly. (author)

  6. Link between chemotactic response to Ni2+ and its adsorption onto the Escherichia coli cell surface. (United States)

    Borrok, David; Borrok, M Jack; Fein, Jeremy B; Kiessling, Laura L


    Bacterial chemotaxis is of medical, biological, and geological significance. Despite its importance, current chemotaxis measurements fail to account for the speciation of the chemical effector and the protonation state of the bacterial surface. We hypothesize that adsorption of Ni2+ onto the surface of Escherichia coli can influence its effective concentration and therefore influence its ability to induce a repellent response. By measuring repellent response at different pH values, the influence of Ni2+ adsorption on chemotaxis was assessed. In addition, we tested the effect of different Ni2+ chelating agents. Our data indicate that adsorption reactions influence the chemotactic response to Ni2+. We use potentiometric titration and Ni2+ adsorption experiments to develop and constrain a thermodynamic model capable of quantifying the concentration of Ni2+ at the bacteria/solution interface. Results from this model predict that the concentration of adsorbed Ni2+ is linearly proportional to the magnitude of the chemotactic response in E. coli. If adsorption is linked to chemotaxis in other cases, then chemotactic responses in realistic settings depend on a number of environmental factors such as pH, competing binding agents (e.g., aqueous organic acids, natural organic matter, mineral surfaces, etc.), and ionic strength. Our modeling approach quantifies adsorbed species on bacterial surfaces and may be used to predict the responses of different species to a variety of chemoeffectors. Our data suggest that specified changes in environmental conditions can be used to tune chemotactic responses in natural biological and geological settings.

  7. The magnetic moment of Ni in the Laves phase compound GdNi2

    International Nuclear Information System (INIS)

    Yano, Kazuo; Umehara, Izuru; Miyazawa, Tomoaki; Adachi, Yoshiya; Sato, Kiyoo


    Magnetization and inverse susceptibility of the Laves phase compound GdNi 2 were investigated and analyzed in detail by employing molecular-field analysis. Both the temperature dependence of the magnetization and the Curie-Weiss (C-W) law-like linear relationship of inverse susceptibility are reproduced in terms of a two-sublattice model and it is seen that the magnetic structure of GdNi 2 is ferrimagnetic and Ni in GdNi 2 retains a magnetic moment of about 0.24μ B

  8. Equilibrium ion exchange studies of Ni2+ on homoionic forms of clinoptilolite

    Directory of Open Access Journals (Sweden)

    Joshua Gorimbo


    Full Text Available A natural zeolite (clinoptilolite that is mined in KwaZulu-Natal, South Africa, was evaluated for the removal of Ni2+ from wastewater. In particular, the effect of zeolite modification on Ni2+ removal from synthetic wastewater was investigated. The natural clinoptilolite was pretreated with 2 M metal chlorides for 24 h to yield near homoionic Na+, K+ and Ca2+ forms. A comparison of the isotherms for the Na+-Ni2+, K+-Ni2+, Ca2+-Ni2+ and natural-Ni2+ systems gave insight into how the displaced ion affects the selectivity of the clinoptilolite for Ni2+. The Na+, K+ and natural forms show highly selective convex isotherms whereas the Ca2+ form has a concave graph suggesting that the selectivity series is Ca2+> Ni2+> (Na+, K+, natural. Thermodynamic properties revealed that the Ni2+ sorption capacity increases as the values of the equilibrium constant and Gibbs free energy increase with increasing temperature from 298.15 K to 348.15 K. The enthalpy change was positive for all forms of clinoptilolite; values of 26.00 kJ/mol, 18.72 kJ/mol and 42.05 kJ/mol were obtained for exchange of Ni2+ into Na+, K+ and Ca2+ forms, respectively. The positive changes in enthalpy provide an indication that the sorption reaction is endothermic for Ni(II. The Gibbs free energy values were all negative except for Ca2+-exchanged clinoptilolite at 298.15 K and 308.15 K, for which the values were positive 3.10 kJ/mol and 0.53 kJ/mol, respectively. The entropy values for Ni2+ sorption were also positive; values of 0.12 kJ/mol.K, 0.08 kJ/mol.K and 0.14 kJ/mol.K were obtained for the Na+, K+ and Ca2+ forms, respectively. As expected, the enthalpy obtained from the Van’t Hoff plot is dependent not only on the metal ion being adsorbed, but also on the ion being displaced. Pretreatment of the zeolite enhances the removal efficiency provided that monovalent ions are used for the pretreatment. Thus clinoptilolite is an effective low-cost absorbent for the removal of Ni2+ from

  9. Microstructural investigations of Ni and Ni2Al3 coatings exposed in biomass power plants

    DEFF Research Database (Denmark)

    Wu, D. L.; Dahl, K. V.; Christiansen, T. L.


    temperature pack cementation. After exposure, microstructural investigations were performed by light optical and electron microscopy (SEM-EDS). Electroplated Ni coatings were not protective in straw firing power plants and exhibited similar corrosion morphology as uncoated tubes. For Ni2Al3 coatings......The present work investigates the corrosion resistance of Ni and Ni2Al3 coated austenitic stainless steel (TP347H) tubes, which were exposed in a biomass-fired boiler with an outlet steam temperature of 540 °C for 6757 h. The Ni2Al3 coating was produced by electroplating Ni followed by low......, the nickel aluminide layer was no longer adherent to the tube and was only found within the deposit. However, Ni2Al3 coatings had provided some protection compared to uncoated and Ni coated tubes. The formation of nickel chloride binds aggressive chlorine and slows down the active oxidation mechanism...

  10. Magnetism and superconductivity in ErNi2B2C

    Indian Academy of Sciences (India)

    in modulation vector and harmonic content. Studies of the vortex lattice show the presence of a 45. ◦ reorientation transition and a distorted hexagonal to square transition as a function of applied field. Further distortions of the vortex lattice occur at TN, but no changes are seen at TF. Keywords. (RE)Ni2B2C; ErNi2B2C; vortex ...

  11. Ni(2+)-zeolite/ferrosphere and Ni(2+)-silica/ferrosphere beads for magnetic affinity separation of histidine-tagged proteins. (United States)

    Vereshchagina, T A; Fedorchak, M A; Sharonova, O M; Fomenko, E V; Shishkina, N N; Zhizhaev, A M; Kudryavtsev, A N; Frank, L A; Anshits, A G


    Magnetic Ni(2+)-zeolite/ferrosphere and Ni(2+)-silica/ferrosphere beads (Ni-ferrosphere beads - NFB) of a core-shell structure were synthesized starting from coal fly ash ferrospheres having diameters in the range of 0.063-0.050 mm. The strategy of NFB fabrication is an oriented chemical modification of the outer surface preserving the magnetic core of parent beads with the formation of micro-mesoporous coverings. Two routes of ferrosphere modification were realized, such as (i) hydrothermal treatment in an alkaline medium resulting in a NaP zeolite layer and (ii) synthesis of micro-mesoporous silica on the glass surface using conventional methods. Immobilization of Ni(2+) ions in the siliceous porous shell of the magnetic beads was carried out via (i) the ion exchange of Na(+) for Ni(2+) in the zeolite layer or (ii) deposition of NiO clusters in the zeolite and silica pores. The final NFB were tested for affinity in magnetic separation of the histidine-tagged green fluorescent protein (GFP) directly from a cell lysate. Results pointed to the high affinity of the magnetic beads towards the protein in the presence of 10 mM EDTA. The sorption capacity of the ferrosphere-based Ni-beads with respect to GFP was in the range 1.5-5.7 mg cm(-3).

  12. Biosorpsi Ni2+ oleh Nannochloropsis Salina pada Medium Terpapar Ca2+

    Directory of Open Access Journals (Sweden)

    Yusafir Hala


    Full Text Available Research on biosorption of Ni2+ by N. salina in Ca2+ exposed medium has been done.  This study aimed to determine the growth and efficiency of N. salina towards Ni2+ in Conwy Medium with addition of Ca2+.  Exposure of mixed ions of Ni2+ 5 ppm and Ca2+ with variation of concentrations 10, 30, 50 ppm was conducted at the beginning of the growth of N. salina.  The growth of N. salina was observed every day by counting the number of N. salina population using a microscope and haemocytometer.  The concentration of metal ions after the exposure was determined by atomic absorption spectrophotometer.  The growth of N. salina in medium with exposed metal ions is lower than the control.  The maximum sorption efficiency of Ni2+ as a single ion is 55.2%. After exposure of mixed ions of Ni2+ and Ca2+ with variation of concentrations 10, 30, 50 ppm, the sorption efficiency of Ni2+ in sequents are 17.6%; 17.8%; and 19.6%; while the maximum sorption efficiency of N. salina towards Ca2+ are 5.1%; 7.1%; and 4.0% respectively.DOI :   

  13. Electronic, magnetic and mechanical properties of (Fe,Ni)2Nb from density functional theory (United States)

    Qi, J. J.; Zhou, Y.; Wang, W.; Qian, L. H.; Lv, Z. Q.; Fu, W. T.


    A comprehensive analysis of the phase stability, electronic structure, magnetic and mechanical properties of the Laves phases Fe2Nb and Ni2Nb with C14, C15 and C36 structures has been presented using first-principles calculations. The effects of pressure on the formation energy and magnetic properties of Fe2Nb and Ni2Nb have been discussed. The effects of the composition on the mechanical properties of (Fe,Ni)2Nb have also been discussed. The results show that the electrons in Fe2Nb transfer from Fe to Nb, while the electrons shift from Nb to Ni in Ni2Nb. Fe2Nb and Ni2Nb with C14, C15 and C36 structure are of strong metallicity, and the metallicity of C15 phase is stronger than that of C14 and C36 types. The magnetic moments of Fe2Nb are similar to each other, and the value of C14-Fe2Nb is little bigger than that of the two others. The magnetic moments of Fe2Nb decrease with increasing pressure and the values decline evidently from 0 to 20 GPa. The hardness of C15 phase, with stronger metallicity, is lower than that of C14 phase and C36 phase. For (Fe,Ni)2Nb, the hardness decreases with increasing Ni and the ability to resist deformation increases with decreasing Ni.

  14. Novel preparation of highly dispersed Ni2P embedded in carbon framework and its improved catalytic performance (United States)

    Wang, Shan; Wang, Kang; Wang, Xitao


    Highly dispersed Ni2P embedded in carbon framework with different phosphidation temperature was prepared through carbonizing Ni-alginate gel and followed by phosphidation with PPh3 in liquid phase. The significant effects of phosphidation temperature on Ni2P particle size and catalytic properties for isobutane dehydrogenation to isobutene were investigated. The results showed that Ni2P catalyst derived from the Ni-alginate gel (Ni2P-ADC), consisting of Ni2P particles embedded in carbon walls, possessed smaller particle size and more active site compared with Ni2P catalyst supported on active carbon (Ni2P/AC) prepared by impregnation method. The Ni2P-ADC catalyst phosphorized at 578 K for 3 h exhibited the highest catalytic performance, with the corresponding selectivity of isobutene approaching 89% and conversion approaching 15% after reaction for 4.5 h at 833 K, whereas Ni2P/AC catalyst prepared by impregnation method displays a much lower catalytic activity. The improved catalytic performance of the Ni2P-ADC can be ascribed to the smaller and highly dispersed Ni2P particles incorporated into carbon framework resulting from Ni-alginate gel.

  15. Two-dimensional correlation spectroscopic studies on coordination between organic ligands and Ni2+ions. (United States)

    Bao, Ya-Nan; Zeng, Yi-Wei; Guo, Ran; Ablikim, Mesude; Shi, Hai-Fang; Yang, Li-Min; Yang, Zhan-Lan; Xu, Yi-Zhuang; Noda, Isao; Wu, Jin-Guang


    3 A 2g → 3 T 1g (P) transition band of Ni 2+ is used to probe the coordination of Ni 2+ . Two-dimensional asynchronous spectra (2DCOS) are generated using the Double Asynchronous Orthogonal Sample Design (DAOSD), Asynchronous Spectrum with Auxiliary Peaks (ASAP) and Two-Trace Two-Dimensional (2T2D) approaches. Cross peaks relevant to the 3 A 2g → 3 T 1g (P) transition band of Ni 2+ are utilized to probe coordination between Ni 2+ and various ligands. We studied the spectral behavior of the 3 A 2g → 3 T 1g (P) transition band when Ni 2+ is coordinated with ethylenediaminetetraacetic acid disodium salt (EDTA). The pattern of cross peaks in 2D asynchronous spectrum demonstrates that coordination brings about significant blue shift of the band. In addition, the absorptivity of the band increases remarkably. The interaction between Ni 2+ and galactitol is also investigated. Although no clearly observable change is found on the 3 A 2g → 3 T 1g (P) transition band when galactitol is introduced, the appearance of cross peak in 2D asynchronous spectrum demonstrates that coordination indeed occurs between Ni 2+ and galactitol. Furthermore, the pattern of cross peak indicates that peak position, bandwidth and absorptivity of the 3 A 2g → 3 T 1g (P) transition band of Ni(galactitol) x 2+ is considerably different from those of Ni(H 2 O) 6 2+ . Thus, 2DCOS is helpful to reveal subtle spectral variation, which might be helpful in shedding light on the physical-chemical nature of coordination. Copyright © 2017. Published by Elsevier B.V.

  16. Phase diagram of Ni2+ ions complexes with polyU×polyA×polyU

    Directory of Open Access Journals (Sweden)

    Usenko E. L.


    Full Text Available Aim. To investigate Ni2+ ion effect on the conformational equilibrium of the three-stranded polynucleotide polyU×polyA×polyU and to ascertain thermodynamic parameters of the metal complex formation. Methods. The differential UV spectroscopy and thermal denaturation. Results. Dependences of conformational transition (Tm of poly U×polyA×polyU (A2U on Ni2+ ion con- centration (up to 0.001 M under conditions close to physiological ones (0.1 M Na+, pH 7 were obtained. At [Ni2+] < 3×10–4 M two branches are observed in the phase diagram, corresponding to A2U → polyA×polyU (AU + polyU (3→2 and AU→polyA + polyU (2→1 transitions. Only A2U→polyU + polyA + polyU (3→1 transition is realized at higher Ni2+ concentrations and upon A2U heating. Effective binding constants are determined for Ni2+ ions with AU (850 M–1 and A2U (1300 M–1 as well as 3→2 transition enthalpy (DH3→2 = 4±1 kcal/mol×triplet. Conclusions. By the equilibrium binding theory the thermodynamic nature of (Tm2→3 different behavior in the phase diagram of AU in the presence of Mg2+ and Ni2+ ions was determined. A larger difference of the magnesium affinity to A2U and AU as compared with that to AU and poly A results in (Tm2→3 decrease whereas the opposite ratio of Ni2+ ion binding constants induces its increasing

  17. Comparative DFT study of van der Waals complexes: rare-gas dimers, alkaline-earth dimers, zinc dimer, and zinc-rare-gas dimers. (United States)

    Zhao, Yan; Truhlar, Donald G


    Recent interest in the application of density functional theory prompted us to test various functionals for the van der Waals interactions in the rare-gas dimers, the alkaline-earth metal dimers, zinc dimer, and zinc-rare-gas dimers. In the present study, we report such tests for 18 DFT functionals, including both some very recent functionals and some well-established older ones. We draw the following conclusions based on the mean errors in binding energies and complex geometries: (1) B97-1 gives the best performance for predicting the geometry of rare-gas dimers, whereas M05-2X and B97-1 give the best energetics for rare-gas dimers. (2) PWB6K gives the best performance for the prediction of the geometry of the alkaline-earth metal dimers, zinc dimers, and zinc-rare-gas dimers. M05-2X gives the best energetics for the metal dimers, whereas B97-1 gives the best energetics for the zinc-rare-gas dimers. (3) The M05 functional is unique in providing good accuracy for both covalent transition-metal dimers and van der Waals metal dimers. (4) The combined mean percentage unsigned error in geometries and energetics shows that M05-2X and MPWB1K are the overall best methods for the prediction of van der Waals interactions in metal and rare-gas van der Waals dimers.

  18. Preparation of geopolymer-based inorganic membrane for removing Ni(2+) from wastewater. (United States)

    Ge, Yuanyuan; Yuan, Yuan; Wang, Kaituo; He, Yan; Cui, Xuemin


    A type of novel free-sintering and self-supporting inorganic membrane for wastewater treatment was fabricated in this study. This inorganic membrane was synthesised using metakaolin and sodium silicate solutions moulded according to a designed molar ratio (SiO2/Al2O3=2.96, Na2O/Al2O3=0.8 and H2O/Na2O=19) which formed a homogenous structure and had a relative concentration pore size distribution, via scanning electron microscopy (SEM) and Brunauer-Emmett-Teller (BET) analyses. In this work, the Ni(2+) removal effect of geopolymer inorganic membrane was studied under different pH value, initial concentration of Ni(2+) solutions and initial operation temperature. Results showed that geopolymer inorganic membrane efficiently removes Ni(2+) from wastewater because of the combined actions of the adsorption and rejection of this membrane on Ni(2+) during membrane separation. Therefore, geopolymer inorganic membrane may have positive potential applications in removing Ni(2+) or other heavy metal ions from aqueous industrial wastewater. Copyright © 2015 Elsevier B.V. All rights reserved.

  19. Adventures in Holographic Dimer Models

    Energy Technology Data Exchange (ETDEWEB)

    Kachru, Shamit; /Stanford U., Phys. Dept. /SLAC; Karch, Andreas; /Washington U., Seattle; Yaida, Sho; /Stanford U., Phys. Dept.


    We abstract the essential features of holographic dimer models, and develop several new applications of these models. Firstly, semi-holographically coupling free band fermions to holographic dimers, we uncover novel phase transitions between conventional Fermi liquids and non-Fermi liquids, accompanied by a change in the structure of the Fermi surface. Secondly, we make dimer vibrations propagate through the whole crystal by way of double trace deformations, obtaining nontrivial band structure. In a simple toy model, the topology of the band structure experiences an interesting reorganization as we vary the strength of the double trace deformations. Finally, we develop tools that would allow one to build, in a bottom-up fashion, a holographic avatar of the Hubbard model.

  20. Quantum efficiencies of near-infrared emission from Ni2+-doped glass-ceramics

    International Nuclear Information System (INIS)

    Suzuki, Takenobu; Arai, Yusuke; Ohishi, Yasutake


    A systematic method to evaluate potentials of Ni 2+ -doped transparent glass-ceramics as a new broadband optical gain media is presented. At first, near-infrared emission of various ceramics were investigated to explore the suitable crystalline phase to be grown in the glass-ceramics. The quantum efficiency of Ni 2+ near-infrared emission estimated by the Struck-Fonger analysis was higher than 95% for spinel-type structure gallate crystals MgGa 2 O 4 and LiGa 5 O 8 at room temperature. Transparent glass-ceramics containing Ni 2+ :LiGa 5 O 8 could be prepared and the quantum efficiency for the glass-ceramics was measured to be about 10%. This value shows a potential of Ni-doped transparent glass-ceramics as a broadband gain media

  1. Electronic structure and X-ray spectroscopic properties of YbNi2P2

    International Nuclear Information System (INIS)

    Shcherba, I.D.; Bekenov, L.V.; Antonov, V.N.; Noga, H.; Uskokovic, D.; Zhak, O.; Kovalska, M.V.


    Highlights: • We present new experimental and theoretical data for YbNi 2 P 2 . • The presence of divalent and trivalent Yb ion found in YbNi 2 P 2 . • The calculation show good agreement with the experimental measurements. - Abstract: X-ray absorption spectrum at the Yb L 3 edge and X-ray emission spectra of Ni and P at the K and L 2,3 edges have been studied experimentally and theoretically in the mixed valent compound YbNi 2 P 2 with ThCr 2 Si 2 type crystal structure. The electronic structure of YbNi 2 P 2 is investigated using the fully relativistic Dirac linear muffin-tin orbital (LMTO) band-structure method. The effect of the spin–orbit (SO) interaction and Coulomb repulsion U on the electronic structure of YbNi 2 P 2 is examined in the frame of the LSDA + SO + U method. The core-hole effect in the final states as well as the effect of the electric quadrupole E 2 transitions have been investigated. A good agreement between the theory and the experiment was found. Both the trivalent and the divalent Yb ions in YbNi 2 P 2 are reflected in the experimentally measured Yb L 3 X-ray absorption spectrum simultaneously. We found that the best agreement between the experimental spectrum and sum of the theoretically calculated Yb 2+ and Yb 3+ spectra is achieved with 73% ytterbium ions in 2+ state and 27% ions in 3+ state.

  2. Magnetic studies of Co2+, Ni2+, and Zn2+-modified DNA double-crossover lattices (United States)

    Dugasani, Sreekantha Reddy; Oh, Young Hoon; Gnapareddy, Bramaramba; Park, Tuson; Kang, Won Nam; Park, Sung Ha


    We fabricated divalent-metal-ion-modified DNA double-crossover (DX) lattices on a glass substrate and studied their magnetic characteristics as a function of ion concentrations [Co2+], [Ni2+] and [Zn2+]. Up to certain critical concentrations, the DNA DX lattices with ions revealed discrete S-shaped hysteresis, i.e. characteristics of strong ferromagnetism, with significant changes in the coercive field, remanent magnetization, and susceptibility. Induced magnetic dipoles formed by metal ions in DNA duplex in the presence of a magnetic field imparted ferromagnetic behaviour. By considering hysteresis and the magnitude of magnetization in a magnetization-magnetic field curve, Co2+-modified DNA DX lattices showed a relatively strong ferromagnetic nature with an increasing (decreasing) trend of coercive field and remanent magnetization when [Co2+] ≤ 1 mM ([Co2+] > 1 mM). In contrast, Ni2+ and Zn2+-modified DNA DX lattices exhibited strong and weak ferromagnetic behaviours at lower (≤1 mM for Ni2+ and ≤0.5 mM for Zn2+) and higher (>1 mM for Ni2+ and >0.5 mM for Zn2+) concentrations of ions, respectively. About 1 mM of [Co2+], [Ni2+] and [Zn2+] in DNA DX lattices was of special interest with regard to physical characteristics and was identified to be an optimum concentration of each ion. Finally, we measured the temperature-dependent magnetic characteristics of the metal-ion-modified DNA DX lattices. Nonzero magnetization and inverse susceptibility with almost constant values were observed between 25 and 300 K, with no indication of a magnetic transition. This indicated that the magnetic Curie temperatures of Co2+, Ni2+ and Zn2+-modified DNA DX lattices were above 300 K.

  3. Kinetics of DNA tile dimerization. (United States)

    Jiang, Shuoxing; Yan, Hao; Liu, Yan


    Investigating how individual molecular components interact with one another within DNA nanoarchitectures, both in terms of their spatial and temporal interactions, is fundamentally important for a better understanding of their physical behaviors. This will provide researchers with valuable insight for designing more complex higher-order structures that can be assembled more efficiently. In this report, we examined several spatial factors that affect the kinetics of bivalent, double-helical (DH) tile dimerization, including the orientation and number of sticky ends (SEs), the flexibility of the double helical domains, and the size of the tiles. The rate constants we obtained confirm our hypothesis that increased nucleation opportunities and well-aligned SEs accelerate tile-tile dimerization. Increased flexibility in the tiles causes slower dimerization rates, an effect that can be reversed by introducing restrictions to the tile flexibility. The higher dimerization rates of more rigid tiles results from the opposing effects of higher activation energies and higher pre-exponential factors from the Arrhenius equation, where the pre-exponential factor dominates. We believe that the results presented here will assist in improved implementation of DNA tile based algorithmic self-assembly, DNA based molecular robotics, and other specific nucleic acid systems, and will provide guidance to design and assembly processes to improve overall yield and efficiency.

  4. Dynamics and energetics of Ge(001) dimers

    NARCIS (Netherlands)

    van Houselt, Arie; van Gastel, Raoul; Poelsema, Bene; Zandvliet, Henricus J.W.


    The dynamic behavior of surface dimers on Ge(001) has been studied by positioning the tip of a scanning tunneling microscope over single flip-flopping dimers and measuring the tunneling current as a function of time. We observe that not just symmetric, but also asymmetric appearing dimers exhibit

  5. Synthesis and analysis of Fe 3, Co 2 and Ni 2: PEO+ PVP blended ...

    Indian Academy of Sciences (India)

    Blended polymer films of polyethylene oxide + polyvinyl pyrrolidone (PEO + PVP) containing transition metal (TM) ions like Fe3+, Co2+ and Ni2+ have been synthesized by a solution casting method. For these films, structural, thermal, magnetic and optical properties have been studied. X-ray diffraction results reveal the ...

  6. A colorimetric probe for the detection of Ni2+ in water based on Ag ...

    African Journals Online (AJOL)

    A Ni2+ based colorimetric probe based on glutathione-stabilized silver/copper nanoparticles (GSH-Ag-Cu alloy NPs) in an electrospun polymer matrix is reported. Glutathione-Ag-Cu alloy NPs were characterized by ultraviolet-visible spectroscopy (UV-vis), scanning electron microscopy (SEM) and transmission electron ...

  7. Two new 1D chains of Ni2Na2 heterometallic double half-cubane ...

    Indian Academy of Sciences (India)

    Keywords. Coordination polymers; cluster; Ni 2 II , 1D chain; magnetism; DFT. Abstract. An equimolar mixture of Ni(NO3)2·6H2O and pyridine-2-aldehyde with two equivalents of NaN3 in methanol in the presence of NaOMe resulted in the formation of light green precipitate which upon crystallization from dimethylformamide ...

  8. Molecular dynamics investigation of Na+ in Na2Ni2TeO6

    International Nuclear Information System (INIS)

    Sau, Kartik; Kumar, P. Padma


    An inter-atomic potential for Na 2 Ni 2 TeO 6 in the Parrinello- Rahman-Vashishta (PRV) model is parameterized empirically. The potential reproduces variety of structural and transport properties of that material in good agreement with recent experimental results. The study provides fresh insights on the migration channels and mechanism of Na + in the system

  9. Thermodynamic studies on the adsorption of Cu2+, Ni2+ and Cd2+ ...

    African Journals Online (AJOL)

    Amine-modified bentonite (TEPA-Bn) has been prepared with tetraethylenepentamine (TEPA) as a modifier. The structure of Ca-based bentonite (Ca-Bn), TEPA-Bn and TEPA-Bn after adsorbing Cu2+,Ni2+,Cd2+ had been characterized by Fourier transform infrared (FTIR) spectroscopy, X-ray diffraction (XRD) and ...

  10. Adsorption equilibrium isotherms of Pb 2+ , Ni 2+ And Cd 2+ onto ...

    African Journals Online (AJOL)

    This study reports the adsorption equilibrium of lead (Pb2+), nickel (Ni2+) and cadmium (Cd2+) from aqueous solution by chicken's eggshells. The eggshells were collected from within Obafemi Awolowo University, Ile-Ife, Nigeria. They were washed with distilled water, air dried, pulverized, sieved into different particle sizes ...

  11. Adsorption of Cu 2+ and Ni 2+ ions from their aqueous solutions ...

    African Journals Online (AJOL)

    The adsorption of Cu2+ and Ni2+ions at room temperature (27°C) onto two types of biomass produced from orange mesocarp namely: untreated orange mesocarp (Me) of 250 μm particle size and xanthated orange mesocarp (XMe) produced from Me of 250 μm particle size were studied. The results obtained showed that ...

  12. Magnetism and superconductivity in ErNi 2 B 2 C

    Indian Academy of Sciences (India)

    We have performed a series of neutron diffraction experiments from the magnetic order and the vortex lattice in single crystal ErNi2B2C. The incommensurate magnetic structure develops additional even harmonics below the `ferromagnetic' ordering temperature, F of 2.3 K. This feature and the existence of rods of diffuse ...

  13. Rubidium dimers in paraffin-coated cells

    International Nuclear Information System (INIS)

    Acosta, V M; Windes, D; Corsini, E; Ledbetter, M P; Karaulanov, T; Budker, D; Jarmola, A; Auzinsh, M; Rangwala, S A; Jackson Kimball, D F


    Measurements were made to determine the density of rubidium dimer vapor in paraffin-coated cells. The number density of dimers and atoms in similar paraffin-coated and uncoated cells was measured by optical spectroscopy. Due to the relatively low melting point of paraffin, a limited temperature range of 43-80 0 C was explored, with the lower end corresponding to a dimer density of less than 10 7 cm -3 . With 1 min integration time, a sensitivity to dimer number density of better than 10 6 cm -3 was achieved. No significant difference in dimer density between the cells was observed.

  14. [Preparation of porous ceramics based on waste ceramics and its Ni2+ adsorption characteristics]. (United States)

    Zhang, Yong-Li; Wang, Cheng-Zhi; Shi, Ce; Shang, Ling-Ling; Ma, Rui; Dong, Wan-Li


    The preparation conditions of porous ceramics were determined by SEM, XRD and FT-IR characterizations as well as the nickel removal ability of porous ceramics to be: the mass fraction w of sesbania powder doped was 4%, and the calcination temperature was 800 degrees C. SEM and pore structure characterization illustrated that calcination caused changes in the structure and morphology of waste ceramics. With the increase of calcination temperature, the specific surface area and pore volume decreased, while the aperture increased. EDS analyses showed that the main elements of both the original waste porcelain powder and the porous ceramics were Si, Al and O. The SEM, XRD and FT-IR characterization of porous ceramics illustrated that the structure of porous ceramics was stable before and after adsorption. The series of experiments of Ni2+ adsorption using these porous ceramics showed that when the dosage of porous ceramics was 10 g x L(-1), the adsorption time was 60 min, the pH value was 6.32, and the concentration of nickel-containing wastewater was below 100 mg x L(-1), the Ni2+ removal of wastewater reached 89.7%. Besides, the porous ceramics showed higher removal efficiency on nickel in the wastewater. The Ni(2+)-containing wastewater was processed by the porous ceramics prepared, and the adsorption dynamics and adsorption isotherms of Ni2+ in wastewater by porous ceramics were investigated. The research results showed that the Ni2+ adsorption process of porous ceramics was in accordance with the quasi second-order kinetic model (R2 = 0.999 9), with Q(e) of 9.09 mg x g(-1). The adsorption process can be described by the Freundlich equation and Langmuir equation, and when the temperature increased from 20 degrees C to 40 degrees C, the maximum adsorption capacity Q(m) increased from 14.49 mg x g(-1) to 15.38 mg x g(-1).

  15. Elastic properties of Ni2MnGa from first-principles calculations

    International Nuclear Information System (INIS)

    Ozdemir Kart, S.; Cagin, T.


    Research highlights: In this study, we have performed spin-polarized total energy calculations aiming to develop microscopic understanding of magnetic shape memory behavior of Ni 2 MnGa. This paper is devoted to determine the mechanical properties of Ni 2 MnGa in both austenitic and martensitic structures. To the best of our knowledge, this work presents the elastic constants of Ni 2 MnGa in the structure of 5M martensite, for the first time. We have also re-calculated elastic constants for cubic and nonmodulated (NM) structures by using the potential with e/a = 7.5. The elastic constants are predicted by straining the cubic L2 1 , 5M pseudo-tetragonal and NM tetragonal martensitic structures. Because of the special significance of the isotropic bulk modulus, shear modulus, Young's modulus and Poisson's ratio for technological applications, we have also calculated these quantities from the elastic constants. - Abstract: Elastic properties of Ni 2 MnGa in both austenitic and martensitic structures are determined by using ab initio methods based on density functional theory (DFT) within the spin-polarized generalized-gradient approximation. The tetragonal shear elastic constant C' takes a very small value in the austenitic phase, indicating the elastic instability results in a phase transition to martensitic structure. Isotropic mechanical properties such as bulk modulus, shear modulus, Young's modulus and Poisson's ratio are predicted. The trend of the Debye temperatures calculated for three structures of Ni 2 MnGa is comparable with that of the experiment.

  16. Adsorption of Ni2+ from aqueous solution by magnetic Fe@graphite nano-composite

    Directory of Open Access Journals (Sweden)

    Konicki Wojciech


    Full Text Available The removal of Ni2+ from aqueous solution by iron nanoparticles encapsulated by graphitic layers (Fe@G was investigated. Nanoparticles Fe@G were prepared by chemical vapor deposition CVD process using methane as a carbon source and nanocrystalline iron. The properties of Fe@G were characterized by X-ray Diffraction method (XRD, High-Resolution Transmission Electron Microscopy (HRTEM, Fourier Transform-Infrared Spectroscopy (FTIR, BET surface area and zeta potential measurements. The effects of initial Ni2+ concentration (1–20 mg L−1, pH (4–11 and temperature (20–60°C on adsorption capacity were studied. The adsorption capacity at equilibrium increased from 2.96 to 8.78 mg g−1, with the increase in the initial concentration of Ni2+ from 1 to 20 mg L−1 at pH 7.0 and 20oC. The experimental results indicated that the maximum Ni2+ removal could be attained at a solution pH of 8.2 and the adsorption capacity obtained was 9.33 mg g−1. The experimental data fitted well with the Langmuir model with a monolayer adsorption capacity of 9.20 mg g−1. The adsorption kinetics was found to follow pseudo-second-order kinetic model. Thermodynamics parameters, ΔHO, ΔGO and ΔSO, were calculated, indicating that the adsorption of Ni2+ onto Fe@G was spontaneous and endothermic in nature.

  17. Isomers and electronic states of Ni2O2H2 and evaluation of the effect of charge on the electronic properties and reactivity of Ni2O2. (United States)

    Hübner, Olaf; Himmel, Hans-Jörg


    Different isomers of Ni2O2H2 are investigated by multireference configuration interaction (MRCI) calculations, based on complete active space self-consistent field (CASSCF) calculations. The lowest-lying Ni2(OH)2 isomer has a rhombic shape with two OH(-) groups bridging two Ni(I) ions. Its ground term is a (1)Ag term. At a relative energy of 1.06 eV, there is a chain-like NiONi(OH2) isomer. A rhombic (NiH)2O2 isomer with Ni-H bonds has a considerably higher energy of 2.93 eV. Both Ni2(OH)2 and NiONi(OH2) feature a large number of low-lying electronic terms that in the case of Ni2(OH)2 form Heisenberg spin ladders due to the coupling of the electrons of two Ni(I) ions (3d(8)4s(1)) with S = 3/2. For the reaction Ni2O2 + H2 → Ni2(OH)2, the reaction energy is estimated to -2 eV. Finally, neutral and charged Ni2O2 and their hydrogenation products (Ni2O2H2(0/+)) are compared.

  18. Fiber optic D dimer biosensor (United States)

    Glass, Robert S.; Grant, Sheila A.


    A fiber optic sensor for D dimer (a fibrinolytic product) can be used in vivo (e.g., in catheter-based procedures) for the diagnosis and treatment of stroke-related conditions in humans. Stroke is the third leading cause of death in the United States. It has been estimated that strokes and stroke-related disorders cost Americans between $15-30 billion annually. Relatively recently, new medical procedures have been developed for the treatment of stroke. These endovascular procedures rely upon the use of microcatheters. These procedures could be facilitated with this sensor for D dimer integrated with a microcatheter for the diagnosis of clot type, and as an indicator of the effectiveness, or end-point of thrombolytic therapy.

  19. Dissociative attachment to lithium dimers

    International Nuclear Information System (INIS)

    Wadehra, J.M.


    The cross sections and the rates of production of negative ions of atomic lithium by the process of dissociative electron attachment to lithium dimers are obtained by using the resonant scattering theory. Both the cross sections as well as the rates of attachment are enhanced if the lithium molecule is initially vibrationally excited. General expressions for approximately obtaining the rates of electron attachment to any vibrational level of Li 2 are presented

  20. Novel covalently linked insulin dimer engineered to investigate the function of insulin dimerization

    DEFF Research Database (Denmark)

    Vinther, Tine N.; Norrman, Mathias; Strauss, Holger M.


    An ingenious system evolved to facilitate insulin binding to the insulin receptor as a monomer and at the same time ensure sufficient stability of insulin during storage. Insulin dimer is the cornerstone of this system. Insulin dimer is relatively weak, which ensures dissociation into monomers...... and insulin stability and function, we engineered a covalently linked insulin dimer in which two monomers were linked by a disulfide bond. The structure of this covalent dimer was identical to the self-association dimer of human insulin. Importantly, this covalent dimer was capable of further oligomerization...

  1. Neutron diffraction study of dense-Kondo compound CeNi2Al5

    International Nuclear Information System (INIS)

    Munoz, A.; Givord, F.; Boucherie, J.X.; Flouquet, J.; Isikawa, Y.; Mizushima, T.; Sakurai, J.; Mori, K.; Oliveira, I.S.


    Intermetallic CeNi 2 Al 5 is a dense-Kondo compound with a magnetic transition temperature at 2.6 K. We have carried out a neutron diffraction measurement to study a magnetic structure of CeNi 2 Al 5 using a powder sample and a single crystalline sample. It is found that the magnetic structure is an incommensurate sinusoidal one with a propagation vector k = (0.5, 0.405, 0.083) and that the amplitude of magnetic moment is 1.54 μ Β and the direction of magnetic moment is declined 8 deg. from the b-axis toward the a-axis. (authors). 3 refs., 2 figs

  2. Real space analysis of Compton profile of Heusler alloy Ni2TiAl (United States)

    Sahariya, Jagrati; Mund, H. S.; Ahuja, B. L.


    Electron momentum density of Ni2TiAl alloy has been studied using Compton scattering technique. The experiment has been performed using 20 Ci 137Cs (661.65 keV) Compton spectrometer at an intermediate resolution of 0.34 a.u. To interpret the experimental data, we have calculated the Compton profiles using Hartree Fock and density functional theories within the frame work of linear combination of atomic orbitals (LCAO) method. The experimental data have been interpreted in term of autocorrelation function B(z) of the one electron wave function. The experimental B(z) function has been compared with the LCAO based theoretical B(z), to analyze the electronic and structural properties of Ni2TiAl.

  3. Different magnetic properties of rhombohedral and cubic Ni2+ doped indium oxide nanomaterials

    Directory of Open Access Journals (Sweden)

    Qingbo Sun


    Full Text Available Transition metal ions doped indium oxide nanomaterials were potentially used as a kind of diluted magnetic semiconductors in transparent spintronic devices. In this paper, the influences of Ni2+ doped contents and rhombohedral or cubic crystalline structures of indium oxide on magnetic properties were investigated. We found that the magnetic properties of Ni2+ doped indium oxide could be transferred from room temperature ferromagnetisms to paramagnetic properties with increments of doped contents. Moreover, the different crystalline structures of indium oxide also greatly affected the room temperature ferromagnetisms due to different lattice constants and almost had no effects on their paramagnetic properties. In addition, both the ferromagnetic and paramagnetic properties were demonstrated to be intrinsic and not caused by impurities.

  4. Complexation of Cu2+, Ni2+ and UO22+ by radiolytic degradation products of bitumen

    International Nuclear Information System (INIS)

    Loon, L.R. Van; Kopajtic, Z.


    The radiolytic degradation of bitumen was studied under conditions which reflect those which will exist in the near field of a cementitious radioactive waste repository. The potential complexation capacity of the degradation products was studied and complexation experiments with Cu 2+ , Ni 2+ and UO 2 2+ were performed. In general 1:1 complexes with Cu 2+ , Ni 2+ and UO 2 2+ , with log K values of between 5.7 and 6.0 for Cu 2+ , 4.2 for Ni 2+ and 6.1 for UO 2 2+ , were produced at an ionic strength of 0.1 M. The composition of the bitumen water was analysed by GC-MS and IC. The major proportion of the bitumen degradation products in solution were monocarboxylic acids (acetic acid, formic acid, myric acid, stearic acid ...), dicarboxylic acids (oxalic acid, phthalic acid) and carbonates. The experimentally derived log K data are in good agreement with the literature and suggest that oxalate determines the speciation of Cu 2+ , Ni 2+ and UO 2 2+ in the bitumen water below pH=7. However, under the high pH conditions typical of the near field of a cementitious repository, competition with OH-ligands will be large and oxalate, therefore, will not play a significant role in the speciation of radionuclides. The main conclusion of the study is that the radiolytic degradation products of bitumen will have no influence on radionuclide speciation in a cementitious near field and, as such, need not to be considered in the appropriate safety assessment models. (author) 12 figs., 11 tabs., 31 refs

  5. Small-Angle Neutron Scattering and Magnetization Study of HoNi2B2C


    Ramazanoglu, M.; Laver, M.; Yagmurcu, A.; Choi, E. -M.; Lee, S. -I.; Knigavko, A.; Gaulin, B. D.


    The superconducting and magnetic properties of HoNi2B2C single crystals are investigated through transport, magnetometry and small-angle neutron scattering measurements. In the magnetic phases that enter below the superconducting critical temperature, the small-angle neutron scattering data uncover networks of magnetic surfaces. These likely originate from uncompensated moments e.g. at domain walls pinned to crystallographic grain boundaries. The field and temperature dependent behaviour appe...

  6. Interdependence of magnetism and superconductivity in the borocarbide TmNi2B2C

    DEFF Research Database (Denmark)

    Nørgaard, K.; Eskildsen, M.R.; Andersen, N.H.


    We have discovered anew antiferromagnetic phase in TmNi2B2C by neutron diffraction. The ordering vector is Q(A) = (0.48,0,0) and the phase appears shove a critical in-plans magnetic field of 0.9 T. The field was applied in order to test the assumption that the zero-field magnetic structure at Q...

  7. Solitary waves in dimer binary collision model (United States)

    Ahsan, Zaid; Jayaprakash, K. R.


    Solitary wave propagation in nonlinear diatomic (dimer) chains is a very interesting topic of research in the study of nonlinear lattices. Such waves were recently found to be supported by the essentially nonlinear granular lattice and Toda lattice. An interesting aspect of this discovery is attributed to the realization of a spectrum of the mass ratio (the only system parameter governing the dynamics) that supports the propagation of such waves corresponding to the considered interaction potential. The objective of this exposition is to explore solitary wave propagation in the dimer binary collision (BC) model. Interestingly, the dimer BC model supports solitary wave propagation at a discrete spectrum of mass ratios similar to those observed in granular and Toda dimers. Further, we report a qualitative and one-to-one correspondence between the spectrum of the mass ratio corresponding to the dimer BC model and those corresponding to granular and Toda dimer chains.

  8. Electronic structures and relevant physical properties of Ni2MnGa alloy films

    International Nuclear Information System (INIS)

    Kim, K. W.; Kim, J. B.; Huang, M. D.; Lee, N. N.; Lee, Y. P.; Kudryavtsev, Y. V.; Rhee, J. Y.


    The electronic structures and physical properties of the ordered and disordered Ni 2 MnGa alloy films were investigated in this study. Ordered and disordered Ni 2 MnGa alloy films were prepared by flash evaporation onto substrates maintained at 720 K and 150 K, respectively. The results show that the ordered films behave in nearly the same way as the bulk Ni 2 MnGa ferromagnetic shape-memory alloy, including the martensitic transformation at 200 K. It was also revealed that the film deposition onto substrates cooled by liquid nitrogen leads to the formation of a substantially-disordered or an amorphous phase which is not ferromagnetically ordered at room temperature. An annealing of such an amorphous film restores its crystallinity and also recovers the ferromagnetic order. It was also clarified how the structural disordering in the films influences the physical properties, including the loss of ferromagnetism in the disordered films, by performing electronic-structure calculations and a photoemission study.

  9. Enzymatic oxidative dimerization of silymarin flavonolignans

    Czech Academy of Sciences Publication Activity Database

    Gavezzotti, P.; Vavříková, Eva; Valentová, Kateřina; Fronza, G.; Kudanga, T.; Kuzma, Marek; Riva, S.; Biedermann, David; Křen, Vladimír


    Roč. 109, NOV 2014 (2014), s. 24-30 ISSN 1381-1177 R&D Projects: GA MŠk(CZ) LD13041; GA ČR(CZ) GP14-14373P Institutional support: RVO:61388971 Keywords : Silybin dimers * Silydianin dimer * Silymarin Subject RIV: CE - Biochemistry Impact factor: 2.128, year: 2014

  10. Directed diffusion of reconstituting dimers

    Energy Technology Data Exchange (ETDEWEB)

    Barma, Mustansir [Department of Theoretical Physics, Tata Institute of Fundamental Research, Mumbai 400005 (India); Grynberg, Marcelo D [Departamento de Fisica, Universidad Nacional de La Plata (1900) La Plata (Argentina); Stinchcombe, Robin B [Isaac Newton Institute for Mathematical Sciences, 20 Clarkson Road, Cambridge CB3 0EH (United Kingdom)


    We discuss the dynamical aspects of an asymmetric version of assisted diffusion of hard core particles on a ring studied by Menon et al (1997 J. Stat. Phys. 86 1237). The asymmetry brings in phenomena like kinematic waves and effects of the Kardar-Parisi-Zhang non-linearity, which combine with the feature of strongly broken ergodicity, a characteristic of the model. A central role is played by a single non-local invariant, the irreducible string, whose interplay with the driven motion of reconstituting dimers, arising from the assisted hopping, determines the asymptotic dynamics and scaling regimes. These are investigated both analytically and numerically through sector-dependent mappings to the asymmetric simple exclusion process.

  11. Luminescence Characteristics of Ni2+ Ion-Doped Glasses and Glass-Ceramics in Relation to Its Coordination Number (United States)

    Khonthon, Sasithorn; Morimoto, Shigeki; Ohishi, Yasutake

    Ni2+ ions occupy the tetrahedral (4), trigonal bipyramid (5) and octahedral (6) sites in glasses and glass-ceramics. The color changes depending on coordination number, typically pink for tetrahedral site, brown for trigonal bipyramid and tetrahedral sites and green to blue for octahedral site, respectively. The broad near infrared (NIR) emission peaking at around 1220 nm was observed for octahedral Ni2+ ions. This emission is due to 3T2(F)→3A2(F) transition.

  12. Pressure effects of the magnetic structures of TbNi2Si2 in external fields

    International Nuclear Information System (INIS)

    Kawano, S.; Fukui, S.; Onodera, A.; Amita, F.; Katano, S.


    Single crystal neutron diffraction studies of the field-induced magnetic structures of TbNi 2 Si 2 have been performed at 1.7 K without pressure and under 0.7 GPa using a cryomagnetic high pressure system. Without pressure at 1.7 K four intermediate structures have been identified between a zero-field simple antiferromagnetic structure and a fully ferromagnetic one. Under 0.7 GPa two field-induced phases with an antiphase-type modulation along the left angle 110 right angle direction was newly observed above 4 T, while below 3.3 T zero pressure structures are still retained. (orig.)

  13. Electronic structure of Ni2TiAl: Theoretical aspects and Compton scattering measurement (United States)

    Sahariya, Jagrati; Ahuja, B. L.


    In this paper, we report electron momentum density of Ni2TiAl alloy using an in-house 20 Ci 137Cs (661.65 keV) Compton spectrometer. The experimental data have been analyzed in terms of energy bands and density of states computed using linear combination of atomic orbitals (LCAO) method. In the LCAO computations, we have considered local density approximation, generalized gradient approximation and recently developed second order generalized gradient approximation within the frame work of density functional theory. Anisotropies in theoretical Compton profiles along [1 0 0], [1 1 0] and [1 1 1] directions are also explained in terms of energy bands.

  14. Pauli paramagnetic effects on vortices in superconducting TmNi2B2C

    DEFF Research Database (Denmark)

    DeBeer-Schmitt, L.; Eskildsen, Morten Ring; Ichioka, M.


    The magnetic field distribution around the vortices in TmNi2B2C in the paramagnetic phase was studied experimentally as well as theoretically. The vortex form factor, measured by small-angle neutron scattering, is found to be field independent up to 0.6H(c2) followed by a sharp decrease at higher...... fields. The data are fitted well by solutions to the Eilenberger equations when paramagnetic effects due to the exchange interaction with the localized 4f Tm moments are included. The induced paramagnetic moments around the vortex cores act to maintain the field contrast probed by the form factor....

  15. Intensity of two-photon absorption transitions for Ni2+ in MgO

    International Nuclear Information System (INIS)

    Sztucki, J.; Daoud, M.; Kibler, M.


    The parity-allowed two-photon transitions between the ground state 3 A 2 (T 2 ) of the configuration 3d 8 in cubical symmetry and the excited states of the same configuration are obtained via a simple model. This model is developed in a symmetry adapted framework by using second-order mechanisms and ionic wave-functions. It is applied to the recent experimental results obtained by McClure and co-workers for Ni 2+ in MgO. (author) 21 refs.; 2 tabs

  16. Microstructure and Abrasive Wear Resistance of 18Cr-4Ni-2.5Mo Cast Steel

    Directory of Open Access Journals (Sweden)

    Kalandyk B.


    Full Text Available An influence of a decreased Cr content on the microstructure of the highly alloyed Cr-Ni cast steel, duplex type, melted under laboratory conditions, was characterized in the paper. The microstructure investigations were performed in the initial state and after the heat treatment (solution annealing at 1060°C as well as the phase transformation kinetics at continuous cooling was measured. The wear resistance of the investigated cast steel was tested and compared with the 24%Cr-5%Ni-2.5%Mo cast steel.

  17. Activity of platinum/carbon and palladium/carbon catalysts promoted by Ni2 P in direct ethanol fuel cells. (United States)

    Li, Guoqiang; Feng, Ligang; Chang, Jinfa; Wickman, Björn; Grönbeck, Henrik; Liu, Changpeng; Xing, Wei


    Ethanol is an alternative fuel for direct alcohol fuel cells, in which the electrode materials are commonly based on Pt or Pd. Owing to the excellent promotion effect of Ni2 P that was found in methanol oxidation, we extended the catalyst system of Pt or Pd modified by Ni2 P in direct ethanol fuel cells. The Ni2 P-promoted catalysts were compared to commercial catalysts as well as to reference catalysts promoted with only Ni or only P. Among the studied catalysts, Pt/C and Pd/C modified by Ni2 P (30 wt %) showed both the highest activity and stability. Upon integration into the anode of a homemade direct ethanol fuel cell, the Pt-Ni2 P/C-30 % catalyst showed a maximum power density of 21 mW cm(-2) , which is approximately two times higher than that of a commercial Pt/C catalyst. The Pd-Ni2 P/C-30 % catalyst exhibited a maximum power density of 90 mW cm(-2) . This is approximately 1.5 times higher than that of a commercial Pd/C catalyst. The discharge stability on both two catalysts was also greatly improved over a 12 h discharge operation. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Comparative study of the magnetic properties of La3Ni2B‧O9 for B‧ = Nb, Taor Sb (United States)

    Chin, Chun-Mann; Battle, Peter D.; Blundell, Stephen J.; Hunter, Emily; Lang, Franz; Hendrickx, Mylène; Paria Sena, Robert; Hadermann, Joke


    Polycrystalline samples of La3Ni2NbO9 and La3Ni2TaO9 have been characterised by X-ray and neutron diffraction, electron microscopy, magnetometry and muon spin relaxation (μSR); the latter technique was also applied to La3Ni2SbO9. On the length scale of a neutron diffraction experiment, the six-coordinate sites of the monoclinic perovskite structure are occupied in a 1:1 ordered manner by Ni and a random ⅓Ni/⅔B‧ mixture. Electron microscopy demonstrated that this 1:1 ordering is maintained over microscopic distances, although diffuse scattering indicative of short-range ordering on the mixed site was observed. No magnetic Bragg scattering was observed in neutron diffraction patterns collected from La3Ni2B‧O9 (B‧ = Nb or Ta) at 5 K although in each case μSR identified the presence of static spins below 30 K. Magnetometry showed that La3Ni2NbO9 behaves as a spin glass below 29 K but significant short-range interactions are present in La3Ni2TaO9 below 85 K. The contrasting properties of these compounds are discussed in terms of their microstructure.

  19. Catalytic dehydrogenation of isobutane in the presence of hydrogen over Cs-modified Ni2P supported on active carbon (United States)

    Xu, Yanli; Sang, Huanxin; Wang, Kang; Wang, Xitao


    In this article, an environmentally friendly non-noble-metal class of Cs-Ni2P/active carbon (AC) catalyst was prepared and demonstrated to exhibit enhanced catalytic performance in isobutane dehydrogenation. The results of activity tests reveal that Ni/AC catalyst was highly active for isobutane cracking, which led to the formation of abundant methane and coke. After the introduction of phosphorus through impregnation with ammonium di-hydrogen phosphate and H2-temperature programmed reduction, undesired cracking reactions were effectively inhibited, and the selectivity to isobutene and stability of catalyst increased remarkably. The characterization results indicate that, after the addition of phosphorous, the improvement of dehydrogenation selectivity is ascribed to the partial positive charges carried on Ni surface in Ni2P particles, which decreases the strength of Nisbnd C bond between Ni and carbonium-ion intermediates and the possibility of excessive dehydrogenation. In addition, Cs-modified Ni2P/AC catalysts display much higher catalytic performance as compared to Ni2P/AC catalyst. Cs-Ni2P-6.5 catalyst has the highest catalytic performance, and the selectivity to isobutene higher than 93% can be obtained even after 4 h reaction. The enhancement in catalytic performance of the Cs-modified catalysts is mainly attributed to the function of Cs to improve the dispersion of Ni2P particles, transfer electron from Cs to Ni, and decrease acid site number and strength.

  20. Transport Properties of EuNi2Ge2 under High Pressure (United States)

    Wada, Hirofumi; Goki, Yusuke; Mitsuda, Akihiro


    Transverse magnetoresistance (MR) and Hall effect have been measured for EuNi2Ge2 single crystals under high pressures up to 2.0 GPa. The compound undergoes a valence transition from a nearly trivalent state to a divalent state with increasing temperature above 1.6 GPa. It was found that the transverse MR of EuNi2Ge2 is negative at low temperatures in the nearly trivalent state, although the compound is nonmagnetic. The origin of the negative MR is discussed. In the temperature dependence of the Hall resistivity ρH, large jumps associated with the valence transition were observed at the valence transition temperature. We also examined the field-induced valence transition by the MR and ρH measurements. A marked change in the Hall coefficient was observed at the valence transition field. Our analyses suggest that the ordinary Hall effect plays a dominant role in the changes in ρH at the valence transition.

  1. Structural and optical studies of pHEMA encapsulated ZnS:Ni2+ nanoparticles (United States)

    Mohan, R.; Sankarrajan, S.; Thiruppathi, G.


    In this study, ZnS:Ni2+ nanostructures have been synthesized through chemical precipitation method using poly (2-hydroxyethyl methacrylate) (pHEMA) as capping agent. The structural, morphological and optical properties at different pHEMA concentration of ZnS:Ni2+ were studied by using X-ray diffraction (XRD), high resolution transmission electron microscopy (HR-TEM), UV-Vis Spectroscopy (UV-Vis), fourier transform infrared spectroscopy (FT-IR), Photoluminescence (PL). The Average crystalline size of the nanoparticles was found to be in the range of ∼3.59-4.36 nm. The surface morphological analysis reveals that the pHEMA capped nanoparticles showed homogeneous smooth surface. HR-TEM analysis reminds the original size of pHEMA capped nanoparticles. The band gap investigation revealed the size dependent of quantum confined nanoparticles. The immobilized nanoparticles in pHEMA matrix were verified by FT-IR studies. Novel luminescence properties have been observed for uncapped and pHEMA capped ZnS nanoparticles. The optimal capping concentration was successfully determined and its influence on photoluminescence behavior has been thoroughly analyzed.

  2. Interplay between magnetism and superconductivity in HoNi2B2C revisited (United States)

    Alleno, E.; Singh, S.; Dhar, S. K.; André, G.


    In this work the magnetic and superconducting properties of HoNi2B2C were investigated by using powder neutron diffraction and the specific heat and upper critical field (Hc2) measurements as a function of temperature. Below T=8 K, three distinct anomalies at the temperatures TN=5.2 K, TH1=5.6 K and TM=6.0 K were observed in the specific heat of HoNi2B2C, as reported in the literature. Our neutron data confirm the transitions to the Néel structure (qN=c*) at TN and to the modulated structure (qM=0.586a*) at TM. The peak at TH1=5.7 K in the specific heat data, whose exact nature was not known hitherto, is now attributed to the onset of a qH1=0.905c* magnetic helical structure as seen in our neutron data. Comparison between the thermal evolution of the magnetic structures and the temperature dependence of the upper critical field confirms that the first Hc2(T) depression at 6.1 K arises from the qM=0.586a* modulated magnetic structure. The second depression in Hc2(T) below 5.7 K can be ascribed to the qH1=0.905c* magnetic helical structure.

  3. Effects of Ni2+ doping on the performances of lithium iron pyrophosphate cathode material (United States)

    Zheng, Jun-chao; Ou, Xing; Zhang, Bao; Shen, Chao; Zhang, jia-feng; Ming, Lei; Han, Ya-dong


    The Li2Fe1-xNixP2O7/C (x = 0.00, 0.02, 0.04, 0.06, 0.08, 0.10) composites were successfully synthesized for the first time by a conventional solid state route. The solid state reaction mechanism, crystal structure, morphology, and electrochemical performance of the samples are characterized in detail. The XRD results show that Ni2+ is incorporated in the lattice of Li2FeP2O7 and the monoclinic structure does not change after doping. Among all the samples, the Li2Fe0.98Ni0.02P2O7/C composite delivers the highest discharge capacity of 110.2 mAh g-1 at 0.025C, and possesses a capacity retention ratio of 90.1% after 100 cycles at 0.05C, demonstrating the best rate performance and cycle stability in the potential range of 2.0-4.5 V. Electrochemical impedance spectroscopy (EIS) results reveal that the Li2Fe0.98Ni0.02P2O7/C sample has a lower charge transfer resistance and a higher Li-ion diffusion coefficient compared to other samples. The results indicate Ni2+-doping in Li2FeP2O7/C can effectively enhance the electrochemical performance of this monoclinic compound, especially at a high charge/discharge rate.

  4. Multiband superconductivity of heavy electrons in a TlNi2Se2 single crystal. (United States)

    Wang, Hangdong; Dong, Chiheng; Mao, Qianhui; Khan, Rajwali; Zhou, Xi; Li, Chenxia; Chen, Bin; Yang, Jinhu; Su, Qiping; Fang, Minghu


    We have made the first observation of superconductivity in TlNi2Se2 at T(C)=3.7  K, and it appears to involve heavy electrons with an effective mass m*=(14-20)m(b), as inferred from the normal-state electronic specific heat and the upper critical field, H(C2)(T). We found that the zero-field electronic specific-heat data, C(es)(T) (0.5  K≤Tsuperconductor, which is consistent with the band calculation for the isostructural KNi2S2. It is also found that the electronic specific-heat coefficient in the mixed state γN(H) exhibits a H(1/2) behavior, which is considered as a common feature of the d-wave superconductors. TlNi2Se2, as a d-electron system with heavy electron superconductivity, may be a bridge between cuprate- or iron-based and conventional heavy-fermion superconductors.

  5. Anisotropy of the Vortex Magnetic Field Distribution in LuNi2B2 (United States)

    Eskildsen, M. R.; Debeer-Schmitt, L.; Rovira, K.; Jenkins, N.; Dewhurst, C. D.; Bud'Ko, S. L.; Canfield, P. C.


    It is well known that the vortex lattice (VL) symmetry and orientation in type-II superconductors is very sensitive to any anisotropy within the screening current plane. A classic example is the sequence of transitions from hexagonal to rhombic to square symmetry, which was first observed in the borocarbide superconductors and explained by a Fermi surface anisotropy coupled with the non-local electrodynamics responsible for vortex-vortex interactions. Recently, however, this is mounting experimental evidence for a strong gap anisotropy and possible point nodes in the basal plane of these materials. Here we report on small-angle neutron scattering studies of the VL in a carefully annealed, high quality LuNi2B2C single crystal, which permitted us to measure the VL form factor for a large number of reflections. These measurements allow a reconstruction of the real space profile of the magnetic field around the vortices, reflecting the basal plane anisotropy of the screening currents in LuNi2B2C. The results will be compared to predictions for both Fermi surface and gap anisotropies, and will serve as a valuable reference for more complicated compounds as e.g. Sr2RuO4, heavy fermions and high-Tc's.

  6. Adsorption kinetic parameters of Fe3+ and Ni2+ ions by gyrolite

    Directory of Open Access Journals (Sweden)

    Kestutis Baltakys


    Full Text Available In this work the adsorption kinetic parameters for Fe3+ and Ni2+ ions by gyrolite are presented. Additionally, the adsoption mechanism was described by using pseudo first order and pseudo second order  equations. It was determined that the adsorption capacity of gyrolite and intrusion of heavy metals ions in its structure depends on reaction time and the pH value of adsorptive. It was observed that the incorporation of Fe3+ ions occurs more intensive than Ni2+ ions. It was found that in the acidic solution the intrusion of Fe3+ ions into gyrolite structure proceeds by two types of chemical reaction mechanisms: substitution and addition. Meanwhile, nickel ions were participated only in substitution reaction: gyrolite-Ca0 + Mex+ ↔ gyrolite-Me0 + Ca2+. It was observed that the pseudo second order model fit well for iron and nickel ions adsorption mechanism. It was estimated that the adsorption reactions are not reversible process and the crystal structure of gyrolite is stable. Moreover, synthetic adsorbent and the products of sorption were characterized by XRD, STA and FT-IR methods.DOI:

  7. Biotransformation and Cytotoxic Activity of Guaiacol Dimer

    Directory of Open Access Journals (Sweden)

    Galuh Widiyarti


    Full Text Available Guaiacol, a phenolic compound is known as an anticancer. Dimerization of guaiacol has been done by biotransformation using peroxidase enzyme as biocatalyst. This enzyme was isolated from Indonesian plant, kailan (Brassica oleraceae var. alboglabra. Analysis of dimerization product was carried out by TLC, IR, LC-MS, and NMR. Whilst analysis of in-vitro cytotoxic activity was carried out by MTT method against breast cancer T47D and MCF7 cells. The result showed that the dimerization reaction gave O-para dehydroguaiacol. The in-vitro cytotoxic activity analysis showed that O-para dehydroguaiacol compound has potency as anti-breast cancer.

  8. Synthesis of new dimeric carvacrol compounds

    Directory of Open Access Journals (Sweden)

    Uttam B. More


    Full Text Available The polymer supported carvacrol anion was reacted with 1,2-dibromoethane, 1,4-dibromoethane, oxalyl dichloride, malonyl dichloride, succinyl dichloride, glutaroyl dichloride, and adipoyl dichloride to afford the corresponding dimeric carvacryl ethers or esters

  9. The two-state dimer receptor model: a general model for receptor dimers. (United States)

    Franco, Rafael; Casadó, Vicent; Mallol, Josefa; Ferrada, Carla; Ferré, Sergi; Fuxe, Kjell; Cortés, Antoni; Ciruela, Francisco; Lluis, Carmen; Canela, Enric I


    Nonlinear Scatchard plots are often found for agonist binding to G-protein-coupled receptors. Because there is clear evidence of receptor dimerization, these nonlinear Scatchard plots can reflect cooperativity on agonist binding to the two binding sites in the dimer. According to this, the "two-state dimer receptor model" has been recently derived. In this article, the performance of the model has been analyzed in fitting data of agonist binding to A(1) adenosine receptors, which are an example of receptor displaying concave downward Scatchard plots. Analysis of agonist/antagonist competition data for dopamine D(1) receptors using the two-state dimer receptor model has also been performed. Although fitting to the two-state dimer receptor model was similar to the fitting to the "two-independent-site receptor model", the former is simpler, and a discrimination test selects the two-state dimer receptor model as the best. This model was also very robust in fitting data of estrogen binding to the estrogen receptor, for which Scatchard plots are concave upward. On the one hand, the model would predict the already demonstrated existence of estrogen receptor dimers. On the other hand, the model would predict that concave upward Scatchard plots reflect positive cooperativity, which can be neither predicted nor explained by assuming the existence of two different affinity states. In summary, the two-state dimer receptor model is good for fitting data of binding to dimeric receptors displaying either linear, concave upward, or concave downward Scatchard plots.

  10. Adsorption of dimeric surfactants in lamellar silicates

    Energy Technology Data Exchange (ETDEWEB)

    Balcerzak, Mateusz; Pietralik, Zuzanna [Department of Macromolecular Physics, Faculty of Physics, A. Mickiewicz University, Umultowska 85, 61-614 Poznań (Poland); Domka, Ludwik [Department of Metalorganic Chemistry, Faculty of Chemistry, A. Mickiewicz University, Grunwaldzka 6, 60-780 Poznań (Poland); Skrzypczak, Andrzej [Institute of Chemical Technology, Poznań University of Technology, Berdychowo 4, 60-965 Poznań (Poland); Kozak, Maciej, E-mail: [Department of Macromolecular Physics, Faculty of Physics, A. Mickiewicz University, Umultowska 85, 61-614 Poznań (Poland)


    Highlights: • The intercalation of dimeric surfactants changed the morphology of MMT samples. • XRD indicated structures formed by surfactant molecules in interlayer space. • The four-step thermal decomposition of dimeric surfactant, confirms intercalation. - Abstract: The adsorption of different types of cationic surfactants in lamellar silicates changes their surface character from hydrophilic to hydrophobic. This study was undertaken to obtain lamellar silicates modified by a series of novel dimeric (gemini) surfactants of different length alkyl chains and to characterise these organophilised materials. Synthetic sodium montmorillonite SOMASIF® ME 100 (M) and enriched bentonite of natural origin (Nanoclay – hydrophilic bentonite®) were organophilised with dimeric (gemini) surfactants (1,1′-(1,4-butanediyl)bis(alkoxymethyl)imidazolium dichlorides). As a result of surfactant molecule adsorption in interlamellar space, the d-spacing (d{sub 001}) increased from 0.97 nm (for the anhydrous structure) to 2.04 nm. A Fourier transform infrared spectroscopy (FTIR) analysis of the modified systems reveals bands assigned to the stretching vibrations of the CH{sub 2} and CH{sub 3} groups and the scissoring vibrations of the NH group from the structure of the dimeric surfactants. Thermogravimetric (TG) and derivative thermogravimetric (DTG) studies imply a four-stage process of surfactant decomposition. Scanning electron microscopy (SEM) images provide information on the influence of dimeric surfactant intercalation into the silicate structures. Particles of the modified systems show a tendency toward the formation of irregularly shaped agglomerates.

  11. Retroviral RNA Dimerization: From Structure to Functions

    Directory of Open Access Journals (Sweden)

    Noé Dubois


    Full Text Available The genome of the retroviruses is a dimer composed by two homologous copies of genomic RNA (gRNA molecules of positive polarity. The dimerization process allows two gRNA molecules to be non-covalently linked together through intermolecular base-pairing. This step is critical for the viral life cycle and is highly conserved among retroviruses with the exception of spumaretroviruses. Furthermore, packaging of two gRNA copies into viral particles presents an important evolutionary advantage for immune system evasion and drug resistance. Recent studies reported RNA switches models regulating not only gRNA dimerization, but also translation and packaging, and a spatio-temporal characterization of viral gRNA dimerization within cells are now at hand. This review summarizes our current understanding on the structural features of the dimerization signals for a variety of retroviruses (HIVs, MLV, RSV, BLV, MMTV, MPMV…, the mechanisms of RNA dimer formation and functional implications in the retroviral cycle.

