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Sample records for vanadium metal ii

  1. Vanadium

    OpenAIRE

    Pourret, Olivier; Dia, Aline

    2017-01-01

    International audience; Vanadium (chemical symbol, V) is a d-block transition metal,silver in color, appearing in the first long period of the peri-odic table between titanium and chromium. Vanadium hastwo stable isotopes: 50V and 51V, with atomic abundance of0.25 % and 99.75 %, respectively. Vanadium has several oxidation forms (between 2+ and 5+). In the lithosphere, Voccurs as reducing V(III) form, whereas in oxidizing con- ditions V prevails under V(IV) form. Vanadium(II) is partic- ularl...

  2. Kinetics of Vanadium Extraction from Hot Metal by Basic Slag

    Science.gov (United States)

    Zhang, Tao; Xie, Bing; Liu, Xuan; Diao, Jiang; Zhang, Zhen; Li, Hong-Yi

    Extracting vanadium from vanadium containing hot metal by LD process has been proven an effective solution for the utilization of vanadium-titanium magnetite ore, but the systematic analyses of vanadium extraction rate and mechanism by basic slag are seldom reported. In this study, mathematical model of vanadium transfer from metal to slag was formulated and the rates of vanadium extraction of hot metal with basic slag were investigated. The results indicated that the apparent vanadium extraction rate constant, k p , were in the range of 1.33˜9.07×10-4g/(cm3·s). And the rate constant was increased with the increase of final slag basicity, reaction temperature and stirring gas flow. The apparent of mass transfer parameter decreases significantly from 0.13 cm3/ s to 0 cm3/ s in 20min, and the data changed as negative due to the decrease of slag oxidation and recovery of vanadium from slag to metal.

  3. Iron(II)- or vanadium(IV)-containing siliceous gels

    OpenAIRE

    Hutter, Frank; Schmidt, Helmut K.; Scholze, Horst

    1986-01-01

    Iron(II)-containing SiO2 gels can be prepared by the hydrolysis and condensation of tetramethoxysilane in methanolic solutions of iron(II) chloride. These gels show an absorption at 1000 nm indicating the presence of iron(II). In opposition to that, iron(II) cannot be introduced into organically modified gels of the 3-glycidyloxypropyltrimethoxysilane type. Vanadium(IV) can be incorporated into both gels. Unlike the SiO2 gels, the organically modified gels are compact and elastic. The spectra...

  4. Vanadium

    Science.gov (United States)

    Kelley, Karen D.; Scott, Clinton T.; Polyak, Désirée E.; Kimball, Bryn E.; Schulz, Klaus J.; DeYoung, John H.; Seal, Robert R.; Bradley, Dwight C.

    2017-12-19

    Vanadium is used primarily in the production of steel alloys; as a catalyst for the chemical industry; in the making of ceramics, glasses, and pigments; and in vanadium redox-flow batteries (VRBs) for large-scale storage of electricity. World vanadium resources in 2012 were estimated to be 63 million metric tons, which include about 14 million metric tons of reserves. The majority of the vanadium produced in 2012 was from China, Russia, and South Africa.Vanadium is extracted from several different types of mineral deposits and from fossil fuels. These deposits include vanadiferous titanomagnetite (VTM) deposits, sandstone-hosted vanadium (with or without uranium) deposits (SSV deposits), and vanadium-rich black shales. VTM deposits are the principal source of vanadium and consist of magmatic accumulations of ilmenite and magnetite containing 0.2 to 1 weight percent vanadium pentoxide (V2O5). SSV deposits are another important source; these deposits have average ore grades that range from 0.1 to greater than 1 weight percent V2O5. The United States has been and is currently the main producer of vanadium from SSV deposits, particularly those on the Colorado Plateau. Vanadium-rich black shales occur in marine successions that were deposited in epeiric (inland) seas and on continental margins. Concentrations in these shales regularly exceed 0.18 weight percent V2O5 and can be as high as 1.7 weight percent V2O5. Small amounts of vanadium have been produced from the Alum Shale in Sweden and from ferrophosphorus slag generated during the reduction of phosphate to elemental phosphorus in ore from shales of the Phosphoria Formation in Idaho and Wyoming. Because vanadium enrichment occurs in beds that are typically only a few meters thick, most of the vanadiferous black shales are not currently economic, although they may become an important resource in the future. Significant amounts of vanadium are recovered as byproducts of petroleum refining, and processing of coal, tar

  5. Brain Metal Distribution and Neuro-Inflammatory Profiles after Chronic Vanadium Administration and Withdrawal in Mice

    Directory of Open Access Journals (Sweden)

    Oluwabusayo R. Folarin

    2017-07-01

    Full Text Available Vanadium is a potentially toxic environmental pollutant and induces oxidative damage in biological systems including the central nervous system (CNS. Its deposition in brain tissue may be involved in the pathogenesis of certain neurological disorders which after prolonged exposure can culminate into more severe pathology. Most studies on vanadium neurotoxicity have been done after acute exposure but in reality some populations are exposed for a lifetime. This work was designed to ascertain neurodegenerative consequences of chronic vanadium administration and to investigate the progressive changes in the brain after withdrawal from vanadium treatment. A total of 85 male BALB/c mice were used for the experiment and divided into three major groups of vanadium treated (intraperitoneally (i.p. injected with 3 mg/kg body weight of sodium metavanadate and sacrificed every 3 months till 18 months; matched controls; and animals that were exposed to vanadium for 3 months and thereafter the metal was withdrawn. Brain tissues were obtained after animal sacrifice. Sagittal cut sections of paraffin embedded tissue (5 μm were analyzed by the Laser ablation-inductively coupled plasma-mass spectrometry (LA–ICP–MS to show the absorption and distribution of vanadium metal. Also, Haematoxylin and Eosin (H&E staining of brain sections, and immunohistochemistry for Microglia (Iba-1, Astrocytes (GFAP, Neurons (Neu-N and Neu-N + 4′,6-diamidine-2′-pheynylindole dihydrochloride (Dapi Immunofluorescent labeling were observed for morphological and morphometric parameters. The LA–ICP–MS results showed progressive increase in vanadium uptake with time in different brain regions with prediction for regions like the olfactory bulb, brain stem and cerebellum. The withdrawal brains still show presence of vanadium metal in the brain slightly more than the controls. There were morphological alterations (of the layering profile, nuclear shrinkage in the prefrontal

  6. Investigating the air oxidation of V(II) ions in a vanadium redox flow battery

    Science.gov (United States)

    Ngamsai, Kittima; Arpornwichanop, Amornchai

    2015-11-01

    The air oxidation of vanadium (V(II)) ions in a negative electrolyte reservoir is a major side reaction in a vanadium redox flow battery (VRB), which leads to electrolyte imbalance and self-discharge of the system during long-term operation. In this study, an 80% charged negative electrolyte solution is employed to investigate the mechanism and influential factors of the reaction in a negative-electrolyte reservoir. The results show that the air oxidation of V(II) ions occurs at the air-electrolyte solution interface area and leads to a concentration gradient of vanadium ions in the electrolyte solution and to the diffusion of V(II) and V(III) ions. The effect of the ratio of the electrolyte volume to the air-electrolyte solution interface area and the concentrations of vanadium and sulfuric acid in an electrolyte solution is investigated. A higher ratio of electrolyte volume to the air-electrolyte solution interface area results in a slower oxidation reaction rate. The high concentrations of vanadium and sulfuric acid solution also retard the air oxidation of V(II) ions. This information can be utilized to design an appropriate electrolyte reservoir for the VRB system and to prepare suitable ingredients for the electrolyte solution.

  7. Hydrogen stabilization of metallic vanadium dioxide in single-crystal nanobeams

    Science.gov (United States)

    Wei, Jiang; Ji, Heng; Guo, Wenhua; Nevidomskyy, Andriy H.; Natelson, Douglas

    2012-06-01

    Vanadium dioxide is a strongly correlated material that undergoes a metal-insulator transition from a high-temperature, rutile metal to a monoclinic insulating state at 67 °C. In recent years, experiments on single-crystal vanadium-dioxide nanowires grown by physical vapour deposition have shed light on the crucial role of strain in the structural and electronic phase diagram of this material, including evidence for a new M2 phase, but the detailed physics of this material is still not fully understood. The transition temperature can be reduced by doping with tungsten, but this process is not reversible. Here, we show that the metal-insulator transition in nanoscale beams of vanadium dioxide can be strongly modified by doping with atomic hydrogen using the catalytic spillover method. We also show that this process is completely reversible, and that the metal-insulator transition eventually vanishes when the doping exceeds a threshold value. Raman and conventional optical microscopy, electron diffraction and transmission electron microscopy provide evidence that the structure of the metallic post-hydrogenation state is similar to that of the rutile state. First-principles electronic structure calculations confirm that a distorted rutile structure is energetically favoured following hydrogenation, and also that such doping favours metallicity from both the Mott and Peierls perspectives. We anticipate that hydrogen doping will be a powerful tool for examining the metal-insulator transition and for engineering the properties of vanadium dioxide.

  8. Organometallic benzene-vanadium wire: A one-dimensional half-metallic ferromagnet

    DEFF Research Database (Denmark)

    Maslyuk, V.; Bagrets, A.; Meded, V.

    2006-01-01

    methods. We predict that the ground state of the wire is a 100% spin-polarized ferromagnet (half-metal). Its density of states is metallic at the Fermi energy for the minority electrons and shows a semiconductor gap for the majority electrons. We find that the half-metallic behavior is conserved up to 12......% longitudinal elongation of the wire. Ab initio electron transport calculations reveal that finite size vanadium-benzene clusters coupled to ferromagnetic Ni or Co electrodes will work as nearly perfect spin filters....

  9. A Vanadium Dioxide Metamaterial Disengaged from Insulator-to-Metal Transition.

    Science.gov (United States)

    Jeong, Young-Gyun; Han, Sanghoon; Rhie, Jiyeah; Kyoung, Ji-Soo; Choi, Jae-Wook; Park, Namkyoo; Hong, Seunghun; Kim, Bong-Jun; Kim, Hyun-Tak; Kim, Dai-Sik

    2015-10-14

    We report that vanadium dioxide films patterned with λ/100000 nanogaps exhibit an anomalous transition behavior at millimeter wavelengths. Most of the hybrid structure's switching actions occur well below the insulator to metal transition temperature, starting from 25 °C, so that the hysteresis curves completely separate themselves from their bare film counterparts. It is found that thermally excited intrinsic carriers are responsible for this behavior by introducing enough loss in the context of the radically modified electromagnetic environment in the vicinity of the nanogaps. This phenomenon newly extends the versatility of insulator to metal transition devices to encompass their semiconductor properties.

  10. Electrochemistry of vanadium(II and the electrodeposition of aluminum-vanadium alloys in the aluminum chloride-1-ethyl-3-methylimidazolium chloride molten salt

    Directory of Open Access Journals (Sweden)

    Tsuda T.

    2003-01-01

    Full Text Available The electrochemical behavior of vanadium(II was examined in the 66.7-33.3 mole percent aluminum chloride-1-ethyl-3-methylimidazolium chloride molten salt containing dissolved VCl2 at 353 K. Voltammetry experiments revealed that V(II could be electrochemically oxidized to V(III and V(IV. However at slow scan rates the V(II/V(III electrode reaction is complicated by the rapid precipitation of V(III as VCl3. The reduction of V(II occurs at potentials considerably negative of the Al(III/Al electrode reaction, and Al-V alloys cannot be electrodeposited from this melt. However electrodeposition experiments conducted in VCl2-saturated melt containing the additive, 1-ethyl-3-methylimidazolium tetrafluoroborate, resulted in Al-V alloys. The vanadium content of these alloys increased with increasing cathodic current density or more negative applied potentials. X-ray analysis of Al-V alloys that were electrodeposited on a rotating copper wire substrate indicated that these alloys did not form or contain an intermetallic compound, but were non-equilibrium or metastable solid solutions. The chloride-pitting corrosion properties of these alloys were examined in aqueous NaCl by using potentiodynamic polarization techniques. Alloys containing ~10 a/o vanadium exhibited a pitting potential that was 0.3 V positive of that for pure aluminum.

  11. Vanadium as barrier to prevent inter diffusion between metallic fuel and clad material

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Kang Soo; Lee, Seok Hee; Kalita, Deep Jyoti; Woo, Sung Pil; Yoon, Young Soo [Yonsei Univ., Shinchondong, Seoul (Korea, Republic of); Kim, Jun Hwan; Baek, Jong Hyuk [Korea Atomic Energy Research Institute, Daejeon (Korea, Republic of)

    2012-10-15

    Sodium cooled Fast Reactor (SFR) has been considered as next generation nuclear reactor because of its ability of recycling nuclear fuel. Specially, U Zr metal fuel in nuclear reactor has advantages such as ease of fabrication, high thermal conductivity, proliferation resistance and a good stability for sodium which have proven efficient in extending the fusion possibility. In spite of advantages, metal fuel can be inconvenient to use cladding. Actinide elements cause a FCCI (Fuel Clad Chemical Interaction) and eutectic reaction with Fe as nuclear cladding components at just above 650 .deg. C. Since nuclear cladding thickness is decreased during the combusting U Zr metal fuel, the interaction place in the cladding is brittle and less strength. It was reported that the eutectic melting between U Pu Zr and Fe occurs above 650 .deg. C. For such reasons, liner related materials and process have been studied by many research groups. In order to apply this nuclear cladding liner, Zr and V metals show better properties to preventing FCCI. Although liner materials prevent FCCI to an extent, it cannot block it perfectly. In this study, we attempt a combination of vanadium (V) and vanadium foil double layer in between a 420J2(Fe based 12Cr steel) and misch metal. The V thin film was deposited with various RF power. The results of diffusion couple tests at 660 .deg. C for 25 hours showed that a combination of the V thin films and foil exhibited a better shielding for FCCI.

  12. X-Ray Absorption Studies of Vanadium-Containing Metal Oxide Nanocrystals

    Energy Technology Data Exchange (ETDEWEB)

    Hohn, Keith, L.

    2006-01-09

    Metal oxide nanocrystals offer significant potential for use as catalysts or catalyst supports due to their high surface areas and unique chemical properties that result from the high number of exposed corners and edges. However, little is known about the catalytic activity of these materials, especially as oxidation catalysts. This research focused on the preparation, characterization and use of vanadium-containing nanocrystals as selective oxidation catalysts. Three vanadium-containing nanocrystals were prepared using a modified sol-gel procedure: V/MgO, V/SiO2, and vanadium phosphate (VPO). These represent active oxidation catalysts for a number of industrially relevant reactions. The catalysts were characterized by x-ray diffraction and Raman, UV-VIS, infrared and x-ray absorption spectroscopies with the goal of determining the primary structural and chemical differences between nanocrystals and microcrystals. The catalytic activity of these catalysts was also studied in oxidative dehydrogenation of butane and methanol oxidation to formaldehyde. V/MgO nanocrystals were investigated for activity in oxidative dehydrogenation of butane and compared to conventional V/MgO catalysts. Characterization of V/MgO catalysts using Raman spectroscopy and x-ray absorption spectroscopy showed that both types of catalysts contained magnesium orthovanadate at vanadium loadings below 15 weight%, but above that loading, magnesium pyrovanadate may have been present. In general, MgO nanocrystals had roughly half the crystal size and double the surface area of the conventional MgO. In oxidative dehydrogenation of butane, nanocrystalline V/MgO gave higher selectivity to butene than conventional V/MgO at the same conversion. This difference was attributed to differences in vanadium domain size resulting from the higher surface areas of the nanocrystalline support, since characterization suggested that similar vanadium phases were present on both types of catalysts. Experiments in

  13. Determination of vanadium in refractory metals, steel, cast iron, alloys and silicates by extraction of an NBPHA complex from a sulphuric-hydrofluoric acid medium.

    Science.gov (United States)

    Donaldson, E M

    1970-07-01

    A method for determining up to 0.15% of vanadium in high-purity niobium and tantalum metals, cast iron, steel, non-ferrous alloys and silicates is described. The proposed method is based on the extraction of a red vanadium(V)-N-benzoyl-N-phenylhydroxylamine complex into chloroform from a sulphuric-hydrofluoric acid medium containing excess of ammonium persulphate as oxidant. The molar absorptivity of the complex is 428 l.mole(-1).mm(-5) at 475 nm, the wavelength of maximum absorption. Interference from chromium(VI) and cerium(IV) is eliminated by reduction with iron(II). Common ions, including large amounts of titanium, zirconium, molybdenum and tungsten, do not interfere.

  14. Multilevel radiative thermal memory realized by the hysteretic metal-insulator transition of vanadium dioxide

    Energy Technology Data Exchange (ETDEWEB)

    Ito, Kota, E-mail: kotaito@mosk.tytlabs.co.jp; Nishikawa, Kazutaka; Iizuka, Hideo [Toyota Central Research and Development Labs, Nagakute, Aichi 480-1192 (Japan)

    2016-02-01

    Thermal information processing is attracting much interest as an analog of electronic computing. We experimentally demonstrated a radiative thermal memory utilizing a phase change material. The hysteretic metal-insulator transition of vanadium dioxide (VO{sub 2}) allows us to obtain a multilevel memory. We developed a Preisach model to explain the hysteretic radiative heat transfer between a VO{sub 2} film and a fused quartz substrate. The transient response of our memory predicted by the Preisach model agrees well with the measured response. Our multilevel thermal memory paves the way for thermal information processing as well as contactless thermal management.

  15. The role of Glutathione, Cysteine and D-Penicillamine in exchanging Palladium and Vanadium metals from albumin metal complex.

    Science.gov (United States)

    Mukhtiar, Muhammad; Jan, Syed Umer; Ullah, Ihsan; Hussain, Abid; Ullah, Izhar; Gul, Rahman; Ali, Essa; Jabbar, Abdul; Kuthu, Zulfiqar Hussan; Wasim, Muhammad; Khan, Muhammad Farid

    2017-11-01

    Thiol groups are extensively present across biological systems being found in range of small molecules (e.g. Glutathione, Homo-cysteine) and proteins (e.g. albumin, haemo-globin). Albumin is considered to be a major thiol containing protein present in circulating Plasma. Albumin contains a single thiolate group located at cysteine-34(cys-34) at its active site. Albumin also binds a wide variety of metals and metals complexes at various sites around the protein. Usually heavy metals are preferentially attached with the thiol group of albumin. The binding of heavy metals at cys-34 provides a mechanism by which the residence time of potentially toxic species in the body can be increased. In this research we have assessed the oxidative modification of and metal binding capacity of cys-34 with heavy metals Palladium and Vanadium to investigate the ease with which it is possible to effect disulfide-thiol exchange at this sites/or remove a metal bound at this position. Both the metals were treated with albumin and then the albumin metals (Pd and V) complexes were treated with small thoil molecules like Glutathione, Cysteine and D-Penicillamine. Our finding showed that the albumin thiol group retained the metals with itself by forming some strong bonding with the Thiols group, it is concluded from this finding that if by chance both the metals enter the living system; strongly disturb the chemistry and physiological function of this bio-molecule.

  16. Vanadium and cadmium in vivo effects in teleost cardiac muscle: metal accumulation and oxidative stress markers.

    Science.gov (United States)

    Soares, S S; Martins, H; Gutiérrez-Merino, C; Aureliano, M

    2008-03-01

    Several biological studies associate vanadium and cadmium with the production of reactive oxygen species (ROS), leading to lipid peroxidation and antioxidant enzymes alterations. The present study aims to analyse and compare the oxidative stress responses induced by an acute intravenous exposure (1 and 7 days) to a sub-lethal concentration (5 mM) of two vanadium solutions, containing different vanadate n-oligomers (n=1-5 or n=10), and a cadmium solution on the cardiac muscle of the marine teleost Halobatrachus didactylus (Lusitanian toadfish). It was observed that vanadium is mainly accumulated in mitochondria (1.33+/-0.26 microM), primarily when this element was administrated as decameric vanadate, than when administrated as metavanadate (432+/-294 nM), while the highest content of cadmium was found in cytosol (365+/-231 nM). Indeed, decavanadate solution promotes stronger increases in mitochondrial antioxidant enzymes activities (catalase: +120%; superoxide dismutase: +140%) than metavanadate solution. On contrary, cadmium increases cytosolic catalase (+111%) and glutathione peroxidases (+50%) activities. It is also observed that vanadate oligomers induce in vitro prooxidant effects in toadfish heart, with stronger effects induced by metavanadate solution. In summary, vanadate and cadmium are differently accumulated in blood and cardiac subcellular fractions and induced different responses in enzymatic antioxidant defence mechanisms. In the present study, it is described for the first time the effects of equal doses of two different metals intravenously injected in the same fish species and upon the same exposure period allowing to understand the mechanisms of vanadate and cadmium toxicity in fish cardiac muscle.

  17. Selective Separation and Extraction of Vanadium (V) Over Manganese (II) from Co-Leaching Solution of Roasted Stone Coal and Pyrolusite Using Solvent Extraction

    Science.gov (United States)

    Cai, Z. L.; Feng, Y. L.; Zhou, Y. Z.; Li, H. R.; Wang, W. D.

    2013-11-01

    Based on the novel technology for selective separation and extraction of vanadium (V) over manganese (II) from co-leaching solution of roasted stone coal and pyrolusite using solvent extraction, the extraction effect of vanadium (V) and manganese (II) has been studied and many technical conditions have also been optimized. Meanwhile, countercurrent simulation experiments were conducted to verify the results of the experiments. The results indicated that with three countercurrent extraction stages, 99.21% vanadium (V) was extracted using 5% (v/v) N235 and 5% (v/v) secondary octyl alcohol at initial aqueous pH of 3.0 and O/A phase ratio of 1.0. Vanadium (V) could be completely stripped after three-stage countercurrent experiments with 20 wt.% NH4Cl at O/A phase ratio of 1.0. The process flow sheet for the recovery of vanadium (V), as well as manganese (II), was proposed.

  18. Thermally driven analog of the Barkhausen effect at the metal-insulator transition in vanadium dioxide

    Energy Technology Data Exchange (ETDEWEB)

    Huber-Rodriguez, Benjamin; Ji, Heng; Chen, Chih-Wei [Department of Physics and Astronomy, Rice University, Houston, Texas 77005 (United States); Kwang, Siu Yi [Department of Physics, National University of Singapore, Singapore 117551 (Singapore); Hardy, Will J. [Applied Physics Program, Rice Quantum Institute, Rice University, Houston, Texas 77005 (United States); Morosan, Emilia [Department of Physics and Astronomy, Rice University, Houston, Texas 77005 (United States); Department of Chemistry, Rice University, Houston, Texas 77005 (United States); Department of Materials Science and Nanoengineering, Rice University, Houston, Texas 77005 (United States); Natelson, Douglas [Department of Physics and Astronomy, Rice University, Houston, Texas 77005 (United States); Department of Materials Science and Nanoengineering, Rice University, Houston, Texas 77005 (United States); Department of Electrical and Computer Engineering, Rice University, Houston, Texas 77005 (United States)

    2014-09-29

    The physics of the metal-insulator transition (MIT) in vanadium dioxide remains a subject of intense interest. Because of the complicating effects of elastic strain on the phase transition, there is interest in comparatively strain-free means of examining VO{sub 2} material properties. We report contact-free, low-strain studies of the MIT through an inductive bridge approach sensitive to the magnetic response of VO{sub 2} powder. Rather than observing the expected step-like change in susceptibility at the transition, we argue that the measured response is dominated by an analog of the Barkhausen effect, due to the extremely sharp jump in the magnetic response of each grain as a function of time as the material is cycled across the phase boundary. This effect suggests that future measurements could access the dynamics of this and similar phase transitions.

  19. Large phonon entropy drives the metallization of vanadium dioxide (VO2)

    Science.gov (United States)

    Hong, Jiawang

    2015-03-01

    Vanadium dioxide (VO2) exhibits a first-order metal-insulator transition (MIT) near room temperature, where conductivity is suppressed and the lattice changes from tetragonal to monoclinic on cooling. This MIT in VO2 has attracted intense interest from both fundamental and technological perspectives. However, most studies performed in the past 50 years have focused on the electronic structure and energetics of the transition, ignoring the role of phonons and their entropic contribution to the phase stability. Much of the reason is that the standard tool of neutron scattering does not yield coherent scattering from V nuclei, and first-principles methods with harmonic approximation cannot capture the stable phonons for the rutile phase. We close this gap by using a combination of ab initio molecular dynamics calculations and neutron/x-ray scattering to establish that the entropy driving the MIT is dominated by soft, anharmonic phonons of the metallic phase. The MIT results from the competition between lower electronic energy in insulating M1 phase due to the Peierls instability, and the higher entropy of the metallic rutile phase resulting from soft anharmonic phonons. This understanding of the role of lattice dynamics and their relationship to electronic structure provides a critical component for developing more complete physical models of phase competition in functional transition metal oxides. Theoretical calculations were performed using the NERSC at LBNL. Modeling of neutron data was performed in CAMM, measurements were funded by the US DOE, BES, Materials Science and Engineering Division.

  20. Toxic metal tolerance in native plant species grown in a vanadium mining area.

    Science.gov (United States)

    Aihemaiti, Aikelaimu; Jiang, Jianguo; Li, De'an; Li, Tianran; Zhang, Wenjie; Ding, Xutong

    2017-09-29

    Vanadium (V) has been extensively mined in China and caused soil pollution in mining area. It has toxic effects on plants, animals and humans, posing potential health risks to communities that farm and graze cattle adjacent to the mining area. To evaluate in situ phytoremediation potentials of native plants, V, chromium, copper and zinc concentrations in roots and shoots were measured and the bioaccumulation (BAF) and translocation (TF) efficiencies were calculated. The results showed that Setaria viridis accumulated greater than 1000 mg kg-1 V in its shoots and exhibited TF > 1 for V, Cr, Zn and BAF > 1 for Cu. The V accumulation amount in the roots of Kochia scoparia also surpassed 1000 mg kg-1 and showed TF > 1 for Zn. Chenopodium album had BAF > 1 for V and Zn and Daucus carota showed TF > 1 for Cu. Eleusine indica presented strong tolerance and high metal accumulations. S. viridis is practical for in situ phytoextractions of V, Cr and Zn and phytostabilisation of Cu in V mining area. Other species had low potential use as phytoremediation plant at multi-metal polluted sites, but showed relatively strong resistance to V, Cr, Cu and Zn toxicity, can be used to vegetate the contaminated soils and stabilise toxic metals in V mining area.