  12. Modulation of the conductance of a 2,2′-bipyridine-functionalized peptidic ion channel by Ni2+ (United States)

    Pilz, Claudia S.


    An α-helical amphipathic peptide with the sequence H2N-(LSSLLSL)3-CONH2 was obtained by solid phase synthesis and a 2,2′-bipyridine was coupled to its N-terminus, which allows complexation of Ni2+. Complexation of the 2,2′-bipyridine residues was proven by UV/Vis spectroscopy. The peptide helices were inserted into lipid bilayers (nano black lipid membranes, nano-BLMs) that suspend the pores of porous alumina substrates with a pore diameter of 60 nm by applying a potential difference. From single channel recordings, we were able to distinguish four distinct conductance states, which we attribute to an increasing number of peptide helices participating in the conducting helix bundle. Addition of Ni2+ in micromolar concentrations altered the conductance behaviour of the formed ion channels in nano-BLMs considerably. The first two conductance states appear much more prominent demonstrating that the complexation of bipyridine by Ni2+ results in a considerable confinement of the observed multiple conductance states. However, the conductance levels were independent of the presence of Ni2+. Moreover, from a detailed analysis of the open lifetimes of the channels, we conclude that the complexation of Ni2+ diminishes the frequency of channel events with larger open times. Electronic supplementary material The online version of this article (doi:10.1007/s00249-008-0298-8) contains supplementary material, which is available to authorized users. PMID:18347789

  13. Ni2+-based immobilized metal ion affinity chromatography of lactose operon repressor protein from Escherichia coli. (United States)

    Velkov, Tony; Jones, Alun; Lim, Maria L R


    A two-step chromatographic sequence is described for the purification of native lactose operon repressor protein from Escherichia coli cells. The first step involves Ni(2+)-based immobilized metal ion affinity chromatography of the soluble cytoplasmic extract. This method provides superior speed, resolution and yield than the established phosphocellulose cation-exchange chromatographic procedure. Anion-exchange chromatography is used for further purification to >95% purity. The identity and purity of the lactose repressor protein were demonstrated using sodium dodecylsulphate polyacrylamide electrophoresis, crystallization, tryptic finger-printing mass spectrometry, and inducer binding assays. The purified lac repressor exhibited inducer sensitivity for operator DNA binding and undergoes a conformational change upon inducer binding. By all these extensive biochemical criteria, the purified protein behaves exactly as that described for the Escherichia coli lactose operon repressor.

  14. Mechanical properties and corrosion behaviour of 18Cr-11Ni-2,5Mo cast steel

    Directory of Open Access Journals (Sweden)

    M. Starowicz


    Full Text Available The study discusses the effect of variable carbon concentration (0,02; 0,07 and 0,14% on the mechanical properties and corrosion resistance in 3,0% NaCl solution of 18Cr-11Ni-2,5Mo austenitic cast steel. It has been proved that at the concentration of 0,07%C, products made of the examined cast steel reveal on their surface some symptoms of local corrosion. Carbon concentration raised to 0,14%C results in advanced intercrystalline corrosion and the onset of local corrosion. Carbon concentration increased from 0,02 to 0,14% also results in the tensile strength UTS raised from 487MPa to 579MPa (a nearly 20% increase with elongation El reduced from 55,3% to 49,6%, and reduction of area RA from 69,3% to 53,4%.

  15. D-dimers (DD) in CVST. (United States)

    Wang, Hui Fang; Pu, Chuan Qiang; Yin, Xi; Tian, Cheng Lin; Chen, Ting; Guo, Jun Hong; Shi, Qiang


    We were interested in further confirming whether D-dimers (DD) are indeed elevated in cerebral venous sinus thrombosis (CVST) as reported in those studies. CVST patients who had a plasma D-dimer test (139 cases) were included and divided into two groups: elevated D-dimer group (EDG) (>0.5 μg/mL; 65 cases) and normal D-dimer group (NDG) (≤0.5 μg/mL; 74 cases). The two groups were compared in terms of demographic data, clinical manifestation, laboratory and imaging data, using inferential statistical methods. The chi-squared and Fisher exact test showed that, compared to the NDG (74 cases), patients with elevated D-dimer levels were more likely to have a shorter symptom duration (SD) (30 ± 83.9 versus 90 ± 58.9 d, p = 0.003), more risk factors (75.4% versus 52.7%, p = 0.006), higher multiple venous sinus involvement (75.4% versus 59.5%, p = 0.037), increased fibrinogen (43.1% versus 18.9%, p = 0.037) and higher levels of blood glucose (18.3% versus 11%, p = 0.037). According to correlation analyses, D-dimer levels were positively correlated with number of venous sinuses involvement (NVS) (r = 0.321, p = 0.009) in the EDG. Multivariate logistic regression analysis showed that SD (OR, 0.025; 95% CI, 1.324-6.043; p = 0.000), NVS (OR, 1.573; 95% CI, 1.15-2.151; p = 0.005) and risk factors (OR, 3.321; 95% CI, 1.451-7.564; p = 0.004) were significantly different between the two groups. D-dimer is elevated in patients with acute/subacute CVST.

  16. Camelliin B and nobotanin I, macrocyclic ellagitannin dimers and related dimers, and their antitumor activity. (United States)

    Yoshida, T; Chou, T; Haba, K; Okano, Y; Shingu, T; Miyamoto, K; Koshiura, R; Okuda, T


    Camelliin B and nobotanin I, dimeric hydrolyzable tannins of a new class having macrocyclic structures, were isolated from Camellia japonica and Heterocentron roseum, respectively. Nobotanin G and H of the structures related to nobotanin I, were also obtained from H. roseum. Camelliin B and also woodfordin C, a macrocyclic dimer from Woodfordia fruticosa, exhibited marked host-mediated antitumor activities.

  17. Calix[4]arene supported clusters: a dimer of [Mn(III)Mn(II)] dimers

    DEFF Research Database (Denmark)

    Taylor, Stephanie M; McIntosh, Ruaraidh D; Beavers, Christine M


    Phosphinate ligands allow for the transformation of a calix[4]arene supported [Mn(III)(2)Mn(II)(2)] tetramer cluster motif into an unusual [Mn(III)Mn(II)](2) dimer of dimers; the clusters self-assemble in the crystal to form bi-layer arrays reminiscent of the typical packing of calixarene solvates....

  18. Dimerization of Protegrin-1 in Different Environments

    Directory of Open Access Journals (Sweden)

    Yiannis N. Kaznessis


    Full Text Available The dimerization of the cationic β-hairpin antimicrobial peptide protegrin-1 (PG1 is investigated in three different environments: water, the surface of a lipid bilayer membrane, and the core of the membrane. PG1 is known to kill bacteria by forming oligomeric membrane pores, which permeabilize the cells. PG1 dimers are found in two distinct, parallel and antiparallel, conformations, known as important intermediate structural units of the active pore oligomers. What is not clear is the sequence of events from PG1 monomers in solution to pores inside membranes. The step we focus on in this work is the dimerization of PG1. In particular, we are interested in determining where PG1 dimerization is most favorable. We use extensive molecular dynamics simulations to determine the potential of mean force as a function of distance between two PG1 monomers in the aqueous subphase, the surface of model lipid bilayers and the interior of these bilayers. We investigate the two known distinct modes of dimerization that result in either a parallel or an antiparallel β-sheet orientation. The model bilayer membranes are composed of anionic palmitoyl-oleoyl-phosphatidylglycerol (POPG and palmitoyl-oleoyl-phosphatidylethanolamine (POPE in a 1:3 ratio (POPG:POPE. We find the parallel PG1 dimer association to be more favorable than the antiparallel one in water and inside the membrane. However, we observe that the antiparallel PG1 β-sheet dimer conformation is somewhat more stable than the parallel dimer association at the surface of the membrane. We explore the role of hydrogen bonds and ionic bridges in peptide dimerization in the three environments. Detailed knowledge of how networks of ionic bridges and hydrogen bonds contribute to peptide stability is essential for the purpose of understanding the mechanism of action for membrane-active peptides as well as for designing peptides which can modulate membrane properties. The findings are suggestive of the

  19. Plasmonic nanospherical dimers for color pixels

    KAUST Repository

    Alrasheed, Salma


    Display technologies are evolving more toward higher resolution and miniaturization. Plasmonic color pixels can offer solutions to realize such technologies due to their sharp resonances and selective scattering and absorption at particular wavelengths. Metal nanosphere dimers are capable of supporting plasmon resonances that can be tuned to span the entire visible spectrum. In this article, we demonstrate numerically bright color pixels that are highly polarized and broadly tuned using periodic arrays of metal nanosphere dimers on a glass substrate. We show that it is possible to obtain RGB pixels in the reflection mode. The longitudinal plasmon resonance of nanosphere dimers along the axis of the dimer is the main contributor to the color of the pixel, while far-field diffractive coupling further enhances and tunes the plasmon resonance. The computational method used is the finite-difference time-domain method. The advantages of this approach include simplicity of the design, bright coloration, and highly polarized function. In addition, we show that it is possible to obtain different colors by varying the angle of incidence, the periodicity, the size of the dimer, the gap, and the substrate thickness.

  20. Multiply charged monopoles in cubic dimer model (United States)

    Ganesh Jaya, Sreejith; Powell, Stephen


    The classical cubic dimer model is a 3D statistical mechanical system whose degrees of freedom are dimers that occupy the edges between nearest neighbour vertices of a cubic lattice. Dimer occupancies are subject to the local constraint that every vertex is associated with exactly one dimer. In the presence of an aligning interaction, it is known that the system exhibits an unconventional continuous thermal phase transition from a symmetry broken columnar phase to a Coulomb-phase. The transition is in the NCCP1 universality class, which also describes the Neel-VBS transition in the JQ model and the S =1/2 Heisenberg model with suppression of hedgehog defects. Using Monte-Carlo simulations of a pair of defects in a background of fluctuating dimers, we calculate the scaling exponents for fugacities of monopole defects of charge Q = 2 and 3 at this critical point. Our estimates suggest that Q = 3 monopoles are relevant and could therefore drive the JQ model away from the NCCP1 critical point on a hexagonal lattice.

  1. Effect of Molybdenum on the Corrosion Behavior of High-Entropy Alloys CoCrFeNi2 and CoCrFeNi2Mo0.25 under Sodium Chloride Aqueous Conditions

    Directory of Open Access Journals (Sweden)

    Alvaro A. Rodriguez


    Full Text Available The corrosion behavior of high-entropy alloys (HEAs CoCrFeNi2 and CoCrFeNi2Mo0.25 was investigated in 3.5 wt. percent sodium chloride (NaCl at 25°C by electrochemical methods. Their corrosion parameters were compared to those of HASTELLOY® C-276 (UNS N10276 and stainless steel 316L (UNS 31600 to assess the suitability of HEAs for potential industrial applications in NaCl simulating seawater type environments. The corrosion rates were calculated using corrosion current determined from electrochemical experiments for each of the alloys. In addition, potentiodynamic polarization measurements can indicate active, passive, and transpassive behavior of the metal as well as potential susceptibility to pitting corrosion. Cyclic voltammetry (CV can confirm the alloy susceptibility to pitting corrosion. Electrochemical impedance spectroscopy (EIS elucidates the corrosion mechanism under studied conditions. The results of the electrochemical experiments and scanning electron microscopy (SEM analyses of the corroded surfaces revealed general corrosion on alloy CoCrFeNi2Mo0.25 and HASTELLOY C-276 and pitting corrosion on alloy CoCrFeNi2 and stainless steel 316L.

  2. Synthesis and reactivity of NHC-supported Ni2(μ(2)-η(2),η(2)-S2)-bridging disulfide and Ni2(μ-S)2-bridging sulfide complexes. (United States)

    Olechnowicz, Frank; Hillhouse, Gregory L; Jordan, Richard F


    The (IPr)Ni scaffold stabilizes low-coordinate, mononuclear and dinuclear complexes with a diverse range of sulfur ligands, including μ(2)-η(2),η(2)-S2, η(2)-S2, μ-S, and μ-SH motifs. The reaction of {(IPr)Ni}2(μ-Cl)2 (1, IPr = 1,3-bis(2,6-diisopropylphenyl)imidazolin-2-ylidene) with S8 yields the bridging disulfide species {(IPr)ClNi}2(μ(2)-η(2),η(2)-S2) (2). Complex 2 reacts with 2 equiv of AdNC (Ad = adamantyl) to yield a 1:1 mixture of the terminal disulfide compound (IPr)(AdNC)Ni(η(2)-S2) (3a) and trans-(IPr)(AdNC)NiCl2 (4a). 2 also reacts with KC8 to produce the Ni-Ni-bonded bridging sulfide complex {(IPr)Ni}2(μ-S)2 (6). Complex 6 reacts with H2 to yield the bridging hydrosulfide compound {(IPr)Ni}2(μ-SH)2 (7), which retains a Ni-Ni bond. 7 is converted back to 6 by hydrogen atom abstraction by 2,4,6-(t)Bu3-phenoxy radical. The 2,6-diisopropylphenyl groups of the IPr ligand provide lateral steric protection of the (IPr)Ni unit but allow for the formation of Ni-Ni-bonded dinuclear species and electronically preferred rather than sterically preferred structures.

  3. Dynamic interplay between adhesive and lateral E-cadherin dimers

    DEFF Research Database (Denmark)

    Klingelhöfer, Jörg; Laur, Oscar Y; Troyanovsky, Regina B


    E-cadherin, an adhesive transmembrane protein of epithelial adherens junctions, forms two types of detergent-resistant dimers: adhesive dimers consisting of cadherin molecules derived from two neighboring cells and lateral dimers incorporating cadherins of the same cell. Both dimers depend...... on the integrity of the same residue, Trp156. While the relative amounts of these complexes are not certain, we show here that in epithelial A-431 cells, adhesive dimers may be a prevalent form. Inactivation of the calcium-binding sites, located between successive cadherin ectodomains, drastically reduced...... the amount of adhesive dimers and concomitantly increased the amount of lateral dimers. A similar interdependence of adhesive and lateral dimers was observed in digitonin-permeabilized cells. In these cells, adhesive dimers immediately disassembled after lowering the Ca2+ concentration below 0.1 m...

  4. Evidence for momentum-dependent heavy-fermionic electronic structures: Soft x-ray ARPES for the superconductor CeNi2Ge2 in the normal state (United States)

    Nakatani, Y.; Aratani, H.; Fujiwara, H.; Mori, T.; Tsuruta, A.; Tachibana, S.; Yamaguchi, T.; Kiss, T.; Yamasaki, A.; Yasui, A.; Yamagami, H.; Miyawaki, J.; Ebihara, T.; Saitoh, Y.; Sekiyama, A.


    We present clear experimental evidence for the momentum-dependent heavy fermionic electronic structures of the 4 f -based strongly correlated system CeNi2Ge2 by soft x-ray angle-resolved photoemission spectroscopy. A comparison between the experimental three-dimensional quasiparticle dispersion of LaNi2Ge2 and CeNi2Ge2 has revealed that heavy fermionic electronic structures are seen in the region surrounding a specific momentum. Furthermore, the wave vectors between the observed "heavy spots" are consistent with a result of neutron scattering reflecting magnetic correlations, which could be a trigger for the superconductivity in CeNi2Ge2 .

  5. Photoionization of helium dimers; Photoionisation von Heliumdimeren

    Energy Technology Data Exchange (ETDEWEB)

    Havermeier, Tilo


    The helium dimer is one of the most weakly bound systems in the universe. This makes it an interesting quantum mechanical object for investigation. These Van der Waals Clusters can be produced in an expansion of a cryogenic gas jet through a small nozzle into vacuum. In the present experiment we examine the interaction of He dimers with synchrotron radiation at an energy range from 64 to 78 eV. We observed different pathways leading to single ionization of both He atoms of the dimer compound. This two close standing ions begin now to dissociate in cause of their coulomb potential. All charged fragments were detected in coincidence with a COLTRIMS system. Especially Interatomic Coulombic Decay (ICD) and the two step process (TS1) were clearly identified. Furthermore a distribution of the internuclear distance was obtained from the measured Kinetic Energy Release (KER). (orig.)

  6. Ni2P Makes Application of the PtRu Catalyst Much Stronger in Direct Methanol Fuel Cells. (United States)

    Chang, Jinfa; Feng, Ligang; Liu, Changpeng; Xing, Wei


    PtRu is regarded as the best catalyst for direct methanol fuel cells, but the performance decay resulting from the loss of Ru seriously hinders commercial applications. Herein, we demonstrated that the presence of Ni2 P largely reduces Ru loss, which thus makes the application of PtRu much stronger in direct methanol fuel cells. Outstanding catalytic activity and stability were observed by cyclic voltammetry. Upon integrating the catalyst material into a practical direct methanol fuel cell, the highest maximum power density was achieved on the PtRu-Ni2P/C catalyst among the reference catalysts at different temperatures. A maximum power density of 69.9 mW cm(-2) at 30 °C was obtained on PtRu-Ni2P/C, which is even higher than the power density of the state-of-the-art commercial PtRu catalyst at 70 °C (63.1 mW cm(-2)). Moreover, decay in the performance resulting from Ru loss was greatly reduced owing to the presence of Ni2 P, which is indicative of very promising applications. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Influence of structural transition on the electronic structures and physical properties of Ni2MnGa alloy films

    International Nuclear Information System (INIS)

    Kim, K. W.; Kudryavtsev, Y. V.; Rhee, J. Y.; Lee, N. N.; Lee, Y. P.


    Ordered and disordered Ni 2 MnGa alloy films were prepared by flash evaporation onto substrates maintained at 720 K and 150 K, respectively. The results show that the ordered films behave in nearly the same way as the bulk Ni 2 MnGa ferromagnetic shape-memory alloy, including the martensitic transformation at 200 K, while the disordered films exhibit characteristics of amorphous alloys. It was also found that the disordering in Ni 2 MnGa alloy films did not change to any appreciable magnetic ordering down to 4 K. Annealing of the disordered films restores the ordered structure with an almost full recovery of the magnetic, magneto-optical and transport properties of the ordered Ni 2 MnGa alloy films. It was also understood, for the first time, how the structural ordering in the films influences the physical properties, including the surprising loss of ferromagnetism in the disordered films, as a result of performing electronic-structure calculations.

  8. Ultrafine and highly disordered Ni 2 Fe 1 nanofoams enabled highly efficient oxygen evolution reaction in alkaline electrolyte

    Energy Technology Data Exchange (ETDEWEB)

    Fu, Shaofang; Song, Junhua; Zhu, Chengzhou; Xu, Gui-Liang; Amine, Khalil; Sun, Chengjun; Li, Xiaolin; Engelhard, Mark H.; Du, Dan; Lin, Yuehe


    Nickel iron hydroxides are the most promising non-noble electrocatalysts for oxygen evolution reaction (OER) in alkaline media. By in situ reduction of metal precursors, compositionally controlled three-dimensional (3D) NixFeyB nanofoams (NFs) are synthesized with high surface area and uniformly distributed bimetallic networks. The resultant ultrafine amorphous Ni2Fe1B NFs exhibit extraordinary electrocatalytic performance toward OER and overall water splitting in alkaline media. At a potential as low as 1.42 V (vs. RHE), Ni2Fe1B NFs can deliver a current density of 10 mA/cm2 and show negligible activity loss after 12 hours’ stability test. Even at large current flux of 100 mA/cm2, an ultralow overpotential of 0.27 V is achieved, which is about 0.18 V more negative than benchmark RuO2. Both ex-situ Mӧssbauer spectroscopy and X-ray Absorption Spectroscopy (XAS) reveal a phase separation and transformation for the Ni2Fe1B catalyst during OER process. The evolution of oxidation state and disordered structure of Ni2Fe1B might be a key to the high catalytic performance for OER.

  9. Field-induced magnetic phases in the normal and superconducting states of ErNi2B2C

    DEFF Research Database (Denmark)

    Jensen, A.; Toft, K.N.; Abrahamsen, A.B.


    We present a comprehensive neutron-diffraction study of the magnetic structures of ErNi2B2C in the presence of a magnetic field applied along [010], [110], or [001]. In zero field, the antiferromagnetic structure is transversely polarized with Qapproximate to0.55a* and the moments along the b...

  10. Neutron diffraction study of anomalous high-field magnetic phases in TmNi2B2C

    DEFF Research Database (Denmark)

    Toft, K.N.; Abrahamsen, A.B.; Eskildsen, M.R.


    We present a (B,T)-phase diagram of the magnetic superconductor TmNi2B2C obtained by neutron scattering. The measurements were performed in magnetic fields up to 6 T applied along the crystalline a axis. The observed phases are characterized by three ordering vectors, Q(F)=(0.094,0.094,0),Q(AI)=(0.......90Yb0.10)Ni2B2C the Q(F)-->Q(AI) phase transition is also observed but at a larger transition field compared to the undoped compound. In (Tm0.85Yb0.15)Ni2B2C the Q(F) phase persists up to at least 1.8 T. The magnetic correlation length of the Q(AI) phase in TmNi2B2C measured parallel and perpendicular.......483,0,0), and Q(AII)=(0.496,0,0), all with the magnetic moment along the c axis. In zero and low fields the Tm 4f-moments order in a long wavelength transverse spin density wave with Q=Q(F). The magnetic Q(AI) structure is stabilized by an applied field of 1 T and a transition to Q(AII) is observed at 4 T...

  11. Nanocrystal Growth in Thermally Treated Fe75Ni2Si8B13C2 Amorphous Alloy

    Czech Academy of Sciences Publication Activity Database

    Minić, Dragica M.; Blagojević, V.; Minić, Dušan M.; David, Bohumil; Pizúrová, Naděžda; Žák, Tomáš

    43A, č. 9 (2012), s. 3062-3069 ISSN 1073-5623 R&D Projects: GA MŠk 1M0512 Institutional support: RVO:68081723 Keywords : Nanocrystal growth * Fe75Ni2Si8B13C2 * Amorphous alloy Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 1.627, year: 2012

  12. Active thermochemical tables: water and water dimer. (United States)

    Ruscic, Branko


    A new partition function for water dimer in the temperature range 200-500 K was developed by exploiting the equations of state for real water vapor, liquid water, and ice, and demonstrated to be significantly more accurate than any proposed so far in the literature. The new partition function allows the Active Thermochemical Tables (ATcT) approach to be applied on the available experimental and theoretical data relating to water dimer thermochemistry, leading to accurate water dimer enthalpies of formation of -499.115 ± 0.052 kJ mol(-1) at 298.15 K and -491.075 ± 0.080 kJ mol(-1) at 0 K. With the current ATcT enthalpy of formation of the water monomer, -241.831 ± 0.026 kJ mol(-1) at 298.15 K (-238.928 kJ mol(-1) at 0 K), this leads to the dimer bond dissociation enthalpy at 298.15 K of 15.454 ± 0.074 kJ mol(-1) and a 0 K bond dissociation energy of 13.220 ± 0.096 kJ mol(-1) (1105 ± 8 cm(-1)), the latter being in perfect agreement with recent experimental and theoretical determinations. The new partition function of water dimer allows the extraction and tabulation of heat capacity, entropy, enthalpy increment, reduced Gibbs energy, enthalpy of formation, and Gibbs energy of formation. Newly developed tabulations of analogous thermochemical properties for gas-phase water monomer and for water in condensed phases are also given, allowing the computations of accurate equilibria between the dimer and monomer in the 200-500 K range of temperatures.

  13. End binding proteins are obligatory dimers.

    Directory of Open Access Journals (Sweden)

    Indrani Sen

    Full Text Available End binding (EB proteins are responsible for the recruitment of an array of microtubule plus-end tracking proteins (+TIPs to growing microtubules ends. EBs encompass an N-terminal calponin homology domain that confers microtubule tip tracking activity to the protein. The C-terminal domain of EBs contains a coiled coil that mediates the parallel dimerization of EB monomers. This part of the protein is also responsible for partner binding. While dimerization is not essential for microtubule tip tracking by EBs it is a prerequisite for +TIP partner binding. The concentration of EBs in cells has been estimated to be in the range of hundreds of nanomoles. In contrast, in in vitro single molecule experiments EB concentrations of subnanomoles are employed. From a mechanistic point of view it is important to assess the oligomerization state of EBs at physiologically and experimentally relevant protein concentrations, in particular if the goal of a study is to model the behavior of EB-dependent dynamic +TIP networks. Here we have determined the stability of the EB1 and EB3 dimers using multi-angle light scattering and fluorescence analytical ultracentrifugation. We show that these EBs form stable dimers and do not dissociate even at very low nanomolar concentrations. The dimers remained stable at both room temperature as well as at the physiologically relevant temperature of 37°C. Together, our results reveal that EBs are obligatory dimers, a conclusion that has implications for the mechanistic understanding of these key proteins involved in the orchestration of dynamic protein networks at growing microtubule ends.

  14. Effects of Ni(2+) on aluminum hydroxide scale formation and transformation on a simulated drinking water distribution system. (United States)

    Wang, Wendong; Song, Shan; Zhang, Xiaoni; Mitchell Spear, J; Wang, Xiaochang; Wang, Wen; Ding, Zhenzhen; Qiao, Zixia


    Observations of aluminum containing sediments/scales formed within the distribution pipes have been reported for several decades. In this study, the effect of Ni(2+) on the formation and transformation processes of aluminum hydroxide sediment in a simulated drinking water distribution system were investigated using X-ray diffraction spectrum (XRD), Fourier transform infrared spectrum (FT-IR), scanning electron microscope (SEM), and thermodynamic calculation methods. It was determined that the existence of Ni(2+) had notable effects on the formation of bayerite. In the system without Ni(2+) addition, there was no X-ray diffraction signal observed after 400 d of aging. The presence of Ni(2+), however, even when present in small amounts (Ni/Al=1:100) the formation of bayerite would occur in as little as 3d at pH 8.5. As the molar ratio of Ni/Al increase from 1:100 to 1:10, the amount of bayerite formed on the pipeline increased further; meanwhile, the specific area of the pipe scale decreased from 160 to 122 m(2)g(-1). In the system with Ni/Al molar ratio at 1:3, the diffraction spectrum strength of bayerite became weaker, and disappeared when Ni/Al molar ratios increased above 1:1. At these highs Ni/Al molar ratios, Ni5Al4O11⋅18H2O was determined to be the major component of the pipe scale. Further study indicated that the presence of Ni(2+) promoted the formation of bayerite and Ni5Al4O11⋅18H2O under basic conditions. At lower pH (6.5) however, the existence of Ni(2+) had little effect on the formation of bayerite and Ni5Al4O11⋅18H2O, rather the adsorption of amorphous Al(OH)3 for Ni(2+) promoted the formation of crystal Ni(OH)2. Copyright © 2013 Elsevier Ltd. All rights reserved.

  15. On the asymptotics of dimers on tori


    Kenyon, Richard W.; Sun, Nike; Wilson, David B.


    We study asymptotics of the dimer model on large toric graphs. Let $\\mathbb L$ be a weighted $\\mathbb{Z}^2$-periodic planar graph, and let $\\mathbb{Z}^2 E$ be a large-index sublattice of $\\mathbb{Z}^2$. For $\\mathbb L$ bipartite we show that the dimer partition function on the quotient $\\mathbb{L}/(\\mathbb{Z}^2 E)$ has the asymptotic expansion $\\exp[A f_0 + \\text{fsc} + o(1)]$, where $A$ is the area of $\\mathbb{L}/(\\mathbb{Z}^2 E)$, $f_0$ is the free energy density in the bulk, and $\\text{fsc...

  16. A Novel Dimer of α-Tocopherol

    Directory of Open Access Journals (Sweden)

    Anjan Patel


    Full Text Available Decomposition of the complex 4, formed between the α-tocopherol ortho-quinone methide (2 and NMMO, by fast heating from −78∘C to 70∘C in inert solvents produces a novel α-tocopherol dimer with 6H,12H-dibenzo[b,f][1,5]dioxocine structure (5 which—in contrast to the well-known spiro-dimer of α-tocopherol (3—is symmetrical. This is the first example of a direct reaction of the highly transient zwitterionic, aromatic precursor 2a in the formation of the ortho-quinone methide 2.

  17. Factorized ground state in dimerized spin chains

    Energy Technology Data Exchange (ETDEWEB)

    Giorgi, Gian Luca, E-mail: gianluca@ifisc.uib-csic.e [Institute for Cross-Disciplinary Physics and Complex Systems, IFISC (CSIC-UIB), Campus Universitat Illes Balears, E-07122 Palma de Mallorca (Spain)


    The possibility of observing factorized ground states in dimerized spin systems is studied. A set of sufficient conditions is derived which allows one to establish whether or not it is possible to have factorization both in nearest-neighbour and long-range Hamiltonians. These conditions can be derived by forcing factorization for each of the pairwise terms of the total Hamiltonian. Due to the peculiar structure of a dimerized chain, an antiferromagnetic factorized ground state of the kind |nearr), |nearr), |nwarr), |nwarr) (forbidden in regular chains) is possible.

  18. Investigation of magnetic and electrical transport properties of Dy2Ni2Sn (United States)

    Karmakar, S. K.; Giri, S.; Majumdar, S.


    The magnetic and transport properties of the ternary rare-earth compound Dy2Ni2Sn are reported. The compound undergoes a long range antiferromagnetic ordering below TN=43 K with a collinear structure. A second transition is observed below about Tt=28 K, where spin canting takes place. We find clear thermal hysteresis in our magnetization data between 20 and 45 K, indicating the first order nature of the magnetic transitions occurring at TN and Tt. Clear signature of metamagnetism is observed in the canted antiferromagnetic phase. The change in entropy on the application of magnetic field (magnetocaloric effect) was calculated from the isothermal magnetization data and it shows negative and positive peaks at TN and Tt respectively. The thermal variation of resistivity shows clear peak like signature near TN, which gets suppressed under applied magnetic field resulting negative magnetoresistance. The low temperature resistivity (below Tt) can be well fitted with the model available for spin dependent s-f scattering in antiferromagnetic system having well localized moments. The data also indicate short range correlations well above the antiferromagnetic transition point, which might be related to the two dimensional spin-spin correlations in this layered compound.

  19. Microstructure and Abrasive Wear Resistance of 18Cr-4Ni-2.5Mo Cast Steel

    Directory of Open Access Journals (Sweden)

    B. Kalandyk


    Full Text Available An influence of a decreased Cr content on the microstructure of the highly alloyed Cr-Ni cast steel, duplex type, melted under laboratoryconditions, was characterized in the paper. The microstructure investigations were performed in the initial state and after the heat treatment (solution annealing at 1060C as well as the phase transformation kinetics at continuous cooling was measured. The wear resistance of the investigated cast steel was tested and compared with the 24%Cr-5%Ni-2.5%Mo cast steel.The Cr content decrease, in ferritic-austenitic cast steels (duplex, from 24-26%Cr to 18% leads to the changes of the castingsmicrostructure and eliminating of a brittle  phase. In dependence of the casting cooling rate, apart from ferrite and austenite, also fine martensite precipitates occur in the casting structure. It was shown that the investigated cast steel is characterised by a slightly lower wear resistance than the typical cast steel duplex grades.

  20. Zeolite Synthesized from Coal Fly Ash Produced by a Gasification Process for Ni2+ Removal from Water

    Directory of Open Access Journals (Sweden)

    Yixin Zhang


    Full Text Available There are increasing demands and great potential of coal gasification in China, but there is a lack of studies focused on the disposal and utilization of coal fly ash produced by the gasification process. In this study, a coal fly ash sample derived from a gasifier in Jincheng, China, was utilized as raw material for the synthesis of zeolite by alkali fusion followed by hydrothermal treatments. The effects of operation conditions on the cation exchange capacity (CEC of synthesized zeolite were investigated. The synthesized zeolite with the highest CEC (270.4 meq/100 g, with abundant zeolite X and small amount of zeolite A, was produced by 1.5 h alkali fusion under 550 °C with NaOH/coal fly ash ratio 1.2 g/g followed by 15 h hydrothermal treatment under 90 °C with liquid/solid ratio 5 mL/g and applied in Ni2+ removal from water. The removal rate and the adsorption capacity of Ni2+ from water by the synthesized zeolite were determined at the different pH, contact time, adsorbent dose and initial Ni2+ concentration. The experimental data of adsorption were interpreted in terms of Freundlich and Langmuir equations. The adsorption of Ni2+ by the synthesized zeolite was found to fit sufficient using the Langmuir isotherm. More than 90% of Ni2+ in water could be removed by synthesized zeolite under the proper conditions. We show that the coal fly ash produced by the gasification process has great potential to be used as an alternative and cheap source in the production of adsorbents.

  1. Biological consequences of cyclobutane pyrimidine dimers

    NARCIS (Netherlands)

    Vink, A.A.; Roza, L.


    In the skin many molecules may absorb ultraviolet (UV) radiation upon exposure. In particular, cellular DNA strongly absorbs shorter wavelength solar UV radiation, resulting in various types of DNA damage. Among the DNA photoproducts produced the cyclobutane pyrimidine dimers (CPDs) are predominant.

  2. Stability and Formation of Isobutylene Dimers. (United States)

    Goldsmith, Robert H.


    Isobutylene is an important bulk chemical for the petroleum industry. Dimerization and hydrogenation reactions produce the standard fuel octane rating comparison. This classic chemistry is often misrepresented in modern texts, however, and this paper attempts to correlate the physical organic principles that apply. (Author)

  3. Spectroscopic Observation of CS_2 Dimer (United States)

    Rezaei, M.; Oliaee, J. Norooz; Moazzen-Ahmadi, N.; McKellar, A. R. W.


    Infrared spectra of the CS_2 dimer are observed in the region of the CS_2 ν_3 fundamental band (˜ 1535 Cm-1) using a tuneable diode laser spectrometer. The weakly-bound complex is formed in a pulsed supersonic slit-jet expansion of a dilute gas mixture of carbon disulfide in helium. Contrary to the planar slipped-parallel geometry previously observed for (CO_2)_2, (N_2O)_2 and (OCS)_2, the CS_2 dimer exhibits a cross-shaped structure with D2d symmetry. Two bands were observed and analyzed: the fundamental (C-S asymmetric stretch) and a combination involving this mode plus an intermolecular vibration. In both cases, the rotational structure corresponds to a perpendicular (Δ K = ± 1) band of a symmetric rotor molecule. The intermolecular center of mass separation (C-C distance) is determined to be 3.539(7) {Å}. Thanks to symmetry, this is the only parameter required to characterize the structure, if the monomer geometry is assumed to remain unchanged in the dimer. From the band centers of the fundamental and combination band an intermolecular frequency of 10.96 Cm-1 is obtained, which we assign as the torsional bending mode. This constitutes the first high resolution spectroscopic investigation of CS_2 dimer.

  4. Synthesis and characterization of monomeric and dimeric ...

    African Journals Online (AJOL)

    The two complexes are isostructural, with the central metal atom lying on a crystallographic 2-fold axis. Both complexes are approximately octahedral, the coordination being provided by two trans pyridine nitrogen atoms and two cis amine nitrogen atoms from the oxime ligands, and by two cis chlorides. The dimeric ...

  5. Enhanced Photocatalytic Hydrogen Evolution by Loading Cd0.5Zn0.5S QDs onto Ni2P Porous Nanosheets (United States)

    Xiao, Lingfeng; Su, Tong; Wang, Zhuo; Zhang, Kun; Peng, Xiaoniu; Han, Yibo; Li, Quan; Wang, Xina


    Ni2P has been decorated on CdS nanowires or nanorods for efficient photocatalytic H2 production, whereas the specific surface area remains limited because of the large size. Here, the composites of Cd0.5Zn0.5S quantum dots (QDs) on thin Ni2P porous nanosheets with high specific surface area were constructed for noble metal-free photocatalytic H2 generation. The porous Ni2P nanosheets, which were formed by the interconnection of 15-30 nm-sized Ni2P nanoparticles, allowed the uniform loading of 7 nm-sized Cd0.5Zn0.5S QDs and the loading density being controllable. By tuning the content of Ni2P, H2 generation rates of 43.3 μM h- 1 (1 mg photocatalyst) and 700 μM h- 1 (100 mg photocatalyst) and a solar to hydrogen efficiency of 1.5% were achieved for the Ni2P-Cd0.5Zn0.5S composites. The effect of Ni2P content on the light absorption, photoluminescence, and electrochemical property of the composite was systematically studied. Together with the band structure calculation based on density functional theory, the promotion of Ni2P in charge transfer and HER activity together with the shading effect on light absorption were revealed. Such a strategy can be applied to other photocatalysts toward efficient solar hydrogen generation.

  6. First-Principles Investigations of the Structural, Anisotropic Mechanical, Thermodynamic and Electronic Properties of the AlNi2Ti Compound

    Directory of Open Access Journals (Sweden)

    Shuli Tang


    Full Text Available In this paper, the electronic, mechanical and thermodynamic properties of AlNi2Ti are studied by first-principles calculations in order to reveal the influence of AlNi2Ti as an interfacial phase on ZTA (zirconia toughened alumina/Fe. The results show that AlNi2Ti has relatively high mechanical properties, which will benefit the impact or wear resistance of the ZTA/Fe composite. The values of bulk, shear and Young’s modulus are 164.2, 63.2 and 168.1 GPa respectively, and the hardness of AlNi2Ti (4.4 GPa is comparable to common ferrous materials. The intrinsic ductile nature and strong metallic bonding character of AlNi2Ti are confirmed by B/G and Poisson’s ratio. AlNi2Ti shows isotropy bulk modulus and anisotropic elasticity in different crystallographic directions. At room temperature, the linear thermal expansion coefficient (LTEC of AlNi2Ti estimated by quasi-harmonic approximation (QHA based on Debye model is 10.6 × 10−6 K−1, close to LTECs of zirconia toughened alumina and iron. Therefore, the thermal matching of ZTA/Fe composite with AlNi2Ti interfacial phase can be improved. Other thermodynamic properties including Debye temperature, sound velocity, thermal conductivity and heat capacity, as well as electronic properties, are also calculated.

  7. Adsorptive performance of un-calcined sodium exchanged and acid modified montmorillonite for Ni2+ removal: Equilibrium, kinetics, thermodynamics and regeneration studies

    International Nuclear Information System (INIS)

    Ijagbemi, Christianah Olakitan; Baek, Mi-Hwa; Kim, Dong-Su


    The efficacy of un-calcined sodium exchanged (Na-MMT) and acid modified montmorillonite (A-MMT) has been investigated for adsorptive removal of Ni 2+ from aqueous solution. Physico-chemical parameters such as pH, initial Ni 2+ concentration, and equilibrium contact time were studied in a series of batch adsorption experiments. The equilibrium time of contact for both adsorbents was about 230 min. The Redlich-Peterson model best described the equilibrium sorption of Ni 2+ onto Na-MMT and the Dubinin-Radushkevich model was the best model in predicting the equilibrium sorption of Ni 2+ onto A-MMT. The kinetics of Ni 2+ uptake by Na-MMT and A-MMT followed the pseudo second-order chemisorption mechanism. Sorptions of Ni 2+ onto Na-MMT and A-MMT were spontaneous and endothermic. Regeneration was tried for several cycles with a view to recover the adsorbed Ni 2+ and also to restore Na-MMT and A-MMT to their original states. The un-calcined Na-MMT and A-MMT have adsorptive potentials for removal of Ni 2+ from aqueous bodies.

  8. Effect of Abrasive Machining on the Electrical Properties Cu86Mn12Ni2 Alloy Shunts

    Directory of Open Access Journals (Sweden)

    Siti Nabilah Misti


    Full Text Available This paper studies the effect of abrasive trimming on the electrical properties of Cu86Mn12Ni2 Manganin alloy shunt resistors. A precision abrasive trimming system for fine tuning the resistance tolerance of high current Manganin shunt resistors is proposed. The system is shown to be capable of reducing the resistance tolerance of 100 μΩ shunts from their standard value of ±5% to <±1% by removing controlled amounts of Manganin material using a square cut trim geometry. The temperature coefficient of resistance (TCR, high current, and high temperature performance of the trimmed shunts was compared to that of untrimmed parts to determine if trimming had any detrimental effect on these key electrical performance parameters of the device. It was shown that the TCR value was reduced following trimming with typical results of +106 ppm/°C and +93 ppm/°C for untrimmed and trimmed parts respectively. When subjected to a high current of 200 A the trimmed parts showed a slight increase in temperature rise to 203 °C, as compared to 194 °C for the untrimmed parts, but both had significant temporary increases in resistance of up to 1.3 μΩ. The results for resistance change following high temperature storage at 200 °C for 168 h were also significant for both untrimmed and trimmed parts with shifts of 1.85% and 2.29% respectively and these results were related to surface oxidation of the Manganin alloy which was accelerated for the freshly exposed surfaces of the trimmed part.

  9. Determination of the Tetramer-Dimer Equilibrium Constant of Rabbit ...

    African Journals Online (AJOL)

    Hemoglobin is a tetrameric protein which is able to dissociate into dimers. The dimers can in turn dissociate into tetramers. It has been found that dimers are more reactive than tetramers. The difference in the reactivity of these two species has been used to determine the tetramerdimer dissociation constant of various ...

  10. Stochastic optimization-based study of dimerization kinetics

    Indian Academy of Sciences (India)

    Keywords. Stochastic optimization; dimerization kinetics; sensitivity analysis; stochastic simulation algorithm; probability distribution function. ... To this end, we study dimerization kinetics of protein as a model system. We follow the dimerization kinetics using a stochastic simulation algorithm and combine it with three ...

  11. Ultraviolet Spectrum And Chemical Reactivity Of CIO Dimer (United States)

    Demore, William B.; Tschuikow-Roux, E.


    Report describes experimental study of ultraviolet spectrum and chemical reactivity of dimer of chlorine monoxide (CIO). Objectives are to measure absorption cross sections of dimer at near-ultraviolet wavelengths; determine whether asymmetrical isomer (CIOCIO) exists at temperatures relevant to Antarctic stratosphere; and test for certain chemical reactions of dimer. Important in photochemistry of Antarctic stratosphere.

  12. Ethanol water azeotrope Study. Molecular characterization of ethanol dimers, hetero dimers and hetero trimers of ethanol water

    International Nuclear Information System (INIS)

    Mejia, Sol M; Espinal, Juan F; Mondragon, Fanor


    In this investigation, as a first stage, we studied the structure and stability of the dimers,hetero dimers and hetero trimers like aggregates of ethanol and ethanol water respectively. Molecular modelling using hybrid B3LYP of the density functional theory (DFT) was used in this research. O-H bond lengths, hydrogen bond distances, CCOH dihedral angles, enthalpies and Gibbs free energies of dimerization and trimerization and vibrational frequencies of stretching O-H for the dimers and hetero dimers in function of the redshift undergone by proton donor molecules were analyzed. The results shows that the monomers arrange into aggregates which undergo geometric changes induced by the hydrogen bonds. For hetero dimers and hetero trimers the enhancement of the hydrogen bonds where the proton donor molecule corresponds to water was observed. In general, the dimers are more stable than the hetero dimers. We propose the formation of C-H-O hydrogen bonds in some hetero trimers

  13. Preparation of Chitosan Coated Magnetic Hydroxyapatite Nanoparticles and Application for Adsorption of Reactive Blue 19 and Ni2+ Ions

    Directory of Open Access Journals (Sweden)

    Van Cuong Nguyen


    Full Text Available An adsorbent called chitosan coated magnetic hydroxyapatite nanoparticles (CS-MHAP was prepared with the purpose of improvement for the removal of Ni2+ ions and textile dye by coprecipitation. Structure and properties of CS-MHAP were characterized by scanning electron microscopy (SEM, X-ray diffraction (XRD, Fourier transform infrared spectroscopy (FTIR, and vibrating sample magnetometer (VSM. Weight percent of chitosan was investigated by thermal gravimetric analysis (TGA. The prepared CS-MHAP presents a significant improvement on the removal efficiency of Ni2+ ions and reactive blue 19 dye (RB19 in comparison with chitosan and magnetic hydroxyapatite nanoparticles. Moreover, the adsorption capacities were affected by several parameters such as contact time, initial concentration, adsorbent dosage, and initial pH. Interestingly, the prepared adsorbent could be easily recycled from an aqueous solution by an external magnet and reused for adsorption with high removal efficiency.

  14. Study of electric resistivity in function of temperature in Ni2Mn (Sn1-x Inx) type Heuster alloys

    International Nuclear Information System (INIS)

    Fraga, G.L.F.


    The electric resistivity as a function of temperature and concentration was measured in the range 4.2 2 Mn (Sn i-x In x ), with x = 0; 0.02; 0.05; 0.10; 0.15; 0.85; 0.90; 0.95; 0.98 and 1.00. In the lower temperature region (7 n - law. The 0 2 function; the linear term is mostly ascribed to electron-phonon scattering process and the quadratic one to magnetic scattering mechanism. For the ternary alloys Ni 2 MnSn and Ni 2 MnIn the experimental magnetic term BT 2 is well fitted by the Kasuya's magnetic spin-disorder model. (author) [pt

  15. Destruction and Accompanying Phenomena in a Ferromagnetic Ni2MnGa Single Crystal with a Shape-Memory Effect (United States)

    Ostrikov, O. M.; Shmatok, E. V.


    Features of the shape of a macroscopic interplanar crack have been studied, and phenomena accompanying destruction in a monocrystalline ferromagnetic Ni2MnGa alloy with shape memory have been analyzed. It has been established that the initiation of destruction in Ni2MnGa is actively influenced by the processes of slip and interaction of twin boundaries in twin planes which are at small angles to each other, and also by the formation of Rose channels. On the source side of the surface at which the crack has nucleated, it is tooth-shaped. On this surface, there are signs of rotation of the crystal lattice from twins with boundaries parallel and perpendicular to the crack's edges. The opening of the crack in its boundary regions leads to partial untwining.

  16. Large D-Dimer Fluctuation in Normal Pregnancy

    DEFF Research Database (Denmark)

    Hedengran, Katrine K; Andersen, Malene R; Stender, Steen


    Introduction. D-dimer levels increase throughout pregnancy, hampering the usefulness of the conventional threshold for dismissing thromboembolism. This study investigates the biological fluctuation of D-dimer in normal pregnancy. Methods. A total of 801 healthy women with expected normal...... pregnancies were recruited. D-dimer was repeatedly measured during pregnancy, at active labor, and on the first and second postpartum days. Percentiles for each gestational week were calculated. Each individual D-dimer was normalized by transformation into percentiles for the relevant gestational age...... normal pregnancy, repeated D-dimer measurements are of no clinical use in the evaluation of thromboembolic events during pregnancy....

  17. Properties of a magnetic superconductor with weak magnetization-application to ErNi2B2C

    International Nuclear Information System (INIS)

    Ng, T.K.; Leung, W.T.


    Using a Ginsburg-Landau free-energy functional, we study the H-T phase diagram of a weak magnetic superconductor, where the magnetization from the magnetic component is marginal in supporting a spontaneous vortex phase. In particular, the competition between the spiral state and spontaneous vortex phase is analysed. Our theory is applied to understand the magnetic properties of ErNi 2 B 2 C. (orig.)

  18. Highly selective colorimetric detection of Ni2+ using silver nanoparticles cofunctionalized with adenosine monophosphate and sodium dodecyl sulfonate (United States)

    Feng, Jiayu; Jin, Weiwei; Huang, Pengcheng; Wu, Fangying


    We report a dual-ligand strategy based on silver nanoparticles (AgNPs) for highly selective detection of Ni2+ using colorimetric techniques. Adenosine monophosphate (AMP) and sodium dodecyl sulfonate (SDS) were both used as ligands to modify AgNPs. The presence of Ni2+ induces the aggregation of AgNPs through cooperative electrostatic interaction and metal-ligand interaction, resulting in a color change from bright yellow to orange. The cofunctionalized AgNPs showed obvious advantages over the ones functionalized only by AMP or SDS in terms of selectivity. Under the optimized conditions, this sensing platform for Ni2+ works in the concentration range of 4.0 to 60 μM and has a low detection limit of 0.60 μM. In addition, the colorimetric assay is very fast, and the whole analysis can be completed within a few minutes. Thus, it can be directly used in tap water and lake water samples. [Figure not available: see fulltext.

  19. Sorption properties of an amorphous hydroxo titanate towards Pb(2+), Ni(2+), and Cu(2+) ions in aqueous solution. (United States)

    Volpe, Angela; Pagano, Michele; Pastore, Carlo; Cuocci, Corrado; Milella, Antonella


    Titanates may be selectively used as inorganic adsorbents for heavy metal ions owing to their stability and fast adsorption kinetics. Nevertheless, the synthesis of such materials usually requires extreme reaction conditions. In this work, a new titanium-based material was rapidly synthesized under mild laboratory conditions. The obtained amorphous hydroxo titanate was tested for heavy metal sorption through kinetic and equilibrium batch tests, which indicated that the new material had high adsorption rates and adsorption capacities towards Cu(2+), Ni(2+) and Pb(2) ions. Adsorption kinetics were pseudo-second order, and equilibrium data fitted the Langmuir isotherm model. The calculated maximum adsorption capacities of Cu(2+), Ni(2+) and Pb(2+) in deionized water were around 1 mmol g(-1), and they decreased for Cu(2+) and Ni(2+) in the presence of Na(+), Ca(2+) and Mg(2+) ions, whereas the alkali metal ions did not influence Pb(2+) uptake. The efficiency of adsorption and recovery of lead ions were evaluated through column dynamic tests, by feeding the column with groundwater and tap water spiked with Pb(2+). The high performance of the hydroxo titanate over several cycles of retention and elution suggested that the product is potentially useful for the solid phase extraction of lead at trace levels in natural water samples, with potential use in metal pre-concentration for analytical applications.

  20. Energy-Saving Electrolytic Hydrogen Generation: Ni2P Nanoarray as a High-Performance Non-Noble-Metal Electrocatalyst. (United States)

    Tang, Chun; Zhang, Rong; Lu, Wenbo; Wang, Zao; Liu, Danni; Hao, Shuai; Du, Gu; Asiri, Abdullah M; Sun, Xuping


    It is highly attractive but challenging to develop earth-abundant electrocatalysts for energy-saving electrolytic hydrogen generation. Herein, we report that Ni 2 P nanoarrays grown in situ on nickel foam (Ni 2 P/NF) behave as a durable high-performance non-noble-metal electrocatalyst for hydrazine oxidation reaction (HzOR) in alkaline media. The replacement of the sluggish anodic oxygen evolution reaction with such the more thermodynamically favorable HzOR enables energy-saving electrochemical hydrogen production with the use of Ni 2 P/NF as a bifunctional catalyst for anodic HzOR and cathodic hydrogen evolution reaction. When operated at room temperature, this two-electrode electrolytic system drives 500 mA cm -2 at a cell voltage as low as 1.0 V with strong long-term electrochemical durability and 100 % Faradaic efficiency for hydrogen evolution in 1.0 m KOH aqueous solution with 0.5 m hydrazine. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Fibrillar dimer formation of islet amyloid polypeptides

    Energy Technology Data Exchange (ETDEWEB)

    Chiu, Chi-cheng [Univ. of Chicago, IL (United States); Argonne National Lab. (ANL), Argonne, IL (United States); de Pablo, Juan J. [Univ. of Chicago, IL (United States); Argonne National Lab. (ANL), Argonne, IL (United States)


    Amyloid deposits of human islet amyloid polypeptide (hIAPP), a 37-residue hormone co-produced with insulin, have been implicated in the development of type 2 diabetes. Residues 20 – 29 of hIAPP have been proposed to constitute the amyloidogenic core for the aggregation process, yet the segment is mostly unstructured in the mature fibril, according to solid-state NMR data. Here we use molecular simulations combined with bias-exchange metadynamics to characterize the conformational free energies of hIAPP fibrillar dimer and its derivative, pramlintide. We show that residues 20 – 29 are involved in an intermediate that exhibits transient β-sheets, consistent with recent experimental and simulation results. By comparing the aggregation of hIAPP and pramlintide, we illustrate the effects of proline residues on inhibition of the dimerization of IAPP. The mechanistic insights presented here could be useful for development of therapeutic inhibitors of hIAPP amyloid formation.

  2. Fibrillar dimer formation of islet amyloid polypeptides (United States)

    Chiu, Chi-cheng; de Pablo, Juan J.


    Amyloid deposits of human islet amyloid polypeptide (hIAPP), a 37-residue hormone co-produced with insulin, have been implicated in the development of type 2 diabetes. Residues 20 - 29 of hIAPP have been proposed to constitute the amyloidogenic core for the aggregation process, yet the segment is mostly unstructured in the mature fibril, according to solid-state NMR data. Here we use molecular simulations combined with bias-exchange metadynamics to characterize the conformational free energies of hIAPP fibrillar dimer and its derivative, pramlintide. We show that residues 20 - 29 are involved in an intermediate that exhibits transient β-sheets, consistent with recent experimental and simulation results. By comparing the aggregation of hIAPP and pramlintide, we illustrate the effects of proline residues on inhibition of the dimerization of IAPP. The mechanistic insights presented here could be useful for development of therapeutic inhibitors of hIAPP amyloid formation.

  3. An introduction to the dimer model

    International Nuclear Information System (INIS)

    Kenyon, R.


    A perfect matching of a graph is a subset of edges which covers every vertex exactly once, that is, for every vertex there is exactly one edge in the set with that vertex as endpoint. The dimer model is the study of the set of perfect matchings of a (possibly infinite) graph. The most well-known example is when the graph is Z 2 , for which perfect matchings are equivalent (via a simple duality) to domino tilings, that is, tilings of the plane with 2 x 1 and 1 x 2 rectangles. In the first three sections we study domino tilings of the plane and of finite polygonal regions, or equivalently, perfect matchings on Z 2 and subgraphs of Z 2 . In the last two sections we study the FK-percolation model and the dimer model on a more general family of planar graphs

  4. PT -symmetric dimer of coupled nonlinear oscillators

    Indian Academy of Sciences (India)

    In this case there are three solutions of the coupled dimer eqs (1) and (2) out of which we present two solutions now and the third one (a novel superposed solution) in the next subsection. Solution I: It is easy to check that u(t) = ±v(t) = Adn[β(t + t0), m]. (22) is an exact solution provided. (ǫ + δ)β2 = −2β2, (2 − m)β2 = −1 ± k.

  5. Electronic structure of the water dimer cation

    Czech Academy of Sciences Publication Activity Database

    Pieniazek, P. A.; Vande Vondele, J.; Jungwirth, Pavel; Krylov, A. I.; Bradforth, S. E.


    Roč. 112, č. 27 (2008), s. 6159-6170 ISSN 1089-5639 R&D Projects: GA ČR(CZ) GA202/06/0286 Grant - others:NSF(US) CHE-0617060 Institutional research plan: CEZ:AV0Z40550506 Keywords : water dimer * ionization * proton transfer * ab initio Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.871, year: 2008

  6. On the dimerization of linear polymers

    International Nuclear Information System (INIS)

    Aragao Carvalho, C. de.


    We use the continuum limit of the Su-Schrieffer-Heeger model for linear polymers to construct its effective potential (Gibbs free energy) both at zero and finite temperature. We study both trans and cis-polymers. Our results show that, depending on a renormalization condition to be extracted from experiment, there are several possibilities for the minima of the dimerized ground state of cis-polymers. All calculations are done in the one-loop approximation. (author). 16 refs, 3 figs

  7. Palmitoylated APP Forms Dimers, Cleaved by BACE1 (United States)

    Fenn, Rebecca H.; Barren, Cory; Tanzi, Rudolph E.; Kovacs, Dora M.


    A major rate-limiting step for Aβ generation and deposition in Alzheimer’s disease brains is BACE1-mediated cleavage (β-cleavage) of the amyloid precursor protein (APP). We previously reported that APP undergoes palmitoylation at two cysteine residues (Cys186 and Cys187) in the E1-ectodomain. 8–10% of total APP is palmitoylated in vitro and in vivo. Palmitoylated APP (palAPP) shows greater preference for β-cleavage than total APP in detergent resistant lipid rafts. Protein palmitoylation is known to promote protein dimerization. Since dimerization of APP at its E1-ectodomain results in elevated BACE1-mediated cleavage of APP, we have now investigated whether palmitoylation of APP affects its dimerization and whether this leads to elevated β-cleavage of the protein. Here we report that over 90% of palAPP is dimerized while only ~20% of total APP forms dimers. PalAPP-dimers are predominantly cis-oriented while total APP dimerizes in both cis- and trans-orientation. PalAPP forms dimers 4.5-times more efficiently than total APP. Overexpression of the palmitoylating enzymes DHHC7 and DHHC21 that increase palAPP levels and Aβ release, also increased APP dimerization in cells. Conversely, inhibition of APP palmitoylation by pharmacological inhibitors reduced APP-dimerization in coimmunoprecipitation and FLIM/FRET assays. Finally, in vitro BACE1-activity assays demonstrate that palmitoylation-dependent dimerization of APP promotes β-cleavage of APP in lipid-rich detergent resistant cell membranes (DRMs), when compared to total APP. Most importantly, generation of sAPPβ-sAPPβ dimers is dependent on APP-palmitoylation while total sAPPβ generation is not. Since BACE1 shows preference for palAPP dimers over total APP, palAPP dimers may serve as novel targets for effective β-cleavage inhibitors of APP as opposed to BACE1 inhibitors. PMID:27875558

  8. Enhanced activity of Pt/CNTs anode catalyst for direct methanol fuel cells using Ni2P as co-catalyst (United States)

    Li, Xiang; Luo, Lanping; Peng, Feng; Wang, Hongjuan; Yu, Hao


    The direct methanol fuel cell is a promising energy conversion device because of the utilization of the state-of-the-art platinum (Pt) anode catalyst. In this work, novel Pt/Ni2P/CNTs catalysts were prepared by the H2 reduction method. It was found that the activity and stability of Pt for methanol oxidation reaction (MOR) could be significantly enhanced while using nickel phosphide (Ni2P) nanoparticles as co-catalyst. X-ray photoelectron spectroscopy revealed that the existence of Ni2P affected the particle size and electronic distribution of Pt obviously. Pt/CNTs catalyst, Pt/Ni2P/CNTs catalysts with different Ni2P amount were synthesized, among which Pt/6%Ni2P/CNTs catalyst exhibited the best MOR activity of 1400 mAmg-1Pt, which was almost 2.5 times of the commercial Pt/C-JM catalyst. Moreover, compared to other Pt-based catalysts, this novel Pt/Ni2P/CNTs catalyst also exhibited higher onset current density and better steady current density. The result of this work may provide positive guidance to the research on high efficiency and stability of Pt-based catalyst for direct methanol fuel cells.

  9. Hydroconversion of methyl laurate on bifunctional Ni2P/AlMCM-41 catalyst prepared via in situ phosphorization using triphenylphosphine (United States)

    Zhao, Sha; Zhang, Zhena; Zhu, Kongying; Chen, Jixiang


    A series of Ni2P/AlMCM-41-x bifunctional catalysts with different Si/Al ratios (x) were synthesized by in situ phosphorization of Ni/AlMCM-41-x with triphenylphosphine (nominal Ni/P ratio of 0.75) at 300 °C on a fixed-bed reactor. For comparison, NiP/AlMCM-41-5-TPR was also prepared by the TPR method from the supported nickel phosphate with the Ni/P ratio of 1.0, during which metallic Ni rather than Ni2P formed. TEM images show that Ni and Ni2P particles uniformly distributed in Ni2P/AlMCM-41-x and NiP/AlMCM-41-5-TPR. The Ni2P/AlMCM-41-x acidity increased with decreasing the Si/Al ratio. In the hydroconversion of methyl laurate, the conversions were close to 100% on all catalysts at 360 °C, 3.0 MPa, methyl laurate WHSV of 2 h-1 and H2/methyl laurate ratio of 25. As to Ni2P/AlMCM-41-x, with decreasing the Si/Al ratio, the total selectivity to C11 and C12 hydrocarbons decreased, while the total selectivity to isoundecane and isododecane (Si-C11+i-C12) firstly increased and then decreased. Ni2P/AlMCM-41-5 gave the largest Si-C11+i-C12 of 43.2%. While NiP/AlMCM-41-5-TPR gave higher Si-C11+i-C12 than Ni2P/AlMCM-41-5, it was more active for the undesired Csbnd C bond cleavage and methanation. We propose that the in-situ phosphorization adopted here is a promising approach to preparing Ni2P-based bifunctional catalysts.

  10. MspA nanopores from subunit dimers.

    Directory of Open Access Journals (Sweden)

    Mikhail Pavlenok

    Full Text Available Mycobacterium smegmatis porin A (MspA forms an octameric channel and represents the founding member of a new family of pore proteins. Control of subunit stoichiometry is important to tailor MspA for nanotechnological applications. In this study, two MspA monomers were connected by linkers ranging from 17 to 62 amino acids in length. The oligomeric pore proteins were purified from M. smegmatis and were shown to form functional channels in lipid bilayer experiments. These results indicated that the peptide linkers did not prohibit correct folding and localization of MspA. However, expression levels were reduced by 10-fold compared to wild-type MspA. MspA is ideal for nanopore sequencing due to its unique pore geometry and its robustness. To assess the usefulness of MspA made from dimeric subunits for DNA sequencing, we linked two M1-MspA monomers, whose constriction zones were modified to enable DNA translocation. Lipid bilayer experiments demonstrated that this construct also formed functional channels. Voltage gating of MspA pores made from M1 monomers and M1-M1 dimers was identical indicating similar structural and dynamic channel properties. Glucose uptake in M. smegmatis cells lacking porins was restored by expressing the dimeric mspA M1 gene indicating correct folding and localization of M1-M1 pores in their native membrane. Single-stranded DNA hairpins produced identical ionic current blockades in pores made from monomers and subunit dimers demonstrating that M1-M1 pores are suitable for DNA sequencing. This study provides the proof of principle that production of single-chain MspA pores in M. smegmatis is feasible and paves the way for generating MspA pores with altered stoichiometries. Subunit dimers enable better control of the chemical and physical properties of the constriction zone of MspA. This approach will be valuable both in understanding transport across the outer membrane in mycobacteria and in tailoring MspA for nanopore

  11. Characterization of divalent and trivalent species generated in the chemical and electrochemical oxidation of a dimeric pincer complex of nickel. (United States)

    Spasyuk, Denis M; Gorelsky, Serge I; van der Est, Art; Zargarian, Davit


    The electrolytic and chemical oxidation of the dimeric pincer complex [κ(P),κ(C),κ(N),μ(N)-(2,6-(i-Pr(2)POC(6)H(3)CH(2)NBn)Ni](2) (1; Bn = CH(2)Ph) has been investigated by various analytic techniques. Cyclic voltammetry measurements have shown that 1 undergoes a quasi-reversible, one electron, Ni-based redox process (ΔE(0)(1/2) = -0.07 V vs Cp(2)Fe/[Cp(2)Fe](+)), and spectroelectrochemical measurements conducted on the product of the electrolytic oxidation, [1](+•), have shown multiple low-energy electronic transitions in the range of 10,000-15,000 cm(-1). Computational studies using Density Functional Theory (B3LYP) have corroborated the experimentally obtained structure of 1, provided the electronic structure description, and helped interpret the experimentally obtained absorption spectra for 1 and [1](+·). These calculations indicate that the radical cation [1](+·) is a dimeric, mixed-valent species (class III) wherein most of the spin density is delocalized over the two nickel centers (Ni(+2.5)(2)N(2)), but some spin density is also present over the two nitrogen atoms (Ni(2+)(2)N(2)·). Examination of alternative structures for open shell species generated from 1 has shown that the spin density distribution is highly sensitive toward changes in the ligand environment of the Ni ions. NMR, UV-vis, electron paramagnetic resonance (EPR), and single crystal X-ray diffraction analyses have shown that chemical oxidation of 1 with N-Bromosuccinimide (NBS) follows a complex process that gives multiple products, including the monomeric trivalent species κ(P),κ(C),κ(N)-{2,6-(i-Pr(2)PO)(C(6)H(3))(CH═NBn)}NiBr(2) (2). These studies also indicate that oxidation of 1 with 1 equiv of NBS gives an unstable, paramagnetic intermediate that decomposes to a number of divalent species, including succinimide and the monomeric divalent complexes κ(P),κ(C),κ(N)-{2,6-(i-Pr(2)PO)(C(6)H(3))(CH═NBn)}NiBr (3) and κ(P),κ(C),κ(N)-{2,6-(i-Pr(2)PO)(C(6)H(3))(CH(2)N

  12. Study of dimerization reaction during cathodic splitting of halogen. Dimerization during reduction of butyl iodide

    International Nuclear Information System (INIS)

    Tomilov, A.P.


    The process of electrochemical reduction of butyl iodide in methanol in the presence of sodium methylate was studied. It was ascertained that the yield of dimer product, i. e. octane, depends essentially on the cathode material. Copper and iron (steel 3) proved the most active agents in dimerization process. Conditions (current density 0.03-0.10 A/cm 2 , 0 deg C, 0.005 M CH 3 ONa), under which octane yield amounts to 83-84% in matter, were found [ru

  13. Rapid and efficient removal of Ni(2+) from aqueous solution by the one-pot synthesized EDTA-modified magnetic nanoparticles. (United States)

    Chen, Junyong; Hao, Yongmei; Chen, Man


    A facile one-pot process has been proposed to prepare the novel ethylenediaminetetraacetic acid (EDTA)-modified magnetite nanoparticles (EDTA-MNPs). The bared Fe3O4 magnetite nanoparticles and EDTA-MNPs were characterized using FTIR spectroscopy, TEM, VSM, and X-ray diffraction. The application of the modified magnetite nanoparticles for metal ion uptake was studied using Ni(2+) as a model. The adsorption was fast and the equilibrium was established within 5 min, and the adsorption kinetics of Ni(2+) onto EDTA-MNPs followed the pseudo second-order chemisorption mechanism. Maximum adsorption capacity for Ni(2+) reached as high as 41.3 mg/g at pH 6. The successive adsorption-desorption studies indicated that the EDTA-MNPs kept the adsorption and desorption efficiencies constant over ten cycles. Importantly, EDTA-MNPs were able to remove nearly 100 % of Ni(2+) from real water.