  1. Bioaccumulation of vanadium and other trace metals in livers of Alaskan cetaceans and pinnipeds.

    Science.gov (United States)

    Mackey, E A; Becker, P R; Demiralp, R; Greenberg, R R; Koster, B J; Wise, S A

    1996-05-01

    Concentrations for 38 elements are routinely measured in the marine mammal liver tissues archived in the National Biomonitoring Specimen Bank (NBSB). Results show that hepatic concentrations of vanadium, selenium, silver, cadmium, and mercury are positively correlated with age for beluga whales (Delphinapterus leucas) and of vanadium, selenium, cadmium, and mercury with length for ringed seals (Phoca hispada). Many researchers have reported linear correlations of hepatic selenium, cadmium, and mercury with marine mammal age; however, there is only one other report of a linear correlation of hepatic vanadium with marine mammal age. Vanadium levels are at or below detection limits (marine mammals from the NBSB but are present at levels ranging from 0.02 to 1.2 micrograms/g of wet weight in the tissues of Alaskan marine mammals. Although only three bearded seal (Eriganthus barbatus) and three bow-head whale (Balaena mysticetus) liver samples have been analyzed, hepatic vanadium levels also increased with animal size for these species. The presence of relatively high levels of vanadium in the livers of these Alaskan animals may reflect a unique dietary source of vanadium, a unique geochemical source of vanadium, or anthropogenic input to the Alaskan marine environment.

  2. The strong reactions of Lewis-base noble-metals with vanadium and other acidic transition metals

    Energy Technology Data Exchange (ETDEWEB)

    Ebbinghaus, Bartley B. [Univ. of California, Berkeley, CA (United States)

    1991-05-01

    The noble metals often thought of as unreactive solids,react strongly with nearly 40% of the elements in the periodictable: group IIIB-VB transition metals, lanthanides, theactinides, and group IIIA-IVA non-transition metals. These strong reactions arise from increased bonding/electron transfer fromnonbonding electrons d electron pairs on the noble metal tovacant orbitals on V, etc. This effect is a generalized Lewis acid-base interaction. The partial Gibbs energy of V in the noblemetals has been measured as a function of concentration at a temperature near 1000C. Thermodynamics of the intermetallics are determined by ternary oxide equilibria, ternary carbide equilibria, and the high-temperature galvanic cell technique. These experimental methods use equilibrated solid composite mixtures in which grains of V oxides or of V carbides are interspersed with grains of V-NM(noble-metal) alloys. In equilibrium the activity of V in the oxide or the carbide equals the activity in the alloy. Consequently, the thermodynamics available in the literature for the V oxides and V carbides are reviewed. Test runs on the galvanic cell were attempted. The V oxide electrode reacts with CaF2, ThO2, YDT(0.85ThO2-0.15YO1.5), and LDT(0.85ThO2- 0.15LaO1.5) to interfere with the measured data observed toward the beginning of a galvanic cell experiment are the most accurate. The interaction of vanadium at infinite dilution in the noble-metals was determined.

  3. The strong reactions of Lewis-base noble-metals with vanadium and other acidic transition metals

    Energy Technology Data Exchange (ETDEWEB)

    Ebbinghaus, B.B.

    1991-05-01

    The noble metals often thought of as unreactive solids,react strongly with nearly 40% of the elements in the periodictable: group IIIB-VB transition metals, lanthanides, theactinides, and group IIIA-IVA non-transition metals. These strong reactions arise from increased bonding/electron transfer fromnonbonding electrons d electron pairs on the noble metal tovacant orbitals on V, etc. This effect is a generalized Lewis acid-base interaction. The partial Gibbs energy of V in the noblemetals has been measured as a function of concentration at a temperature near 1000C. Thermodynamics of the intermetallics are determined by ternary oxide equilibria, ternary carbide equilibria, and the high-temperature galvanic cell technique. These experimental methods use equilibrated solid composite mixtures in which grains of V oxides or of V carbides are interspersed with grains of V-NM(noble-metal) alloys. In equilibrium the activity of V in the oxide or the carbide equals the activity in the alloy. Consequently, the thermodynamics available in the literature for the V oxides and V carbides are reviewed. Test runs on the galvanic cell were attempted. The V oxide electrode reacts with CaF[sub 2], ThO[sub 2], YDT(0.85ThO[sub 2]-0.15YO[sub 1.5]), and LDT(0.85ThO[sub 2]- 0.15LaO[sub 1.5]) to interfere with the measured data observed toward the beginning of a galvanic cell experiment are the most accurate. The interaction of vanadium at infinite dilution in the noble-metals was determined.

  4. Effect of transition metal impurities on the strength of grain boundaries in vanadium

    Energy Technology Data Exchange (ETDEWEB)

    Wu, Xuebang; Kong, Xiang-Shan; You, Yu-Wei; Liu, Wei; Liu, C. S., E-mail: csliu@issp.ac.cn [Key Laboratory of Materials Physics, Institute of Solid State Physics, Chinese Academy of Sciences, P.O. Box 1129, Hefei 230031 (China); Chen, Jun-Ling; Luo, G.-N. [Institute of Plasma Physics, Chinese Academy of Sciences, Hefei 230031 (China)

    2016-09-07

    Effects of 3d (Ti-Ni), 4d (Zr-Pd), and 5d (Hf-Pt) transition metal impurities on strength of two representative vanadium grain boundaries (GBs), symmetric Σ3(111) and asymmetric Σ5(210), were studied by first-principles calculations within the framework of the Rice-Wang thermodynamic model and within the computational tensile test. The desirable elements to increase the GB cohesion were predicted based on their segregation and strengthening behaviors across the different GB sites. It reveals that the elements Ti, Zr, Hf, Nb, and Ta are good choices for the GB cohesion enhancers. In addition, the GB strengthening by solutes is sensitive to the GB structures. The elements Cr, Mn, Fe, Co, and Ni decrease the GB strength of the Σ3(111) GB but they can increase the cohesion of the Σ5(210) GB. Furthermore, the origin of Ti-induced change of the GB strength was uncovered by analyzing the atomic bonds and electronic structures as well as the tensile strength. This work provides a theoretical guidance to screen promising alloying elements in V-based materials with improved resistance to GB decohesion and also helps us to understand the formation mechanism of Ti-rich precipitates in the V-Cr-Ti alloys under neutron or ion irradiation environments.

  5. Stage-by-stage modeling of the mechanism of semiconductor–metal phase transition in vanadium dioxide

    Directory of Open Access Journals (Sweden)

    Aleksander V. Il'inskiy

    2017-10-01

    Full Text Available The algorithm of stage-by-stage qualitative modeling of the mechanism of a semiconductor–metal phase transition in vanadium dioxide has been proposed. The basis for the model is a statement that the transition is complex in character and consists of the anhysteretic, purely electronic Моtt transition occurring over a wide temperature range, and the temperature-abrupt structural Peierls transition having a thermal hysteresis. The initial stage of the model is based on the solution of a quantum-mechanical problem of an electronic spectrum of a linear vanadium-ion's chain. The model is completed by consideration of correlation effects and a martensitic character of the structural transition through taking consecutively account of results obtained by X-ray, spectroscopic, impedansmetric and magnetic resonance methods.

  6. Brain Metal Distribution and Neuro-Inflammatory Profiles after Chronic Vanadium Administration and Withdrawal in Mice

    OpenAIRE

    Folarin, Oluwabusayo R.; Snyder, Amanda M.; Peters, Douglas G.; Funmilayo Olopade; Connor, James R.; Olopade, James O

    2017-01-01

    Vanadium is a potentially toxic environmental pollutant and induces oxidative damage in biological systems including the central nervous system (CNS). Its deposition in brain tissue may be involved in the pathogenesis of certain neurological disorders which after prolonged exposure can culminate into more severe pathology. Most studies on vanadium neurotoxicity have been done after acute exposure but in reality some populations are exposed for a lifetime. This work was designed to ascertain n...

  7. Removal of toxic metals from vanadium-contaminated soils using a washing method: Reagent selection and parameter optimization.

    Science.gov (United States)

    Jiang, Jianguo; Yang, Meng; Gao, Yuchen; Wang, Jiaming; Li, Dean; Li, Tianran

    2017-08-01

    Vanadium (V) contamination in soils is an increasing worldwide concern facing human health and environmental conservation. The fractionation of a metal influences its mobility and biological toxicity. We analyzed the fractionations of V and several other metals using the BCR three-step sequential extraction procedure. Among methods for removing metal contamination, soil washing is an effective permanent treatment. We conducted experiments to select the proper reagents and to optimize extraction conditions. Citric acid, tartaric acid, oxalic acid, and Na2EDTA all exhibited high removal rates of the extractable state of V. With a liquid-to-solid ratio of 10, washing with 0.4 mol/L citric acid, 0.4 mol/L tartaric acid, 0.4 mol/L oxalic acid, and 0.12 mol/L Na2EDTA led to removal rates of 91%, 88%, 88%, and 61%, respectively. The effect of multiple washing on removal rate was also explored. According to the changes observed in metal fractionations, differences in removal rates among reagents is likely associated with their pKa value, pH in solution, and chemical structure. We concluded that treating with appropriate washing reagents under optimal conditions can greatly enhance the remediation of vanadium-contaminated soils. Copyright © 2017 Elsevier Ltd. All rights reserved.

  8. Vanadium(II)-diamine complexes: synthesis, UV-Visible, infrared, thermogravimetry, magnetochemistry and INDO/S characterisation

    OpenAIRE

    Niedwieski Antonio C.; Hitchcock Peter B.; Motta Neto Joaquim D. da; Wypych Fernando; Leigh G. Jeffery; Nunes Fábio S

    2003-01-01

    The synthesis, spectroscopic characterisation and reactivity of a series of vanadium(II) complexes, [VCl2(diamine)2] (diamine = dmeda: N,N'-dimethylethane-1,2-diamine, deeda: N,N'diethylethane-1,2-diamine, tmeda: N,N,N',N'-tetramethylethane-1,2-diamine, dieda: N,N'diisopropylethane-1,2-diamine, teeda: N,N,N',N'-tetraethylethane-1,2-diamine, dtbeda: N,N'-ditert-butylethane-1,2-diamine and dfeda: N,N'-diphenylethane-1,2-diamine) are reported. Some of these complexes can be converted into the tr...

  9. Effects of metal compounds with distinct physicochemical properties on iron homeostasis and antibacterial activity in the lungs: chromium and vanadium.

    Science.gov (United States)

    Cohen, Mitchell D; Sisco, Maureen; Prophete, Colette; Yoshida, Kotaro; Chen, Lung-chi; Zelikoff, Judith T; Smee, Jason; Holder, Alvin A; Stonehuerner, Jacqueline; Crans, Debbie C; Ghio, Andrew J

    2010-02-01

    In situ reactions of metal ions or their compounds are important mechanisms by which particles alter lung immune responses. The authors hypothesized that major determinants of the immunomodulatory effect of any metal include its redox behavior/properties, oxidation state, and/or solubility, and that the toxicities arising from differences in physicochemical parameters are manifest, in part, via differential shifts in lung iron (Fe) homeostasis. To test the hypotheses, immunomodulatory potentials for both pentavalent vanadium (VV; as soluble metavanadate or insoluble vanadium pentoxide) and hexavalent chromium (CrVI; as soluble sodium chromate or insoluble calcium chromate) were quantified in rats after inhalation (5h/day for 5 days) of each at 100 microg metal/m3. Differences in effects on local bacterial resistance between the two VV, and between each CrVI, agents suggested that solubility might be a determinant of in situ immunotoxicity. For the soluble forms, VV had a greater impact on resistance than CrVI, indicating that redox behavior/properties was likely also a determinant. The soluble VV agent was the strongest immunomodulant. Regarding Fe homeostasis, both VV agents had dramatic effects on airway Fe levels. Both also impacted local immune/airway epithelial cell Fe levels in that there were significant increases in production of select cytokines/chemokines whose genes are subject to regulation by HIF-1 (whose intracellular longevity is related to cell Fe status). Our findings contribute to a better understanding of the role that metal compound properties play in respiratory disease pathogenesis and provide a rationale for differing pulmonary immunotoxicities of commonly encountered ambient metal pollutants.

  10. Analyzing optical properties of thin vanadium oxide films through semiconductor-to-metal phase transition using spectroscopic ellipsometry

    Science.gov (United States)

    Sun, Jianing; Pribil, Greg K.

    2017-11-01

    We investigated the optical behaviors of vanadium dioxide (VO2) films through the semiconductor-to-metal (STM) phase transition using spectroscopic ellipsometry. Correlations between film thickness and refractive index were observed resulting from the absorbing nature of these films. Simultaneously analyzing data at multiple temperatures using Kramers-Kronig consistent oscillator models help identify film thickness. Nontrivial variations in resulting optical constants were observed through STM transition. As temperature increases, a clear increase is observed in near infrared absorption due to Drude losses that accompany the transition from semiconducting to metallic phases. Thin films grown on silicon and sapphire substrate present different optical properties and thermal hysteresis due to lattice stress and compositional differences.

  11. Vanadium oxide based cpd. useful as a cathode active material - is used in lithium or alkali metal batteries to prolong life cycles

    DEFF Research Database (Denmark)

    1997-01-01

    A mixt. of metallic iron particles and vanadium pentoxide contg. V in its pentavalent state in a liq. is reacted to convert at least some of the pentavalent V to its tetravalent state and form a gel. The liq. phase is then sepd. from the oxide based gel to obtain a solid material(I) comprising Fe...

  12. Long-term risks of metal contaminants in drinking water: a critical appraisal of guideline values for arsenic and vanadium

    Directory of Open Access Journals (Sweden)

    Riccardo Crebelli

    Full Text Available Metal contaminants in drinking water represent a relevant health issue in several areas of the world. In Italy, because of the geological features of the territory, high arsenic and vanadium are frequently reported in ground waters in concentrations above current guideline values. The implications for public health of the presence of contaminants above their legal limit are directly related to the biological basis of the guideline value. In the case of arsenic there are still major uncertainties in the mechanism of carcinogenesis which prevent a precise evaluation of long-term risks. Thus, the guideline value endorsed in the European Community (10 µg/L has to be considered as a pragmatic tool rather than a quality objective, bearing in mind that "every effort should be made to keep concentrations as low as reasonably possible" (WHO, 2011. A reverse situation holds for vanadium, for which a strict national limit (50 µg/L was previously proposed in consideration of data gaps, and for which new evidence indicated a less stringent health-based limit.

  13. Measurement of Pollution Levels Caused by Heavy Metals of Vanadium, Nickel, Lead and Copper Using Bivalve Shells of Timoclea imbricata Species On Bahrakan Coast in Spring 2013

    Directory of Open Access Journals (Sweden)

    Moosavian

    2014-10-01

    Full Text Available Background Bivalves have been used to study pollution level caused by heavy metals due to their biological characteristics. Bahrakan region includes Bahrakansar, Hendijan, Norouz and Soroush oil fields, and current information regarding sea management, especially from the protective aspect is very little. Objectives This study aimed to assess region pollution with heavy metals. For this purpose, pollution caused by heavy metals in bivalves was assessed and compared with the standard values. Materials and Methods Bivalve sampling was performed using Grab to determine the pollution content with heavy metals of vanadium, nickel, lead and copper in five different stations on 15 samples (3 samples for each station in spring 2013. The digestion process was completed using the Yap method, then the concentrations of mentioned metals were measured using the ICP device in each of digested samples. Results Nickel (13.12 ± 6.07 mg/kg had the highest total average concentration and the lowest for lead (1.15 ± 0.28 mg/kg. Concentrations of nickel, vanadium and lead were higher than the WHO international standards, but much lower for copper regarding the same standards. Concentrations of nickel and vanadium were higher than copper compared to FAO, but lower than lead regarding the presented allowable limit. Conclusions Nickel and vanadium had the highest concentration among other metals. Since these two metals are used as oil pollution parameters and the region is rich in oil, it can be concluded that oil pollution is present in the region. The existing oil pollution threatens all the living organisms in the area. Therefore, it would be of great importance to examine pollution sources of this region. The results can be used to constantly monitor the amount of heavy metals in bivalves of Timoclea imbricate species in this region.

  14. Lead (II) and nickel (II) adsorption kinetics from aqueous metal ...

    African Journals Online (AJOL)

    This paper discusses the kinetics of lead (II) and Nickel (II) ions adsorption from aqueous solutions using chemically modified and unmodified agricultural adsorbents at 28°C, pH 6.2 and 0.01M NaCl ionic strength. The removal of the two metals were found to increase with increase in chemical modification, the sequence ...

  15. Synthesis, structural characterization and antioxidant activity of some vanadium(IV), Mo(VI)/(IV) and Ru(II) complexes of pyridoxal Schiff base derivatives

    Science.gov (United States)

    Elsayed, Shadia A.; Noufal, Aya M.; El-Hendawy, Ahmed M.

    2017-09-01

    New complexes containing vanadium(IV), Mo(VI)/(IV) and Ru(II) derived from Schiff base of pyridoxal and S-benzyldithiocarbazate (H2pysb) or p-toluidine (Hpytol) have been prepared. The structures of the described compounds were elucidated by elemental analyses, spectroscopic techniques (IR, 1H NMR, UV-Vis and EPR) magnetism, molar conductivity and thermal analysis measurements. Their redox behaviors were also studied by cyclic voltammetry. The ligand H2pysb showed coordination to the metal ions in a dibasic tridenate manner through deprotonated phenolate oxygen, azomethine nitrogen and thiolate sulfur, while Hpytol behaved as monobasic bidentate through phenolate oxygen and azomethine nitrogen. The complexes were tested for their antioxidant activity by 2,2-diphenyl-1-picrylhydrazyl radical (DPPH) and the data obtained revealed that the scavenging activity of the complexes towards DPPH is high for the oxovanadium(IV) complexes with lower IC50 values which are comparable to ascorbic acid as a standard antioxidant. The EC50 concentration ratio together with other antioxidant parameters are also reported.

  16. metal complexes of copper(ii)

    African Journals Online (AJOL)

    Zinc(II) complex is diamagnetic. The cobalt(II) complex was found with paramagnetic character (4.11 B.M.). Also, in the FT-IR spectra of oligomer-metal complexes, there was no evidence associated with coordinated water molecules. Because this band generally was observed at 3700-3500 cm-1 region as a broad band.

  17. Biogeochemical controls on the speciation and aquatic toxicity of vanadium and other metals in sediments from a river reservoir

    Energy Technology Data Exchange (ETDEWEB)

    Nedrich, Sara M.; Chappaz, Anthony; Hudson, Michelle L.; Brown, Steven S.; Burton, G. Allen

    2018-01-01

    Effects of hydrologic variability on reservoir biogeochemistry are relatively unknown, particularly for less studied metals like vanadium (V). Further, few studies have investigated the fate and effects of sediment-associated V to aquatic organisms in hydrologically variable systems. Our primary objective was to assess effects of hydrologic manipulation on speciation and toxicity of V (range: 635 to 1620 mg kg- 1) and other metals to Hyalella azteca and Daphnia magna. Sediments were collected from a reservoir located in a former mining area and microcosm experiments were conducted to emulate 7-day drying and inundation periods. Despite high sediment concentrations, V bioavailability remained low with no significant effects to organism survival, growth, or reproduction. The lack of V toxicity was attributed to reduced speciation (III, IV), non-labile complexation, and sorption to Al/Fe/Mn-oxyhydroxides. Zinc (Zn) increased in surface and porewater with inundation, for some sediments exceeding the U.S. EPA threshold for chronic toxicity. While no effects of Zn to organism survival or growth were observed, Zn body concentrations were negatively correlated with H. azteca growth. Results from this study indicate that V bioavailability and environmental risk is dependent on V-speciation, and V is less influenced by hydrologic variability than more labile metals such as Zn.

  18. Metal-insulator transition properties of sputtered silicon-doped and un-doped vanadium dioxide films at terahertz range

    Science.gov (United States)

    Zhang, Huafu; Wu, Zhiming; Niu, Ruihua; Wu, Xuefei; he, Qiong; Jiang, Yadong

    2015-03-01

    Silicon-doped and un-doped vanadium dioxide (VO2) films were synthesized on high-purity single-crystal silicon substrates by means of reactive direct current magnetron sputtering followed by thermal annealing. The structure, morphology and metal-insulator transition properties of silicon-doped VO2 films at terahertz range were measured and compared to those of un-doped VO2 films. X-ray diffraction and scanning electron microscopy indicated that doping the films with silicon significantly affects the preferred crystallographic orientation and surface morphologies (grain size, pores and characteristics of grain boundaries). The temperature dependence of terahertz transmission shows that the transition temperature, hysteresis width and transition sharpness greatly depend on the silicon contents while the transition amplitude was relatively insensitive to the silicon contents. Interestingly, the VO2 film doped with a silicon content of 4.6 at.% shows excellent terahertz switching characteristics, namely a small hysteresis width of 4.5 °C, a giant transmission modulation ratio of about 82% and a relatively low transition temperature of 56.1 °C upon heating. This work experimentally indicates that silicon doping can effectively control not only the surface morphology but also the metal-insulator transition characteristics of VO2 films at terahertz range.

  19. Vanadium(II-diamine complexes: synthesis, UV-Visible, infrared, thermogravimetry, magnetochemistry and INDO/S characterisation

    Directory of Open Access Journals (Sweden)

    Niedwieski Antonio C.

    2003-01-01

    Full Text Available The synthesis, spectroscopic characterisation and reactivity of a series of vanadium(II complexes, [VCl2(diamine2] (diamine = dmeda: N,N'-dimethylethane-1,2-diamine, deeda: N,N'diethylethane-1,2-diamine, tmeda: N,N,N',N'-tetramethylethane-1,2-diamine, dieda: N,N'diisopropylethane-1,2-diamine, teeda: N,N,N',N'-tetraethylethane-1,2-diamine, dtbeda: N,N'-ditert-butylethane-1,2-diamine and dfeda: N,N'-diphenylethane-1,2-diamine are reported. Some of these complexes can be converted into the trinuclear cation [V3(µCl3(µ3Cl2(diamine 3]+ through the reaction with [V2(µ-Cl3(thf3]+ under mild conditions. The compounds were characterised by microanalysis, positive ion FAB mass spectrometry, UVvisible and infrared spectroscopies, thermogravimetric analysis and magnetic moment measurements in the solid state. We characterised fully by single-crystal X-ray diffraction analysis the complex [VCl2(deeda2]. The stability of [VCl2(diamine2] as they vary with the different diamines is correlated with crystal field and infrared parameters along with decomposition temperatures and the calculated molecular orbital energies. We also presented a new synthetic route to prepare [V3(µ-Cl3(µ3-Cl2(diamine 3]+ which allows a better control of the reaction pathway, avoiding the formation of undesired redox reaction products.

  20. Influence of oxygen flow rate on metal-insulator transition of vanadium oxide thin films grown by RF magnetron sputtering

    Energy Technology Data Exchange (ETDEWEB)

    Ma, Xu; Liu, Xinkun; Li, Haizhu; Huang, Mingju [Henan University, Key Lab of Informational Opto-Electronical Materials and Apparatus, School of Physics and Electronics, Kaifeng (China); Zhang, Angran [South China Normal University, Institute of Electronic Paper Displays, South China Academy of Advanced Optoelectronics, Guangzhou (China)

    2017-03-15

    High-quality vanadium oxide (VO{sub 2}) films have been fabricated on Si (111) substrates by radio frequency (RF) magnetron sputtering deposition method. The sheet resistance of VO{sub 2} has a significant change (close to 5 orders of magnitude) in the process of the metal-insulator phase transition (MIT). The field emission-scanning electron microscope (FE-SEM) results show the grain size of VO{sub 2} thin films is larger with the increase of oxygen flow. The X-ray diffraction (XRD) results indicate the thin films fabricated at different oxygen flow rates grow along the (011) crystalline orientation. As the oxygen flow rate increases from 3 sccm to 6 sccm, the phase transition temperature of the films reduces from 341 to 320 K, the width of the thermal hysteresis loop decreases from 32 to 9 K. The thin films fabricated in the condition of 5 sccm have a high temperature coefficient of resistance (TCR) -3.455%/K with a small resistivity of 2.795 ρ/Ω cm. (orig.)

  1. Interplay of electron-electron and electron-phonon interaction in the metal to insulator transition in vanadium oxides.

    Energy Technology Data Exchange (ETDEWEB)

    Baldassarre, Leonetta [CNR-INFM COHERENTIA, Roma (Italy); Experimentalphysik II, Universitaet Augsburg (Germany); Department of Physics, University of Rome ' La Sapienza' (Italy); Arcangeletti, Emanuele; Perucchi, Andrea; Nicoletti, Daniele; Di Castro, Daniele; Marini, Carlo; Postorino, Paolo; Lupi, Stefano [CNR-INFM COHERENTIA, Roma (Italy); Department of Physics, University of Rome ' La Sapienza' (Italy)

    2008-07-01

    Several families of vanadium oxides display metal to insulator transitions (MIT) often driven by both temperature (T) and pressure (P) with jumps of conductivity up to 7 orders of magnitude. While the transition in V{sub 2}O{sub 3} is considered as induced mainly by electronic correlation (Mott-Hubbard transition), the MIT mechanism that drives the electronic transition in VO{sub 2} is still unclear, probably determined by an interplay between electronic and lattice degrees of freedom. Here we present a complete investigation of MIT as a function of T and P of V{sub 2}O{sub 3} and VO{sub 2}. Infrared measurements have been performed in a wide range of T (10-600 K) and P (0-15 GPa) in order to cover the rich phase diagrams of those materials. P-dependent Raman measurements have also been performed on VO{sub 2} so to follow also the lattice dynamics. Moreover, the high temperature incoherent phase is discussed in V{sub 2}O{sub 3}, the ideal playground to study the correlation effects on the low-energy electrodynamics.