  14. Cuboid Ni2 P as a Bifunctional Catalyst for Efficient Hydrogen Generation from Hydrolysis of Ammonia Borane and Electrocatalytic Hydrogen Evolution. (United States)

    Du, Yeshuang; Liu, Chao; Cheng, Gongzhen; Luo, Wei


    The design of high-performance catalysts for hydrogen generation is highly desirable for the upcoming hydrogen economy. Herein, we report the colloidal synthesis of nanocuboid Ni 2 P by the thermal decomposition of nickel chloride hexahydrate (NiCl 2 ⋅6 H 2 O) and trioctylphosphine. The obtained nanocuboid Ni 2 P was characterized by using powder X-ray diffraction, transmission electron microscopy, energy-dispersive X-ray spectroscopy, X-ray photoelectron spectroscopy, and inductively coupled plasma atomic emission spectroscopy. For the first time, the as-synthesized nanocuboid Ni 2 P is used as a bifunctional catalyst for hydrogen generation from the hydrolysis of ammonia borane and electrocatalytic hydrogen evolution. Owing to the strong synergistic electronic effect between Ni and P, the as-synthesized Ni 2 P exhibits catalytic performance that is superior to its counterpart without P doping. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Improving the binding capacity of Ni2+ decorated porous magnetic silica spheres for histidine-rich protein separation. (United States)

    Benelmekki, M; Caparros, C; Xuriguera, E; Lanceros-Mendez, S; Rodriguez-Carmona, E; Mendoza, R; Corchero, J L; Martinez, Ll M


    Biomagnetic immobilization of histidine-rich proteins based on the single-step affinity adsorption of transition metal ions continues to be a suitable practice as a cost effective and a up scaled alternative to the to multiple-step chromatographic separations. In our previous work, we synthesised Porous Magnetic silica (PMS) spheres by one-step hydrothermal-assisted modified-stöber method. The obtained spheres were decorated with Ni(2+) and Co(2+), and evaluated for the capture of a H6-Tagged green fluorescence protein (GFP-H6) protein. The binding capacity of the obtained spheres was found to be slightly higher in the case Ni(2+) decorated PMS spheres (PMSNi). However, comparing with commercial products, the binding capacity was found to be lower than the expected. In this way, the present work is an attempt to improve the binding capacity of PMSNi to histidine-rich proteins. We find that increasing the amount of Ni(2+) onto the surface of the PMS spheres leads to an increment of the binding capacity to GFP-H6 by a factor of two. On the other hand, we explore how the size of histidine-rich protein can affect the binding capacity comparing the results of the GFP-6H to those of the His-tagged α-galactosidase (α-GLA). Finally, we demonstrate that the optimization of the magnetophoresis parameters during washing and eluting steps can lead to an additional improvement of the binding capacity. Copyright © 2012 Elsevier B.V. All rights reserved.

  16. Sodium layer chiral distribution and spin structure of Na$_2$Ni$_2$TeO$_6$ with a honeycomb network


    Karna, Sunil K.; Zhao, Y.; Sankar, R.; Avdeev, M.; Tseng, P. C.; Wang, C. W.; Shu, G. J.; Matan, K.; Guo, G. Y.; Chou, F. C.


    The nature of Na ion distribution, diffusion path, and the spin structure of $P2$-type Na$_2$Ni$_2$TeO$_6$ with a Ni honeycomb network has been explored. The nuclear density distribution of Na ions reveals a 2D chiral pattern within Na layers without breaking the original 3D crystal symmetry, which has been achieved uniquely via an inverse Fourier transform (iFT)-assisted neutron diffraction technique. The Na diffusion pathway described by the calculated iso-surface of Na ion bond valence sum...

  17. Al-Doped Ni2P nanosheet array: a superior and durable electrocatalyst for alkaline hydrogen evolution. (United States)

    Du, Huitong; Xia, Lian; Zhu, Shuyun; Qu, Fei; Qu, Fengli


    It is highly desired to develop high-efficiency and low-cost catalysts for the hydrogen evolution reaction (HER). Herein, we report the development of an Al-doped Ni 2 P nanosheet array on Ti mesh as a high-performance and durable electrocatalyst for the HER in 1.0 M KOH. Such a catalyst demands an overpotential of 129 mV to afford 10 mA cm -2 and maintains its catalytic activity for at least 20 h. This work offers us a promising cost-effective catalyst for large-scale electrolytic production of hydrogen fuels.

  18. Improving the binding capacity of Ni2+ decorated porous magnetic silica spheres for histidine-rich protein separation


    Benelmekki, Maria; Caparrós Vázquez, Cristina Maria; Xuriguera, Elena; Lanceros Méndez, Senentxu; Rodriguez-Carmona, Escar; Mendoza, R; Corchero, Jose Luis; Martinez, lluis Maria


    Biomagnetic immobilization of histidine-rich proteins based on the single-step affinity adsorption of transition metal ions continues to be a suitable practice as a cost effective and a up scaled alternative to the to multiple-step chromatographic separations. In our previous work [12], we synthesised Porous Magnetic silica (PMS) spheres by one-step hydrothermal-assisted modified-stöber method. The obtained spheres were decorated with Ni2+ and Co2+, and evaluated for the capture of a H6-Tagge...

  19. Dimeric assembly of enterocyte brush border enzymes

    DEFF Research Database (Denmark)

    Danielsen, E M


    The noncovalent, dimeric assembly of small intestinal brush border enzymes was studied by sedimentation analysis in density gradients of extracts of pulse-labeled pig jejunal mucosal explants. Like aminopeptidase N (EC, sucrase-isomaltase (EC, aminopeptidase A (EC 3...... appearance of the liposome-reconstituted enzyme [Norén et al. (1986) J. Biol. Chem. 261, 12306-12309], showing only the inner, membrane-anchored domains of the monomers to be in close contact with one another while the outer domains are far apart. In contrast to the other brush border enzymes studied...

  20. Dimerization and oligomerization of the chaperone calreticulin

    DEFF Research Database (Denmark)

    Jørgensen, Charlotte S; Ryder, L Rebekka; Steinø, Anne


    protein. Using PAGE, urea gradient gel electrophoresis, capillary electrophoresis and MS, we show that dimerization through the SH group can be induced by lowering the pH to 5-6, heating, or under conditions that favour partial unfolding such as urea concentrations above 2.6 m or SDS concentrations above...... that favour partial unfolding or an intramolecular local conformational change that allows oligomerization, resulting in a heterogeneous mixture of oligomers consisting of up to 10 calreticulin monomers. The oligomeric calreticulin was very stable, but oligomerization was partially reversed by addition of 8 m...

  1. Kinetics of the dimerization of retroviral proteases: The "fireman's grip" and dimerization

    Czech Academy of Sciences Publication Activity Database

    Ingr, Marek; Kondrová, Taťána; Stříšovský, Kvido; Majerová, E.; Konvalinka, Jan


    Roč. 12, - (2003), s. 2173-2182 ISSN 0961-8368 R&D Projects: GA MZd NI6339 Institutional research plan: CEZ:AV0Z4055905 Keywords : retroviral protease * dimerization * HIV protease Subject RIV: CE - Biochemistry Impact factor: 3.787, year: 2003

  2. Photocatalytic removal of Congo red dye using MCM-48/Ni2O3 composite synthesized based on silica gel extracted from rice husk ash; fabrication and application. (United States)

    Shaban, Mohamed; Abukhadra, Mostafa R; Hamd, Ahmed; Amin, Ragab R; Abdel Khalek, Ahmed


    MCM-48 mesoporous silica was successfully synthesized from silica gel extracted from rice husk ash and loaded by nickel oxide (Ni 2 O 3 ). The resulted composite was characterized using X-ray diffraction, scanning electron microscope, and UV-vis spectrophotometer. The role of MCM-48 as catalyst support in enhancing the photocatalytic properties of nickel oxide was evaluated through the photocatalytic degradation of Congo red dye under visible light source. MCM-48 as catalyst support for Ni 2 O 3 shows considerable enhancement in the adsorption capacity by 17% and 29% higher than the adsorption capacity of MCM-48 and Ni 2 O 3 , respectively. Additionally, the photocatalytic degradation percentage increased by about 64% relative to the degradation percentage using Ni 2 O 3 as a single component. The adsorption mechanism of MCM-48/Ni 2 O 3 is chemisorption process of multilayer form. The using of MCM-48 as catalyst support for Ni 2 O 3 enhanced the adsorption capacity and the photocatalytic degradation through increasing the surface area and prevents the nickel oxide particles from agglomeration. This was done through fixing nickel oxide particles throughout the porous structure which providing more exposed active adsorption sites and active photocatalyst sites for the incident photons. Based on the obtained results, supporting of nickel oxide particles onto MCM-48 are promising active centers for the degradation of Congo red dye molecules. Copyright © 2017 Elsevier Ltd. All rights reserved.

  3. Origin of Both Right- and Left-Handed Helicities in a Supramolecular Gel with and without Ni2+at the Supramolecular Level. (United States)

    Go, Misun; Choi, Heekyoung; Moon, Cheol Joo; Park, Jaehyeon; Choi, Yeonweon; Lee, Shim Sung; Choi, Myong Yong; Jung, Jong Hwa


    We demonstrate the different origins of helical directions in polymeric gels derived from a hydrazone reaction in the absence and presence of Ni 2+ . The right-handed helicity of polymeric gels without Ni 2+ originates from the enantiomeric d-form alanine moiety embedded in the building block. However, the right-handed helicity is inverted to a left-handed helicity upon the addition of Ni 2+ , indicating that added Ni 2+ greatly affects the conformation of the polymeric gel by overcoming the influence of the enantiomer embedded in the building block on the helicity at the supramolecular level. More interestingly, the ratio of the right-toleft-handed helical fibers varies with the concentration of Ni 2+ , which converts from 100% right-handed helical fiber to 90% left-handed helical fiber. In the presence of Ni 2+ , both right- and left-handed helical fibers coexist at the supramolecular level. Some fibers also exhibit both right- and left-handed helicities in a single fiber.

  4. In-situ conversion of rGO/Ni2P composite from GO/Ni-MOF precursor with enhanced electrochemical property (United States)

    Lv, Zijian; Zhong, Qin; Bu, Yunfei


    Owing to the metalloid characteristic and superior electrical conductivity, the metal phosphides have received increasing interests in energy storage systems. Here, xrGO/Ni2P composites are successfully synthesized via an In-situ phosphorization process with GO/Ni-MOF as precursors. Compared to pure Ni2P, the xrGO/Ni2P composites appear enhanced electrochemical properties in terms of the specific capacitance and cycling performance as electrodes for supercapacitors. Especially, the 2rGO/Ni2P electrode shows a highest specific capacitance of 890 F g-1 at 1 A g-1 among the obtained composites. The enhancement can be attributed to the inherited structure from Ni-MOF and the well assembled of rGO and Ni2P through the In-situ conversion process. Moreover, when applied as positive electrode in a hybrid supercapacitor, an energy density of 35.9 W h kg-1 at a power density of 752 W kg-1 has been achieved. This work provides an In-situ conversion strategy for the synthesis of rGO/Ni2P composite which might be a promising electrode material for SCs.

  5. Tunneling anisotropic magnetoresistance via molecular π orbitals of Pb dimers (United States)

    Schöneberg, Johannes; Ferriani, Paolo; Heinze, Stefan; Weismann, Alexander; Berndt, Richard


    Pb dimers on a ferromagnetic surface are shown to exhibit large tunneling anisotropic magnetoresistance (TAMR) due to molecular π orbitals. Dimers oriented differently with respect to the magnetization directions of a ferromagnetic Fe double layer on W(110) were made with a scanning tunneling microscope. Depending on the dimer orientations, TAMR is absent or as large as 20% at the Fermi level. General arguments and first-principles calculations show that mixing of molecular orbitals due to spin-orbit coupling, which leads to TAMR, is maximal when the magnetization is oriented parallel to the dimer axis.

  6. The role of dimerization in prion replication. (United States)

    Tompa, Peter; Tusnády, Gábor E; Friedrich, Peter; Simon, István


    The central theme in prion diseases is the conformational transition of a cellular protein from a physiologic to a pathologic (so-called scrapie) state. Currently, two alternative models exist for the mechanism of this autocatalytic process; in the template assistance model the prion is assumed to be a monomer of the scrapie conformer, whereas in the nucleated polymerization model it is thought to be an amyloid rod. A recent variation on the latter assumes disulfide reshuffling as the mechanism of polymerization. The existence of stable dimers, let alone their mechanistic role, is not taken into account in either of these models. In this paper we review evidence supporting that the dimerization of either the normal or the scrapie state, or both, has a decisive role in prion replication. The contribution of redox changes, i.e., the temporary opening and possible rearrangement of the intramolecular disulfide bridge is also considered. We present a model including these features largely ignored so far and show that it adheres satisfactorily to the observed phenomenology of prion replication.

  7. Rotational Spectrum of Propargyl Alcohol Dimer (United States)

    Mani, Devendra; Arunan, E.


    Propargyl alcohol is a molecule of interest to astrophysics as well as combustion studies. Rotational-tunneling spectra of propargyl alcohol monomer is well known and shows that the molecule exists in gauche form. Recently we reported microwave spectra of Ar...propargyl alcohol complex. Propargyl alcochol exists in gauche form in the complex as well. In this study we have recorded pure rotational spectra of propargyl alcohol dimer between 4-13 GHz range.A total of 47 transitions, 24 a-type, 16 b-type and 7 c-type, have been observed and fitted with semi rigid rotor asymmetric top hamiltonian. The fitted rotational constants are: A = 2321.83323(47) MHz, B = 1150.47726(24) MHz and C = 1124.89000(20) MHz. The standard deviation for the fit is 2.5 kHz. The experimental rotational constants are very close to the structure predicted by ab-initio calculations in which two gauche-propargyl alcohol moieties are in three point contact stabilized by O-H...O, O-H...pi and C-H...pi interactions. Few transitions for duterated isotopologues of the dimer have also been observed and search for the remaining transitions is in progress. Details will be presented in the talk. E. Hirota,J. Mol. Spectrosc. 26 (1968) 335-350. J.C. Pearson, B.J. Drouin, J. Mol. Spectrosc. 234 (2005) 149-156. D. Mani, E. Arunan, ChemPhysChem 14 (2013) 754-763.

  8. Investigation of the spin-1 honeycomb antiferromagnet BaNi2V2O8 with easy-plane anisotropy (United States)

    Klyushina, E. S.; Lake, B.; Islam, A. T. M. N.; Park, J. T.; Schneidewind, A.; Guidi, T.; Goremychkin, E. A.; Klemke, B.; Mânsson, M.


    The magnetic properties of the two-dimensional, S =1 honeycomb antiferromagnet BaNi2V2O8 have been comprehensively studied using dc susceptibility measurements and inelastic neutron scattering techniques. The magnetic excitation spectrum is found to be dispersionless within experimental resolution between the honeycomb layers, while it disperses strongly within the honeycomb plane where it consists of two gapped spin-wave modes. The magnetic excitations are compared to linear spin-wave theory allowing the Hamiltonian to be determined. The first- and second-neighbor magnetic exchange interactions are antiferromagnetic and lie within the ranges 10.90 meV ≤Jn≤13.35 meV and 0.85 meV ≤Jn n≤1.65 meV, respectively. The interplane coupling Jout is four orders of magnitude weaker than the intraplane interactions, confirming the highly two-dimensional magnetic behavior of this compound. The sizes of the energy gaps are used to extract the magnetic anisotropies and reveal substantial easy-plane anisotropy and a very weak in-plane easy-axis anisotropy. Together these results reveal that BaNi2V2O8 is a candidate compound for the investigation of vortex excitations and Berezinsky-Kosterliz-Thouless phenomenon.

  9. Cooperative effect of monoclinic distortion and sinusoidal modulation in the martensitic structure of Ni2FeGa

    International Nuclear Information System (INIS)

    Lu, J.B.; Yang, H.X.; Tian, H.F.; Zeng, L.J.; Ma, C.; Feng, L.; Wu, G.H.; Li, J.Q.; Jansen, J.


    The structural features of the '5M' martensitic phase in Ni 2 FeGa alloys have been determined by electron diffraction using the multi-slice least-squares (MSLS) method. The results demonstrate that the '5M' phase contains an evident cooperative effect of monoclinic distortion and sinusoidal modulation along the [110] c direction. Theoretical simulations based on our refined data suggest that the '5M' martensitic phase observed in Ni-Fe-Ga and Ni-Mn-Ga has visible common behaviors in both stacking sequence and local structural distortion. Considering the cooperative effect of monoclinic distortion and sinusoidal modulation, we demonstrate that the '7M' martensitic phase could adopt two equivalent structural phases corresponding with the stacking sequences of (43 - ) 2 and (52 - ) 2 , respectively. - Graphical abstract: The structural model of the '5M' Ni 2 FeGa martensite viewed along the [001] c (i.e. [010] m ) zone axis, demonstrating the cooperative effect of monoclinic distortion and sinusoidal modulation along the [110] c direction.

  10. Equilibrium and kinetics studies for the adsorption of Ni2+ and Fe3+ ions from aqueous solution by graphene oxide

    Directory of Open Access Journals (Sweden)

    Konicki Wojciech


    Full Text Available In this study, the adsorption of Ni2+ and Fe3+ metal ions from aqueous solutions onto graphene oxide (GO have been explored. The effects of various experimental factors such as pH of the solution, initial metal ion concentration and temperature were evaluated. The kinetic, equilibrium and thermodynamic studies were also investigated. The adsorption rate data were analyzed using the pseudo-first-order kinetic model, the pseudo-second-order kinetic model and the intraparticle diffusion model. Kinetic studies indicate that the adsorption of both ions follows the pseudo-second-order kinetics. The isotherms of adsorption data were analyzed by adsorption isotherm models such as Langmuir and Freundlich. Equilibrium data fitted well with the Langmuir model. The maximum adsorption capacities of Ni2+ and Fe3+ onto GO were 35.6 and 27.3 mg g−1, respectively. In addition, various thermodynamic parameters, such as enthalpy (ΔHO, entropy (ΔSO and Gibbs free energy (ΔGO, were calculated.

  11. Facile synthesis of CoNi2S4/Co9S8 composites as advanced electrode materials for supercapacitors (United States)

    Zhao, Fenglin; Huang, Wanxia; Zhang, Hongtao; Zhou, Dengmei


    In this paper, a facile chemical bath deposition method was utilized to synthesize three-dimensional nanostructured CoNi2S4/Co9S8 (CNSCS) composites as advanced electrode materials for high performance supercapacitors. CNSCS composites showed remarkable electrochemical performance owing to the high porosity, appropriate pore size distribution, novel architecture and synergistic effect of Ni/Co ions. The electrochemical tests revealed that CNSCS composites exhibited high specific capacitance (1183.3 Fg-1 at the current density of 2 Ag-1), excellent rate performance (74.9% retention with tenfold current density increase) and outstanding cycle life stability. Moreover, the effect of temperature on electrochemical performance of CNSCS composites was investigated and the results indicated the specific capacitance of CoNi2S4/Co9S8 can keep relatively stable in a wide temperature from 0 °C to 50 °C. These results indicated that the synthesized CNSCS composites can be a promising electrode materials candidate for supercapacitors and chemical bath deposition is a promising processing route for CNSCS composites production.

  12. A novel mechanism of “metal gel-shift” by histidine-rich Ni2+-binding Hpn protein from Helicobacter pylori strain SS1 (United States)

    Ito, Yuki; Masumoto, Junya; Morita, Eugene Hayato; Hayashi, Hidenori


    Sodium dodecyl sulphate-polyacrylamide gel electrophoresis (SDS-PAGE) is a universally used method for determining approximate molecular weight (MW) in protein research. Migration of protein that does not correlate with formula MW, termed “gel shifting” appears to be common for histidine-rich proteins but not yet studied in detail. We investigated “gel shifting” in Ni2+-binding histidine-rich Hpn protein cloned from Helicobacter pylori strain SS1. Our data demonstrate two important factors determining “gel shifting” of Hpn, polyacrylamide-gel concentration and metal binding. Higher polyacrylamide-gel concentrations resulted in faster Hpn migration. Irrespective of polyacrylamide-gel concentration, preserved Hpn-Ni2+ complex migrated faster (3–4 kDa) than apo-Hpn, phenomenon termed “metal gel-shift” demonstrating an intimate link between Ni2+ binding and “gel shifting”. To examine this discrepancy, eluted samples from corresponding spots on SDS-gel were analyzed by matrix-assisted laser desorption/ionization-time-of-flight mass spectrometry (MALDI-TOF-MS). The MW of all samples was the same (6945.66±0.34 Da) and identical to formula MW with or without added mass of Ni2+. MALDI-TOF-MS of Ni2+-treated Hpn revealed that monomer bound up to six Ni2+ ions non-cooperatively, and equilibrium between protein-metal species was reliant on Ni2+ availability. This corroborates with gradually increased heterogeneity of apo-Hpn band followed by compact "metal-gel shift" band on SDS-PAGE. In view of presented data metal-binding and “metal-gel shift” models are discussed. PMID:28207866

  13. Stochastic optimization-based study of dimerization kinetics

    Indian Academy of Sciences (India)

    Abstract. We investigate the potential of numerical algorithms to decipher the kinetic parameters involved in multi-step chemical reactions. To this end, we study dimerization kinetics of protein as a model system. We follow the dimerization kinetics using a stochastic simulation algorithm and combine it with three different.

  14. Exact Solution of a Generalized Nonlinear Schrodinger Equation Dimer

    DEFF Research Database (Denmark)

    Christiansen, Peter Leth; Maniadis, P.; Tsironis, G.P.


    We present exact solutions for a nonlinear dimer system defined throught a discrete nonlinear Schrodinger equation that contains also an integrable Ablowitz-Ladik term. The solutions are obtained throught a transformation that maps the dimer into a double Sine-Gordon like ordinary nonlinear...

  15. Two Populations Mean-Field Monomer-Dimer Model (United States)

    Alberici, Diego; Mingione, Emanuele


    A two populations mean-field monomer-dimer model including both hard-core and attractive interactions between dimers is considered. The pressure density in the thermodynamic limit is proved to satisfy a variational principle. A detailed analysis is made in the limit of one population is much smaller than the other and a ferromagnetic mean-field phase transition is found.

  16. Palladium dimers adsorbed on graphene: A DFT study

    International Nuclear Information System (INIS)

    Kaur, Gagandeep; Gupta, Shuchi; Dharamvir, Keya


    The 2D structure of graphene shows a great promise for enhanced catalytic activity when adsorbed with palladium. We performed a systematic density functional theory (DFT) study of the adsorption of palladium dimer (Pd 2 ) on graphene using SIESTA package, in the generalized gradient approximation (GGA). The adsorption energy, geometry, and charge transfer of Pd 2 -graphene system are calculated. Both horizontal and vertical orientations of Pd 2 on graphene are studied. Our calculations revealed that the minimum energy configuration for Pd dimer is parallel to the graphene sheet with its two atoms occupying centre of adjacent hexagonal rings of graphene sheet. Magnetic moment is induced for Pd dimer adsorbed on graphene in vertical orientation while horizontal orientation of Pd dimer on graphene do not exhibit magnetism. Insignificant energy differences among adsorption sites means that dimer mobility on the graphene sheet is high. There is imperceptible distortion of graphene sheet perpendicular to its plane. However, some lateral displacements are seen

  17. Metal membrane with dimer slots as a universal polarizer

    DEFF Research Database (Denmark)

    Zhukovsky, Sergei; Zalkovskij, Maksim; Malureanu, Radu


    for the electromagnetic response of an arbitrary dimer based on the Green functions approach. The theory confirms that a great variety of polarization properties, such as birefringence, chirality and elliptical dichroism, can be achieved in a metal layer with such slot-dimer patterning (i.e. in a metasurface). Optical......In this work, we show theoretically and confirm experimentally that thin metal membranes patterned with an array of slot dimers (or their Babinet analogue with metal rods) can function as a versatile spectral and polarization filter. We present a detailed covariant multipole theory...... properties of the metasurface can be extensively tuned by varying the geometry (shape and dimensions) of the dimer, for example, by adjusting the sizes and mutual placement of the slots (e.g. inter-slot distance and alignment angle). Three basic shapes of dimers are analyzed: II-shaped (parallel slots), V...

  18. Family C 7TM receptor dimerization and activation

    DEFF Research Database (Denmark)

    Bonde, Marie Mi; Sheikh, Søren P; Hansen, Jakob Lerche


    The family C seven transmembrane (7TM) receptors constitutes a small and especially well characterized subfamily of the large 7TM receptor superfamily. Approximately 50% of current prescription drugs target 7TM receptors, this biologically important family represents the largest class of drug......-targets today. It is well established that family C 7TM receptors form homo- or hetero-dimers on the cell surface of living cells. The large extra-cellular domains (ECD) have been crystallized as a dimer in the presence and absence of agonist. Upon agonist binding, the dimeric ECD undergoes large conformational...... changes that lead to receptor activation. Despite extensive studies of the receptor transmembrane domain, several key features, including the exact organization of the complete receptor dimer, the sequence of events leading to receptor activation, and the functional significance of dimerization, have yet...

  19. Dimer Coverings on Random Polyomino Chains (United States)

    Xiao, Chuanqi; Chen, Haiyan


    A polyomino chain is a planar square lattice that can be constructed by successively attaching squares to the previous one in two possible ways. A random polyomino chain is then generated by incorporating the Bernoulli distribution to the two types of attachment, which describes a zeroth-order Markov process. Let (ℜn, p) be the ensemble of random polyomino chains with n squares, where p∈[0,1] is a constant. Then, in this paper, we determine the explicit expression for the expectation of the number of dimer coverings over (ℜn, p). Our result shows that, with only one exception, i.e., p = 0, the average of the logarithm of this expectation is asymptotically nonzero when n → ∞.

  20. Experimental sorption of Ni 2+, Cs + and Ln 3+ onto a montmorillonite up to 150°C (United States)

    Tertre, Emmanuel; Berger, Gilles; Castet, Sylvie; Loubet, Michel; Giffaut, Eric


    The effect of temperature on the sorption of cations onto a dioctahedral smectite was investigated by running batch experiments at 25, 40, 80 and 150°C. We measured the distribution coefficient (Kd) of Cs +, Ni 2+ and 14 lanthanides (Ln 3+) between solutions and the montmorillonite fraction of the MX80 bentonite at various pH and ionic strengths. Up to 80°C we used a conventional experimental protocol derived from Coppin et al. (2002). At 150°C, the experiments were conducted in a PTFE reactor equipped with an internal filter allowing the sampling of clear aliquots of solution. The results show a weak but measurable influence of the temperature on the elements sorption. Kd's for Ni 2+ and Ln 3+ increase by a factor 2 to 5 whereas temperature raises from 25 to 150°C. This effect seems higher at high ionic strength. The estimated apparent endothermic sorption enthalpies are 33 ± 10 kJ.mol -1 and 39 ± 15 kJ.mol -1 for Ni 2+ and Eu 3+, respectively. On the other hand, the temperature effect on Cs + sorption is only evidenced at low ionic strength and under neutral conditions where the Kd decreases by a factor 3 between 25 and 150°C. Apparent exothermic sorption enthalpy for Cs + on the montmorillonite is -19 ± 5 kJ.mol -1. Experiments conducted at the four temperatures with the coexistence of all of the cations in the reacting solution (100 ppb of each element in the starting solution) or only one of them, produced similar values of Kd. This suggests the absence of competition between the sorbed cations, and consequently a low degree of saturation of the available sites. A fractionation of the lanthanides spectrum is also observed at high pH and high ionic strength whatever the temperature. The conclusion of this study is that the temperature dependence on sorption reflects, as the fractionation of REE or the pH and ionic strength effects, the chemical process which controls the overall reaction. In the case of an exchange dominated reaction (low pH and low

  1. Dualism of Sensitivity and Selectivity of Porphyrin Dimers in Electroanalysis. (United States)

    Lisak, Grzegorz; Tamaki, Takashi; Ogawa, Takuji


    This work uncovers the application of porphyrin dimers for the use in electroanalysis, such as potentiometric determination of ions. It also puts in question a current perception of an occurrence of the super-Nernstian response, as a result of the possible dimerization of single porphyrins within an ion-selective membrane. To study that, four various porphyrin dimers were used as ionophores, namely, freebase-freebase, Zn-Zn, Zn-freebase, and freebase-Zn. Since the Zn-freebase and freebase-Zn porphyrin dimers carried both anion- and cation-sensitive porphyrin units, their application in ISEs was utilized in both anion- and cation-sensitive sensors. With respect to the lipophilic salt added, both porphyrins dimers were found anion- and cation-sensitive. This allowed using a single molecule as novel type of versatile ionophore (anion- and cation-selective), simply by varying the membrane composition. All anion-sensitive sensors were perchlorate-sensitive, while the cation-selective sensors were silver-sensitive. The selectivity of the sensors depended primarily on the porphyrin dimers in the ion-selective membrane. Furthermore, the selectivity of cation-sensitive dimer based sensors was found significantly superior to the ones measured for the single porphyrin unit based sensors (precursors of the porphyrin dimers). Thus, the dimerization of single porphyrins may actually be a factor to increase or modulate porphyrin selectivity. Moreover, in the case of cation-sensitive sensors, the selectivity vastly depended on the order of porphyrin units in the dimer. This opens a new approach of regulating and adjusting sensitivity and selectivity of the sensor through the application of complex porphyrin systems with more than one porphyrin units with mix sensitive porphyrins.

  2. Efficient isolation of major procyanidin A-type dimers from peanut skins and B-type dimers from grape seeds

    NARCIS (Netherlands)

    Appeldoorn, M.M.; Sanders, M.B.; Vincken, J.P.; Cheynier, V.; Guerneve, Le C.; Gruppen, H.


    In order to fully explore the biofunctional potential of proanthocyanidins (PA), isolated and well-characterised PA dimers are of great importance. Current methods to obtain pure A- and B-type dimers are laborious, because they comprise multiple chromatographic steps, often yielding only one or two

  3. Effect of Temperature on the Kinetics of Sorption of Co2+ and Ni2+ Ions by a Sorbent Based on an Inositol Hexaphosphoric Acid Derivative (United States)

    Yarusova, S. B.; Makarenko, N. V.; Gordienko, P. S.; Karpenko, M. A.; Novikova, E. S.


    Data on the effect temperature has on the kinetics of the removal of Co2+ and Ni2+ ions under static conditions by a sorbent based on a derivative of phytic acid fabricated from rice production waste are presented. It is shown that when the temperature is raised from 20 to 60°C, the sorption capacity of the sorbent based on phytic acid increases over the period of sorption and within 180 min reaches values of 1.4 mmol g-1 for Co2+ ions and 1.3 mmol g-1 for Ni2+ ions. It is established that for the investigated range of temperatures, order n of the sorption of Co2+ and Ni2+ ions is <1, which characterizes the reactions accompanied by diffusion processes. It is found that the process of removal of Co2+ and Ni2+ ions is characterized with low activation energy (20.74 kJ mol-1 for Co2+ ions and 14.2 kJ mol-1 for Ni2+ ions). It is also demonstrated that the sorption process in the considered time frame is best described by a kinetic model of a pseudo-second order, as is indicated by respective correlation coefficients.

  4. Synergetic Effect of Ni2P/SiO2 and γ-Al2O3 Physical Mixture in Hydrodeoxygenation of Methyl Palmitate

    Directory of Open Access Journals (Sweden)

    Ivan V. Shamanaev


    Full Text Available The Ni2P/SiO2 catalyst, which was prepared by in situ temperature-programmed reduction and in the mixture with the inert (SiC, SiO2 or acidic (γ-Al2O3 material was studied in methyl palmitate hydrodeoxygenation (HDO. Methyl palmitate HDO was carried out at temperatures of 270–330 °C, H2/feed volume ratio of 600 Nm3/m3, and H2 pressure of 3.0 MPa. Ni2P/SiO2 catalyst, diluted with γ-Al2O3 showed a higher activity than Ni2P/SiO2 catalyst diluted with SiC or SiO2. The conversion of methyl palmitate increased significantly in the presence of γ-Al2O3 most probably due to the acceleration of the acid-catalyzed reaction of ester hydrolysis. The synergism of Ni2P/SiO2 and γ-Al2O3 in methyl palmitate HDO can be explained by the cooperation of the metal sites of Ni2P/SiO2 and the acid sites of γ-Al2O3 in consecutive metal-catalyzed and acid-catalyzed reactions of HDO. The obtained results let us conclude that the balancing of metal and acid sites plays an important role in the development of the efficient catalyst for the HDO of fatty acid esters over supported phosphide catalysts.

  5. Low-temperature activation and deactivation of high-Curie-temperature ferromagnetism in a new diluted magnetic semiconductor: Ni2+-Doped SnO2. (United States)

    Archer, Paul I; Radovanovic, Pavle V; Heald, Steve M; Gamelin, Daniel R


    We report the synthesis of colloidal Ni(2+)-doped SnO(2) (Ni(2+):SnO(2)) nanocrystals and their characterization by electronic absorption, magnetic circular dichroism, X-ray absorption, magnetic susceptibility, scanning electron microscopy, and X-ray diffraction measurements. The Ni(2+) dopants are found to occupy pseudooctahedral Sn(4+) cation sites of rutile SnO(2) without local charge compensation. The paramagnetic nanocrystals exhibit robust high-Curie-temperature (T(C)) ferromagnetism (M(s)(300 K) = 0.8 mu(B)/Ni(2+), T(C) > 300 K) when spin-coated into films, attributed to the formation of interfacial fusion defects. Facile reversibility of the paramagnetic-ferromagnetic phase transition is also observed. This magnetic phase transition is studied as a function of temperature, time, and atmospheric composition, from which the barrier to ferromagnetic activation (E(a)) is estimated to be 1200 cm(-1). This energy is associated with ligand mobility on the surfaces of the Ni(2+):SnO(2) nanocrystals. The phase transition is reversed under air but not under N(2), from which the microscopic identity of the activating defect is proposed to be interfacial oxygen vacancies.

  6. The substitution of Fe2+ ions by Ni2+ ions in the green rust 2 compound studied by Moessbauer effect

    International Nuclear Information System (INIS)

    Refait, P.; Bauer, P.; Olowe, A.A.; Genin, J.M.R.


    Green rust 2 is usually obtained by oxidizing an initial mixture of FeSO 4 and NaOH solutions and a complete oxidation leads mainly towards γ oxyhydroxide known as lepidocrocite. By adding some NiSO 4 one can stop at the first stage and Moessbauer spectra reveal only ferric doublets. This implies that the initial formula 4Fe(OH) 2 , 2FeOOH, FeSO 4 of green rust 2 must be replaced by xNi(OH) 2 , (6-x)FeOOH, NiSO 4 , where x scans from 2 to 4. It also means that all initial ferrous ions become oxidized into the ferric state leaving the Ni 2+ ions unchanged. Therefore the end product of oxidation is the nickel containing green rust 2 at the place of the usual lepidocrocite. (orig.)

  7. Infrared thermography videos of the elastocaloric effect for shape memory alloys NiTi and Ni2FeGa

    Directory of Open Access Journals (Sweden)

    Garrett J. Pataky


    Full Text Available Infrared thermogrpahy was utilized to record the temperature change during tensile loading cycles of two shape memory alloy single crystals with pseudoelastic behavior. During unloading, a giant temperature drop was measured in the gage section due to the elastocaloric effect. This data article provides a video of a [001] oriented Ni2FeGa single crystal, including the corresponding stress–strain curve, shows the temperature drop over one cycle. The second video of a [148] oriented NiTi single crystal depicts the repeatability of the elastocaloric effect by showing two consecutive cycles. The videos are supplied in this paper. For further analysis and enhanced discussion of large temperature change in shape memory alloys, see Pataky et al. [1

  8. Phonon dispersion in the ferromagnetic shape memory alloy Ni2MnGa studied by neutron spectroscopy

    International Nuclear Information System (INIS)

    Vorderwisch, P.; Shapiro, S.M.


    Neutron spectroscopy is an ideal technique to study the structure and dynamics of crystals. For the ferromagnetic shape memory alloy Ni 2 MnGa, all previously obtained information from inelastic neutron scattering experiments is restricted to the phonon dispersion in the austenitic (fcc) phase of alloys with different compositions. For the (tetragonally distorted) martensitic phase recent inelastic neutron scattering data are presented. These new data were taken on a single crystal with stoichiometric composition. A single-variant martensitic phase of the sample has been obtained by the application of magnetic fields in horizontal or vertical direction with respect to the scattering plane used in the experiments. The measured phonon-dispersion curves are compared with recently published ab initio (zero-temperature) phonon-dispersion calculations. The anomalous phonon behavior observed in both, the austenitic and martensitic phase is discussed

  9. Effect of Co(2+) and Ni(2+)-doped zinc borate nano crystalline powders by co-precipitation method. (United States)

    Shim, Jaesool; Venkata Reddy, Ch; Sarma, G V S S; Narayana Murthy, P; Ravikumar, R V S S N


    A simple co-precipitation method has been used for the synthesis of Co(2+) and Ni(2+)-doped zinc borate nanopowders. X-ray diffraction (XRD), Fourier transform infrared (FT-IR), UV/Vis absorption, Scanning electron microscope (SEM) with EDS and photoluminescence (PL) spectroscopies techniques has been employed for their characterization. Powder X-ray diffraction data reveals that the crystal structure belongs to monoclinic for both as-prepared samples. SEM images showed surface morphology of the prepared samples. Optical absorption spectra showed the characteristic bands of doped ions in octahedral site symmetry. From the optical absorption data crystal field and inter-electronic repulsion parameters are evaluated. The FT-IR spectra showed the characteristic vibrational bands related to ZnO, BO3 and BO4 molecules. Photoluminescence spectra exhibited the emission bands in ultraviolet and blue regions. Copyright © 2015 Elsevier B.V. All rights reserved.

  10. Note on the magnetic and magneto-optical properties of Ni2In type 3d transition metal compounds

    International Nuclear Information System (INIS)

    Buschow, K.H.J.; Engen, P.G. van


    The ternary compounds PtMnGa, PtMnAl, FeNiIn, FeMnIn, FeNiGe, FeCoGe, FeMnGe, CoNiSn, FeNiSn, FeCoSn, and MnCoSn are found to crystallize in the hexagonal Ni 2 In structure. The lattice constants of these compounds are determined and their magnetic properties studied in the range 4.2 to 300 K. It is found that most of these compounds are ferromagnetic. For several of the compounds the complex polar Kerr effect is studied at room temperature in the energy range 0.6 to 4.4 eV. (author)

  11. Magnetic and magnetocaloric properties of martensitic Ni2Mn1.4Sn0.6 Heusler alloy

    International Nuclear Information System (INIS)

    Chernenko, Volodymyr A.; Barandiarán, Jose M.; Rodriguez Fernández, Jesus; Rojas, Daniel P.; Gutiérrez, Jon; Lázpita, Patricia; Orue, Iñaki


    The evolutions of magnetic properties at low temperatures and the influence of magnetic field on the temperature dependence of specific heat in martensitic Ni 2 Mn 1.4 Sn 0.6 Heusler alloy are studied. The frequency-dependent blocking temperature and considerable exchange bias below it are measured in the martensitic phase. From the analysis of the specific heat curves under magnetic field, a large inverse magnetocaloric effect manifested as the magnetic field induced rise of isothermal magnetic entropy and/or magnetic field induced adiabatic temperature decrease in the vicinity of the reverse magnetostructural transformation and a significant value of the conventional magnetocaloric effect at the Curie temperature are obtained. The Debye temperature and electronic coefficient equal to Θ D =310±2 K and γ= 16.6±0.3 mJ/K 2 mol, respectively, do not depend on the magnetic field.

  12. Advances in Chemistry and Pharmacology of Triterpenoid Synthetic Dimers. (United States)

    Bednarczyk-Cwynar, Barbara; Günther, Andrzej


    This review focuses on advances in chemistry and pharmacology of synthetic triterpenoid dimers, obtained from natural compounds. Synthetic triterpenoid dimers are divided into specific subgroups based on the structure of main triterpenoid monomeric skeleton. Synthetic triterpenoid derivatives of dimeric structure can be obtained through the covalent linkage of the C-3 hydroxyl or another group, via the C-2 atom or the C-17 carboxyl group (mainly anhydrides, amides or esters). Some triterpenes can undergo chemical transformations leading to the formation of cyclic dimers or other types of dimers. Most of the obtained triterpenoid dimers have been subjected to pharmacological tests evaluating their biological activity, mainly antiviral (HIV-1 RT, HCVpp, VSVpp, HIV-RT-C8166-CCR5), cytotoxic (against e.g. 388, MCF-7, SF-268, NCIH460, KM20L2, DU-145, Hep-G2, A549, BGC-823, PC-3), anti-inflammatory (iNOS, RAW 264.7) and antidiabetic (RMGPa inhibition). The authors also reported the ability of some of the obtained cyclic triterpenoid dimers to recognize anions and to form self-assembled structures. Copyright© Bentham Science Publishers; For any queries, please email at

  13. Asymmetric monometallic nanorod nanoparticle dimer and related compositions and methods

    KAUST Repository

    Han, Yu


    The fabrication of asymmetric monometallic nanocrystals with novel properties for plasmonics, nanophotonics and nanoelectronics. Asymmetric monometallic plasmonic nanocrystals are of both fundamental synthetic challenge and practical significance. In an example, a thiol-ligand mediated growth strategy that enables the synthesis of unprecedented Au Nanorod-Au Nanoparticle (AuNR-AuNP) dimers from pre-synthesized AuNR seeds. Using high-resolution electron microscopy and tomography, crystal structure and three-dimensional morphology of the dimer, as well as the growth pathway of the AuNP on the AuNR seed, was investigated for this example. The dimer exhibits an extraordinary broadband optical extinction spectrum spanning the UV, visible, and near infrared regions (300 - 1300 nm). This unexpected property makes the AuNR-AuNP dimer example useful for many nanophotonic applications. In two experiments, the dimer example was tested as a surface- enhanced Raman scattering (SERS) substrate and a solar light harvester for photothermal conversion, in comparison with the mixture of AuNR and AuNP. In the SERS experiment, the dimer example showed an enhancement factor about 10 times higher than that of the mixture, when the excitation wavelength (660 nm) was off the two surface plasmon resonance (SPR) bands of the mixture. In the photothermal conversion experiment under simulated sunlight illumination, the dimer example exhibited an energy conversion efficiency about 1.4 times as high as that of the mixture.

  14. Role of cyclobutane dimers in UV-denaturation of DNA

    International Nuclear Information System (INIS)

    Zavil'gel'skij, G.B.; Zuev, A.V.


    UV irradiation of double-stranded DNA produces local denatured regions. The evidence presented indicates that these single-stranded regions arise from photoproducts other than pyrimidine dimers. The irradiation of T2 DNA at 8x10 4 erg/mm 2 (254 nm) produces 6-8% thymine dimers, amd Tsub(mel) drops by 12-14 deg C, accompanied by a significant broadening of the transition profile. The kinetics of denatured region formation and lowering Tsub(mel) corresponds to that of formation of crosslinkages and differs markedly from the kinetics of formation of cyclobutane pyrimidine dimers. Treatment of UV-irradiated DNA with light in the presence of yeast photoreactivating enzyme monomerizes almost all thymine dimers but does not change the Tsub(mel). Local denatured regions are detected in UV-irradiated DNA and are absent from AcPhM-sensibilized DNA, which contains 20-25% thymine dimers, as determined by the accridine orange fluorescence technique. S1 nuclease from Aspergillis oryzae produces single-strand breaks in UV-irradiated DNA of phage PM2 but is not active on AcPhM-treated PM2 DNA, which contains about 50 thymine dimers. It is supposed that the formation of a cyclobutane dimer only weakens the hydrogen bonds in the AT base pair rather than breaks them. Local denatured regions are thought to arise from the accumulation in UV-irradiated DNA (254 nm) of the sufficient number of photoproducts with impaired ability to base pairing

  15. Vison excitations in near-critical quantum dimer models (United States)

    Strübi, G.; Ivanov, D. A.


    We study vison excitations in a quantum dimer model interpolating between the Rokhsar-Kivelson models on the square and triangular lattices. In the square-lattice case, the model is known to be critical and characterized by U(1) topological quantum numbers. Introducing diagonal dimers brings the model to a Z2 resonating-valence-bond phase. We study variationally the emergence of vison excitations at low concentration of diagonal dimers, close to the critical point. We find that, in this regime, vison excitations are large in size and their structure resembles vortices in type-II superconductors.

  16. Family C 7TM receptor dimerization and activation

    DEFF Research Database (Denmark)

    Bonde, Marie Mi; Sheikh, Søren P; Hansen, Jakob Lerche


    changes that lead to receptor activation. Despite extensive studies of the receptor transmembrane domain, several key features, including the exact organization of the complete receptor dimer, the sequence of events leading to receptor activation, and the functional significance of dimerization, have yet...... to be fully defined. This review presents the biochemical support for family C 7TM receptor dimerization and discusses its importance for receptor biosynthesis, surface expression, ligand binding and activation, since lessons learnt here may well be applicable to the whole superfamily of 7TM receptors....

  17. Glycine transporter dimers: evidence for occurrence in the plasma membrane

    DEFF Research Database (Denmark)

    Bartholomäus, Ingo; Milan-Lobo, Laura; Nicke, Annette


    by fluorescence resonance energy transfer microscopy. Endoglycosidase treatment and surface biotinylation further revealed that complex-glycosylated GlyTs form dimers located at the cell surface. Furthermore, substitution of tryptophan 469 of GlyT2 by an arginine generated a transporter deficient in dimerization......Different Na(+)/Cl(-)-dependent neurotransmitter transporters of the SLC6a family have been shown to form dimers or oligomers in both intracellular compartments and at the cell surface. In contrast, the glycine transporters (GlyTs) GlyT1 and -2 have been reported to exist as monomers in the plasma...

  18. Subsurface dimerization in III-V semiconductor (001) surfaces

    DEFF Research Database (Denmark)

    Kumpf, C.; Marks, L.D.; Ellis, D.


    We present the atomic structure of the c(8 X 2) reconstructions of InSb-, InAs-, and GaAs-(001) surfaces as determined by surface x-ray diffraction using direct methods. Contrary to common belief, group III dimers are not prominent on the surface, instead subsurface dimerization of group m atoms...... takes place in the second bilayer, accompanied by a major rearrangement of the surface atoms above the dimers to form linear arrays. By varying the occupancies of four surface sites the (001)-c(8 X 2) reconstructions of III-V semiconductors can be described in a unified model....

  19. Photoelectron Spectroscopy of 4-Bromochlorobenzene Dimer and Trimer Anions

    International Nuclear Information System (INIS)

    Kim, Namdoo


    I investigated the electron attachment to 4-BCB dimer and trimer anions using anion photoelectron spectroscopy and theoretical calculations. I found that an excess electron can be delocalized to these clusters through extended π-network. However, the nature of the ion core is different for the dimer and trimer. For the heterodimer anions, the geometry is determined by the differences in electronegativity of the molecules. Dimer anions with a large electronegativity difference have T-shaped geometries and those with a small electronegativity difference have PD geometries

  20. Selective binding and magnetic separation of His-tagged proteins using Fe3O4/PAM/NTA-Ni2+ Magnetic Nanoparticles (United States)

    Guo, Huiling; Li, Mengyun; Tu, Shu; Sun, Honghao


    Fe3O4 nanoparticles coated with polyacrylamide (PAM) were synthesized. The magnetic core, with an average hydrodynamic size of 235.5 nm, allowed the magnetic nanoparticles (MNPs) rapid separation from solutions under an external magnetic field. NTA-Ni2+ was modified on the surface of Fe3O4/PAM MNPs to selectively trap his-tagged green fluorescent protein (GFP). The results showed that Fe3O4/PAM/NTA-Ni2+ MNPs exhibited remarkable capability of selective binding and separating his-tagged GFP. The adsorption efficiency was 93.37%.

  1. Density function theoretical investigation on the Ni3PP structure and the hydrogen adsorption property of the Ni2P(0001) surface


    Ariga, Hiroko; Kawashima, Mayumi; Takakusagi, Satoru; Asakura, Kiyotaka


    The electronic and structural properties of a phosphorus-terminated structure of Ni2P(0001) surface (Ni3PP) are investigated by density functional theory (DFT) calculations. Phosphorus adsorption largely stabilizes the Ni2P(0001) surface by creating Ni-P bonds on the Ni trimer. Atomic hydrogen can adsorb on the topmost P site although its adsorption energy is much lower than its adsorption energy on the Ni trimer site of the Ni3P2 surface. Our results suggest that the Ni trimer is the key fac...

  2. Dimer-based model for heptaspanning membrane receptors. (United States)

    Franco, Rafael; Casadó, Vicent; Mallol, Josefa; Ferré, Sergi; Fuxe, Kjell; Cortés, Antonio; Ciruela, Francisco; Lluis, Carmen; Canela, Enric I


    The existence of intramembrane receptor-receptor interactions for heptaspanning membrane receptors is now fully accepted, but a model considering dimers as the basic unit that binds to two ligand molecules is lacking. Here, we propose a two-state-dimer model in which the ligand-induced conformational changes from one component of the dimer are communicated to the other. Our model predicts cooperativity in binding, which is relevant because the other current models fail to address this phenomenon satisfactorily. Our two-state-dimer model also predicts the variety of responses elicited by full or partial agonists, neutral antagonists and inverse agonists. This model can aid our understanding of the operation of heptaspanning receptors and receptor channels, and, potentially, be important for improving the treatment of cardiovascular, neurological and neuropsychyatric diseases.

  3. Dimers on Surface Graphs and Spin Structures. I

    DEFF Research Database (Denmark)

    Cimasoni, David; Reshetikhin, Nicolai


    Partition functions for dimers on closed oriented surfaces are known to be alternating sums of Pfaffians of Kasteleyn matrices. In this paper, we obtain the formula for the coefficients in terms of discrete spin structures....

  4. Naturally Occurring Diterpenoid Dimers: Source, Biosynthesis, Chemistry and Bioactivities. (United States)

    Lin, Li-Gen; Ung, Carolina Oi Lam; Feng, Zhe-Ling; Huang, Li; Hu, Hao


    Diterpenoid dimers are rare in nature and mainly found in higher plants including the families Acanthaceae, Annonaceae, Asteraceae, Calceolariaceae, Chrysobalanaceae, Cupressaceae, Euphorbiaceae, Fabaceae, Lamiaceae, Liliaceae, Meliaceae, Rhizophoraceae, Taxaceae, Velloziaceae, and Zingiberaceae. In addition, a few diterpenoid dimers have been also reported from fungi (Psathyrellaceae), liverworts (Scapaniaceae), and a gorgonian (Gorgoniidae). They feature a wide variety of structures due to different core skeletons, linkage patterns, substituents, and configurations. Accordingly, diterpenoid dimers exhibit a broad range of bioactivities, including cytotoxic, anti-inflammatory, antimicrobial, antimalarial, and antifouling properties, which have attracted more and more research interests in the past decades. This review with 176 metabolites from 109 references provides a comprehensive and up-to-date overview of the source, biosynthesis, structure, synthesis, and bioactivities of diterpenoid dimers. Georg Thieme Verlag KG Stuttgart · New York.

  5. Atomic model for the dimeric FOregion of mitochondrial ATP synthase. (United States)

    Guo, Hui; Bueler, Stephanie A; Rubinstein, John L


    Mitochondrial adenosine triphosphate (ATP) synthase produces the majority of ATP in eukaryotic cells, and its dimerization is necessary to create the inner membrane folds, or cristae, characteristic of mitochondria. Proton translocation through the membrane-embedded F O region turns the rotor that drives ATP synthesis in the soluble F 1 region. Although crystal structures of the F 1 region have illustrated how this rotation leads to ATP synthesis, understanding how proton translocation produces the rotation has been impeded by the lack of an experimental atomic model for the F O region. Using cryo-electron microscopy, we determined the structure of the dimeric F O complex from Saccharomyces cerevisiae at a resolution of 3.6 angstroms. The structure clarifies how the protons travel through the complex, how the complex dimerizes, and how the dimers bend the membrane to produce cristae. Copyright © 2017, American Association for the Advancement of Science.

  6. Antiplasmodial dimeric chalcone derivatives from the roots of Uvaria siamensis. (United States)

    Salae, Abdul-Wahab; Chairerk, Orapan; Sukkoet, Piyanut; Chairat, Therdsak; Prawat, Uma; Tuntiwachwuttikul, Pittaya; Chalermglin, Piya; Ruchirawat, Somsak


    Four dimeric chalcone derivatives, 8″,9″-dihydrowelwitschin H, uvarins A-C, a naphthalene derivative, 2-hydroxy-3-methoxy-6-(4'- hydroxyphenyl)naphthalene, and the known dimeric chalcones, dependensin and welwitschin E, flavonoids, a cyclohexane oxide derivative, an aromatic aldehyde were isolated from the roots of Uvaria siamensis (Annonaceae). The structures of the compounds were elucidated by spectroscopic analysis, as well as by comparison with literature data. The isolated compounds with a sufficient amount for biological assays were evaluated for their antimalarial, antimycobacterial, and cytotoxic activities. The dimeric chalcones 8″,9″-dihydrowelwitschin H, uvarins B and C, dependensin and welwitschin E showed strong antiplasmodial activity with IC 50 values of 3.10, 3.02, 3.09, 4.21 and 3.99 μg/mL, respectively. A possible biosynthesis pathway of the dimeric chalcones is discussed. Copyright © 2016 Elsevier Ltd. All rights reserved.

  7. Thymine Dimerization in DNA is an Ultrafast Photoreaction


    Schreier, Wolfgang J.; Schrader, Tobias E.; Koller, Florian O.; Gilch, Peter; Crespo-Hernández, Carlos E.; Swaminathan, Vijay N.; Carell, Thomas; Zinth, Wolfgang; Kohler, Bern


    Femtosecond time-resolved infrared spectroscopy is used to study the formation of cyclobutane dimers in the all-thymine oligonucleotide (dT)18 by ultraviolet light at 272 nanometers. The appearance of marker bands in time-resolved spectra indicate that dimers are fully formed ∼1 picosecond after ultraviolet excitation. The ultrafast appearance of this mutagenic photolesion points to an approximately barrierless excited-state reaction for bases that are properly oriented at the instant of ligh...

  8. The influence of strain on the diffusion of Si dimers on Si(001)

    NARCIS (Netherlands)

    Zoethout, E.; Zoethout, E.; Gurlu, O.; Gürlü, O.; Zandvliet, Henricus J.W.; Poelsema, Bene


    The influence of lattice mismatch-induced tensile strain on the diffusion of Si dimers on Si(001) has been studied. The rate of surface diffusion of a Si dimer along the substrate dimer rows is relatively insensitive to tensile strain, whereas the rate of diffusion for a Si dimer across the

  9. Fracture Toughness Evaluation of a Ni2MnGa Alloy Through Micro Indentation Under Magneto-Mechanical Loading (United States)

    Goanţă, Viorel; Ciocanel, Constantin


    Ni2MnGa is a ferromagnetic alloy that exhibits the shape memory effect either induced by an externally applied magnetic field or mechanical stress. Due to the former, the alloy is commonly called magnetic shape memory alloy or MSMA. The microstructure of the MSMA consists of tetragonal martensite variants (three in the most general case) that are characterized by a magnetization vector which is aligned with the short side of the tetragonal unit cell. Exposing the MSMA to a magnetic field causes the magnetization vector to rotate and align with the external field, eventually leading to variant reorientation. The variant reorientation is observed macroscopically in the form of recoverable strain of up to 6% [1, 2]. As the magnetic field induced reorientation happens instantaneously [1, 3], MSMAs are suitable for fast actuation, sensing, or power harvesting applications. However, actuation applications are limited by the maximum actuation stress of the material that is about 3.5MPa at approximately 2 to 3% reorientation strain. During MSMA fatigue magneto-mechanical characterization studies [4, 5] it was observed that cracks nucleate and grow on the surface of material samples, after a relatively small number of cycles, leading to loss in material performance. This triggered the need for understanding the mechanisms that govern crack nucleation and growth in MSMAs, as well as the nature of the material, i.e. ductile or brittle. The experimental study reported in this paper was carried out to determine material's fracture toughness, the predominant crack growth directions, and the orientation of the cracks relative to the mechanical loading direction and to the material's microstructure. A fixture has been developed to allow Vickers micro indentation of 3mm by 3mm by 20mm Ni2MnGa samples exposed to different levels of magnetic field and/or mechanical stress. Using the measured characteristics of the impression generated during micro indentation, the lengths of

  10. Hydrodynamic Torques and Rotations of Superparamagnetic Bead Dimers (United States)

    Pease, Christopher; Etheridge, J.; Wijesinghe, H. S.; Pierce, C. J.; Prikockis, M. V.; Sooryakumar, R.

    Chains of micro-magnetic particles are often rotated with external magnetic fields for many lab-on-a-chip technologies such as transporting beads or mixing fluids. These applications benefit from faster responses of the actuated particles. In a rotating magnetic field, the magnetization of superparamagnetic beads, created from embedded magnetic nano-particles within a polymer matrix, is largely characterized by induced dipoles mip along the direction of the field. In addition there is often a weak dipole mop that orients out-of-phase with the external rotating field. On a two-bead dimer, the simplest chain of beads, mop contributes a torque Γm in addition to the torque from mip. For dimers with beads unbound to each other, mop rotates individual beads which generate an additional hydrodynamic torque on the dimer. Whereas, mop directly torques bound dimers. Our results show that Γm significantly alters the average frequency-dependent dimer rotation rate for both bound and unbound monomers and, when mop exceeds a critical value, increases the maximum dimer rotation frequency. Models that include magnetic and hydrodynamics torques provide good agreement with the experimental findings over a range of field frequencies.

  11. Short lived maleimide triplet dimers. Kinetics and consequences

    International Nuclear Information System (INIS)

    Von Sonntag, J.


    Complete text of publication follows. The photochemistry of maleimide in non-aqueous solution is governed by the coexistence of two different triplet states, the keto triplet and a dimer triplet. This biradical is formed in the reaction of the keto triplet adding to the double bond of a ground state maleimide, in competition with electron transfer, (k 3 MI+MI = 2.6 x 10 9 dm 3 mol -1 s -1 ). Its spectrum is identical with that of the maleimide H-adduct radical (λ max = 370 ... 380 nm, broad, λ max = 255 nm, narrow, λ min = 290 nm). Its lifetime is 110 ns. While protolysis is confined to maleimide and aqueous solutions, the dimer triplet is found in acetonitrile as well. Dimer triplet formation is also observed with N-ethylmaleimide. Multi-wavelength 'global' analysis of the time profiles allowed us to separate the transient spectra and kinetics of the monomer and dimer triplet. The cyclobutane dimer yield (determined by GC) is independent of maleimide concentration. This proves that the dimer triplet does not contribute significantly to the initiation of a free-radical polymerisation. Time-dependent Hartree-Fock calculations agree with the experimental data and further confirm the proposed mechanisms

  12. Pair Interaction of Catalytical Sphere Dimers in Chemically Active Media

    Directory of Open Access Journals (Sweden)

    Jing-Min Shi


    Full Text Available We study the pair dynamics of two self-propelled sphere dimers in the chemically active medium in which a cubic autocatalytic chemical reaction takes place. Concentration gradient around the dimer, created by reactions occurring on the catalytic sphere surface and responsible for the self-propulsion, is greatly influenced by the chemical activities of the environment. Consequently, the pair dynamics of two dimers mediated by the concentration field are affected. In the particle-based mesoscopic simulation, we combine molecular dynamics (MD for potential interactions and reactive multiparticle collision dynamics (RMPC for solvent flow and bulk reactions. Our results indicate three different configurations between a pair of dimers after the collision, i.e., two possible scenarios of bound dimer pairs and one unbound dimer pair. A phase diagram is sketched as a function of the rate coefficients of the environment reactions. Since the pair interactions are the basic elements of larger scale systems, we believe the results may shed light on the understanding of the collective dynamics.

  13. VUV spectroscopy of rare gas van der Waals dimers

    International Nuclear Information System (INIS)

    Dehmer, P.M.; Pratt, S.T.


    We have undertaken a systematic study of the photoionization spectra of the homonuclear and heteronuclear rare gas dimers in order to better understand the nature of the bonding in the Rydberg states adnd ions of these molecules. We have obtained results for Ar 2 , Kr 2 , Xe 2 , NeAr, NeKr, NeXe, ArKr, ArXe, and KrXe. Of the remaining dimer species (Ne 2 and the Herare gas dimers), only Ne 2 has been studied using photoionization mass spectrometry. The results of the present series of experiments provide information both on the excited states of the neutral dimers and on the ground and excited states of the dimer ions. Using the data obtained in these measurements, we are able to compile for the first time a nearly complete list of ground state dissociation energies for the homonuclear and heteronuclear rare gas dimer ions. Somewhat less complete results are obtained for the excited states of these species. The observed trends in binding energy provide an excellent example of the systematic changes that occur as a result of changes in atomic orbital energies, polarizability, and internuclear distance, and these trends can be explained qualitatively in terms of simple molecular orbital theory

  14. Adsorption of Zn(2+) and Ni(2+) in a binary aqueous solution by biosorbents derived from sawdust and water hyacinth (Eichhornia crassipes). (United States)

    Gwenzi, Willis; Musarurwa, Tinashe; Nyamugafata, Phillip; Chaukura, Nhamo; Chaparadza, Allen; Mbera, Sharron


    The Zn(2+) and Ni(2+) adsorption capacities of six biosorbents derived from water hyacinth (Eichhornia crassipes) (WH) and sawdust (SD) were investigated, with activated carbon as the control. The biosorbents were raw biomass (WH, SD), charred WH (BWH) and SD and sulphonated bio-chars of WH and SD. The effect of the initial solution pH and Zn(2+) and Ni(2+) concentrations on adsorption capacity was studied, and adsorption isotherms for Zn(2+) and Ni(2+) evaluated. The initial solution pH significantly influenced adsorption (p adsorption on all biosorbents. The adsorption capacities of the biosorbents were statistically (p ≤ 0.05) similar to or higher than that of activated carbon. The effects of pyrolysis and bio-char sulphonation on adsorption were inconsistent and dependent on biomass type; in most cases bio-char was a better biosorbent than the original biomass, while sulphonation resulted in less or comparable adsorption. Adsorption data obeyed at least one of three isotherms (linear, Langmuir and Freundlich) (r(2) = 0.90-0.995, p < 0.05). The study revealed that low-cost biosorbents may be used as alternatives to activated carbon in applications including selective separation of Zn(2+) from multi-metal ion solutions containing Ni(2+), and water and wastewater treatment.

  15. Structural stability of the square flux line lattice in YNi2B2C and LuNi2B2C studied with small angle neutron scattering

    DEFF Research Database (Denmark)

    Eskildsen, M.R.; Gammel, P.L.; Barber, B.P.


    We have studied the flux line lattice in YNi2B2C and LuNi2B2C, the nonmagnetic end members of the borocarbide superconductors using small angle neutron scattering and transport. For fields, H parallel to c, we find a square symmetric lattice which disorders rapidly above H/H-c2 similar to 0.2, well...

  16. Ni2+ binds to active site of hen egg-white lysozyme and quenches fluorescence of Trp62 and Trp108

    International Nuclear Information System (INIS)

    Li Shujie; Nakagawa, Atsushi; Tsukihara, Tomitake


    We found that the maximum emission of the tryptophyl fluorescence of hen egg-white lysozyme is shifted from 337 to 323 nm and quenched to the extent of 55% with an increase in concentrations of NiCl 2 from 0 to 2 M in 50 mM Na acetate buffer (pH 4.7). In contrast, NaCl does not influence the fluorescence of lysozyme up to 2 M. To elucidate the particular effects of Ni 2+ on the tryptophyl fluorescence of lysozyme, we have measured the assembly behavior and secondary structure of lysozyme in various concentrations of NiCl 2 , and determined the structures of lysozyme crystals grown in 0.3, 0.5, and 1.0 M NiCl 2 , respectively. The results of analytical centrifugation and circular dichroism experiments show that lysozyme keeps a monomer state and has an identical secondary structure, irrespective of NiCl 2 concentrations. The crystal structures show that all crystals grown in different concentrations of NiCl 2 have an identical main chain and side chain conformation. And one Ni 2+ binding with Oδ atom of Asp52 in the active site and coordinating with five water molecules to form hexagonal coordination has been determined for each crystal structure. Based on these results, we have proposed that Ni 2+ quenches the fluorescence of Trp62 and Trp108 due to the binding of Ni 2+ to the active site of lysozyme

  17. Sepiolite functionalized with N-[3-(trimethoxysilylpropyl]-ethylenediamine triacetic acid trisodium salt. Part II: Sorption of Ni2+ from aqueous solutions

    Directory of Open Access Journals (Sweden)

    Lazarević Slavica S.


    Full Text Available sorption of Ni2+ on the sepiolite functionalized by covalent grafting of N-[3-(trimethoxysilylpropyl]ethylenediamine triacetic acid trisodium salt, MSEAS, was studied in batch experiments as a function of the initial metal concentration, the equilibration time, pH value, and temperature. The modification of sepiolite resulted in an enhanced Ni2+ retention with a capacity of 0.261 mmol/g at 298 K. The retention of Ni2+ ions occurred dominantly by specific sorption and exchange of Mg2+ ions from the sepiolite structure. The sorption process followed pseudo-second-order kinetics. The sorption equilibrium results were best described by the non-linear form of the Langmuir Sorption Equation. The values of the thermodynamic parameters (enthalpy, free energy and entropy were calculated from temperature dependent sorption isotherms and these values showed that the sorption of Ni2+ onto modified sepiolite was endothermic. [Projekat Ministarstva nauke Republike Srbije, br. III 45019 i FP7 NANOTECH FTM No. 245916

  18. First Principles Study on Structure Stability and Mechanical Properties of YNi2B2C and LuNi2B2C under Pressure

    Directory of Open Access Journals (Sweden)

    Lili Liu


    Full Text Available The pressure effects on the lattice parameters and elastic constants of the tetragonal RNi 2 B 2 C (R=Y, Lu are investigated by means of the first principles. The predicted lattice constants and elastic constants of YNi 2 B 2 C and LuNi 2 B 2 C at 0 GPa agree well with the available data. By the elastic stability criteria under isotropic pressure, it is predicted that YNi 2 B 2 C and LuNi 2 B 2 C with tetragonal structure are not mechanically stable above 93 GPa and 50 GPa, respectively. Pugh’s modulus ratio, Poisson’s ratio, Vickers hardness, elastic anisotropy and Debye temperature of YNi 2 B 2 C in the pressure range of 0–100 GPa and LuNi 2 B 2 C in the pressure range of 0-60 GPa are further investigated. It is shown that the ductility and Debye temperature of tetragonal RNi 2 B 2 C (R=Y, Lu increase with increasing pressure, and LuNi 2 B 2 C is more ductile and lower Debye temperature than YNi 2 B 2 C under different pressures.

  19. Carbon nanofibers (CNFs) supported cobalt- nickel sulfide (CoNi2S4) nanoparticles hybrid anode for high performance lithium ion capacitor. (United States)

    Jagadale, Ajay; Zhou, Xuan; Blaisdell, Douglas; Yang, Sen


    Lithium ion capacitors possess an ability to bridge the gap between lithium ion battery and supercapacitor. The main concern of fabricating lithium ion capacitors is poor rate capability and cyclic stability of the anode material which uses sluggish faradaic reactions to store an electric charge. Herein, we have fabricated high performance hybrid anode material based on carbon nanofibers (CNFs) and cobalt-nickel sulfide (CoNi 2 S 4 ) nanoparticles via simple electrospinning and electrodeposition methods. Porous and high conducting CNF@CoNi 2 S 4 electrode acts as an expressway network for electronic and ionic diffusion during charging-discharging processes. The effect of anode to cathode mass ratio on the performance has been studied by fabricating lithium ion capacitors with different mass ratios. The surface controlled contribution of CNF@CoNi 2 S 4 electrode was 73% which demonstrates its excellent rate capability. Lithium ion capacitor fabricated with CNF@CoNi 2 S 4 to AC mass ratio of 1:2.6 showed excellent energy density of 85.4 Wh kg -1 with the power density of 150 W kg -1 . Also, even at the high power density of 15 kW kg -1 , the cell provided the energy density of 35 Wh kg -1 . This work offers a new strategy for designing high-performance hybrid anode with the combination of simple and cost effective approaches.