  2. VANADIUM ALLOYS

    Science.gov (United States)

    Smith, K.F.; Van Thyne, R.J.

    1959-05-12

    This patent deals with vanadium based ternary alloys useful as fuel element jackets. According to the invention the ternary vanadium alloys, prepared in an arc furnace, contain from 2.5 to 15% by weight titanium and from 0.5 to 10% by weight niobium. Characteristics of these alloys are good thermal conductivity, low neutron capture cross section, good corrosion resistance, good welding and fabricating properties, low expansion coefficient, and high strength.

  3. Mesoscopic quantum effects in a bad metal, hydrogen-doped vanadium dioxide

    Science.gov (United States)

    Hardy, Will J.; Ji, Heng; Paik, Hanjong; Schlom, Darrell G.; Natelson, Douglas

    2017-05-01

    The standard treatment of quantum corrections to semiclassical electronic conduction assumes that charge carriers propagate many wavelengths between scattering events, and succeeds in explaining multiple phenomena (weak localization magnetoresistance (WLMR), universal conductance fluctuations, Aharonov-Bohm oscillations) observed in polycrystalline metals and doped semiconductors in various dimensionalities. We report apparent WLMR and conductance fluctuations in H x VO2, a poor metal (in violation of the Mott-Ioffe-Regel limit) stabilized by the suppression of the VO2 metal-insulator transition through atomic hydrogen doping. Epitaxial thin films, single-crystal nanobeams, and nanosheets show similar phenomenology, though the details of the apparent WLMR seem to depend on the combined effects of the strain environment and presumed doping level. Self-consistent quantitative analysis of the WLMR is challenging given this and the high resistivity of the material, since the quantitative expressions for WLMR are derived assuming good metallicity. These observations raise the issue of how to assess and analyze mesoscopic quantum effects in poor metals.

  4. Vanadium(II)-diamine complexes: synthesis, UV-Visible, infrared, thermogravimetry, magnetochemistry and INDO/S characterisation

    Energy Technology Data Exchange (ETDEWEB)

    Niedwieski, Antonio C.; Motta Neto, Joaquim D. da; Wypych, Fernando; Nunes, Fabio S. [Parana Univ., Curitiba, PR (Brazil). Dept. de Quimica]. E-mail: fsnunes@quimica.ufpr.br; Hitchcock, Peter B.; Leigh, G. Jeffery [University of Sussex, Brighton (United Kingdom). School of Chemistry, Physics and Environmental Science

    2003-10-01

    The synthesis, spectroscopic characterisation and reactivity of a series of vanadium(II) complexes, [VCl{sub 2}(diamine){sub 2}] (diamine = dmeda: N,N'-dimethylethane-1,2-diamine, deeda: N,N'-diethylethane-1,2-diamine, tmeda: N,N,N',N-tetramethylmethane-1,2-diamine, dieda: N,N'-diisopropylethane-1,2- diamine, teeda: N,N,N',N'-tetraethylethane-1,2-diamine, dtbeda: N,N'-ditert-butylethane-1,2-diamine and dfeda: N,N'-diphenylethane-1,2-diamine) are reported. Some of these complexes can be converted into the trinuclear cation [V{sub 3}({mu}-Cl){sub 3}({mu}{sub 3}-Cl){sub 2}(diamine){sub 3}]{sup +} through the reaction with [V{sub 2}({mu}-Cl){sub 3}(thf){sub 3}]{sup +}under mild conditions. The compounds were characterised by microanalysis, positive ion FAB mass spectrometry, UV-visible and infrared spectroscopies, thermogravimetric analysis and magnetic moment measurements in the solid state. We characterised fully by single-crystal X-ray diffraction analysis the complex [VCl{sub 2}(deeda){sub 2}]. The stability of [VCl{sub 2}(diamine){sub 2}] as they vary with the different diamines is correlated with crystal field and infrared parameters along with decomposition temperatures and the calculated molecular orbital energies. We also presented a new synthetic route to prepare [V{sub 3}({mu}-Cl){sub 3}({mu}{sub 3}-Cl){sub 2}(diamine){sub 3}]{sup +} which allows a better control of the reaction pathway, avoiding the formation of undesired redox reaction products. (author)

  5. First-Principle Predictions of Electronic Properties and Half-Metallic Ferromagnetism in Vanadium-Doped Rock-Salt SrO

    Science.gov (United States)

    Berber, Mohamed; Doumi, Bendouma; Mokaddem, Allel; Mogulkoc, Yesim; Sayede, Adlane; Tadjer, Abdelkader

    2018-01-01

    We have used first-principle methods of density functional theory within the full potential linearized augmented plane wave scheme to investigate the electronic and magnetic properties of cubic rock-salt, SrO, doped with vanadium (V) impurity as Sr1- x V x O at various concentrations, x = 0.25, 0.5, and 0.75. We have found that the ferromagnetic state arrangement of Sr1- x V x O is more stable compared to the anti-ferromagnetic state configuration. The electronic structures have a half-metallic (HM) ferromagnetic (F) behavior for Sr0.75V0.25O and Sr0.5V0.5O. This feature results from the metallic and semiconducting natures of majority-spin and minority-spin bands, respectively. The HMF gap decreases with the increasing concentration of vanadium atoms due to the broadening of 3 d (V) levels in the gap, and hence the Sr0.25V0.75O becomes metallic ferromagnetic. The Sr0.75V0.25O revealed a large HM gap with spin polarization of 100%. The Sr1- x V x O compound at low concentrations seems a better candidate to explore the half-metallicity for practical spintronics applications.

  6. First-Principle Predictions of Electronic Properties and Half-Metallic Ferromagnetism in Vanadium-Doped Rock-Salt SrO

    Science.gov (United States)

    Berber, Mohamed; Doumi, Bendouma; Mokaddem, Allel; Mogulkoc, Yesim; Sayede, Adlane; Tadjer, Abdelkader

    2017-09-01

    We have used first-principle methods of density functional theory within the full potential linearized augmented plane wave scheme to investigate the electronic and magnetic properties of cubic rock-salt, SrO, doped with vanadium (V) impurity as Sr1-x V x O at various concentrations, x = 0.25, 0.5, and 0.75. We have found that the ferromagnetic state arrangement of Sr1-x V x O is more stable compared to the anti-ferromagnetic state configuration. The electronic structures have a half-metallic (HM) ferromagnetic (F) behavior for Sr0.75V0.25O and Sr0.5V0.5O. This feature results from the metallic and semiconducting natures of majority-spin and minority-spin bands, respectively. The HMF gap decreases with the increasing concentration of vanadium atoms due to the broadening of 3d (V) levels in the gap, and hence the Sr0.25V0.75O becomes metallic ferromagnetic. The Sr0.75V0.25O revealed a large HM gap with spin polarization of 100%. The Sr1-x V x O compound at low concentrations seems a better candidate to explore the half-metallicity for practical spintronics applications.

  7. Factors controlling enrichment of vanadium and nickel in the bitumen of organic sedimentary rocks

    Energy Technology Data Exchange (ETDEWEB)

    Lewan, M.D. (Amoco Production Co., Tulsa, OK); Maynard, J.B.

    1982-12-01

    Enriched concentrations of vanadium and nickel have been noted in a variety of naturally occurring organic substances including crude oils, asphalts, and organic matter in some sedimentary rocks. Vanadium and nickel concentrations in bitumens extracted from a variety of organic sedimentary rock types of different geological ages and geographical areas range from less than 0.2 to 4760 ppm and less than 7 to 1240 ppm, respectively. Vanadium concentrations showed a polymodal frequency distribution. The concentrations of these two metals showed no significant correlations with bitumen content, organic carbon content, or proportionality between bitumen and organic carbon contents. Enriched vanadium and nickel concentrations greater than 100 ppm are only observed in bitumens that are associated with Type II and Type I kerogens. Conversely, bitumens associated with Type III kerogens contained vanadium and nickel concentrations less than 100 ppm. The high stability of vanadium and nickel in crude oils, asphalts, and bitumens suggest that they occur in tetrapyrrole complexes. The complexes may occur as free molecules or assimulated subunits in macromolecules within the bitumen. Vanadium and nickel are preferentially concentrated in tetrapyrrole complexes because of their availability in anaerobic systems, small atomic radii, and favorable electron configurations. The potential for an organic sediment to be enriched in these two metals depends upon the amount of tetrapyrroles preserved in its organic matter. Tetrapyrrole preservation preferentially decreases in organic matter as exposure time to aerobic conditions increases. The potential for vanadium and nickel enrichment is therefore the highest in organic matter derived from algae that encountered anaerobic conditions early in their depositional history.

  8. Study of thermal degradation of vanadium and titanium acetylacetonate derivatives

    Energy Technology Data Exchange (ETDEWEB)

    Dyagileva, L.M.; Tsyganova, E.I.; Mar' in, V.P.; Aleksandrov, Yu.A. (Gor' kovskij Gosudarstvennyj Univ. (USSR). Nauchno-Issledovatel' skij Inst. Khimii)

    1982-09-01

    Kinetics and products of vanadium (+3), vanadyl (+3) and titanium (+3) acetylacetonates thermal degradation have been studied in vapor phase in the closed system at 300-470 deg C. Gaseous composition of pyrolysis has been determined at different levels of decomposition. It is supposed that vanadium and metal vanadium mixed oxides become vanadium (+3) pyrolysis products. It is shown that metal oxidation level does not affect the thermal degradation rate. Central atom substitution leads to the change in thermal stability. Titanium (+3) acetylacetate derivatives are less stable than vanadium (+3) ones.

  9. Annealing effects on the structural and optical properties of vanadium oxide film obtained by the hot-filament metal oxide deposition technique (HFMOD)

    Energy Technology Data Exchange (ETDEWEB)

    Scarminio, Jair; Silva, Paulo Rogerio Catarini da, E-mail: scarmini@uel.br, E-mail: prcsilva@uel.br [Universidade Estadual de Londrina (UEL), PR (Brazil). Departamento de Fisica; Gelamo, Rogerio Valentim, E-mail: rogelamo@gmail.com [Universidade Federal do Triangulo Mineiro (UFTM), Uberaba, MG (Brazil); Moraes, Mario Antonio Bica de, E-mail: bmoraes@mailhost.ifi.unicamp.br [Universidade Estadual de Campinas (UNICAMP), SP (Brazil)

    2017-01-15

    Vanadium oxide films amorphous, nonstoichiometric and highly absorbing in the optical region were deposited on ITO-coated glass and on silicon substrates, by the hot-filament metal oxide deposition technique (HFMOD) and oxidized by ex-situ annealing in a furnace at 200, 300, 400 and 500 deg C, under an atmosphere of argon and rarefied oxygen. X-ray diffraction, Raman and Rutherford backscattering spectroscopy as well as optical transmission were employed to characterize the amorphous and annealed films. When annealed at 200 and 300 deg C the as-deposited opaque films become transparent but still amorphous. Under treatments at 400 and 500 deg C a crystalline nonstoichiometric V{sub 2}O{sub 5} structure is formed. All the annealed films became semiconducting, with their optical absorption coefficients changing with the annealing temperature. An optical gap of 2.25 eV was measured for the films annealed at 400 and 500 deg C. The annealing in rarefied oxygen atmosphere proved to be a useful and simple ex-situ method to modulate the structural and optical properties of vanadium oxide films deposited by HFMOD technique. This technique could be applied to other amorphous and non-absorbing oxide films, replacing the conventional and sometimes expensive method of modulate desirable film properties by controlling the film deposition parameters. Even more, the HFMOD technique can be an inexpensive alternative to deposit metal oxide films. (author)

  10. Highly active, bi-functional and metal-free B4C-nanoparticle-modified graphite felt electrodes for vanadium redox flow batteries

    Science.gov (United States)

    Jiang, H. R.; Shyy, W.; Wu, M. C.; Wei, L.; Zhao, T. S.

    2017-10-01

    The potential of B4C as a metal-free catalyst for vanadium redox reactions is investigated by first-principles calculations. Results show that the central carbon atom of B4C can act as a highly active reaction site for redox reactions, due primarily to the abundant unpaired electrons around it. The catalytic effect is then verified experimentally by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) tests, both of which demonstrate that B4C nanoparticles can enhance the kinetics for both V2+/V3+ and VO2+/VO2+ redox reactions, indicating a bi-functional effect. The B4C-nanoparticle-modified graphite felt electrodes are finally prepared and tested in vanadium redox flow batteries (VRFBs). It is shown that the batteries with the prepared electrodes exhibit energy efficiencies of 88.9% and 80.0% at the current densities of 80 and 160 mA cm-2, which are 16.6% and 18.8% higher than those with the original graphite felt electrodes. With a further increase in current densities to 240 and 320 mA cm-2, the batteries can still maintain energy efficiencies of 72.0% and 63.8%, respectively. All these results show that the B4C-nanoparticle-modified graphite felt electrode outperforms existing metal-free catalyst modified electrodes, and thus can be promising electrodes for VRFBs.

  11. Kinetics of oxidation of D-arabinose and D-xylose by vanadium (V in the presence of manganese II as homogeneous catalyst

    Directory of Open Access Journals (Sweden)

    Ezekiel O. Odebunmi

    2010-12-01

    Full Text Available Kinetics of oxidation of D-arabinose and D-xylose by acidic solution of vanadium (V ions in the presence of manganese (II has been reported. First-order dependence of the reaction rate was observed on [sugars] and [H+] at low concentrations throughout the oxidation reaction and a zero-order dependence on [sugar] and [H+] was observed at high concentrations. First-order kinetics with respect to [Mn (II] was also observed throughout the oxidation for both sugars. The results indicate the effect of Cl- concentration is negligible. The reaction rates increase with the ionic strength of the medium. Various activation parameters were evaluated and provide further support to the proposed mechanism. Formic acid was reported as one of the oxidation products of these sugars.

  12. Biomonitoring of humans exposed to arsenic, chromium, nickel, vanadium, and complex mixtures of metals by using the micronucleus test in lymphocytes.

    Science.gov (United States)

    Annangi, Balasubramanyam; Bonassi, Stefano; Marcos, Ricard; Hernández, Alba

    Various metals have demonstrated genotoxic and carcinogenic potential via different mechanisms. Until now, biomonitoring and epidemiological studies have been carried out to assess the genotoxic risk to exposed human populations. In this sense, the use of the micronucleus assay in peripheral blood lymphocytes has proven to be a useful tool to determine increased levels of DNA damage, as a surrogate biomarker of cancer risk. Here we review those biomonitoring studies focused on people exposed to arsenic, chromium, nickel, vanadium and complex mixtures of metals. Only those studies that used the frequency of micronuclei in binucleated (BNMN) cells have been taken into consideration, although the inclusion of other biomarkers of exposure and genotoxicity are also reflected and discussed. Regarding arsenic, most of the occupational and environmental biomonitoring studies find an increase in BNMN among the exposed individuals. Thus, it seems conclusive that arsenic exposure increases the risk of exposed human populations. However, a lack of correlation between the level of exposure and the increase in BNMN is also common, and a limited number of studies evaluated the genotype as a risk modulator. As for chromium, a BNMN increase in occupationally exposed subjects and a correlation between level of exposure and effect is found consistently in the available literature. However, the quality score of the studies is only medium-low. On the other hand, the studies evaluating nickel and vanadium are scarce and lacks a correct characterization of the individual exposure, which difficult the building of clear conclusions. Finally, several studies with medium-high quality scores evaluated a more realistic scenario of exposure which takes into account a mixture of metals. Among them, those which correctly characterized and measured the exposure were able to find association with the level of BNMN. Also, several genes associated with DNA damage repair such as OGG1 and XRCC1 were

  13. Memory Deficit Recovery after Chronic Vanadium Exposure in Mice

    Directory of Open Access Journals (Sweden)

    Oluwabusayo Folarin

    2016-01-01

    Full Text Available Vanadium is a transitional metal with an ability to generate reactive oxygen species in the biological system. This work was designed to assess memory deficits in mice chronically exposed to vanadium. A total of 132 male BALB/c mice (4 weeks old were used for the experiment and were divided into three major groups of vanadium treated, matched controls, and animals exposed to vanadium for three months and thereafter vanadium was withdrawn. Animals were tested using Morris water maze and forelimb grip test at 3, 6, 9, and 12 months of age. The results showed that animals across the groups showed no difference in learning but had significant loss in memory abilities after 3 months of vanadium exposure and this trend continued in all vanadium-exposed groups relative to the controls. Animals exposed to vanadium for three months recovered significantly only 9 months after vanadium withdrawal. There was no significant difference in latency to fall in the forelimb grip test between vanadium-exposed groups and the controls in all age groups. In conclusion, we have shown that chronic administration of vanadium in mice leads to memory deficit which is reversible but only after a long period of vanadium withdrawal.

  14. Memory Deficit Recovery after Chronic Vanadium Exposure in Mice.

    Science.gov (United States)

    Folarin, Oluwabusayo; Olopade, Funmilayo; Onwuka, Silas; Olopade, James

    2016-01-01

    Vanadium is a transitional metal with an ability to generate reactive oxygen species in the biological system. This work was designed to assess memory deficits in mice chronically exposed to vanadium. A total of 132 male BALB/c mice (4 weeks old) were used for the experiment and were divided into three major groups of vanadium treated, matched controls, and animals exposed to vanadium for three months and thereafter vanadium was withdrawn. Animals were tested using Morris water maze and forelimb grip test at 3, 6, 9, and 12 months of age. The results showed that animals across the groups showed no difference in learning but had significant loss in memory abilities after 3 months of vanadium exposure and this trend continued in all vanadium-exposed groups relative to the controls. Animals exposed to vanadium for three months recovered significantly only 9 months after vanadium withdrawal. There was no significant difference in latency to fall in the forelimb grip test between vanadium-exposed groups and the controls in all age groups. In conclusion, we have shown that chronic administration of vanadium in mice leads to memory deficit which is reversible but only after a long period of vanadium withdrawal.

  15. Bioaccumulation of Vanadium by Vanadium-Resistant Bacteria Isolated from the Intestine of Ascidia sydneiensis samea.

    Science.gov (United States)

    Romaidi; Ueki, Tatsuya

    2016-06-01

    Isolation of naturally occurring bacterial strains from metal-rich environments has gained popularity due to the growing need for bioremediation technologies. In this study, we found that the vanadium concentration in the intestine of the vanadium-rich ascidian Ascidia sydneiensis samea could reach 0.67 mM, and thus, we isolated vanadium-resistant bacteria from the intestinal contents and determined the ability of each bacterial strain to accumulate vanadium and other heavy metals. Nine strains of vanadium-resistant bacteria were successfully isolated, of which two strains, V-RA-4 and S-RA-6, accumulated vanadium at a higher rate than did the other strains. The maximum vanadium absorption by these bacteria was achieved at pH 3, and intracellular accumulation was the predominant mechanism. Each strain strongly accumulated copper and cobalt ions, but accumulation of nickel and molybdate ions was relatively low. These bacterial strains can be applied to protocols for bioremediation of vanadium and heavy metal toxicity.

  16. studies on transition metal complexes of herbicidal compounds. ii

    African Journals Online (AJOL)

    a

    Cobalt(II) complex exhibits thermochromism. Antimicrobial studies on E. coli and S. aureus show the absence of growth inhibitory activities for HEATZ and its metal complexes which is attributed to the combined effect of derivatization of ATZ and metal complexation. KEY WORDS: Metal complexes, Atrazine derivatives, ...

  17. The near-infrared Ca II triplet as a metallicity indicator - II. Extension to extremely metal-poor metallicity regimes

    Science.gov (United States)

    Carrera, R.; Pancino, E.; Gallart, C.; del Pino, A.

    2013-09-01

    We extend our previous calibration of the infrared Ca II triplet (CaT) as a metallicity indicator to the metal-poor regime by including observations of 55 field stars with [Fe/H] down to -4.0 dex. While we previously solved the saturation at high metallicity using a combination of a Lorentzian and a Gaussian to reproduce the line profiles, in this paper we address the non-linearity at low metallicity following the suggestion of Starkenburg et al. of adding two non-linear terms to the relation among the [Fe/H], luminosity and strength of the calcium triplet lines. Our calibration thus extends from -4.0 to +0.5 in metallicity and is presented using four different luminosity indicators: V - VHB, MV, MI and MK. The calibration obtained in this paper results in a tight correlation between [Fe/H] abundances measured from high-resolution spectra and [Fe/H] values derived from the CaT, over the whole metallicity range covered.

  18. Vanadium recycling in the United States in 2004

    Science.gov (United States)

    Goonan, Thomas G.

    2011-01-01

    As one of a series of reports that describe the recycling of metal commodities in the United States, this report discusses the flow of vanadium in the U.S. economy in 2004. This report includes a description of vanadium supply and demand in the United States and illustrates the extent of vanadium recycling and recycling trends. In 2004, apparent vanadium consumption, by end use, in the United States was 3,820 metric tons (t) in steelmaking and 232 t in manufacturing, of which 17 t was for the production of superalloys and 215 t was for the production of other alloys, cast iron, catalysts, and chemicals. Vanadium use in steel is almost entirely dissipative because recovery of vanadium from steel scrap is chemically impeded under the oxidizing conditions in steelmaking furnaces. The greatest amount of vanadium recycling is in the superalloy, other-alloy, and catalyst sectors of the vanadium market. Vanadium-bearing catalysts are associated with hydrocarbon recovery and refining in the oil industry. In 2004, 2,850 t of vanadium contained in alloy scrap and spent catalysts was recycled, which amounted to about 44 percent of U.S. domestic production. About 94 percent of vanadium use in the United States was dissipative (3,820 t in steel/4,050 t in steel+fabricated products).

  19. Adsorption of strontium (II) metal ions using phosphonate ...

    Indian Academy of Sciences (India)

    tium (II) metal ion recovery using diethylallylphosphonate as staring material. .... gold nanoparticles, used as an active catalyst for breaking the double bond of alkene ..... Table 2. Repetition experiments on effect of pH on strontium adsorption. Polymer. Metal. Sr recovery. Sr recovery. Sr recovery concentration concentration.

  20. Vanadium Oxidation State Determination by X-Ray Absorption Spectroscopy

    Science.gov (United States)

    Duchesne, Marc A.; Nakano, Jinichiro; Hu, Yongfeng; MacLennan, Aimee; Hughes, Robin W.; Bennett, James; Nakano, Anna

    Vanadium is found in slags produced during metal refinement and fossil fuel combustion/gasification. The oxidation state of vanadium in slag has technological and environmental implications. For example, it may affect slag flow and refractory wear inside reactors, as well as leachability and toxicity of industrial by-products. Determination of vanadium's oxidation state in crystalline phases can be achieved via the widely adopted X-ray diffraction (XRD) technique. However, this technique does not provide information on vanadium in amorphous phases. The objective of this research is to determine the oxidation state of vanadium in petroleum coke gasification samples and laboratory samples using X-ray absorption spectroscopy (XAS) with Canadian Light Source's soft X-ray micro-characterization beamline (SXRMB). Linear combination fitting of XAS spectra with reference samples allowed quantitative determination of vanadium speciation.

  1. Vanadium pentoxide nanoparticles mimic vanadium haloperoxidases and thwart biofilm formation

    Science.gov (United States)

    Natalio, Filipe; André, Rute; Hartog, Aloysius F.; Stoll, Brigitte; Jochum, Klaus Peter; Wever, Ron; Tremel, Wolfgang

    2012-08-01

    Marine biofouling--the colonization of small marine microorganisms on surfaces that are directly exposed to seawater, such as ships' hulls--is an expensive problem that is currently without an environmentally compatible solution. Biofouling leads to increased hydrodynamic drag, which, in turn, causes increased fuel consumption and greenhouse gas emissions. Tributyltin-free antifouling coatings and paints based on metal complexes or biocides have been shown to efficiently prevent marine biofouling. However, these materials can damage the environment through metal leaching (for example, of copper and zinc) and bacteria resistance. Here, we show that vanadium pentoxide nanowires act like naturally occurring vanadium haloperoxidases to prevent marine biofouling. In the presence of bromide ions and hydrogen peroxide, the nanowires catalyse the oxidation of bromide ions to hypobromous acid (HOBr). Singlet molecular oxygen (1O2) is formed and this exerts strong antibacterial activity, which prevents marine biofouling without being toxic to marine biota. Vanadium pentoxide nanowires have the potential to be an alternative approach to conventional anti-biofouling agents.

  2. The metal-insulator transition in vanadium dioxide: A view at bulk and surface contributions for thin films and the effect of annealing

    Science.gov (United States)

    Yin, W.; West, K. G.; Lu, J. W.; Pei, Y.; Wolf, S. A.; Reinke, P.; Sun, Y.

    2009-06-01

    Vanadium dioxide is investigated as potential oxide barrier in spin switches, and in order to incorporate VO2 layers in complex multilayer devices, it is necessary to understand the relation between bulk and surface/interface properties. Highly oriented VO2 thin films were grown on (0001) sapphire single crystal substrates with reactive bias target ion beam deposition. In the analysis of the VO2 films, bulk-sensitive methods [x-ray diffraction (XRD) and transport measurements] and surface sensitive techniques [photoelectron spectroscopy (PES) and scanning tunneling microscopy and spectroscopy] were employed. The samples were subjected to heating cycles with annealing temperatures of up to 425 and 525K. Prior to annealing the VO2 films exhibit the transition from the monoclinic to the tetragonal phase with the concurrent change in conductivity by more than a factor of 103 and their phase purity is confirmed by XRD. Annealing to 425K and thus cycling across the metal-insulator transition (MIT) temperature has no impact on the bulk properties of the VO2 film but the surface undergoes irreversible electronic changes. The observation of the valence band with PES during the annealing illustrates that the surface adopts a partially metallic character, which is retained after cooling. Annealing to a higher temperature (525K ) triggers a modification of the bulk, which is evidenced by a considerable reduction in the MIT characteristics, and a degradation in crystallite morphology. The local measurement of the conductivity with scanning tunneling spectroscopy shows the transition of the surface from predominantly semiconducting surface prior to annealing to a surface with an overwhelming contribution from metallic sections afterward. The spatial distribution of metallic regions cannot be linked in a unique manner to the crystallite size or location within the crystallites. The onset of oxygen depletion at the surface is held responsible for this behavior. The onset of bulk

  3. Van der Waals Epitaxial Growth of 2D Metallic Vanadium Diselenide Single Crystals and their Extra-High Electrical Conductivity.

    Science.gov (United States)

    Zhang, Zhepeng; Niu, Jingjing; Yang, Pengfei; Gong, Yue; Ji, Qingqing; Shi, Jianping; Fang, Qiyi; Jiang, Shaolong; Li, He; Zhou, Xiebo; Gu, Lin; Wu, Xiaosong; Zhang, Yanfeng

    2017-10-01

    2D metallic transition-metal dichalcogenides (MTMDs) have recently emerged as a new class of materials for the engineering of novel electronic phases, 2D superconductors, magnets, as well as novel electronic applications. However, the mechanical exfoliation route is predominantly used to obtain such metallic 2D flakes, but the batch production remains challenging. Herein, the van der Waals epitaxial growth of monocrystalline, 1T-phase, few-layer metallic VSe 2 nanosheets on an atomically flat mica substrate via a "one-step" chemical vapor deposition method is reported. The thickness of the VSe 2 nanosheets is precisely tuned from several nanometers to several tenths of nanometers. More significantly, the 2D VSe 2 single crystals are found to present an excellent metallic feature, as evidenced by the extra-high electrical conductivity of up to 10 6 S m -1 , 1-4 orders of magnitude higher than that of various conductive 2D materials. The thickness-dependent charge-density-wave phase transitions are also examined through low-temperature transport measurements, which reveal that the synthesized 2D metallic 1T-VSe 2 nanosheets should serve as good research platforms for the detecting novel many-body states. These results open a new path for the synthesis and property investigations of nanoscale-thickness 2D MTMDs crystals. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. The toxicity of vanadium on gastrointestinal, urinary and reproductive system, and its influence on fertility and fetuses malformations

    OpenAIRE

    Aleksandra Wilk; Dagmara Szypulska-Koziarska; Barbara Wiszniewska

    2017-01-01

    Vanadium is a transition metal that has a unique and beneficial effect on both humans and animals. For many years, studies have suggested that vanadium is an essential trace element. Its biological properties are of interest due to its therapeutic potential, including in the treatment of diabetes mellitus. Vanadium deficiencies can lead to a range of pathologies. However, excessive concentration of this metal can cause irreversible damage to various tissues and organs. Vanadium toxicity mainl...

  5. Metallic fuels: The EBR-II legacy and recent advances

    Energy Technology Data Exchange (ETDEWEB)

    Douglas L. Porter; Steven L. Hayes; J. Rory Kennedy

    2012-09-01

    Experimental Breeder Reactor – II (EBR-II) metallic fuel was qualified for high burnup to approximately 10 atomic per cent. Subsequently, the electrometallurgical treatment of this fuel was demonstrated. Advanced metallic fuels are now investigated for increased performance, including ultra-high burnup and actinide burning. Advances include additives to mitigate the fuel/cladding chemical interaction and uranium alloys that combine Mo, Ti and Zr to improve alloy performance. The impacts of the advances—on fabrication, waste streams, electrorefining, etc.—are found to be minimal and beneficial. Owing to extensive research literature and computational methods, only a modest effort is required to complete their development.

  6. Strain engineering and one-dimensional organization of metal-insulator domains in single-crystal vanadium dioxide beams.

    Science.gov (United States)

    Cao, J; Ertekin, E; Srinivasan, V; Fan, W; Huang, S; Zheng, H; Yim, J W L; Khanal, D R; Ogletree, D F; Grossman, J C; Wu, J

    2009-11-01

    Correlated electron materials can undergo a variety of phase transitions, including superconductivity, the metal-insulator transition and colossal magnetoresistance. Moreover, multiple physical phases or domains with dimensions of nanometres to micrometres can coexist in these materials at temperatures where a pure phase is expected. Making use of the properties of correlated electron materials in device applications will require the ability to control domain structures and phase transitions in these materials. Lattice strain has been shown to cause the coexistence of metallic and insulating phases in the Mott insulator VO(2). Here, we show that we can nucleate and manipulate ordered arrays of metallic and insulating domains along single-crystal beams of VO(2) by continuously tuning the strain over a wide range of values. The Mott transition between a low-temperature insulating phase and a high-temperature metallic phase usually occurs at 341 K in VO(2), but the active control of strain allows us to reduce this transition temperature to room temperature. In addition to device applications, the ability to control the phase structure of VO(2) with strain could lead to a deeper understanding of the correlated electron materials in general.

  7. Mg II Absorbers: Metallicity Evolution and Cloud Morphology

    Science.gov (United States)

    Lan, Ting-Wen; Fukugita, Masataka

    2017-12-01

    Metal abundance and its evolution are studied for Mg II quasar absorption line systems from their weak, unsaturated spectral lines using stacked spectra from the archived data of the Sloan Digital Sky Survey. They show an abundance pattern that resembles that of the Galactic halo or Small Magellanic Cloud, with metallicity [Z/H] showing an evolution from redshift z = 2 to 0.5: metallicity becomes approximately solar or even larger at z≈ 0. We show that the evolution of the metal abundance traces the cumulative amount of the hydrogen fuel consumed in star formation in galaxies. With the aid of a spectroscopic simulation code, we infer the median gas density of the cloud to be roughly 0.3 {{cm}}-3, with which the elemental abundance in various ionization stages, in particular C I, is consistently explained. This gas density implies that the size of the Mg II clouds is of the order of 0.03 kpc, which suggests that individual Mg II clouds around a galaxy are of a baryonic mass typically {10}3 {M}⊙ . This means that Mg II clouds are numerous and “foamy,” rather than a large entity that covers a sizable fraction of galaxies with a single cloud.

  8. Adsorption of strontium (II) metal ions using phosphonate ...

    Indian Academy of Sciences (India)

    The metal binding was examined by the energy dispersive spectroscopy and scanning electron microscopy for the adsorbed Sr(II). Batch adsorption studies were performed by varying three parameters, namely initial pH, adsorbentdose and the contact time. The reaction kinetics was determined by the Langmuir, Freundlich, ...

  9. Dependence of Vanadium Recovery

    African Journals Online (AJOL)

    a large-scale vanadium processing or separation processes where vanadium is a contaminant. However, the ... in a separating funnel, swirled manually and later on a mechanical shaker operated at 120 rpm for 2 minutes ..... (40% v/v) TBP and the relevant scheme for extraction would be according to Equation 7. VOCl + n ...

  10. Structure and function of vanadium haloperoxidases

    NARCIS (Netherlands)

    Wever, R.; Michibata, H.

    2012-01-01

    Vanadium haloperoxidases contain the bare metal oxide vanadate as a prosthetic group and differ strongly from the heme peroxidases in substrate specificity and molecular properties. The substrates of these enzymes are limited to halides and sulfides, which in the presence of hydrogen peroxide are

  11. Role of metal d states in II-VI semiconductors

    Energy Technology Data Exchange (ETDEWEB)

    Wei, S.; Zunger, A.

    1988-05-15

    All-electron band-structure calculations and photoemission experiments on II-VI semiconductors both exhibit a metal d subband inside the main valence band. It has nevertheless been customary in pseudopotential and tight-binding approaches to neglect the metal d band by choosing Hamiltonian parameters which place this band inside the chemically inert atomic cores. Using all-electron self-consistent electronic-structure techniques (which treat the outermost d electrons on the same footing as other valence electrons) and comparing the results to those obtained by methods which remove the d band from the valence spectrum, we study their effects on valence properties. For II-VI semiconductors we find that p-d repulsion and hybridization (i) lower the band gaps, (ii) reduce the cohesive energy, (iii) increase the equilibrium lattice parameters, (iv) reduce the spin-orbit splitting, (v) alter the sign of the crystal-field splitting, (vi) increase the valence-band offset between common-anion II-VI semiconductors, and (vii) modify the charge distributions of various II-VI systems and their alloys. p-d repulsion is also shown to be responsible for the occurrence of deep Cu acceptor levels in II-VI semiconductors (compared with shallow acceptors of Zn in III-V), for the anomalously small band gaps in chalcopyrites, and for the negative exchange splitting in ferromagnetic MnTe.

  12. Vanadium Extraction from Shale via Sulfuric Acid Baking and Leaching

    Science.gov (United States)

    Shi, Qihua; Zhang, Yimin; Liu, Tao; Huang, Jing

    2018-01-01

    Fluorides are widely used to improve vanadium extraction from shale in China. Sulfuric acid baking-leaching (SABL) was investigated as a means of recovering vanadium which does not require the use of fluorides and avoids the productions of harmful fluoride-containing wastewater. Various effective factors were systematically studied and the experimental results showed that 90.1% vanadium could be leached from the shale. On the basis of phase transformations and structural changes after baking the shale, a mechanism of vanadium extraction from shale via SABL was proposed. The mechanism can be described as: (1) sulfuric acid diffusion into particles; (2) the formation of concentrated sulfuric acid media in the particles after water evaporation; (3) hydroxyl groups in the muscovite were removed and transient state [SO4 2-] was generated; and (4) the metals in the muscovite were sulfated by active [SO4 2-] and the vanadium was released. Thermodynamics modeling confirmed this mechanism.

  13. Exploring electrolyte preference of vanadium nitride supercapacitor electrodes

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Bo; Chen, Zhaohui; Lu, Gang [Department of Electrical Engineering and Automation, Luoyang Institute of Science and Technology, Luoyang 471023 (China); Wang, Tianhu [School of Electrical Information and Engineering, Jiangsu University of Technology, Changzhou 213001 (China); Ge, Yunwang, E-mail: ywgelit@126.com [Department of Electrical Engineering and Automation, Luoyang Institute of Science and Technology, Luoyang 471023 (China)

    2016-04-15

    Highlights: • Hierarchical VN nanostructures were prepared on graphite foam. • Electrolyte preference of VN supercapacitor electrodes was explored. • VN showed better capacitive property in organic and alkaline electrolytes than LiCl. - Abstract: Vanadium nitride hierarchical nanostructures were prepared through an ammonia annealing procedure utilizing vanadium pentoxide nanostructures grown on graphite foam. The electrochemical properties of hierarchical vanadium nitride was tested in aqueous and organic electrolytes. As a result, the vanadium nitride showed better capacitive energy storage property in organic and alkaline electrolytes. This work provides insight into the charge storage process of vanadium nitride and our findings can shed light on other transition metal nitride-based electrochemical energy storage systems.

  14. Effect of vanadium substitution for zirconium on the glass forming ability and mechanical properties of a Zr{sub 65}Cu{sub 17.5}Ni{sub 10}Al{sub 7.5} bulk metallic glass

    Energy Technology Data Exchange (ETDEWEB)

    Khademian, Nima, E-mail: nkhademian@gmail.com [Department of Mechanics, Islamshahr Branch, Islamic Azad University (IAU), Tehran (Iran, Islamic Republic of); Gholamipour, Reza [Iranian Research Organization for Science and Technology (IROST), Tehran (Iran, Islamic Republic of); Shahri, Farzad; Tamizifar, Morteza [Faculty of Engineering and High-Tech., Iran University of Industries and Mines (IUIM), Tehran (Iran, Islamic Republic of)

    2013-01-05

    Highlights: Black-Right-Pointing-Pointer The addition of V is effective for a decrease in GFA of Zr-based BMGs. Black-Right-Pointing-Pointer Mechanical properties of Zr-based BMGs are enhanced largely due to V addition. Black-Right-Pointing-Pointer Correlations among the elastic moduli, fracture strength, Vicker's hardness and glass transition for Zr-based BMGs. Black-Right-Pointing-Pointer Critical resolved shear stress ({tau}) of the Zr{sub 65-x}Cu{sub 17.5}Ni{sub 10}Al{sub 7.5}V{sub x} alloys decreases with the increase of V content. - Abstract: Effect of vanadium on the thermal and mechanical properties of the Zr{sub 65}Cu{sub 17.5}Ni{sub 10}Al{sub 7.5} bulk metallic glass has been studied. The vanadium substitution for zirconium in the bulk metallic glass leads to the decrease of the glass forming ability in constant cooling rate; as well as co-precipitation of Zr{sub 2}Ni and Zr{sub 2}Cu crystalline phases in amorphous matrix. The size of the crystallites are about 20-50 nm in amorphous matrix and they act as a barrier against of rapid propagation of shear bands. In fact, the nanocrystalline phases in amorphous matrix cause the increase of the strain and the quasi-static compression strength about 58% and 20%, respectively.

  15. Analysis and prediction of stacking sequences in intercalated lamellar vanadium phosphates

    Energy Technology Data Exchange (ETDEWEB)

    Gautier, Romain [Institut des Sciences Chimiques de Rennes, UMR 6226 CNRS - Ecole Nationale Superieure de Chimie de Rennes (France); Centre Nationale de la Recherche Scientifique (CNRS), Institut des Materiaux Jean Rouxel (IMN), Universite de Nantes (France); Fourre, Yoann; Furet, Eric; Gautier, Regis; Le Fur, Eric [Institut des Sciences Chimiques de Rennes, UMR 6226 CNRS - Ecole Nationale Superieure de Chimie de Rennes (France)

    2015-04-15

    An approach is presented that enables the analysis and prediction of stacking sequences in intercalated lamellar vanadium phosphates. A comparison of previously reported vanadium phosphates reveals two modes of intercalation: (i) 3d transition metal ions intercalated between VOPO{sub 4} layers and (ii) alkali/alkaline earth metal ions between VOPO{sub 4}.H{sub 2}O layers. Both intercalations were investigated using DFT calculations in order to understand the relative shifts of the vanadium phosphate layers. These calculations in addition to an analysis of the stacking sequences in previously reported materials enable the prediction of the crystal structures of M{sub x}(VOPO{sub 4}).yH{sub 2}O (M = Cs{sup +}, Cd{sup 2+} and Sn{sup 2+}). Experimental realization and structural determination of Cd(VOPO{sub 4}){sub 2}.4H{sub 2}O by single-crystal X-ray diffraction confirmed the predicted stacking sequences. (Copyright copyright 2015 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  16. Chemical characteristics of aerosols in the Kuroshio area. II. Chemical forms and size distributions of trace metals

    Science.gov (United States)

    Chen, Liqi; Yu, Qun; Yang, Xulin; Tang, Rongkun

    1993-12-01

    Aerosol samples were collected with a Sierrer Model 235 cascade impactor in the marine atmosphere over the Kuroshio area in consecutive four seasons from 1987 to 1988. Na, Cl, Al, V, and water soluble and acid soluble Mn, Fe, Pb, Cu, V, Cd were determined by neutron activation analysis and atomic absorption spectrophotometry, respectively. Seawater source chemical species in the aerosols appeared in high content in large over 3.6 μm diameter particles, and crustal source vanadium appeared in 3.6 μm diameter particles, but pollution source vanadium appeared in less than 0.52 μm diameter particles. Trace metals in the aerosols mostly had the highest concentration of water soluble metals on fine particles, and acid soluble metals on large particles. The concentrations of trace metals in the aerosols were higher in autumn and winter, lower in spring and summer.

  17. Synthesis and characterization of thermally stable oligomer-metal complexes of copper(II), nickel(II), zinc(II) and cobalt(II) derived from oligo-p-nitrophenylazomethinephenol

    OpenAIRE

    Ufuk S. Vural; Hasan Mart; H. Okkes Demir; Ozlem Sarıöz; Vefa Muradoğlu; M. Cihangir Koç

    2006-01-01

    Thermally stable metal complexes based on oligomers were prepared by the reaction between oligo-p-nitrophenilazomethinephenol (ONPAP) and Cu(II), Ni(II), Zn(II) and Co(II) ions. The properties of oligomer-metal complexes were studied by elemental, FT-IR and magnetic moments analyses. The thermal stabilities of the oligomer-metal complexes were compared by thermogravimetric (TG) and differential thermal (DTA) analyses. According to TG, oligomer-metal complexes were stable against to temperatur...

  18. Phosphonate ligands encourage a platonic relationship between cobalt(II) and alkali metal ions.

    Science.gov (United States)

    Langley, Stuart; Helliwell, Madeleine; Raftery, James; Tolis, Evangelos I; Winpenny, Richard E P

    2004-01-21

    Two new cobalt(ii) cages are reported where the metal core has a high symmetry related to a Platonic solid; the choice of alkali metal used in the base used for deprotonation appears to influence the resulting structures.

  19. DNA and HSA interaction of Vanadium (IV), Copper (II), and Zinc (II) complexes derived from an asymmetric bidentate Schiff-base ligand: multi spectroscopic, viscosity measurements, molecular docking, and ONIOM studies.

    Science.gov (United States)

    Dehkhodaei, Monireh; Sahihi, Mehdi; Amiri Rudbari, Hadi; Momenbeik, Fariborz

    2018-03-01

    The interaction of three complexes [Zn(II), Cu(II), and V(IV)] derived from an asymmetric bidentate Schiff-base ligand with DNA and HSA was studied using fluorescence quenching, UV-Vis spectroscopy, viscosity measurements, and computational methods [molecular docking and our Own N-layered Integrated molecular Orbital and molecular Mechanics (ONIOM)]. The obtained results revealed that the DNA and HSA affinities for binding of the synthesized compounds follow as V(IV) > Zn(II) > Cu(II) and Zn(II) > V(IV) > Cu(II), respectively. The distance between these compounds and HSA was obtained based on the Förster's theory of non-radiative energy transfer. Furthermore, computational molecular docking was carried out to investigate the DNA- and HSA-binding pose of the compounds. Molecular docking calculations showed that H-bond, hydrophobic, and π-cation interactions have dominant role in stability of the compound-HSA complexes. ONIOM method was utilized to investigate the HSA binding of the compounds more precisely in which molecular-mechanics method (UFF) and semi-empirical method (PM6) were selected for the low layer and the high layer, respectively. The results show that the structural parameters of the compounds changed along with binding, indicating the strong interaction between the compounds with HSA and DNA. Viscosity measurements as well as computational docking data suggest that all metal complexes interact with DNA, presumably by groove-binding mechanism.

  20. Synthesis and characterization of thermally stable oligomer-metal complexes of copper(II, nickel(II, zinc(II and cobalt(II derived from oligo-p-nitrophenylazomethinephenol

    Directory of Open Access Journals (Sweden)

    Ufuk S. Vural

    2006-12-01

    Full Text Available Thermally stable metal complexes based on oligomers were prepared by the reaction between oligo-p-nitrophenilazomethinephenol (ONPAP and Cu(II, Ni(II, Zn(II and Co(II ions. The properties of oligomer-metal complexes were studied by elemental, FT-IR and magnetic moments analyses. The thermal stabilities of the oligomer-metal complexes were compared by thermogravimetric (TG and differential thermal (DTA analyses. According to TG, oligomer-metal complexes were stable against to temperature and thermooxidative decomposition. The weight losses of oligomer-metal complexes were found to be 5 and 50 % at 200 and > 850 (Cu(II, 172 and 600 (Ni(II, 252 and > 850 (Zn(II and 174 and 510 (Co(II, oC, respectively. Based on half degradation temperature parameters Cu(II and Zn(II complexes were more resistant than the others.

  1. Synthesis, characterization, X-ray crystal structures and antibacterial activities of Schiff base ligands derived from allylamine and their vanadium(IV), cobalt(III), nickel(II), copper(II), zinc(II) and palladium(II) complexes

    Science.gov (United States)

    Amiri Rudbari, Hadi; Iravani, Mohammad Reza; Moazam, Vahid; Askari, Banafshe; Khorshidifard, Mahsa; Habibi, Neda; Bruno, Giuseppe

    2016-12-01

    A new Schiff base ligand, HL2, and four new Schiff base complexes, NiL12, PdL12, NiL22 and ZnL22, have been prepared and characterized by elemental analysis (CHN), FT-IR and UV-Vis spectroscopy. 1H and 13C NMR techniques were employed for characterization of the ligand (HL2) and the diamagnetic complexes (PdL12 and ZnL22). The molecular structures of PdL12, NiL22 and ZnL22 complexes were determined by the single crystal X-ray diffraction technique. The crystallographic data reveal that in these complexes the metal centers are four-coordinated by two phenolate oxygen and two imine nitrogen atoms of two Schiff base ligands. The geometry around the metal center in the PdL12 and NiL22 complexes is square-planar and for ZnL22 it is a distorted tetrahedral.In the end, five new (HL2, NiL12, PdL12, NiL22 and ZnL22) and six reported (HL1, VOL12, CoL13, CuL12, ZnL12 and Zn2L14) Schiff base compounds were tested for their in vitro antimicrobial activity against Staphylococcus aureus and Escherichia coli as examples of Gram-positive and Gram-negative bacterial strains, respectively, by disc diffusion method.

  2. DFT Studies on the Mechanism of the Vanadium-Catalyzed Deoxydehydration of Diols.

    Science.gov (United States)

    Galindo, Agustín

    2016-03-07

    The mechanism of the vanadium-catalyzed deoxydehydration of glycols to alkenes by phosphanes (Chapman, G.; Nicholas, K. M. Chem. Commun. 2013, 49, 8199-8201) has been investigated with density functional calculations. Two alternative pathways, A and B, have been evaluated, and the three stages generally recognized in DODH processes have been identified: (i) activation of the diol by condensation on the vanadium complex and eventual formation of vanadium-glycolate, (ii) oxygen atom transfer to phosphane with reduction to a vanadium(III) species, and, finally, (iii) alkene extrusion from the vanadium-glycolate with regeneration of the starting catalyst. Pathway B, in which the reduction by the phosphane from vanadium(V) to V(III) species occurred before the diol condensation, is energetically preferred to pathway A, in which the diol activation preceded the oxo-transfer to the phosphane reductant.

  3. Multivariate optimization of a procedure employing microwave-assisted digestion for the determination of nickel and vanadium in crude oil by ICP OES.

    Science.gov (United States)

    Dos Anjos, Shirlei L; Alves, Jeferson C; Rocha Soares, Sarah A; Araujo, Rennan G O; de Oliveira, Olivia M C; Queiroz, Antonio F S; Ferreira, Sergio L C

    2018-02-01

    This work presents the optimization of a sample preparation procedure using microwave-assisted digestion for the determination of nickel and vanadium in crude oil employing inductively coupled plasma optical emission spectrometry (ICP OES). The optimization step was performed utilizing a two-level full factorial design involving the following factors: concentrated nitric acid and hydrogen peroxide volumes, and microwave-assisted digestion temperature. Nickel and vanadium concentrations were used as responses. Additionally, a multiple response based on the normalization of the concentrations by the highest values was built to establish a compromise condition between the two analytes. A Doehlert matrix optimized the instrumental conditions of the ICP OE spectrometer. In this design, the plasma robustness was used as chemometric response. The experiments were performed using a digested oil sample solution doped with magnesium(II) ions, as well as a standard magnesium solution. The optimized method allows for the determination of nickel and vanadium with quantification limits of 0.79 and 0.20μgg-1, respectively, for a digested sample mass of 0.1g. The precision (expressed as relative standard deviations) was determined using five replicates of two oil samples and the results obtained were 1.63% and 3.67% for nickel and 0.42% and 4.64% for vanadium. Bismuth and yttrium were also tested as internal standards, and the results demonstrate that yttrium allows for a better precision for the method. The accuracy was confirmed by the analysis of the certified reference material trace element in fuel oil (CRM NIST 1634c). The proposed method was applied for the determination of nickel and vanadium in five crude oil samples from Brazilian Basins. The metal concentrations found varied from 7.30 to 33.21μgg-1 for nickel and from 0.63 to 19.42μgg-1 for vanadium. Copyright © 2017. Published by Elsevier B.V.

  4. Determination of Vanadium Binding Mode on Seawater-Contacted Polyamidoxime Adsorbents

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Zhicheng [Lawrence Berkeley National Laboratory (LBNL); Rao, Linfeng [Lawrence Berkeley National Laboratory (LBNL); Abney, Carter W. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Bryantsev, Vyacheslav [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Ivanov, Aleksandr [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

    2017-09-01

    Adsorbents developed for the recovery of uranium from seawater display poor selectivity over other transition metals present in the ocean, with vanadium particularly problematic. To improve selectivity, an indispensable step is the positive identification of metal binding environments following actual seawater deployment. In this work we apply x-ray absorption fine structure (XAFS) spectroscopy to directly investigate the vanadium binding environment on seawater-deployed polyamidoxime adsorbents. Comparison of the x-ray absorption near edge spectra (XANES) reveal marked similarities to recently a reported non-oxido vanadium (V) structure formed upon binding with cyclic imidedioxime, a byproduct of generating amidoxime functionalities. Density functional theory (DFT) calculations provided a series of putative vanadium binding environments for both vanadium (IV) and vanadium (V) oxidation states, and with both amidoxime and cyclic imidedioxime. Fits of the extended XAFS (EXAFS) data confirmed vanadium (V) is bound exclusively by the cyclic imidedioxime moiety in a 1:2 metal:ligand fashion, though a modest structural distortion is also observed compared to crystal structure data and computationally optimized geometries which is attributed to morphology effects from the polymer graft chain and the absence of crystal packing interactions. These results demonstrate that improved selectivity for uranium over vanadium can be achieved by suppressing the formation of cyclic imidedioxime during preparation of polyamidoxime adsorbents for seawater uranium recovery.