  20. Observation of a field-driven structural phase transition in the flux line lattice in ErNi2B2C

    DEFF Research Database (Denmark)

    Eskildsen, M.R.; Gammel, P.L.; Barber, B.P.


    Small-angle neutron scattering and magnetic decoration both demonstrate a topological transition in the flux line lattice (FLL) in ErNi2B2C. The high-field square lattice slowly transforms into a hexagonal lattice via an area preserving [100] rhombohedral distortion below roughly 500 Oe. The square...

  1. Dimeric forms of cholinesterase in Sipunculus nudus. (United States)

    Talesa, V; Principato, G B; Giovannini, E; Di Giovanni, M V; Rosi, G


    In developing a research on the cholinesterase (ChE) evolution in Invertebrata, this enzyme was studied in the unsegmented marine worm Sipunculus nudus. ChE activity was solubilized through three successive steps of extraction. These fractions are noted as low-salt (LSS), detergent (DS) and high-salt soluble (HSS) and represent 27%, 68% and 5% of total activity, respectively. LSS and DS ChE were purified to homogeneity by affinity chromatography on edrophonium-Sepharose gel. Purification factors of 1700 (LSS) and 1090 (DS) were obtained. The small amount of HSS ChE prevented a similar purification and an extensive characterization. Based on SDS/PAGE and density-gradient centrifugation, both LSS and DS enzymes show a M(r) value of about 130,000 and are likely G2 globular dimers of a 67,000 subunit. Moreover, LSS ChE seems to be an amphiphilic form including a hydrophobic domain, while DS ChE is probably linked to the cell membrane by a phosphatidylinositol anchor. Both LSS and DS enzymes hydrolyze at the highest rate propionylthiocholine. However, they also show a fairly high catalytic efficiency with other thiocholine esters as substrates, thus suggesting a wide and little-specialized conformation of the active site. Based on immunological cross-reactivity trials, LSS and DS ChE from S. nudus show a reduced structural affinity with a molluscan (Murex brandaris) enzyme. HSS ChE, an acetylcholinesterase, is also solubilized by heparin, like typical vertebrate HSS asymmetric enzymes. However, it lacks fast-sedimenting forms and an enzyme-anchoring collagenous structure.

  2. Woodfordin C, a macro-ring hydrolyzable tannin dimer with antitumor activity, and accompanying dimers from Woodfordia fruticosa flowers. (United States)

    Yoshida, T; Chou, T; Nitta, A; Miyamoto, K; Koshiura, R; Okuda, T


    Three new dimeric hydrolyzable tannins, woodfordins A, B and C, along with seven known hydrolyzable tannins, including oenothein B, a dimer exhibiting marked host-mediated antitumor activity, were isolated from an Indonesian crude drug, Sidowayah [dried flowers of Woodfordia fruticosa (L.) Kurz (Lythraceae)]. The structures of the new tannins were elucidated based on chemical and spectral evidence. Woodfordin C, having a macro-ring structure, was also found to exhibit a significant antitumor activity.

  3. Influence of intermartensitic transitions on transport properties of Ni$_{2.16}Mn_{0.84}$Ga alloy

    CERN Document Server

    Khovailo, V V; Wedel, C; Takagi, T; Abe, T; Sugiyama, K


    Magnetic, transport, and x-ray diffraction measurements of ferromagnetic shape memory alloy Ni$_{2.16}$Mn$_{0.84}$Ga revealed that this alloy undergoes an intermartensitic transition upon cooling, whereas no such a transition is observed upon subsequent heating. The difference in the modulation of the martensite forming upon cooling from the high-temperature austenitic state [5-layered (5M) martensite], and the martensite forming upon the intermartensitic transition [7-layered (7M) martensite] strongly affects the magnetic and transport properties of the alloy and results in a large thermal hysteresis of the resistivity $\\rho$ and magnetization $M$. The intermartensitic transition has an especially marked influence on the transport properties, as is evident from a large difference in the resistivity of the 5M and 7M martensite, $(\\rho_{\\mathrm{5M}} - \\rho_{\\mathrm{7M}})/\\rho _{\\mathrm{5M}} \\approx 15%$, which is larger than the jump of resistivity at the martensitic transition from the cubic austenitic phase ...

  4. Magnetic and structural properties of the magnetic shape memory compound Ni2Mn1.48Sb0.52

    International Nuclear Information System (INIS)

    Brown, P J; Gandy, A P; Neumann, K U; Sheikh, A; Ziebeck, K R A; Ishida, K; Oikawa, K; Ito, W; Kainuma, R; Kanomata, T; Ouladdiaf, B


    Magnetization and high resolution neutron powder diffraction measurements on the magnetic shape memory compound Ni 2 Mn 1.48 Sb 0.52 have confirmed that it is ferromagnetic below 350 K and undergoes a structural phase transition at T M ∼310 K. The high temperature phase has the cubic L2 1 structure with a = 5.958 A, with the excess manganese atoms occupying the 4(b) Sb sites. In the cubic phase above ∼310 K the manganese moments are ferromagnetically aligned. The magnetic moment at the 4(a) site is 1.57(12) μ B and it is almost zero (0.15(9) μ B ) at the 4(b) site. The low temperature orthorhombic phase which is only fully established below 50 K has the space group Pmma with a cell related to the cubic one by a Bain transformation a orth = (a cub + b cub )/2; b orth = c cub and c orth = (a cub - b cub ). The change in cell volume is ∼2.5%. The spontaneous magnetization of samples cooled in fields less than 0.5 T decreases at temperatures below T M and at 2 K the magnetic moment per formula unit in fields up to 5.5 T is 2.01(5) μ B . Neutron diffraction patterns obtained below ∼132 K gave evidence for a weak incommensurate magnetic modulation with propagation vector (2/3, 1/3, 0).

  5. Effect of Cavitation on Surface Damage of 16.7Cr-10Ni-2Mo Stainless Steel in Marine Environment

    International Nuclear Information System (INIS)

    Chong, Sang-Ok; Han, Min-Su; Kim, Seong-Jong


    Stainless steel is generally known to have characteristics of excellent corrosion resistance and durability, but in a marine environment it can suffer from localized corrosion due to the breakdown of passivity film due to chloride ion in seawater. Furthermore, the damage behaviors are sped up under a cavitation environment because of complex damage from electrochemical corrosion and cavitation-erosion. In this study the characteristics of electrochemical corrosion and cavitation erosion behavior were evaluated on 16.7Cr-10Ni-2Mo stainless steel under a cavitation environment in natural seawater. The electrochemical experiments have been conducted at both static conditions and dynamic conditions inducing cavitation with different current density parameters. The surface morphology and damage behaviors were compared after the experiment. After the cavitation test with time variables morphological examinations on damaged specimens were analyzed by using a scanning electron microscope and a 3D microscope. the galvanostatic experiment gave a cleaner surface morphology presented with less damage depth at high current density regions. It is due to the effect of water cavitation peening under the cavitation condition. In the cavitation experiment, with amplitude of 30 μm and seawater temperature of 25 ℃, weight loss and cavitation-erosion damage depth were dramatically increased after 5 hours inducing cavitation

  6. Giant barocaloric effect in hexagonal Ni2In-type Mn-Co-Ge-In compounds around room temperature (United States)

    Wu, Rong-Rong; Bao, Li-Fu; Hu, Feng-Xia; Wu, Hui; Huang, Qing-Zhen; Wang, Jing; Dong, Xiao-Li; Li, Guan-Nan; Sun, Ji-Rong; Shen, Fei-Ran; Zhao, Tong-Yun; Zheng, Xin-Qi; Wang, Li-Chen; Liu, Yao; Zuo, Wen-Liang; Zhao, Ying-Ying; Zhang, Ming; Wang, Xian-Cheng; Jin, Chang-Qing; Rao, Guang-Hui; Han, Xiu-Feng; Shen, Bao-Gen


    The most widespread cooling techniques based on gas compression/expansion encounter environmental problems. Thus, tremendous effort has been dedicated to develop alternative cooling technique and search for solid state materials that show large caloric effects. An application of pressure to a material can cause a change in temperature, which is called the barocaloric effect. Here we report the giant barocaloric effect in a hexagonal Ni2In-type MnCoGe0.99In0.01 compound involving magnetostructural transformation, Tmstr, which is accompanied with a big difference in the internal energy due to a great negative lattice expansion(ΔV/V ~ 3.9%). High resolution neutron diffraction experiments reveal that the hydrostatic pressure can push the Tmstr to a lower temperature at a rate of 7.7 K/kbar, resulting in a giant barocaloric effect. The entropy change under a moderate pressure of 3 kbar reaches 52 Jkg-1K-1, which exceeds that of most materials, including the reported giant magnetocaloric effect driven by 5 T magnetic field that is available only by superconducting magnets.

  7. Magnetoresistance in Co/2D MoS2/Co and Ni/2D MoS2/Ni junctions. (United States)

    Zhang, Han; Ye, Meng; Wang, Yangyang; Quhe, Ruge; Pan, Yuanyuan; Guo, Ying; Song, Zhigang; Yang, Jinbo; Guo, Wanlin; Lu, Jing


    Semiconducting single-layer (SL) and few-layer MoS2 have a flat surface, free of dangling bonds. Using density functional theory coupled with non-equilibrium Green's function method, we investigate the spin-polarized transport properties of Co/2D MoS2/Co and Ni/2D MoS2/Ni junctions with MoS2 layer numbers of N = 1, 3, and 5. Well-defined interfaces are formed between MoS2 and metal electrodes. The junctions with a SL MoS2 spacer are almost metallic owing to the strong coupling between MoS2 and the ferromagnets, while those are tunneling with a few layer MoS2 spacer. Both large magnetoresistance and tunneling magnetoresistance are found when fcc or hcp Co is used as an electrode. Therefore, flat single- and few-layer MoS2 can serve as an effective nonmagnetic spacer in a magnetoresistance or tunneling magnetoresistance device with a well-defined interface.

  8. Dimerization in Highly Concentrated Solutions of Phosphoimidazolide Activated Monomucleotides (United States)

    Kanavarioti, Anastassia


    Phosphoimidazolide activated ribomononucleotides (*pN) are useful substrates for the non-enzymatic synthesis of polynucleotides. However, dilute neutral aqueous solutions of *pN typically yield small amounts of dimers and traces of polymers; most of *pN hydrolyzes to yield nucleoside 5'-monophosphate. Here we report the self-condensation of nucleoside 5'-phosphate 2-methylimidazolide (2-MeImpN with N = cytidine, uridine or guanosine) in the presence of Mg2+ in concentrated solutions, such as might have been found in an evaporating lagoon on prebiotic Earth. The product distribution indicates that oligomerization is favored at the expense of hydrolysis. At 1.0 M, 2-MeImpU and 2-MeImpC produce about 65% of oligomers including 4% of the 3',5'-linked dimer. Examination of the product distribution of the three isomeric dimers in a self-condensation allows identification of reaction pathways that lead to dimer formation. Condensations in a concentrated mixture of all three nucleotides (U,C,G mixtures) is made possible by the enhanced solubility of 2-MeImpG in such mixtures. Although percent yield of internucleotide linked dimers is enhanced as a function of initial monomer concentration, pyrophosphate dimer yields remain practically unchanged at about 20% for 2-MeImpU, 16% for 2-MeImpC and 25% of the total pyrophosphate in the U,C,G mixtures. The efficiency by which oligomers are produced in these concentrated solutions makes the evaporating lagoon scenario a potentially interesting medium for the prebiotic synthesis of dimers and short RNAs.

  9. Dimer coverings on random multiple chains of planar honeycomb lattices

    International Nuclear Information System (INIS)

    Ren, Haizhen; Zhang, Fuji; Qian, Jianguo


    We study dimer coverings on random multiple chains. A multiple chain is a planar honeycomb lattice constructed by successively fusing copies of a ‘straight’ condensed hexagonal chain at the bottom of the previous one in two possible ways. A random multiple chain is then generated by admitting the Bernoulli distribution on the two types of fusing, which describes a zeroth-order Markov process. We determine the expectation of the number of the pure dimer coverings (perfect matchings) over the ensemble of random multiple chains by the transfer matrix approach. Our result shows that, with only two exceptions, the average of the logarithm of this expectation (i.e., the annealed entropy per dimer) is asymptotically nonzero when the fusing process goes to infinity and the length of the hexagonal chain is fixed, though it is zero when the fusing process and the length of the hexagonal chain go to infinity simultaneously. Some numerical results are provided to support our conclusion, from which we can see that the asymptotic behavior fits well to the theoretical results. We also apply the transfer matrix approach to the quenched entropy and reveal that the quenched entropy of random multiple chains has a close connection with the well-known Lyapunov exponent of random matrices. Using the theory of Lyapunov exponents we show that, for some random multiple chains, the quenched entropy per dimer is strictly smaller than the annealed one when the fusing process goes to infinity. Finally, we determine the expectation of the free energy per dimer over the ensemble of the random multiple chains in which the three types of dimers in different orientations are distinguished, and specify a series of non-random multiple chains whose free energy per dimer is asymptotically equal to this expectation. (paper)

  10. Hydrogen Dimers in Giant-planet Infrared Spectra (United States)

    Fletcher, Leigh N.; Gustafsson, Magnus; Orton, Glenn S.


    Despite being one of the weakest dimers in nature, low-spectral-resolution Voyager/IRIS observations revealed the presence of (H2)2 dimers on Jupiter and Saturn in the 1980s. However, the collision-induced H2–H2 opacity databases widely used in planetary science have thus far only included free-to-free transitions and have neglected the contributions of dimers. Dimer spectra have both fine-scale structure near the S(0) and S(1) quadrupole lines (354 and 587 cm‑1, respectively), and broad continuum absorption contributions up to ±50 cm‑1 from the line centers. We develop a new ab initio model for the free-to-bound, bound-to-free, and bound-to-bound transitions of the hydrogen dimer for a range of temperatures (40–400 K) and para-hydrogen fractions (0.25–1.0). The model is validated against low-temperature laboratory experiments, and used to simulate the spectra of the giant planets. The new collision-induced opacity database permits high-resolution (0.5–1.0 cm‑1) spectral modeling of dimer spectra near S(0) and S(1) in both Cassini Composite Infrared Spectrometer observations of Jupiter and Saturn, and in Spitzer Infrared Spectrometer (IRS) observations of Uranus and Neptune for the first time. Furthermore, the model reproduces the dimer signatures observed in Voyager/IRIS data near S(0) on Jupiter and Saturn, and generally lowers the amount of para-H2 (and the extent of disequilibrium) required to reproduce IRIS observations.

  11. Glycine transporter dimers: evidence for occurrence in the plasma membrane. (United States)

    Bartholomäus, Ingo; Milan-Lobo, Laura; Nicke, Annette; Dutertre, Sébastien; Hastrup, Hanne; Jha, Alok; Gether, Ulrik; Sitte, Harald H; Betz, Heinrich; Eulenburg, Volker


    Different Na(+)/Cl(-)-dependent neurotransmitter transporters of the SLC6a family have been shown to form dimers or oligomers in both intracellular compartments and at the cell surface. In contrast, the glycine transporters (GlyTs) GlyT1 and -2 have been reported to exist as monomers in the plasma membrane based on hydrodynamic and native gel electrophoretic studies. Here, we used cysteine substitution and oxidative cross-linking to show that of GlyT1 and GlyT2 also form dimeric complexes within the plasma membrane. GlyT oligomerization at the cell surface was confirmed for both GlyT1 and GlyT2 by fluorescence resonance energy transfer microscopy. Endoglycosidase treatment and surface biotinylation further revealed that complex-glycosylated GlyTs form dimers located at the cell surface. Furthermore, substitution of tryptophan 469 of GlyT2 by an arginine generated a transporter deficient in dimerization that was retained intracellulary. Based on these results and GlyT structures modeled by using the crystal structure of the bacterial homolog LeuT(Aa), as a template, residues located within the extracellular loop 3 and at the beginning of transmembrane domain 6 are proposed to contribute to the dimerization interface of GlyTs.

  12. Effects of Dimerization of Serratia marcescens Endonuclease on Water Dynamics.

    Energy Technology Data Exchange (ETDEWEB)

    Chen, Chuanying; Beck, Brian W.; Krause, Kurt; Weksberg, Tiffany E.; Pettitt, Bernard M.


    The research described in this product was performed in part in the Environmental Molecular Sciences Laboratory, a national scientific user facility sponsored by the Department of Energy's Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory. The dynamics and structure of Serratia marcescens endonuclease and its neighboring solvent are investigated by molecular dynamics (MD). Comparisons are made with structural and biochemical experiments. The dimer form is physiologic and functions more processively than the monomer. We previously found a channel formed by connected clusters of waters from the active site to the dimer interface. Here, we show that dimerization clearly changes correlations in the water structure and dynamics in the active site not seen in the monomer. Our results indicate that water at the active sites of the dimer is less affected compared with bulk solvent than in the monomer where it has much slower characteristic relaxation times. Given that water is a required participant in the reaction, this gives a clear advantage to dimerization in the absence of an apparent ability to use both active sites simultaneously.

  13. Facilitated Transport of Zn2+, Ni2+ and Co2+ by Liquid Membrane Using a Tertio Amine as Carrier

    Directory of Open Access Journals (Sweden)

    Hassaine-Sadi F.


    Full Text Available The environmental impact of the emissions of heavy metals (Zn2+, Ni2+, Co2+ present in the industrial effluents become extensive more and more. The discharge of toxic metals into environment is a serious problem facing numerous industries. So the search for extraction techniques to remove those heavy metals are increasing interest. Liquid membranes have shown great potentiel in this way especially in cases where metal concentrations are relatively low and other techniques cannot be applied efficiently.The fundamental parameters influencing the transport of the zinc (II, nickel (II and cobalt (II through the liquid membrane have been examined (the acidity, the time of transport. The coupling that makes itself thanks to the membrane (extractant + diluent permits to define the different phases of transfer and to determine the mechanisms of transportation membranaires. In thi study of th facilitated transport of zinc, nickel, cobalt ions by liquid membranes containing Tri-n-octyl amine as carrier. The chemical variable exam permitted to determine the parameters giving the extraction efficiency and reextraction optimum. Some performances have been gotten so much to the level of the extraction that of the reextraction. A chemical modelization has allowed to identify the extraction mechanism and transport. The coupling required a real optimization of the set of the parameters. The symmetrical behavior of the two compartments showed that the extraction – reextraction association permits to achieve a transportation, one counter - transportation and a positive coupling. This lets predict an applications as well in the field of metalliferous processing liquid waste not very in charge as in that of the industrial wastes. This also allows an effective protection of the environment while being profitable.

  14. Simultaneous investigation of thermal, acoustic, and magnetic emission during martensitic transformation in single-crystalline Ni2MnGa (United States)

    Tóth, László Z.; Daróczi, Lajos; Szabó, Sándor; Beke, Dezső L.


    Simultaneous thermal, acoustic, and magnetic emission (AE and ME) measurements during thermally induced martensitic transformation in Ni2MnGa single crystals demonstrate that all three types of the above noises display many coincident peaks and the same start and finish temperatures. The amplitude and energy distribution functions for AE and ME avalanches satisfy power-law behavior, corresponding to the symmetry of the martensite. At zero external magnetic field asymmetry in the exponents was obtained: their value was larger for heating than for cooling. Application of constant, external magnetic fields (up to B =722 mT) leads to the disappearance of the above asymmetry, due to the decrease of the multiplicity of the martensite variants. Time correlations (i.e., the existence of nonhomogeneous temporal processes) within AE as well as ME emission events are demonstrated by deviations from the uncorrelated behavior on probability distributions of waiting times as well as of a sequence of number of events. It is shown that the above functions collapse on universal master curves for cooling and heating as well as for AE and ME noises. The analysis of the existence of temporal correlations between AE and ME events revealed that at short times the acoustic signals show a time delay relative to the magnetic one, due to the time necessary for the propagation of the ultrasound. At intermediate times, as expected, the magnetic signal is delayed, i.e., the magnetic domain rearrangement followed the steps of structural transformation. At much longer times the deviation from an uncorrelated (Poisson-type) behavior is attributed to the nonhomogeneity of the avalanche statistics.

  15. Giant negative thermal expansion in bonded MnCoGe-based compounds with Ni2In-type hexagonal structure. (United States)

    Zhao, Ying-Ying; Hu, Feng-Xia; Bao, Li-Fu; Wang, Jing; Wu, Hui; Huang, Qing-Zhen; Wu, Rong-Rong; Liu, Yao; Shen, Fei-Ran; Kuang, Hao; Zhang, Ming; Zuo, Wen-Liang; Zheng, Xin-Qi; Sun, Ji-Rong; Shen, Bao-Gen


    MnCoGe-based compounds undergo a giant negative thermal expansion (NTE) during the martensitic structural transition from Ni2In-type hexagonal to TiNiSi-type orthorhombic structure. High-resolution neutron diffraction experiments revealed that the expansion of unit cell volume can be as large as ΔV/V ∼ 3.9%. The optimized compositions with concurrent magnetic and structural transitions have been studied for magnetocaloric effect. However, these materials have not been considered as NTE materials partially due to the limited temperature window of phase transition. The as-prepared MnCoGe-based compounds are quite brittle and naturally collapse into powders. By using a few percents (3-4%) of epoxy to bond the powders, we introduced residual stress in the bonded samples and thus realized the broadening of structural transition by utilizing the specific characteristics of lattice softening enforced by the stress. As a result, giant NTE (not only the linear NTE coefficient α but also the operation-temperature window) has been achieved. For example, the average α̅ as much as -51.5 × 10(-6)/K with an operating temperature window as wide as 210 K from 122 to 332 K has been observed in a bonded MnCo0.98Cr0.02Ge compound. Moreover, in the region between 250 and 305 K near room temperature, the α value (-119 × 10(-6)/K) remains nearly independent of temperature. Such an excellent performance exceeds that of most other materials reported previously, suggesting it can potentially be used as a NTE material, particularly for compensating the materials with large positive thermal expansions.

  16. Ab initio calculations of martensitic phase behavior in Ni2FeGa magnetic shape memory alloys

    International Nuclear Information System (INIS)

    Soykan, C.; Özdemir Kart, S.; Sevik, C.; Çağın, T.


    Highlights: • L2 1 , NM and 5M phases have the energy minimum at a = 5.76 Å, c/a = 1.33 and c/a = 0.99. • Decrement in moment of Ni and increment in that of Fe reflect electrons transfer. • Differences in minority DOS over MT lead to stabilize the final structure. • C' taking small value in L2 1 leads to elastic instability in MT. - Abstract: A series of spin polarized energy calculations based on density functional theory (DFT) have been carried out to investigate the structural, magnetic, electronic and mechanical properties of Ni 2 FeGa magnetic shape memory alloys (MSMA’s) in the austenitic and martensitic structures. We report that L2 1 austenitic phase is metastable at a = 5.76 Å, the NM tetragonal and 5M monoclinic martensitic structures are stable at c/a = 1.33 and c/a = 0.99, respectively. That the electron removes from Ni to Fe site during phase transformation to martensite is confirmed by the increment in the magnetic moment of Ni, while decrement in that of Fe. The analysis of the partial density of states show that some distinguishable differences in the minority spin states occur upon martensitic phase transformation, such as, the replacement of the Fe states (e g and t 2g ) above Fermi level by only Fe-t 2g states during L2 1 -5M transformation and the splitting of Fe-t 2g states near Fermi level during 5M-NM transformation (through 7M). These changes lower the energy of the system, indicating that the final structure becomes stable. The soft tetragonal shear constant C′ of the austenitic phase designates the ease of the phase transition into martensitic phase. It is shown that the results calculated in this study are in good agreement with the previous calculations and the available experiments

  17. Optofluidic taming of a colloidal dimer with a silicon nanocavity

    Energy Technology Data Exchange (ETDEWEB)

    Pin, C.; Renaut, C. [Groupe d' Optique de Champ Proche - LRC CEA n°DSM-08-36, Laboratoire Interdisciplinaire Carnot de Bourgogne, UMR CNRS n°6303- Université de Bourgogne, Dijon (France); University Grenoble Alpes, INAC-SP2M-SINAPS, F-38000 Grenoble, France and CEA, INAC-SP2M-SINAPS, F-38000 Grenoble (France); University Grenoble Alpes, CNRS, CEA-Leti Minatec, LTM, F-38054 Grenoble Cedex (France); Cluzel, B., E-mail:; Fornel, F. de [Groupe d' Optique de Champ Proche - LRC CEA n°DSM-08-36, Laboratoire Interdisciplinaire Carnot de Bourgogne, UMR CNRS n°6303- Université de Bourgogne, Dijon (France); Peyrade, D. [University Grenoble Alpes, CNRS, CEA-Leti Minatec, LTM, F-38054 Grenoble Cedex (France); Picard, E.; Hadji, E. [University Grenoble Alpes, INAC-SP2M-SINAPS, F-38000 Grenoble, France and CEA, INAC-SP2M-SINAPS, F-38000 Grenoble (France)


    We report here the optical trapping of a heterogeneous colloidal dimer above a photonic crystal nanocavity used as an on-chip optical tweezer. The trapped dimer consists of a cluster of two dielectric microbeads of different sizes linked by van der Waals forces. The smallest bead, 1 μm in diameter, is observed to be preferentially trapped by the nanotweezer, leaving the second bead untrapped. The rotational nature of the trapped dimer Brownian motion is first evidenced. Then, in the presence of a fluid flow, control of its orientation and rotation is achieved. The whole system is found to show high rotational degrees of freedom, thereby acting as an effective flow-sensitive microscopic optical ball joint.

  18. Potentiation of endothelin-1-induced prostaglandin E2 formation by Ni(2+) and Sr(2+) in murine osteoblastic MC3T3-E1 cells. (United States)

    Leis, Hans Jörg; Windischhofer, Werner


    Cation recognition mechanisms beyond calcium-sensing receptors are still largely unexplored and consequently there is surprisingly little information on linking of this primary event to key metabolic features of different cell systems, such as arachidonic acid metabolism. However, information on the modulatory role of extracellular cations in cellular function is scarce. In this study we have demonstrated, that Ni(2+) and Sr(2+) potentiate endothelin-1 induced prostaglandin E2 formation in the osteoblastic cell line, MC3T3-E1, even in the absence of extracellular calcium. The effect is strictly dependent of receptor-mediated signal transduction processes evoked by endothelin-1 and arachidonate release involves cytosolic phospholipase A2 activity. The ligation sites, at least for Ni(2+) are extracellular. The data suggest a novel activation mechanism for arachidonate release and subsequent prostaglandin formation that does not require calcium. Copyright © 2015 Elsevier GmbH. All rights reserved.

  19. Microstructural, mechanical and tribological investigation of 30CrMnSiNi2A ultra-high strength steel under various tempering temperatures (United States)

    Arslan Hafeez, Muhammad; Farooq, Ameeq


    The aim of the research was to investigate the variation in microstructural, mechanical and tribological characteristics of 30CrMnSiNi2A ultra-high strength steel as a function of tempering temperatures. Steel was quenched at 880 °C and tempered at five different tempering temperatures ranging from 250 °C to 650 °C. Optical microscopy and pin on disc tribometer was used to evaluate the microstructural and wear properties. Results show that characteristics of 30CrMnSiNi2A are highly sensitive to tempering temperatures. Lathe and plate shaped martensite obtained by quenching transform first into ε-carbide, second cementite, third coarsened and spheroidized cementite and finally into recovered ferrite and austenite. Hardness, tensile and yield strengths decreased while elongation increased with tempering temperatures. On the other hand, wear rate first markedly decreased and then increased. Optimum amalgamation of characteristics was achieved at 350 °C.

  20. Synthesis, characterization and tin/copper-nitrogen substitutional effect on photocatalytic activity of honeycomb ordered P2-Na2Ni2TeO6 (United States)

    Kadari, Ramaswamy; Velchuri, Radha; Sreenu, K.; Ravi, Gundeboina; Munirathnam, Nagegownivari R.; Vithal, Muga


    We have successfully prepared visible light active tin/copper-nitrogen co-doped honeycomb ordered P2-Na2Ni2TeO6 photocatalysts by solid state/ion exchange methods. Powder XRD, TG analysis, SEM, surface area, O-N-H analysis, ICP-OES, FT-IR and UV-DRS measurements are employed to characterize all the samples. All the doped compositions adopted hexagonal lattice with space group P63/mcm. The photocatalytic activity of all the samples was studied against the degradation of methyl violet (MV) and methylene blue (MB) under visible light irradiation. The variation of the photocatalytic activity due to the substitution of cation, anion and co-doping in Na2Ni2TeO6 is investigated. Co-doped samples have exhibited higher activity compared to rest of the materials. The role of reactive intermediate species in the photocatalytic degradation of dyes is also studied using appropriate scavengers.

  1. Dimerization effect of sucrose octasulfate on rat FGF1

    DEFF Research Database (Denmark)

    Kulahin, Nikolaj; Kiselyov, Vladislav; Kochoyan, Artur


    signalling pathways. The structure of rat FGF1 crystallized in the presence of SOS has been determined at 2.2 A resolution. SOS-mediated dimerization of FGF1 was observed, which was further supported by gel-filtration experiments. The major contributors to the sulfate-binding sites in rat FGF1 are Lys113......, Lys118, Arg122 and Lys128. An arginine at position 116 is a consensus residue in mammalian FGF molecules; however, it is a serine in rat FGF1. This difference may be important for SOS-mediated FGF1 dimerization in rat....

  2. Construction of covalently coupled, concatameric dimers of 7TM receptors

    DEFF Research Database (Denmark)

    Terpager, Marie; Scholl, D Jason; Kubale, Valentina


    -Ala repeats flanked by flexible spacers and positively charged residues to ensure correct inside-out orientation plus an extracellular HA-tag to construct covalently coupled dimers of 7TM receptors. Such 15 TM concatameric homo- and heterodimers of the beta(2)-adrenergic and the NK(1) receptors, which...... for either of the protomers, which was not observed upon simple coexpression of the two receptors. It is concluded that covalently joined 7TM receptor dimers with surprisingly normal receptor properties can be constructed with use of an artificial transmembrane connector, which perhaps can be used to fuse...

  3. Dimer-flipping-assisted diffusion on a Si(001) surface

    International Nuclear Information System (INIS)

    Zi, J.; Min, B. J.; Lu, Y.; Wang, C. Z.; Ho, K. M.


    The binding sites and diffusion pathways of Si adatoms on a c(4x2) reconstructed Si(001) surface are investigated by a tight-binding method with an environment-dependent silicon potential in conjunction with ab initio calculations using the Car--Parrinello method. A new diffusion pathway along the trough edge driven by dimer flipping is found with a barrier of 0.74 eV, comparable to that of 0.68 eV along the top of the dimer rows

  4. Some peculiarities of ScFe2 and ScNi2 interaction with ammonia in the presence of NH4Cl

    International Nuclear Information System (INIS)

    Shilkin, S.P.; Fokin, V.N.; Fokina, Eh.Eh.; Tarasov, B.P.; Korobkov, I.I.


    Interaction of ScFe 2 and ScNi 2 intermetallic compounds with ammonia in the presence of NH 4 Cl (10 mass % from intermetallide introduced in reaction) as an activator of the process in initial ammonia pressure 0.6-0.8 MPa is investigated. Possibility of preparation of crystalline intermetallide hydrides and amorphous products in highly dispersed state at different temperature are shown. It is established that intermetallides decompose in ammonia medium at ≥ 450 Deg C [ru

  5. Vavřínite Ni2SbTe2, a new mineral species from the Kunratice Cu–Ni sulfide deposit, Czech Republic

    Czech Academy of Sciences Publication Activity Database

    Laufek, F.; Drábek, M.; Skála, Roman; Haloda, J.; Táborský, Z.; Císařová, I.


    Roč. 45, č. 5 (2007), s. 1213-1219 ISSN 0008-4476 Institutional research plan: CEZ:AV0Z30130516 Keywords : vavřínite * new mineral species * Ni–Sb telluride, * electron-microprobe data * reflectance data * synthetic Ni2SbTe2, X-ray-diffraction data * crystal structure * Kunratice (Czech Republic) Subject RIV: DB - Geology ; Mineralogy Impact factor: 1.057, year: 2007

  6. Characterization of pack cemented Ni2Al3 coating exposed to KCl(s) induced corrosion at 600 °C

    DEFF Research Database (Denmark)

    Dahl, Kristian Vinter; Slomian, A.; Lomholt, Trine Nybo


    Oxidation of Ni2Al3 produced by pack aluminizing of pure nickel was studied with and without 0.10 mg cm−2 KCl(s) deposit in an environment containing 5% O2, 40% H2O and 55% N2 at 600 °C for up to 168 h. Oxide microstructure and composition was investigated by SEM/EDX, BIB, TEM and GDOES. Oxidised...

  7. A Case Study of Landfill Leachate Using Coal Bottom Ash for the Removal of Cd2+, Zn2+ and Ni2+

    Directory of Open Access Journals (Sweden)

    Julia Ayala


    Full Text Available The removal of Cd2+, Zn2+ and Ni2+ by coal bottom ash has been investigated. In single metal system, metal uptake was studied in batch adsorption experiments as a function of pH (2–3, contact time (5–180 min, initial metal concentration (50–400 mg/L, adsorbent concentration (5–40 g/L, particle size, and ionic strength (0–1 M NaCl. Removal percentages of metals ions increased with increasing pH and dosage. Removal efficiency at lower concentrations was greater than at higher values. The maximum amount of metal ion adsorbed in milligrams per gram was 35.4, 35.1 and 34.6 mg/g for Zn2+, Cd2+ and Ni2+, respectively, starting out from an initial solution at pH 3. Simultaneous removal of Zn2+, Cd2+ and Ni2+ ions from ternary systems was also investigated and compared with that from single systems. Cd2+ uptake was significantly affected by the presence of competing ions at pH 2. The results obtained in the tests with landfill leachate showed that bottom ash is effective in simultaneously removing several heavy metals such as Ni, Zn, Cd, As, Mn, Cu, Co, Se, Hg, Ag, and Pb.

  8. TEOA-mediated formation of hollow core-shell structured CoNi2S4 nanospheres as a high-performance electrode material for supercapacitors (United States)

    Liang, Jun; Li, Meng; Chai, Yao; Luo, Min; Li, Li


    In this study, we report for the first time a cost-effective and general approach for the high-yield synthesis of a hierarchical core-shell and hollow structure of ternary CoNi2S4 in a triethanolamine (TEOA)-assisted hydrothermal system. It is found that a continuous increase in TEOA usages facilitates the formation and transformation of hierarchical CoNi2S4 hollow nanospheres, and the formation mechanism of the unique structure is revealed to be assembly-then-inside-out evacuation and Ostwald ripening mechanism during the sulfidation process. More importantly, when used as faradaic electrode for supercapacitors, the hierarchical hollow CoNi2S4 nanospheres display not only exceptional pseudocapacitve performance with high specific capacitance (2035 Fg-1 at 1 Ag-1) and excellent rate capability (1215 Fg-1 at 20 Ag-1), but also superior cycling stability, with only about 8.7% loss over 3000 cycles at 10 Ag-1. This work can provide some guidance for us in the structural and compositional tuning of mixed binary-metal sulfides toward many desired applications.

  9. Chemical Pressure-Driven Enhancement of the Hydrogen Evolving Activity of Ni2P from Nonmetal Surface Doping Interpreted via Machine Learning. (United States)

    Wexler, Robert B; Martirez, John Mark P; Rappe, Andrew M


    The activity of Ni 2 P catalysts for the hydrogen evolution reaction (HER) is currently limited by strong H adsorption at the Ni 3 -hollow site. We investigate the effect of surface nonmetal doping on the HER activity of the Ni 3 P 2 termination of Ni 2 P(0001), which is stable at modest electrochemical conditions. Using density functional theory (DFT) calculations, we find that both 2 p nonmetals and heavier chalcogens provide nearly thermoneutral H adsorption at moderate surface doping concentrations. We also find, however, that only chalcogen substitution for surface P is exergonic. For intermediate surface concentrations of S, the free energy of H adsorption at the Ni 3 -hollow site is -0.11 eV, which is significantly more thermoneutral than the undoped surface (-0.45 eV). We use the regularized random forest machine learning algorithm to discover the relative importance of structure and charge descriptors, extracted from the DFT calculations, in determining the HER activity of Ni 2 P(0001) under different doping concentrations. We discover that the Ni-Ni bond length is the most important descriptor of HER activity, which suggests that the nonmetal dopants induce a chemical pressure-like effect on the Ni 3 -hollow site, changing its reactivity through compression and expansion.

  10. Magnetic and transport properties of Ni2MnGa-BaTiO3 metal-insulator particulate composite with percolation threshold

    International Nuclear Information System (INIS)

    Won, C.J.; Kambale, R.C.; Hur, N.


    Highlights: → The Ni 2 MnGa-BaTiO 3 type composites were first time prepared by solid state reaction. → Temperature dependent magnetic properties reveal two kinds of transitions in these composite. → The present materials show negative magnetoresistance effect. → The present studies on magnetic and electrical transport of metal/insulator (NMG/BTO) composites shows the resistivity change associated to filamentary conducting path at percolation threshold. - Abstract: Here we report the magnetic and transport properties of the metal/insulator (f NMG )Ni 2 MnGa/(1 - f NMG )BaTiO 3 composites. The X-ray diffraction study confirms the formation of both the phases in composite. The microstructure reveals that the conducting Ni 2 MnGa particles are well dispersed in an insulating BaTiO 3 matrix. Temperature dependent magnetization shows two transitions one above 300 K and other below 150 K. The temperature dependence resistivity near the percolation threshold f NMG = 0.4 had drastic changes which is higher than the f NMG = 0.5. Also the negative magnetoresistance effect was observed for the studied materials. We suggest that magnetic and transport properties at the percolation threshold can be adjusted by the strain from the surrounding insulator particle.

  11. Biophysical characterization of the dimer and tetramer interface interactions of the human cytosolic malic enzyme. (United States)

    Murugan, Sujithkumar; Hung, Hui-Chih


    The cytosolic NADP(+)-dependent malic enzyme (c-NADP-ME) has a dimer-dimer quaternary structure in which the dimer interface associates more tightly than the tetramer interface. In this study, the urea-induced unfolding process of the c-NADP-ME interface mutants was monitored using fluorescence and circular dichroism spectroscopy, analytical ultracentrifugation and enzyme activities. Here, we demonstrate the differential protein stability between dimer and tetramer interface interactions of human c-NADP-ME. Our data clearly demonstrate that the protein stability of c-NADP-ME is affected predominantly by disruptions at the dimer interface rather than at the tetramer interface. First, during thermal stability experiments, the melting temperatures of the wild-type and tetramer interface mutants are 8-10°C higher than those of the dimer interface mutants. Second, during urea denaturation experiments, the thermodynamic parameters of the wild-type and tetramer interface mutants are almost identical. However, for the dimer interface mutants, the first transition of the urea unfolding curves shift towards a lower urea concentration, and the unfolding intermediate exist at a lower urea concentration. Third, for tetrameric WT c-NADP-ME, the enzyme is first dissociated from a tetramer to dimers before the 2 M urea treatment, and the dimers then dissociated into monomers before the 2.5 M urea treatment. With a dimeric tetramer interface mutant (H142A/D568A), the dimer completely dissociated into monomers after a 2.5 M urea treatment, while for a dimeric dimer interface mutant (H51A/D90A), the dimer completely dissociated into monomers after a 1.5 M urea treatment, indicating that the interactions of c-NADP-ME at the dimer interface are truly stronger than at the tetramer interface. Thus, this study provides a reasonable explanation for why malic enzymes need to assemble as a dimer of dimers.

  12. Biophysical characterization of the dimer and tetramer interface interactions of the human cytosolic malic enzyme.

    Directory of Open Access Journals (Sweden)

    Sujithkumar Murugan

    Full Text Available The cytosolic NADP(+-dependent malic enzyme (c-NADP-ME has a dimer-dimer quaternary structure in which the dimer interface associates more tightly than the tetramer interface. In this study, the urea-induced unfolding process of the c-NADP-ME interface mutants was monitored using fluorescence and circular dichroism spectroscopy, analytical ultracentrifugation and enzyme activities. Here, we demonstrate the differential protein stability between dimer and tetramer interface interactions of human c-NADP-ME. Our data clearly demonstrate that the protein stability of c-NADP-ME is affected predominantly by disruptions at the dimer interface rather than at the tetramer interface. First, during thermal stability experiments, the melting temperatures of the wild-type and tetramer interface mutants are 8-10°C higher than those of the dimer interface mutants. Second, during urea denaturation experiments, the thermodynamic parameters of the wild-type and tetramer interface mutants are almost identical. However, for the dimer interface mutants, the first transition of the urea unfolding curves shift towards a lower urea concentration, and the unfolding intermediate exist at a lower urea concentration. Third, for tetrameric WT c-NADP-ME, the enzyme is first dissociated from a tetramer to dimers before the 2 M urea treatment, and the dimers then dissociated into monomers before the 2.5 M urea treatment. With a dimeric tetramer interface mutant (H142A/D568A, the dimer completely dissociated into monomers after a 2.5 M urea treatment, while for a dimeric dimer interface mutant (H51A/D90A, the dimer completely dissociated into monomers after a 1.5 M urea treatment, indicating that the interactions of c-NADP-ME at the dimer interface are truly stronger than at the tetramer interface. Thus, this study provides a reasonable explanation for why malic enzymes need to assemble as a dimer of dimers.

  13. Liposomes of dimeric artesunate phospholipid: A combination of dimerization and self-assembly to combat malaria. (United States)

    Ismail, Muhammad; Ling, Longbing; Du, Yawei; Yao, Chen; Li, Xinsong


    Artemisinin and its derivatives are highly effective drugs in the treatment of P. falciparum malaria. However, their clinical applications face challenges because of short half-life, poor bioavailability and growing drug resistance. In this article, novel dimeric artesunate phospholipid (Di-ART-GPC) based liposomes were developed by combination of dimerization and self-assembly to address these shortcomings. Firstly, Di-ART-GPC conjugate was synthesized by a facile esterification of artesunate (ART) and glycerophosphorylcholine (GPC) and confirmed by MS, 1 H NMR and 13 C NMR. The conjugate was then assembled to form liposomes without excipient by thin film hydration method. The assembled Di-ART-GPC liposomes have typical multilamellar vesicle structure with bilayer morphology as determined by transmission electron microscopy (TEM) and cryogenic electron microscopy (cryo-EM). Moreover, the liposomes displayed an average hydrodynamic diameter of 190 nm and negative zeta potential at -20.35 mV as determined by Zetasizer. The loading capacity of ART was calculated approximately 77.6% by weight with this liposomal formulation after a simple calculation. In vitro drug release and degradation results showed that the Di-ART-GPC liposomes were stable in neutral physiological conditions but effectively degraded to release parent ART in simulated weakly acidic microenvironment. In vivo pharmacokinetics study revealed that Di-ART-GPC liposomes and conjugate have longer retention half-life in bloodstream. Importantly, Di-ART-GPC liposomes (IC 50 0.39 nM) and the conjugate (IC 50 1.90 nM) demonstrated excellent in vitro antiplasmodial activities without causing hemolysis of erythrocytes, which were superior to free ART (IC 50 5.17 nM) and conventional ART-loaded liposomes (IC 50 3.13 nM). Furthermore, the assembled liposomes resulted in enhanced parasites killing in P. berghei-infected mice in vivo with delayed recrudescence and improved survivability

  14. Facile synthesis of dimer phase of coronene and its optical properties

    Energy Technology Data Exchange (ETDEWEB)

    Hayakawa, T.; Song, H.; Ishii, Y.; Kawasaki, S., E-mail: [Nagoya Institute of Technology, Gokiso, Showa, Nagoya, Aichi (Japan)


    We synthesized very pure dimer phase of coronene by simple heat-treatment and subsequent sublimation purification. It was found that the dimer phase emits very bright red light under the irradiation of low energy ultra-violet light.

  15. On the Elusive Twelfth Vibrational State of Beryllium Dimer

    Czech Academy of Sciences Publication Activity Database

    Patkowski, K.; Špirko, Vladimír; Szalewicz, K.


    Roč. 326, č. 5958 (2009), s. 1382-1384 ISSN 0036-8075 Institutional research plan: CEZ:AV0Z40550506 Keywords : potential function * beryllium dimer * morphed potentials Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 29.747, year: 2009

  16. Photodissociation pathways and lifetimes of protonated peptides and their dimers

    DEFF Research Database (Denmark)

    Gopalan, Aravind; Klærke, Benedikte; Rajput, Jyoti


    rate constants also confirmed a statistical nature of the photodissociation processes in the dipeptide monomers and dimers. The classical RRKM expression gives a rate constant as an analytical function of the number of active vibrational modes in the system, estimated separately on the basis...

  17. Determining Equilibrium Constants for Dimerization Reactions from Molecular Dynamics Simulations

    NARCIS (Netherlands)

    De Jong, Djurre H.; Schafer, Lars V.; De Vries, Alex H.; Marrink, Siewert J.; Berendsen, Herman J. C.; Grubmueller, Helmut


    With today's available computer power, free energy calculations from equilibrium molecular dynamics simulations "via counting" become feasible for an increasing number of reactions. An example is the dimerization reaction of transmembrane alpha-helices. If an extended simulation of the two helices

  18. Asymmetric electron capture in HCI collisions with rare gas dimers (United States)

    Matsumoto, J.; Leredde, A.; Fléchard, X.; Shiromaru, H.; Rangama, J.; Zhou, C. L.; Iskandar, W.; Guillous, S.; Hennecart, D.; Mery, A.; Gervais, B.; Cassimi, A.


    Low-energy collisions between different rare gas dimers (Ar2, Ne2) and different projectiles (O3+, Ar9+, Xe20+) show that the weight of the different fragmentation processes, Coulomb explosion and Radiative Charge Transfer, strongly depends on the projectile charge state. This result is understood in term of impact parameter from which the electrons are captured on the projectile.

  19. DNAzyme-Controlled Cleavage of Dimer and Trimer Origami Tiles. (United States)

    Wu, Na; Willner, Itamar


    Dimers of origami tiles are bridged by the Pb(2+)-dependent DNAzyme sequence and its substrate or by the histidine-dependent DNAzyme sequence and its substrate to yield the dimers T1-T2 and T3-T4, respectively. The dimers are cleaved to monomer tiles in the presence of Pb(2+)-ions or histidine as triggers. Similarly, trimers of origami tiles are constructed by bridging the tiles with the Pb(2+)-ion-dependent DNAzyme sequence and the histidine-dependent DNAzyme sequence and their substrates yielding the trimer T1-T5-T4. In the presence of Pb(2+)-ions and/or histidine as triggers, the programmed cleavage of trimer proceeds. Using Pb(2+) or histidine as trigger cleaves the trimer to yield T5-T4 and T1 or the dimer T1-T5 and T4, respectively. In the presence of Pb(2+)-ions and histidine as triggers, the cleavage products are the monomer tiles T1, T5, and T4. The different cleavage products are identified by labeling the tiles with 0, 1, or 2 streptavidin labels and AFM imaging.

  20. Fe65-PTB2 Dimerization Mimics Fe65-APP Interaction

    Directory of Open Access Journals (Sweden)

    Lukas P. Feilen


    Full Text Available Physiological function and pathology of the Alzheimer’s disease causing amyloid precursor protein (APP are correlated with its cytosolic adaptor Fe65 encompassing a WW and two phosphotyrosine-binding domains (PTBs. The C-terminal Fe65-PTB2 binds a large portion of the APP intracellular domain (AICD including the GYENPTY internalization sequence fingerprint. AICD binding to Fe65-PTB2 opens an intra-molecular interaction causing a structural change and altering Fe65 activity. Here we show that in the absence of the AICD, Fe65-PTB2 forms a homodimer in solution and determine its crystal structure at 2.6 Å resolution. Dimerization involves the unwinding of a C-terminal α-helix that mimics binding of the AICD internalization sequence, thus shielding the hydrophobic binding pocket. Specific dimer formation is validated by nuclear magnetic resonance (NMR techniques and cell-based analyses reveal that Fe65-PTB2 together with the WW domain are necessary and sufficient for dimerization. Together, our data demonstrate that Fe65 dimerizes via its APP interaction site, suggesting that besides intra- also intermolecular interactions between Fe65 molecules contribute to homeostatic regulation of APP mediated signaling.

  1. Dimeric Complexes of Tryptophan with M2+ Metal Ions

    NARCIS (Netherlands)

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


    IRMPD spectroscopy using the FELIX free electron laser and a Fourier transform ICR mass spectrometer was used to characterize the structures of electrosprayed dimer complexes M(2+)Trp(2) of tryptophan with a series of eight doubly charged metal ions, including alkaline earths Ca, Sr, and Ba, and

  2. One-pot Solvent-free Catalytic Dimerization Reaction of ...

    Indian Academy of Sciences (India)

    Abstract. In this study, we report a smooth one-pot, solvent-free catalytic dimerization of phenylacetylene. (1) to 1-phenylnaphthalene (2) by Cu/C at room temperature in good yield (∼100%). In the computational study, the structure of the 1-phenylnaphthalene was optimized by DFT-B3LYP/6-31G* method. The rotation.

  3. Cationic zinc (II) dimers and one dimensional coordination polymer ...

    Indian Academy of Sciences (India)

    Home; Journals; Journal of Chemical Sciences; Volume 126; Issue 5 ... Special issue on Chemical Crystallography Volume 126 Issue 5 September 2014 pp 1409-1415 ... These new molecules, dimers and polymer, were characterized by FT-IR, NMR, UV-vis, fluorescent and single crystal X-ray diffraction techniques.

  4. Spectroscopic observation and structure of CS2 dimer (United States)

    Rezaei, M.; Norooz Oliaee, J.; Moazzen-Ahmadi, N.; McKellar, A. R. W.


    Infrared spectra of the CS2 dimer are observed in the region of the CS2 ν3 fundamental band (˜1535 cm-1) using a tunable diode laser spectrometer. The weakly bound complex is formed in a pulsed supersonic slit-jet expansion of a dilute gas mixture of carbon disulfide in helium. Contrary to the planar slipped-parallel geometry previously observed for (CO2)2, (N2O)2, and (OCS)2, the CS2 dimer exhibits a cross-shaped structure with D2d symmetry. Two bands were observed and analyzed: the fundamental (C-S asymmetric stretch) and a combination involving this mode plus an intermolecular vibration. In both cases, the rotational structure corresponds to a perpendicular (ΔK = ±1) band of a symmetric rotor molecule. The intermolecular center of mass separation (C-C distance) is determined to be 3.539(7) Å. Thanks to symmetry, this is the only parameter required to characterize the structure, if the monomer geometry is assumed to remain unchanged in the dimer. From the band centers of the fundamental and combination band an intermolecular frequency of 10.96 cm-1 is obtained, which we assign as the torsional bending mode. This constitutes the first high resolution spectroscopic investigation of CS2 dimer.

  5. Emergence of biaxial nematic phases in solutions of semiflexible dimers (United States)

    Vaghela, Arvin; Teixeira, Paulo I. C.; Terentjev, Eugene M.


    We investigate the isotropic, uniaxial nematic and biaxial nematic phases, and the transitions between them, for a model lyotropic mixture of flexible molecules consisting of two rigid rods connected by a spacer with variable bending stiffness. We apply density-functional theory within the Onsager approximation to describe strictly excluded-volume interactions in this athermal model and to self-consistently find the orientational order parameters dictated by its complex symmetry, as functions of the density. Earlier work on lyotropic ordering of rigid bent-rod molecules is reproduced and extended to show explicitly the continuous phase transition at the Landau point, at a critical bend angle of 36∘. For flexible dimers with no intrinsic biaxiality, we find that a biaxial nematic phase can nevertheless form at a sufficiently high density and low bending stiffness. For bending stiffness κ >0.86 kBT , this biaxial phase manifests as dimer bending fluctuations occurring preferentially in one plane. When the dimers are more flexible, κ the modal shape of the fluctuating dimer is a V with an acute opening angle, and one of the biaxial order parameters changes sign, indicating a rotation of the directors. These two regions are separated by a narrow strip of uniaxial nematic in the phase diagram, which we generate in terms of the spacer stiffness and particle density.

  6. Characteristics of thymine dimer excision from xeroderma pigmentosum chromatin

    International Nuclear Information System (INIS)

    Fujiwara, Y.; Kano, Y.


    We investigated thymine dimer excision from xeroderma pigmentosum (XP) chromatin in the cell-free reconstruction system. The normal-cell extract performed specific dimer excision from native chromatin and DNA isolated from 100 J/m 2 -irradiated cells. Such an excision in vitro was rapid and required high concentrations of extract. The extracts of XP group A, C and G cells were unable to excise from their own native-chromatin, but capable of excising from chromatin deprived of loosely bound nonhistone proteins with 0.35 M NaCl, as were from purified DNA. Thus, group A, C and G cells are most likely to be defective in the specific XP factors facilitating the excising activity under multicomponent regulation at the chromatin level. Further, either of group A, C and G extracts successfully complemented the native chromatin of the alternative groups. Uniquely, the XP group D extract excised dimers from native chromatin in the normal fashion under the condition. These results suggest that XP group A, C, D and G cells examined may not be defective in the dimer specific endonuclease and exonuclease per se. 19 references, 3 figures, 2 tables

  7. Core-to-core dimers forming switchable mesophase

    Czech Academy of Sciences Publication Activity Database

    Horčic, M.; Svoboda, J.; Novotná, Vladimíra; Pociecha, D.; Gorecka, E.


    Roč. 53, č. 18 (2017), s. 2721-2724 ISSN 1359-7345 R&D Projects: GA ČR GA15-02843S Institutional support: RVO:68378271 Keywords : liquid crystals * bent-core mesogens * dimers Subject RIV: JJ - Other Materials OBOR OECD: Nano-materials (production and properties) Impact factor: 6.319, year: 2016

  8. Plasma D-dimer concentration in patients with systemic sclerosis

    Directory of Open Access Journals (Sweden)

    Montagnana Martina


    Full Text Available Abstract Background Systemic sclerosis (SSc is an autoimmune disorder of the connective tissue characterized by widespread vascular lesions and fibrosis. Little is known so far on the activation of the hemostatic and fibrinolytic systems in SSc, and most preliminary evidences are discordant. Methods To verify whether SSc patients might display a prothrombotic condition, plasma D-dimer was assessed in 28 consecutive SSc patients and in 33 control subjects, matched for age, sex and environmental habit. Results and discussion When compared to healthy controls, geometric mean and 95% confidence interval (IC95% of plasma D-dimer were significantly increased in SSc patients (362 ng/mL, IC 95%: 361–363 ng/mL vs 229 ng/mL, IC95%: 228–231 ng/mL, p = 0.005. After stratifying SSc patients according to disease subset, no significant differences were observed between those with limited cutaneous pattern and controls, whereas patients with diffuse cutaneous pattern displayed substantially increased values. No correlation was found between plasma D-dimer concentration and age, sex, autoantibody pattern, serum creatinine, erythrosedimentation rate, nailfold videocapillaroscopic pattern and pulmonary involvement. Conclusion We demonstrated that SSc patients with diffuse subset are characterized by increased plasma D-dimer values, reflecting a potential activation of both the hemostatic and fibrinolytic cascades, which might finally predispose these patients to thrombotic complications.

  9. Identification of Trimer and Dimer of 4-hydroxy-3-methoxy ...

    African Journals Online (AJOL)

    The effect of intermolecular hydrogen bonding on the molecular structure of vanillin has been studied using negative ion chemical ionization (NICl) mass spectrometry methods. The [Trimer-H2O] and [Dimer-H2O] were observed at m/z 438 and 286 respectively in NICl (CH4) mass spectrum of vanillin. The NICl (Cl) mass ...

  10. Designer interface peptide grafts target estrogen receptor alpha dimerization

    International Nuclear Information System (INIS)

    Chakraborty, S.; Asare, B.K.; Biswas, P.K.; Rajnarayanan, R.V.


    The nuclear transcription factor estrogen receptor alpha (ERα), triggered by its cognate ligand estrogen, regulates a variety of cellular signaling events. ERα is expressed in 70% of breast cancers and is a widely validated target for anti-breast cancer drug discovery. Administration of anti-estrogen to block estrogen receptor activation is still a viable anti-breast cancer treatment option but anti-estrogen resistance has been a significant bottle-neck. Dimerization of estrogen receptor is required for ER activation. Blocking ERα dimerization is therefore a complementary and alternative strategy to combat anti-estrogen resistance. Dimer interface peptide “I-box” derived from ER residues 503–518 specifically blocks ER dimerization. Recently using a comprehensive molecular simulation we studied the interaction dynamics of ERα LBDs in a homo-dimer. Based on this study, we identified three interface recognition peptide motifs LDKITDT (ERα residues 479–485), LQQQHQRLAQ (residues 497–506), and LSHIRHMSNK (residues 511–520) and reported the suitability of using LQQQHQRLAQ (ER 497–506) as a template to design inhibitors of ERα dimerization. Stability and self-aggregation of peptide based therapeutics poses a significant bottle-neck to proceed further. In this study utilizing peptide grafted to preserve their pharmacophoric recognition motif and assessed their stability and potential to block ERα mediated activity in silico and in vitro. The Grafted peptides blocked ERα mediated cell proliferation and viability of breast cancer cells but did not alter their apoptotic fate. We believe the structural clues identified in this study can be used to identify novel peptidometics and small molecules that specifically target ER dimer interface generating a new breed of anti-cancer agents. - Highlights: • Designer peptide grafts retain core molecular recognition motif during MD simulations. • Designer peptide grafts with Poly-ALA helix form stable

  11. Designer interface peptide grafts target estrogen receptor alpha dimerization

    Energy Technology Data Exchange (ETDEWEB)

    Chakraborty, S. [Laboratory of Computational Biophysics & Bioengineering, Department of Physics, Tougaloo College, Tougaloo, MS 39174 (United States); Asare, B.K. [Department of Pharmacology and Toxicology, University of Buffalo, Buffalo, NY 14214 (United States); Biswas, P.K., E-mail: [Laboratory of Computational Biophysics & Bioengineering, Department of Physics, Tougaloo College, Tougaloo, MS 39174 (United States); Rajnarayanan, R.V., E-mail: [Department of Pharmacology and Toxicology, University of Buffalo, Buffalo, NY 14214 (United States)


    The nuclear transcription factor estrogen receptor alpha (ERα), triggered by its cognate ligand estrogen, regulates a variety of cellular signaling events. ERα is expressed in 70% of breast cancers and is a widely validated target for anti-breast cancer drug discovery. Administration of anti-estrogen to block estrogen receptor activation is still a viable anti-breast cancer treatment option but anti-estrogen resistance has been a significant bottle-neck. Dimerization of estrogen receptor is required for ER activation. Blocking ERα dimerization is therefore a complementary and alternative strategy to combat anti-estrogen resistance. Dimer interface peptide “I-box” derived from ER residues 503–518 specifically blocks ER dimerization. Recently using a comprehensive molecular simulation we studied the interaction dynamics of ERα LBDs in a homo-dimer. Based on this study, we identified three interface recognition peptide motifs LDKITDT (ERα residues 479–485), LQQQHQRLAQ (residues 497–506), and LSHIRHMSNK (residues 511–520) and reported the suitability of using LQQQHQRLAQ (ER 497–506) as a template to design inhibitors of ERα dimerization. Stability and self-aggregation of peptide based therapeutics poses a significant bottle-neck to proceed further. In this study utilizing peptide grafted to preserve their pharmacophoric recognition motif and assessed their stability and potential to block ERα mediated activity in silico and in vitro. The Grafted peptides blocked ERα mediated cell proliferation and viability of breast cancer cells but did not alter their apoptotic fate. We believe the structural clues identified in this study can be used to identify novel peptidometics and small molecules that specifically target ER dimer interface generating a new breed of anti-cancer agents. - Highlights: • Designer peptide grafts retain core molecular recognition motif during MD simulations. • Designer peptide grafts with Poly-ALA helix form stable

  12. 2-Ethynylpyridine dimers: IR spectroscopic and computational study (United States)

    Bakarić, Danijela; Spanget-Larsen, Jens


    2-ethynylpyridine (2-EP) presents a multifunctional system capable of participation in hydrogen-bonded complexes utilizing hydrogen bond donating (tbnd Csbnd H, Aryl-H) and hydrogen bond accepting functions (N-atom, Ctbnd C and pyridine π-systems). In this work, IR spectroscopy and theoretical calculations are used to study possible 2-EP dimer structures as well as their distribution in an inert solvent such as tetrachloroethene. Experimentally, the tbnd Csbnd H stretching vibration of the 2-EP monomer absorbs close to 3300 cm-1, whereas a broad band with maximum around 3215 cm-1 emerges as the concentration rises, indicating the formation of hydrogen-bonded complexes involving the tbnd Csbnd H moiety. The Ctbnd C stretching vibration of monomer 2-EP close to 2120 cm-1 is, using derivative spectroscopy, resolved from the signals of the dimer complexes with maximum around 2112 cm-1. Quantum chemical calculations using the B3LYP + D3 model with counterpoise correction predict that the two most stable dimers are of the π-stacked variety, closely followed by dimers with intermolecular tbnd Csbnd H⋯N hydrogen bonding; the predicted red shifts of the tbnd Csbnd H stretching wavenumbers due to hydrogen bonding are in the range 54-120 cm-1. No species with obvious hydrogen bonding involving the Ctbnd C or pyridine π-systems as acceptors are predicted. Dimerization constant at 25 °C is estimated to be K2 = 0.13 ± 0.01 mol-1 dm3.

  13. Biological activity and dimerization state of modified phytochrome A proteins.

    Directory of Open Access Journals (Sweden)

    Peng Liu

    Full Text Available To assess potential physical interactions of type I phyA with the type II phyB-phyE phytochromes in vivo, transgenes expressing fusion gene forms of phyA were introduced into the Arabidopsis phyA mutant background. When a single c-Myc (myc epitope is added to either the N- or C-terminus of phyA, the constructs completely complement phyA mutant phenotypes. However, addition of larger tags, such as six consecutive myc epitopes or the yellow fluorescent protein sequence, result in fusion proteins that show reduced activity. All the tagged phyA proteins migrate as dimers on native gels and co-immunoprecipitation reveals no binding interaction of phyA to any of the type II phys in the dark or under continuous far-red light. Dimers of the phyA 1-615 amino acid N-terminal photosensory domain (NphyA, generated in vivo with a yeast GAL4 dimerization domain and attached to a constitutive nuclear localization sequence, are expressed at a low level and, although they cause a cop phenotype in darkness and mediate a very low fluence response to pulses of FR, have no activity under continuous FR. It is concluded that type I phyA in its Pr form is present in plants predominantly or exclusively as a homodimer and does not stably interact with type II phys in a dimer-to-dimer manner. In addition, its activity in mediating response to continuous FR is sensitive to modification of its N- or C-terminus.

  14. Brug af D-dimer til at udelukke dyb venøs trombose i overekstremiteterne

    DEFF Research Database (Denmark)

    Ahler-Toftehøj, Hans-Ulrik; Mikkelsen, Peter


    D-dimer is often used to exclude deep venous thrombosis, primarily in the lower extremities. We describe a 38-year-old man who had deep venous thrombosis in the left vena subclavia in spite of a normal D-dimer. Only one inconclusive survey compares the value of D-dimer and upper extremity deep...

  15. Age- and sex-dependent reference intervals for D-dimer

    DEFF Research Database (Denmark)

    Haase, Christine; Joergensen, Maja; Ellervik, Christina


    A low D-dimer is commonly used to exclude venous thromboembolism in low risk patients. However, the reference intervals are poorly defined and D-dimer has been shown to increase by patient age. We aimed to establish age- and sex-dependent D-dimer reference intervals and to test the consequence of...... of different cut-off limits....

  16. In Situ Structural Characterization of Ferric Iron Dimers in Aqueous Solutions

    DEFF Research Database (Denmark)

    Zhu, Mengqiang; Puls, Brendan W.; Frandsen, Cathrine


    destructively with that from paths belonging to Fe(OH2)63+ monomers that coexist with the dimers, leading to a less apparent Fe shell in the EXAFS Fourier transform. This might be a reason why the characteristic Fe–Fe distance was not detected in previous EXAFS studies. The existence of μ-oxo dimers is further...... confirmed by Mössbauer analyses of analogous quick frozen solutions. This work also explores the electronic structure and the relative stability of the μ-oxo dimer in a comparison to the dihydroxo dimer using density function theory (DFT) calculations. The identification of such dimers in aqueous solutions...

  17. Optimization of Preparation of Activated Carbon from Ricinus communis Leaves by Microwave-Assisted Zinc Chloride Chemical Activation: Competitive Adsorption of Ni2+ Ions from Aqueous Solution

    Directory of Open Access Journals (Sweden)

    M. Makeswari


    Full Text Available The preparation of activated carbon (AC from Ricinus communis leaves was investigated in this paper. Orthogonal array experimental design method was used to optimize the preparation of AC using microwave assisted zinc chloride. Optimized parameters were radiation power of 100 W, radiation time of 8 min, concentration of zinc chloride of 30% by volume, and impregnation time of 24 h, respectively. The surface characteristics of the AC prepared under optimized conditions were examined by pHZPC, SEM-EDAX, XRD, and FTIR. Competitive adsorption of Ni2+ ions on Ricinus communis leaves by microwave assisted zinc chloride chemical activation (ZLRC present in binary and ternary mixture was compared with the single metal solution. The effects of the presence of one metal ion on the adsorption of the other metal ion were investigated. The experimental results indicated that the uptake capacity of one metal ion was reduced by the presence of the other metal ion. The extent of adsorption capacity of the binary and ternary metal ions tested on ZLRC was low (48–69% as compared to single metal ions. Comparisons with the biosorption of Ni2+ ions by the biomass of ZLRC in the binary (48.98–68.41%-~Ni-Cu and 69.76–66.29%-~Ni-Cr and ternary solution (67.32–57.07%-~Ni–Cu and Cr could lead to the conclusion that biosorption of Ni2+ ions was reduced by the influence of Cu2+ and Cr3+ ions. The equilibrium data of the adsorption was well fitted to the Langmuir isotherm. The adsorption process follows the pseudo-second-order kinetic model.

  18. Arabidopsis thaliana Contains Both Ni2+ and Zn2+ Dependent Glyoxalase I Enzymes and Ectopic Expression of the Latter Contributes More towards Abiotic Stress Tolerance in E. coli.