  5. Effects of vanadium on population growth and Na-K-ATPase activity of the brackish water hydroid Cordylophora caspia

    Energy Technology Data Exchange (ETDEWEB)

    Ringelband, U.; Karbe, L. [Institut fuer Hydrobiologie und Fischereiwissenschaft, Hamburg (Germany)

    1996-07-01

    Vanadium, a relatively abundant heavy metal, enters the environment naturally through rock weathering. A large fraction of vanadium input is of human origin. The combustion of petroleum- and coal-products, which contain relatively high concentrations of vanadium, is one of the most important sources of the enrichment of vanadium in the environment. As it is used as an alloy, and vanadium rich iron-ores of various origin are used in steel production, the residual slag-stones of the steel industry can contain considerable vanadium concentrations. Wherever slag-stones serve as a cheap and convenient material in riverbank reinforcement, vanadium can leach into the aquatic environment. Vanadium is regarded as an essential trace element for higher animals. Cantley et al. indicated a regulatory function of vanadate in vivo. Although considerable information is available on the toxic effects of vanadium on humans, very little is known about the toxicity of vanadium towards aquatic organisms, especially invertebrates. Bell and Sargent have shown an inhibition of Na-K-ATPase activity in gills of the eel Anguilla anguilla. Holleland and Towle have demonstrated the inhibition of Na-K-ATPase activity in the gills of the shore crab Carcinus maenas. The aim of this study was to determine the toxicity of vanadium towards the brackish water hydroid Cordylophora caspia. Hydroids are known to be particularly sensitive to heavy metals and their asexual reproduction can be used in a well-established population growth test. Furthermore, the effects of vanadium on Na-K-ATPase activity in hydroids were studied in in vivo experiments, wherein the animals were exposed to sublethal concentrations of vanadium. In addition, the inhibition of Na-K-ATPase was measured in vitro, by adding vanadium to a microsomal preparation. 16 refs., 4 figs.

  6. A novel process for the recovery of iron, titanium, and vanadium from vanadium-bearing titanomagnetite: sodium modification-direct reduction coupled process

    Science.gov (United States)

    Zhang, Yi-min; Yi, Ling-yun; Wang, Li-na; Chen, De-sheng; Wang, Wei-jing; Liu, Ya-hui; Zhao, Hong-xin; Qi, Tao

    2017-05-01

    A sodium modification-direct reduction coupled process was proposed for the simultaneous extraction of V and Fe from vanadium- bearing titanomagnetite. The sodium oxidation of vanadium oxides to water-soluble sodium vanadate and the transformation of iron oxides to metallic iron were accomplished in a single-step high-temperature process. The increase in roasting temperature favors the reduction of iron oxides but disfavors the oxidation of vanadium oxides. The recoveries of vanadium, iron, and titanium reached 84.52%, 89.37%, and 95.59%, respectively. Moreover, the acid decomposition efficiency of titanium slag reached 96.45%. Compared with traditional processes, the novel process provides several advantages, including a shorter flow, a lower energy consumption, and a higher utilization efficiency of vanadium-bearing titanomagnetite resources.

  7. Complexation of vanadium with amidoxime and carboxyl groups. Uncovering the competitive role of vanadium in uranium extraction from seawater

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Cong-Zhi; Wu, Qun-Yan; Lan, Jian-Hui; Shi, Wei-Qun [Chinese Academy of Sciences, Beijing (China). Inst. of High Energy Physics; Chai, Zhi-Fang [Chinese Academy of Sciences, Beijing (China). Inst. of High Energy Physics; Soochow Univ., Suzhou (China). School of Radiological and Interdisciplinary Sciences (RAD-X); Wu, Guo-Zhong [Chinese Academy of Sciences, Shanghai (China). Shanghai Inst. of Applied Physics

    2017-09-01

    At present, amidoxime-based adsorbents are considered to be the most promising materials for extraction of uranium from seawater. However, the high concentrations of transition metals especially vanadium strongly compete with uranium in the sequestration process, which is extremely limited the commercial use of amidoxime-based adsorbents. In this work, the coordination modes, bonding nature, and stabilities of possible vanadium(IV) (VO{sup 2+}) and (V) (VO{sub 2}{sup +}, VO{sup 3+}, V{sup 5+}) complexes with amidoximate (AO{sup -}), carboxyl (Ac{sup -}), glutarimidedioximate (HA{sup -}) and deprotonated glutarimidedioximate (A{sup 2-}) on single and double alkyl chains (R=C{sub 13}H{sub 26}) are systematically explored by quantum chemical calculations. Different from the uranyl (UO{sub 2}{sup 2+}) complexes, the AO{sup -} groups of the vanadium(IV) and (V) complexes prefer to coordinate as monodentate and chelate ligands, while few species with AO{sup -} groups in η{sup 2}-binding mode have been observed in the vanadium complexes. Besides, the vanadium complexes are predicted to have obvious covalent metal-ligand bonds. According to thermodynamic stability analysis, all the vanadium complexes with AO{sup -}, Ac{sup -}, HA{sup -} and A{sup 2-} ligands on double alkyl chains are found to be more stable than corresponding complexes with ligands on a single chain. The synergistic effect of the amidoxime and carboxyl groups can be observed in most of VO{sub 2}{sup +} and VO{sup 3+} complexes with mixed ligands (AO{sup -}/Ac{sup -}). The vanadium(IV) and (V) complexes are more stable than the corresponding uranyl complexes, and the adsorption capability of the amidoxime-based adsorbents toward vanadium(V) ions decrease in the order of VO{sub 2}{sup +}>VO{sup 3+}> V{sup 5+}. The dioxovanadium cation VO{sub 2}{sup +} is predicted to form multinuclear vanadium complex in the sequestration process, possibly resulting in higher stable VO{sub 2}{sup +} complexes. Therefore

  8. Heavy metal / polyacid interaction : an electrochemical study of the binding of Cd(II), Pb(II) and Zn(II) to polycarboxylic and humic acids

    NARCIS (Netherlands)

    Cleven, R.F.M.J.

    1984-01-01

    Polyelectrolyte effects in the interaction of heavy metal ions with model polycarboxylic acids have been described, in order to establish the relevance of these effects in the interaction of heavy metal ions with naturally occurring humic and fulvic acids. The model systems consisted of Cd(II),

  9. Synthesis, spectral characterization thermal stability, antimicrobial studies and biodegradation of starch–thiourea based biodegradable polymeric ligand and its coordination complexes with [Mn(II, Co(II, Ni(II, Cu(II, and Zn(II] metals

    Directory of Open Access Journals (Sweden)

    Nahid Nishat

    2016-09-01

    Full Text Available A biodegradable polymer was synthesized by the modification reaction of polymeric starch with thiourea which is further modified by transition metals, Mn(II, Co(II, Ni(II, Cu(II and Zn(II. All the polymeric compounds were characterized by (FT-IR spectroscopy, 1H NMR spectroscopy, 13C NMR spectroscopy, UV–visible spectra, magnetic moment measurements, thermogravimetric analysis (TGA and antibacterial activities. Polymer complexes of Mn(II, Co(II and Ni(II show octahedral geometry, while polymer complexes of Cu(II and Zn(II show square planar and tetrahedral geometry, respectively. The TGA revealed that all the polymer metal complexes are more thermally stable than their parental ligand. In addition, biodegradable studies of all the polymeric compounds were also carried out through ASTM-D-5338-93 standards of biodegradable polymers by CO2 evolution method which says that coordination decreases biodegradability. The antibacterial activity was screened with the agar well diffusion method against some selected microorganisms. Among all the complexes, the antibacterial activity of the Cu(II polymer–metal complex showed the highest zone of inhibition because of its higher stability constant.

  10. Manufacturing processes of cellular metals. Part II. Solid route, metals deposition, other processes; Procesos de fabricacion de metales celulares. Parte II: Via solida, deposicion de metales otros procesos

    Energy Technology Data Exchange (ETDEWEB)

    Fernandez, P.; Cruz, L. J.; Coleto, J.

    2009-07-01

    At the first part of this paper review a description about cellular metal processes by liquid route, was made. In this second part, solid processes and metals deposition are described. In similar way, the different kind of processes in each case are reviewed; making a short description about the main parameters involved and the advantages and drawbacks in each of them. (Author) 147 refs.

  11. The toxicity of vanadium on gastrointestinal, urinary and reproductive system, and its influence on fertility and fetuses malformations.

    Science.gov (United States)

    Wilk, Aleksandra; Szypulska-Koziarska, Dagmara; Wiszniewska, Barbara

    2017-09-25

    Vanadium is a transition metal that has a unique and beneficial effect on both humans and animals. For many years, studies have suggested that vanadium is an essential trace element. Its biological properties are of interest due to its therapeutic potential, including in the treatment of diabetes mellitus. Vanadium deficiencies can lead to a range of pathologies. However, excessive concentration of this metal can cause irreversible damage to various tissues and organs. Vanadium toxicity mainly manifests in gastrointestinal symptoms, including diarrhea, vomiting, and weight reduction. Vanadium also exhibits hepatotoxic and nephrotoxic properties, including glomerulonephritis and pyelonephritis. Vanadium compounds may also lead to partial degeneration of the seminiferous epithelium of the seminiferous tubules in the testes and can affect male fertility. This paper describes the harmful effects of vanadium on the morphology and physiology of both animal and human tissues, including the digestive system, the urinary tract, and the reproductive system. What is more, the following study includes data concerning the correlation between the above-mentioned metal and its influence on fertility and fetus malformations. Additionally, this research identifies the doses of vanadium which lead to pathological alterations becoming visible within tissues. Moreover, this study includes information about the protective efficacy of some substances in view of the toxicity of vanadium.

  12. Adsorption kinetics and isotherm of vanadium with melamine.

    Science.gov (United States)

    Peng, Hao; Liu, Zuohua; Tao, Changyuan

    2017-05-01

    Melamine, possessing three free amino groups and three aromatic nitrogen atoms in its molecule, has great potential as an adsorbent for metal ions. We investigated three impact factors of the adsorption process: the initial pH of the vanadium solution, contact time and reaction temperature. The adsorption kinetics could be accurately described by the pseudo-second-order kinetic model. Langmuir and Freundlich models fitted well with the experimental equilibrium data, and the maximal adsorption capacity was found to be 1,428.57 mg vanadium/g melamine, and the Freundlich model showed the adsorption is privilege type.

  13. Studies on transition metal complexes of herbicidal compounds. II ...

    African Journals Online (AJOL)

    2(2-Hydroxyethyl)hydrazino-4-ethylamino-6-isopropylamino-s-triazine (HEATZ), a derivative of 2-chloro-4-ethylamino-6-isopropylamino-s-triazine, atrazine (ATZ) – a well known herbicide has been studied for complex formation with cobalt(II), nickel(II), and copper(II). Analytical, conductance, thermal, and spectral studies ...

  14. Zinc (II) metal ion complexes of Chitosan: Toward heterogeneous ...

    African Journals Online (AJOL)

    The Application of Zn(II)-Chit for the polymerization of VAc yielded PVAc in good yield. The catalyst efficiency of Zn(II)-Chit for the polymerization of VAc was considerably high in terms of induction period and percentage yield of PVAc. Keywords: Chitosan, Zn(II)-Chitosan Complex, Catalyst, Polymerization, Polyvinyl Acetate ...

  15. Platinum-Vanadium Oxide Nanotube Hybrids

    Science.gov (United States)

    Mello, Filipe L. S.; Costa, Lídia O. O.; Hernández, Eduardo Padrón; de Farias, Andréa M. Duarte; Fraga, Marco A.

    2010-06-01

    The present contribution reports on the features of platinum-based systems supported on vanadium oxide nanotubes. The synthesis of nanotubes was carried out using a commercial vanadium pentoxide via hydrothermal route. The nanostructured hybrid materials were prepared by wet impregnation using two different platinum precursors. The formation of platinum nanoparticles was evaluated by applying distinct reduction procedures. All nanostructured samples were essentially analysed by X-ray diffraction and transmission electron microscopy. After reduction, transmission electron microscopy also made it possible to estimate particle size distribution and mean diameter calculations. It could be seen that all reduction procedures did not affect the nanostructure of the supports and that the formation of metallic nanoparticles is quite efficient with an indistinct distribution along the nanotubes. Nevertheless, the reduction procedure determined the diameter, dispersion and shape of the metallic particles. It could be concluded that the use of H2PtCl6 is more suitable and that the use of hydrogen as reducing agent leads to a nanomaterial with unagglomerated round-shaped metallic particles with mean size of 6-7 nm.

  16. Platinum–Vanadium Oxide Nanotube Hybrids

    Directory of Open Access Journals (Sweden)

    Hernández EduardoPadrón

    2010-01-01

    Full Text Available Abstract The present contribution reports on the features of platinum-based systems supported on vanadium oxide nanotubes. The synthesis of nanotubes was carried out using a commercial vanadium pentoxide via hydrothermal route. The nanostructured hybrid materials were prepared by wet impregnation using two different platinum precursors. The formation of platinum nanoparticles was evaluated by applying distinct reduction procedures. All nanostructured samples were essentially analysed by X-ray diffraction and transmission electron microscopy. After reduction, transmission electron microscopy also made it possible to estimate particle size distribution and mean diameter calculations. It could be seen that all reduction procedures did not affect the nanostructure of the supports and that the formation of metallic nanoparticles is quite efficient with an indistinct distribution along the nanotubes. Nevertheless, the reduction procedure determined the diameter, dispersion and shape of the metallic particles. It could be concluded that the use of H2PtCl6 is more suitable and that the use of hydrogen as reducing agent leads to a nanomaterial with unagglomerated round-shaped metallic particles with mean size of 6–7 nm.

  17. Molecular operation of metals into the function and state of photosystem II.

    Science.gov (United States)

    Gaziyev, Arif; Aliyeva, Samira; Kurbanova, Inna; Ganiyeva, Rena; Bayramova, Sona; Gasanov, Ralphreed

    2011-12-01

    Action sites of different metals in the electron transport reactions of Photosystem II (PS II) evaluated by delayed fluorescence in the ms range (ms DF) and pigment-pigment, pigment-protein and protein-protein interaction states by electrophoretic measurements are presented. The main targets for the metals action were shown to be:(i) Cd(2+), Ni(2+), Co(2+)-Y(z) or CaMn(4)-cluster on the donor site with dependence on pH;(ii) Ni(2+), Co(2+), Zn(2+), Al(3+), Mn(2+) between Q(A) and Q(B) on the acceptor site; effect of Al(3+) and Mn(2+) is observed only in acidic pH. Investigated metals bring about monomerization of oligomeric and dimeric chlorophyll-protein complexes (CPC) and destabilization of protein-protein interactions. Molecular mechanisms of metals interference with the structure of PS II are discussed.

  18. Vanadium Doped Tungsten Oxide Material - Electrical Physical and Sensing Properties

    Directory of Open Access Journals (Sweden)

    Shishkin N. Y.

    2008-05-01

    Full Text Available The electrical physical and sensing (to VOCs and inorganic gases properties of vanadium doped tungsten oxide in the regions of phase transition temperature were investigated. Vanadium oxide (II dimerization was observed in the doped material, corresponding to new phase transition. The extreme sensitivity and selectivity to chemically active gases and vapors in small concentrations: CO, NOx, NH3 acetone, ethanol near phase transitions temperature was found. Sensor elements were manufactured for the quantitative detection (close to 1 ppm of alcohol and ammonia.

  19. Theoretical study of vanadium oxides interaction with Y-zeolite.

    Science.gov (United States)

    Arroyo, M; Sansores, L E; Salcedo, R; Montoya, J A

    2008-12-01

    A current problem about oils and feedstock in fluid catalytic cracking (FCC) is the continuous cumulative deposition of metal contaminants on the catalyst, resulting in important modifications of its properties. Vanadium plays a detrimental role on the catalyst components because enhances the destruction of the Y-zeolite structure during regeneration stage when it is exposed by steam and oxygen at high temperatures. Knowledge of the mechanism interaction of vanadium with the catalyst is important to improve FCC performance. Quantum Molecular Dynamics calculations were done introducing the VO, V2O3, VO2 or V2O5 molecules at the center of a Y-zeolite ring simulating regeneration conditions. The results indicate that the principal reaction is carried out among the zeolite and the vanadium atoms of molecules. This happens, when interaction is presented, since the loss of a hydrogen atom of the active place causes high degree of oxygen reactivity.

  20. Complex research of vanadium dioxide in the homoginuity field

    Science.gov (United States)

    Surikov, Vad I.; Semenyuk, N. A.; Surikov, Val I.; Kuznetsova, Y. V.; Pavlovskaya, O. Y.

    2018-01-01

    The complex research results of vanadium dioxide VÜ2±x obtained with X-ray analysis method, a method of vacuum adiabatic calorimeter and Faraday method are discussed. The samples temperature dependences of electrical resistivity, heat capacity, and also magnetic susceptibility are presented and they prove that these characteristics jump abruptly in the phase transition area. Thermophysical, electrical, magnetic properties of vanadium dioxide are established to vary with the oxygen content in the samples. Values of Debye characteristic temperatures θD for samples VO2±x determined at temperature 150 K are presented. Values of entropy change as an amount of electronic and phonon components at phase transition were calculated. The results obtained allow to consider the phase transition of a metal semiconductor as a Mott-Peierls transition, and also to use vanadium dioxide in temperature sensors manufacture.

  1. The determination of vanadium in brines by atomic absorption spectroscopy

    Science.gov (United States)

    Crump-Wiesner, Hans J.; Feltz, H.R.; Purdy, W.C.

    1971-01-01

    A standard addition method is described for the determination of vanadium in brines by atomic absorption spectroscopy with a nitrous oxide-acetylene flame. Sample pH is adjusted to 1.0 with concentrated hydrochloric acid and the vanadium is directly extracted with 5% cupferron in methyl isobutyl ketone (MIBK). The ketone layer is then aspirated into the flame and the recorded absorption values are plotted as a function of the concentration of the added metal. As little as 2.5 ??g l-1 of vanadium can be detected under the conditions of the procedure. Tungsten and tin interfere when present in excess of 5 and 10 ??g ml-1, respectively. The concentrations of the two interfering ions normally found in brines are well below interference levels. ?? 1971.

  2. The role of vanadium in the chemical defense of the solitary tunicate, Phallusia nigra.

    Science.gov (United States)

    Odate, Shobu; Pawlik, Joseph R

    2007-03-01

    Ascidians (sea squirts) may defend themselves from predators, biofouling competitors, and bacterial infection by producing secondary metabolites or sequestering acid, but many species also accumulate heavy metals, most notably vanadium. The defensive functions of heavy metals in ascidians remain unclear, and to this end, the solitary Caribbean tunicate, Phallusia nigra, was studied to localize vanadium in its tissues and to assess the defensive properties of vanadium-containing compounds. As determined by flame atomic absorption spectroscopy, the internal tissues and blood contained the highest vanadium concentrations (mean values of 2280 and 1886 ppm dry mass, respectively), followed by the tunic surface (871 ppm dry mass). Results of laboratory feeding assays with the bluehead wrasse, Thalassoma bifasciatum, confirmed outcomes of past studies that demonstrated that vanadyl sulfate (VOSO4.6H20) and sodium vanadate (Na3VO4) were unpalatable to fish, although these salts do not accurately reflect the chelation environment or oxidation state of vanadium in living tunicates. Fresh preparations of whole tunic, internal tissues, and blood were unpalatable to fish, but freezing and thawing of internal tissues and blood rendered them palatable. Crude organic extracts of whole tunic and internal tissues contained vanadium metabolites (225 and 750 ppm dry mass, respectively) and were palatable to T. bifasciatum; crude extracts also exhibited no antimicrobial effects against a panel of four marine bacteria known to be pathogens of marine invertebrates (Vibrio parahaemolyticus, Vibrio harveyi, Leucothrix mucor, and Deleya marina). Nonacidic vanadium (+3) complexes neither deterred predation nor inhibited microbial growth, whereas acidic aqua vanadium (+3 and +4) complexes were unpalatable to 7 bifasciatum and exhibited antimicrobial activity. Difficulties in decoupling low pH from oxidation state and chelation environment of vanadium prevent definitive conclusions about the

  3. Metal-ion dependent catalytic properties of Sulfolobus solfataricus class II α-mannosidase

    DEFF Research Database (Denmark)

    Nielsen, Jonas Willum; Poulsen, Nina Rødtness; Johnsson, Anna Margit Susanne

    2012-01-01

    The active site for the family GH38 class II α-mannosidase is constituted in part by a divalent metal ion, mostly Zn(2+), as revealed in the crystal structures of enzymes from both animal and bacterial sources. The metal ion coordinates to the bound substrate and side chains of conserved amino ac...

  4. Five coordinate M(II)-diphenolate [M = Zn(II), Ni(II), and Cu(II)] Schiff base complexes exhibiting metal- and ligand-based redox chemistry.

    Science.gov (United States)

    Franks, Mark; Gadzhieva, Anastasia; Ghandhi, Laura; Murrell, David; Blake, Alexander J; Davies, E Stephen; Lewis, William; Moro, Fabrizio; McMaster, Jonathan; Schröder, Martin

    2013-01-18

    Five-coordinate Zn(II), Ni(II), and Cu(II) complexes containing pentadentate N(3)O(2) Schiff base ligands [1A](2-) and [1B](2-) have been synthesized and characterized. X-ray crystallographic studies reveal five coordinate structures in which each metal ion is bound by two imine N-donors, two phenolate O-donors, and a single amine N-donor. Electron paramagnetic resonance (EPR) spectroscopic studies suggest that the N(3)O(2) coordination spheres of [Cu(1A)] and [Cu(1B)] are retained in CH(2)Cl(2) solution and solid-state superconducting quantum interference device (SQUID) magnetometric studies confirm that [Ni(1A)] and [Ni(1B)] adopt high spin (S = 1) configurations. Each complex exhibits two reversible oxidation processes between +0.05 and +0.64 V vs [Fc](+)/[Fc]. The products of one- and two-electron oxidations have been studied by UV/vis spectroelectrochemistry and by EPR spectroscopy which confirm that each oxidation process for the Zn(II) and Cu(II) complexes is ligand-based with sequential formation of mono- and bis-phenoxyl radical species. In contrast, the one-electron oxidation of the Ni(II) complexes generates Ni(III) products. This assignment is supported by spectroelectrochemical and EPR spectroscopic studies, density functional theory (DFT) calculations, and the single crystal X-ray structure of [Ni(1A)][BF(4)] which contains Ni in a five-coordinate distorted trigonal bipyramidal geometry.

  5. Coordination Modes of a Schiff Base Derived from Substituted 2-Aminothiazole with Chromium(III, Manganese(II, Iron(II, Cobalt(II, Nickel(II and Copper(II Metal Ions: Synthesis, Spectroscopic and Antimicrobial Studies

    Directory of Open Access Journals (Sweden)

    Ambit Thakar

    2011-01-01

    Full Text Available Transition metal complexes of Cr(III, Mn(II, Fe(II, Co(II, Ni(II and Cu(II metal ions with general stoichiometry [ML2.2H2O] and [ML3], where M= Mn(II, Cr(III, Fe(II, Co(II, Ni(II and Cu(II, L= Schiff base derived from the condensation of 2-amino-4(4’-phenyl/methylphenyl-5-methyl-thiazole with 4-acetyl-1(3-chloro phenyl-3-methyl-2-pyrazoline-5-ones, have been synthesized and structurally characterized by elemental analysis, molar conductance measurements, magnetic susceptibility measurements and spectral techniques like IR, UV, 1H NMR, 13C NMR and Mass Spectra. All the complexes were found to be octahedral geometry. The ligand and its complexes have been screened for their antifungal and antibacterial activities against three fungi, i.e. Alternaria brassicae, Aspergillus niger and Fesarium oxysporum and two bacteria, i.e. Xanthomonas compestris and Pseudomonas aeruginosa.

  6. Micellar effect on metal-ligand complexes of Co(II, Ni(II, Cu(II and Zn(II with citric acid

    Directory of Open Access Journals (Sweden)

    Nageswara Rao Gollapalli

    2009-12-01

    Full Text Available Chemical speciation of citric acid complexes of Co(II, Ni(II, Cu(II and Zn(II was investigated pH-metrically in 0.0-2.5% anionic, cationic and neutral micellar media. The primary alkalimetric data were pruned with SCPHD program. The existence of different binary species was established from modeling studies using the computer program MINIQUAD75. Alkalimetric titrations were carried out in different relative concentrations (M:L:X = 1:2:5, 1:3:5, 1:5:3 of metal (M to citric acid. The selection of best chemical models was based on statistical parameters and residual analysis. The species detected were MLH, ML2, ML2H and ML2H2. The trend in variation of stability constants with change in mole fraction of the medium is explained on the basis of electrostatic and non-electrostatic forces. Distributions of the species with pH at different compositions of micellar media are also presented.

  7. Reductive mineralization of cellulose with vanadium, iron and tungsten chlorides and access to MxOymetal oxides and MxOy/C metal oxide/carbon composites.

    Science.gov (United States)

    Henry, Aurélien; Hesemann, Peter; Alauzun, Johan G; Boury, Bruno

    2017-10-15

    M x O y and M x O y /C composites (M=V, Fe and W) were obtained by mineralization of cellulose with several metal chlorides. Cellulose was used both as a templating agent and as an oxygen and a carbon source. Soluble chloride molecules (VOCl 3 and WCl 6 ) and a poorly soluble ionic chloride compound (FeCl 3 ) were chosen as metal oxide precursors. In a first time, primary metal oxide/cellulose composites were obtained via a thermal treatment by reacting urea impregnated filter paper with the corresponding metal chlorides in an autoclave at 150°C after 3days. After either pyrolysis or calcination steps of these intermediate materials, interesting metal oxides with various morphologies were obtained (V 2 O 5, V 2 O 3 , Fe 3 O 4 , WO 3, H 0.23 WO 3 ), composites (V 2 O 3 /C) as well as carbides (hexagonal W 2 C and WC, Fe 3 C) This result highlight the reductive role that can play cellulose during the pyrolysis step that allows to tune the composition of M x O y /C composites. The materials were characterized by FTIR, Raman, TGA, XRD and SEM. This study highlights that cellulose can be used for a convenient preparation of a variety of highly demanded M x O y and M x O y /C composites with original shapes and morphologies. Copyright © 2017 Elsevier Ltd. All rights reserved.