    Directory of Open Access Journals (Sweden)

    Muskan Jain

    Full Text Available The glyoxalase pathway is ubiquitously found in all the organisms ranging from prokaryotes to eukaryotes. It acts as a major pathway for detoxification of methylglyoxal (MG, which deleteriously affects the biological system in stress conditions. The first important enzyme of this system is Glyoxalase I (GLYI. It is a metalloenzyme which requires divalent metal ions for its activity. This divalent metal ion can be either Zn2+ as found in most of eukaryotes or Ni2+ as seen in prokaryotes. In the present study, we have found three active GLYI enzymes (AtGLYI2, AtGLYI3 and AtGLYI6 belonging to different metal activation classes coexisting in Arabidopsis thaliana. These enzymes have been found to efficiently complement the GLYI yeast mutants. These three enzymes have been characterized in terms of their activity, metal dependency, kinetic parameters and their role in conferring tolerance to multiple abiotic stresses in E. coli and yeast. AtGLYI2 was found to be Zn2+ dependent whereas AtGLYI3 and AtGLYI6 were Ni2+ dependent. Enzyme activity of Zn2+ dependent enzyme, AtGLYI2, was observed to be exceptionally high (~250-670 fold as compared to Ni2+ dependent enzymes, AtGLYI3 and AtGLYI6. The activity of these GLYI enzymes correlated well to their role in stress tolerance. Heterologous expression of these enzymes in E. coli led to better tolerance against various stress conditions. This is the first report of a higher eukaryotic species having multiple active GLYI enzymes belonging to different metal activation classes.

  19. Adsorção de Cd 2+, Ni 2+ e Zn 2+ em soluções aquosas usando anidrita e lama vermelha

    Directory of Open Access Journals (Sweden)

    Fabiano Tomazini da Conceição

    Full Text Available RESUMO Vários minerais e resíduos industriais têm sido estudados para uso como adsorvente, entre eles a lama vermelha e a anidrita. A lama vermelha é um resíduo insolúvel gerado em grande quantidade durante o processamento da bauxita. A anidrita é um sulfato de cálcio (CaSO4 cristalizado sob a forma rômbica e usada como matéria-prima na indústria. Nesta investigação, a capacidade de adsorção de Cd2+, Ni2+ e Zn2+ pela anidrita e pela lama vermelha foi avaliada usando isotermas de adsorção de Langmuir e Freundlich. Os materiais empregados apresentaram adsorção ≥75±1% para todos os metais em soluções aquosas com concentração de 0,5 mmol.25 mL-1. As isotermas baseadas no modelo de Langmuir foram as mais apropriadas para descrever o fenômeno de remoção de Cd2+, Ni2+ e Zn2+ para a anidrita e a lama vermelha, com valores de capacidade máxima de adsorção de 0,47 e 0,51 mmol.g-1 para o Cd2+, 1,18 e 1,56 mmol.g-1 para o Ni2+ e 0,84 e 1,47 mmol.g-1 para o Zn2+, respectivamente. Esses valores foram superiores a outros valores exibidos por materiais empregados como adsorventes descritos em estudos prévios.

  20. Effects of Dimers on Cooperation in the Spatial Prisoner's Dilemma Game

    International Nuclear Information System (INIS)

    Li Haihong; Cheng Hongyan; Dai Qionglin; Ju Ping; Yang Junzhong; Zhang Mei


    We investigate the evolutionary prisoner's dilemma game in structured populations by introducing dimers, which are defined as that two players in each dimer always hold a same strategy. We find that influences of dimers on cooperation depend on the type of dimers and the population structure. For those dimers in which players interact with each other, the cooperation level increases with the number of dimers though the cooperation improvement level depends on the type of network structures. On the other hand, the dimers, in which there are not mutual interactions, will not do any good to the cooperation level in a single community, but interestingly, will improve the cooperation level in a population with two communities. We explore the relationship between dimers and self-interactions and find that the effects of dimers are similar to that of self-interactions. Also, we find that the dimers, which are established over two communities in a multi-community network, act as one type of interaction through which information between communities is communicated by the requirement that two players in a dimer hold a same strategy. (general)

  1. Synthesis and Characterization of Hollow Magnetic Alloy (GdNi2, Co5Gd Nanospheres Coated with Gd2O3

    Directory of Open Access Journals (Sweden)

    Wang Li


    Full Text Available Uniform magnetic hollow nanospheres (GdNi2, Co5Gd coated with Gd2O3 have been successfully prepared on a large scale via a urea-based homogeneous precipitation method using silica (SiO2 spheres as sacrificed templates, followed by subsequent heat treatment. Nitrogen sorption measurements and scanning electron microscope reveal that these hollow-structured magnetic nanospheres have the mesoporous shells that are composed of a large amount of uniform nanoparticles. After reduction treatment, these nanoparticles exhibit superparamagnetism that might have potential applications in medicine. Furthermore, the developed synthesis route may provide an important guidance for the preparation of other multifunctional hollow spherical materials.

  2. Anchor of Ni2+ on the Agmatine Sulfate-Modified Electrodes for the Determination of H2O2 in Food (United States)

    Yan, Yuhua; Zhang, Zhonghui; Xiao, Mingshu; Zhou, Hualan


    A method was developed to conveniently and rapidly determine hydrogen peroxide (H2O2) in food. The glassy carbon electrode (GCE) modified with agmatine sulfate (AS) easily anchoring nickel ion was attached to AS with polyamine structure. As a result, more Ni2+ was obtained and transformed to Ni(OH)2/NiOOH on the AS-GCE, which caused the electrode to own much better electrocatalytic performance on H2O2. Based on these, the content of H2O2 in thin sheet of bean curd sample was detected with standard addition method, by which good results were obtained.

  3. Structure, magnetic and thermo-mechanic properties of Ni2.14Mn0.81Fe0.05Ga Heusler alloy

    International Nuclear Information System (INIS)

    Borisenko, I.D.; Koledov, V.V.; Khovajlo, V.V.; Khudaverdyan, T.O.; Shavrov, V.G.; Grechishkin, R.M.; Krasnoperov, E.P.; Li, Ya.; Tszyan, Ch.


    The influence of a strong magnetic field, single-axis pressure and intensive ultrasound on the process of structural (martensitic) transition on polycrystals of ferromagnetic alloy Ni 2.14 Mn 0.81 Fe 0.05 Ga with shape memory was studied experimentally. It is shown that magnetic field up to 8 T shifts without essential distortions the temperature hysteresis loop of martensitic transition to the range of higher temperatures, single-axis pressure blurs the martensitic transition, expanding the temperature hysteresis loop, while ultrasonic vibration may result in contraction of the hysteresis loop [ru

  4. Crystal structure of the martensite phase in the ferromagnetic shape memory compound Ni2MnGa studied by electron diffraction

    International Nuclear Information System (INIS)

    Fukuda, Takashi; Kushida, Hiroaki; Todai, Mitsuharu; Kakeshita, Tomoyuki; Mori, Hirotaro


    The electron diffraction patterns of Ni 2 MnGa show six satellites at ±q M , ±2q M and ±3q M , with q M = 0.427(5) g 22 -bar 0 between fundamental reflections in the martensite phase, and two satellites at ±q I , with q I = 0.340(5) g 22 -bar 0 in the intermediate phase, meaning that these phases have incommensurate structures. In addition, the diffraction pattern of the intermediate phase continuously changes to that of the parent phase via the X-phase, suggesting the existence of a multicritical phenomenon.

  5. Association of atoms into universal dimers using an oscillating magnetic field. (United States)

    Langmack, Christian; Smith, D Hudson; Braaten, Eric


    In a system of ultracold atoms near a Feshbach resonance, pairs of atoms can be associated into universal dimers by an oscillating magnetic field with a frequency near that determined by the dimer binding energy. We present a simple expression for the transition rate that takes into account many-body effects through a transition matrix element of the contact. In a thermal gas, the width of the peak in the transition rate as a function of the frequency is determined by the temperature. In a dilute Bose-Einstein condensate of atoms, the width is determined by the inelastic scattering rates of a dimer with zero-energy atoms. Near an atom-dimer resonance, there is a dramatic increase in the width from inelastic atom-dimer scattering and from atom-atom-dimer recombination. The recombination contribution provides a signature for universal tetramers that are Efimov states consisting of two atoms and a dimer.

  6. Emergence of a Dimer-Dimer Interaction in the Low-Energy Effective Quantum-Dimer Model of a Diamond-Like-Decorated Square-Lattice Heisenberg Antiferromagnets with Further Neighbor Couplings (United States)

    Hirose, Yuhei; Oguchi, Akihide; Fukumoto, Yoshiyuki


    We study spin-1/2 Heisenberg antiferromagnets on a diamond-like-decorated square lattice perturbed by two kinds of further neighbor couplings. In our previous study [" xlink:type="simple">J. Phys. Soc. Jpn. 85, 094002 (2016)], the second-order effective Hamiltonian for the Heisenberg model perturbed by a further neighbor coupling was found to be a square-lattice quantum-dimer model with a finite hopping amplitude, t > 0, and no dimer-dimer interaction, v = 0. In this study, we introduce another kind of further neighbor coupling and show that it leads to an attractive interaction between dimers, which suggests the stabilization of the columnar phase of the square-lattice quantum-dimer model. The calculated v/t is presented as a function of the ratio of the two exchange parameters in the Heisenberg model.

  7. Solution structure of the dimeric cytoplasmic domain of syndecan-4

    DEFF Research Database (Denmark)

    Shin, J; Lee, W; Lee, D


    cytoplasmic domain is dependent on its oligomeric status, the conformation of the syndecan-4 cytoplasmic domain itself is important in the understanding of its biological roles. Gel filtration results show that the syndecan-4 cytoplasmic domain (4L) itself forms a dimer stabilized by ionic interactions......The syndecans, transmembrane proteoglycans which are involved in the organization of cytoskeleton and/or actin microfilaments, have important roles as cell surface receptors during cell-cell and/or cell-matrix interactions. Since previous studies indicate that the function of the syndecan-4...... in the center of the dimeric twist similar to our previously reported 4V structure. The overall topology of the central variable region within the 4L structure is very similar to that of 4V complexed with the phosphatidylinositol 4,5-bisphosphate; however, the intersubunit interaction mode is affected...

  8. Dimers on two types of lattices on the Klein bottle (United States)

    Lu, Fuliang; Zhang, Lianzhu


    The problem of enumerating close-packed dimers, or perfect matchings, on two types of lattices (the so-called 8.8.4 and 8.8.6 lattices) embedded on the Klein bottle is considered, and we obtain the explicit expression of the number of close-packed dimers and entropy. Our results imply that 8.8.4 lattices have the same entropy under three different boundary conditions (cylindrical, toroidal and Klein bottle) and 8.8.6 lattices have the same property. This article is part of ‘Lattice models and integrability’, a special issue of Journal of Physics A: Mathematical and Theoretical in honour of F Y Wu's 80th birthday.

  9. Stability of gold atoms and dimers adsorbed on graphene

    International Nuclear Information System (INIS)

    Varns, R; Strange, P


    We report density functional theory (DFT) calculations for gold atoms and dimers on the surface of graphene. The calculations were performed using the plane wave pseudopotential method. Calculations were performed for a variety of geometries, and both the graphene surface and gold atoms were allowed to fully relax. In agreement with experiment, our results show that the gold-gold interaction is considerably stronger than the gold-graphene interaction, implying that uniform coverage could not be attained. The minimum energy configuration for a single gold atom is found to be directly above a carbon atom, while for the dimer it is perpendicular to the surface and directly above a carbon-carbon bond. Our results are consistent with previous similar calculations

  10. Oxidative catalytic dimerization of methane: Syngas process alternative

    International Nuclear Information System (INIS)

    Salvi, G.


    A review of research progress relative to the direct conversion of methane into liquid hydrocarbons through oxidative catalytic dimerization indicates that high carbon (C 2 ) yields can be obtained in experimental conditions in which there is a high linear gas velocity, i.e., velocities greater than 0.45 m/s, at temperatures ranging between 800 and 850 degrees C, and with volumetric methane/oxygen ratios of 2 to 10. The high linear velocities have the function of preventing back-mixing phenomena and consequent product degradation. The suitable integration of dimerization (exothermic) with cracking (endothermic) of ethane to ethylene and higher olefins, as well as, oligomerization of the olefins to liquid hydrocarbons (synthesis fuels) can allow for the development of an very interesting process from both technical and economic points of view, especially for those countries with a mix of abundant natural gas reserves and scarce petroleum resources

  11. A new phenylspirodrimane dimer from the fungus Stachybotrys chartarum. (United States)

    Ding, Zhang-Gui; Ding, Jian-Hai; Zhao, Jiang-Yuan; Chunyu, Wei-Xun; Li, Ming-Gang; Gu, Shao-Jie; Wang, Fei; Wen, Meng-Liang


    A new phenylspirodrimane dimer, named stachartarin A (1), was isolated from cultures of the tin mine tailings-associated fungus Stachybotrys chartarum. Its structures were elucidated by means of spectroscopic methods. At the same time, the compound was tested for its cytotoxicity against HL-60, SMMC-7721, A-549, MCF-7, and SW480 cells. Copyright © 2018 Elsevier B.V. All rights reserved.

  12. A new dimeric anthraquinone from endophytic Talaromyces sp. YE3016. (United States)

    Xie, Xiao-Song; Fang, Xiao-Wei; Huang, Rong; Zhang, Shou-Peng; Wei, Hong-Xia; Wu, Shao-Hua


    A new unsymmetrical dimeric anthraquinone, 3-demethyl-3-(2-hydroxypropyl)-skyrin (1) was isolated from the solid-state fermentation extract of an endophytic fungal strain Talaromyces sp. YE 3016, together with five known compounds, skyrin (2), oxyskyrin (3), emodin (4), 1,3,6-trihydroxy-8-methyl-anthraquinone (5) and ergosterol (6). The structure of the new compound was elucidated on the basis of spectroscopic analysis. Compounds 1-3 exhibited moderate cytotoxic activities against MCF-7 cell line.

  13. Plasmonic dimer antennas for surface enhanced Raman scattering. (United States)

    Höflich, Katja; Becker, Michael; Leuchs, Gerd; Christiansen, Silke


    Electron beam induced deposition (EBID) has recently been developed into a method to directly write optically active three-dimensional nanostructures. For this purpose a metal-organic precursor gas (here dimethyl-gold(III)-acetylacetonate) is introduced into the vacuum chamber of a scanning electron microscope where it is cracked by the focused electron beam. Upon cracking the aforementioned precursor gas, 3D deposits are realized, consisting of gold nanocrystals embedded in a carbonaceous matrix. The carbon content in the deposits hinders direct plasmonic applications. However, it is possible to activate the deposited nanostructures for plasmonics by coating the EBID structures with a continuous silver layer of a few nanometers thickness. Within this silver layer collective motions of the free electron gas can be excited. In this way, EBID structures with their intriguing precision at the nanoscale have been arranged in arrays of free-standing dimer antenna structures with nanometer sized gaps between the antennas that face each other with an angle of 90°. These dimer antenna ensembles can constitute a reproducibly manufacturable substrate for exploiting the surface enhanced Raman effect (SERS). The achieved SERS enhancement factors are of the order of 10⁴ for the incident laser light polarized along the dimer axes. To prove the signal enhancement in a Raman experiment we used the dye methyl violet as a robust test molecule. In future applications the thickness of such a silver layer on the dimer antennas can easily be varied for tuning the plasmonic resonances of the SERS substrate to match the resonance structure of the analytes to be detected.

  14. Synthesis and anti-inflammatory activity of phenylbutenoid dimer analogs

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Sung Soo; Fang, Yuan Ying; Park, Hae Eil [Kangwon National University, Chuncheon (Korea, Republic of)


    Several phenylbutenoid dimer (PBD) analogs were synthesized and evaluated for their inhibitory activities against nitric oxide (NO) production and TNF-α release. The PBD analogs were synthesized via Diels–Alder and subsequent Schlosser reactions as key steps. Among the tested compounds, two analogs (8c, 8f) exhibited much stronger inhibitory activity against LPS-stimulated NO production and TNF-α release in RAW 264.7 cells than that of wogonin.

  15. Antimicrobial Oligophenalenone Dimers from the Soil Fungus Talaromyces stipitatus


    Zang , Yi; Genta-Jouve , Grégory; Escargueil , Alexandre E.; Larsen , Annette K.; Guedon , Laura; Nay , Bastien; Prado , Soizic


    International audience; New polyketide-derived oligophenalenone dimers, 9a-epi-bacillisporin E (1) and bacillisporins F–H (2–5), along with the known bacillisporin A (6), were isolated from the fungus Talaromyces stipitatus. Their structures and absolute configurations were determined on the basis of spectroscopic analyses, electronic circular dichroism, and GIAO NMR shift calculation followed by DP4 analysis. The antimicrobial activity of these compounds was evaluated against a panel of huma...

  16. Dimerization effect of sucrose octasulfate on rat FGF1

    International Nuclear Information System (INIS)

    Kulahin, N.; Kiselyov, V.; Kochoyan, A.; Kristensen, O.; Kastrup, Jette S.; Berezin, V.; Bock, E.; Gajhede, M.


    The work describes the sucrose octasulfate-mediated dimerization of rat FGF1 by gel-filtration experiments and crystal structure determination. Fibroblast growth factors (FGFs) constitute a family of at least 23 structurally related heparin-binding proteins that are involved in regulation of cell growth, survival, differentiation and migration. Sucrose octasulfate (SOS), a chemical analogue of heparin, has been demonstrated to activate FGF signalling pathways. The structure of rat FGF1 crystallized in the presence of SOS has been determined at 2.2 Å resolution. SOS-mediated dimerization of FGF1 was observed, which was further supported by gel-filtration experiments. The major contributors to the sulfate-binding sites in rat FGF1 are Lys113, Lys118, Arg122 and Lys128. An arginine at position 116 is a consensus residue in mammalian FGF molecules; however, it is a serine in rat FGF1. This difference may be important for SOS-mediated FGF1 dimerization in rat

  17. On the photophysics and photochemistry of the water dimer

    Energy Technology Data Exchange (ETDEWEB)

    Segarra-Marti, Javier; Merchan, Manuela [Instituto de Ciencia Molecular, Universitat de Valencia, P.O. Box 22085, 46071 Valencia (Spain); Roca-Sanjuan, Daniel; Lindh, Roland [Department of Chemistry - Angstroem, Theoretical Chemistry Program, Uppsala University, Box 518, 75120 Uppsala (Sweden)


    The photochemistry of the water dimer irradiated by UV light is studied by means of the complete active space perturbation theory//complete active space self-consistent field (CASPT2//CASSCF) method and accurate computational approaches like as minimum energy paths. Both electronic structure computations and ab initio molecular dynamics simulations are carried out. The results obtained show small shifts relative to a single water molecule on the vertical excitation energies of the dimer due to the hydrogen bond placed between the water donor (W{sub D}) and the water acceptor (W{sub A}). A red-shift and a blue-shift are predicted for the W{sub D} and W{sub A}, respectively, supporting previous theoretical and experimental results. The photoinduced chemistry of the water dimer is described as a process occurring between two single water molecules in which the effect of the hydrogen bond plays a minor role. Thus, the photoinduced decay routes correspond to two photodissociation processes, one for each water molecule. The proposed mechanism for the decay channels of the lowest-lying excited states of the system is established as the photochemical production of a hydrogen-bonded H{sub 2}O Horizontal-Ellipsis HO species plus a hydrogen H atom.

  18. Cooperative Formation of Icosahedral Proline Clusters from Dimers (United States)

    Jacobs, Alexander D.; Jovan Jose, K. V.; Horness, Rachel; Raghavachari, Krishnan; Thielges, Megan C.; Clemmer, David E.


    Ion mobility spectrometry-mass spectrometry and Fourier transform infrared spectroscopy (FTIR) techniques were combined with quantum chemical calculations to examine the origin of icosahedral clusters of the amino acid proline. When enantiopure proline solutions are electrosprayed (using nanospray) from 100 mM ammonium acetate, only three peaks are observed in the mass spectrum across a concentration range of five orders of magnitude: a monomer [Pro+H]+ species, favored from 0.001 to 0.01 mM proline concentrations; a dimer [2Pro+H]+ species, the most abundant species for proline concentrations above 0.01 mM; and, the dimer and dodecamer [12Pro+2H]2+ for 1.0 mM and more concentrated proline solutions. Electrospraying racemic D/ L-proline solutions from 100 mM ammonium acetate leads to a monomer at low proline concentrations (0.001 to 0.1 mM), and a dimer at higher concentrations (>0.09 mM), as well as a very small population of 8 to 15 Pro clusters that comprise species from 2Pro. [Figure not available: see fulltext.

  19. Correlative SEM SERS for quantitative analysis of dimer nanoparticles. (United States)

    Timmermans, F J; Lenferink, A T M; van Wolferen, H A G M; Otto, C


    A Raman microscope integrated with a scanning electron microscope was used to investigate plasmonic structures by correlative SEM-SERS analysis. The integrated Raman-SEM microscope combines high-resolution electron microscopy information with SERS signal enhancement from selected nanostructures with adsorbed Raman reporter molecules. Correlative analysis is performed for dimers of two gold nanospheres. Dimers were selected on the basis of SEM images from multi aggregate samples. The effect of the orientation of the dimer with respect to the polarization state of the laser light and the effect of the particle gap size on the Raman signal intensity is observed. Additionally, calculations are performed to simulate the electric near field enhancement. These simulations are based on the morphologies observed by electron microscopy. In this way the experiments are compared with the enhancement factor calculated with near field simulations and are subsequently used to quantify the SERS enhancement factor. Large differences between experimentally observed and calculated enhancement factors are regularly detected, a phenomenon caused by nanoscale differences between the real and 'simplified' simulated structures. Quantitative SERS experiments reveal the structure induced enhancement factor, ranging from ∼200 to ∼20 000, averaged over the full nanostructure surface. The results demonstrate correlative Raman-SEM microscopy for the quantitative analysis of plasmonic particles and structures, thus enabling a new analytical method in the field of SERS and plasmonics.

  20. Dissociative Ionization of Argon Dimer by Intense Femtosecond Laser Pulses. (United States)

    Cheng, Qian; Xie, Xiguo; Yuan, Zongqiang; Zhong, Xunqi; Liu, Yunquan; Gong, Qihuang; Wu, Chengyin


    We experimentally and theoretically studied dissociative ionization of argon dimer driven by intense femtosecond laser pulses. In the experiment, we measured the ion yield and the angular distribution of fragmental ions generated from the dissociative ionization channels of (1,1) (Ar 2 2+ → Ar + + Ar + ) and (2,1) (Ar 2 3+ → Ar 2+ + Ar + ) using a cold target recoil ion momentum spectroscopy. The channel ratio of (2,1)/(1,1) is 4.5-7.5 times of the yield ratio of double ionization to single ionization of argon monomer depending on the laser intensity. The measurement verified that the ionization of Ar + is greatly enhanced if there exists a neighboring Ar + separated by a critical distance. In addition, the fragmental ions exhibit an anisotropic angular distribution with the peak along the laser polarization direction and the full width at half maximum becomes broader with increasing laser intensity. Using a full three-dimensional classical ensemble model, we calculated the angle-dependent multiple ionization probability of argon dimer in intense laser fields. The results show that the experimentally observed anisotropic angular distribution of fragmental ions can be attributed to the angle-dependent enhanced ionization of the argon dimer in intense laser fields.

  1. Theoretical investigation on the 2e/12c bond and second hyperpolarizability of azaphenalenyl radical dimers: Strength and effect of dimerization (United States)

    Zhong, Rong-Lin; Xu, Hong-Liang; Sun, Shi-Ling; Qiu, Yong-Qing; Zhao, Liang; Su, Zhong-Min


    An increasing number of chemists have focused on the investigations of two-electron/multicenter bond (2e/mc) that was first introduced to describe the structure of radical dimers. In this work, the dimerization of two isoelectronic radicals, triazaphenalenyl (TAP) and hexaazaphenalenyl (HAP) has been investigated in theory. Results show TAP2 is a stable dimer with stronger 2e/12c bond and larger interaction energy, while HAP2 is a less stable dimer with larger diradical character. Interestingly, the ultraviolet-visible absorption spectra suggest that the dimerization induces a longer wavelength absorption in visible area, which is dependent on the strength of dimerization. Significantly, the amplitude of second hyperpolarizability (γyyyy) of HAP2 is 1.36 × 106 a.u. that is larger than 7.79 × 104 a.u. of TAP2 because of the larger diradical character of HAP2. Therefore, the results indicate that the strength of radical dimerization can be effectively detected by comparing the magnitude of third order non-linear optical response, which is beneficial for further theoretical and experimental studies on the properties of complexes formed by radical dimerization.

  2. Qualitative point-of-care D-dimer testing compared with quantitative D-dimer testing in excluding pulmonary embolism in primary care

    NARCIS (Netherlands)

    Lucassen, W. A. M.; Erkens, P. M. G.; Geersing, G. J.; Büller, H. R.; Moons, K. G. M.; Stoffers, H. E. J. H.; van Weert, H. C. P. M.


    General practitioners can safely exclude pulmonary embolism (PE) by using the Wells PE rule combined with D-dimer testing. To compare the accuracy of a strategy using the Wells rule combined with either a qualitative point-of-care (POC) D-dimer test performed in primary care or a quantitative

  3. Correlation between phonon anomaly along [211] and the Fermi surface nesting features with associated electron-phonon interactions in Ni2FeGa: A first principles study

    International Nuclear Information System (INIS)

    Chabungbam, Satyananda; Sahariah, Munima B.


    First principles calculation reaffirms the presence of phonon anomaly along [211] direction in Ni 2 FeGa shape memory alloy supporting the experimental findings of J. Q. Li et al. Fermi surface scans have been performed in both austenite and martensite phase to see the possible Fermi nesting features in this alloy. The magnitude of observed Fermi surface nesting vectors in (211) plane exactly match the phonon anomaly wavevectors along [211] direction. Electron-phonon calculation in the austenite phase shows that there is significant electron-phonon coupling in this alloy which might arise out of the lattice coupling between lower acoustic modes and higher optical modes combined with the observed strong Fermi nesting features in the system. - Highlights: • Transverse acoustic (TA 2 ) modes show anomaly along [211] direction in Ni 2 FeGa. • The phonon anomaly wavevector has been correlated with the Fermi nesting vectors. • Electron-phonon coupling calculation shows significant coupling in this system. • Max. el-ph coupling occurs in transition frequencies from acoustic to optical modes

  4. Crystal structure of calcium dinickel(II iron(III tris(orthophosphate: CaNi2Fe(PO43

    Directory of Open Access Journals (Sweden)

    Said Ouaatta


    Full Text Available The title compound, CaNi2Fe(PO43, was synthesized by solid-state reactions. Its structure is closely related to that of α-CrPO4 in the space group Imma. Except for two O atoms in general positions, all atoms are located in special positions. The three-dimensional framework is built up from two types of sheets extending parallel to (100. The first sheet is made up from two edge-sharing [NiO6] octahedra, leading to the formation of [Ni2O10] double octahedra that are connected to two PO4 tetrahedra through a common edge and corners. The second sheet results from rows of corner-sharing [FeO6] octahedra and PO4 tetrahedra forming an infinite linear chain. These layers are linked together through common corners of PO4 tetrahedra and [FeO6] octahedra, resulting in an open three-dimensional framework that delimits two types of channels parallel to [100] and [010] in which the eightfold-coordinated CaII cations are located.

  5. Solvation and electronic spectrum of Ni2+ ion in aqueous and ammonia solutions: A sequential Monte Carlo/TD-DFT study

    International Nuclear Information System (INIS)

    Aguilar, Charles M.; De Almeida, Wagner B.; Rocha, Willian R.


    A sequential Monte Carlo/Quantum Mechanics approach was used to investigate the solvent effects on d → d transition of the Ni 2+ ion in aqueous and ammonia solutions. A set of Lennard-Jones parameters were generated by modification of the UFF Force Field. The structural results obtained for the liquid structure around the Ni 2+ ion are in very good agreement with the experimental findings. The water molecules in the second coordination shell interact strongly with the first shell, with hydrogen bonds of -14.6 ± 3.3 kcal mol -1 which is 30% stronger than in the ammonia complex. The electronic spectrum was evaluated within the TD-DFT approach on the gas phase geometry and also on the Monte Carlo generated clusters, including the long range solvent effects by means of the PCM continuum model. We show that the computed electronic transitions are all red-shifted compared with the experimental results and, the agreement with the experimental values are only qualitative

  6. Toxic metals (Ni2+, Pb2+, Hg2+) binding affinity of dissolved organic matter (DOM) derived from different ages municipal landfill leachate (United States)

    Rikta, S. Y.; Tareq, Shafi M.; Uddin, M. Khabir


    Solid waste production is rapidly increasing in Bangladesh and landfill leachate is the consequence of the decomposition of this waste. These leachates contain heavy metals and significant amount of dissolved organic matter (DOM). DOM is known to have considerable role in heavy metals speciation. Hence, it is important to characterize DOM/leachate and evaluate toxic metals binding affinity of DOM. The objectives of this study were to characterize the DOM in landfill leachate through physico-chemical and optical analyses and to investigate the toxic metals (Ni2+, Pb2+ and Hg2+) binding affinity of three different ages (fresh sample L-1, young sample L-2 and mature sample L-3) DOM samples. Results suggested that leachate is a potential pollutant which contained very high organic pollutant load. Conditional stability constant (Log K) and percentages of fluorophores that correspond to metal binding (% f) values indicated that young DOM sample (L-2) had the highest binding affinity to all the three metals ions. In general, DOM samples showed the following order affinity to the metal ions; Ni2+ binding affinity: L-2 > L-3 > L-1, Pb2+ binding affinity: L-2 > L-3 > L-1 and Hg2+ binding affinity: L-2 > L-1 > L-3.

  7. Nanosized carbon black combined with Ni2O3 as "universal" catalysts for synergistically catalyzing carbonization of polyolefin wastes to synthesize carbon nanotubes and application for supercapacitors. (United States)

    Wen, Xin; Chen, Xuecheng; Tian, Nana; Gong, Jiang; Liu, Jie; Rümmeli, Mark H; Chu, Paul K; Mijiwska, Ewa; Tang, Tao


    The catalytic carbonization of polyolefin materials to synthesize carbon nanotubes (CNTs) is a promising strategy for the processing and recycling of plastic wastes, but this approach is generally limited due to the selectivity of catalysts and the difficulties in separating the polyolefin mixture. In this study, the influence of nanosized carbon black (CB) and Ni2O3 as a novel combined catalyst system on catalyzing carbonization of polypropylene (PP), polyethylene (PE), polystyrene (PS) and their blends was investigated. We showed that this combination was efficient to promote the carbonization of these polymers to produce CNTs with high yields and of good quality. Catalytic pyrolysis and model carbonization experiments indicated that the carbonization mechanism was attributed to the synergistic effect of the combined catalysts rendered by CB and Ni2O3: CB catalyzed the degradation of PP, PE, and PS to selectively produce more aromatic compounds, which were subsequently dehydrogenated and reassembled into CNTs via the catalytic action of CB together with Ni particles. Moreover, the performance of the synthesized CNTs as the electrode of supercapacitor was investigated. The supercapacitor displayed a high specific capacitance as compared to supercapacitors using commercial CNTs and CB. This difference was attributed to the relatively larger specific surface areas of our synthetic CNTs and their more oxygen-containing groups.

  8. Bonding and magnetic response properties of several toroid structures. Insights of the role of Ni2S2 as a building block from relativistic density functional theory calculations. (United States)

    Muñoz-Castro, Alvaro


    Relativistic density functional calculations were carried out on several nickel toroid mercaptides of the general formula [Ni(μ-SR)(2)](n), with the aim to characterize and analyze their stability and magnetic response properties, in order to gain more insights into their stabilization and size-dependent behavior. The Ni-ligand interaction has been studied by means projected density of states and energy decomposition analysis, which denotes its stabilizing character. The graphical representation of the response to an external magnetic field is applied for the very first time taking into account the spin-orbit term. This map allows one to clearly characterize the magnetic behavior inside and in the closeness of the toroid structure showing the prescence of paratropic ring currents inside the Ni(n) ring, and by contrast, diatropic currents confined in each Ni(2)S(2) motif denoting an aromatic behavior (in terms of magnetic criteria). The calculated data suggests that the Ni(2)S(2) moiety can be regarded as a stable constructing block, which can afford several toroid structures of different nuclearities in agreement with that reported in the experimental literature. In addition, the effects of the relativistic treatment over the magnetic response properties on these lighter compounds are denoted by comparing nonrelativistic, scalar relativistic, and scalar plus spin-orbit relativistic treatments, showing their acting, although nonpronunced, role.

  9. Removal of Heavy Metals Pb2+, Cu2+, Zn2+, Cd2+, Ni2+, Co2+ and Fe3+ from Aqueous Solutions by using Xanthium Pensylvanicum

    Directory of Open Access Journals (Sweden)



    Full Text Available The hazardous ill effects of heavy metals on the environment and public health is a matter of serious concern. Biosorption is emerging as a sustainable effective technology. Heavy metals in water resources are one of the most important environmental problems of countries. The intensification of industrial activity and environmental stress greatly contributes to the significant rise of heavy metal pollution in water resources making threats on terrestrial and aquatic life. The toxicity of metal pollution is slow and interminable, as these metal ions are non bio-degradable. The adsorption capacity of Xanthium Pensylvanicum towards metal ions such as Pb2+, Cu2+, Zn2+, Cd2+, Ni2+, Co2+ and Fe3+, was studied. The adsorption capacity was performed by batch experiments as a function of process parameters (such as sorption time and pH. Experimental results showed that the removal percentages increasing of metal ions at pH=4, initial concentration of metal ions 10 mg/L, and after 90 min of shaking was: Zn2+ < Cd2+ < Cu2+ < Pb2+ < Ni2+ < Fe3+ < Co2+.

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


    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.

  11. An asymmetric A-B-A' metallo-supramolecular triblock copolymer linked by Ni(2+)-bis-terpyridine complexes at one junction. (United States)

    Li, Haixia; Wei, Wei; Xiong, Huiming


    A metallo-supramolecular triblock copolymer polystyrene-b-polyisoprene-[Ni(2+)]-polystyrene (SI-[Ni(2+)]-S') has been efficiently prepared using a one-pot, two-step procedure, where the blocks are held by bis-terpyridine complexes at the junction of SI-S'. This specific metallo-supramolecular chemistry is demonstrated to be a robust approach to potentially broaden the diversity of block copolymers. The location of the metal-ligand complexes has a profound influence on the phase separation of the triblock copolymer in the bulk, which results in a distinctive phase segregation between the end blocks and leads to an unexpected asymmetry of the triblock copolymer. The metal-ligand complexes are found to be preferentially located on the adjacent spherical domain and form a core-shell structure. The resulting multiphase material exhibits distinct elastomeric properties with significant toughness and creep recovery behavior. This type of triblock copolymer is anticipated to be a novel class of hybrid thermo-plastic elastomeric material with wide tunability and functionality.

  12. Characterization on the Microstructure Evolution and Toughness of TIG Weld Metal of 25Cr2Ni2MoV Steel after Post Weld Heat Treatment

    Directory of Open Access Journals (Sweden)

    Xia Liu


    Full Text Available The microstructure and toughness of tungsten inert gas (TIG backing weld parts in low-pressure steam turbine welded rotors contribute significantly to the total toughness of the weld metal. In this study, the microstructure evolution and toughness of TIG weld metal of 25Cr2Ni2MoV steel low-pressure steam turbine welded rotor under different post-weld heat treatment (PWHT conditions are investigated. The fractography and microstructure of weld metal after PWHT are characterized by optical microscope, SEM, and TEM, respectively. The Charpy impact test is carried out to evaluate the toughness of the weld. The optical microscope and SEM results indicate that the as-welded sample is composed of granular bainite, acicular ferrite and blocky martensite/austenite (M-A constituent. After PWHT at 580 °C, the blocky M-A decomposes into ferrite and carbides. Both the number and size of precipitated carbides increase with holding time. The impact test results show that the toughness decreases dramatically after PWHT and further decreases with holding time at 580 °C. The precipitated carbides are identified as M23C6 carbides by TEM, which leads to the dramatic decrease in the toughness of TIG weld metal of 25Cr2Ni2MoV steel.

  13. Characterization of a metal resistant Pseudomonas sp. isolated from uranium mine for its potential in heavy metal (Ni2+, Co2+, Cu2+, and Cd2+) sequestration. (United States)

    Choudhary, Sangeeta; Sar, Pinaki


    Heavy metal sequestration by a multimetal resistant Pseudomonas strain isolated from a uranium mine was characterized for its potential application in metal bioremediation. 16S rRNA gene analysis revealed phylogenetic relatedness of this isolate to Pseudomonas fluorescens. Metal uptake by this bacterium was monophasic, fast saturating, concentration and pH dependent with maximum loading of 1048 nmol Ni(2+) followed by 845 nmol Co(2+), 828 nmol Cu(2+) and 700 nmol Cd(2+)mg(-1) dry wt. Preferential metal deposition in cell envelope was confirmed by TEM and cell fractionation. FTIR spectroscopy and EDX analysis revealed a major role of carboxyl and phosphoryl groups along with a possible ion exchange mechanism in cation binding. Binary system demonstrated selective metal binding affinity in the order of Cu(2+)>Ni(2+)>Co(2+)>Cd(2+). A comparison with similar metal uptake reports considering live bacteria strongly indicated the superiority of this strain in metal sequestration, which could be useful for developing efficient metal removal system.

  14. Neutral dipole-dipole dimers: A new field in science (United States)

    Kosower, Edward M.; Borz, Galina


    Dimer formation with dipole neutralization produces species such as low polarity water (LPW) compatible with hydrophobic surfaces (Phys. Chem. Chem. Phys. 2015, 17, 24895-24900) Dimerization and dipole neutralization occurs for N-methylacetamide on polyethylene, a behavior drastically different from its contortions in acetonitrile on AgBr:AgCl planar crystals (AgX) (ChemPhysChem 2014, 15, 3598-3607). The weak infrared absorption of the amide dimer on polyethylene is shown experimentally. Dimerization of palmitic acid is shown along with some of the many ramifications for intracellular systems. Polyoligomers of water are present on polyethylene surfaces. Some high resolution spectra of three of the polyoligomers of water are shown along with a mechanistic scheme for polyoligomer formation and dissolution. The structures of some of the oligomers are known from spectroscopic studies of water on AgX. The scope of the article begins with PE, generally accepted as hydrophobic. The IR of PE revealed not only that water was present but that it appeared in two forms, oligomers (O) and polyoligomers (PO). How did we recognize what they were? These species had been observed as especially strong "marker" peaks in the spectra1 of water placed on planar AgX, a platform developed by Katzir and his coworkers [6]. But there was a problem: the proximity to PE of oligomers with substantial (calculated) dipole moments and thus polarity, including cyclic hexamers of water (chair and boat forms), the cyclic pentamer, the books I and II, and the cyclic trimer [7a]. Another link was needed, a role perfectly fit by the already cited low polarity water (LPW). The choice was experimentally supported by the detection of low intensity absorption in the bending region.Some important generalities flow from these results. What other dimers might be present in the biological or chemical world? Palmitic acid dimer (PAD) would be a candidate for decreasing the polarity of the acid (PA). Another

  15. Acetic acid dimers in a nitrogen matrix: Observation of structures containing the higher-energy conformer (United States)

    Lopes, Susy; Domanskaya, Alexandra V.; Räsänen, Markku; Khriachtchev, Leonid; Fausto, Rui


    Acetic acid (AA) dimers are studied experimentally by infrared spectroscopy in a N2 matrix and theoretically at the MP2/6-311++G(2d,2p) level of approximation. This work is focused on the first preparation and characterization of structures containing the higher-energy (cis) conformer of AA. Nine trans-trans, fourteen trans-cis, and six cis-cis dimers are theoretically predicted. Five trans-trans and a number of trans-cis dimers are identified in the experiments, but no indication of cis-cis dimers is found. Two trans-trans dimers and the trans-cis dimers are reported for the first time. One trans-cis dimer is prepared by selective vibrational excitation of the structurally related trans-trans dimer, which converts one of the trans subunits to the cis form. Several trans-cis dimers are obtained by annealing of a matrix containing both trans and cis monomers of AA. Tunneling-induced conversion of the trans-cis dimers into trans-trans forms (including two new trans-trans forms) is observed at low temperatures.

  16. A potential new, stable state of the E-cadherin strand-swapped dimer in solution. (United States)

    Schumann-Gillett, Alexandra; Mark, Alan E; Deplazes, Evelyne; O'Mara, Megan L


    E-cadherin is a transmembrane glycoprotein that facilitates inter-cellular adhesion in the epithelium. The ectodomain of the native structure is comprised of five repeated immunoglobulin-like domains. All E-cadherin crystal structures show the protein in one of three alternative conformations: a monomer, a strand-swapped trans homodimer and the so-called X-dimer, which is proposed to be a kinetic intermediate to forming the strand-swapped trans homodimer. However, previous studies have indicated that even once the trans strand-swapped dimer is formed, the complex is highly dynamic and the E-cadherin monomers may reorient relative to each other. Here, molecular dynamics simulations have been used to investigate the stability and conformational flexibility of the human E-cadherin trans strand-swapped dimer. In four independent, 100 ns simulations, the dimer moved away from the starting structure and converged to a previously unreported structure, which we call the Y-dimer. The Y-dimer was present for over 90% of the combined simulation time, suggesting that it represents a stable conformation of the E-cadherin dimer in solution. The Y-dimer conformation is stabilised by interactions present in both the trans strand-swapped dimer and X-dimer crystal structures, as well as additional interactions not found in any E-cadherin dimer crystal structures. The Y-dimer represents a previously unreported, stable conformation of the human E-cadherin trans strand-swapped dimer and suggests that the available crystal structures do not fully capture the conformations that the human E-cadherin trans homodimer adopts in solution.

  17. Characterization of Hepatitis C Virus Core Protein Dimerization by Atomic Force Microscopy. (United States)

    Li, Wenhui; Kou, Xiaolong; Xu, Jiachao; Zhou, Wei; Zhao, Rong; Zhang, Zhen; Fang, Xiaohong


    Dimerization of core protein is a crucial step in the formation of the hepatitis C virus (HCV) nucleocapsid, and inhibition of dimer formation is regarded as an attractive approach to design anti-HCV drugs. In this work, we developed the atomic force microscopy based single molecular force spectroscopy (AFM-SMFS) method for the characterization of core protein dimerization with the advantages of small amount of sample consumption and no need of labeling. Interaction force of the core protein with its antibody or aptamer was analyzed to investigate its stoichiometry and binding property. The two specific binding forces were detected due to the probing of dimeric and monomeric core protein, respectively. Moreover, the binding property of protein dimer was different from the monomer. Our work offers a new approach to study the dimerization of core protein, as well as other proteins, and to screen the HCV candidate inhibitors.

  18. Complex Relationship between Ligand Binding and Dimerization in the Epidermal Growth Factor Receptor

    Directory of Open Access Journals (Sweden)

    Nicholas J. Bessman


    Full Text Available The epidermal growth factor receptor (EGFR plays pivotal roles in development and is mutated or overexpressed in several cancers. Despite recent advances, the complex allosteric regulation of EGFR remains incompletely understood. Through efforts to understand why the negative cooperativity observed for intact EGFR is lost in studies of its isolated extracellular region (ECR, we uncovered unexpected relationships between ligand binding and receptor dimerization. The two processes appear to compete. Surprisingly, dimerization does not enhance ligand binding (although ligand binding promotes dimerization. We further show that simply forcing EGFR ECRs into preformed dimers without ligand yields ill-defined, heterogeneous structures. Finally, we demonstrate that extracellular EGFR-activating mutations in glioblastoma enhance ligand-binding affinity without directly promoting EGFR dimerization, suggesting that these oncogenic mutations alter the allosteric linkage between dimerization and ligand binding. Our findings have important implications for understanding how EGFR and its relatives are activated by specific ligands and pathological mutations.

  19. Cytotoxicity and radical intensity of eugenol, isoeugenol or related dimers. (United States)

    Atsumi, T; Fujisawa, S; Satoh, K; Sakagami, H; Iwakura, I; Ueha, T; Sugita, Y; Yokoe, I


    To investigate the possible link between radicals and cytotoxicity of eugenol-related compounds, dimer compounds were synthesized from eugenol (4-allyl-2-methoxyphenol) or isoeugenol (4-propenyl-2-methoxyphenol): bis-eugenol (3,3'-dimethoxy-5,5'-di-2-propenyl-1,1'-biphenyl-2,2'-diol); dehydrodiisoeugenol (2-(3-methoxy-4-hydroxyphenyl)-3-methyl-5-(1-propenyl)-7-methoxy-2,3- dihydrobenzofuran) and alpha-di-isoeugenol (r-l-ethyl-5-hydroxy-t-3-(4-hydroxy-3-methoxyphenyl)-6-methoxy-c-2- methylindane). Both the cytotoxic activity and the DNA synthesis inhibitory activity of these compounds against a salivary gland tumor cell line (HSG) and normal human gingival fibroblast (HGF) were decreased in the order of: dehydrodiisoeugenol, alpha-di-isoeugenol > isoeugenol > eugenol > bis-eugenol. Electron spin resonance (ESR) spectroscopy showed that dehydrodiisoeugenol, alpha-di-isoeugenol and eugenol, but not isoeugenol and bis-eugenol, produced phenoxyl radicals under alkaline condition (pH > 9.5). However, benzyl radicals were produced during the dimerization of isoeugenol to dehydrodiisoeugenol. The radical intensity of alpha-di- and dehydrodiisoeugenol appeared at relatively later incubation time than eugenol, suggesting that their phenoxyl radical was more stable than that of eugenol. Such a phenoxyl radical is produced by scavenging free radicals, during the inhibition of lipid peroxidation. Higher cytotoxic activity of isoeugenol dimers was thought to be induced by interaction with cell membranes via the lipophilic radical. The present study supports the notion that relative cytotoxicity of chemicals can be evaluated by measuring the radical intensity using ESR.

  20. Structure of the dimeric form of CTP synthase from Sulfolobus solfataricus

    DEFF Research Database (Denmark)

    Lauritsen, Iben; Willemoës, Martin; Jensen, Kaj Frank


    CTP synthase catalyzes the last committed step in de novo pyrimidine-nucleotide biosynthesis. Active CTP synthase is a tetrameric enzyme composed of a dimer of dimers. The tetramer is favoured in the presence of the substrate nucleotides ATP and UTP; when saturated with nucleotide, the tetramer c....... solfataricus CTP synthase according to a structural alignment with the E. coli enzyme all have large thermal parameters in the dimeric form. Furthermore, they are seen to undergo substantial movement upon tetramerization....

  1. Species A rotavirus NSP3 acquires its translation inhibitory function prior to stable dimer formation.

    Directory of Open Access Journals (Sweden)

    Hugo I Contreras-Treviño

    Full Text Available Species A rotavirus non-structural protein 3 (NSP3 is a translational regulator that inhibits or, under some conditions, enhances host cell translation. NSP3 binds to the translation initiation factor eIF4G1 and evicts poly-(A binding protein (PABP from eIF4G1, thus inhibiting translation of polyadenylated mRNAs, presumably by disrupting the effect of PABP bound to their 3'-ends. NSP3 has a long coiled-coil region involved in dimerization that includes a chaperone Hsp90-binding domain (HS90BD. We aimed to study the role in NSP3 dimerization of a segment of the coiled-coil region adjoining the HS90BD. We used a vaccinia virus system to express NSP3 with point mutations in conserved amino acids in the coiled-coil region and determined the effects of these mutations on translation by metabolic labeling of proteins as well as on accumulation of stable NSP3 dimers by non-dissociating Western blot, a method that separates stable NSP3 dimers from the monomer/dimerization intermediate forms of the protein. Four of five mutations reduced the total yield of NSP3 and the formation of stable dimers (W170A, K171E, R173E and R187E:K191E, whereas one mutation had the opposite effects (Y192A. Treatment with the proteasome inhibitor MG132 revealed that stable NSP3 dimers and monomers/dimerization intermediates are susceptible to proteasome degradation. Surprisingly, mutants severely impaired in the formation of stable dimers were still able to inhibit host cell translation, suggesting that NSP3 dimerization intermediates are functional. Our results demonstrate that rotavirus NSP3 acquires its function prior to stable dimer formation and remain as a proteasome target throughout dimerization.

  2. Dimerization of 3He in 3He-4He mixture films

    International Nuclear Information System (INIS)

    Bashkin, E.


    3 He atoms dissolved in superfluid 4 He may form dimers ( 3 He) 2 in two-dimensional geometries. Dimer formation is studied in films of dilute 3 He- 4 He mixture. After designing a schematic 3 He- 3 He interaction potential, the dimer binding energy is calculated for various substrates. It is shown that 3 He impurity states localized near the substrate give rise to the highest magnitudes of the binding energy. (author). 32 refs., 6 figs.,; 1 tab

  3. Laccase-mediated dimerization of the flavonolignan silybin

    Czech Academy of Sciences Publication Activity Database

    Gažák, Radek; Sedmera, Petr; Marzorati, M.; Riva, S.; Křen, Vladimír


    Roč. 50, 2-4 (2008), s. 87-92 ISSN 1381-1177 R&D Projects: GA AV ČR KJB400200701; GA MŠk OC D25.001; GA MŠk(CZ) LC06010; GA MŠk OC 170; GA MŠk ME 922 Grant - others:CZ(CZ) Bilateral Czech-Italian inter-academic projec Institutional research plan: CEZ:AV0Z50200510 Keywords : silybin * silymarin * dimer formation Subject RIV: EE - Microbiology, Virology Impact factor: 2.015, year: 2008

  4. Dimerization of Carboxylic Acids: An Equation of State Approach

    DEFF Research Database (Denmark)

    Tsivintzelis, Ioannis; Kontogeorgis, Georgios; Panayiotou, Costas


    The association term of the nonrandom hydrogen bonding theory, which is an equation of state model, is extended to describe the dimerization of carboxylic acids in binary mixtures with inert solvents and in systems of two different acids. Subsequently, the model is applied to describe the excess....... Consequently, the observed endothermic dissolution process is mainly attributed to the hindering of polar interactions. Furthermore, upon mixing of two carboxylic acids, the rearrangement of hydrogen bonds due to the formation of cross associating species results in an insignificant contribution to the heats...

  5. Bethe Ansatz Solutions of the Bose-Hubbard Dimer

    Directory of Open Access Journals (Sweden)

    Jon Links


    Full Text Available The Bose-Hubbard dimer Hamiltonian is a simple yet effective model for describing tunneling phenomena of Bose-Einstein condensates. One of the significant mathematical properties of the model is that it can be exactly solved by Bethe ansatz methods. Here we review the known exact solutions, highlighting the contributions of V.B. Kuznetsov to this field. Two of the exact solutions arise in the context of the Quantum Inverse Scattering Method, while the third solution uses a differential operator realisation of the su(2 Lie algebra.

  6. Antimicrobial Oligophenalenone Dimers from the Soil Fungus Talaromyces stipitatus. (United States)

    Zang, Yi; Genta-Jouve, Grégory; Escargueil, Alexandre E; Larsen, Annette K; Guedon, Laura; Nay, Bastien; Prado, Soizic


    New polyketide-derived oligophenalenone dimers, 9a-epi-bacillisporin E (1) and bacillisporins F-H (2-5), along with the known bacillisporin A (6), were isolated from the fungus Talaromyces stipitatus. Their structures and absolute configurations were determined on the basis of spectroscopic analyses, electronic circular dichroism, and GIAO NMR shift calculation followed by DP4 analysis. The antimicrobial activity of these compounds was evaluated against a panel of human pathogenic bacteria. Among them, bacillisporin H (5) exhibited antimicrobial activity together with modest cytotoxicity against HeLa cells.

  7. A Facile Method to In-Situ Synthesize Porous Ni2GeO4 Nano-Sheets on Nickel Foam as Advanced Anode Electrodes for Li-Ion Batteries

    Directory of Open Access Journals (Sweden)

    Delong Ma


    Full Text Available A strategy for growth of porous Ni2GeO4 nanosheets on conductive nickel (Ni foam with robust adhesion as a high-performance electrode for Li-ion batteries is proposed and realized, through a facile two-step method. It involves the low temperature hydro-thermal synthesis of bimetallic (Ni, Ge hydroxide nanosheets precursor on Ni foam substrates and subsequent thermal transformation to porous Ni2GeO4 nanosheets. The as-prepared Ni2GeO4 nanosheets possess many interparticle mesopores with a size range from 5 to 15 nm. The hierarchical structure of porous Ni2GeO4 nanosheets supported by Ni foam promises fast electron and ion transport, large electroactive surface area, and excellent structural stability. The efficacy of the specially designed structure is demonstrated by the superior electrochemical performance of the generated Ni2GeO4 nanosheets including a high capacity of 1.8 mA·h·cm−2 at a current density of 50 μA·cm−2, good cycle stability, and high power capability at room temperature. Because of simple conditions, this fabrication strategy may be easily extended to other mixed metal oxides (MxGeOy.

  8. Radiation-induced tetramer-to-dimer transition of Escherichia coli lactose repressor

    International Nuclear Information System (INIS)

    Goffinont, S.; Davidkova, M.; Spotheim-Maurizot, M.


    The wild type lactose repressor of Escherichia coli is a tetrameric protein formed by two identical dimers. They are associated via a C-terminal 4-helix bundle (called tetramerization domain) whose stability is ensured by the interaction of leucine zipper motifs. Upon in vitro γ-irradiation the repressor losses its ability to bind the operator DNA sequence due to damage of its DNA-binding domains. Using an engineered dimeric repressor for comparison, we show here that irradiation induces also the change of repressor oligomerisation state from tetramer to dimer. The splitting of the tetramer into dimers can result from the oxidation of the leucine residues of the tetramerization domain.

  9. Modified field enhancement and extinction by plasmonic nanowire dimers due to nonlocal response

    DEFF Research Database (Denmark)

    Toscano, Giuseppe; Raza, Søren; Jauho, Antti-Pekka


    it in a wide frequency range against analytical results for the extinction cross section of a cylindrical plasmonic nanowire. Our main results concern more complex geometries, namely cylindrical and bow-tie nanowire dimers that can strongly enhance optical fields. For both types of dimers we find that nonlocal...... response can strongly affect both the field enhancement in between the dimers and their respective extinction cross sections. In particular, we give examples of blueshifted maximal field enhancements near hybridized plasmonic dimer resonances that are still large but nearly two times smaller than...

  10. Dimer and String Formation during Low Temperature Silicon Deposition on Si(100)

    DEFF Research Database (Denmark)

    Smith, A. P.; Jonsson, Hannes


    We present theoretical results based on density functional theory and kinetic Monte Carlo simulations of silicon deposition and address observations made in recently reported low temperature scanning tunneling microscopy studies. A mechanism is presented which explains dimer formation on top...... of the substrate's dimer rows at 160 K and up to room temperature, while between-row dimers and longer strings of adatoms (''diluted dimer rows'') form at higher temperature. A crossover occurs at around room temperature between two different mechanisms for adatom diffusion in our model....

  11. Observation of an aromatic radical anion dimer: (C10F8)2 sm-bullet -

    International Nuclear Information System (INIS)

    Werst, D.W.


    Radical cation dimers are observed for many alkenes and aromatic hydrocarbons as products of the reaction between monomer radical cation and neutral molecule. In most cases, the dimer radical anions, formed via reaction of the monomer radical anion with a neutral molecule, have not been observed. Here we report the observation of the dimer radical anion of octafluoronaphthalene, formed by reaction of C 10 F 8 ·- with the neutral parent molecules in nonpolar solvents following pulse radiolysis. Both monomer and dimer ions have been characterized by EPR spectra obtained by the time-resolved fluorescence-detected magnetic resonance

  12. Solid-phase synthesis of 2{sup '}-O-methoxyethyl oligonucleotides using dimeric phosphoramidate blocks

    Energy Technology Data Exchange (ETDEWEB)

    Yu, Gi Weon; Kang, Yong Han [Dept. of Applied Chemistry, Hanyang University, Ansan (Korea, Republic of)


    This research focused on the method of using dimeric phosphoramidite blocks to synthesize oligonucleotides for development as oligonucleotide drugs. A 16-mer oligonucleotide with the randomly selected sequence of C*C*T*C*G*C *T*C*T*C*G*C*C* C*G*C was synthesized using CC, GC, and TC dimers, a combination of monomers and dimers, or only monomers as building blocks. Using dimer blocks in this synthetic method provided a significant decrease in critical impurities that had similar properties to the main product, which was confirmed by LC-MS and HPLC analysis.

  13. Experimental Observation of Strongly Bound Dimers of Sulfuric Acid: Application to Nucleation in the Atmosphere

    DEFF Research Database (Denmark)

    Petaja, Tuukka; Sipila, Mikko; Paasonen, Pauli


    Sulfuric acid is a key compound in atmospheric nucleation. Here we report on the observation of a close-to-collision-limited sulfuric acid dimer formation in atmospherically relevant laboratory conditions in the absence of measurable quantities of ammonia or organics. The observed dimer formation...... compound(s) with (a) concentration(s) high enough to prevent the dimer evaporation. Such a stabilizing compound should be abundant enough in any natural environment and would therefore not limit the formation of sulfuric acid dimers in the atmosphere....

  14. Evaluation of rolling contact fatigue of induction heated 13Cr-2Ni-2Mo Stainless steel bar with Si3N4-ball (United States)

    Yadoiwa, Ariyasu; Mizobe, Koshiro; Kida, Katsuyuki


    13Cr % martensitic stainless steels were used in various industry, because they have excellent corrosion resistance and high hardness among other stainless steels. They are also expected as a bearing material, however, the research on rolling contact fatigue (RCF) is not enough. In this study, 13Cr-2Ni-2Mo stainless steels were quenched by induction heating and their RCF lives were evaluated. A Si3N4-ball was used in order to apply higher stress (Pmax = 5.6 GPa) than our previous tests (Pmax=5.3 GPa), in a single-ball RCF testing machine. It was found that the basic life (L10) was 2.20×106 cycles and Median life (L50) was 6.04×106 cycles. In addition, Weibull modulus became higher than the previous tests.

  15. Low-temperature magnetothermal transport investigation of a Ni-based superconductor BaNi2As2: evidence for fully gapped superconductivity. (United States)

    Kurita, N; Ronning, F; Tokiwa, Y; Bauer, E D; Subedi, A; Singh, D J; Thompson, J D; Movshovich, R


    We have performed low-temperature specific heat and thermal conductivity measurements of the Ni-based superconductor BaNi2As2 (T{c}=0.7 K) in a magnetic field. In a zero field, thermal conductivity shows T-linear behavior in the normal state and exhibits a BCS-like exponential decrease below T{c}. The field dependence of the residual thermal conductivity extrapolated to zero temperature is indicative of a fully gapped superconductor. This conclusion is supported by the analysis of the specific heat data, which are well fit by the BCS temperature dependence from T{c} down to the lowest temperature of 0.1 K.

  16. Adsorption of Cs+, Ni2+ and lanthanides onto a kaolinite and Na-montmorillonite up to 1500C: an experimental and modeling study

    International Nuclear Information System (INIS)

    Tertre, E.


    The motivation for this study is to assess the temperature effect on the clay minerals sorption properties. Sorption and desorption of Cs + , Ni 2+ et Ln 3+ onto a montmorillonite and a kaolinite were performed by batch experiments between 25 and 150 C, and in different pH and ionic strengths conditions. Sorption enthalpies varying between 0 and 80 kJ/mol were then calculated. For europium, surface spectroscopic analyses confirmed that the mechanism involved is adsorption, including at 150 C. Moreover, this method allowed us to obtain qualitatively the different adsorption equilibrium occurring during the reaction. An acid/base study of the clay surfaces was performed in order to assess the temperature effect on the surface charge of these minerals. Then, a surface complexation model including edge sites and structural sites was proposed to interpret the acid/base data and the europium sorption data. (author)

  17. High-resolution resonant magnetic x-ray scattering on TbNi2B2C: Determination of the modulation wave vector in the orthorhombic phase

    International Nuclear Information System (INIS)

    Song, C.; Wermeille, D.; Goldman, A. I.; Canfield, P. C.; Rhee, J. Y.; Harmon, B. N.


    Resonant magnetic x-ray scattering measurements have been performed on a single crystal of TbNi 2 B 2 C to uniquely determine the modulation wave vector in the low-temperature orthorhombic phase. Below the transition temperature of 14.4(±0.1)K, two magnetic satellite peaks develop, centered on (h00) orth charge reflections. Our study shows that the longitudinal modulation of the magnetic moment is along the longer basal plane axes of the orthorhombic phase. Power law fits to the temperature dependence of the structural distortion, a/b-1, and the magnetic scattering intensity result in the same exponent, β, and transition temperature evidencing explicitly that the structural phase transition is magneto-elastic in origin

  18. First-principles investigations of the five-layer modulated martensitic structure in Ni2Mn(AlxGa1-x) alloys

    International Nuclear Information System (INIS)

    Luo, H.B.; Li, C.M.; Hu, Q.M.; Kulkova, S.E.; Johansson, B.; Vitos, L.; Yang, R.


    In this paper, the five-layer modulated (5M) martensitic structures of Ni 2 Mn(Al x Ga 1-x ), with x = 0, 0.1 and 0.2, are investigated by the use of the exact muffin-tin orbital method in combination with the coherent potential approximation. The 5M martensite is modeled by varying c/a (shear) and wave-like displacements of the atoms on (1 1 0) plane (shuffle) scaled by η according to Martynov and Kokorin (J. Phys. III 2, 739 (1992)). For Ni 2 MnGa, we obtain 5M martensite with equilibrium c/a of 0.92 and η of 0.08, in reasonable agreement with the experiment results (0.94 and 0.06, respectively). c/a and η are linearly coupled to each other. Al-doping increases c/a and decreases η, but the linear c/a ∼ η coupling remains. Comparing the total energies of the 5M martensite and L2 1 austenite, we find that the martensite is more stable than the austenite. Al-doping increases the relative stability of the austenite and finally becomes energetically degenerated with the 5M martensite at an Al atomic fraction (x) of about 0.26. The relative phase stability is analyzed based on the calculated density of states. The calculated total magnetic moments μ 0 as a function of c/a exhibit a maximum around the equilibrium c/a. Al-doping reduces μ 0 .

  19. How Does Thymine DNA Survive Ultrafast Dimerization Damage?

    Directory of Open Access Journals (Sweden)

    Hongjuan Wang


    Full Text Available The photodimerization reaction between the two adjacent thymine bases within a single strand has been the subject of numerous studies due to its potential to induce DNA mutagenesis and possible tumorigenesis in human skin cells. It is well established that the cycloaddition photoreaction takes place on a picosecond time scale along barrierless or low barrier singlet/triplet pathways. However, the observed dimerization quantum yield in different thymine multimer is considerable lower than might be expected. A reasonable explanation is required to understand why thymine in DNA is able to survive ultrafast dimerization damage. In this work, accurate quantum calculations based on the combined CASPT2//CASSCF/AMBER method were conducted to map the excited state relaxation pathways of the thymine monomer in aqueous solution and of the thymine oligomer in DNA. A monomer-like decay pathway, induced by the twisting of the methyl group, is found to provide a bypass channel to ensure the photostability of thymine in single-stranded oligomers. This fast relaxation path is regulated by the conical intersection between the bright SCT(1ππ* state with the intra-base charge transfer character and the ground state to remove the excess excitation energy, thereby achieving the ground-state recovery with high efficiency.

  20. Identification of a dimeric KDG aldolase from Agrobacterium tumefaciens. (United States)

    Soares da Costa, Tatiana P; Patel, Madhvi; Desbois, Sebastien; Gupta, Ruchi; Faou, Pierre; Perugini, Matthew A


    Agrobacterium tumefaciens is a Gram-negative bacterium and causative agent of Crown Gall disease that infects a variety of economically important plants. The annotated A. tumefaciens genome contains 10 putative dapA genes, which code for dihydrodipicolinate synthase (DHDPS). However, we have recently demonstrated that only one of these genes (dapA7) encodes a functional DHDPS. The function of the other nine putative dapA genes is yet to be determined. Here, we demonstrate using bioinformatics that the product of the dapA5 gene (DapA5) possesses all the catalytic residues canonical to 2-keto-3-deoxygluconate (KDG) aldolase, which is a class I aldolase involved in glucose metabolism. We therefore expressed, purified, and characterized recombinant DapA5 using mass spectrometry, circular dichroism spectroscopy, analytical ultracentrifugation, and enzyme kinetics. The results show that DapA5 (1) adopts an α/β structure consistent with the TIM-barrel fold of KDG aldolases, (2) possesses KDG aldolase enzyme activity, and (3) exists as a tight dimer in solution. This study shows for the first time that dapA5 from A. tumefaciens encodes a functional dimeric KDG aldolase. © 2017 Wiley Periodicals, Inc.

  1. Gossypolhemiquinone, a dimeric sesquiterpenoid identified in cotton (Gossypium). (United States)

    Stipanovic, Robert; Puckhaber, Lorraine; Frelichowski, James; Esquivel, Jesus; Westbrook, John; O'Neil, Mike; Bell, Alois; Dowd, Michael; Hake, Kater; Duke, Sara


    The report that the cotton leaf perforator, Bucculatrix thurberiella, is one of the few insect herbivores to attack Gossypium thurberi prompted an investigation of the terpenoids present in the leaves of this wild species of cotton. Members of Gossypium produce subepidermal pigment glands in their leaves that contain the dimeric sesquiterpenoid gossypol as well as other biosynthetically related terpenoids. In addition to gossypol, a previously unknown dimeric sesquiterpenoid, gossypolhemiquinone (GHQ), was identified in trace amounts in G. thurberi, a member of the D genome. Other members of the D genome of Gossypium were subsequently found to contain this compound, but GHQ was not detected in commercial cotton cultivars. When fed to Helicoverpa zea in an artificial diet, GHQ delayed days-to-pupation, reduced pupal weights, and survival to adulthood to a lesser or equal extent than gossypol in comparison to the control diet. However, GHQ had a synergistic effect on survival and days-to-pupation when combined with gossypol at the highest dosage tested (0.18%; 15.5:84.5 GHQ:gossypol). Because gossypol exhibits anti-cancer activity, GHQ was also evaluated for its anti-cancer activity against the National Cancer Institute's 60-Human Tumor Cell Line Screen. Significant inhibitory activity against most of these cell lines was not observed, but the results may offer some promise against leukemia cancer cell lines. Published by Elsevier Ltd.

  2. Structures of DNA containing psoralen crosslink and thymine dimer

    International Nuclear Information System (INIS)

    Kim, S.H.; Pearlman, D.A.; Holbrook, S.R.; Pirkle, D.