  8. Slag-metal reactions during welding: Part II. Theory

    Science.gov (United States)

    Mitra, U.; Eagar, T. W.

    1991-02-01

    A kinetic model is developed to describe the transfer of alloying elements between the slag and the metal during flux-shielded welding. The model accounts for changes in alloy recovery based on the geometry of the resulting weld bead. It also distinguishes compositional differences between single-pass and multiple-pass weld beads. It is further shown that the final weld metal oxygen content is directly related to the weld solidification time as well as the type of flux used.

  9. Synthesis, characterization and biocidal activity of some transition metal(II) complexes with isatin salicylaldehyde acyldihydrazones.

    Science.gov (United States)

    Singh, Vinod P; Singh, Shweta; Singh, Divya P

    2012-06-01

    Cobalt(II), nickel(II), copper(II), zinc(II) and cadmium(II) complexes with two new unsymmetrical ligands, isatin salicylaldehyde oxalic acid dihydrazide (isodh) and isatin salicylaldehyde malonic acid dihydrazide (ismdh) were synthesized and characterized by elemental analyses, electrical conductance, magnetic moments, electronic, NMR, ESR and IR spectral studies. The isodh acts as a dibasic tetra dentate ligand bonding through two >C=N-, a deprotonated phenolate and deprotonated indole enolate groups to the metal. The ismdh ligand shows monobasic tetra dentate behaviour in bonding with metal ion through two >C=N-, indole >C=O and a deprotonated phenolate group. The electronic spectral data suggest 4-coordinate square planar geometry for Co(II), Ni(II) and Cu(II) complexes of isodh, whereas, 6-coordinate octahedral structure for the ismdh complexes. The ESR studies also indicate a square planar and distorted octahedral environment around Cu(II) for isodh and ismdh complexes, respectively. Most of the metal complexes show better antifungal activity than the standard and a significant antibacterial activity against various fungi and bacteria.

  10. Metal (II) Complexes Derived from Naphthofuran-2-carbohydrazide and Diacetylmonoxime Schiff Base: Synthesis, Spectroscopic, Electrochemical, and Biological Investigation

    Science.gov (United States)

    Sumathi, R. B.; Halli, M. B.

    2014-01-01

    A new Schiff base and a new series of Co(II), Ni(II), Cu(II), Cd(II), and Hg(II) complexes were synthesized by the condensation of naphthofuran-2-carbohydrazide and diacetylmonoxime. Metal complexes of the Schiff base were prepared from their chloride salts of Co(II), Ni(II), Cu(II), Cd(II), and Hg(II) in ethanol. The ligand along with its metal complexes have been characterized on the basis of analytical data, IR, electronic, mass, 1HNMR, ESR spectral data, thermal studies, magnetic susceptibility, and molar conductance measurements. The nonelectrolytic behaviour of the complexes was assessed from the measured low conductance data. The elemental analysis of the complexes confirm the stoichiometry of the type CuL2Cl2 and MLCl2 where M = Ni(II), Co(II), Cd(II), and Hg(II) and L = Schiff base. The redox property of the Cu(II) complex was investigated by electrochemical method using cyclic voltammetry. In the light of these results, Co(II), Ni(II), and Cu(II) complexes are assigned octahedral geometry, Cd(II), and Hg(II) complexes tetrahedral geometry. In order to evaluate the effect of metal ions upon chelation, both the ligand and its metal complexes were screened for their antibacterial and antifungal activities by minimum inhibitory concentration (MIC) method. The DNA cleaving capacity of all the complexes was analysed by agarose gel electrophoresis method. PMID:24592203

  11. Effect of Cl2 plasma treatment and annealing on vanadium based metal contacts to Si-doped Al0.75Ga0.25N

    Science.gov (United States)

    Lapeyrade, Mickael; Alamé, Sabine; Glaab, Johannes; Mogilatenko, Anna; Unger, Ralph-Stephan; Kuhn, Christian; Wernicke, Tim; Vogt, Patrick; Knauer, Arne; Zeimer, Ute; Einfeldt, Sven; Weyers, Markus; Kneissl, Michael

    2017-09-01

    In order to understand the electrical properties of V/Al/Ni/Au metal contacts to Si-doped Al0.75Ga0.25N layers, X-ray photoelectron spectroscopy analysis was performed on differently treated AlGaN:Si surfaces before metal deposition, and transmission electron microscopy was used to study the semiconductor-metal interface after contact annealing at 900 °C. Cl2 plasma etching of AlGaN increases the aluminum/nitrogen ratio at the surface, and Al oxide or oxynitride is always formed by any surface treatment applied after etching. After contact annealing, a complex interface structure including amorphous AlOx and different metal phases such as Al-Au-Ni, V-Al, and V2N were found. The electrical properties of the contacts were determined by thermionic emission and/or thermionic field emission in the low voltage regime. Nearly ohmic contacts on AlGaN surfaces exposed to a Cl2 plasma were only obtained by annealing the sample at a temperature of 815 °C under N2/NH3 prior to metallization. By this treatment, the oxygen contamination on the surface could be minimized, resulting in a larger semiconductor area to be in direct contact with metal phases such as Al-rich Al-Au-Ni or V-Al and leading to a contact resistivity of 2.5 × 10-2 Ω cm2. This treatment can be used to significantly reduce the operating voltage of current deep ultraviolet light emitting diodes which will increase their wall plug efficiency and lower the thermal stress during their operation.

  12. Transition metal M(II complexes with isonicotinoylhydrazone-9-anthraldehyde

    Directory of Open Access Journals (Sweden)

    Dianu M.L.

    2010-01-01

    Full Text Available New complexes of isonicotinoylhydrazone-9-anthraldehyde with Cu(II, Co(II and Ni(II have been prepared and characterized by analytical and physico-chemical techniques, such as elemental and thermal analyses, magnetic susceptibility and conductivity measurements, and electronic, EPR and IR spectral studies. The infrared spectral studies revealed the bidentate or monodentate nature of the Schiff base in the complexes; the pyridine nitrogen does not participate in the coordination. A tetrahedral geometry is suggested for the nitrate-complexes and an octahedral geometry for the others. Thermal studies support the chemical formulation of these complexes.

  13. BIOSORPTION OF METAL IONS Pb(II, Cu(II, AND Cd(II ON Sargassum duplicatum IMMOBILIZED SILICA GEL MATRIX

    Directory of Open Access Journals (Sweden)

    Buhani Buhani

    2010-06-01

    Full Text Available Sargassum duplicatum algae biomass is biological material which has a potency to be used as a biosorbent adsorb metal ions from industrial liquid waste, because it has effective functional group as a ligand. However, the ability of the algae biomass in adsorbing of heavy metal ions has some problem such as; tiny size, low density, and easy to be degradated by other microorganism. In addition, algae biomass can not be used directly in adsorption column for its application as the biosorbent. In order to improve physical and chemical prpperties of algae biomass, it needs to be immobilized on silica gel matrix. Series of experiment have been done, morphology analysis of adsorbent surface was performed by using Scanning Electron Microscopy (SEM and adsorption process to examine the effectiveness of algae biomass immobilized in adsorbing Pb(II, Cu(II, and Cd(II was performed using batch method at 27 °C. Concentration of metal was determined by using Atomic Absorption Spectrophotometer (AAS and identification of functional group was conducted using Spectrophotometer Infrared (IR. Data obtained showed that interacting among metal ions with algae biomass is optimum at a range of 60 minutes. Adsorption energies of metal ions resulted from the interaction of metal ions with the functional group of -C=O group from carboxyl and amide on algae biomass and -Si-OH group from silica were at a range of 21.09-25.05 kJ/mole.   Keywords: biosorption, silica gel, Sargassum duplicatum, immobilization

  14. Synthesis, Crystal Structure, and Magnetic Properties of a New Mixed Metal (Co(II), Ni(II)) Cubane.

    Science.gov (United States)

    Elmehdawi, Ramadan Mohamed; El-Kaheli, Mohamed Nasir; Abuhmaiera, Ramadan Gamodi; Treish, Fathia Ali; Ben Younes, Mufida El Mabruk; Bazzicalupi, Carla; Guerri, Annalisa; Caneschi, Andrea; Amjad, Asma

    2017-02-14

    The mixed Co(II)/Ni(II) complex, [Co2.67Ni1.33L₄(CH₃COO)₂][BPh₄]₂·0.75H₂O where HL = 4-(salicylaldimine)antipyrine, was isolated as an orange solid from the reaction of 4-(salicylaldimine)antipyrine, with mixed cobalt(II) acetate and nickel(II) acetate in ethanol. The complex was characterized by Frustrated Total Internal Reflection (FTIR), UltraViolet Visible spectroscopy (UV-Vis), X-ray single crystal diffraction, and by elemental analysis. The complex is composed of two symmetry independent cationic units, A and B. The two units are essentially isostructural; nevertheless, small differences exist between them. The units contain four metal atoms, arranged at the corners of a distorted cubane-like core alternately with phenoxy oxygen of the Schiff base. The overall eight corners occupied by metal ions in the asymmetric unit are shared between cobalt and nickel in a 5.33:2.67 ratio. Each metal divalent cation binds three coordinated sites from the corresponding tridentate Schiff base ligand, the fourth one is bound by the acetate oxygen, the fifth and the sixth donor sites come from the phenolate oxygens of other Schiff base ligands. Intermolecular hydrogen bonds join the complexes to the water molecules present in the crystal packing. The magnetic characterization was carried out for this new complex and for its isostructural counterpart containing only cobalt ions. The magnetic measurements for the cobalt(II)/nickel(II) mixed compound indicate either antiferromagnetic interactions among the two cubanes or an anisotropic contribution, whereas a ferromagnetic interaction is observed within the cubane, for both the complexes, as expected by geometrical considerations. A comparison between the magnetic properties of the pure cobalt(II) derivative and similar systems discussed in literature, is presented.

  15. Synthesis, Crystal Structure, and Magnetic Properties of a New Mixed Metal (Co(II, Ni(II Cubane

    Directory of Open Access Journals (Sweden)

    Ramadan Mohamed Elmehdawi

    2017-02-01

    Full Text Available The mixed Co(II/Ni(II complex, [Co2.67Ni1.33L4(CH3COO2][BPh4]2·0.75H2O where HL = 4-(salicylaldimineantipyrine, was isolated as an orange solid from the reaction of 4-(salicylaldimineantipyrine, with mixed cobalt(II acetate and nickel(II acetate in ethanol. The complex was characterized by Frustrated Total Internal Reflection (FTIR, UltraViolet Visible spectroscopy (UV-Vis, X-ray single crystal diffraction, and by elemental analysis. The complex is composed of two symmetry independent cationic units, A and B. The two units are essentially isostructural; nevertheless, small differences exist between them. The units contain four metal atoms, arranged at the corners of a distorted cubane-like core alternately with phenoxy oxygen of the Schiff base. The overall eight corners occupied by metal ions in the asymmetric unit are shared between cobalt and nickel in a 5.33:2.67 ratio. Each metal divalent cation binds three coordinated sites from the corresponding tridentate Schiff base ligand, the fourth one is bound by the acetate oxygen, the fifth and the sixth donor sites come from the phenolate oxygens of other Schiff base ligands. Intermolecular hydrogen bonds join the complexes to the water molecules present in the crystal packing. The magnetic characterization was carried out for this new complex and for its isostructural counterpart containing only cobalt ions. The magnetic measurements for the cobalt(II/nickel(II mixed compound indicate either antiferromagnetic interactions among the two cubanes or an anisotropic contribution, whereas a ferromagnetic interaction is observed within the cubane, for both the complexes, as expected by geometrical considerations. A comparison between the magnetic properties of the pure cobalt(II derivative and similar systems discussed in literature, is presented.

  16. Electronic Structure of Rare-Earth Metals. II. Positron Annihilation

    DEFF Research Database (Denmark)

    Williams, R. W.; Mackintosh, Allan

    1968-01-01

    The angular correlation of the photons emitted when positrons annihilate with electrons has been studied in single crystals of the rare-earth metals Y, Gd, Tb, Dy, Ho, and Er, and in a single crystal of an equiatomic alloy of Ho and Er. A comparison of the results for Y with the calculations...... of Loucks shows that the independent-particle model gives a good first approximation to the angular distribution, although correlation effects probably smear out some of the structure. The angular distributions from the heavy rare-earth metals are very similar to that from Y and can be understood...... surface normal to the c axis. The same aspects of the Fermi surface are believed to be important in determining the stability of the periodic magnetic structures formed in some of the metals, and there is a strong correlation between the structure in the angular distribution and the magnetic properties...

  17. Influence of Environmental Factors and Relationships between Vanadium, Chromium, and Calcium in Human Bone

    Directory of Open Access Journals (Sweden)

    Natalia Lanocha-Arendarczyk

    2016-01-01

    Full Text Available The aim of this study was to investigate the impact of environmental factors on the concentrations of vanadium (V, chromium (Cr, and calcium (Ca and to examine the synergistic or antagonistic relationships between these metals, in cartilage (C, cortical bone (CB, and spongy bone (SB samples obtained following hip joint surgery on patients with osteoarthritis in NW Poland. We found significantly higher concentrations of V and Cr in spongy bone in patients who consumed game meat and also those with prosthetic implants. Chromium levels were significantly lower in patients with kidney diseases. The greatest positive correlations were found between spongy bone V and (i the amount of consumed beer and (ii seafood diet. Correlation analysis also showed a significant correlation between Cr levels and seafood diet. To a certain extent these results indicate that the concentrations of V, Cr, and Ca in the human hip joint tissues are connected with occupational exposure, kidney diseases, diet containing game meat, sea food, beer, and the presence of implants. Furthermore, we noted new types of interactions in specific parts of the femoral head. Vanadium may contribute to the lower bone Ca levels, especially in the external parts (cartilage and cortical bone.

  18. Axial coordination in nickel and vanadium porphyrins: Transient and difference raman spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Shelnutt, J.; Alston, K.; Findsen, E.; Ondrias, M.

    1986-04-01

    Nickel and vanadium tetrapyrroles occurring in coal and petroleum are of biological origin and their present day molecular structures provide a valuable chemical fossil marker of the diagenesis of the deposits. Both Ni- and V-porphyrins add axial ligands at the metal site. The authors have investigated the equilibrium properties and nanosecond dynamics of axial ligation in Ni(II)- and V(IV)-porphyrin complexes, Ni-porphyrin-reconstituted heme proteins, and Ni-porphyrin polymers using resonance Raman spectroscopy. The state of axial coordination is recognized by characteristic frequencies of Raman oxidation-state and core-size marker lines arising from the vibrations of the porphyrin ring, and the frequencies distinguish between 4-, 5-, and 6-coordination. For the Ni-porphyrins, 4- and 6-coordinate species are observed in coordinating solvents, while 5-coordinate Ni occurs only in the protein matrix. The axial ligand-Ni stretching mode frequency is influenced by the conformation of the protein matrix. Ligand affinity is affected by porphyrin structure, ligand basicity, and the porphyrin's environment. The authors also investigated photoinduced ligand-release and ligand binding kinetics using transient Raman spectroscopy. The protein matrix has a strong influence on the kinetics of ligand rebinding. For vanadium porphyrins, similar shifts in the marker lines characterize 5- and 6-coordinate forms.

  19. Influence of Environmental Factors and Relationships between Vanadium, Chromium, and Calcium in Human Bone.

    Science.gov (United States)

    Lanocha-Arendarczyk, Natalia; Kosik-Bogacka, Danuta I; Kalisinska, Elzbieta; Sokolowski, Sebastian; Kolodziej, Lukasz; Budis, Halina; Safranow, Krzysztof; Kot, Karolina; Ciosek, Zaneta; Tomska, Natalia; Galant, Katarzyna

    2016-01-01

    The aim of this study was to investigate the impact of environmental factors on the concentrations of vanadium (V), chromium (Cr), and calcium (Ca) and to examine the synergistic or antagonistic relationships between these metals, in cartilage (C), cortical bone (CB), and spongy bone (SB) samples obtained following hip joint surgery on patients with osteoarthritis in NW Poland. We found significantly higher concentrations of V and Cr in spongy bone in patients who consumed game meat and also those with prosthetic implants. Chromium levels were significantly lower in patients with kidney diseases. The greatest positive correlations were found between spongy bone V and (i) the amount of consumed beer and (ii) seafood diet. Correlation analysis also showed a significant correlation between Cr levels and seafood diet. To a certain extent these results indicate that the concentrations of V, Cr, and Ca in the human hip joint tissues are connected with occupational exposure, kidney diseases, diet containing game meat, sea food, beer, and the presence of implants. Furthermore, we noted new types of interactions in specific parts of the femoral head. Vanadium may contribute to the lower bone Ca levels, especially in the external parts (cartilage and cortical bone).

  20. Design, spectral characterization and biological studies of transition metal(II) complexes with triazole Schiff bases

    Science.gov (United States)

    Hanif, Muhammad; Chohan, Zahid H.

    2013-03-01

    A new series of three biologically active triazole derived Schiff base ligands L1-L3 have been synthesized in equimolar reaction of 3-amino-1H-1,2,4-triazole with pyrrol-2-carboxaldehyde, 4-bromo-thiophene-2-carboxaldehyde, and 5-iodo-2-hydroxy benzaldehyde. The prepared Schiff bases were used for further complex formation reaction with different metal elements like Co(II), Ni(II), Cu(II) and Zn(II) as chlorides by using a molar ratio of ligand:metal as 2:1. The structure and bonding nature of all the compounds were identified by their physical, spectral and analytical data. All the metal(II) complexes possessed an octahedral geometry except the Cu(II) complexes which showed a distorted octahedral geometry. All the synthesized compounds, were studied for their in vitro antibacterial, and antifungal activities, against four Gram-negative (Escherichia coli, Shigella sonnei, Pseudomonas aeruginosa and Salmonella typhi) and two Gram-positive (Bacillus subtilis and Staphylococcus aureus) bacterial strains and against six fungal strains (Trichophyton longifusus, Candida albicans, Aspergillus flavus, Microsporum canis, Fusarium solani and Candida glabrata) by using agar-well diffusion method. It has been shown that all the synthesized compounds showed moderate to significant antibacterial activity against one or more bacterial strains. In vitro Brine Shrimp bioassay was also carried out to investigate the cytotoxic properties of these compounds. The data also revealed that the metal complexes showed better activity than the ligands due to chelation/coordination.

  1. Allergic reaction to vanadium causes a diffuse eczematous eruption and titanium alloy orthopedic implant failure.

    Science.gov (United States)

    Engelhart, Sally; Segal, Robert J

    2017-04-01

    Allergy as a cause of adverse outcomes in patients with implanted orthopedic hardware is controversial. Allergy to titanium-based implants has not been well researched, as titanium is traditionally thought to be inert. We highlight the case of a patient who developed systemic dermatitis and implant failure after surgical placement of a titanium alloy (Ti6Al4V) plate in the left foot. The hardware was removed and the eruption cleared in the following weeks. The plate and screws were submitted for metal analysis. The elemental composition of both the plate and screws included 3 major elements-titanium, aluminum, and vanadium-as well as trace elements. Metal analysis revealed that the plate and screws had different microstructures, and electrochemical studies demonstrated that galvanic corrosion could have occurred between the plate and screws due to their different microstructures, contributing to the release of vanadium in vivo. The patient was patch tested with several metals including components of the implant and had a positive patch test reaction only to vanadium trichloride. These findings support a diagnosis of vanadium allergy and suggests that clinicians should consider including vanadium when patch testing patients with a suspected allergic reaction to vanadium-containing implants.

  2. Transition metal coordination chemistry ofN,N-bis(2-{pyrid-2-ylethyl})hydroxylamine.

    Science.gov (United States)

    Belock, Christopher W; Cetin, Anil; Barone, Natalie V; Ziegler, Christopher J

    2008-08-18

    Although directly relevant to metal mediated biological nitrification as well as the coordination chemistry of peroxide, the metal complexes of hydroxylamines and their functionalized variants remain largely unexplored. The chelating hydroxylamine ligand N,N-bis(2-{pyrid-2-ylethyl})hydroxylamine can be readily generated via a solvent free reaction in high purity; however, the ligand is prone to decomposition which can hamper metal reaction. N,N-bis(2-{pyrid-2-ylethyl})hydroxylamine forms stable complexes with chromium(III), manganese(II), nickel(II), and cadmium(II) ions, coordinating in a side-on mode in the case of chromium and via the nitrogen in the case of the latter three metal ions. The hydroxylamine ligand can also be reduced to form N,N-bis(2-{pyrid-2-ylethyl})amine upon exposure to a stoichiometric amount of the metal salts cobalt(II) nitrate, vanadium(III) chloride, and iron(II) chloride. In the reaction with cobalt nitrate, the reduced ligand then chelates to the metal to form [N,N-bis(2-{pyrid-2-ylethyl})amine]dinitrocobalt(II). Upon reaction with vanadium(III) chloride and iron(III) chloride, the reduced ligand is isolated as the protonated free base, resulting from a metal-mediated decomposition reaction.

  3. A new Mannich base and its transition metal (II) complexes ...

    Indian Academy of Sciences (India)

    The monomeric and non-electrolytic nature of the complexes is evidenced by their magnetic susceptibility and low conductance data. The electrochemical property of the ligand and its complexes in acetonitrile solution was studied by cyclic voltammetry. The X-band ESR spectra of the Cu(II) complex in DMSO at 300 and 77 ...

  4. Selective extraction of vanadium from the APV-precipitated waste water

    Science.gov (United States)

    Li, Cui; Li, Hong-Yi; Tu, Chun-Bin; Zhang, Tao; Fang, Hai-Xing; Xie, Bing

    In the process of precipitating ammonium polyvanadate (APV) to produce vanadium pentoxide in Pan-steel in China, rest waste water usually contains about 24 333mg/L V(V), 2 100g/L Cr(VI),20 500mg/L Si(IV) and 20 100g/L Na2SO4. In order to recover valuable and also toxic metal ions contained in the waste water, effective extraction method of using anion exchange resin was realized to extract Vanadium selectively, leading to effective separation between vanadium and chromium. To ensure vanadium was absorbed by the resin, V(V) and Cr(VI) were reduced to V(IV) and Cr(III) by NaHSO3, respectively, and then V(IV) was oxidized by H2O2 to V(V) anions. Effects of temperature, solution pH, concentration of ions and absorbing time on vanadium absorption rate were investigated. Chromium was precipitated from rest solution while vanadium was eluted from resin by NaOH solution and then precipitated. Results showed that vanadium recovery of 73% could be obtained in optimized condition. The resin could be regenerated by 3% hydrochloric acid, which indicated the recyclability of the resin and thus low cost of this established method.

  5. Large Spin Hall Angle in Vanadium Film

    Science.gov (United States)

    Wang, Tao; Fan, Xin; Wang, Wenrui; Xie, Yunsong; Warsi, Muhammad A.; Wu, Jun; Chen, Yunpeng; Lorenz, Virginia O.; Xiao, John Q.

    We report the large spin Hall angle observed in Vanadium film with small grain size and distorted lattice parameter. The spin Hall angle is quantified by measuring current-induced spin-orbit torque in V/CoFeB bilayer using optical spin torque magnetometer based on polar magneto-optical Kerr effect (MOKE). The spin Hall angle as large as θSH = -0.071 has been observed in V/CoFeB bilayer Structural analysis, using X-ray diffraction (XRD), transmission electron microscopy (TEM) and selected area electron diffraction (SAED), confirms films grown at room temperature have very small grain size and enlarged lattice parameter. The Vanadium films with distorted crystal structure also have high resistivity (>200 μΩ cm) and long spin diffusion length (~16.3 nm) measured via spin pumping experiment. This finding of spin Hall effect enhancement in more disordered structure will provide insights for understanding and exploiting materials with strong spin orbit interaction, especially in light 3d transition metals which promise long spin diffusion length.

  6. Adsorption of Cu(II), Zn(II), Cd(II) and Pb(II) by dead Avena fatua biomass and the effect of these metals on their growth.

    Science.gov (United States)

    Areco, María Mar; Saleh-Medina, Leila; Trinelli, María Alcira; Marco-Brown, Jose Luis; Dos Santos Afonso, María

    2013-10-01

    The biosorption of copper(II), zinc(II), cadmium(II) and lead(II) from aqueous solutions by dead Avena fatua biomass and the effect of these metals on the growth of this wild oat were investigated. Pseudo-first- and second-order and intra-particle diffusion models were applied to describe the kinetic data and to evaluate the rate constants. The adsorption kinetics of all the metals follows a pseudo-second-order model. The adsorption capacity was determined, and the Freundlich and Langmuir models were applied. The experimental data obtained for all the metals are best described by the Langmuir model. A. fatua was characterized using scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDS), and zeta potential. The results obtained evidence the presence of Zn(II), Cu(II), Cd(II) or Pb(II) on the surface of the weed. The growth of A. fatua was affected by the presence of all metals. The decrease in the growth rate with increasing metal concentration was more noticeable for zinc. Copyright © 2013 Elsevier B.V. All rights reserved.