    UV irradiation by itself or in conjunction with other chemicals can cause covalent damages to DNA in living cells. To overcome the detrimental effect of DNA damage, cells developed a repair mechanism by which damaged DNA is repaired. In the absence of such repair, cell malfunction or cell death can occur. Two most studied radiation-induced DNA damage are thymine dimer formation by UV irradiation and psoralen crosslink by combination of psoralens and UV: In the former, two adjacent thymine bases on a strand of DNA are fused by forming cyclobutane ring, and in the latter, one pyrimidine on one DNA strand is crosslinked to another pyrimidine on the other strand via a psoralen. The authors' objective is to deduce the structure of DNA segment which contains a psoralen crosslink or a thymine dimer using the combination of results of X-ray crystallographic studies, molecular model building, and energy minimization. These structural features may be important for understanding the biological effects of such damages and for the recognition by the repair enzymes

  3. Dimerization of a Viral SET Protein Endows its Function

    Energy Technology Data Exchange (ETDEWEB)

    H Wei; M Zhou


    Histone modifications are regarded as the most indispensible phenomena in epigenetics. Of these modifications, lysine methylation is of the greatest complexity and importance as site- and state-specific lysine methylation exerts a plethora of effects on chromatin structure and gene transcription. Notably, paramecium bursaria chlorella viruses encode a conserved SET domain methyltransferase, termed vSET, that functions to suppress host transcription by methylating histone H3 at lysine 27 (H3K27), a mark for eukaryotic gene silencing. Unlike mammalian lysine methyltransferases (KMTs), vSET functions only as a dimer, but the underlying mechanism has remained elusive. In this study, we demonstrate that dimeric vSET operates with negative cooperativity between the two active sites and engages in H3K27 methylation one site at a time. New atomic structures of vSET in the free form and a ternary complex with S-adenosyl homocysteine and a histone H3 peptide and biochemical analyses reveal the molecular origin for the negative cooperativity and explain the substrate specificity of H3K27 methyltransferases. Our study suggests a 'walking' mechanism, by which vSET acts all by itself to globally methylate host H3K27, which is accomplished by the mammalian EZH2 KMT only in the context of the Polycomb repressive complex.

  4. Proteolysis of truncated hemolysin A yields a stable dimerization interface

    Energy Technology Data Exchange (ETDEWEB)

    Novak, Walter R.P.; Bhattacharyya, Basudeb; Grilley, Daniel P.; Weaver, Todd M. (Wabash); (UW)


    Wild-type and variant forms of HpmA265 (truncated hemolysin A) fromProteus mirabilisreveal a right-handed, parallel β-helix capped and flanked by segments of antiparallel β-strands. The low-salt crystal structures form a dimeric structureviathe implementation of on-edge main-chain hydrogen bonds donated by residues 243–263 of adjacent monomers. Surprisingly, in the high-salt structures of two variants, Y134A and Q125A-Y134A, a new dimeric interface is formedviamain-chain hydrogen bonds donated by residues 203–215 of adjacent monomers, and a previously unobserved tetramer is formed. In addition, an eight-stranded antiparallel β-sheet is formed from the flap regions of crystallographically related monomers in the high-salt structures. This new interface is possible owing to additional proteolysis of these variants after Tyr240. The interface formed in the high-salt crystal forms of hemolysin A variants may mimic the on-edge β-strand positioning used in template-assisted hemolytic activity.

  5. Function of E-protein dimers expressed in catfish lymphocytes (United States)

    Hikima, Jun-ichi; Lennard Richard, Mara L.; Wilson, Melanie R.; Miller, Norman W.; Warr, Gregory W.


    E-proteins are essential class I bHLH transcription factors that play a role in lymphocyte development. In catfish lymphocytes the predominant E-proteins expressed are CFEB (a homologue of HEB) and E2A1, which both strongly drive transcription. In this study the role of homodimerization versus heterodimerization in the function of these catfish E-proteins was addressed through the use of expression constructs encoding forced dimers. Constructs expressing homo- and heterodimers were transfected into catfish B cells and shown to drive transcription from the catfish IGH enhancer. Expression from an artificial promoter containing a trimer of μE5 motifs clearly demonstrated that the homodimer of E2A1 drove transcription more strongly (by a factor of 10–25) than the CFEB homodimer in catfish B and T cells, while the heterodimer showed intermediate levels of transcriptional activation. Both CFEB1 and E2A1 proteins dimerized in vitro, and the heterodimer CFEB1-E2A1 was shown to bind the canonical μE5 motif. PMID:17870169

  6. The (6-4) Dimeric Lesion as a DNA Photosensitizer. (United States)

    Vendrell-Criado, Victoria; Rodríguez-Muñiz, Gemma M; Lhiaubet-Vallet, Virginie; Cuquerella, M Consuelo; Miranda, Miguel A


    Based on our previous investigations into the photophysical properties of the 5-methyl-2-pyrimidone (Pyo) chromophore, we now extend our studies to the photobehavior of the dimeric (6-4) thymine photoproducts (6-4 PP) to evaluate their capability to act as instrinsic DNA photosensitizers. The lesion presents significant absorption in the UVB/UVA region, weak fluorescence emission, a singlet-excited-state energy of approximately 351 kJ mol(-1) , and a triplet-excited-state energy of 297 kJ mol(-1) . Its triplet transient absorption has a maximum at 420-440 nm, a lifetime of around 7 μs, and a high formation quantum yield, ΦISC =0.86. This species is efficiently quenched by thymidine. Its DNA photosensitizing properties are demonstrated by a series of experiments run on a pBR322 plasmid. The lesion photoinduces both single-strand breaks and the formation of cyclobutane thymine dimers. Altogether, these results show that, the substitution of the pyrimidone ring at C4 by a 5-hydroxy-5,6-dihydrothymine does not cancel out the photosensitization properties of the chromophore. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Intermolecular Coulombic Decay (ICD) Occuring in Triatomic Molecular Dimer (United States)

    Iskandar, Wael; Gatton, Averell; Gaire, Bishwanath; Champenois, Elio; Larsen, Kirk; Shivaram, Niranjan; Moradmand, Ali; Severt, Travis; Williams, Joshua; Slaughter, Daniel; Weber, Thorsten


    For over two decades, the production of ICD process has been extensively investigated theoretically and experimentally in different systems bounded by a week force (ex. van-der-Waals or Hydrogen force). Furthermore, the ICD process has been demonstrated a strong implication in biological system (DNA damage and DNA repair mechanism) because of the production of genotoxic low energy electrons during the decay cascade. Studying large complex system such as triatomic molecular dimer may be helpful for further exploration of ``Auger electron driven cancer therapy''. The present experiment investigates the dissociation dynamics happened in collision between a photons and CO2 dimer. We will focus more specifically on the CO2++CO2+ fragmentation channel and the detection in coincidence of the two ionic fragments and the two electrons will be done using a COld Target Recoil Ion Momentum Spectroscopy (COLTRIMS). The measurements of the Kinetic Energy Release of the two fragments and the relative angular distribution of the electrons in the molecular frame reveal that the ICD is the only mechanism responsible for the production of this fragmentation channel.

  8. Biocompatible Amphiphilic Hydrogel-Solid Dimer Particles as Colloidal Surfactants. (United States)

    Chen, Dong; Amstad, Esther; Zhao, Chun-Xia; Cai, Liheng; Fan, Jing; Chen, Qiushui; Hai, Mingtan; Koehler, Stephan; Zhang, Huidan; Liang, Fuxin; Yang, Zhenzhong; Weitz, David A


    Emulsions of two immiscible liquids can slowly coalesce over time when stabilized by surfactant molecules. Pickering emulsions stabilized by colloidal particles can be much more stable. Here, we fabricate biocompatible amphiphilic dimer particles using a hydrogel, a strongly hydrophilic material, and achieve large contrast in the wetting properties of the two bulbs, resulting in enhanced stabilization of emulsions. We generate monodisperse single emulsions of alginate and shellac solution in oil using a flow-focusing microfluidics device. Shellac precipitates from water and forms a solid bulb at the periphery of the droplet when the emulsion is exposed to acid. Molecular interactions result in amphiphilic dimer particles that consist of two joined bulbs: one hydrogel bulb of alginate in water and the other hydrophobic bulb of shellac. Alginate in the hydrogel compartment can be cross-linked using calcium cations to obtain stable particles. Analogous to surfactant molecules at the interface, the resultant amphiphilic particles stand at the water/oil interface with the hydrogel bulb submerged in water and the hydrophobic bulb in oil and are thus able to stabilize both water-in-oil and oil-in-water emulsions, making these amphiphilic hydrogel-solid particles ideal colloidal surfactants for various applications.

  9. Cell-permeant and photocleavable chemical inducer of dimerization. (United States)

    Zimmermann, Mirjam; Cal, Ruben; Janett, Elia; Hoffmann, Viktor; Bochet, Christian G; Constable, Edwin; Beaufils, Florent; Wymann, Matthias P


    Chemical inducers of dimerization (CIDs) have been developed to orchestrate protein dimerization and translocation. Here we present a novel photocleavable HaloTag- and SNAP-tag-reactive CID (MeNV-HaXS) with excellent selectivity and intracellular reactivity. Excitation at 360 nm cleaves the methyl-6-nitroveratryl core of MeNV-HaXS. MeNV-HaXS covalently links HaloTag- and SNAP-tag fusion proteins, and enables targeting of selected membranes and intracellular organelles. MeNV-HaXS-mediated translocation has been validated for plasma membrane, late endosomes, lysosomes, Golgi, mitochondria, and the actin cytoskeleton. Photocleavage of MeNV-HaXS liberates target proteins and provides access to optical manipulation of protein relocation with high spatiotemporal and subcellular precision. MeNV-HaXS supports kinetic studies of protein dynamics and the manipulation of subcellular enzyme activities, which is exemplified for Golgi-targeted cargo and the assessment of nuclear import kinetics. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Electron transfer reactions induced by the triplet state of thiacarbocyanine dimers

    International Nuclear Information System (INIS)

    Chibisov, Alexander K.; Slavnova, Tatyana D.; Goerner, Helmut


    The photoinduced electron transfer between either cationic 5,5 ' -dichloro-3,3 ' ,9-triethylthiacarbocyanine (1) or a structurally similar anionic dye (2) and appropriate donors, e.g. ascorbic acid, and acceptors, e.g. methyl viologen, was studied by ns-laser photolysis. In aqueous solution the dyes in the ground state are present as an equilibrated mixture of dimers and monomers, whereas the triplet state is mainly populated from dimers. The triplet states of both dimers and monomers are quenched by electron donors or acceptors and the rate constant for quenching is generally 2-4 times higher for dimers than for monomers. The kinetics of triplet decay and radical formation and decay as a result of primary and secondary electron transfer were analyzed. While the one-electron reduced dimer decays due to back reactions, the one-electron oxidized dimer rapidly dissociates into the monomer and the monomeric dye radical. For the dimeric dye/donor/acceptor systems the primary photoinduced electron transfer occurs either from the donor or to the acceptor yielding the dimeric dye radicals. The one-electron reduced dimer can be efficiently oxidized by acceptors, e.g. the rate constant for reaction of the dimeric dye radical of 1 with methyl viologen (photoreductive pathway of sensitization) is 1.6x10 9 M -1 s -1 . The photooxidative pathway of sensitization is more complicated; after dissociation of the dimeric dye radical, the monomeric dye radical is reduced in a secondary electron transfer from ascorbic acid, e.g. with a rate constant of 1x10 9 M -1 s -1 for 2, yielding the monomer. On increasing the donor concentration the photooxidative pathway of sensitization is switched to a photoreductive one

  11. Anti-parallel dimer and tetramer formation of propylene carbonate

    Directory of Open Access Journals (Sweden)

    Ayana Tagawa


    Full Text Available Raman scattering and infrared (IR absorption spectra of enantiopure (R-propylene carbonate ((RPC and racemic propylene carbonate (PC were recorded at room temperature, 25 °C, in benzene (Bz solution and in the pure liquid state to investigate the presence of dimers and other higher order intermolecular associations. (RPC and PC both demonstrated a strong C=O stretching vibrational band. The band exhibited changes in its shape and resonance wavenumber highly dependent on the concentrations of PCs, whereas a difference between the chirality of (RPC and PC had little influence. In an extremely dilute condition, doubly split bands were observed at 1807 and 1820 cm-1 in both Raman and IR spectra, which are assigned to the characteristic bands of isolated monomeric PCs. An additional band appeared at 1795 cm-1 in a dilute to concentrated regime, and its magnitude strengthened with increasing concentrations accompanied with slight increasing in the magnitude of 1807 cm-1 band in Raman spectra, while an increase in the magnitude of 1807 cm-1 band was clearly greater than that of 1795 cm-1 band in IR spectra. The spectrum changes at 1795 and 1807 cm-1 were attributed to characteristics of anti-parallel dimer formation of PCs caused by strong dipole-dipole interactions between C=O groups. Moreover, another additional signal was clearly observed at 1780-1790 cm-1 in a concentrated regime, and became the primary signal in the pure liquid state with slight increasing in the intensity of 1795 cm-1 band in Raman spectra. On the other hand, in IR spectra the observed increasing of 1780-1790 cm-1 band was much less than that of 1795 cm-1 band. These newly found spectrum changes in the concentrated regime are attributed to the formation of anti-parallel tetramers of PCs based on the characteristics of band selection rule found in Raman and IR spectra. Equilibrium constants for the anti-parallel dimer (KD and tetramer formation (KT of PCs in Bz solution and in

  12. Anti-parallel dimer and tetramer formation of propylene carbonate (United States)

    Tagawa, Ayana; Numata, Tomoko; Shikata, Toshiyuki


    Raman scattering and infrared (IR) absorption spectra of enantiopure (R)-propylene carbonate ((R)PC) and racemic propylene carbonate (PC) were recorded at room temperature, 25 °C, in benzene (Bz) solution and in the pure liquid state to investigate the presence of dimers and other higher order intermolecular associations. (R)PC and PC both demonstrated a strong C=O stretching vibrational band. The band exhibited changes in its shape and resonance wavenumber highly dependent on the concentrations of PCs, whereas a difference between the chirality of (R)PC and PC had little influence. In an extremely dilute condition, doubly split bands were observed at 1807 and 1820 cm-1 in both Raman and IR spectra, which are assigned to the characteristic bands of isolated monomeric PCs. An additional band appeared at 1795 cm-1 in a dilute to concentrated regime, and its magnitude strengthened with increasing concentrations accompanied with slight increasing in the magnitude of 1807 cm-1 band in Raman spectra, while an increase in the magnitude of 1807 cm-1 band was clearly greater than that of 1795 cm-1 band in IR spectra. The spectrum changes at 1795 and 1807 cm-1 were attributed to characteristics of anti-parallel dimer formation of PCs caused by strong dipole-dipole interactions between C=O groups. Moreover, another additional signal was clearly observed at 1780-1790 cm-1 in a concentrated regime, and became the primary signal in the pure liquid state with slight increasing in the intensity of 1795 cm-1 band in Raman spectra. On the other hand, in IR spectra the observed increasing of 1780-1790 cm-1 band was much less than that of 1795 cm-1 band. These newly found spectrum changes in the concentrated regime are attributed to the formation of anti-parallel tetramers of PCs based on the characteristics of band selection rule found in Raman and IR spectra. Equilibrium constants for the anti-parallel dimer (KD) and tetramer formation (KT) of PCs in Bz solution and in the pure

  13. Study of structural stability and damaging effect on membrane for four Aβ42 dimers.

    Directory of Open Access Journals (Sweden)

    Wei Feng

    Full Text Available Increasing evidence shows that Aβ oligomers are key pathogenic molecules in Alzheimer's disease. Among Aβ oligomers, dimer is the smallest aggregate and toxic unit. Therefore, understanding its structural and dynamic properties is quite useful to prevent the formation and toxicity of the Aβ oligomers. In this study, we performed molecular dynamic simulations on four Aβ42 dimers, 2NCb, CNNC, NCNC and NCCN, within the hydrated DPPC membrane. Four Aβ42 dimers differ in the arrangements of two Aβ42 peptides. This study aims to investigate the impact of aggregation pattern of two Aβ peptides on the structural stability of the Aβ42 dimer and its disruption to the biological membrane. The MD results demonstrate that the NCCN, CNNC and NCNC have the larger structural fluctuation at the N-terminus of Aβ42 peptide, where the β-strand structure converts into the coil structure. The loss of the N-terminal β-strand further impairs the aggregate ability of Aβ42 dimer. In addition, inserting Aβ42 dimer into the membrane can considerably decrease the average APL of DPPC membrane. Moreover this decrease effect is largely dependent on the distance to the location of Aβ42 dimer and its secondary structure forms. Based on the results, the 2NCb is considered as a stable dimeric unit for aggregating the larger Aβ42 oligomer, and has a potent ability to disrupt the membrane.

  14. Dimerization inhibits the activity of receptor-like protein-tyrosine phosphatase-alpha

    DEFF Research Database (Denmark)

    Jiang, G; den Hertog, J; Su, J


    that dimerization can negatively regulate activity, through the interaction of an inhibitory 'wedge' on one monomer with the catalytic cleft of domain 1 in the other monomer. Here we show that dimerization inhibits the activity of a full-length RPTP in vivo. We generated stable disulphide-bonded full...

  15. The intrinsically disordered RNR inhibitor Sml1 is a dynamic dimer

    DEFF Research Database (Denmark)

    Danielsson, Jens; Liljedahl, Leena; Ba´ra´ny-Wallje, Elsa


    . Sml1 belongs to the class of intrinsically disordered proteins with a high degree of dynamics and very little stable structure. Earlier suggestions for a dimeric structure of Sml1 were confirmed, and from translation diffusion NMR measurements, a dimerization dissociation constant of 0.1 mM at 4...... natively disordered proteins....

  16. Synchronized oscillations of dimers in biphasic charged fd-virus suspensions. (United States)

    Kang, K; Piao, S H; Choi, H J


    Micron-sized colloidal spheres that are dispersed in an isotropic-nematic biphasic host suspension of charged rods (fd-virus particles) are shown to spontaneously form dimers, which exhibit a synchronized oscillatory motion. Dimer formation is not observed in the monophase of isotropic and nematic suspensions. The synchronized oscillations of dimers are connected to the inhomogeneous state of the host suspension of charged rods (fd viruses) where nematic domains are in coexistence with isotropic regions. The synchronization of oscillations occurs in bulk states, in the absence of an external field. With a low field strength of an applied electric field, the synchronization is rather reduced, but it recovers again when the field is turned off. In this Rapid Communication, we report this observation as an example of the strange attractor, occurring in the mixture of PS (polystyrene) dimers in an isotropic-nematic coexistence biphasic fd-virus network. Furthermore, we highlight that the synchronization of PS-dimer oscillations is the result of a global bifurcation diagram, driven by a delicate balance between the short-attractive "twisted" interaction of PS dimers and long-ranged electrostatic repulsive interactions of charged fd rods. The interest is then in the local enhancement of "twist-nematic" elasticity in reorientation of the dimer oscillations. An analysis of image-time correlations is provided with the data movies and Fourier transforms of averaged orientations for the synchronized oscillations of dimers in the biphasic I-N coexistence concentration of charged fd-virus suspensions.

  17. Genetic predictors of fibrin D-dimer levels in healthy adults

    NARCIS (Netherlands)

    N.L. Smith (Nicholas); J.E. Huffman (Jennifer E.); D.P. Strachan (David); J. Huang (Jian); A. Dehghan (Abbas); S. Trompet (Stella); L.M. Lopez (Lorna M.); S.Y. Shin (So Youn); J. Baumert (Jens); V. Vitart (Veronique); J.C. Bis (Joshua); S.H. Wild (Sarah); A. Rumley (Ann); Q. Yang (Qiong Fang); A.G. Uitterlinden (André); D.J. Stott (David. J.); G. Davies (Gareth); A.M. Carter (Angela M.); B. Thorand (Barbara); O. Polašek (Ozren); B. McKnight (Barbara); H. Campbell (Harry); A.R. Rudnicka (Alicja); M.H. Chen (Min-hsin); B.M. Buckley (Brendan M.); S.E. Harris (Sarah); A. Peters (Annette); D. Pulanic (Drazen); T. Lumley (Thomas); A.J.M. de Craen (Anton J.M.); D.C. Liewald (David C.); C. Gieger (Christian); I. Ford (Ian); A.J. Gow (Alan J.); M. Luciano (Michelle); D.J. Porteous (David J.); X. Guo (Xiuqing); N. Sattar (Naveed); A. Tenesa (Albert); M. Cushman (Mary Ann); P.E. Slagboom (Eline); P.M. Visscher (Peter M.); T.D. Spector (Tim); T. Illig (Thomas); I. Rudan (Igor); E.G. Bovill (Edwin G.); A.F. Wright (Alan); W.L. McArdle (Wendy); G.H. Tofler (Geoffrey); A. Hofman (Albert); R.G.J. Westendorp (Rudi); J.M. Starr (John); P.J. Grant (Peter J.); M. Karakas (Mahir); N.D. Hastie (Nicholas D.); B.M. Psaty (Bruce); J.F. Wilson (James); G.D.O. Lowe (Gordon); C.J. O'Donnell (Christopher); J.C.M. Witteman (Jacqueline); J.W. Jukema (Jan Wouter); I.J. Deary (Ian); N. Soranzo (Nicole); W. Koenig (Wolfgang); C. Hayward (Caroline)


    textabstractBACKGROUND: Fibrin fragment D-dimer, one of several peptides produced when crosslinked fibrin is degraded by plasmin, is the most widely used clinical marker of activated blood coagulation. To identity genetic loci influencing D-dimer levels, we performed the first large-scale,

  18. Synthesis and Diels–Alder cycloaddition reaction of norbornadiene and benzonorbornadiene dimers

    Directory of Open Access Journals (Sweden)

    Bilal Nişancı


    Full Text Available Dimeric forms of norbornadiene and benzonorbornadiene were synthesized starting with known monobromide derivatives. The Diels–Alder cycloaddition reaction of dimers with TCNE and PTAD was investigated and new norbornenoid polycyclics were obtained. All compounds were characterized properly using NMR spectroscopy.

  19. Evidence for the dimerization-mediated catalysis of methionine sulfoxide reductase A from Clostridium oremlandii. (United States)

    Lee, Eun Hye; Lee, Kitaik; Kwak, Geun-Hee; Park, Yeon Seung; Lee, Kong-Joo; Hwang, Kwang Yeon; Kim, Hwa-Young


    Clostridium oremlandii MsrA (CoMsrA) is a natively selenocysteine-containing methionine-S-sulfoxide reductase and classified into a 1-Cys type MsrA. CoMsrA exists as a monomer in solution. Herein, we report evidence that CoMsrA can undergo homodimerization during catalysis. The monomeric CoMsrA dimerizes in the presence of its substrate methionine sulfoxide via an intermolecular disulfide bond between catalytic Cys16 residues. The dimeric CoMsrA is resolved by the reductant glutaredoxin, suggesting the relevance of dimerization in catalysis. The dimerization reaction occurs in a concentration- and time-dependent manner. In addition, the occurrence of homodimer formation in the native selenoprotein CoMsrA is confirmed. We also determine the crystal structure of the dimeric CoMsrA, having the dimer interface around the two catalytic Cys16 residues. A central cone-shaped hole is present in the surface model of dimeric structure, and the two Cys16 residues constitute the base of the hole. Collectively, our biochemical and structural analyses suggest a novel dimerization-mediated mechanism for CoMsrA catalysis that is additionally involved in CoMsrA regeneration by glutaredoxin.

  20. Fabrication and characterization of Au dimer antennas on glass pillars with enhanced plasmonic response

    DEFF Research Database (Denmark)

    Sadeghi, Pedram; Wu, Kaiyu; Rindzevicius, Tomas


    -difference time-domain (FDTD) and finite-element method (FEM) simulations. Additionally, measured spectra are accompanied by dark-field microscopy images of the dimers, showing the pronounced change in color. Placing nanoantennas on nanopillars with a height comparable to the in-plane dimer dimensions results...

  1. Cold-active alkaline phosphatase is irreversibly transformed into an inactive dimer by low urea concentrations. (United States)

    Hjörleifsson, Jens Guðmundur; Ásgeirsson, Bjarni


    Alkaline phosphatase is a homodimeric metallo-hydrolase where both Zn(2+) and Mg(2+) are important for catalysis and stability. Cold-adapted alkaline phosphatase variants have high activity at low temperatures and lower thermal stability compared with variants from mesophilic hosts. The instability, and thus inactivation, could be due to loose association of the dimers and/or loosely bound Mg(2)(+) in the active site, but this has not been studied in detail for the cold-adapted variants. Here, we focus on using the intrinsic fluorescence of Trp in alkaline phosphatase from the marine bacterium Vibrio splendidus (VAP) to probe for dimerization. Trp→Phe substitutions showed that two out of the five native Trp residues contributed mostly to the fluorescence emission. One residue, 15Å away from the active site (W460) and highly solvent excluded, was phosphorescent and had a distant role in substrate binding. An additional Trp residue was introduced to the dimer interface to act as a possible probe for dimerization. Urea denaturation curves indicated that an inactive dimer intermediate, structurally equivalent to the native state, was formed before dimer dissociation took place. This is the first example of the transition of a native dimer to an inactive dimer intermediate for alkaline phosphatase without using mutagenesis, ligands, or competitive inhibition. Copyright © 2016 Elsevier B.V. All rights reserved.

  2. Factors associated with D-dimer levels in HIV-infected individuals

    DEFF Research Database (Denmark)

    Borges, Alvaro H; O'Connor, Jemma L; Phillips, Andrew N


    than men, though a steeper increase of D-dimer with age occurred in men. Hepatitis B/C co-infection was the only co-morbidity associated with higher D-dimer levels. In this subgroup, the degree of hepatic fibrosis, as demonstrated by higher hyaluronic acid levels, but not viral load of hepatitis...

  3. A Model for Dimerization of the SOX Group E Transcription Factor Family.

    Directory of Open Access Journals (Sweden)

    Sarah N Ramsook

    Full Text Available Group E members of the SOX transcription factor family include SOX8, SOX9, and SOX10. Preceding the high mobility group (HMG domain in each of these proteins is a thirty-eight amino acid region that supports the formation of dimers on promoters containing tandemly inverted sites. The purpose of this study was to obtain new structural insights into how the dimerization region functions with the HMG domain. From a mutagenic scan of the dimerization region, the most essential amino acids of the dimerization region were clustered on the hydrophobic face of a single, predicted amphipathic helix. Consistent with our hypothesis that the dimerization region directly contacts the HMG domain, a peptide corresponding to the dimerization region bound a preassembled HMG-DNA complex. Sequence conservation among Group E members served as a basis to identify two surface exposed amino acids in the HMG domain of SOX9 that were necessary for dimerization. These data were combined to make a molecular model that places the dimerization region of one SOX9 protein onto the HMG domain of another SOX9 protein situated at the opposing site of a tandem promoter. The model provides a detailed foundation for assessing the impact of mutations on SOX Group E transcription factors.

  4. A riboswitch regulates RNA dimerization and packaging in human immunodeficiency virus type 1 virions

    NARCIS (Netherlands)

    Ooms, Marcel; Huthoff, Hendrik; Russell, Rodney; Liang, Chen; Berkhout, Ben


    The genome of retroviruses, including human immunodeficiency virus type I (HIV-1), consists of two identical RNA strands that are packaged as noncovalently linked dimers. The core packaging and dimerization signals are located in the downstream part of the untranslated leader of HIV-1 RNA-the Psi

  5. The use of D-dimer in specific clinical conditions: a narrative review

    NARCIS (Netherlands)

    Bruinstroop, E.; van de Ree, M. A.; Huisman, M. V.


    The use of D-dimer in combination with a clinical decision rule has been widely investigated in pulmonary embolism and deep venous thrombosis. Although it has been shown to be safe in excluding venous thromboembolism, the clinician is often faced with specific situations in which the use of D-dimer

  6. D-Dimer assay as a non invasive test for the diagnosis of left atrial ...

    African Journals Online (AJOL)

    Background: Systemic embolism is a serious and sometime fatal complication of rheumatic MS. Objective: We assessed the predictive power of D-Dimer level to predict occurrence of left atrial (LA) thrombi in patients with rheumatic mitral stenosis (MS). Methods: D-dimer levels were analyzed for 24 patients with rheumatic ...

  7. Reversible dimerization of 20 kilodalton human growth hormone (hGH). (United States)

    Nagatomi, Y; Ikeda, M; Uchida, H; Wada, M; Kobayashi, H; Hashimoto, Y; Mabuchi, K; Hayakawa, M; Kusuhara, N; Honjo, M


    A noncovalent dimer of the 22 kilodalton human growth hormone (22 K-hGH) is known to have diminished somatogenic activity compared with monomeric 22 K-hGH. In the present study, we examined the biological activity and physicochemical behaviour of a noncovalent dimer of the 20 kilodalton human growth hormone (20 K-hGH), an isoform of 22 K-hGH. Analysis of the equilibrium between monomeric and associated forms revealed that the associated 20 K-hGH was present in the dimeric form in aqueous solution. The kinetics of dimerization in rat plasma followed the theory of dissociation-association equilibrium, and more than 99% of 20 K-hGH molecules existed as a monomer in the equilibrium state at the physiological hGH concentration. Analysis of the pharmacokinetics showed that the ratio of the administrated dimer in rat circulation decreased from 43% to less than 4% in 2 h. A preparation of noncovalent dimeric 20 K-hGH had essentially the same degree of biological potency as that of a monomer in both in vitro and in vivo bioassays. In conclusion, dimerization of 20 K-hGH is reversible both in vitro and in vivo and a noncovalent dimer can function as a pharmaceutically active component of a 20 K-hGH preparation, in contrast to a 22 K-hGH preparation. Copyright 2000 Harcourt Publishers Ltd.

  8. Dynamic models of G-protein coupled receptor dimers: indications of asymmetry in the rhodopsin dimer from molecular dynamics simulations in a POPC bilayer (United States)

    Filizola, Marta; Wang, Simon X.; Weinstein, Harel


    Based on the growing evidence that G-protein coupled receptors (GPCRs) form homo- and hetero-oligomers, models of GPCR signaling are now considering macromolecular assemblies rather than monomers, with the homo-dimer regarded as the minimal oligomeric arrangement required for functional coupling to the G-protein. The dynamic mechanisms of such signaling assemblies are unknown. To gain some insight into properties of GPCR dimers that may be relevant to functional mechanisms, we study their current structural prototype, rhodopsin. We have carried out nanosecond time-scale molecular dynamics (MD) simulations of a rhodopsin dimer and compared the results to the monomer simulated in the same type of bilayer membrane model composed of an equilibrated unit cell of hydrated palmitoyl-oleoyl-phosphatidyl choline (POPC). The dynamic representation of the homo-dimer reveals the location of structural changes in several regions of the monomeric subunits. These changes appear to be more pronounced at the dimerization interface that had been shown to be involved in the activation process [Proc Natl Acad Sci USA 102:17495, 2005]. The results are consistent with a model of GPCR activation that involves allosteric modulation through a single GPCR subunit per dimer.

  9. Age-Adjusted D-Dimer in the Prediction of Pulmonary Embolism: Does a Normal Age-Adjusted D-Dimer Rule Out PE?

    Directory of Open Access Journals (Sweden)

    Jacob Ortiz


    Full Text Available Risk assessment for pulmonary embolism (PE currently relies on physician judgment, clinical decision rules (CDR, and D-dimer testing. There is still controversy regarding the role of D-dimer testing in low or intermediate risk patients. The objective of the study was to define the role of clinical decision rules and D-dimer testing in patients suspected of having a PE. Records of 894 patients referred for computed tomography pulmonary angiography (CTPA at a University medical center were analyzed. The clinical decision rules overall had an ROC of approximately 0.70, while signs of DVT had the highest ROC (0.80. A low probability CDR coupled with a negative age-adjusted D-dimer largely excluded PE. The negative predictive value (NPV of an intermediate CDR was 86–89%, while the addition of a negative D-dimer resulted in NPVs of 94%. Thus, in patients suspected of having a PE, a low or intermediate CDR does not exclude PE; however, in patients with an intermediate CDR, a normal age-adjusted D-dimer increases the NPV.

  10. Mechanism for Controlling the Dimer-Monomer Switch and Coupling Dimerization to Catalysis of the Severe Acute Respiratory Syndrome Coronavirus 3C-Like Protease

    Energy Technology Data Exchange (ETDEWEB)

    Shi,J.; Sivaraman, J.; Song, J.


    Unlike 3C protease, the severe acute respiratory syndrome coronavirus (SARS-CoV) 3C-like protease (3CLpro) is only enzymatically active as a homodimer and its catalysis is under extensive regulation by the unique extra domain. Despite intense studies, two puzzles still remain: (i) how the dimer-monomer switch is controlled and (ii) why dimerization is absolutely required for catalysis. Here we report the monomeric crystal structure of the SARS-CoV 3CLpro mutant R298A at a resolution of 1.75 Angstroms . Detailed analysis reveals that Arg298 serves as a key component for maintaining dimerization, and consequently, its mutation will trigger a cooperative switch from a dimer to a monomer. The monomeric enzyme is irreversibly inactivated because its catalytic machinery is frozen in the collapsed state, characteristic of the formation of a short 310-helix from an active-site loop. Remarkably, dimerization appears to be coupled to catalysis in 3CLpro through the use of overlapped residues for two networks, one for dimerization and another for the catalysis.

  11. Detectability of H2-Ar and H2-Ne Dimers in Jovian Atmospheres

    Directory of Open Access Journals (Sweden)

    Young-Key Minn


    Full Text Available The detection of jovian hydrogen-hydrogen dimers through the clear telluric 2-micron window(Kim et al. 1995, Trafton et al. 1997 suggests possibility to detect noble gases in the form of dimer with hydrogen in jovian atmospheres. Since noble gases do not have spectral structures in the infrared, it has been difficult to derive their abundances in the atmospheres of jovian planets. If there is a significant component of noble gases other than helium in the jovian atmospheres. it might be detected through its dimer spectrum with hydrogen molecule. The relatively sharp spectral structures of hydrogen-argon and hydrogen-neon dimers compared with those of hydrogen-hydrogen dimers are useful for the detection, if an adequate signal-to-noise (S/N is obtained. If we use a large telescope, such as the Keck telescope, with a long exposure time (>24 hours, then H2-Ar spectral structure may be detected.

  12. Spin quantum tunneling via entangled states in a dimer of exchange coupled single-molecule magnets (United States)

    Tiron, R.; Wernsdorfer, W.; Aliaga-Alcalde, N.; Foguet-Albiol, D.; Christou, G.


    A new family of supramolecular, antiferromagnetically exchange-coupled dimers of single-molecule magnets (SMMs) has recently been reported [W. Wernsdorfer, N. Aliaga-Alcalde, D.N. Hendrickson, and G. Christou, Nature 416, 406 (2002)]. Each SMM acts as a bias on its neighbor, shifting the quantum tunneling resonances of the individual SMMs. Hysteresis loop measurements on a single crystal of SMM-dimers have now established quantum tunneling of the magnetization via entangled states of the dimer. This shows that the dimer really does behave as a quantum-mechanically coupled dimer. The transitions are well separated, suggesting long coherence times compared to the time scale of the energy splitting. This result is of great importance if such systems are to be used for quantum computing. It also allows the measurement of the longitudinal and transverse superexchange coupling constants [Phys. Rev. Lett. 91, 227203 (2003)].

  13. Changes in fibrin D-dimer, fibrinogen, and protein S during pregnancy

    DEFF Research Database (Denmark)

    Hansen, Anette Tarp; Andreasen, Birgitte Horst; Salvig, Jannie Dalby


    Background. Pregnancy is a hypercoagulable state with a 5- to 10- fold higher risk of venous thromboembolism. Existing reference intervals for fibrin D-dimer (D-dimer), functional fibrinogen (fibrinogen) and protein S, free antigen (protein S) are based on non-pregnant patients and reference...... intervals for pregnant patients are warranted. Objectives. The aim of the present study was to contribute to the establishment of reference intervals for D-dimer, fibrinogen and protein S during pregnancy and to discuss the use of the analyses during pregnancy. Methods. We included 55 healthy pregnant women...... in gestational week 11–17, with normal current pregnancy. Blood samples were collected in gestational weeks 11–17, 21–27 and 34–37. The three plasma parameters D-dimer, fibrinogen and protein S were analysed by STA-R Evolution®. Results. A significant rise in D-dimer was found from first to second trimester (p...

  14. Samarium (III) acetate-chloride hydrates: dimers and chains

    International Nuclear Information System (INIS)

    Meyer, G.; Lossin, A.; Schleid, T.


    Except for samarium chloride and samarium acetate, the system Sm 3+ /Ac - /Cl - /H 2 0 contains two acetate-chloride hydrates, [SmAc(H 2 0) 6 ]Cl 2 . H 2 0 (1) and [SmAc 2 (H 2 0) 3 ]Cl (2). Single crystals of 1 are obtained from an aqueous acetic-acid solution of SmCl 3 .6H 2 0 by slow isothermal evaporation at room temperature, those of 2 analogously but from a solution of SmOCl. 1 crystallizes with the triclinic system and contains centro-symmetric dimers with nine-coordinate Sm 3+ (six aquo ligands and one tridentate bridging acetate anion). 2 crystallizes with the monoclinic system with one-dimensional infinite chains, and Sm 3+ again in a ninefold oxygen coordination (three aquo and two tridentate bridging acetate ligands)

  15. Regioselective dimerization of ferulic acid in a micellar solution

    DEFF Research Database (Denmark)

    Larsen, E; Andreasen, Mette Findal; Christensen, L P


    -hydroxy-3-methoxyphenyl)-3,7-dioxabicyclo[3.3.0]octane-2,6-dione (18%) as the main product. The use of micelles appears to be not only a new way to synthesize regioisomeric ferulic acid dehydrodimers but may also help to understand the regiospecificity of dimeric hydroxycinnamate formation in vivo...... that regioisomeric ferulic acid dehydrodimers can be obtained in one step from trans-ferulic acid after attachment to these micelles and using the biomimetic peroxidase-H2O2 system. The surfactant hexadecyltrimethylammonium hydroxide yielded trans-4-(4-hydroxy-3-methoxybenzylidene)-2-(4-hydroxy-3-methoxyphenyl)-5......-oxotetrahydrofuran-3-carboxylic acid (25%), (E,E)-4,4'-dihydroxy-5,5'-dimethoxy-3,3'-bicinnamic acid (21%), and trans-5-[(E)-2-carboxyvinyl]-2-(4-hydroxy-3-methoxyphenyl)-7-methoxy-2,3-dihydrobenzofuran-3-carboxylic acid (14%), whereas the surfactant tetradecyltrimethylammonium bromide gave 4-cis, 8-cis-bis(4...

  16. Phosphorus Dimerization in Gallium Phosphide at High Pressure

    Energy Technology Data Exchange (ETDEWEB)

    Lavina, Barbara [High Pressure Science and Engineering Center, University of Nevada, Las Vegas, Nevada 89154, United States; Department of Physics and Astronomy, University of Nevada, Las Vegas, Nevada 89154, United States; Kim, Eunja [Department of Physics and Astronomy, University of Nevada, Las Vegas, Nevada 89154, United States; Cynn, Hyunchae [Lawrence Livermore National Laboratory, Livermore, California 94550, United States; Weck, Philippe F. [Sandia National Laboratories, Albuquerque, New Mexico 87185, United States; Seaborg, Kelly [High Pressure Science and Engineering Center, University of Nevada, Las Vegas, Nevada 89154, United States; Department of Physics and Astronomy, University of Nevada, Las Vegas, Nevada 89154, United States; Siska, Emily [High Pressure Science and Engineering Center, University of Nevada, Las Vegas, Nevada 89154, United States; Meng, Yue [HPCAT, Carnegie Institution of Washington, Argonne, Illinois 60439, United States; Evans, William [Lawrence Livermore National Laboratory, Livermore, California 94550, United States


    Using combined experimental and computational approaches, we show that at 43 GPa and 1300 K gallium phosphide adopts the super-Cmcm structure, here indicated with its Pearson notation oS24. First-principles enthalpy calculations demonstrate that this structure is more thermodynamically stable above ~20 GPa than previously proposed polymorphs. Here, in contrast to other polymorphs, the oS24 phase shows a strong bonding differentiation and distorted fivefold coordination geometries of both P atoms. The shortest bond of the phase is a single covalent P–P bond measuring 2.171(11) Å at synthesis pressure. Phosphorus dimerization in GaP sheds light on the nature of the super-Cmcm phase and provides critical new insights into the high-pressure polymorphism of octet semiconductors. Bond directionality and anisotropy explain the relatively low symmetry of this high-pressure phase.

  17. Calculation of vibrational spectra for dioxouranium monochloride monomer and dimers (United States)

    Umreiko, D. S.; Shundalau, M. B.; Zazhogin, A. P.; Komyak, A. I.


    Structural models were built and spectral characteristics were calculated based on ab initio calculations for the monomer and dimers of dioxouranium monochoride UO2Cl. The calculations were carried out in the effective core potential LANL2DZ approximation for the uranium atom and all-electron basis sets using DFT methods for oxygen and chlorine atoms (B3LYP/cc-pVDZ). The monomer UO2Cl was found to possess an equilibrium planar (close to T-shaped) configuration with C2v symmetry. The obtained spectral characteristics were analyzed and compared with experimental data. The adequacy of the proposed models and the qualitative agreement between calculation and experiment were demonstrated.

  18. Amorphous Silica-Promoted Lysine Dimerization: a Thermodynamic Prediction (United States)

    Kitadai, Norio; Nishiuchi, Kumiko; Nishii, Akari; Fukushi, Keisuke


    It has long been suggested that mineral surfaces played a crucial role in the abiotic polymerization of amino acids that preceded the origin of life. Nevertheless, it remains unclear where the prebiotic process took place on the primitive Earth, because the amino acid-mineral interaction and its dependence on environmental conditions have yet to be understood adequately. Here we examined experimentally the adsorption of L-lysine (Lys) and its dimer (LysLys) on amorphous silica over a wide range of pH, ionic strength, adsorbate concentration, and the solid/water ratio, and determined the reaction stoichiometries and the equilibrium constants based on the extended triple-layer model (ETLM). The retrieved ETLM parameters were then used, in combination with the equilibrium constant for the peptide bond formation in bulk water, to calculate the Lys-LysLys equilibrium in the presence of amorphous silica under various aqueous conditions. Results showed that the silica surface favors Lys dimerization, and the influence varies greatly with changing environmental parameters. At slightly alkaline pH (pH 9) in the presence of a dilute NaCl (1 mM), the thermodynamically attainable LysLys from 0.1 mM Lys reached a concentration around 50 times larger than that calculated without silica. Because of the versatility of the ETLM, which has been applied to describe a wide variety of biomolecule-mineral interactions, future experiments with the reported methodology are expected to provide a significant constraint on the plausible geological settings for the condensation of monomers to polymers, and the subsequent chemical evolution of life.

  19. Intermolecular potential energy surface for CS2 dimer. (United States)

    Farrokhpour, Hossein; Mombeini, Zainab; Namazian, Mansoor; Coote, Michelle L


    A new four-dimensional intermolecular potential energy surface for CS(2) dimer is obtained by ab initio calculation of the interaction energies for a range of configurations and center-of-mass separation distances for the first time. The calculations were performed using the supermolecular approach at the Møller-Plesset second-order perturbation (MP2) level of theory with the augmented correlation consistent basis sets (aug-cc-pVxZ, x = D, T) and corrected for the basis-set superposition error using the full counterpoise correction method. A two-point extrapolation method was used to extrapolate the calculated energy points to the complete basis set limit. The effect of using the higher levels of theory, quadratic configuration interaction containing single, double, and perturbative triple excitations QCISD(T) and coupled cluster singles, doubles and perturbative triples excitations CCSD(T), on the shape of potential energy surface was investigated. It is shown that the MP2 level of theory apparently performs extremely poorly for describing the intermolecular potential energy surface, overestimating the total energy by a factor of nearly 1.73 in comparison with the QCISD(T) and CCSD(T) values. The value of isotropic dipole-dipole dispersion coefficient (C(6) ) of CS(2) fluid was obtained from the extrapolated MP2 potential energy surface. The MP2 extrapolated energy points were fitted to well-known analytical potential functions using two different methods to represent the potential energy surface analytically. The most stable configuration of the dimer was determined at R = 6.23 au, α = 90°, β = 90°, and γ = 90°, with a well depth of 3.980 kcal mol(-1) at the MP2 level of theory. Finally, the calculated second virial coefficients were compared with experimental values to test the quality of the presented potential energy surface. Copyright © 2010 Wiley Periodicals, Inc.

  20. Plant Kinesin-Like Calmodulin Binding Protein Employs Its Regulatory Domain for Dimerization.

    Directory of Open Access Journals (Sweden)

    Maia V Vinogradova

    Full Text Available Kinesin-like calmodulin binding protein (KCBP, a Kinesin-14 family motor protein, is involved in the structural organization of microtubules during mitosis and trichome morphogenesis in plants. The molecular mechanism of microtubule bundling by KCBP remains unknown. KCBP binding to microtubules is regulated by Ca(2+-binding proteins that recognize its C-terminal regulatory domain. In this work, we have discovered a new function of the regulatory domain. We present a crystal structure of an Arabidopsis KCBP fragment showing that the C-terminal regulatory domain forms a dimerization interface for KCBP. This dimerization site is distinct from the dimerization interface within the N-terminal domain. Side chains of hydrophobic residues of the calmodulin binding helix of the regulatory domain form the C-terminal dimerization interface. Biochemical experiments show that another segment of the regulatory domain located beyond the dimerization interface, its negatively charged coil, is unexpectedly and absolutely required to stabilize the dimers. The strong microtubule bundling properties of KCBP are unaffected by deletion of the C-terminal regulatory domain. The slow minus-end directed motility of KCBP is also unchanged in vitro. Although the C-terminal domain is not essential for microtubule bundling, we suggest that KCBP may use its two independent dimerization interfaces to support different types of bundled microtubule structures in cells. Two distinct dimerization sites may provide a mechanism for microtubule rearrangement in response to Ca(2+ signaling since Ca(2+- binding proteins can disengage KCBP dimers dependent on its C-terminal dimerization interface.

  1. Numerical investigation of radiative properties and surface plasmon resonance of silver nanorod dimers on a substrate

    International Nuclear Information System (INIS)

    An, Wei; Zhu, Tong; Zhu, QunZhi


    When the distance between two silver nanoparticles is small enough, interparticle surface plasmon coupling has a great impact on their radiative properties. It is becoming a promising technique to use in the sensing and imaging. A model based on finite difference time domain method is developed to investigate the effect of the assembled parameters on the radiative properties and the field-enhancement effect of silver nanorod dimer. The numerical results indicate that the radiative properties of silver nanorod dimer are very sensitive to the assembled angle and the polarization orientation of incident wave. There is great difference on the intensity and location of field-enhancement effect for the cases of different assembled angle and polarization. The most intensive field-enhancement effect occurs in the middle of two nanorods when two nanorods is assembled head to head and the polarization orientation parallels to the length axis of nanorods. Moreover, compared with the single nanorod, the wavelength of extinction peak of dimer has a red-shift, and the intensity of field-enhancement effect on the dimer is more intensive than that of single particle. With the increasing of particle length, extinction cross-section of silver nanorod dimer rises, while extinction efficiency and scattering efficiency firstly increase then drop down gradually. In addition, the extinction peaks of silver nanorod dimer on the substrate are smaller than that without the substrate, and their extinction peaks has a red-shift compared with that without the substrate. -- Highlights: ► Radiative properties of silver nanorod dimer are very sensitive to the assembled angle. ► The projective length of nanorod dimer on the polarization orientation is crucial. ► Compared with single nanorod, wavelength of extinction peak of dimer has a red-shift. ► Extinction peaks of dimer on the substrate are smaller than that without the substrate

  2. Study of Paramagnetic Monohydrates MeSO4.1H2O (Me = Mn2+, Co2+, Fe2+, Ni2+, Cu2+

    Directory of Open Access Journals (Sweden)

    Jelšovská Kamila


    Full Text Available Nuclear magnetic resonance (NMR of protons of crystrallization water in isomorphous paramagnetic monohydrates MeSO4.1H2O with Me = Mn2+ , Co2+ , Fe2+ , Ni2+ , Cu2+ is studied in the present paper. Several physically important parameters characterizing the studied substances were derived from the NMR spectra. In this paper we analysed the dependences of the NMR second moment M2 on the magnitude of the external magnetic field induction Br and the temperature. The proton NMR spectra in paramagnetic hydrates have an asymmetric form caused by the anisotropy of the local magnetic field acting on resonating nuclei and their second moments, M2, depend linearly on the square of the external magnetic field Br. The parameters M20 (the part of the second moment M2 which corresponds to the nuclear dipole-dipole interactions and á which characterize nuclear dipole-dipole interactions of protons and paramagnetic ions, respectively, are derived from experimentally obtained dependences of M2 vs Br2. The measurements were performed at the room temperature. Calculations were realized using the approximation where two nearest neighbour ions Me2+ to each water molecule are considered. The temperature dependence of the second moment, which was realised in the temperature range 123-313 K, was more informative than the field one. Besides the individual dependences M2(T measured at fr1 and fr2 we analysed the temperature dependence of the difference ∆M2(T. Beside the second moment M20 the Curie-Weiss constant è and the magnetic moment µi of paramagnetic ions were determined from the temperature dependences. The parameters è and M20 were determined directly from the experimental data. Some knowledge on the crystalline structure for the studied substance was required for the calculation of the magnetic moment µi. By means of the classification of substances according to the Curie-Weiss parameter, the negative value of the temperature parameter è for all studied

  3. New developments in porphyrin-like macrocyclic chemistry: a novel family of dibenzotetraaza[14]annulene-based cofacial dimers. (United States)

    Zwoliński, K M; Eilmes, J


    The first known homoleptic cofacial dimers, based on covalently linked dibenzotetraaza[14]annulenes, were synthesized in reasonable 35-40% yields, without recourse to high-dilution techniques. Dinuclear zinc(ii) dimer showed strong binding affinity toward DABCO. Site-selective monometallation of the dimer, triggered by the linkers' structure, was observed, allowing access to heterobimetallic co-receptors.

  4. Dimerization of imidazoline nitroxide radicals containing alcohol groups in the second position: study by 2 mm EPR (United States)

    Gulin, V. I.; Dikanov, S. A.; Tsvetkov, Yu. D.


    This paper reports the dimerization of imidazoline nitroxides, containing alcohol groups in the second position, in frozen toluene. The parameters of dipole-dipole interaction of electron spins in dimers were determined using 2 mm EPR spectroscopy. A geometrical model for the dimers could be obtained.

  5. Magnetic field induced random pulse trains of magnetic and acoustic noises in martensitic single-crystal Ni2MnGa (United States)

    Daróczi, Lajos; Piros, Eszter; Tóth, László Z.; Beke, Dezső L.


    Jerky magnetic and acoustic noises were evoked in a single variant martensitic Ni2MnGa single crystal (produced by uniaxial compression) by application of an external magnetic field along the hard magnetization direction. It is shown that after reaching the detwinning threshold, spontaneous reorientation of martensite variants (twins) leads not only to acoustic emission but magnetic two-directional noises as well. At small magnetic fields, below the above threshold, unidirectional magnetic emission is also observed and attributed to a Barkhausen-type noise due to magnetic domain wall motions during magnetization along the hard direction. After the above first run, in cycles of decreasing and increasing magnetic field, at low-field values, weak, unidirectional Barkhausen noise is detected and attributed to the discontinuous motion of domain walls during magnetization along the easy magnetization direction. The magnetic noise is also measured by constraining the sample in the same initial variant state along the hard direction and, after the unidirectional noise (as obtained also in the first run), a two-directional noise package is developed and it is attributed to domain rotations. From the statistical analysis of the above noises, the critical exponents, characterizing the power-law behavior, are calculated and compared with each other and with the literature data. Time correlations within the magnetic as well as acoustic signals lead to a common scaled power function (with β =-1.25 exponent) for both types of signals.

  6. Formation of nano-laminated structures in a dry sliding wear-induced layer under different wear mechanisms of 20CrNi2Mo steel (United States)

    Yin, Cun-hong; Liang, Yi-long; Jiang, Yun; Yang, Ming; Long, Shao-lei


    The microstructures of 20CrNi2Mo steel underneath the contact surface were examined after dry sliding. Scanning Electronic Microscopy (SEM), Transmission Electron Microscopy (TEM), Electron Backscattered Diffraction (EBSD) and an ultra-micro-hardness tester were used to characterize the worn surface and dry sliding wear-induced layer. Martensite laths were ultra-refined due to cumulative strains and a large strain gradient that occurred during cyclic loading in wear near the surface. The microstructure evolution in dominant abrasive wear differs from that in adhesive wear. In dominant abrasive wear, only bent martensite laths with high-density deformation dislocations were observed. In contrast, in dominant adhesive wear, gradient structures were formed along the depth from the wear surface. Cross-sectional TEM foils were prepared in a focused ion beam (FIB) to observe the gradient structures in a dry sliding wear-induced layer at depths of approximately 1-5 μm and 5-20 μm. The gradient structures contained nano-laminated structures with an average thickness of 30-50 nm and bent martensite laths. We found that the original martensite laths coordinated with the strain energy and provided origin boundaries for the formation of gradient structures. Geometrically necessary boundaries (GNBs) and isolated dislocation boundaries (IDBs) play important roles in forming the nano-laminated structures.

  7. Effects of inorganic acids and divalent hydrated metal cations (Mg(2+), Ca(2+), Co(2+), Ni(2+)) on γ-AlOOH sol-gel process. (United States)

    Zhang, Jian; Xia, Yuguo; Zhang, Li; Chen, Dairong; Jiao, Xiuling


    In-depth understanding of the sol-gel process plays an essential role in guiding the preparation of new materials. Herein, the effects of different inorganic acids (HCl, HNO3 and H2SO4) and divalent hydrated metal cations (Mg(2+), Ca(2+), Co(2+), Ni(2+)) on γ-AlOOH sol-gel process were studied based on experiments and density functional theory (DFT) calculations. In these experiments, the sol originating from the γ-AlOOH suspension was formed only with the addition of HCl and HNO3, but not with H2SO4. Furthermore, the DFT calculations showed that the strong adsorption of HSO4(-) on the surface of the γ-AlOOH particles, and the hydrogen in HSO4(-) pointing towards the solvent lead to an unstable configuration of electric double layer (EDL). In the experiment, the gelation time sequence of γ-AlOOH sol obtained by adding metal ions changed when the ionic strength was equal to or greater than 0.198 mol kg(-1). The DFT calculations demonstrated that the adsorption energy of hydrated metal ions on the γ-AlOOH surface can actually make a difference in the sol-gel process.

  8. Separation and Characterization of Angiotensin I Converting Enzyme (ACE Inhibitory Peptides from Saurida elongata Proteins Hydrolysate by IMAC-Ni2+

    Directory of Open Access Journals (Sweden)

    Lixia Sun


    Full Text Available Lizard fish protein hydrolysates (LFPH were prepared from Lizard fish (Saurida elongata proteins possessing powerful angiotensin I converting enzyme (ACE inhibitory activity and the fraction (LFPH-I with high ACE inhibitory activity was obtained through ultrafiltration. The active Fraction (F2 was isolated from LFPH-I using immobilized metal affinity chromatography (IMAC-Ni2+. Analysis of amino acid levels revealed that F2 eluted from IMAC was enriched in Met, His, Tyr, Pro, Ile, and Leu compared to the crude peptide LFPH-I. F2 with the high ACE inhibitory activity (IC50 of 0.116 mg·mL−1 was further separated by a reverse-phase column to yield a novel ACE inhibitory peptide with IC50 value of 52 μM. The ACE inhibitory peptide was identified as Arg-Tyr-Arg-Pro, RYRP. The present study demonstrated that IMAC may be a useful tool for the separation of ACE inhibitory peptides from protein hydrolysate.

  9. Friction and Wear Properties of AlxCrCuFeNi2 High-entropy Alloys with Multi-principal-elements

    Directory of Open Access Journals (Sweden)

    LIU Yong


    Full Text Available Orthogonal test was carried out with ball-on-disc friction and wear tester in dry, deionized water, and simulated rain water under three loads (5, 10, 15N, respectively. The behavior of two materials at different loads under different environment was compared, the friction and wear properties of the alloys under the simulated service situation was explored. The composition of the samples was examined by X-ray diffraction (XRD. The contour of wear scars was detected by a three-dimensional surface profiler based on scanning white light interferometry. Optical electron microscope is used to observe the structure. The morphology of the worn surfaces were observed by scanning electron microscopy (SEM and the wear mechanism was analyzed. Results show that due to the increase of Al, the body-centered cubic phase (bcc substitutes the face-centered cubic (fcc which attributed to the high hardness of Al1.3CrCuFeNi2 leading to good wear property. In dry condition, the wear mechanism are oxidation, adhesion, plastic deformation, and mild abrasive wear while in liquid, the abrasive is dominated along with oxidation and slight adhesive behavior.

  10. Preparation and properties of a novel macro porous Ni2+-imprinted chitosan foam adsorbents for adsorption of nickel ions from aqueous solution. (United States)

    Guo, Na; Su, Shi-Jun; Liao, Bing; Ding, Sang-Lan; Sun, Wei-Yi


    In this study, novel macro porous Ni 2+ -imprinted chitosan foam adsorbents (F-IIP) were prepared using sodium bicarbonate and glycerine to obtain a porogen for adsorbing nickel ions from aqueous solutions. The use of the ion-imprinting technique for adsorbents preparation improved the nickel ion selectivity and adsorption capacity. We characterised the imprinted porous foam adsorbents in terms of the effects of the initial pH value, initial metal ion concentration, and contact time on the adsorption of nickel ions. The adsorption process was described best by Langmuir monolayer adsorption models, and the maximum adsorption capacity calculated from the Langmuir equation was 69.93mgg -1 . The kinetic data could be fitted to a pseudo-second-order equation. Our analysis of selective adsorption demonstrated the excellent preference of the F-IIP foams for nickel ions compared with other coexisting metal ions. Furthermore, tests over five cycle runs suggested that the F-IIP foam adsorbents had good durability and efficiency. Copyright © 2017 Elsevier Ltd. All rights reserved.

  11. Thermally activated 3D to 2D structural transformation of [Ni2(en)2(H2O)6(pyr)]·4H2O flexible coordination polymer

    International Nuclear Information System (INIS)

    Begović, Nebojša N.; Blagojević, Vladimir A.; Ostojić, Sanja B.; Radulović, Aleksandra M.; Poleti, Dejan; Minić, Dragica M.


    Thermally activated 3D to 2D structural transformation of the binuclear [Ni 2 (en) 2 (H 2 O) 6 (pyr)]·4H 2 O complex was investigated using a combination of theoretical and experimental methods. Step-wise thermal degradation (dehydration followed by release of ethylene diamine) results in two layered flexible coordination polymer structures. Dehydration process around 365 K results in a conjugated 2D structure with weak interlayer connectivity. It was shown to be a reversible 3D to 2D framework transformation by a guest molecule, and rehydration of the dehydration product occurs at room temperature in saturated water vapor. Rehydrated complex exhibits lower dehydration temperature, due to decreased average crystalline size, with higher surface area resulting in easier release and diffusion of water during dehydration. Thermal degradation of dehydration around 570 K, results in loss of ethylene diamine, producing a related 2D layered polymer structure, without interconnectivity between individual polymer layers. - Highlights: • Reversible 3D to 2D framework topochemical transformation on dehydration around 365 K. • Resulting polymer exhibits 2D layered structure with weak interlayer connectivity. • Dehydration is fully reversible in saturated water vapor at room temperature. • Further degradation around 570 K yields 2D polymer without interlayer connectivity. • 2D polymer exhibits conjugated electronic system

  12. Identification of Ni2C electronic states in graphene-Ni(111) growth through resonant and dichroic angle-resolved photoemission at the C K -edge (United States)

    Drera, G.; Cepek, C.; Patera, L. L.; Bondino, F.; Magnano, E.; Nappini, S.; Africh, C.; Lodi-Rizzini, A.; Joshi, N.; Ghosh, P.; Barla, A.; Mahatha, S. K.; Pagliara, S.; Giampietri, A.; Pintossi, C.; Sangaletti, L.


    The graphene-Ni(111) (GrNi) growth via chemical vapor deposition has been explored by resonant, angle-resolved, and dichroic photoemission spectroscopy (soft x-ray Res-ARPES) in order to identify the possible contributions to the electronic structure deriving from different phases that can coexist in this complex system. We provide evidences of electronic states so far unexplored at the Γ ¯ point of GrNi, appearing at the C K -edge resonance. These states show both circular dichroism (CD) and k dependence, suggesting a long-range orbital ordering, as well as a coherent matching with the underlying lattice. Through a comparison of core-level photoemission, valence band resonances, and constant initial-state spectroscopy, we demonstrate that these states are actually induced by a low residual component of nickel carbide (Ni2C ). These results also show that caution must be exercised while interpreting x-ray magnetic circular dichroism collected on C K -edge with Auger partial yield method, due to the presence of CD in photoelectron spectra unrelated to magnetic effects.

  13. Thermodynamic characterization of Ni3TeO6, Ni2Te3O8 and NiTe2O5 (United States)

    Dawar, Rimpi; Babu, R.; Ananthasivan, K.; Anthonysamy, S.


    Measurement of vapour pressure of TeO2(g) over the biphasic mixture Ni3TeO6 (s) + NiO(s) in the temperature range 1143-1272 K was carried out using transpiration-thermogravimetric technique (TTG). Gibbs energy of formation of Ni3TeO6 was obtained from the temperature dependence of vapour pressure of TeO2 (g) generated by the incongruent vapourisation reaction, Ni3TeO6 (s) → NiO(s) + TeO2 (g) + 1/2 O2 in the temperature range 1143-1272 K. An isoperibol type drop calorimeter was used to measure the enthalpy increments of Ni3TeO6, Ni2Te3O8 and NiTe2O5. Thermodynamic functions viz., heat capacity, entropy and Gibbs energy functions of these compounds were derived from the experimentally measured enthalpy increment values. Third-law analysis was carried out to ascertain absence of temperature dependent systematic errors in the measurement of vapour pressure of TeO2 (g). A value of -1265.1 ± 1.5 kJ mol-1 was obtained for Δ Hf,298K o (Ni3TeO6) using third-law analysis.

  14. Comparative toxicity of VO3-, CrO42-, Mn2+, Co2+, Ni2+, Cu2+, Zn2+, and Cd2+ to lettuce seedlings

    International Nuclear Information System (INIS)

    Berry, W.L.


    Lettuce seeds imbibed, germinated, and grown in a 0.1-strength modified Hoagland culture solution were subjected to a series of increasing concentrations of individual heavy metals up to and exceeding lethal levels. After an exposure of 5 days, seedlings were harvested, examined, and measured to determine toxic effects. A log--log plot of root length (yield) vs. heavy metal concentration was made for each metal to produce a dose response curve. The curves showed a growth plateau at low concentrations of the respective metals which was equivalent to the growth of the control. All metals inhibited root growth and caused lethal toxicity in the sub- and low-milliequivalent range. When concentrations of the tested metals exceeded their thresholds of acute toxicity, root growth was inhibited. In the zone of inhibition, between the acute toxic threshold and complete inhibition, the log--log dose response curves were approximately linear or were a series of linear steps. The threshold toxicity and the response slope were characteristic for each metal. Seedling lettuce showed a monophasic response to VO 3 - , Cu 2+ , and Zn 2+ ; a biphasic response to CrO 4 2 -, Mn 2+ , Ni 2+ , and Cd 2+ ; and a quadraphasic response to Co 2+ . The acute toxicity threshold on an equivalent basis increased according to the following sequence: Cd 2+ much less than VO 3 - 2+ 2+ 2+ 4 2- 2+ much less than Mn 2+ . On this basis, Cd 2+ is the most toxic of the trace elements tested

  15. Kinetic and theoretical studies on the protonation of [Ni(2-SC6H4N){PhP(CH2CH2PPh2)2}]+: nitrogen versus sulfur as the protonation site. (United States)

    Petrou, Athinoula L; Koutselos, Andreas D; Wahab, Hilal S; Clegg, William; Harrington, Ross W; Henderson, Richard A


    The complexes [Ni(4-Spy)(triphos)]BPh(4) and [Ni(2-Spy)(triphos)]BPh(4) {triphos = PhP(CH(2)CH(2)PPh(2))(2), 4-Spy = 4-pyridinethiolate, 2-Spy = 2-pyridinethiolate} have been prepared and characterized both spectroscopically and using X-ray crystallography. In both complexes the triphos is a tridentate ligand. However, [Ni(4-Spy)(triphos)](+) comprises a 4-coordinate, square-planar nickel with the 4-Spy ligand bound to the nickel through the sulfur while [Ni(2-Spy)(triphos)](+) contains a 5-coordinate, trigonal-bipyramidal nickel with a bidentate 2-Spy ligand bound to the nickel through both sulfur and nitrogen. The kinetics of the reactions of [Ni(4-Spy)(triphos)](+) and [Ni(2-Spy)(triphos)](+) with lutH(+) (lut = 2,6-dimethylpyridine) in MeCN have been studied using stopped-flow spectrophotometry, and the two complexes show very different reactivities. The reaction of [Ni(4-Spy)(triphos)](+) with lutH(+) is complete within the deadtime of the stopped-flow apparatus (2 ms) and corresponds to protonation of the nitrogen. However, upon mixing [Ni(2-Spy)(triphos)](+) and lutH(+) a reaction is observed (on the seconds time scale) to produce an equilibrium mixture. The mechanistic interpretation of the rate law has been aided by the application of MSINDO semiempirical and ADF calculations. The kinetics and calculations are consistent with the reaction between [Ni(2-Spy)(triphos)](+) and lutH(+) involving initial protonation of the sulfur followed by dissociation of the nitrogen and subsequent transfer of the proton from sulfur to nitrogen. The factors affecting the position of protonation and the coupling of the coordination state of the 2-pyridinethiolate ligand to the site of protonation are discussed.