  7. Symmetry Relationship and Strain-Induced Transitions between Semiconducting (M1 and M2) and Metallic (R) Phases of Vanadium Dioxide

    Energy Technology Data Exchange (ETDEWEB)

    Budai, John D [ORNL; Ivanov, Ilia N [ORNL; Kalinin, Sergei V [ORNL; Kolmakov, Andrei [ORNL; Luk' yanchuk, Prof. Igor A. [University of Picardie Jules Verne, Amiens, France; Strelcov, Evgheni [Southern Illinois University; Tischler, Jonathan Zachary [ORNL; Tselev, Alexander [ORNL

    2010-01-01

    The ability to synthesize VO{sub 2} in the form of single-crystalline nanobeams and nano- and microcrystals uncovered a number of previously unknown aspects of the metal-insulator transition (MIT) in this oxide. In particular, several reports demonstrated that the MIT can proceed through competition between two monoclinic (insulating) phases M1 and M2 and the tetragonal (metallic) R phase under influence of strain. The nature of such phase behavior has been not identified. Here we show that the competition between M1 and M2 phases is purely lattice-symmetry-driven. Within the framework of the Ginzburg-Landau formalism, both M phases correspond to different directions of the same four-component structural order parameter, and as a consequence, the M2 phase can appear under a small perturbation of the M1 structure such as doping or stress. We analyze the strain-controlled phase diagram of VO{sub 2} in the vicinity of the R-M2-M1 triple point using the Ginzburg-Landau formalism and identify and experimentally verify the pathways for strain-control of the transition. These insights open the door toward more systematic approaches to synthesis of VO{sub 2} nanostructures in desired phase states and to use of external fields in the control of the VO{sub 2} phase states. Additionally, we report observation of the triclinic T phase at the heterophase domain boundaries in strained quasi-two-dimensional VO{sub 2} nanoplatelets, and theoretically predict phases that have not been previously observed.

  8. Transition Metal(II) Complexes with Cefotaxime-Derived Schiff Base: Synthesis, Characterization, and Antimicrobial Studies

    Science.gov (United States)

    Amzoiu, Emilia; Spînu, Cezar Ionuţ

    2014-01-01

    New [ML2(H2O)2] complexes, where M = Co(II), Ni(II), Cu(II), and Zn(II) while L corresponds to the Schiff base ligand, were synthesized by condensation of cefotaxime with salicylaldehyde in situ in the presence of divalent metal salts in ethanolic medium. The complexes were characterized by elemental analyses, conductance, and magnetic measurements, as well as by IR and UV-Vis spectroscopy. The low values of the molar conductance indicate nonelectrolyte type of complexes. Based on spectral data and magnetic moments, an octahedral geometry may be proposed for Co(II), Ni(II), and Zn(II) complexes while a tetragonal geometry for Cu(II) complex. Molecular structure of the Schiff base ligand and its complexes were studied using programs dedicated to chemical modeling and quantomolecular calculation of chemical properties. All the synthesized complexes were tested for in vitro antibacterial activity against some pathogenic bacterial strains, namely Escherichia coli, Klebsiella pneumoniae, Pseudomonas aeruginosa, Bacillus subtilis, and Staphylococcus aureus. The MIC values shown by the complexes against these bacterial strains revealed that the metal complexes possess superior antibacterial activity than the Schiff base. PMID:24688454

  9. Ternary complexes between adenosine 5' -triphosphoric acid, 2,2'-bipyridyl and the divalent metal ions manganese (II), cobalt (II), copper (II), and zinc (II). Preparation and physiochemical properties.

    Science.gov (United States)

    Cini, R; Orioli, P

    1981-04-01

    A series of ternary complexes between adenosine 5'-triphosphoric acid (ATP), 2,2'-bipyridyl, and the transition metal ions manganese (II), cobalt(II), copper (II), and zinc(II) in the ratio 1:1:1 have been prepared. The solid compounds are crystalline and can be formulated as [M(II)-H2ATP-2,2'-Bipyridyl]2 . 4H2O (MATPbipy). X-ray powder patterns show them to be all isomorphous. Potentiometric titrations in aqueous solutions are in agreement with the presence of two ionizable protons. Ultraviolet and visible spectra, epr, and magnetic susceptibility measurements suggest that the metal ions have a high-spin distorted octahedral coordination. From infrared spectra it can be deduced that ATP coordinates to the metal only through the oxygen atoms of the phosphate groups. These compounds, which are particularly stable towards hydrolysis, form possible models for ATP transport in biological fluids.

  10. On the connection between mode II and mode III effective thresholds in metals

    Directory of Open Access Journals (Sweden)

    Tomáš Vojtek

    2017-07-01

    Full Text Available . Closure-free long cracks under the remote mode III loading grow in a more complicated way than those under the remote mode II. For bcc metals, a coplanar in-plane spreading of tongues driven by the local mode II loading components at crack-front asperities prevails while twisting of crack-front segments to mode I, often leading to factory-roof morphology, is typical for other materials. In bcc metals, therefore, the formulation of a quantitative relationship connecting effective thresholds in modes II and III demands to calculate the local mode II components of stress intensity factors at typical asperities of a crack front loaded in the remote mode III. Therefore, a numerical model of a serrated crack front was created and the results were compared with experimentally determined ratio of mode II and III effective thresholds for the ARMCO iron. Although the calculated crack-front roughness needs an experimental verification, the preliminary results indicate that the model can provide a quantitative explanation of the experimentally observed ratio of mode II and mode III effective thresholds in bcc metals.

  11. Acute toxicity of vanadium to two species of freshwater fish

    Energy Technology Data Exchange (ETDEWEB)

    Knudtson, B.K.

    1979-09-01

    Goldfish (Carassius auratus) and guppies (Lebistes reticulatus) were the two freshwater, thermophilous fishes chosen for use in this study. These species were selected for the following reasons: (1) low cost/individual, (2) ready availability, (3) ease of care and handling, (4) suspected differences between the two species in their responses to this metal, and (5) the usefulness of both as generalized models for the response of freshwater and marine fishes to vanadium.

  12. Sulfur-vanadium oxide gel composites as thin film cathodes for rechargeable lithium batteries

    Energy Technology Data Exchange (ETDEWEB)

    Mukherjee, S.P.; Gavrilov, A.B.; Skotheim, T.A.

    1998-07-01

    A class of novel electroactive cathode materials based on composites produced from elemental sulfur and vanadium oxide xerogels or aerogels has been developed as models for lithium battery applications. The use of elemental sulfur in rechargeable lithium batteries has been hindered due to certain limitations such as, very low electronic conductivity and the out-diffusion of polysulfides during the cycling process which reduces the cycling efficiency. Vanadium oxide xerogels and aerogels have certain desirable characteristic physico-chemical properties, such as, high surface areas with nono-scale interconnecting porosity, high electronic conductivity, non- or nanocrystallinity, and oxidation reduction catalytic activity. Since these properties may improve the performance of sulfur based rechargeable batteries, a family of composite cathodes containing elemental sulfur and vanadium oxide gels were produced. The performance of the composites cathodes, in thin film form, were evaluated in coin cells and AA cells with metallic lithium anodes and liquid electrolytes. The multifunctional role of vanadium oxide gels on the cell performance of the cells having composite cathodes has been qualitatively explored. Results indicate that the cathodes having xerogel composites based on vanadium oxide sol from vanadium oxide isopropoxide can be made with high sulfur content (80 wt %) and with low carbon content (5 wt %) and without any polymer binder. This shows the contribution of adhesive properties and electronic conductivity of vanadium oxide xerogels. A significant suppression of polysulfide out-diffusion is observed with appropriate processing of the composite cathodes. It is anticipated that the nanoscale interconnecting porosity of gels plays an important role in this behavior. An excellent rate capability is observed with the vanadium-oxide sulfur composite cathodes indicating the contribution of intrinsic electrochemical properties of the vanadium oxide.

  13. Influences of Mn(II) and V(IV) on Bacterial Surface Chemistry and Metal Reactivity

    Science.gov (United States)

    French, S.; Fakra, S.; Glasauer, S.

    2009-05-01

    Microorganisms in terrestrial and marine environments are typically bathed in solutions that contain a range of metal ions, toxic and beneficial. Bacteria such as Shewanella putrefaciens CN32 are metabolically versatile in their respiration, and the reductive dissolution of widely dispersed metals such as Fe(III), Mn(IV), or V(V) can present unique challenges if nearby bodies of water are used for irrigation or drinking. In redox transition zones, dissimilatory metal reduction (DMR) by bacteria can lead to generation of high concentrations of soluble metals. It has been shown that metals will associate with negatively charged bacterial membranes, and the mechanisms of metal reduction are well defined for many species of bacteria. The interaction of metals with the cell wall during DMR is, however, not well documented; very little is known about the interaction of respired transition metals with membrane lipids. Furthermore, bacterial surfaces tend to change in response to their immediate environments. Variations in conditions such as oxygen or metal presence may affect surface component composition, including availability of metal reactive sites. Our research seeks to characterize the biochemical nature of metal-membrane interactions, as well as identify the unique changes at the cell surface that arise as a result of metal presence in their environments. We have utilized scanning transmission X-ray microscopy (STXM) to examine the dynamics of soluble Mn(II) and V(IV) interactions with purified bacterial membranes rather than whole cells. This prevents intracellular interferences, and allows for near edge X-ray absorption fine structure (NEXAFS) spectroscopic analyses of cell surface and surface-associated components. NEXAFS spectra for carbon, nitrogen, and oxygen edges indicate that Mn(II) and V(IV) induce biological modifications of the cell membrane in both aerobic and anaerobic conditions. These changes depend not only on the metal, but also on the presence of

  14. Expressed sequence tag analysis of vanadocytes in a vanadium-rich ascidian, Ascidia sydneiensis samea.

    Science.gov (United States)

    Yamaguchi, Nobuo; Kamino, Kei; Ueki, Tatsuya; Michibata, Hitoshi

    2004-01-01

    Some species in the family Ascidiidae accumulate vanadium at concentrations in excess of 350 mM, which corresponds to about 10(7) times higher than that in seawater. In these species signet ring cells, with a single huge vacuole in which vanadium ion is contained, function as vanadium-accumulating cells, vanadocytes. To investigate the mechanism underlying this phenomenon, we performed an expressed sequence tag (EST) analysis of a complementary DNA library from vanadocytes of a vanadium-rich ascidian, Ascidia sydneiensis samea. We determined the nucleotide sequences of 1000 ESTs and performed a BLAST analysis against the SwissProt database. We found 93 clones of metal-related gene homologues, including the ferritin heavy subunit, hemocyanin, and metallothionein. Two ESTs, in particular, exhibited significant similarity to vanabins that have been extracted from A. sydneiensis samea blood cells as low molecular weight vanadium-binding proteins. We have named the genes encoding these ESTs vanabin3 and vanabin4. Immobilized metal ion affinity chromatography revealed that these novel vanabin homologues bind vanadium(IV) ions.

  15. Trace Metal Levels in Water and Sediment from the Sakumo II and ...

    African Journals Online (AJOL)

    , Ghana. CK Tay, R Asmah, CA Biney. Abstract. Trace metal (Cu, Zn, Pb, Mn, Fe and Cd) levels were determined in water and sediment from the Sakumo II and Muni lagoons and the Mamahuma and Gbagbla Ankonu feeder streams, which ...

  16. Two different zinc (II)-aqua complexes held up by a metal-oxide ...

    Indian Academy of Sciences (India)

    Home; Journals; Journal of Chemical Sciences; Volume 120; Issue 1. Two different zinc(II)-aqua complexes held up by a metal-oxide based support: Synthesis, crystal ... Keywords. Inorganic-organic hybrid material; polyoxometalate supported zinc complexes; crystal structure; supramolecular interactions; catalytic activity.

  17. Kinetic modeling of metal ion transport for desorption of Pb(II) ion ...

    African Journals Online (AJOL)

    The kinetics of desorption of lead (II) ion from metal loaded adsorbent of mercaptoacetic acid modified and unmodified oil palm (Elaeis guineensis) fruit fiber was studied using different solutions, at different contact times. At the end of 25 minutes, 79.19%, 75.99%, 57.14%, 50.56% and 32.72% of Pb2+ were desorbed using ...

  18. Mechanical, thermal and laser damage threshold analyses of II group metal complexes of thiourea

    Energy Technology Data Exchange (ETDEWEB)

    Dhanuskodi, S., E-mail: dhanus2k3@yahoo.com [School of Physics, Bharathidasan University, Tiruchirappalli 620 024, Tamil Nadu (India); Sabari Girisun, T.C. [School of Physics, Bharathidasan University, Tiruchirappalli 620 024, Tamil Nadu (India); Department of Physics, Bishop Heber College, Tiruchirappalli 620 017, Tamil Nadu (India); Bhagavannarayana, G. [Material Characterization Division, National Physical laboratory, New Delhi 110 012 (India); Uma, S.; Phillip, J. [Sophisticated Test and Instrumentation Center, Cochin University of Science and Technology, Cochin 682 022 (India)

    2011-04-15

    Research highlights: {yields} The role of the Group II metal ions in improving the stability is discussed. {yields} BTCC has a higher heat capacity than BTZC. {yields} Elastic stiffness is found to be higher for BTCC than BTZC. {yields} Microscopy studies confirm the damage is due to thermo-chemical ablation. {yields} BTCC has a higher laser damage threshold than BTZC. - Abstract: Single crystals of thiourea metal complexes with selected Group II metal ions, Zinc and Cadmium, have been grown by solvent evaporation technique. The crystals grown are bisthiourea zinc chloride (BTZC) and bisthiourea cadmium chloride (BTCC). Following an improved photopyroelectric technique, the thermal transport properties have been determined. It is found that BTCC has a higher heat capacity (304.09 J kg{sup -1} K{sup -1}) than BTZC (255.24 J kg{sup -1} K{sup -1}), and hence BTCC has better thermal stability. Vicker's microhardness measurements reveal that these materials have reverse indentation size effect and belong to the category of soft materials. Elastic stiffness is found to be higher for BTCC (1.57 GPa) than BTZC (0.76 GPa). The roles of the Group II metal ions in improving the mechanical and thermal stability of the metal complexes are discussed. Multi-shot laser damage studies on these materials reveal that BTCC has a higher laser damage threshold (15 GW cm{sup -2}) than BTZC (6 GW cm{sup -2}).

  19. A Disposable Alkaline Phosphatase-Based Biosensor for Vanadium Chronoamperometric Determination

    Science.gov (United States)

    Alvarado-Gámez, Ana Lorena; Alonso-Lomillo, María Asunción; Domínguez-Renedo, Olga; Arcos-Martínez, María Julia

    2014-01-01

    A chronoamperometric method for vanadium ion determination, based on the inhibition of the enzyme alkaline phosphatase, is reported. Screen-printed carbon electrodes modified with gold nanoparticles were used as transducers for the immobilization of the enzyme. The enzymatic activity over 4-nitrophenyl phosphate sodium salt is affected by vanadium ions, which results in a decrease in the chronoamperometric current registered. The developed method has a detection limit of 0.39 ± 0.06 μM, a repeatability of 7.7% (n = 4) and a reproducibility of 8% (n = 3). A study of the possible interferences shows that the presence of Mo(VI), Cr(III), Ca(II) and W(VI), may affect vanadium determination at concentration higher than 1.0 mM. The method was successfully applied to the determination of vanadium in spiked tap water. PMID:24569772

  20. A Disposable Alkaline Phosphatase-Based Biosensor for Vanadium Chronoamperometric Determination

    Directory of Open Access Journals (Sweden)

    Ana Lorena Alvarado-Gámez

    2014-02-01

    Full Text Available A chronoamperometric method for vanadium ion determination, based on the inhibition of the enzyme alkaline phosphatase, is reported. Screen-printed carbon electrodes modified with gold nanoparticles were used as transducers for the immobilization of the enzyme. The enzymatic activity over 4-nitrophenyl phosphate sodium salt is affected by vanadium ions, which results in a decrease in the chronoamperometric current registered. The developed method has a detection limit of 0.39 ± 0.06 µM, a repeatability of 7.7% (n = 4 and a reproducibility of 8% (n = 3. A study of the possible interferences shows that the presence of Mo(VI, Cr(III, Ca(II and W(VI, may affect vanadium determination at concentration higher than 1.0 mM. The method was successfully applied to the determination of vanadium in spiked tap water.

  1. Determination of vanadium accumulation in onion root cells (Allium cepa L.) and its correlation with toxicity.

    Science.gov (United States)

    Marcano, Letty; Carruyo, Ingrid; Fernández, Yusmary; Montiel, Xiomara; Torrealba, Zaida

    2006-08-01

    The vanadium is a metal that presents great interest from the toxicological point of view, because of the numerous alterations that can take place in different biological systems. This work evaluated the capacity of vanadium accumulation and its correlation with genotoxic effects in root cells of Allium cepa L. The bulbs were cultivated in renovated filtered water each 24 h, at a temperature of 25 +/- 0.5 degrees C, in darkness and constant aeration. Treatments were carried out under the same experimental conditions, using water solutions of vanadium of 25, 50, 75 and 100 microg/g for 0, 12, 24, 48 and 72 h. A control was carried out where metal solution was substituted by distilled water. After the treatment, the meristems were fixed with alcohol--acetic acid (3:1) and stained according to the technique of Feulgen. The capacity of accumulation was determined by GFAAS. The analysis of the results revealed an accumulation of the metal for all times and concentrations. No correlation was presented among vanadium accumulation, growth and mitotic index; however, positive correlation was given with the induction of chromosomic aberrations. In conclusion, vanadium is able to induce cytotoxic effect in the exposed roots, but only genotoxic effect was correlated with metal accumulation.

  2. Test of the metallization of the EMCM for Belle II pixel detector

    Energy Technology Data Exchange (ETDEWEB)

    Klose, Daniel; Andricek, Ladislav; Koffmane, Christian; Ninkovic, Jelena; Richter, Rainer; Schopper, Florian; Wassatsch, Andreas [Halbleiterlabor der Max-Planck-Gesellschaft, Muenchen (Germany); Avella, Paola; Kiesling, Christian; Moser, Hans-Guenther; Mueller, Felix; Valentan, Manfred [Max-Planck-Institut fuer Physik, Muenchen (Germany); Collaboration: Belle II-Collaboration

    2015-07-01

    In order to achieve excellent single point resolution and to keep multiple scattering at a minimum with low material budget, DEPFET sensors were chosen as inner two layers of the VXD (Vertex Detector) for the Belle II experiment. DEPFET sensors also offer a low power consumption and a high signal to noise ratio, even for thin sensors. The Electrical Multi-Chip Module (EMCM) was designed in the interest of studying especially the metal layer interconnectivity for the steering and regulation of the DEPFET matrix of the detectors for Belle II. The main goal of this study of the metal system is to get insights on the feasibility and reliability of the technology and collect information on its production yield. This study is done on wafer level. Specially designed test structures and testing strategies, developed to be able to identify all possible causes of reduction of the yield, are presented. Finally results obtained from the optimized metallization technology are shown.

  3. Physicochemical impact studies of gamma rays on "aspirin" analgesics drug and its metal complexes in solid form: Synthesis, spectroscopic and biological assessment of Ca(II), Mg(II), Sr(II) and Ba(II) aspirinate complexes

    Science.gov (United States)

    Refat, Moamen S.; Sharshar, T.; Elsabawy, Khaled M.; Heiba, Zein K.

    2013-09-01

    Metal aspirinate complexes, M2(Asp)4, where M is Mg(II), Ca(II), Sr(II) or Ba(II) are formed by refluxed of aspirin (Asp) with divalent non-transition metal ions of group (II) and characterized by elemental analysis and spectroscopic measurements (infrared, electronic, 1H NMR, Raman, X-ray powder diffraction and scanning electron microscopy). Elemental analysis of the chelates suggests the stoichiometry is 1:2 (metal:ligand). Infrared spectra of the complexes agree with the coordination to the central metal atom through three donation sites of two oxygen atoms of bridge bidentate carboxylate group and oxygen atom of sbnd Cdbnd O of acetyl group. Infrared spectra coupled with the results of elemental analyzes suggested a distorted octahedral structure for the M(II) aspirinate complexes. Gamma irradiation was tested as a method for stabilization of aspirin as well as their complexes. The effect of gamma irradiation, with dose of 80 Gy, on the properties of aspirinate complexes was studied. The aspirinate chelates have been screened for their in vitro antibacterial activity against four bacteria, gram-positive (Bacillus subtilis and Staphylococcus aureus) and gram-negative (Escherichia coli and Pseudomonas aeruginosa) and two strains of fungus (Aspergillus flavus and Candida albicans). The metal chelates were shown to possess more antibacterial activity than the free aspirin chelate.

  4. Characterization of Irradiated Metal Waste from the Pyrometallurgical Treatment of Used EBR-II Fuel

    Energy Technology Data Exchange (ETDEWEB)

    B.R. Westphal; K.C. Marsden; W.M. McCartin; S.M. Frank; D.D. Keiser, Jr.; T.S. Yoo; D. Vaden; D.G. Cummings; K.J. Bateman; J. J. Giglio; T. P. O' Holleran; P. A. Hahn; M. N. Patterson

    2013-03-01

    As part of the pyrometallurgical treatment of used Experimental Breeder Reactor-II fuel, a metal waste stream is generated consisting primarily of cladding hulls laden with fission products noble to the electrorefining process. Consolidation by melting at high temperature [1873 K (1600 degrees C)] has been developed to sequester the noble metal fission products (Zr, Mo, Tc, Ru, Rh, Te, and Pd) which remain in the iron-based cladding hulls. Zirconium from the uranium fuel alloy (U-10Zr) is also deposited on the hulls and forms Fe-Zr intermetallics which incorporate the noble metals as well as residual actinides during processing. Hence, Zr has been chosen as the primary indicator for consistency of the metal waste. Recently, the first production-scale metal waste ingot was generated and sampled to monitor Zr content for Fe-Zr intermetallic phase formation and validation of processing conditions. Chemical assay of the metal waste ingot revealed a homogeneous distribution of the noble metal fission products as well as the primary fuel constituents U and Zr. Microstructural characterization of the ingot confirmed the immobilization of the noble metals in the Fe-Zr intermetallic phase.

  5. Catalytic oxidations by vanadium complexes

    NARCIS (Netherlands)

    Ligtenbarg, A.G J; Hage, R.; Feringa, B.L.

    Vanadium haloperoxidases catalyse the oxidation of halides leading to halogenation of substrates or, in the absence of suitable substrates, to oxidation of hydrogen peroxide into singlet oxygen and water. Furthermore, V-haloperoxidases are capable to give enantioselective sulfoxidation under the

  6. Vanadium Compounds as PTP Inhibitors

    Directory of Open Access Journals (Sweden)

    Elsa Irving

    2017-12-01

    Full Text Available Phosphotyrosine signaling is regulated by the opposing actions of protein tyrosine kinases (PTKs and protein tyrosine phosphatases (PTPs. Here we discuss the potential of vanadium derivatives as PTP enzyme inhibitors and metallotherapeutics. We describe how vanadate in the V oxidized state is thought to inhibit PTPs, thus acting as a pan-inhibitor of this enzyme superfamily. We discuss recent developments in the biological and biochemical actions of more complex vanadium derivatives, including decavanadate and in particular the growing number of oxidovanadium compounds with organic ligands. Pre-clinical studies involving these compounds are discussed in the anti-diabetic and anti-cancer contexts. Although in many cases PTP inhibition has been implicated, it is also clear that many such compounds have further biochemical effects in cells. There also remain concerns surrounding off-target toxicities and long-term use of vanadium compounds in vivo in humans, hindering their progress through clinical trials. Despite these current misgivings, interest in these chemicals continues and many believe they could still have therapeutic potential. If so, we argue that this field would benefit from greater focus on improving the delivery and tissue targeting of vanadium compounds in order to minimize off-target toxicities. This may then harness their full therapeutic potential.

  7. Characterization of vanadium flow battery

    Energy Technology Data Exchange (ETDEWEB)

    Bindner, H.; Ekman, C.; Gehrke, O.; Isleifsson, F.

    2010-10-15

    This report summarizes the work done at Risoe DTU testing a vanadium flow battery as part of the project 'Characterisation of Vanadium Batteries' (ForskEl project 6555) with the partners PA Energy A/S and OI Electric A/S under the Danish PSO energy research program. A 15kW/120kWh vanadium battery has been installed as part of the distributed energy systems experimental facility, SYSLAB, at Risoe DTU. A test programme has been carried out to get hands-on experience with the technology, to characterize the battery from a power system point of view and to assess it with respect to integration of wind energy in the Danish power system. The battery has been in operation for 18 months. During time of operation the battery has not shown signs of degradation of performance. It has a round-trip efficiency at full load of approximately 60% (depending on temperature and SOC). The sources of the losses are power conversion in cell stacks/electrolyte, power converter, and auxiliary power consumption from pumps and controller. The response time for the battery is limited at 20kW/s by the ramp rate of the power converter. The battery can thus provide power and frequency support for the power system. Vanadium battery is a potential technology for storage based services to the power system provided investment and O and M cost are low enough and long term operation is documented. (Author)

  8. Structural and spectroscopic characterization of iron(II), cobalt(II), and nickel(II) ortho-dihalophenolate complexes: insights into metal-halogen secondary bonding.

    Science.gov (United States)

    Machonkin, Timothy E; Boshart, Monica D; Schofield, Jeremy A; Rodriguez, Meghan M; Grubel, Katarzyna; Rokhsana, Dalia; Brennessel, William W; Holland, Patrick L

    2014-09-15

    Metal complexes incorporating the tris(3,5-diphenylpyrazolyl)borate ligand (Tp(Ph2)) and ortho-dihalophenolates were synthesized and characterized in order to explore metal-halogen secondary bonding in biorelevant model complexes. The complexes Tp(Ph2)ML were synthesized and structurally characterized, where M was Fe(II), Co(II), or Ni(II) and L was either 2,6-dichloro- or 2,6-dibromophenolate. All six complexes exhibited metal-halogen secondary bonds in the solid state, with distances ranging from 2.56 Å for the Tp(Ph2)Ni(2,6-dichlorophenolate) complex to 2.88 Å for the Tp(Ph2)Fe(2,6-dibromophenolate) complex. Variable temperature NMR spectra of the Tp(Ph2)Co(2,6-dichlorophenolate) and Tp(Ph2)Ni(2,6-dichlorophenolate) complexes showed that rotation of the phenolate, which requires loss of the secondary bond, has an activation barrier of ~30 and ~37 kJ/mol, respectively. Density functional theory calculations support the presence of a barrier for disruption of the metal-halogen interaction during rotation of the phenolate. On the other hand, calculations using the spectroscopically calibrated angular overlap method suggest essentially no contribution of the halogen to the ligand-field splitting. Overall, these results provide the first quantitative measure of the strength of a metal-halogen secondary bond and demonstrate that it is a weak noncovalent interaction comparable in strength to a hydrogen bond. These results provide insight into the origin of the specificity of the enzyme 2,6-dichlorohydroquinone 1,2-dioxygenase (PcpA), which is specific for ortho-dihalohydroquinone substrates and phenol inhibitors.