  16. Thermal entanglement in an orthogonal dimer-plaquette chain with alternating Ising–Heisenberg coupling

    International Nuclear Information System (INIS)

    Paulinelli, H G; De Souza, S M; Rojas, Onofre


    In this paper we explore the entanglement in an orthogonal dimer-plaquette Ising–Heisenberg chain, assembled between plaquette edges, also known as orthogonal dimer plaquettes. The quantum entanglement properties involving an infinite chain structure are quite important, not only because the mathematical calculation is cumbersome but also because real materials are well represented by infinite chains. Using the local gauge symmetry of this model, we are able to map onto a simple spin-1 like Ising and spin-1/2 Heisenberg dimer model with single effective ion anisotropy. Thereafter this model can be solved using the decoration transformation and transfer matrix approach. First, we discuss the phase diagram at zero temperature of this model, where we find five ground states, one ferromagnetic, one antiferromagnetic, one triplet–triplet disordered and one triplet–singlet disordered phase, beside a dimer ferromagnetic–antiferromagnetic phase. In addition, we discuss the thermodynamic properties such as entropy, where we display the residual entropy. Furthermore, using the nearest site correlation function it is possible also to analyze the pairwise thermal entanglement for both orthogonal dimers. Additionally, we discuss the threshold temperature of the entangled region as a function of Hamiltonian parameters. We find a quite interesting thin reentrance threshold temperature for one of the dimers, and we also discuss the differences and similarities for both dimers. (paper)

  17. Structural features of the KPI domain control APP dimerization, trafficking, and processing. (United States)

    Ben Khalifa, Naouel; Tyteca, Donatienne; Marinangeli, Claudia; Depuydt, Mathieu; Collet, Jean-François; Courtoy, Pierre J; Renauld, Jean-Christophe; Constantinescu, Stefan; Octave, Jean-Noël; Kienlen-Campard, Pascal


    The two major isoforms of human APP, APP695 and APP751, differ by the presence of a Kunitz-type protease inhibitor (KPI) domain in the extracellular region. APP processing and function is thought to be regulated by homodimerization. We used bimolecular fluorescence complementation (BiFC) to study dimerization of different APP isoforms and mutants. APP751 was found to form significantly more homodimers than APP695. Mutation of dimerization motifs in the TM domain did not affect fluorescence complementation, but native folding of KPI is critical for APP751 homodimerization. APP751 and APP695 dimers were mostly localized at steady state in the Golgi region, suggesting that most of the APP751 and 695 dimers are in the secretory pathway. Mutation of the KPI led to the retention of the APP homodimers in the endoplasmic reticulum. We finally showed that APP751 is more efficiently processed through the nonamyloidogenic pathway than APP695. These findings provide new insight on the particular role of KPI domain in APP dimerization. The correlation observed between dimerization, subcellular localization, and processing suggests that dimerization acts as an efficient regulator of APP trafficking in the secretory compartments that has major consequences on its processing.

  18. Morphological and physiological retinal degeneration induced by intravenous delivery of vitamin A dimers in rabbits

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    Jackie Penn


    Full Text Available The eye uses vitamin A as a cofactor to sense light and, during this process, some vitamin A molecules dimerize, forming vitamin A dimers. A striking chemical signature of retinas undergoing degeneration in major eye diseases such as age-related macular degeneration (AMD and Stargardt disease is the accumulation of these dimers in the retinal pigment epithelium (RPE and Bruch’s membrane (BM. However, it is not known whether dimers of vitamin A are secondary symptoms or primary insults that drive degeneration. Here, we present a chromatography-free method to prepare gram quantities of the vitamin A dimer, A2E, and show that intravenous administration of A2E to the rabbit results in retinal degeneration. A2E-damaged photoreceptors and RPE cells triggered inflammation, induced remolding of the choroidal vasculature and triggered a decline in the retina’s response to light. Data suggest that vitamin A dimers are not bystanders, but can be primary drivers of retinal degeneration. Thus, preventing dimer formation could be a preemptive strategy to address serious forms of blindness.

  19. Effect of thermal sterilization on ferulic, coumaric and cinnamic acids: dimerization and antioxidant activity. (United States)

    Arrieta-Baez, Daniel; Dorantes-Álvarez, Lidia; Martinez-Torres, Rocio; Zepeda-Vallejo, Gerardo; Jaramillo-Flores, Maria Eugenia; Ortiz-Moreno, Alicia; Aparicio-Ozores, Gerardo


    Some phenolic compounds, such as ferulic acid and p-coumaric acid, exist in the form of free acids, in fruits, rice, corn and other grains. Thermal treatment (121 °C at 15-17 psi) for different times on ferulic, p-coumaric and cinnamic acids as well as equimolar mixtures of these acids was investigated. Ferulic and p-coumaric acids underwent decarboxylation, yielding dimeric products formed through their corresponding radical intermediates, while cinnamic acid was recovered unreacted. High-performance liquid chromatography analysis showed no cross-dimerization when equimolar mixtures of pairs of hydroxycinnamic acids were treated under the same conditions. Dimers were characterized as (E)-4',4″-(but-1-ene-1,3-diyl)bis(2'-methoxyphenol)) (dimer of 4-vinylguaiacol) and (E)-4,4'-(but-1-ene-1,3-diyl)diphenol) (dimer of 4-vinylphenol) by nuclear magnetic resonance and mass spectrometry. Sterilization by thermal processing produced dimers of ferulic and coumaric acid. The antioxidant activity of these dimers was greater than that of the respective hydroxycinnamic acids. These results may be relevant for fruits and grains that contain hydroxycinnamic acids and undergo sterilization processes such as canning. Copyright © 2012 Society of Chemical Industry.

  20. Accuracy of D-Dimers to Rule Out Venous Thromboembolism Events across Age Categories

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    G. Der Sahakian


    Full Text Available Background. Strategies combining pretest clinical assessment and D-dimers measurement efficiently and safely rule out venous thromboembolism events (VTE in low- and intermediate-risk patients. Objectives. As process of ageing is associated with altered concentrations of coagulation markers including an increase in D-dimers levels, we investigated whether D-dimers could reliably rule out VTE across age categories. Method. We prospectively assessed the test performance in 1,004 patients visiting the emergency department during the 6-month period with low or intermediate risk of VTE who also received additional diagnostic procedures. Results. 67 patients had VTE with D-dimers levels above the threshold, and 3 patients displayed D-dimers levels below the threshold. We observed that specificity of D-dimers test decreased in an age-dependent manner. However, sensitivity and negative predictive value remained at very high level in each age category including older patients. Conclusion. We conclude that, even though D-dimers level could provide numerous false positive results in elderly patients, its high sensitivity could reliably help physicians to exclude the diagnosis of VTE in every low- and intermediate-risk patient.

  1. Dimerization of the Glucan Phosphatase Laforin Requires the Participation of Cysteine 329 (United States)

    Sánchez-Martín, Pablo; Raththagala, Madushi; Bridges, Travis M.; Husodo, Satrio; Gentry, Matthew S.; Sanz, Pascual; Romá-Mateo, Carlos


    Laforin, encoded by a gene that is mutated in Lafora Disease (LD, OMIM 254780), is a modular protein composed of a carbohydrate-binding module and a dual-specificity phosphatase domain. Laforin is the founding member of the glucan-phosphatase family and regulates the levels of phosphate present in glycogen. Multiple reports have described the capability of laforin to form dimers, although the function of these dimers and their relationship with LD remains unclear. Recent evidence suggests that laforin dimerization depends on redox conditions, suggesting that disulfide bonds are involved in laforin dimerization. Using site-directed mutagenesis we constructed laforin mutants in which individual cysteine residues were replaced by serine and then tested the ability of each protein to dimerize using recombinant protein as well as a mammalian cell culture assay. Laforin-Cys329Ser was the only Cys/Ser mutant unable to form dimers in both assays. We also generated a laforin truncation lacking the last three amino acids, laforin-Cys329X, and this truncation also failed to dimerize. Interestingly, laforin-Cys329Ser and laforin-Cys329X were able to bind glucans, and maintained wild type phosphatase activity against both exogenous and biologically relevant substrates. Furthermore, laforin-Cys329Ser was fully capable of participating in the ubiquitination process driven by a laforin-malin complex. These results suggest that dimerization is not required for laforin phosphatase activity, glucan binding, or for the formation of a functional laforin-malin complex. Cumulatively, these results suggest that cysteine 329 is specifically involved in the dimerization process of laforin. Therefore, the C329S mutant constitutes a valuable tool to analyze the physiological implications of laforin’s oligomerization. PMID:23922729

  2. Antiviral activity of α-helical stapled peptides designed from the HIV-1 capsid dimerization domain

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    Cowburn David


    Full Text Available Abstract Background The C-terminal domain (CTD of HIV-1 capsid (CA, like full-length CA, forms dimers in solution and CTD dimerization is a major driving force in Gag assembly and maturation. Mutations of the residues at the CTD dimer interface impair virus assembly and render the virus non-infectious. Therefore, the CTD represents a potential target for designing anti-HIV-1 drugs. Results Due to the pivotal role of the dimer interface, we reasoned that peptides from the α-helical region of the dimer interface might be effective as decoys to prevent CTD dimer formation. However, these small peptides do not have any structure in solution and they do not penetrate cells. Therefore, we used the hydrocarbon stapling technique to stabilize the α-helical structure and confirmed by confocal microscopy that this modification also made these peptides cell-penetrating. We also confirmed by using isothermal titration calorimetry (ITC, sedimentation equilibrium and NMR that these peptides indeed disrupt dimer formation. In in vitro assembly assays, the peptides inhibited mature-like virus particle formation and specifically inhibited HIV-1 production in cell-based assays. These peptides also showed potent antiviral activity against a large panel of laboratory-adapted and primary isolates, including viral strains resistant to inhibitors of reverse transcriptase and protease. Conclusions These preliminary data serve as the foundation for designing small, stable, α-helical peptides and small-molecule inhibitors targeted against the CTD dimer interface. The observation that relatively weak CA binders, such as NYAD-201 and NYAD-202, showed specificity and are able to disrupt the CTD dimer is encouraging for further exploration of a much broader class of antiviral compounds targeting CA. We cannot exclude the possibility that the CA-based peptides described here could elicit additional effects on virus replication not directly linked to their ability to bind

  3. An artemisinin-derived dimer has highly potent anti-cytomegalovirus (CMV and anti-cancer activities.

    Directory of Open Access Journals (Sweden)

    Ran He

    Full Text Available We recently reported that two artemisinin-derived dimers (dimer primary alcohol 606 and dimer sulfone 4-carbamate 832-4 are significantly more potent in inhibiting human cytomegalovirus (CMV replication than artemisinin-derived monomers. In our continued evaluation of the activities of artemisinins in CMV inhibition, twelve artemisinin-derived dimers and five artemisinin-derived monomers were used. Dimers as a group were found to be potent inhibitors of CMV replication. Comparison of CMV inhibition and the slope parameter of dimers and monomers suggest that dimers are distinct in their anti-CMV activities. A deoxy dimer (574, lacking the endoperoxide bridge, did not have any effect on CMV replication, suggesting a role for the endoperoxide bridge in CMV inhibition. Differences in anti-CMV activity were observed among three structural analogs of dimer sulfone 4-carbamate 832-4 indicating that the exact placement and oxidation state of the sulfur atom may contribute to its anti-CMV activity. Of all tested dimers, artemisinin-derived diphenyl phosphate dimer 838 proved to be the most potent inhibitor of CMV replication, with a selectivity index of approximately 1500, compared to our previously reported dimer sulfone 4-carbamate 832-4 with a selectivity index of about 900. Diphenyl phosphate dimer 838 was highly active against a Ganciclovir-resistant CMV strain and was also the most active dimer in inhibition of cancer cell growth. Thus, diphenyl phosphate dimer 838 may represent a lead for development of a highly potent and safe anti-CMV compound.

  4. SOXE transcription factors form selective dimers on non-compact DNA motifs through multifaceted interactions between dimerization and high-mobility group domains. (United States)

    Huang, Yong-Heng; Jankowski, Aleksander; Cheah, Kathryn S E; Prabhakar, Shyam; Jauch, Ralf


    The SOXE transcription factors SOX8, SOX9 and SOX10 are master regulators of mammalian development directing sex determination, gliogenesis, pancreas specification and neural crest development. We identified a set of palindromic SOX binding sites specifically enriched in regulatory regions of melanoma cells. SOXE proteins homodimerize on these sequences with high cooperativity. In contrast to other transcription factor dimers, which are typically rigidly spaced, SOXE group proteins can bind cooperatively at a wide range of dimer spacings. Using truncated forms of SOXE proteins, we show that a single dimerization (DIM) domain, that precedes the DNA binding high mobility group (HMG) domain, is sufficient for dimer formation, suggesting that DIM : HMG rather than DIM:DIM interactions mediate the dimerization. All SOXE members can also heterodimerize in this fashion, whereas SOXE heterodimers with SOX2, SOX4, SOX6 and SOX18 are not supported. We propose a structural model where SOXE-specific intramolecular DIM:HMG interactions are allosterically communicated to the HMG of juxtaposed molecules. Collectively, SOXE factors evolved a unique mode to combinatorially regulate their target genes that relies on a multifaceted interplay between the HMG and DIM domains. This property potentially extends further the diversity of target genes and cell-specific functions that are regulated by SOXE proteins.

  5. SOXE transcription factors form selective dimers on non-compact DNA motifs through multifaceted interactions between dimerization and high-mobility group domains (United States)

    Huang, Yong-Heng; Jankowski, Aleksander; Cheah, Kathryn S. E.; Prabhakar, Shyam; Jauch, Ralf


    The SOXE transcription factors SOX8, SOX9 and SOX10 are master regulators of mammalian development directing sex determination, gliogenesis, pancreas specification and neural crest development. We identified a set of palindromic SOX binding sites specifically enriched in regulatory regions of melanoma cells. SOXE proteins homodimerize on these sequences with high cooperativity. In contrast to other transcription factor dimers, which are typically rigidly spaced, SOXE group proteins can bind cooperatively at a wide range of dimer spacings. Using truncated forms of SOXE proteins, we show that a single dimerization (DIM) domain, that precedes the DNA binding high mobility group (HMG) domain, is sufficient for dimer formation, suggesting that DIM : HMG rather than DIM:DIM interactions mediate the dimerization. All SOXE members can also heterodimerize in this fashion, whereas SOXE heterodimers with SOX2, SOX4, SOX6 and SOX18 are not supported. We propose a structural model where SOXE-specific intramolecular DIM:HMG interactions are allosterically communicated to the HMG of juxtaposed molecules. Collectively, SOXE factors evolved a unique mode to combinatorially regulate their target genes that relies on a multifaceted interplay between the HMG and DIM domains. This property potentially extends further the diversity of target genes and cell-specific functions that are regulated by SOXE proteins. PMID:26013289

  6. Steroid dimer formation: metal reduction of methyl androst-4-ene-3, 17-dion-19-oate. (United States)

    Templeton, J F; Majgier-Baranowska, H; Marat, K


    Two isomeric dimeric steroids, 3,3'-bis(methyl 3-hydroxyandrost-4-en-17-on-19-oate-3-yl), with symmetrical (alpha, alpha') and unsymmetrical structures (alpha,beta'), have been obtained by reduction of methyl androst-4-ene-3,17-dion-19-oate with zinc in aqueous acetic acid together with the major products, the isomeric methyl 5alpha- and 5beta-androst-3-en-17-on-19-oates. The structures of the dimers and unsaturated products are supported by spectroscopic methods. The symmetrical dimer was also obtained from treatment of the 4-en-3-on-19-oate ester with lithium in ammonia.

  7. Defective thymine dimer excision by cell-free extracts of xeroderma pigmentosum cells

    International Nuclear Information System (INIS)

    Mortelmans, K.; Friedberg, E.C.; Slor, H.; Thomas, G.; Cleaver, J.E.


    Crude extracts of normal human diploid fibroblasts and of human peripheral blood lymphocytes excise thymine dimers from purified ultraviolet-irradiated DNA, or from the DNA presumably present as chromatin in unfractionated cell-free preparations of cells that had been labeled with [ 3 H]thymidine. Extracts of xeroderma pigmentosum cells from complementation groups A, C, and D also excise thymine dimers from purified DNA, but extracts of group A cells do not excise dimers from the DNA of radioactively labeled unfractionated cell-free preparations

  8. Synthesis of ciprofloxacin dimers for evaluation of bacterial permeability in atypical chemical space. (United States)

    Ross, Audrey G; Benton, Bret M; Chin, Donovan; De Pascale, Gianfranco; Fuller, John; Leeds, Jennifer A; Reck, Folkert; Richie, Daryl L; Vo, Jason; LaMarche, Matthew J


    We describe the synthesis and evaluation of a library of variably-linked ciprofloxacin dimers. These structures unify and expand on the use of fluoroquinolones as probes throughout the antibiotic literature. A dimeric analog (19) showed enhanced inhibition of its intracellular target (DNA gyrase), and translation to antibacterial activity in whole cells was demonstrated. Overall, cell permeation was governed by physicochemical properties and bacterial type. A principal component analysis demonstrated that the dimers occupy a unique and privileged region of chemical space most similar to the macrolide class of antibiotics. Copyright © 2015 Elsevier Ltd. All rights reserved.

  9. CO dimer: new potential energy surface and rovibrational calculations. (United States)

    Dawes, Richard; Wang, Xiao-Gang; Carrington, Tucker


    The spectrum of CO dimer was investigated by solving the rovibrational Schrödinger equation on a new potential energy surface constructed from coupled-cluster ab initio points. The Schrödinger equation was solved with a Lanczos algorithm. Several 4D (rigid monomer) global ab initio potential energy surfaces (PESs) were made using a previously reported interpolating moving least-squares (IMLS) fitting procedure specialized to describe the interaction of two linear fragments. The potential has two nonpolar minima giving rise to a complicated set of energy level stacks, which are very sensitive to the shapes and relative depths of the two wells. Although the CO dimer has defied previous attempts at an accurate purely ab initio description our best surface yields results in good agreement with experiment. Root-mean-square (rms) fitting errors of less than 0.1 cm(-1) were obtained for each of the fits using 2226 ab initio data at different levels. This allowed direct assessment of the quality of various levels of ab initio theory for prediction of spectra. Our tests indicate that standard CCSD(T) is slow to converge the interaction energy even when sextuple zeta bases as large as ACV6Z are used. The explicitly correlated CCSD(T)-F12b method was found to recover significantly more correlation energy (from singles and doubles) at the CBS limit. Correlation of the core-electrons was found to be important for this system. The best PES was obtained by extrapolation of calculations at the CCSD(T)(AE)-F12b/CVnZ-F12 (n = 3,4) levels. The calculated energy levels were compared to 105 J ≤ 10 levels from experiment. The rms error for 68 levels with J ≤ 6 is only 0.29 cm(-1). The calculated energy levels were assigned stack labels using several tools. New stacks were found. One of them, stack y1, has an energy lower than many previously known stacks and may be observable.

  10. Aberrant phenotypes of transgenic mice expressing dimeric human erythropoietin

    Directory of Open Access Journals (Sweden)

    Yun Seong-Jo


    Full Text Available Abstract Background Dimeric human erythropoietin (dHuEPO peptides are reported to exhibit significantly higher biological activity than the monomeric form of recombinant EPO. The objective of this study was to produce transgenic (tg mice expressing dHuEPO and to investigate the characteristics of these mice. Methods A dHuEPO-expressing vector under the control of the goat beta-casein promoter, which produced a dimer of human EPO molecules linked by a 2-amino acid peptide linker (Asp-Ile, was constructed and injected into 1-cell fertilized embryos by microinjection. Mice were screened using genomic DNA samples obtained from tail biopsies. Blood samples were obtained by heart puncture using heparinized tubes, and hematologic parameters were assessed. Using the microarray analysis tool, we analyzed differences in gene expression in the spleens of tg and control mice. Results A high rate of spontaneous abortion or death of the offspring was observed in the recipients of dHuEPO embryos. We obtained 3 founder lines (#4, #11, and #47 of tg mice expressing the dHuEPO gene. However, only one founder line showed stable germline integration and transmission, subsequently establishing the only transgenic line (#11. We obtained 2 F1 mice and 3 F2 mice from line #11. The dHuEPO protein could not be obtained because of repeated spontaneous abortions in the tg mice. Tg mice exhibited symptoms such as short lifespan and abnormal blood composition. The red blood cell count, white blood cell count, and hematocrit levels in the tg mice were remarkably higher than those in the control mice. The spleens of the tg mice (F1 and F2 females were 11- and -21-fold larger than those of the control mice. Microarray analysis revealed 2,672 spleen-derived candidate genes; more genes were downregulated than upregulated (849/764. Reverse transcriptase-polymerase chain reaction (RT-PCR and quantitative real-time PCR (qRT-PCR were used for validating the results of the microarray

  11. Spin Quantum Tunneling via Entangled States in a Dimer of Exchange-Coupled Single-Molecule Magnets (United States)

    Tiron, R.; Wernsdorfer, W.; Foguet-Albiol, D.; Aliaga-Alcalde, N.; Christou, G.


    A new family of supramolecular, antiferromagnetically exchange-coupled dimers of single-molecule magnets (SMMs) has recently been reported. Each SMM acts as a bias on its neighbor, shifting the quantum tunneling resonances of the individual SMMs. Hysteresis loop measurements on a single crystal of SMM dimers have now established quantum tunneling of the magnetization via entangled states of the dimer. This shows that the dimer really does behave as a quantum mechanically coupled dimer, and also allows the measurement of the longitudinal and transverse superexchange coupling constants.

  12. Discrete Dipole Approximation Simulation of Nearly Touching Plasmonic Au Dimers and Influence of Particle Shape Assembly on Optical Response. (United States)

    Xu, Xi-Bin; Wang, Yu-Ying; Yi, Zao; Li, Xi-Bo; Luo, Jiang-Shan; Luo, Bing-Chi; Yi, You-Gen; Tang, Yong-Jian


    The method Discrete Dipole Approximation (DDA) is used to calculate the extinction spectra and field distribution of three types of dimers. In the paper we provide a systematic analysis of the optical response of different nanoscopic dimer structures with relatively small gap distances. A description is given about how the energy and excitation cross sections of dimer plasmons depend on nanoparticle separation. Resonance peaks of dimers show red-shift compared with single nanoparticle. Dimers formed by different single particle display distinct optical response. Interaction junctions in dimers can serve as hot spots for field enhancement. Field distribution in gaps made of two flat planes is nearly continuous. Changing gaps between two particles in dimers can tune the resonance wavelength effectively as well as different particle ensembles. Existence of sharp corners can attract and change field distribution. It is not effective volume but the effective cross-section that dominates the extinction efficiency.

  13. Self-Assembling Multifunctional Peptide Dimers for Gene Delivery Systems

    Directory of Open Access Journals (Sweden)

    Kitae Ryu


    Full Text Available Self-assembling multifunctional peptide was designed for gene delivery systems. The multifunctional peptide (MP consists of cellular penetrating peptide moiety (R8, matrix metalloproteinase-2 (MMP-2 specific sequence (GPLGV, pH-responsive moiety (H5, and hydrophobic moiety (palmitic acid (CR8GPLGVH5-Pal. MP was oxidized to form multifunctional peptide dimer (MPD by DMSO oxidation of thiols in terminal cysteine residues. MPD could condense pDNA successfully at a weight ratio of 5. MPD itself could self-assemble into submicron micelle particles via hydrophobic interaction, of which critical micelle concentration is about 0.01 mM. MPD showed concentration-dependent but low cytotoxicity in comparison with PEI25k. MPD polyplexes showed low transfection efficiency in HEK293 cells expressing low level of MMP-2 but high transfection efficiency in A549 and C2C12 cells expressing high level of MMP-2, meaning the enhanced transfection efficiency probably due to MMP-induced structural change of polyplexes. Bafilomycin A1-treated transfection results suggest that the transfection of MPD is mediated via endosomal escape by endosome buffering ability. These results show the potential of MPD for MMP-2 targeted gene delivery systems due to its multifunctionality.

  14. Phosphorous dimerization in GaP high-pressure polymorph

    Energy Technology Data Exchange (ETDEWEB)

    Lavina, Barbara [Univ. of Nevada, Las Vegas, NV (United States). High Pressure Science and Engineering Center (HiPSEC), Dept. of Physics and Astronomy; Kim, Eunja [Univ. of Nevada, Las Vegas, NV (United States). Dept. of Physics and Astronomy; Cynn, Hyunchae [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Weck, Philippe F [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Seaborg, Kelly [Univ. of Nevada, Las Vegas, NV (United States). High Pressure Science and Engineering Center (HiPSEC), Dept. of Physics and Astronomy; Siska, Emily [Univ. of Nevada, Las Vegas, NV (United States). High Pressure Science and Engineering Center (HiPSEC); Meng, Yue [Carnegie Inst. of Washington, Argonne, IL (United States). Geophysical Lab., High Pressure Collaborative Access Team (HPCAT); Evans, Williams [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)


    We report on the experimental and theoretical characterization of a novel GaP polymorph formed by laser heating of a single crystal of GaP-II in its stable region near 43 GPa. Thereby formed unstrained multigrain sample at 43 GPa and 1300 K, allowed high-resolution crystallographic analysis. We find an oS24 as an energetically optimized crystal structure contrary to oS8 reported by Nelmes et al. (1997). Our DFT calculation confirms a stable existence of oS24 between 18 – 50 GPa. The emergence of the oS24 structure is related to the differentiation of phosphorous atoms between those forming P-P dimers and those forming P-Ga bonds only. Bonding anisotropy explains the symmetry lowering with respect to what is generally expected for semiconductors high-pressure polymorphs. The metallization of GaP does not occur through a uniform change of the nature of its bonds but through the formation of an anisotropic phase containing different bond types.

  15. Bright Solitons in a PT-Symmetric Chain of Dimers

    Directory of Open Access Journals (Sweden)

    Omar B. Kirikchi


    Full Text Available We study the existence and stability of fundamental bright discrete solitons in a parity-time- (PT- symmetric coupler composed by a chain of dimers that is modelled by linearly coupled discrete nonlinear Schrödinger equations with gain and loss terms. We use a perturbation theory for small coupling between the lattices to perform the analysis, which is then confirmed by numerical calculations. Such analysis is based on the concept of the so-called anticontinuum limit approach. We consider the fundamental onsite and intersite bright solitons. Each solution has symmetric and antisymmetric configurations between the arms. The stability of the solutions is then determined by solving the corresponding eigenvalue problem. We obtain that both symmetric and antisymmetric onsite mode can be stable for small coupling, in contrast to the reported continuum limit where the antisymmetric solutions are always unstable. The instability is either due to the internal modes crossing the origin or the appearance of a quartet of complex eigenvalues. In general, the gain-loss term can be considered parasitic as it reduces the stability region of the onsite solitons. Additionally, we analyse the dynamic behaviour of the onsite and intersite solitons when unstable, where typically it is either in the form of travelling solitons or soliton blow-ups.

  16. Roughness effect on the efficiency of dimer antenna based biosensor

    Directory of Open Access Journals (Sweden)

    D. Barchiesi


    Full Text Available The fabrication process of nanodevices is continually improved. However, most of the nanodevices, such as biosensors present rough surfaces with mean roughness of some nanometers even if the deposition rate of material is more controlled. The effect of roughness on performance of biosensors was fully addressed for plane biosensors and gratings, but rarely addressed for biosensors based on Local Plasmon Resonance. The purpose of this paper is to evaluate numerically the influence of nanometric roughness on the efficiency of a dimer nano-biosensor (two levels of roughness are considered. Therefore, we propose a general numerical method, that can be applied to any other nanometric shape, to take into account the roughness in a three dimensional model. The study focuses on both the far-field, which corresponds to the experimental detected data, and the near-field, responsible for exciting and then detecting biological molecules. The results suggest that the biosensor efficiency is highly sensitive to the surface roughness. The roughness can produce important shifts of the extinction efficiency peak and a decrease of its amplitude resulting from changes in the distribution of near-field and absorbed electric field intensities.

  17. Dimerization-dependent green and yellow fluorescent proteins. (United States)

    Alford, Spencer C; Ding, Yidan; Simmen, Thomas; Campbell, Robert E


    Dimerization-dependent fluorescent proteins (ddFP) are a recently introduced class of genetically encoded reporters that can be used for the detection of protein interactions in live cells. The progenitor of this class of tools was a red fluorescent ddFP (ddRFP) derived from a homodimeric variant of Discosoma red fluorescent protein. Here, we describe the engineering and application of an expanded palette of ddFPs, which includes green (ddGFP) and yellow (ddYFP) variants. These optimized variants offer several advantages relative to ddRFP including increased in vitro contrast and brightness for ddGFP and increased brightness and a lowered pK a for ddYFP. We demonstrate that both variants are useful as biosensors for protease activity in live cells. Using the ddGFP tool, we generated a highly effective indicator of endomembrane proximity that can be used to image the mitochondria-associated membrane (MAM) interface of endoplasmic reticulum (ER) and mitochondria.

  18. Rotation and Negative Torque in Electrodynamically Bound Nanoparticle Dimers

    Energy Technology Data Exchange (ETDEWEB)

    Sule, Nishant [James; Yifat, Yuval [James; Gray, Stephen K. [Center; Scherer, Norbert F. [James; Department


    We examine the formation and concomitant rotation of electrodynamically bound dimers (EBD) of 150nm diameter Ag nanoparticles trapped in circularly polarized focused Gaussian beams. The rotation frequency of an EBD increases linearly with the incident beam power, reaching high mean values of ~ 4kHz for a relatively low incident power of 14mW. Using a coupled-dipole/effective polarizability model, we reveal that retardation of the scattered fields and electrodynamic interactions can lead to a “negative torque” causing rotation of the EBD in the direction opposite to that of the circular polarization. This intriguing opposite-handed rotation due to negative torque is clearly demonstrated using electrodynamics-Langevin dynamics simulations by changing particle separations and thus varying the retardation effects. Finally, negative torque is also demonstrated in experiments from statistical analysis of the EBD trajectories. These results demonstrate novel rotational dynamics of nanoparticles in optical matter using circular polarization and open a new avenue to control orientational dynamics through coupling to interparticle separation.

  19. Antifungal dimeric chalcone derivative kamalachalcone E from Mallotus philippinensis. (United States)

    Kulkarni, Roshan R; Tupe, Santosh G; Gample, Suwarna P; Chandgude, Macchindra G; Sarkar, Dhiman; Deshpande, Mukund V; Joshi, Swati P


    From the red coloured extract (Kamala) prepared through acetone extraction of the fresh whole uncrushed fruits of Mallotus philippinensis, one new dimeric chalcone (1) along with three known compounds 1-(5,7-dihydroxy-2,2,6-trimethyl-2H-1-benzopyran-8-yl)-3-phenyl-2-propen-1-one (2), rottlerin (3) and 4'-hydroxyrottlerin (4) were isolated. The structure of compound 1 was elucidated by 1D and 2D NMR analyses that included HSQC, HMBC, COSY and ROESY experiments along with the literature comparison. Compounds 1-4 were evaluated for antifungal activity against different human pathogenic yeasts and filamentous fungi. The antiproliferative activity of the compounds was evaluated against Thp-1 cell lines. Compounds 1 and 2 both exhibited IC50 of 8, 4 and 16 μg/mL against Cryptococcus neoformans PRL518, C. neoformans ATCC32045 and Aspergillus fumigatus, respectively. Compound 4, at 100 μg/mL, showed 54% growth inhibition of Thp-1 cell lines.

  20. Extracting Structure Parameters of Dimers for Molecular Tunneling Ionization Model (United States)

    Zhao, Song-Feng; Huang, Fang; Wang, Guo-Li; Zhou, Xiao-Xin


    We determine structure parameters of the highest occupied molecular orbital (HOMO) of 27 dimers for the molecular tunneling ionization (so called MO-ADK) model of Tong et al. [Phys. Rev. A 66 (2002) 033402]. The molecular wave functions with correct asymptotic behavior are obtained by solving the time-independent Schrödinger equation with B-spline functions and molecular potentials which are numerically created using the density functional theory. We examine the alignment-dependent tunneling ionization probabilities from MO-ADK model for several molecules by comparing with the molecular strong-field approximation (MO-SFA) calculations. We show the molecular Perelomov–Popov–Terent'ev (MO-PPT) can successfully give the laser wavelength dependence of ionization rates (or probabilities). Based on the MO-PPT model, two diatomic molecules having valence orbital with antibonding systems (i.e., Cl2, Ne2) show strong ionization suppression when compared with their corresponding closest companion atoms. Supported by National Natural Science Foundation of China under Grant Nos. 11164025, 11264036, 11465016, 11364038, the Specialized Research Fund for the Doctoral Program of Higher Education of China under Grant No. 20116203120001, and the Basic Scientific Research Foundation for Institution of Higher Learning of Gansu Province

  1. Photoinduced High-Frequency Charge Oscillations in Dimerized Systems (United States)

    Yonemitsu, Kenji


    Photoinduced charge dynamics in dimerized systems is studied on the basis of the exact diagonalization method and the time-dependent Schrödinger equation for a one-dimensional spinless-fermion model at half filling and a two-dimensional model for κ-(bis[ethylenedithio]tetrathiafulvalene)2X [κ-(BEDT-TTF)2X] at three-quarter filling. After the application of a one-cycle pulse of a specifically polarized electric field, the charge densities at half of the sites of the system oscillate in the same phase and those at the other half oscillate in the opposite phase. For weak fields, the Fourier transform of the time profile of the charge density at any site after photoexcitation has peaks for finite-sized systems that correspond to those of the steady-state optical conductivity spectrum. For strong fields, these peaks are suppressed and a new peak appears on the high-energy side, that is, the charge densities mainly oscillate with a single frequency, although the oscillation is eventually damped. In the two-dimensional case without intersite repulsion and in the one-dimensional case, this frequency corresponds to charge-transfer processes by which all the bonds connecting the two classes of sites are exploited. Thus, this oscillation behaves as an electronic breathing mode. The relevance of the new peak to a recently found reflectivity peak in κ-(BEDT-TTF)2X after photoexcitation is discussed.

  2. Characterization and modeling of the magnetic field-induced strain and work output in Ni2MnGa magnetic shape memory alloys

    International Nuclear Information System (INIS)

    Kiefer, B.; Karaca, H.E.; Lagoudas, D.C.; Karaman, I.


    This paper is concerned with the experimental characterization and the constitutive modeling of magnetic shape memory alloys (MSMA), in terms of their applicability as actuator materials. The key properties that determine the actuation characteristics are the magnetic field-induced strain (MFIS) and the blocking stress. With the goal of increasing the corresponding actuation output, a material selection strategy was followed which was aimed at obtaining a higher magnetocrystalline anisotropy energy, while keeping the detwinning stress low. This was achieved by choosing a composition in which the separation of the Curie temperature and the martensitic transformation temperatures was large, and then selecting an operating temperature just below the phase transformation temperature. In the selected Ni 51.1 Mn 24.0 Ga 24.9 composition a more than 50% increase of the actuation work output was observed, compared to corresponding data reported in the literature for other off-stoichiometric compositions of the Ni 2 MnGa intermetallic compound. The second part of the paper describes a phenomenological constitutive model that predicts the MFIS hysteresis curves observed in the first part. The model is concerned with the field-induced reorientation of martensitic variants and changes in the magnetic microstructure. Dissipative effects are captured by introducing internal state variables into the free energy function. In its most general form the contributing energy terms are the elastic strain energy, the Zeeman energy, the magnetocrystalline anisotropy energy and appropriate mixing terms. Typical loading cases are considered and the accuracy of the model predictions is evaluated by comparison with the experimental data presented in the first part of this work

  3. Remediation of a contaminated soil by Ni+2 after application of biochar prepared from de-inking paper sludge: Influence on enzyme activities (United States)

    Gascó, G.; Paz-Ferreiro, J.; Araujo, F.; Guerrero, F.; Méndez, A.


    In recent years, an increasing proportion of recycled fibres are used in paper industries due to their important environmental and economical benefits. A ton of pulp produced from recycled paper requires 60% less energy to manufacture than a ton of bleached virgin kraft pulp [1]. However, removing the ink, clay, coatings and contaminants from waste paper in order to produce recycled paper creates large amounts of de-inking paper sludge (DPS). Nowadays, more than 200000 t of DPS were produced in Spain. DPS can be used as amendment due to their high organic matter [2] but the high C/N ratio and the heavy metal content can limit its use. For this reason, the preparation of biochar obtained from pyrolysis process for water remediation [3] and soil contaminated by heavy metal can be an valorisation alternative. The main objective of this work is to study the influence of the biochar application prepared from de-inking sewage sludge in the soil enzyme activities of a contaminated soil by Ni+2 at two different concentrations. For this reason, an incubation experiment was performed and several enzymatic activities (dehydrogenase, b-glucosidase, phosphomoesterase and arylsulphatase) were monitored. The study was completed studying the influence of the biochar application in plant-available metals from soil. [1] Thompson C.G. 1992. Recycled Papers. The Essential Guide, MIT Press, Cambridge. [2] Barriga S., Méndez A., Cámara J., Guerrero F., Gascó G. 2010. Agricultural valorisation of de-inking paper sludge as organic amendment in different soils: Thermal study. Journal of Thermal Analysis and Calorimetry 99: 981-986 [3] Méndez A., Barriga S., Fidalgo J.M., Gascó G. 2009. Adsorbent materials from paper industry waste materials and their use in Cu(II) removal from water. Journal of Hazardous Materials 165: 736-743.

  4. Carboxylate switch between hydro- and carbopalladation pathways in regiodivergent dimerization of alkynes. (United States)

    Zatolochnaya, Olga V; Gordeev, Evgeniy G; Jahier, Claire; Ananikov, Valentine P; Gevorgyan, Vladimir


    Experimental and theoretical investigation of the regiodivergent palladium-catalyzed dimerization of terminal alkynes is presented. Employment of N-heterocyclic carbene-based palladium catalyst in the presence of phosphine ligand allows for highly regio- and stereoselective head-to-head dimerization reaction. Alternatively, addition of carboxylate anion to the reaction mixture triggers selective head-to-tail coupling. Computational studies suggest that reaction proceeds via the hydropalladation pathway favoring head-to-head dimerization under neutral reaction conditions. The origin of the regioselectivity switch can be explained by the dual role of carboxylate anion. Thus, the removal of hydrogen atom by the carboxylate directs reaction from the hydropalladation to the carbopalladation pathway. Additionally, in the presence of the carboxylate anion intermediate, palladium complexes involved in the head-to-tail dimerization display higher stability compared to their analogues for the head-to-head reaction. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Nicotinamidase/pyrazinamidase of Mycobacterium tuberculosis forms homo-dimers stabilized by disulfide bonds. (United States)

    Rueda, Daniel; Sheen, Patricia; Gilman, Robert H; Bueno, Carlos; Santos, Marco; Pando-Robles, Victoria; Batista, Cesar V; Zimic, Mirko


    Recombinant wild-pyrazinamidase from H37Rv Mycobacterium tuberculosis was analyzed by gel electrophoresis under differential reducing conditions to evaluate its quaternary structure. PZAse was fractionated by size exclusion chromatography under non-reducing conditions. PZAse activity was measured and mass spectrometry analysis was performed to determine the identity of proteins by de novo sequencing and to determine the presence of disulfide bonds. This study confirmed that M. tuberculosis wild type PZAse was able to form homo-dimers in vitro. Homo-dimers showed a slightly lower specific PZAse activity compared to monomeric PZAse. PZAse dimers were dissociated into monomers in response to reducing conditions. Mass spectrometry analysis confirmed the existence of disulfide bonds (C72-C138 and C138-C138) stabilizing the quaternary structure of the PZAse homo-dimer. Copyright © 2014 Elsevier Ltd. All rights reserved.

  6. Ortho and para hydrogen dimers on G/SiC(0001): combined STM and DFT study. (United States)

    Merino, P; Švec, M; Martínez, J I; Mutombo, P; Gonzalez, C; Martín-Gago, J A; de Andres, P L; Jelinek, P


    The hydrogen (H) dimer structures formed upon room-temperature H adsorption on single layer graphene (SLG) grown on SiC(0001) are addressed using a combined theoretical-experimental approach. Our study includes density functional theory (DFT) calculations for the full (6√3 × 6√3)R30° unit cell of the SLG/SiC(0001) substrate and atomically resolved scanning tunneling microscopy images determining simultaneously the graphene lattice and the internal structure of the H adsorbates. We show that H atoms normally group in chemisorbed coupled structures of different sizes and orientations. We make an atomic scale determination of the most stable experimental geometries, the small dimers and ellipsoid-shaped features, and we assign them to hydrogen adsorbed in para dimers and ortho dimers configuration, respectively, through comparison with the theory.

  7. Using D-Dimer to Diagnose Painless Acute Aortic Dissection: A Case Report

    Directory of Open Access Journals (Sweden)

    Caroline Barniol


    Case Presentation. We report the case of a 66-year-old Caucasian male who presented a syncope immediately followed by a left-arm weakness while driving his car. Clinical examination was normal, but bilateral jugular vein distension was noted. Electrocardiogram and chest radiography were unremarkable. Among blood tests performed, troponin I test result was negative, and D-dimer test concentration was >4000 ng/mL. Since D-dimer test result was positive, chest computer tomography angiogram was performed and found a thoracic aortic dissection. Conclusion. Our case report shows that acute aortic dissection diagnosis is difficult and must be associated with the interpretation of various clinical signs and D-dimer measurement. It could be helpful for the emergency physician to have a pretest probability D-dimer like in pulmonary embolism diagnosis.

  8. Dimeric ligands for GPCRs involved in human reproduction : synthesis and biological evaluation

    NARCIS (Netherlands)

    Bonger, Kimberly Michelle


    Dimeric ligands for G-protein coupled receptors that are involved in human reproduction, namely the gonadotropin releasing hormone receptor, the luteinizing hormone receptor and the follicle-stimulating hormone receptor, were synthesized and biologically evaluated.

  9. In vitro production of thymine dimer by ultroviolet irradiation of DNA from mesophilic and thermophilic bacteria

    International Nuclear Information System (INIS)

    Yein, F.S.; Stenesh, J.


    Thymine dimer was produced in vitro by ultraviolet irradiation of DNA, isolated from the mesophile Bacillus licheniformis and the thermophile B. stearothermophilus. Irradiation was performed at three different temperaturs (35, 45 and 55 C) and the thymine dimer was isolated and determined. An HPLC procedure was developed that permitted temperature was greater for the thermophile than for the mesophile. Formation of thymine dimer increased with temperature for both organisms but more so for the thermophile; over the temperature range of 35-55 C, the average increase in thymine dimer production for the themrophile was about 4-times that for the mesophile. The melting out temperature, as a function of increasing irradiation temperature, was essentially unchanged for the mesophilic DNA, but decreased progressively for the thermophilic DNA. These results are discussed in terms of the macromolecular theory of to the macromolecular theory of the thermophily. (author). 31 refs.; 4 figs.; 3 tabs

  10. A strategy for complex dimer formation when biomimicry fails: total synthesis of ten coccinellid alkaloids. (United States)

    Sherwood, Trevor C; Trotta, Adam H; Snyder, Scott A


    Although dimeric natural products can often be synthesized in the laboratory by directly merging advanced monomers, these approaches sometimes fail, leading instead to non-natural architectures via incorrect unions. Such a situation arose during our studies of the coccinellid alkaloids, when attempts to directly dimerize Nature's presumed monomeric precursors in a putative biomimetic sequence afforded only a non-natural analogue through improper regiocontrol. Herein, we outline a unique strategy for dimer formation that obviates these difficulties, one which rapidly constructs the coccinellid dimers psylloborine A and isopsylloborine A through a terminating sequence of two reaction cascades that generate five bonds, five rings, and four stereocenters. In addition, a common synthetic intermediate is identified which allows for the rapid, asymmetric formal or complete total syntheses of eight monomeric members of the class.

  11. Van der Waals potential and vibrational energy levels of the ground state radon dimer (United States)

    Sheng, Xiaowei; Qian, Shifeng; Hu, Fengfei


    In the present paper, the ground state van der Waals potential of the Radon dimer is described by the Tang-Toennies potential model, which requires five essential parameters. Among them, the two dispersion coefficients C6 and C8 are estimated from the well determined dispersion coefficients C6 and C8 of Xe2. C10 is estimated by using the approximation equation that C6C10/C82 has an average value of 1.221 for all the rare gas dimers. With these estimated dispersion coefficients and the well determined well depth De and Re the Born-Mayer parameters A and b are derived. Then the vibrational energy levels of the ground state radon dimer are calculated. 40 vibrational energy levels are observed in the ground state of Rn2 dimer. The last vibrational energy level is bound by only 0.0012 cm-1.

  12. Structural proof of a dimeric positive modulator bridging two identical AMPA receptor-binding sites

    DEFF Research Database (Denmark)

    Kaae, Birgitte Høiriis; Harpsøe, Kasper; Kastrup, Jette Sandholm Jensen


    have dramatically increased potencies, more than three orders of magnitude higher than the corresponding monomers. Dimer (R,R)-2a was cocrystallized with the GluR2-S1S2J construct, and an X-ray crystallographic analysis showed (R,R)-2a to bridge two identical binding pockets on two neighboring GluR2......Dimeric positive allosteric modulators of ionotropic glutamate receptors were designed, synthesized, and characterized pharmacologically in electrophysiological experiments. The designed compounds are dimers of arylpropylsulfonamides and have been constructed without a linker. The monomeric...... arylpropylsulfonamides were derived from known modulators and target the cyclothiazide-binding site at the AMPA receptors. The three stereoisomers--R,R, meso, and S,S--of the two constructed dimers were prepared, and in vitro testing showed the R,R forms to be the most potent stereoisomers. The biarylpropylsulfonamides...

  13. Robust Discrimination between Single Gold Nanoparticles and Their Dimers in Aqueous Solution for Ultrasensitive Homogeneous Bioassays

    Directory of Open Access Journals (Sweden)

    Jun Kobayashi


    Full Text Available We propose a robust method to distinguish isolated single gold nanoparticles (AuNP monomers and their dimers under Brownian motion, a key for ultrasensitive homogeneous bioassays, including AuNP sandwich assays. To detect dimers and distinguish them from a larger number of monomers in aqueous solution, single-particle polarization microscopy was performed. For the accurate detection of individual particles, the optical anisotropy and rotational diffusion time are measured because a dimer is much more anisotropic than the nearly spherical monomer and the rotational diffusion time of a dimer is four times that of a monomer. By employing an autocorrelation analysis, we defined a measure of distinguishing that simultaneously enables high detection probability and low error probability. The detection platform offers homogeneous DNA hybridization assays and immunoassays at the subpicomolar level.

  14. Relative stabilities and the spectral signatures of stacked and hydrogen-bonded dimers of serotonin (United States)

    Dev, S.; Giri, K.; Majumder, M.; Sathyamurthy, N.


    The O-HṡṡṡN hydrogen-bonded dimer of serotonin is shown to be more stable than the stacked dimer in its ground electronic state, by using the Møller-Plesset second-order perturbation theory (MP2) and the 6-31g** basis set. The vertical excitation energy for the lowest π → π* transition for the monomer as well as the dimer is predicted by time-dependent density functional theory. The experimentally observed red shift of excitation wavelength on oligomerisation is explained in terms of the change in the HOMO-LUMO energy gap due to complex formation. The impact of dimer formation on the proton magnetic resonance spectrum of serotonin monomer is also examined.

  15. Transformations of griseofulvin in strong acidic conditions--crystal structures of 2'-demethylgriseofulvin and dimerized griseofulvin. (United States)

    Leśniewska, Barbara; Jebors, Said; Coleman, Anthony W; Suwińska, Kinga


    The structure of griseofulvic acid, C16H15ClO6, at 100 K has orthorhombic (P2(1)2(1)2) symmetry. It is of interest with respect to biological activity. The structure displays intermolecular O-H...O, C-H...O hydrogen bonding as well as week C-H...pi and pi...pi interactions. In strong acidic conditions the griseofulvin undergoes dimerization. The structure of dimerized griseofulvin, C34H32C12O12 x C2H6O x H2O, at 100 K has monoclinic (P2(1)) symmetry. The molecule crystallized as a solvate with one ethanol and one water molecule. The dimeric molecules form intermolecular O-H...O hydrogen bonds to solvents molecules only but they interact via week C-H...O, C-H...pi, C-Cl...pi and pi...pi interactions with other dimerized molecules.

  16. Human cystatin C forms an inactive dimer during intracellular trafficking in transfected CHO cells

    DEFF Research Database (Denmark)

    Merz, G S; Benedikz, Eirikur; Schwenk, V


    To define the cellular processing of human cystatin C as well as to lay the groundwork for investigating its contribution to lcelandic Hereditary Cerebral Hemorrhage with Amyloidosis (HCHWA-I), we have characterized the trafficking, secretion, and extracellular fate of human cystatin C...... that the cystatin C dimer, formed during intracellular trafficking, is converted to monomer at or before secretion. Cells in which exit from the endoplasmic reticulum (ER) was blocked with brefeldin A contained the 33 kDa species, indicating that cystatin C dimerization occurs in the ER. After removal of brefeldin......, presumably as a consequence of the low pH of late endosome/lysosomes. As a dimer, cystatin C would be prevented from inhibiting the lysosomal cysteine proteases. These results reveal a novel mechanism, transient dimerization, by which cystatin C is inactivated during the early part of its trafficking through...

  17. Biosynthesis of intestinal microvillar proteins. Dimerization of aminopeptidase N and lactase-phlorizin hydrolase

    DEFF Research Database (Denmark)

    Danielsen, E M


    of dimers of this enzyme therefore occurs prior to the Golgi-associated processing, and the slow rate of dimerization may be the rate-limiting step in the transport from the endoplasmic reticulum to the Golgi complex. For lactase-phlorizin hydrolase, the posttranslational processing includes a proteolytic......The pig intestinal brush border enzymes aminopeptidase N (EC and lactase-phlorizin hydrolase (EC are present in the microvillar membrane as homodimers. Dimethyl adipimidate was used to cross-link the two [35S]methionine-labeled brush border enzymes from cultured mucosal...... explants. For aminopeptidase N, dimerization did not begin until 5-10 min after synthesis, and maximal dimerization by cross-linking of the transient form of the enzyme required 1 h, whereas the mature form of aminopeptidase N cross-linked with unchanged efficiency from 45 min to 3 h of labeling. Formation...

  18. Deciphering the kinetic binding mechanism of dimeric ligands using a potent plasma-stable dimeric inhibitor of postsynaptic density protein-95 as an example

    DEFF Research Database (Denmark)

    Chi, Celestine N; Bach, Anders; Gottschalk, Marie


    Dimeric ligands can be potent inhibitors of protein-protein or enzyme-substrate interactions. They have increased affinity and specificity toward their targets due to their ability to bind two binding sites simultaneously and are therefore attractive in drug design. However, few studies have...... addressed the kinetic mechanism of interaction of such bivalent ligands. We have investigated the binding interaction of a recently identified potent plasma-stable dimeric pentapeptide and PDZ1-2 of postsynaptic density protein-95 (PSD-95) using protein engineering in combination with fluorescence...

  19. Solution-dispersible Au nanocube dimers with greatly enhanced two-photon luminescence and SERS (United States)

    Liu, Xiao-Li; Liang, Shan; Nan, Fan; Yang, Zhong-Jian; Yu, Xue-Feng; Zhou, Li; Hao, Zhong-Hua; Wang, Qu-Quan


    We report the synthesis of 43-nm diameter Au nanocube dimers by using Ag+ ions as competitive ligands to freeze l-cysteine-induced assembly process of the nanocubes to a desirable stage. Ascribed to the resonant interparticle coupling with an newly arising plasmon band at 710 nm and local field enhancement, the two-photon luminescence intensity of the Au nanocube dimers in solution was over 20 times stronger than that of the monomers in the wavelength range 555-620 nm. Furthermore, by coupling Raman tags onto the nanocube surface, a solution-based surface-enhanced Raman scattering (SERS) of the nanocube dimers had an enhancement factor of over 10 times compared to the isolated nanocubes. To sum up, with high stability in solution and attractive optical properties, the Au nanocube dimers have potential applications in in vivo bio-imaging and solution-based SERS.We report the synthesis of 43-nm diameter Au nanocube dimers by using Ag+ ions as competitive ligands to freeze l-cysteine-induced assembly process of the nanocubes to a desirable stage. Ascribed to the resonant interparticle coupling with an newly arising plasmon band at 710 nm and local field enhancement, the two-photon luminescence intensity of the Au nanocube dimers in solution was over 20 times stronger than that of the monomers in the wavelength range 555-620 nm. Furthermore, by coupling Raman tags onto the nanocube surface, a solution-based surface-enhanced Raman scattering (SERS) of the nanocube dimers had an enhancement factor of over 10 times compared to the isolated nanocubes. To sum up, with high stability in solution and attractive optical properties, the Au nanocube dimers have potential applications in in vivo bio-imaging and solution-based SERS. Electronic supplementary information (ESI) available. See DOI: 10.1039/c3nr01170d

  20. Comprehensive prediction in 78 human cell lines reveals rigidity and compactness of transcription factor dimers (United States)

    Jankowski, Aleksander; Szczurek, Ewa; Jauch, Ralf; Tiuryn, Jerzy; Prabhakar, Shyam


    The binding of transcription factors (TFs) to their specific motifs in genomic regulatory regions is commonly studied in isolation. However, in order to elucidate the mechanisms of transcriptional regulation, it is essential to determine which TFs bind DNA cooperatively as dimers and to infer the precise nature of these interactions. So far, only a small number of such dimeric complexes are known. Here, we present an algorithm for predicting cell-type–specific TF–TF dimerization on DNA on a large scale, using DNase I hypersensitivity data from 78 human cell lines. We represented the universe of possible TF complexes by their corresponding motif complexes, and analyzed their occurrence at cell-type–specific DNase I hypersensitive sites. Based on ∼1.4 billion tests for motif complex enrichment, we predicted 603 highly significant cell-type–specific TF dimers, the vast majority of which are novel. Our predictions included 76% (19/25) of the known dimeric complexes and showed significant overlap with an experimental database of protein–protein interactions. They were also independently supported by evolutionary conservation, as well as quantitative variation in DNase I digestion patterns. Notably, the known and predicted TF dimers were almost always highly compact and rigidly spaced, suggesting that TFs dimerize in close proximity to their partners, which results in strict constraints on the structure of the DNA-bound complex. Overall, our results indicate that chromatin openness profiles are highly predictive of cell-type–specific TF–TF interactions. Moreover, cooperative TF dimerization seems to be a widespread phenomenon, with multiple TF complexes predicted in most cell types. PMID:23554463

  1. Effectiveness of d-dimer as a screening test for venous thromboembolism: an update. (United States)

    Pulivarthi, Swaroopa; Gurram, Murali Krishna


    Venous thromboembolism (VTE) is the leading cause of morbidity and mortality among hospitalized patients. We searched the PubMed database and reviewed the articles published until June 2011. Articles related to the D-dimer and VTE were considered to write this paper. Many factors play a key role in changing the sensitivity and specificity of D-dimer testing, including the extent of thrombosis and fibrinolytic activity, duration of symptoms, anticoagulant therapy, comorbidity due to surgical or medical illnesses, inflammatory diseases, cancer, elderly age, pregnancy and the postpartum period, and previous VTE. Many previous studies have shown that the D-dimer test is highly sensitive (>95%) in acute deep venous thrombosis or pulmonary embolism, usually with a cut-off value of 500 μg FEU/l, which reasonably rules out acute VTE, particularly in patients with low clinical probability (LCP) or intermediate clinical probability. Patients with high D-dimer levels upon presentation may prompt a more intense diagnostic approach, irrespective of pretest probability. Studies performed after a negative D-dimer for 3 months proved the high negative predictive value (NPV) of D-dimer testing together with LCP in patients with suspected VTE. Among oncology patients, D-dimer testing has the highest sensitivity and NPV in excluding VTE. The new cutoff values of D-dimer testing were analyzed in a recent prospective study of pregnant women; they are 286 ng DDU/ml, 457 ng DDU/ml, and 644 ng DDU/ml for the first, second, and third trimesters, respectively.

  2. Dimerization of 3He in 3He-4He dilute mixtures filling narrow channels

    International Nuclear Information System (INIS)

    Bashkin, Eugene P.; Wojdylo, John


    We consider dimerization of 3 He in a dilute solution of 3 He in superfluid 4 He filling straight narrow channels that can be found in nanoscale porous media. Dimer formation is facilitated by the restricted geometry and occurs despite the fact that in bulk fluid the interparticle interaction is too weak to lead to a bound state. Dimerization results in the effective 'bosonization' of the system: a Bose quantum fluid of ( 3 He) 2 arises in place of the 3 He Fermi component. At high temperatures, when the 3 He impurity quasiparticles form a Maxwell-Boltzmann gas, a drastic change in the thermodynamics occurs due to the presence of dimers. The specific heat and magnetic susceptibility of the 3 He component, which we calculate at arbitrary degrees of dimerization, show a marked deviation from behavior expected of an undimerized 3 He component. We show that the binding energy--which depends on the channel width--is expected to be sufficiently high to make experimental observation feasible. The presence of ( 3 He) 2 dimers gives rise to an extra absorption mechanism for first sound propagating through the superfluid 4 He, due to resonant absorption and decay of dimers in the acoustic field. We have calculated the absorption coefficient. Several experiments suggest themselves, utilizing, perhaps, K-L zeolites or carbon nanotubes. If the dimers themselves turn out to be attractive, then quadrumers may appear: it may even be the case that a single 3 He polymer will form over the entire length of the channel

  3. Substrate-Induced Dimerization of Engineered Monomeric Variants of Triosephosphate Isomerase from Trichomonas vaginalis.

    Directory of Open Access Journals (Sweden)

    Samuel Lara-Gonzalez

    Full Text Available The dimeric nature of triosephosphate isomerases (TIMs is maintained by an extensive surface area interface of more than 1600 Å2. TIMs from Trichomonas vaginalis (TvTIM are held in their dimeric state by two mechanisms: a ball and socket interaction of residue 45 of one subunit that fits into the hydrophobic pocket of the complementary subunit and by swapping of loop 3 between subunits. TvTIMs differ from other TIMs in their unfolding energetics. In TvTIMs the energy necessary to unfold a monomer is greater than the energy necessary to dissociate the dimer. Herein we found that the character of residue I45 controls the dimer-monomer equilibrium in TvTIMs. Unfolding experiments employing monomeric and dimeric mutants led us to conclude that dimeric TvTIMs unfold following a four state model denaturation process whereas monomeric TvTIMs follow a three state model. In contrast to other monomeric TIMs, monomeric variants of TvTIM1 are stable and unexpectedly one of them (I45A is only 29-fold less active than wild-type TvTIM1. The high enzymatic activity of monomeric TvTIMs contrast with the marginal catalytic activity of diverse monomeric TIMs variants. The stability of the monomeric variants of TvTIM1 and the use of cross-linking and analytical ultracentrifugation experiments permit us to understand the differences between the catalytic activities of TvTIMs and other marginally active monomeric TIMs. As TvTIMs do not unfold upon dimer dissociation, herein we found that the high enzymatic activity of monomeric TvTIM variants is explained by the formation of catalytic dimeric competent species assisted by substrate binding.

  4. Excision of UV-induced pyrimidine dimers from DNA of Chinese hamster CHO cells

    Energy Technology Data Exchange (ETDEWEB)

    Barenfel' d, L.S.; Bikhanskaya, F.L. (AN SSSR, Leningrad. Inst. Tsitologii)


    The sedimentation method in alkali gradients of saccharose when using UV-endonuclease from Micrococcus lutenius has been applied to investigate cleavage of UV-induced pyrimidine dimers from DNA cells (CHO). It is shown that essential part of pyrimidine dimers (approximately 80%) are cleaved during 26 h of postradiation incubation while during the first 17 h after UV-radiation (4J/m/sup 2/) reparation proceeds negligibly (approximately 15%).

  5. Slot-dimer babinet metamaterials as polarization shapers for terahertz waves

    DEFF Research Database (Denmark)

    Zhukovsky, Sergei; Chigrin, D. N.; Lavrinenko, Andrei


    We theoretically study optical properties of free-standing metallic membranes patterned with an array of two-slot elements (dimers) comprising two rectangular slots of different dimensions and orientation. It is shown that these structures feature extraordinary optical transmission with strong...... and spectrally selective polarization conversion capabilities. The output polarization is highly dependent on the dimer geometry, which can be used in the design of compact polarization shapers for terahertz waves....

  6. Non-Ligand-Induced Dimerization is Sufficient to Initiate the Signalling and Endocytosis of EGF Receptor

    Directory of Open Access Journals (Sweden)

    George Kourouniotis


    Full Text Available The binding of epidermal growth factor (EGF to EGF receptor (EGFR stimulates cell mitogenesis and survival through various signalling cascades. EGF also stimulates rapid EGFR endocytosis and its eventual degradation in lysosomes. The immediate events induced by ligand binding include receptor dimerization, activation of intrinsic tyrosine kinase and autophosphorylation. However, in spite of intensified efforts, the results regarding the roles of these events in EGFR signalling and internalization is still very controversial. In this study, we constructed a chimeric EGFR by replacing its extracellular domain with leucine zipper (LZ and tagged a green fluorescent protein (GFP at its C-terminus. We showed that the chimeric LZ-EGFR-GFP was constitutively dimerized. The LZ-EGFR-GFP dimer autophosphorylated each of its five well-defined C-terminal tyrosine residues as the ligand-induced EGFR dimer does. Phosphorylated LZ-EGFR-GFP was localized to both the plasma membrane and endosomes, suggesting it is capable of endocytosis. We also showed that LZ-EGFR-GFP activated major signalling proteins including Src homology collagen-like (Shc, extracellular signal-regulated kinase (ERK and Akt. Moreover, LZ-EGFR-GFP was able to stimulate cell proliferation. These results indicate that non-ligand induced dimerization is sufficient to activate EGFR and initiate cell signalling and EGFR endocytosis. We conclude that receptor dimerization is a critical event in EGF-induced cell signalling and EGFR endocytosis.

  7. Investigation of the hydrated 7-hydroxy-4-methylcoumarin dimer by combined IR/UV spectroscopy

    International Nuclear Information System (INIS)

    Stamm, A.; Schwing, K.; Gerhards, M.


    The first molecular beam investigations on a coumarin dimer and clusters of a coumarin dimer with water both in the neutral (S 0 ) and cationic (D 0 ) electronic ground state are performed. The structure and structural changes due to ionization of the isolated 7-hydroxy-4-methylcoumarin dimer (7H4MC) 2 as well as its mono- and dihydrate (7H4MC) 2 (H 2 O) 1-2 are analyzed by applying combined IR/UV spectroscopy compared with density functional theory calculations. In case of the neutral dimer of 7H4MC a doubly hydrogen-bonded structure is formed. This doubly hydrogen-bonded arrangement opens to a singly hydrogen-bonded structure in the ion presenting a rearrangement reaction within an isolated dimer. By attaching one or two water molecules to the neutral 7H4MC dimer water is inserted into the hydrogen bonds. In contrast to the non-hydrated species this general binding motif with water in a bridging function does not change via ionization but especially for the dihydrate the spatial arrangement of the two 7H4MC units changes strengthening the interaction between the aromatic chromophores. The presented analyses illustrate the strong dependence of binding motifs as a function of successive hydration and charge including a rearrangement reaction

  8. Biosynthesis of intestinal microvillar proteins. Dimerization of aminopeptidase N and lactase-phlorizin hydrolase

    Energy Technology Data Exchange (ETDEWEB)

    Danielsen, E.M. (Univ. of Cophenhagen (Denmark))


    The pig intestinal brush border enzymes aminopeptidase and lactase-phlorizin hydrolase are present in the microvilla membrane as homodimers. Dimethyl adipimidate was used to cross-link the two ({sup 35}S)methionine-labeled brush border enzymes from cultured mucosal explants. For aminopeptidase N, dimerization did not begin until 5-10 min after synthesis, and maximal dimerization by cross-linking of the transient form of the enzyme required 1 h, whereas the mature form of aminopeptidase N cross-linked with unchanged efficiency from 45 min to 3 h of labeling. Formation of dimers of this enzyme therefore occurs prior to the Golgi-associated processing, and the slow rate of dimerization may be the rate-limiting step in the transport from the endoplasmic reticulum to the Golgi complex. For lactase-phlorizin hydrolase, the posttranslational processing includes a proteolytic cleavage of its high molecular weight precursor. Since only the mature form and not the precursor of this enzyme could be cross-linked, formation of tightly associated dimers only takes place after transport out of the endoplasmic reticulum. Dimerization of the two brush border enzymes therefore seems to occur in different organelles of the enterocyte.

  9. Dimers of nineteen-electron sandwich compounds: crystal and electronic structures, and comparison of reducing strengths. (United States)

    Mohapatra, Swagat K; Fonari, Alexandr; Risko, Chad; Yesudas, Kada; Moudgil, Karttikay; Delcamp, Jared H; Timofeeva, Tatiana V; Brédas, Jean-Luc; Marder, Seth R; Barlow, Stephen


    The dimers of some Group 8 metal cyclopentadienyl/arene complexes and Group 9 metallocenes can be handled in air, yet are strongly reducing, making them useful n-dopants in organic electronics. In this work, the X-ray molecular structures are shown to resemble those of Group 8 metal cyclopentadienyl/pentadienyl or Group 9 metal cyclopentadienyl/diene model compounds. Compared to those of the model compounds, the DFT HOMOs of the dimers are significantly destabilized by interactions between the metal and the central CC σ-bonding orbital, accounting for the facile oxidation of the dimers. The lengths of these CC bonds (X-ray or DFT) do not correlate with DFT dissociation energies, the latter depending strongly on the monomer stabilities. Ru and Ir monomers are more reducing than their Fe and Rh analogues, but the corresponding dimers also exhibit much higher dissociation energies, so the estimated monomer cation/neutral dimer potentials are, with the exception of that of [RhCp2 ]2 , rather similar (-1.97 to -2.15 V vs. FeCp2 (+/0) in THF). The consequences of the variations in bond strength and redox potentials for the reactivity of the dimers are discussed. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Role of Side-Chain Conformational Entropy in Transmembrane Helix Dimerization of Glycophorin A (United States)

    Liu, Wei; Crocker, Evan; Siminovitch, David J.; Smith, Steven O.


    Dimerization of the transmembrane domain of glycophorin A is mediated by a seven residue motif LIxxGVxxGVxxT through a combination of van der Waals and hydrogen bonding interactions. One of the unusual features of the motif is the large number of β-branched amino acids that may limit the entropic cost of dimerization by restricting side-chain motion in the monomeric transmembrane helix. Deuterium NMR spectroscopy is used to characterize the dynamics of fully deuterated Val80 and Val84, two essential amino acids of the dimerization motif. Deuterium spectra of the glycophorin A transmembrane dimer were obtained using synthetic peptides corresponding to the transmembrane sequence containing either perdeuterated Val80 or Val84. These data were compared with spectra of monomeric glycophorin A peptides deuterated at Val84. In all cases, the deuterium line shapes are characterized by fast methyl group rotation with virtually no motion about the Cα-Cβ bond. This is consistent with restriction of the side chain in both the monomer and dimer due to intrahelical packing interactions involving the β-methyl groups, and indicates that there is no energy cost associated with dimerization due to loss of conformational entropy. In contrast, deuterium NMR spectra of Met81 and Val82, in the lipid interface, reflected greater motional averaging and fast exchange between different side-chain conformers. PMID:12547806

  11. Dimerization interface of 3-hydroxyacyl-CoA dehydrogenase tunes the formation of its catalytic intermediate.

    Directory of Open Access Journals (Sweden)

    Yingzhi Xu

    Full Text Available 3-Hydroxyacyl-CoA dehydrogenase (HAD, EC is a homodimeric enzyme localized in the mitochondrial matrix, which catalyzes the third step in fatty acid β-oxidation. The crystal structures of human HAD and subsequent complexes with cofactor/substrate enabled better understanding of HAD catalytic mechanism. However, numerous human diseases were found related to mutations at HAD dimerization interface that is away from the catalytic pocket. The role of HAD dimerization in its catalytic activity needs to be elucidated. Here, we solved the crystal structure of Caenorhabditis elegans HAD (cHAD that is highly conserved to human HAD. Even though the cHAD mutants (R204A, Y209A and R204A/Y209A with attenuated interactions on the dimerization interface still maintain a dimerization form, their enzymatic activities significantly decrease compared to that of the wild type. Such reduced activities are in consistency with the reduced ratios of the catalytic intermediate formation. Further molecular dynamics simulations results reveal that the alteration of the dimerization interface will increase the fluctuation of a distal region (a.a. 60-80 that plays an important role in the substrate binding. The increased fluctuation decreases the stability of the catalytic intermediate formation, and therefore the enzymatic activity is attenuated. Our study reveals the molecular mechanism about the essential role of the HAD dimerization interface in its catalytic activity via allosteric effects.

  12. Kinetics of Endophilin N-BAR Domain Dimerization and Membrane Interactions* (United States)

    Capraro, Benjamin R.; Shi, Zheng; Wu, Tingting; Chen, Zhiming; Dunn, Joanna M.; Rhoades, Elizabeth; Baumgart, Tobias


    The recruitment to plasma membrane invaginations of the protein endophilin is a temporally regulated step in clathrin-mediated endocytosis. Endophilin is believed to sense or stabilize membrane curvature, which in turn likely depends on the dimeric structure of the protein. The dynamic nature of the membrane association and dimerization of endophilin is thus functionally important and is illuminated herein. Using subunit exchange Förster resonance energy transfer (FRET), we determine dimer dissociation kinetics and find a dimerization equilibrium constant orders of magnitude lower than previously published values. We characterize N-BAR domain membrane association kinetics under conditions where the dimeric species predominates, by stopped flow, observing prominent electrostatic sensitivity of membrane interaction kinetics. Relative to membrane binding, we find that protein monomer/dimer species equilibrate with far slower kinetics. Complementary optical microscopy studies reveal strikingly slow membrane dissociation and an increase of dissociation rate constant for a construct lacking the amphipathic segment helix 0 (H0). We attribute the slow dissociation kinetics to higher-order protein oligomerization on the membrane. We incorporate our findings into a kinetic scheme for endophilin N-BAR membrane binding and find a significant separation of time scales for endophilin membrane binding and subsequent oligomerization. This separation may facilitate the regulation of membrane trafficking phenomena. PMID:23482561

  13. Analysis of pyrimidine dimer content of isolated DNA by nuclease digestion

    International Nuclear Information System (INIS)

    Farland, W.H.; Sutherland, B.M.


    Isolated DNA is highly susceptible to degradation by exogenous nucleases. Complete digestion is possible with a number of well-characterized enzymes from a variety of sources. Treatment of DNA with a battery of enzymes including both phosphodiesterase and phosphatase activities yields a mixture of nucleosides and inorganic phosphate (P/sub i/) as a final product. Unlike native DNA, ultraviolet-irradiated DNA is resistant to complete digestion. Setlow et al. demonstrated that the structural changes in the DNA responsible for the nuclease resistance were the formation of cyclobutyl pyrimidine dimers, the major photoproduct in UV-irradiated DNA. Using venom phosphodiesterase, they demonstrated that UV irradiation of DNA affected both the rate and extent of enzymatic hydrolysis. In addition, it was demonstrated that the major nuclease-resistant product of this hydrolysis was an oligonucleotide containing dimerized pyrimidines. Treatment of the DNA to split the dimers, either photochemically or photoenzymatically, rendered the polymer more susceptible to hydrolysis by the phosphodiesterase. The specificity of photoreactivating enzyme for pyrimidine dimers lends support to the role of these structures in conferring nuclease resistance to UV-irradiated DNA. The nuclease resistance of DNA containing dimers has been the basis of several assays for the measurement of these photoproducts. Sutherland and Chamberlin reported the development of a rapid and sensitive assay for dimers in 32 P-labeled DNA

  14. Dimers of nineteen-electron sandwich compounds: Crystal and electronic structures, and comparison of reducing strengths

    KAUST Repository

    Mohapatra, Swagat Kumar


    The dimers of some Group 8 metal cyclopentadienyl/ arene complexes and Group 9 metallocenes can be handled in air, yet are strongly reducing, making them useful n-dopants in organic electronics. In this work, the Xray molecular structures are shown to resemble those of Group 8 metal cyclopentadienyl/pentadienyl or Group 9 metal cyclopentadienyl/diene model compounds. Compared to those of the model compounds, the DFT HOMOs of the dimers are significantly destabilized by interactions between the metal and the central C-C σ-bonding orbital, accounting for the facile oxidation of the dimers. The lengths of these C-C bonds (X-ray or DFT) do not correlate with DFT dissociation energies, the latter depending strongly on the monomer stabilities. Ru and Ir monomers are more reducing than their Fe and Rh analogues, but the corresponding dimers also exhibit much higher dissociation energies, so the estimated monomer cation/neutral dimer potentials are, with the exception of that of [RhCp2]2, rather similar (-1.97 to-2.15 V vs. FeCp2 +/0 in THF). The consequences of the variations in bond strength and redox potentials for the reactivity of the dimers are discussed.

  15. Structure of a Rabbit Muscle Fructose-1,6-Bisphosphate Aldolase A Dimer Variant

    Energy Technology Data Exchange (ETDEWEB)

    Sherawat,M.; Tolan, D.; Allen, K.


    Fructose-1,6-bisphosphate aldolase (aldolase) is an essential enzyme in glycolysis and gluconeogenesis. In addition to this primary function, aldolase is also known to bind to a variety of other proteins, a property that may allow it to perform 'moonlighting' roles in the cell. Although monomeric and dimeric aldolases possess full catalytic activity, the enzyme occurs as an unusually stable tetramer, suggesting a possible link between the oligomeric state and these noncatalytic cellular roles. Here, the first high-resolution X-ray crystal structure of rabbit muscle D128V aldolase, a dimeric form of aldolase mimicking the clinically important D128G mutation in humans associated with hemolytic anemia, is presented. The structure of the dimer was determined to 1.7 Angstroms resolution with the product DHAP bound in the active site. The turnover of substrate to produce the product ligand demonstrates the retention of catalytic activity by the dimeric aldolase. The D128V mutation causes aldolase to lose intermolecular contacts with the neighboring subunit at one of the two interfaces of the tetramer. The tertiary structure of the dimer does not significantly differ from the structure of half of the tetramer. Analytical ultracentrifugation confirms the occurrence of the enzyme as a dimer in solution. The highly stable structure of aldolase with an independent active site is consistent with a model in which aldolase has evolved as a multimeric scaffold to perform other noncatalytic functions.

  16. HLA-G Dimers in the Prolongation of Kidney Allograft Survival

    Directory of Open Access Journals (Sweden)

    Maureen Ezeakile


    Full Text Available Human leukocyte antigen-G (HLA-G contributes to acceptance of allografts in solid organ/tissue transplantation. Most studies have determined that soluble HLA-G isoforms are systematically detected in serum/plasma of transplanted patients with significantly fewer episodes of acute and/or chronic rejection of allogeneic tissue/organ. Current models of the interactions of HLA-G and its specific receptors explain it as functioning in a monomeric form. However, in recent years, new data has revealed the ability of HLA-G to form disulfide-linked dimeric complexes with high preferential binding and functional activities. Limited data are available on the role of soluble HLA-G dimers in clinical pathological conditions. We describe here the presence of soluble HLA-G dimers in kidney transplant patients. Our study showed that a high level of HLA-G dimers in plasma and increased expression of the membrane-bound form of HLA-G on monocytes are associated with prolongation of kidney allograft survival. We also determined that the presence of soluble HLA-G dimers links to the lower levels of proinflammatory cytokines, suggesting a potential role of HLA-G dimers in controlling the accompanying inflammatory state.

  17. Quantitation of pyrimidine dimers in DNA from UVB-irradiated alfalfa (Medicago sativa L.) seedlings

    International Nuclear Information System (INIS)

    Quaite, F.E.; Sutherland, B.M.; Sutherland, J.C.


    Depletion of stratospheric ozone will increase the solar ultraviolet radiation in the range from 290-320 nm (UVB) that reaches the surface of the earth, placing an increased UV burden on exposed organisms. One consequence of increased UVB may be decreased productivity of crop plants. A principal lesion caused by UV in DNA is the cyclobutyl pyrimidine dimer. We have adapted a method for measuring these dimers in nanogram quantities of non-radioactive DNA for use in UV-irradiated plants. We find that biologically relevant doses of broad band UVB radiation induce easily detectable frequencies of pyrimidine dimers in the DNA of irradiated alfalfa sprout leaves and that the dose response for dimer formation is linear up to doses of at least 690 J/m 2 . We also find easily measurable frequencies of dimers in the leaves of seedlings grown in glass filtered sunlight but not exposed to additional UVB, suggesting that significant number of dimers are formed in plants exposed to normal sunlight. 27 refs., 3 figs., 1 tab

  18. Complete Structure of an Epithelial Keratin Dimer: Implications for Intermediate Filament Assembly.

    Directory of Open Access Journals (Sweden)

    David J Bray

    Full Text Available Keratins are cytoskeletal proteins that hierarchically arrange into filaments, starting with the dimer sub-unit. They are integral to the structural support of cells, in skin, hair and nails. In skin, keratin is thought to play a critical role in conferring the barrier properties and elasticity of skin. In general, the keratin dimer is broadly described by a tri-domain structure: a head, a central rod and a tail. As yet, no atomistic-scale picture of the entire dimer structure exists; this information is pivotal for establishing molecular-level connections between structure and function in intermediate filament proteins. The roles of the head and tail domains in facilitating keratin filament assembly and function remain as open questions. To address these, we report results of molecular dynamics simulations of the entire epithelial human K1/K10 keratin dimer. Our findings comprise: (1 the first three-dimensional structural models of the complete dimer unit, comprising of the head, rod and tail domains; (2 new insights into the chirality of the rod-domain twist gained from analysis of the full domain structure; (3 evidence for tri-subdomain partitioning in the head and tail domains; and, (4 identification of the residue characteristics that mediate non-covalent contact between the chains in the dimer. Our findings are immediately applicable to other epithelial keratins, such as K8/K18 and K5/K14, and to intermediate filament proteins in general.

  19. Origin of attraction in chalgogen-nitrogen interaction of 1,2,5-chalcogenadiazole dimers. (United States)

    Tsuzuki, Seiji; Sato, Naoki


    Intermolecular interaction in the 1,2,5-chalcogenadiazole dimers was studied by ab initio molecular orbital calculations. Estimated CCSD(T) interaction energies for the thia-, selena- and tellura-diazole dimers are -3.14, -5.29, and -12.42 kcal/mol, respectively. The electrostatic and dispersion interactions are the major sources of the attraction in the dimers, although it was claimed that the orbital mixing (charge-transfer interaction) was the most prominent contribution to the stabilization. The induction (induced polarization) interaction also contributes largely to the attraction in the telluradiazole dimer. The large electrostatic and induction interactions are responsible for the strong attraction in the telluradiazole dimer. The short-range (orbital-orbital) interaction (sum of the exchange-repulsion and charge-transfer interactions) is repulsive. The directionality of the interactions increases in order of S interaction is mainly responsible for the directionality. The strong directionality suggests that the chalcogen-nitrogen interaction plays important roles in controlling the orientation of molecules in those organic crystals. The nature of the chalcogen-nitrogen interaction in the chalcogenadiazole dimers is similar to that of the halogen bond, which is an electrostatically driven noncovalent interaction.

  20. Elucidation of cladofulvin biosynthesis reveals a cytochrome P450 monooxygenase required for anthraquinone dimerization. (United States)

    Griffiths, Scott; Mesarich, Carl H; Saccomanno, Benedetta; Vaisberg, Abraham; De Wit, Pierre J G M; Cox, Russell; Collemare, Jérôme


    Anthraquinones are a large family of secondary metabolites (SMs) that are extensively studied for their diverse biological activities. These activities are determined by functional group decorations and the formation of dimers from anthraquinone monomers. Despite their numerous medicinal qualities, very few anthraquinone biosynthetic pathways have been elucidated so far, including the enzymatic dimerization steps. In this study, we report the elucidation of the biosynthesis of cladofulvin, an asymmetrical homodimer of nataloe-emodin produced by the fungus Cladosporium fulvum A gene cluster of 10 genes controls cladofulvin biosynthesis, which begins with the production of atrochrysone carboxylic acid by the polyketide synthase ClaG and the β-lactamase ClaF. This compound is decarboxylated by ClaH to yield emodin, which is then converted to chrysophanol hydroquinone by the reductase ClaC and the dehydratase ClaB. We show that the predicted cytochrome P450 ClaM catalyzes the dimerization of nataloe-emodin to cladofulvin. Remarkably, such dimerization dramatically increases nataloe-emodin cytotoxicity against mammalian cell lines. These findings shed light on the enzymatic mechanisms involved in anthraquinone dimerization. Future characterization of the ClaM enzyme should facilitate engineering the biosynthesis of novel, potent, dimeric anthraquinones and structurally related compound families.

  1. Investigation of the hydrated 7-hydroxy-4-methylcoumarin dimer by combined IR/UV spectroscopy. (United States)

    Stamm, A; Schwing, K; Gerhards, M


    The first molecular beam investigations on a coumarin dimer and clusters of a coumarin dimer with water both in the neutral (S0) and cationic (D0) electronic ground state are performed. The structure and structural changes due to ionization of the isolated 7-hydroxy-4-methylcoumarin dimer (7H4MC)2 as well as its mono- and dihydrate (7H4MC)2(H2O)1-2 are analyzed by applying combined IR/UV spectroscopy compared with density functional theory calculations. In case of the neutral dimer of 7H4MC a doubly hydrogen-bonded structure is formed. This doubly hydrogen-bonded arrangement opens to a singly hydrogen-bonded structure in the ion presenting a rearrangement reaction within an isolated dimer. By attaching one or two water molecules to the neutral 7H4MC dimer water is inserted into the hydrogen bonds. In contrast to the non-hydrated species this general binding motif with water in a bridging function does not change via ionization but especially for the dihydrate the spatial arrangement of the two 7H4MC units changes strengthening the interaction between the aromatic chromophores. The presented analyses illustrate the strong dependence of binding motifs as a function of successive hydration and charge including a rearrangement reaction.

  2. Overall conformation of covalently stabilized domain-swapped dimer of human cystatin C in solution (United States)

    Murawska, Magdalena; Szymańska, Aneta; Grubb, Anders; Kozak, Maciej


    Human cystatin C (HCC), a small protein, plays a crucial role in inhibition of cysteine proteases. The most common structural form of human cystatin C in crystals is a dimer, which has been evidenced both for the native protein and its mutants. In these structures, HCC dimers were formed through the mechanism of domain swapping. The structure of the monomeric form of human cystatin C was determined for V57N mutant and the mutant with the engineered disulfide bond (L47C)-(G69C) (known as stab1-HCC). On the basis of stab1-HCC, a number of covalently stabilized oligomers, including also dimers have been obtained. The aim of this study was to analyze the structure of the covalently stabilized dimer HCC in solution by the small angle X-ray scattering (SAXS) technique and synchrotron radiation. Experimental data confirmed that in solution this protein forms a dimer, which is characterized by the radius of gyration RG = 3.1 nm and maximum intramolecular distance Dmax = 10.3 nm. Using the ab initio method and program DAMMIN, we propose a low resolution structure of stabilized covalently cystatin C in solution. Stab-HCC dimer adopts in solution an elongated conformation, which is well reconstructed by the ab initio model.

  3. Dislocations and vacancies in two-dimensional mixed crystals of spheres and dimers

    KAUST Repository

    Gerbode, Sharon J.


    In colloidal crystals of spheres, dislocation motion is unrestricted. On the other hand, recent studies of relaxation in crystals of colloidal dimer particles have demonstrated that the dislocation dynamics in such crystals are reminiscent of glassy systems. The observed glassy dynamics arise as a result of dislocation cages formed by certain dimer orientations. In the current study, we use experiments and simulations to investigate the transition that arises when a pure sphere crystal is doped with an increasing concentration of dimers. Specifically, we focus on both dislocation caging and vacancy motion. Interestingly, we find that any nonzero fraction of dimers introduces finite dislocation cages, suggesting that glassy dynamics are present for any mixed crystal. However, we have also identified a vacancy-mediated uncaging mechanism for releasing dislocations from their cages. This mechanism is dependent on vacancy diffusion, which slows by orders of magnitude as the dimer concentration is increased. We propose that in mixed crystals with low dimer concentrations vacancy diffusion is fast enough to uncage dislocations and delay the onset of glassy dislocation dynamics. © 2010 The American Physical Society.

  4. Pathway and mechanism of pH dependent human hemoglobin tetramer-dimer-monomer dissociations.

    Directory of Open Access Journals (Sweden)

    Yao-Xiong Huang

    Full Text Available Hemoglobin dissociation is of great interest in protein process and clinical medicine as well as in artificial blood research. However, the pathway and mechanisms of pH-dependent human Hb dissociation are not clear, whether Hb would really dissociate into monomers is still a question. Therefore, we have conducted a multi-technique investigation on the structure and function of human Hb versus pH. Here we demonstrate that tetramer hemoglobin can easily dissociate into dimer in abnormal pH and the tetramer → dimer dissociation is reversible if pH returns to normal physiological value. When the environmental pH becomes more acidic (8.0, Hb can further dissociate from dimer to monomer. The proportion of monomers increases while the fraction of dimers decreases as pH declines from 6.2 to 5.4. The dimer → monomer dissociation is accompanied with series changes of protein structure thus it is an irreversible process. The structural changes in the dissociated Hbs result in some loss of their functions. Both the Hb dimer and monomer cannot adequately carry and release oxygen to the tissues in circulation. These findings provide a comprehensive understanding on the pH-dependent protein transitions of human Hb, give guideline to explain complex protein processes and the means to control protein dissociation or re-association reaction. They are also of practical value in clinical medicine, blood preservation and blood substitute development.

  5. Reinvestigation of the Structure of Protonated Lysine Dimer (United States)

    Kong, Xianglei


    To better understand inconsistencies between the predicted infrared (IR) spectra of previously suggested isomers of Lys2H+ reported by Wu et al. (J. Am. Soc. Mass Spectrom. 22:1651-1659, 18) and the experimental IR photon dissociation (IRPD) spectrum obtained by Oh et al. (J. Am. Chem. Soc. 127:4076-4083, 4), the structure of Lys2H+ was reinvestigated using IRPD spectroscopy in the extended region 2700-3700 cm-1 and theoretical calculations. The new experimental IRPD spectrum is in good agreement with Oh's spectrum in the corresponding wavelength range. Based on calculations at the MP2/6-311++G(d,p)//B3LYP/6-311++G(d,p) and MP2/6-31 + G(d,p)//MP2/6-31 + G(d,p) levels, a new salt-bridged isomer, ZW1, was found to be the most stable isomer; it is more energetically favored than the previously suggested charge-solvated isomer LL-CS01 by 10 or 26 kJ mol-1. Although the calculated IR spectrum of ZW1 is in good agreement with the experimental one in the range 2700-3700 cm-1, it is in poor agreement with the previous IRPD spectrum in the range 1000-1900 cm-1. This investigation shows that the intermolecular interactions inside the dimer are more complex than previously supposed. It is possible that both salt-bridged and charge-solvated isomers of Lys2H+ are stable in the gas phase, and the isomers generated during ionization are sensitive to the experimental conditions.

  6. Combination Bands of the Nonpolar OCS Dimer Involving Intermolecular Modes (United States)

    Rezaei, M.; Oliaee, J. Norooz; Moazzen-Ahmadi, N.; McKellar, A. R. W.


    Spectra of the nonpolar carbonyl sulfide in the region of the OCS ν_1 fundamental band were observed in a supersonic slit-jet apparatus. The expansion gas was probed using radiation from a tunable diode laser employed in a rapid-scan signal averaging mode. Three bands centered at 2085.906, 2103.504, and 2114.979 cm-1 were observed and anlysed. The rotational assignment and fitting of the bands were made by fixing the lower state parameters to those for the ground state of nonpolar (OCS)_2, thus confirming that they were indeed combination bands of the of the most stable isomer of OCS dimer. The band centered at 2085.906 cm-1 is a combination of the forbidden A_g intramolecular mode plus the geared bend intermolecular mode and that centered at 2114.979 cm-1 is a combination of the allowed B_u intramolecular mode plus the intermolecular van der Waals stretch. The combination at 2103.504 cm-1 can be assigned as a band whose upper state involves four quanta of the intramolecular bend or the B_u intramolecular mode plus two quanta of the intermolecular torsional mode. Isotopic work is needed to conclusively identify the vibrational assignment of this band. Our experimental frequencies for the geared bend and van der Waals modes are in good agreement with a recent high level ab initio calculation by Brown et al. J. Brown, Xiao-Gang Wang, T. Carrington Jr. and Richard Dawes, Journal of Chemical Physics, submitted.

  7. Naturally-occurring dimers of flavonoids as anticarcinogens. (United States)

    Mercader, Andrew G; Pomilio, Alicia B


    Biflavonoids are dimers of flavonoid moieties linked by a C-C or C-O-C bond. Simple, complex, rearranged, natural and ketalized Diels-Alder adducts, benzofuran derivatives, and spirobiflavonoids are some of the structural groups of biflavonoids. These compounds are mainly distributed in the Gymnosperms, Angiosperms (monocots and dicots), ferns (Pteridophyta), and mosses (Bryophyta). Biflavonoids have shown a variety of biological activities, including anticancer, antibacterial, antifungal, antiviral, antiinflammatory, analgesic, antioxidant, vasorelaxant, anticlotting, among others. This work is focused on probably the most potentially relevant biological activity of biflavonoids, the anticancer activity and the involved mechanisms of action, such as induction of apoptosis [inhibition of cyclic nucleotide phosphodiesterases; effects on NF-κB family of transcription factors; activation of caspase(s); inhibition effects on bcl-2 expression, and upregulation of p53 and caspase-3 gene expression]; inhibition of angiogenesis [anti-proliferative effects; activation of Rho-GTPases and ERK signaling pathways; inhibition of FASN activity]; inhibition of pre-mRNA splicing; inhibition of human DNA topoisomerases I and II-α; anti-inflammatory/ immunoregulatory effects [inhibition of XO; inhibition of proinflammatory enzymes, such as PLA2 and COX; effects on cytokines mediated COX-2 and iNOS expression]; modulation of immune response; inhibition of protein tyrosine phosphorylation; antioxidant and analgesic activities in relation to the anticarcinogen behavior. For that reason the structures and anticarcinogenic activities of 83 biflavonoids are thoroughly discussed. The results of this work indicate that biflavonoids strongly affect the cancer cells with little effect on normal cell proliferation, suggesting a therapeutic potential against cancer.

  8. D-dimer assays - A help or hindrance in suspected pulmonary thromboembolism assessment?

    Directory of Open Access Journals (Sweden)

    H K Bayes


    Full Text Available Background : Suspected pulmonary thromboembolism (PTE is a common presentation to acute medical units and can cause diagnostic difficulty. National guidelines on PTE management highlight the need for clinical probability assessment and D-dimer assays to ensure appropriate use of diagnostic imaging. D-dimers are used widely in UK hospitals, yet concern exists regarding their misuse. Aims : In this study we aimed to assess the impact of the introduction of D-dimer assays, combined with clinical probability assessment, for evaluation of suspected PTE in our unit. Materials and Methods : This was a prospective audit of all patients presenting with suspected PTE over two 12-week periods, exactly 1 year apart. D-dimers were introduced into our unit between these two periods. We recorded the clinical probability score, potential causes of false-positive D-dimer assay, diagnostic imaging result, patient outcome, admission rates, and length of inpatient stay. Statistical Analysis : Categorical variables were compared using a 2 x 2 chi-square test or Fisher′s exact test. Groups were compared utilizing the two-sample t-test or Mann-Whitney U test. Results : A total of 190 patients were included in the study; 65% were female. PTE was confirmed in 8.4%. Patients in both audit periods were comparable with regard to suitability for D-dimer measurement. Following D-dimer introduction, 40 out of 110 patients in period 2 could be discharged directly from the emergency department. Of those admitted to hospital, the median length of stay was significantly reduced in period 2 (3 days in period 1 vs 1 day in period 2; P=0.0007. Use of diagnostic imaging was significantly reduced following the introduction of D-dimers (90% in period 1 vs 40% in period 2; P<0.0001. The positive diagnostic yield for PTE on CT pulmonary angiogram (CTPA increased significantly from 10% in period 1 to 23% in period 2 (P=0.039. Conclusion : D-dimers must be used judiciously in the

  9. Vertically cross-linked and porous CoNi2S4 nanosheets-decorated SiC nanowires with exceptional capacitive performance as a free-standing electrode for asymmetric supercapacitors (United States)

    Zhao, Jian; Li, Zhenjiang; Zhang, Meng; Meng, Alan; Li, Qingdang


    In this paper, a simple, low-cost and mild hydrothermal technology of growing vertically cross-linked ternary nickel cobalt sulfides nanosheets (CoNi2S4 NSs) with porous characteristics on SiC nanowires (SiC NWs) supporters with outstanding resistances to oxidation and corrosion, good conductivity and large specific surface area deposited directly on carbon cloth (CC) is successfully developed, forming a new family of free-standing advanced hybrid electrode for asymmetric supercapacitors (ASCs). Such integrated electrode (SiC NWs@CoNi2S4 NSs) manifests intriguing electrochemical characteristics such as high specific capacity (231.1 mA h g-1 at 2 A g-1) and rate capability due to the synergistic effect of SiC NWs and CoNi2S4 NSs with unique morphology. Additionally, an asymmetric supercapacitor is also assembled via using this special hybrid architectures as positive electrode and activated carbon (AC) on Ni foam (NF) as negative electrode, and it can yield a high energy density of 57.8 W h kg-1 with a power density of 1.6 kW kg-1 and long cycling lifespan. This study constitutes an emerging attractive strategy to reasonably design and fabricate novel SiC NWs-based nanostructured electrodes with enhanced capacity, which holds great potential to be the candidate of electrode materials for environmentally benign as well as high-performance energy storage devices.

  10. Quantification of Honeycomb Number-Type Stacking Faults: Application to Na3Ni2BiO6 Cathodes for Na-Ion Batteries. (United States)

    Liu, Jue; Yin, Liang; Wu, Lijun; Bai, Jianming; Bak, Seong-Min; Yu, Xiqian; Zhu, Yimei; Yang, Xiao-Qing; Khalifah, Peter G


    Ordered and disordered samples of honeycomb-lattice Na3Ni2BiO6 were investigated as cathodes for Na-ion batteries, and it was determined that the ordered sample exhibits better electrochemical performance, with a specific capacity of 104 mA h/g delivered at plateaus of 3.5 and 3.2 V (vs Na(+)/Na) with minimal capacity fade during extended cycling. Advanced imaging and diffraction investigations showed that the primary difference between the ordered and disordered samples is the amount of number-type stacking faults associated with the three possible centering choices for each honeycomb layer. A labeling scheme for assigning the number position of honeycomb layers is described, and it is shown that the translational shift vectors between layers provide the simplest method for classifying different repeat patterns. It is demonstrated that the number position of honeycomb layers can be directly determined in high-angle annular dark-field scanning transmission electron microscopy (STEM-HAADF) imaging studies. By the use of fault models derived from STEM studies, it is shown that both the sharp, symmetric subcell peaks and the broad, asymmetric superstructure peaks in powder diffraction patterns can be quantitatively modeled. About 20% of the layers in the ordered monoclinic sample are faulted in a nonrandom manner, while the disordered sample stacking is not fully random but instead contains about 4% monoclinic order. Furthermore, it is shown that the ordered sample has a series of higher-order superstructure peaks associated with 6-, 9-, 12-, and 15-layer periods whose existence is transiently driven by the presence of long-range strain that is an inherent consequence of the synthesis mechanism revealed through the present diffraction and imaging studies. This strain is closely associated with a monoclinic shear that can be directly calculated from cell lattice parameters and is strongly correlated with the degree of ordering in the samples. The present results are

  11. Structure of a rabbit muscle fructose-1, 6-bisphosphate aldolase A dimer variant

    Energy Technology Data Exchange (ETDEWEB)

    Sherawat, Manashi [Department of Physiology and Biophysics, Boston University School of Medicine, 715 Albany Street, Boston, MA 02118-2394 (United States); Tolan, Dean R., E-mail: [Department of Biology, Boston University, 5 Cummington Street, Boston, MA 02215 (United States); Allen, Karen N., E-mail: [Department of Physiology and Biophysics, Boston University School of Medicine, 715 Albany Street, Boston, MA 02118-2394 (United States)


    The X-ray crystallographic structure of a dimer variant of fructose-1, 6-bisphosphate aldolase demonstrates a stable oligomer that mirrors half of the native tetramer. The presence of product demonstrates that this is an active form. Fructose-1, 6-bisphosphate aldolase (aldolase) is an essential enzyme in glycolysis and gluconeogenesis. In addition to this primary function, aldolase is also known to bind to a variety of other proteins, a property that may allow it to perform ‘moonlighting’ roles in the cell. Although monomeric and dimeric aldolases possess full catalytic activity, the enzyme occurs as an unusually stable tetramer, suggesting a possible link between the oligomeric state and these noncatalytic cellular roles. Here, the first high-resolution X-ray crystal structure of rabbit muscle D128V aldolase, a dimeric form of aldolase mimicking the clinically important D128G mutation in humans associated with hemolytic anemia, is presented. The structure of the dimer was determined to 1.7 Å resolution with the product DHAP bound in the active site. The turnover of substrate to produce the product ligand demonstrates the retention of catalytic activity by the dimeric aldolase. The D128V mutation causes aldolase to lose intermolecular contacts with the neighboring subunit at one of the two interfaces of the tetramer. The tertiary structure of the dimer does not significantly differ from the structure of half of the tetramer. Analytical ultracentrifugation confirms the occurrence of the enzyme as a dimer in solution. The highly stable structure of aldolase with an independent active site is consistent with a model in which aldolase has evolved as a multimeric scaffold to perform other noncatalytic functions.

  12. Mutation of Asn28 Disrupts the Dimerization and Enzymatic Activity of SARS 3CL

    Energy Technology Data Exchange (ETDEWEB)

    Barrila, J.; Gabelli, S; Bacha, U; Amzel, M; Freire, E


    Coronaviruses are responsible for a significant proportion of annual respiratory and enteric infections in humans and other mammals. The most prominent of these viruses is the severe acute respiratory syndrome coronavirus (SARS-CoV) which causes acute respiratory and gastrointestinal infection in humans. The coronavirus main protease, 3CL{sup pro}, is a key target for broad-spectrum antiviral development because of its critical role in viral maturation and high degree of structural conservation among coronaviruses. Dimerization is an indispensable requirement for the function of SARS 3CL{sup pro} and is regulated through mechanisms involving both direct and long-range interactions in the enzyme. While many of the binding interactions at the dimerization interface have been extensively studied, those that are important for long-range control are not well-understood. Characterization of these dimerization mechanisms is important for the structure-based design of new treatments targeting coronavirus-based infections. Here we report that Asn28, a residue 11 {angstrom} from the closest residue in the opposing monomer, is essential for the enzymatic activity and dimerization of SARS 3CLpro. Mutation of this residue to alanine almost completely inactivates the enzyme and results in a 19.2-fold decrease in the dimerization K{sub d}. The crystallographic structure of the N28A mutant determined at 2.35 {angstrom} resolution reveals the critical role of Asn28 in maintaining the structural integrity of the active site and in orienting key residues involved in binding at the dimer interface and substrate catalysis. These findings provide deeper insight into complex mechanisms regulating the activity and dimerization of SARS 3CL{sup pro}.

  13. Solution structure of the DNA decamer duplex containing a 3′-T·T base pair of the cis–syn cyclobutane pyrimidine dimer: implication for the mutagenic property of the cis–syn dimer


    Lee, Joon-Hwa; Choi, Yun-Jeong; Choi, Byong-Seok


    The cis–syn dimer is the major DNA photoproduct produced by UV irradiation. In order to determine the origin of the mutagenic property of the cis–syn dimer, we used NMR restraints and molecular dynamics to determine the solution structure of a DNA decamer duplex containing a wobble pair between the 3′-T of the cis–syn dimer and the opposite T residue (CS/TA duplex). The solution structure of the CS/TA duplex revealed that the 3′-T·T base pair of the cis–syn dimer had base pair geometry that w...

  14. Crystal structures and magnetic properties of iron (III)-based phosphates: Na4NiFe(PO4)3 and Na2Ni2Fe(PO4)3

    International Nuclear Information System (INIS)

    Essehli, Rachid; Bali, Brahim El; Benmokhtar, Said; Bouziane, Khalid; Manoun, Bouchaib; Abdalslam, Mouner Ahmed; Ehrenberg, Helmut


    Graphical abstract: A perspective view of the Na 2 Ni 2 Fe(PO 4 ) 3 structure along the [0 0 1] direction. Both compounds seem to exibit antiferromagnetic interactions between magnetic entities at low temperature. Display Omitted Research highlights: → Nasicon and Alluaudite compounds, Iron(III)-based phosphates, Crystal structures of Na 4 NiFe(PO 4 ) 3 and Na 2 Ni 2 Fe(PO 4 ) 3 . → Magnetism behaviours of Na 4 NiFe(PO 4 ) 3 and Na 2 Ni 2 Fe(PO 4 ) 3 . → Antiferromagnetism interactions. → Mossbauer spectroscopy. - Abstract: Crystal structures from two new phosphates Na 4 NiFe(PO 4 ) 3 (I) and Na 2 Ni 2 Fe(PO 4 ) 3 (II) have been determined by single crystal X-ray diffraction analysis. Compound (I) crystallizes in a rhombohedral system (S. G: R-3c, Z = 6, a = 8.7350(9) A, c = 21.643(4) A, R 1 = 0.041, wR 2 =0.120). Compound (II) crystallizes in a monoclinic system (S. G: C2/c, Z = 4, a = 11.729(7) A, b = 12.433(5) A, c = 6.431(2) A, β = 113.66(4) o , R 1 = 0.043, wR 2 =0.111). The three-dimensional structure of (I) is closely related to the Nasicon structural type, consisting of corner sharing [(Ni/Fe)O 6 ] octahedra and [PO 4 ] tetrahedra forming [NiFe(PO 4 ) 3 ] 4+ units which align in chains along the c-axis. The Na + cations fill up trigonal antiprismatic sites within these chains. The crystal structure of (II) belongs to the alluaudite type. Its open framework results from [Ni 2 O 10 ] units of edge-sharing [NiO 6 ] octahedra, which alternate with [FeO 6 ] octahedra that form infinite chains. Coordination of these chains yields two distinct tunnels in which site Na + . The magnetization data of compound (I) reveal antiferromagnetic (AFM) interactions by the onset of deviations from a Curie-Weiss behaviour at low temperature as confirmed by Moessbauer measurements performed at 4.2 K. The corresponding temperature dependence of the reciprocal susceptibility χ -1 follows a typical Curie-Weiss behaviour for T > 105 K. A canted AFM state is proposed for

  15. Detection of UV-induced thymine dimers in individual Cryptosporidium parvum and Cryptosporidium hominis oocysts by immunofluorescence microscopy


    Al-Adhami, B.H.; Nichols, R.A.B.; Kusel, J.R.; O'Grady, J.; Smith, H.V.


    To investigate the effect of UV light on Cryptosporidium parvum and Cryptosporidium hominis oocysts in vitro, we exposed intact oocysts to 4-, 10-, 20-, and 40-mJ·cm−2 doses of UV irradiation. Thymine dimers were detected by immunofluorescence microscopy using a monoclonal antibody against cyclobutyl thymine dimers (anti-TDmAb). Dimer-specific fluorescence within sporozoite nuclei was confirmed by colocalization with the nuclear fluorogen 4′,6′-diamidino-2-phenylindole (DAPI). Oocyst walls we...

  16. Reduced repair of non-dimer photoproducts in a gene transfected into xeroderma pigmentosum cells

    International Nuclear Information System (INIS)

    Protic-Sabljic, Miroslava; Kraemer, K.H.


    Cells from patients with the sun sensitive cancer-prone disease, xeroderma pigmentosum (XP) have defective repair of UV damaged DNA with reduced excision of the major photoproduct, the cyclobutane type pyrimidine dimer. Other (non-dimer) photoproducts, have recently been implicated in UV mutagenesis. Utilizing an expression vector host cell reactivation assay, UV damaged transfecting DNA that was treated by in vitro photoreactivation to reverse pyrimidine dimers while not altering other photoproducts was studied. It was found that the reduced expression of a UV damaged transfecting plasmid in XP complementation group A cells is only partially reversed by photoreactivation. E. coli photolyase treatment of pSV2catSVgpt exposed to 100 or 200 J m -2 of 254 nm radiation removed 99% of the T4 endonuclease V sensitive sites. Transfection of XP12BE(SV40) cells with photoreactivated pSV2catSVgpt showed residual inhibition corresponding to 25 to 37% of the lethal hits to the cat gene. This residual inhibition corresponds to the fraction of non-dimer photoproducts induced by UV. This result implies that XP12BE(SV40) cells do not repair most of the non-dimer photoproducts in DNA. (author)

  17. Laser isotope separation using selective inhibition and encouragement of dimer formation

    International Nuclear Information System (INIS)

    Kivel, B.


    Method and apparatus for inhibiting dimer formation of molecules of a selected isotope type in a cooled flow of gas to enhance the effectiveness of mass difference isotope separation techniques are described. Molecules in the flow containing atoms of the selected isotope type are selectively excited by infrared radiation in order to inhibit the formation of dimers and larger clusters of such molecules, while the molecules not containing atoms of the selected, excited type are encouraged to form dimers and higher order aggregates by the cooling of the gaseous flow. The molecules with the excited isotope will predominate in monomers and will constitute the enriched product stream, while the aggregated group comprising molecules having the unexcited isotope will predominate in dimers and larger clusters of molecules, forming the tails stream. The difference in diffusion coefficientts between particles of the excited and unexcited isotopes is enhanced by the greater mass differences resulting from aggregation of unexcited particles into dimers and larger clusters. Prior art separation techniques which exploit differences in isotopic diffusion rates will consequently exhibit enhanced enrichment per stage by the utilization of the present invention

  18. Single-Molecule Rotational Switch on a Dangling Bond Dimer Bearing. (United States)

    Godlewski, Szymon; Kawai, Hiroyo; Kolmer, Marek; Zuzak, Rafał; Echavarren, Antonio M; Joachim, Christian; Szymonski, Marek; Saeys, Mark


    One of the key challenges in the construction of atomic-scale circuits and molecular machines is to design molecular rotors and switches by controlling the linear or rotational movement of a molecule while preserving its intrinsic electronic properties. Here, we demonstrate both the continuous rotational switching and the controlled step-by-step single switching of a trinaphthylene molecule adsorbed on a dangling bond dimer created on a hydrogen-passivated Ge(001):H surface. The molecular switch is on-surface assembled when the covalent bonds between the molecule and the dangling bond dimer are controllably broken, and the molecule is attached to the dimer by long-range van der Waals interactions. In this configuration, the molecule retains its intrinsic electronic properties, as confirmed by combined scanning tunneling microscopy/spectroscopy (STM/STS) measurements, density functional theory calculations, and advanced STM image calculations. Continuous switching of the molecule is initiated by vibronic excitations when the electrons are tunneling through the lowest unoccupied molecular orbital state of the molecule. The switching path is a combination of a sliding and rotation motion over the dangling bond dimer pivot. By carefully selecting the STM conditions, control over discrete single switching events is also achieved. Combined with the ability to create dangling bond dimers with atomic precision, the controlled rotational molecular switch is expected to be a crucial building block for more complex surface atomic-scale devices.

  19. CT Findings of Disease with Elevated Serum D-Dimer Levels in an Emergency Room Setting

    Energy Technology Data Exchange (ETDEWEB)

    Choi, Ji Youn; Kwon, Woo Cheol; Kim, Young Ju [Dept. of Radiology, Wonju Christian Hospital, Yensei University Wonju College of Medicine, Wonju (Korea, Republic of)


    Pulmonary embolism and deep vein thrombosis are the leading causes of elevated serum D-dimer levels in the emergency room. Although D-dimer is a useful screening test because of its high sensitivity and negative predictive value, it has a low specificity. In addition, D-dimer can be elevated in various diseases. Therefore, information on the various diseases with elevated D-dimer levels and their radiologic findings may allow for accurate diagnosis and proper management. Herein, we report the CT findings of various diseases with elevated D-dimer levels in an emergency room setting, including an intravascular contrast filling defect with associated findings in a venous thromboembolism, fracture with soft tissue swelling and hematoma formation in a trauma patient, enlargement with contrast enhancement in the infected organ of a patient, coronary artery stenosis with a perfusion defect of the myocardium in a patient with acute myocardial infarction, high density of acute thrombus in a cerebral vessel with a low density of affected brain parenchyma in an acute cerebral infarction, intimal flap with two separated lumens in a case of aortic dissection, organ involvement of malignancy in a cancer patient, and atrophy of a liver with a dilated portal vein and associated findings.

  20. DNA Origami Directed Au Nanostar Dimers for Single-Molecule Surface-Enhanced Raman Scattering. (United States)

    Tanwar, Swati; Haldar, Krishna Kanta; Sen, Tapasi


    We demonstrate the synthesis of Au nanostar dimers with tunable interparticle gap and controlled stoichiometry assembled on DNA origami. Au nanostars with uniform and sharp tips were immobilized on rectangular DNA origami dimerized structures to create nanoantennas containing monomeric and dimeric Au nanostars. Single Texas red (TR) dye was specifically attached in the junction of the dimerized origami to act as a Raman reporter molecule. The SERS enhancement factors of single TR dye molecules located in the conjunction region in dimer structures having interparticle gaps of 7 and 13 nm are 2 × 10 10 and 8 × 10 9 , respectively, which are strong enough for single analyte detection. The highly enhanced electromagnetic field generated by the plasmon coupling between sharp tips and cores of two Au nanostars in the wide conjunction region allows the accommodation and specific detection of large biomolecules. Such DNA-directed assembled nanoantennas with controlled interparticle separation distance and stoichiometry, and well-defined geometry, can be used as excellent substrates in single-molecule SERS spectroscopy and will have potential applications as a reproducible platform in single-molecule sensing.

  1. Live cell imaging unveils multiple domain requirements for in vivo dimerization of the glucocorticoid receptor.

    Directory of Open Access Journals (Sweden)

    Diego M Presman


    Full Text Available Glucocorticoids are essential for life, but are also implicated in disease pathogenesis and may produce unwanted effects when given in high doses. Glucocorticoid receptor (GR transcriptional activity and clinical outcome have been linked to its oligomerization state. Although a point mutation within the GR DNA-binding domain (GRdim mutant has been reported as crucial for receptor dimerization and DNA binding, this assumption has recently been challenged. Here we have analyzed the GR oligomerization state in vivo using the number and brightness assay. Our results suggest a complete, reversible, and DNA-independent ligand-induced model for GR dimerization. We demonstrate that the GRdim forms dimers in vivo whereas adding another mutation in the ligand-binding domain (I634A severely compromises homodimer formation. Contrary to dogma, no correlation between the GR monomeric/dimeric state and transcriptional activity was observed. Finally, the state of dimerization affected DNA binding only to a subset of GR binding sites. These results have major implications on future searches for therapeutic glucocorticoids with reduced side effects.

  2. Inhibition of Receptor Dimerization as a Novel Negative Feedback Mechanism of EGFR Signaling.

    Directory of Open Access Journals (Sweden)

    Malgorzata Kluba

    Full Text Available Dimerization of the epidermal growth factor receptor (EGFR is crucial for initiating signal transduction. We employed raster image correlation spectroscopy to continuously monitor the EGFR monomer-dimer equilibrium in living cells. EGFR dimer formation upon addition of EGF showed oscillatory behavior with a periodicity of about 2.5 min, suggesting the presence of a negative feedback loop to monomerize the receptor. We demonstrated that monomerization of EGFR relies on phospholipase Cγ, protein kinase C, and protein kinase D (PKD, while being independent of Ca2+ signaling and endocytosis. Phosphorylation of the juxtamembrane threonine residues of EGFR (T654/T669 by PKD was identified as the factor that shifts the monomer-dimer equilibrium of ligand bound EGFR towards the monomeric state. The dimerization state of the receptor correlated with the activity of an extracellular signal-regulated kinase, downstream of the EGFR. Based on these observations, we propose a novel, negative feedback mechanism that regulates EGFR signaling via receptor monomerization.

  3. TACO: a general-purpose tool for predicting cell-type-specific transcription factor dimers. (United States)

    Jankowski, Aleksander; Prabhakar, Shyam; Tiuryn, Jerzy


    Cooperative binding of transcription factor (TF) dimers to DNA is increasingly recognized as a major contributor to binding specificity. However, it is likely that the set of known TF dimers is highly incomplete, given that they were discovered using ad hoc approaches, or through computational analyses of limited datasets. Here, we present TACO (Transcription factor Association from Complex Overrepresentation), a general-purpose standalone software tool that takes as input any genome-wide set of regulatory elements and predicts cell-type-specific TF dimers based on enrichment of motif complexes. TACO is the first tool that can accommodate motif complexes composed of overlapping motifs, a characteristic feature of many known TF dimers. Our method comprehensively outperforms existing tools when benchmarked on a reference set of 29 known dimers. We demonstrate the utility and consistency of TACO by applying it to 152 DNase-seq datasets and 94 ChIP-seq datasets. Based on these results, we uncover a general principle governing the structure of TF-TF-DNA ternary complexes, namely that the flexibility of the complex is correlated with, and most likely a consequence of, inter-motif spacing.

  4. The immunity-related GTPase Irga6 dimerizes in a parallel head-to-head fashion. (United States)

    Schulte, Kathrin; Pawlowski, Nikolaus; Faelber, Katja; Fröhlich, Chris; Howard, Jonathan; Daumke, Oliver


    The immunity-related GTPases (IRGs) constitute a powerful cell-autonomous resistance system against several intracellular pathogens. Irga6 is a dynamin-like protein that oligomerizes at the parasitophorous vacuolar membrane (PVM) of Toxoplasma gondii leading to its vesiculation. Based on a previous biochemical analysis, it has been proposed that the GTPase domains of Irga6 dimerize in an antiparallel fashion during oligomerization. We determined the crystal structure of an oligomerization-impaired Irga6 mutant bound to a non-hydrolyzable GTP analog. Contrary to the previous model, the structure shows that the GTPase domains dimerize in a parallel fashion. The nucleotides in the center of the interface participate in dimerization by forming symmetric contacts with each other and with the switch I region of the opposing Irga6 molecule. The latter contact appears to activate GTP hydrolysis by stabilizing the position of the catalytic glutamate 106 in switch I close to the active site. Further dimerization contacts involve switch II, the G4 helix and the trans stabilizing loop. The Irga6 structure features a parallel GTPase domain dimer, which appears to be a unifying feature of all dynamin and septin superfamily members. This study contributes important insights into the assembly and catalytic mechanisms of IRG proteins as prerequisite to understand their anti-microbial action.

  5. Role of quaternary structure in muscle creatine kinase stability: tryptophan 210 is important for dimer cohesion. (United States)

    Perraut, C; Clottes, E; Leydier, C; Vial, C; Marcillat, O


    A mutant of the dimeric rabbit muscle creatine kinase (MM-CK) in which tryptophan 210 was replaced has been studied to assess the role of this residue in dimer cohesion and the importance of the dimeric state for the native enzyme stability. Wild-type protein equilibrium unfolding induced by guanidine hydrochloride occurs through intermediate states with formation of a molten globule and a premolten globule. Unlike the wild-type enzyme, the mutant inactivates at lower denaturant concentration and the loss of enzymatic activity is accompanied by the dissociation of the dimer into two apparently compact monomers. However, the Stokes radius of the monomer increases with denaturant concentration as determined by size exclusion chromatography, indicating that, upon monomerization, the protein structure is destabilized. Binding of 8-anilinonaphthalene-1-sulfonate shows that the dissociated monomer exposes hydrophobic patches at its surface, suggesting that it could be a molten globule. At higher denaturant concentrations, both wild-type and mutant follow similar denaturation pathways with formation of a premolten globule around 1.5-M guanidine, indicating that tryptophan 210 does not contribute to a large extent to the monomer conformational stability, which may be ensured in the dimeric state through quaternary interactions.

  6. Fabrication and characterization of Au dimer antennas on glass pillars with enhanced plasmonic response

    Directory of Open Access Journals (Sweden)

    Sadeghi Pedram


    Full Text Available We report on the fabrication and dark-field spectroscopy characterization of Au dimer nanoantennas placed on top of SiO2 nanopillars. The reported process enables the fabrication of nanopillar dimers with gaps down to 15 nm and heights up to 1 μm. A clear dependence of the plasmonic resonance position on the dimer gap is observed for smaller pillar heights, showing the high uniformity and reproducibility of the process. It is shown how increasing the height of nanopillars significantly affects the recorded elastic scattering spectra from Au nanoantennas. The results are compared to finite-difference time-domain (FDTD and finite-element method (FEM simulations. Additionally, measured spectra are accompanied by dark-field microscopy images of the dimers, showing the pronounced change in color. Placing nanoantennas on nanopillars with a height comparable to the in-plane dimer dimensions results in an enhancement of the scattering response, which can be understood through reduced interaction of the near-fields with the substrate. When increasing the pillar height further, scattering by the pillars themselves manifests itself as a strong tail at lower wavelengths. Additionally, strong directional scattering is expected as a result of the interface between the nanoantennas and nanopillars, which is taken into account in simulations. For pillars of height close to the plasmonic resonance wavelength, the scattering spectra become more complex due to additional scattering peaks as a result of larger geometrical nonuniformities.

  7. Characterization of human immunodeficiency virus type 2 envelope glycoproteins: Dimerization of the glycoprotein precursor during processing

    International Nuclear Information System (INIS)

    Rey, M.A.; Krust, B.; Laurent, A.G.; Montagnier, L.; Hovanessian, A.G.


    For glycoproteins with apparent molecular weights of 300,000, 140,000, 125,000, and 36,000 (gp300, gp140, gp125, and gp36) were detectable in human immunodeficiency virus type 2 (HIV-2)-infected cells. They have identical isoelectric points, suggesting that gp300 might be a dimeric form of the immature precursor, gp140. The purified gp300 can be dissociated in a slightly acidic buffer to give rise to monomers of 140,000 molecular weight. Such dissociated monomers and the purified gp140 showed identical patterns of polypeptides after partial proteolysis with Staphylococcus aureus V8 protease. Pulse-chase experiments indicated that gp300 is formed after synthesis of gp140 and before the detection of the mature external envelope glycoprotein, gp125. These results were confirmed by using various inhibitors of glycosylation and inhibitors of trimming enzymes. Dimer formation of the envelope glycoprotein precursor was also observed in cells infected with simian immunodeficiency virus (SIV), a virus closely related to HIV-2. On the other hand, the envelope glycoprotein precursor of HIV-1 did not form a dimer during its processing. Therefore, dimer formation seems to be a specific property of HIV-2 and SIV envelope gene expression. Such transient dimerization of the glycoprotein precursor might be required for its efficient transport to the Golgi apparatus and for its processing

  8. Model-Based Comparison of Antibody Dimerization in Continuous and Batch-Wise Downstream Processing

    Directory of Open Access Journals (Sweden)

    Anton Sellberg


    Full Text Available Monoclonal antibodies are generally produced using a generic platform approach in which several chromatographic separations assure high purity of the product. Dimerization can occur during the fermentation stage and may occur also during the downstream processing. We present here simulations in which a traditional platform approach that consist of protein A capture, followed by cation-exchange and anion-exchange chromatography for polishing is compared to a continuous platform in which dimer removal and virus inactivation are carried out on a size-exclusion column. A dimerization model that takes pH, salt concentration and the concentration of antibodies into account is combined with chromatographic models, to be able to predicted both the separation and the degree to which dimers are formed. Purification of a feed composition that contained 1% by weight of dimer and a total antibody concentration of 1 g/L was modeled using both approaches, and the amount of antibodies in the continuous platform was at least 4 times lower than in the traditional platform. The total processing time was also lower, as the cation-exchange polish could be omitted.

  9. Coupling of two non-processive myosin 5c dimers enables processive stepping along actin filaments. (United States)

    Gunther, Laura K; Furuta, Ken'ya; Bao, Jianjun; Urbanowski, Monica K; Kojima, Hiroaki; White, Howard D; Sakamoto, Takeshi


    Myosin 5c (Myo5c) is a low duty ratio, non-processive motor unable to move continuously along actin filaments though it is believed to participate in secretory vesicle trafficking in vertebrate cells. Here, we measured the ATPase kinetics of Myo5c dimers and tested the possibility that the coupling of two Myo5c molecules enables processive movement. Steady-state ATPase activity and ADP dissociation kinetics demonstrated that a dimer of Myo5c-HMM (double-headed heavy meromyosin 5c) has a 6-fold lower Km for actin filaments than Myo5c-S1 (single-headed myosin 5c subfragment-1), indicating that the two heads of Myo5c-HMM increase F-actin-binding affinity. Nanometer-precision tracking analyses showed that two Myo5c-HMM dimers linked with each other via a DNA scaffold and moved processively along actin filaments. Moreover, the distance between the Myo5c molecules on the DNA scaffold is an important factor for the processive movement. Individual Myo5c molecules in two-dimer complexes move stochastically in 30-36 nm steps. These results demonstrate that two dimers of Myo5c molecules on a DNA scaffold increased the probability of rebinding to F-actin and enabled processive steps along actin filaments, which could be used for collective cargo transport in cells.

  10. Structural and Vibrational Study on Monomer and Dimer Forms and Water Clusters of Acetazolamide

    Directory of Open Access Journals (Sweden)

    Aysen E. Ozel


    Full Text Available Experimental IR and Raman spectra of solid acetazolamide have been analysed by computing the molecular structures and vibrational spectra of monomer and dimer forms and water clusters of acetazolamide. The possible stable conformers of free acetazolamide molecule in the ground state were obtained by scanning the potential energy surface through the dihedral angles, D1 (1S-2C-6S-9N, D2 (4N-5C-12N-14C, and D3 (5C-12N-14C-16C. The final geometry parameters for the obtained stable conformers were determined by means of geometry optimization, carried out at DFT/B3LYP/6-31G++(d,p theory level. Afterwards the possible dimer forms of the molecule and acetazolamide-H2O clusters were formed and their energetically preferred conformations were investigated using the same method and the same level of theory. The effect of BSSE on the structure and energy of acetazolamide dimer has been investigated. The assignment of the vibrational modes was performed based on the potential energy distribution of the vibrational modes, calculated by using GAR2PED program. The experimental vibrational wavenumbers of solid acetazolamide are found to be in better agreement with the calculated wavenumbers of dimer form of acetazolamide than those of its monomeric form. NBO analysis has been performed on both monomer and dimer geometries.

  11. Theoretical analysis of bimetallic nanorod dimer biosensors for label-free molecule detection (United States)

    Das, Avijit; Talukder, Muhammad Anisuzzaman


    In this work, we theoretically analyze a gold (Au) core within silver (Ag) shell (Au@Ag) nanorod dimer biosensor for label-free molecule detection. The incident light on an Au@Ag nanorod strongly couples to localized surface plasmon modes, especially around the tip region. The field enhancement around the tip of a nanorod or between the tips of two longitudinally aligned nanorods as in a dimer can be exploited for sensitive detection of biomolecules. We derive analytical expressions for the interactions of an Au@Ag nanorod dimer with the incident light. We also study the detail dynamics of an Au@Ag nanorod dimer with the incident light computationally using finite difference time domain (FDTD) technique when core-shell ratio, relative position of the nanorods, and angle of incidence of light change. We find that the results obtained using the developed analytical model match well with that obtained using FDTD simulations. Additionally, we investigate the sensitivity of the Au@Ag nanorod dimer, i.e., shift in the resonance wavelength, when a target biomolecule such as lysozyme (Lys), human serum albumin (HSA), anti-biotin (Abn), human catalase (CAT), and human fibrinogen (Fb) protein molecules are attached to the tips of the nanorods.

  12. Modulation of Coiled-Coil Dimer Stability through Surface Residues while Preserving Pairing Specificity. (United States)

    Drobnak, Igor; Gradišar, Helena; Ljubetič, Ajasja; Merljak, Estera; Jerala, Roman


    The coiled-coil dimer is a widespread protein structural motif and, due to its designability, represents an attractive building block for assembling modular nanostructures. The specificity of coiled-coil dimer pairing is mainly based on hydrophobic and electrostatic interactions between residues at positions a, d, e, and g of the heptad repeat. Binding affinity, on the other hand, can also be affected by surface residues that face away from the dimerization interface. Here we show how design of the local helical propensity of interacting peptides can be used to tune the stabilities of coiled-coil dimers over a wide range. By designing intramolecular charge pairs, regions of high local helical propensity can be engineered to form trigger sequences, and dimer stability is adjusted without changing the peptide length or any of the directly interacting residues. This general principle is demonstrated by a change in thermal stability by more than 30 °C as a result of only two mutations outside the binding interface. The same approach was successfully used to modulate the stabilities in an orthogonal set of coiled-coils without affecting their binding preferences. The stability effects of local helical propensity and peptide charge are well described by a simple linear model, which should help improve current coiled-coil stability prediction algorithms. Our findings enable tuning the stabilities of coiled-coil-based building modules match a diverse range of applications in synthetic biology and nanomaterials.

  13. The tripartite motif coiled-coil is an elongated antiparallel hairpin dimer (United States)

    Sanchez, Jacint G.; Okreglicka, Katarzyna; Chandrasekaran, Viswanathan; Welker, Jordan M.; Sundquist, Wesley I.; Pornillos, Owen


    Tripartite motif (TRIM) proteins make up a large family of coiled-coil-containing RING E3 ligases that function in many cellular processes, particularly innate antiviral response pathways. Both dimerization and higher-order assembly are important elements of TRIM protein function, but the atomic details of TRIM tertiary and quaternary structure have not been fully understood. Here, we present crystallographic and biochemical analyses of the TRIM coiled-coil and show that TRIM proteins dimerize by forming interdigitating antiparallel helical hairpins that position the N-terminal catalytic RING domains at opposite ends of the dimer and the C-terminal substrate-binding domains at the center. The dimer core comprises an antiparallel coiled-coil with a distinctive, symmetric pattern of flanking heptad and central hendecad repeats that appear to be conserved across the entire TRIM family. Our studies reveal how the coiled-coil organizes TRIM25 to polyubiquitylate the RIG-I/viral RNA recognition complex and how dimers of the TRIM5α protein are arranged within hexagonal arrays that recognize the HIV-1 capsid lattice and restrict retroviral replication. PMID:24550273


    Directory of Open Access Journals (Sweden)

    Abreu C.R.A.


    Full Text Available The effect of surface topography upon the adsorption of dimer molecules is analyzed by means of grand canonical ensemble Monte Carlo simulations. Heterogeneous surfaces were assumed to consist of a square lattice containing active sites with two different energies. These were distributed in three different configurations: a random distribution of isolated sites; a random distribution of grains with four high-energy sites; and a random distribution of grains with nine high-energy sites. For the random distribution of isolated sites, the results are in good agreement with the molecular simulations performed by Nitta et al. (1997. In general, the comparison with theoretical models shows that the Nitta et al. (1984 isotherm presents good predictions of dimer adsorption both on homogeneous and heterogeneous surfaces with sites having small differences in characteristic energies. The molecular simulation results also show that the energy topology of the solid surfaces plays an important role in the adsorption of dimers on solids with large differences in site energies. For these cases, the Nitta et al. model does not describe well the data on dimer adsorption on random heterogeneous surfaces (grains with one acid site, but does describe reasonably well the adsorption of dimers on more patchwise heterogeneous surfaces (grains with nine acid sites.

  15. Electrostatic Interactions at the Dimer Interface Stabilize the E. coli β Sliding Clamp. (United States)

    Purohit, Anirban; England, Jennifer K; Douma, Lauren G; Tondnevis, Farzaneh; Bloom, Linda B; Levitus, Marcia


    Sliding clamps are ring-shaped oligomeric proteins that encircle DNA and associate with DNA polymerases for processive DNA replication. The dimeric Escherichia coli β-clamp is closed in solution but must adopt an open conformation to be assembled onto DNA by a clamp loader. To determine what factors contribute to the stability of the dimer interfaces in the closed conformation and how clamp dynamics contribute to formation of the open conformation, we identified conditions that destabilized the dimer and measured the effects of these conditions on clamp dynamics. We characterized the role of electrostatic interactions in stabilizing the β-clamp interface. Increasing salt concentration results in decreased dimer stability and faster subunit dissociation kinetics. The equilibrium dissociation constant of the dimeric clamp varies with salt concentration as predicted by simple charge-screening models, indicating that charged amino acids contribute to the remarkable stability of the interface at physiological salt concentrations. Mutation of a charged residue at the interface (Arg-103) weakens the interface significantly, whereas effects are negligible when a hydrophilic (Ser-109) or a hydrophobic (Ile-305) amino acid is mutated instead. It has been suggested that clamp opening by the clamp loader takes advantage of spontaneous opening-closing fluctuations at the clamp's interface, but our time-resolved fluorescence and fluorescence correlation experiments rule out conformational fluctuations that lead to a significant fraction of open states. Copyright © 2017 Biophysical Society. Published by Elsevier Inc. All rights reserved.





    The interaction between the H2 molecule and the PdAg, PdAu, PtAg and PtAu bimetallic dimers deposited on the MgO(100) surface is investigated using density functional theory (DFT). The bimetallic dimers, whose molecular axes are considered to be perpendicular to the support surface, are adsorbed on top of an oxygen atom. Within this adsorption mode, the dimers prefer the orientation in which their Pd or Pt end is closer to the oxygen atom. The Ag and Au ends of the MgO-supported dimers captur...

  17. Domains of macrophage N(O) synthase have divergent roles in forming and stabilizing the active dimeric enzyme. (United States)

    Ghosh, D K; Abu-Soud, H M; Stuehr, D J


    The cytokine-inducible NO synthase (iNOS) is a flavin-containing hemeprotein that must dimerize to generate NO. Trypsin cleaves the dimeric enzyme into an oxygenase domain fragment that remains dimeric, contains heme and H4biopterin, and binds L-arginine and a reductase domain fragment that is monomeric, binds NADPH, FAD, FMN, and catalyzes the reduction of cytochrome c [Ghosh, D. K. & Stuehr, D. J. (1995) Biochemistry 34, 801-807]. The current study investigates the isolated oxygenase and reductase domains of iNOS to understand how they form and stabilize the active dimeric enzyme. The dimeric oxygenase domain dissociated into folded, heme-containing monomers when incubated with 2-5 M urea, whereas the reductase domain unfolded under these conditions and lost its ability to catalyze NADPH-dependent cytochrome c reduction. Spectral analysis of the dissociation reaction showed that it caused structural changes within the oxygenase domain and exposed the distal side of the heme to solvent, enabling it to bind dithiothreitol as a sixth ligand. Importantly, the oxygenase domain monomers could reassociate into a dimeric form even in the absence of the reductase domain. The reaction required L-arginine and H4biopterin and completely reversed the structural changes in heme pocket and protein structure that occurred upon dissociating the original dimer. Together, this confirms that the oxygenase domain contains all of the determinants needed for subunit dimerization and indicates that the dimeric structure greatly affects the heme and protein environment in the oxygenase domain.

  18. Preparation of 177Lu-DOTA/DTPA-Bz-Cys-RGD dimer and biodistribution evaluation in normal mice

    International Nuclear Information System (INIS)

    Sheng Feng; Jia Bing; Wang Fan; He Weiwei; Liu Zhaofei; Zhao Huiyun


    177 Lu-DOTA-Bz-Cys-RGD dimer and 177 Lu-DTPA-Bz-Cys-RGD dimer were prepared, and the in vitro and in vivo properties were compared. TLC and HPLC show that the labeling yields of two radiolabeled compounds are more than 95% under optimal conditions (pH=5.0, reacting at 100 degree C for 15-20 min), and the two radiolabeled compounds show pretty good in vitro stability. HPLC analyses and lg P values reveal that lipophilicity of 177 Lu-DOTA-Bz-Cys- RGD dimer is higher than 177 Lu-DTPA-Bz-Cys-RGD dimer. The uptake of 177 Lu-DTPA-Bz-Cys- RGD dimer in other tissues is significantly higher than that of 177 Lu-DOTA-Bz-Cys-RGD dimer at 4 h postinjection, except for blood and spleen. The in vivo stability of 177 Lu-DOTA-Bz-Cys-RGD dimer is much better than 177 Lu-DTPA-Bz-Cys-RGD dimer. Bz-DOTA is an ideal bifunctional chelator for 177 Lu labeling of RGD dimer. (authors)

  19. Stereoselective C9 carbon-carbon couplings of quinine: synthesis and conformational analysis of new C2-symmetric dimers. (United States)

    Boratyński, Przemysław J; Turowska-Tyrk, Ilona; Skarzewski, Jacek


    An unexpected stereoselective direct dimerization occurred when 9-quinine halide was treated with butyllithium. The reaction of either (9S)- or (9R)-chloroquinine gave the same C2-symmetric dimer with 9R configuration (X-ray structure). A tentative mechanism involving radical recombination is discussed. This highly congested dimer forms two atropisomers, and their reversible interconversion was studied by NMR. Another C2-symmetric (9S)-quinine dimer connected solely by carbon-carbon bonds was obtained by the stereoselective coupling of bis(arylbromomagnesium) derivative with (9S)-chloroquinine.

  20. Gap solitons in a chain of split-ring resonator dimers

    Energy Technology Data Exchange (ETDEWEB)

    Cui, Wei-na, E-mail: [Department of Applied Physics, Nanjing University of Science and Technology, Nanjing 210094 (China); Li, Hong-xia, E-mail: [Department of Applied Physics, Nanjing University of Science and Technology, Nanjing 210094 (China); Sun, Min [Department of Applied Physics, Nanjing University of Science and Technology, Nanjing 210094 (China); Bu, Ling-bing [Collaborative Innovation Center on Forecast and Evaluation of Meteorological Disasters, Key Laboratory for Aerosol-Cloud-Precipitation of China Meteorological Administration, Key Laboratory of Meteorological Disaster of Ministry of Education, Nanjing University of Information Science and Technology, Nanjing 210044 (China)


    Dynamics of a chain of split-ring resonator dimers with Kerr nonlinear interaction are investigated. A dimer is built as a pair of coupled split-ring resonators with different size. It is shown that the gap solitons with frequency lying in the gap exist due to the interaction of the discreteness and nonlinearity. Such localized structures are studied in the phase plane and analytical and numerical expressions are also obtained. - Highlights: • The coupling of the two modes is studied in the chain of split-ring resonator dimers with Kerr nonlinear interaction. • The evolution of the localized structures is studied in the phase plane. • This system supports gap solitons with the frequencies lying in the gap.