  9. Reduction of aqueous transition metal species on the surfaces of Fe(II)-containing oxides

    Science.gov (United States)

    White, A.F.; Peterson, M.L.

    1996-01-01

    Experimental studies demonstrate that structural Fe(II) in magnetite and ilmenite heterogeneously reduce aqueous ferric, cupric, vanadate, and chromate ions at the oxide surfaces over a pH range of 1-7 at 25??C. For an aqueous transition metal m, such reactions are 3[Fe2+Fe3+2]O4(magnetite) + 2/nmz ??? 4[Fe3+2]O3(maghemite) + Fe2+ + 2/nmz-n and 3[Fe2+Ti]O3(ilmenite) + 2/nmz ??? Fe3+2Ti3O9(pseudorutile) + Fe2+ + 2/nmz-n, where z is the valance state and n is the charge transfer number. The half cell potential range for solid state oxidation [Fe(II)] ??? [Fe(III)] is -0.34 to -0.65 V, making structural Fe(II) a stronger reducing agent than aqueous Fe2+ (-0.77 V). Reduction rates for aqueous metal species are linear with time (up to 36 h), decrease with pH, and have rate constants between 0.1 and 3.3 ?? 10-10 mol m-2 s-1. Iron is released to solution both from the above reactions and from dissolution of the oxide surface. In the presence of chromate, Fe2+ is oxidized homogeneously in solution to Fe3+. X-ray photoelectron spectroscopy (XPS) denotes a Fe(III) oxide surface containing reduced Cr(III) and V(IV) species. Magnetite and ilmenite electrode potentials are insensitive to increases in divalent transition metals including Zn(II), Co(II), Mn(II), and Ni(II) and reduced V(IV) and Cr(III) but exhibit a log-linear concentration-potential response to Fe(III) and Cu(II). Complex positive electrode responses occur with increasing Cr(VI) and V(V) concentrations. Potential dynamic scans indicate that the high oxidation potential of dichromate is capable of suppressing the cathodic reductive dissolution of magnetite. Oxide electrode potentials are determined by the Fe(II)/Fe(III) composition of the oxide surface and respond to aqueous ion potentials which accelerate this oxidation process. Natural magnetite sands weathered under anoxic conditions are electrochemically reactive as demonstrated by rapid chromate reduction and the release of aqueous Fe(III) to experimental

  10. Removal of Vanadium(III) and Molybdenum(V) from Wastewater Using Posidonia oceanica (Tracheophyta) Biomass

    Science.gov (United States)

    Pennesi, Chiara; Totti, Cecilia; Beolchini, Francesca

    2013-01-01

    The use of dried and re-hydrated biomass of the seagrass Posidonia oceanica was investigated as an alternative and –low-cost biomaterial for removal of vanadium(III) and molybdenum(V) from wastewaters. Initial characterisation of this biomaterial identified carboxylic groups on the cuticle as potentially responsible for cation sorption, and confirmed the toxic-metal bioaccumulation. The combined effects on biosorption performance of equilibrium pH and metal concentrations were investigated in an ideal single-metal system and in more real-life multicomponent systems. There were either with one metal (vanadium or molybdenum) and sodium nitrate, as representative of high ionic strength systems, or with the two metals (vanadium and molybdenum). For the single-metal solutions, the optimum was at pH 3, where a significant proportion of vanadium was removed (ca. 70%) while there was ca. 40% adsorption of molybdenum. The data obtained from the more real-life multicomponent systems showed that biosorption of one metal was improved both by the presence of the other metal and by high ionic strength, suggesting a synergistic effect on biosorption rather than competition. There data ware used for the development of a simple multi-metal equilibrium model based on the non-competitive Langmuir approach, which was successfully fitted to experimental data and represents a useful support tool for the prediction of biosorption performance in such real-life systems. Overall, the results suggest that biomass of P. oceanica can be used as an efficient biosorbent for removal of vanadium(III) and molybdenum(V) from aqueous solutions. This process thus offers an eco-compatible solution for the reuse of the waste material of leaves that accumulate on the beach due to both human activities and to storms at sea. PMID:24204692

  11. Detection of Toxic Heavy Metal, Co(II) Trace via Voltammetry with Semiconductor Microelectrodes

    Science.gov (United States)

    Ly, Suw Young; Lee, Chang Hyun; Koo, Jae Mo

    2017-01-01

    The cobalt (Co(II)) ion is a main component of alloys and considered to be carcinogenic, especially due to the carcinogenic and toxicological effects in the aquatic environment. The toxic trace of the Co(II) detection was conducted using the infrared photodiode electrode (IPDE) using a working electrode, via the cyclic and square-wave anodic stripping voltammetry. The results indicated a sensitive oxidation peak current of Co(II) on the IPDE. Under the optimal conditions, the common-type glassy carbon, the metal platinum, the carbon paste, and the carbon fiber microelectrode were compared with the IPDE in the electrolyte using the standard Co(II). The IPDE was found to be far superior to the others. PMID:28503262

  12. The use of Apatite II™ to remove divalent metal ions zinc(II), lead(II), manganese(II) and iron(II) from water in passive treatment systems: column experiments.

    Science.gov (United States)

    Oliva, Josep; De Pablo, Joan; Cortina, José-Luis; Cama, Jordi; Ayora, Carlos

    2010-12-15

    The conventional passive treatments for remediation of acid mine drainage using calcite are not totally efficient in the removal of certain heavy metal ions. Although pH increases to 6-7 and promotes the precipitation of trivalent and some divalent metals as hydroxides and carbonates, the remaining concentrations of some divalent metals ions do not fulfill the environmental regulations. In this study, Apatite II™, a biogenic hydroxyapatite, is used as an alternative reactive material to remove Zn(II), Pb(II), Mn(II) and Fe(II). Apatite II™ reacted with acid water releasing phosphate and increasing pH up to 6.5-7, inducing metals to precipitate mainly as metal-phosphates: zinc precipitated as hopeite, Zn(3)(PO(4))(2)·4H(2)O, lead as pyromorfite, Pb(5)(PO(4))(3)OH, manganese as metaswitzerite, Mn(3)(PO(4))(2)·4H(2)O and iron as vivianite, Fe(3)(PO(4))(2)·8H(2)O. Thus, metal concentrations from 30 to 75 mg L(-1) in the inflowing water were depleted to values below 0.10 mg L(-1). Apatite II™ dissolution is sufficiently fast to treat flows as high as 50 m/a. For reactive grain size of 0.5-3mm, the treatment system ends due to coating of the grains by precipitates, especially when iron and manganese are present in the solution. Copyright © 2010 Elsevier B.V. All rights reserved.

  13. Liquid metal blanket module testing and design for ITER/TIBER II

    Energy Technology Data Exchange (ETDEWEB)

    Mattas, R.F.; Cha, Y.; Finn, P.A.; Majumdar, S.; Picologlou, B.; Stevens, H.; Turner, L.

    1988-05-01

    A major goal for ITER is the testing of nuclear components to demonstrate the integrated performance of the most attractive concepts that can lead to a commercial fusion reactor. As part of the ITER/TIBER II study, the test program and design of test models were examined for a number of blanket concepts. The work at Argonne National Laboratory focused on self-cooled liquid metal blankets. A test program for liquid metal blankets was developed based upon the ITER/TIBER II operating schedule and the specific data needs to resolve the key issues for liquid metals. Testing can begin early in reactor operation with liquid metal MHD tests to confirm predictive capability. Combined heat transfer/MHD tests can be performed during initial plasma operation. After acceptable heat transfer performance is verified, tests to determine the integrated high temperature performance in a neutron environment can begin. During the high availability phase operation, long term performance and reliability tests will be performed. It is envisioned that a companion test program will be conducted outside ITER to determine behavior under severe accident conditions and upper performance limits. A detailed design of a liquid metal test module and auxiliary equipment was also developed. The module followed the design of the TPSS blanket. Detailed analysis of the heat transfer and tritium systems were performed, and the overall layout of the systems was determined. In general, the blanket module appears to be capable of addressing most of the testing needs. 8 refs., 27 figs., 11 tabs.

  14. Mixed ligand complexes of alkaline earth metals: Part XII. Mg(II, Ca(II, Sr(II and Ba(II complexes with 5-chlorosalicylaldehyde and salicylaldehyde or hydroxyaromatic ketones

    Directory of Open Access Journals (Sweden)

    MITHLESH AGRAWAL

    2002-04-01

    Full Text Available The reactions of alkaline earth metal chlorides with 5-chlorosalicylaldehyde and salicylaldehyde, 2-hydroxyacetophenone or 2-hydroxypropiophenone have been carried out in 1 : 1 : 1 mole ratio and the mixed ligand complexes of the type MLL’(H2O2 (where M = Mg(II, Ca(II, Sr(II and Ba(II, HL = 5-chlorosalicylaldehyde and HL’ = salicylaldehyde, 2-hydroxyacetophenone or 2-hydroxypropiophenone have been isolated. These complexes were characterized by TLC, conductance measurements, IR and 1H-NMR spectra.

  15. Vanadium As a Potential Membrane Material for Carbon Capture: Effects of Minor Flue Gas Species.

    Science.gov (United States)

    Yuan, Mengyao; Liguori, Simona; Lee, Kyoungjin; Van Campen, Douglas G; Toney, Michael F; Wilcox, Jennifer

    2017-10-03

    Vanadium and its surface oxides were studied as a potential nitrogen-selective membrane material for indirect carbon capture from coal or natural gas power plants. The effects of minor flue gas components (SO 2 , NO, NO 2 , H 2 O, and O 2 ) on vanadium at 500-600 °C were investigated by thermochemical exposure in combination with X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), and in situ X-ray diffraction (XRD). The results showed that SO 2 , NO, and NO 2 are unlikely to have adsorbed on the surface vanadium oxides at 600 °C after exposure for up to 10 h, although NO and NO 2 may have exhibited oxidizing effects (e.g., exposure to 250 ppmv NO/N 2 resulted in an 2.4 times increase in surface V 2 O 5 compared to exposure to just N 2 ). We hypothesize that decomposition of surface vanadium oxides and diffusion of surface oxygen into the metal bulk are both important mechanisms affecting the composition and morphology of the vanadium membrane. The results and hypothesis suggest that the carbon capture performance of the vanadium membrane can potentially be strengthened by material and process improvements such as alloying, operating temperature reduction, and flue gas treatment.

  16. Effects of Vanadium Ions in Different Oxidation States on Myosin ATPase Extracted from the Solitary Ascidian, Halocynthia roretzi (Drasche) : Biochemistry

    OpenAIRE

    Hitoshi, Michibata; YUTAKA, ZENKO; Kenji, YAMADA; Masato, HASEGAWA; TATSURO, TERADA; TAKAHARU, NUMAKUANI; Biological Institute, Faculty of Science, University of Kanazawa; Department of Chemistry, Toyama College of Technology; Marine Biological Station,Tohoku University

    1989-01-01

    Some ascidians are known to accumulate vanadium ion within their tissues by 10^6-fold as that in sea water and store the metal ion in its reduced tetravalent and/or trivalent states. It is also well known that phosphoenzymes are inhibited by pentavalent vanadium ion over a range of 10nM to 1mM. In the present experiment we have therefore examined the effects of vanadium ions in different oxidation states on the activity of myosin ATPase extracted from the mantle of the ascidian, Halocynthia r...

  17. [The vanadium compounds: chemistry, synthesis, insulinomimetic properties].

    Science.gov (United States)

    Fedorova, E V; Buriakina, A V; Vorob'eva, N M; Baranova, N I

    2014-01-01

    The review considers the biological role of vanadium, its participation in various processes in humans and other mammals, and the anti-diabetic effect of its compounds. Vanadium salts have persistent hypoglycemic and antihyperlipidemic effects and reduce the probability of secondary complications in animals with experimental diabetes. The review contains a detailed description of all major synthesized vanadium complexes having antidiabetic activity. Currently, vanadium complexes with organic ligands are more effective and safer than the inorganic salts. Despite the proven efficacy of these compounds as the anti-diabetic agents in animal models, only one organic complex of vanadium is currently under the second phase of clinical trials. All of the considered data suggest that vanadium compound are a new promising class of drugs in modern pharmacotherapy of diabetes.

  18. Metal-ion exchange induced structural transformation as a way of forming novel Ni(II)− and Cu(II)−salicylaldimine structures

    Energy Technology Data Exchange (ETDEWEB)

    Wu, Jing-Yun, E-mail: jyunwu@ncnu.edu.tw; Tsai, Chi-Jou; Chang, Ching-Yun; Wu, Yung-Yuan

    2017-02-15

    A Zn(II)−salicylaldimine complex [Zn(L{sup salpyca})(H{sub 2}O)]{sub n} (1, where H{sub 2}L{sup salpyca}=4-hydroxy-3-(((pyridin-2-yl)methylimino)methyl)benzoic acid), with a one-dimensional (1D) chain structure, has been successfully converted to a discrete Ni(II)−salicylaldimine complex [Ni(L{sup salpyca})(H{sub 2}O){sub 3}] (2) and an infinite Cu(II)−salicylaldimine complex ([Cu(L{sup salpyca})]·3H{sub 2}O){sub n} (3) through a metal-ion exchange induced structural transformation process. However, such processes do not worked by Mn(II) and Co(II) ions. Solid-state structure analyses reveal that complexes 1–3 form comparable coordinative or supramolecular zigzag chains running along the crystallographic [201] direction. In addition, replacing Zn(II) ion by Ni(II) and Cu(II) ions caused changes in coordination environment and sphere of metal centers, from a 5-coordinate intermediate geometry of square pyramidal and trigonal bipyramidal in 1 to a 6-coordinate octahedral geometry in 2, and to a 4-coordiante square planar geometry in 3. This study shows that metal-ion exchange serves as a very efficient way of forming new coordination complexes that may not be obtained through direct synthesis. - Graphical abstract: A Zn(II)−salicylaldimine zigzag chain has been successfully converted to a Ni(II)−salicylaldimine supramolecular zigzag chain and a Cu(II)−salicylaldimine coordinative zigzag chain through metal-ion exchange induced structural transformations, which is not achieved by Mn(II) and Co(II) ions.

  19. New dinuclear copper(II) and zinc(II) complexes for the investigation of sugar-metal ion interactions.

    Science.gov (United States)

    Bera, Manindranath; Patra, Ayan

    2011-10-18

    We have studied the binding interactions of biologically important carbohydrates (D-glucose, D-xylose and D-mannose) with the newly synthesized five-coordinate dinuclear copper(II) complex, [Cu(2)(hpnbpda)(μ-OAc)] (1) and zinc(II) complex, [Zn(2)(hpnbpda)(μ-OAc)] (2) [H(3)hpnbpda=N,N'-bis(2-pyridylmethyl)-2-hydroxy-1,3-propanediamine-N,N'-diacetic acid] in aqueous alkaline solution. The complexes 1 and 2 are fully characterized both in solid and solution using different analytical techniques. A geometrical optimization was made of the ligand H(3)hpnbpda and the complexes 1 and 2 by molecular mechanics (MM+) method in order to establish the stable conformations. All carbohydrates bind to the metal complexes in a 1:1 molar ratio. The binding events have been investigated by a combined approach of FTIR, UV-vis and (13)C NMR spectroscopic techniques. UV-vis spectra indicate a significant blue shift of the absorption maximum of complex 1 during carbohydrate coordination highlighting the sugar binding ability of complex 1. The apparent binding constants of the substrate-bound copper(II) complexes have been determined from the UV-vis titration experiments. The binding ability and mode of binding of these sugar substrates with complex 2 are indicated by their characteristic coordination induced shift (CIS) values in (13)C NMR spectra for carbon atoms C1, C2, and C3 of sugar substrates. Copyright © 2011 Elsevier Ltd. All rights reserved.

  20. 40 CFR Appendix I to Part 266 - Tier I and Tier II Feed Rate and Emissions Screening Limits for Metals

    Science.gov (United States)

    2010-07-01

    ... 40 Protection of Environment 26 2010-07-01 2010-07-01 false Tier I and Tier II Feed Rate and...—Tier I and Tier II Feed Rate and Emissions Screening Limits for Metals Table I-A—Tier I and Tier II...+06 1.8E+03 6.0E+03 6.0E+04 6.0E+03 Table I-B—Tier i and Tier II Feed Rate and Emissions Screening...

  1. Diagnosis of deactivation sources for vanadium catalysts used in SO 2 oxidation reaction and optimization of vanadium extraction from deactivated catalysts

    Science.gov (United States)

    Ksibi, Mohamed; Elaloui, Elimam; Houas, Ammar; Moussa, Noomen

    2003-12-01

    Physico-chemical analysis (X-ray, FTIR) and/or methanol oxidation reaction test were performed on fresh and deactivated vanadium catalysts used in H 2SO 4 manufacturing. It allowed the diagnosis of catalyst deactivation sources, as well as the processes of regenerating and recycling the worn out catalyst in converter. One of these processes is hydrometallurgical method. It consists in treating the deactivated catalyst with alkaline or acidic reagents and forming vanadate solution. A simple and non-costly operation of chemical attack permits the extraction of vanadium from silica in deactivated catalyst. The extracted vanadium can be used for the confection of regenerated catalysts or metallic tools. After optimization, this method can be used for industrial application.

  2. Diagnosis of deactivation sources for vanadium catalysts used in SO{sub 2} oxidation reaction and optimization of vanadium extraction from deactivated catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Ksibi, Mohamed; Elaloui, Elimam; Houas, Ammar; Moussa, Noomen

    2003-12-30

    Physico-chemical analysis (X-ray, FTIR) and/or methanol oxidation reaction test were performed on fresh and deactivated vanadium catalysts used in H{sub 2}SO{sub 4} manufacturing. It allowed the diagnosis of catalyst deactivation sources, as well as the processes of regenerating and recycling the worn out catalyst in converter. One of these processes is hydrometallurgical method. It consists in treating the deactivated catalyst with alkaline or acidic reagents and forming vanadate solution. A simple and non-costly operation of chemical attack permits the extraction of vanadium from silica in deactivated catalyst. The extracted vanadium can be used for the confection of regenerated catalysts or metallic tools. After optimization, this method can be used for industrial application.

  3. Characterization of Vanadium Flow Battery

    DEFF Research Database (Denmark)

    Bindner, Henrik W.; Krog Ekman, Claus; Gehrke, Oliver

    This report summarizes the work done at Risø-DTU testing a vanadium flow battery as part of the project “Characterisation of Vanadium Batteries” (ForskEl project 6555) with the partners PA Energy A/S and OI Electric A/S under the Danish PSO energy research program. A 15kW/120kWh vanadium battery...... has been installed as part of the distributed energy systems experimental facility, SYSLAB, at Risø DTU. A test programme has been carried out to get hands-on experience with the technology, to characterize the battery from a power system point of view and to assess it with respect to integration...... of wind energy in the Danish power system. The battery has been in operation for 18 months. During time of operation the battery has not shown signs of degradation of performance. It has a round-trip efficiency at full load of approximately 60% (depending on temperature and SOC). The sources of the losses...

  4. Metal II complexes of ethambutol as good enzyme inhibitor and promising antioxidant.

    Science.gov (United States)

    Jahangir, Muhammad; Farwa, Ume; Mazhar, Farhana; Malik, Afza; Ahmad, Ejaz

    2016-09-01

    Ethambutoldihydrogenchloride (EMB) with chemical formula C10H24N2O2.2HCl is ethane-1,2-diamine in which one hydrogen attached to each of the nitrogen is substituted by a 1-hydroxybutan-2-yl group (S,S-configuration). It is an FDA approved drug and has been used for treatment of tuberculosis since 1960's. Prolong use of EMB has a side effect of visual impairment and in literature it is related with the depletion of Zn metal from the body. As it is a good chelating agent, many metal II complexes have been synthesized with anti-tubercular activity. The purpose of this work was to synthesize metal II complexes of EMB and to evaluate their antioxidant activity along with enzyme inhibition activity (acetylcholine esterase and protease). The metals used for complex formation were Co, Zn, Fe, Cu and Ni. IR spectral data and physical parameters supported the complex formation. The obtained results showed the synthesized complexes as notable antioxidants and enzyme inhibitors.

  5. Selective speciation improves efficacy and lowers toxicity of platinum anticancer and vanadium antidiabetic drugs.

    Science.gov (United States)

    Doucette, Kaitlin A; Hassell, Kelly N; Crans, Debbie C

    2016-12-01

    Improving efficacy and lowering resistance to metal-based drugs can be addressed by consideration of the coordination complex speciation and key reactions important to vanadium antidiabetic drugs or platinum anticancer drugs under biological conditions. The methods of analyses vary depending on the specific metal ion chemistry. The vanadium compounds interconvert readily, whereas the reactions of the platinum compounds are much slower and thus much easier to study. However, the vanadium species are readily differentiated due to vanadium complexes differing in color. For both vanadium and platinum systems, understanding the processes as the compounds, Lipoplatin and Satraplatin, enter cells is needed to better combat the disease; there are many cellular metabolites, which may affect processing and thus the efficacy of the drugs. Examples of two formulations of platinum compounds illustrate how changing the chemistry of the platinum will result in less toxic and better tolerated drugs. The consequence of the much lower toxicity of the drug, can be readily realized because cisplatin administration requires hospital stay whereas Lipoplatin can be done in an outpatient manner. Similarly, the properties of Satraplatin allow for development of an oral drug. These forms of platinum demonstrate that the direct consequence of more selective speciation is lower side effects and cheaper administration of the anticancer agent. Therefore we urge that as the community goes forward in development of new drugs, control of speciation chemistry will be considered as one of the key strategies in the future development of anticancer drugs. Copyright © 2016 Elsevier Inc. All rights reserved.

  6. Leaching characteristics of vanadium in mine tailings and soils near a vanadium titanomagnetite mining site.

    Science.gov (United States)

    Yang, Jinyan; Tang, Ya; Yang, Kai; Rouff, Ashaki A; Elzinga, Evert J; Huang, Jen-How

    2014-01-15

    A series of column leaching experiments were performed to understand the leaching behaviour and the potential environmental risk of vanadium in a Panzhihua soil and vanadium titanomagnetite mine tailings. Results from sequential extraction experiments indicated that the mobility of vanadium in both the soil and the mine tailings was low, with vanadium readily mobilised. Column experiments revealed that only vanadium in the soil and mine tailing was leachable. The vanadium concentrations in the soil leachates did not vary considerably, but decreased with the leachate volume in the mine tailing leachates. This suggests that there was a smaller pool of leachable vanadium in the mine tailings compared to that in the soil. Drought and rewetting increased the vanadium concentrations in the soil and mine tailing leachates from 20μgL(-1) to 50-90μgL(-1), indicating the potential for high vanadium release following periods of drought. Experiments with soil columns overlain with 4, 8 and 20% volume mine tailings/volume soil exhibited very similar vanadium leaching behaviour. These results suggest that the transport of vanadium to the subsurface is controlled primarily by the leaching processes occurring in soils. Copyright © 2013 Elsevier B.V. All rights reserved.

  7. A Biphenol-Based Chemosensor for Zn(II) and Cd(II) Metal Ions: Synthesis, Potentiometric Studies, and Crystal Structures.

    Science.gov (United States)

    Ambrosi, Gianluca; Formica, Mauro; Fusi, Vieri; Giorgi, Luca; Macedi, Eleonora; Micheloni, Mauro; Paoli, Paola; Rossi, Patrizia

    2016-08-01

    We synthesized and characterized the ligand N,N'-bis[(2,2'-dihydroxybiphen-3-yl)methyl]-N,N'-dimethylethylenediamine (L), which contains two biphenol moieties linked as side arms to an N,N'-dimethylethylenediamine scaffold. The ligand is highly soluble in a 50/50 (v/v) water/ethanol mixture and, in its deprotonated form H-2L(2-), is able to coordinate transition-metal ions such as Ni(II), Zn(II), Cu(II), Cd(II), and Pd(II). The crystal structures of [Ni(H-2L)·2n-BuOH], [Ni(H-2L)·2MeOH], [Cd(H-2L)·2DMF], [Cu(H-2L)(DMF)], and [Pd(H-2L)(DMF)] were also determined and described. Potentiometric titrations were carried out in a mixed solvent with Zn(II), Cu(II), and Ni(II) metal ions to determine the acid-base and stability constants. L was highly fluorescent in the visible range (400 nm). Moreover, its emission intensity increased upon the addition of Zn(II) or Cd(II) ions in an ethanol/water solution and behaved as a chemosensor for the presence of these ions in the solution.

  8. Spectral, NLO, Fluorescence, and Biological Activity of Knoevenagel Condensate of β-Diketone Ligands and Their Metal(II Complexes

    Directory of Open Access Journals (Sweden)

    S. Sumathi

    2011-01-01

    Full Text Available Transition metal complexes of various acetylacetone-based ligands of the type ML (where M=  Cu(II, Ni(II, Co(II; L=  3-(aryl-pentane-2,4-dione have been synthesized. The structural features have been derived from their elemental analysis, magnetic susceptibility, molar conductance, IR, UV-Vis, H1NMR, mass and ESR spectral studies. Conductivity measurements reveal that all the complexes are nonelectrolytic in nature. Spectroscopic and other analytical data of the complexes suggest square planar geometry for copper(II, cobalt(II, and nickel(II complexes of 3-(3-phenylallylidenepentane-2,4-dione and octahedral geometry for other metal(II complexes. The redox behaviors of the copper(II complexes have been studied by cyclic voltammetry. The free ligands and their metal complexes have been screened for their in vitro biological activities against bacteria and fungus. The metal(II complexes are found to possess increased activities compared to those of the free ligands. All synthesized compounds may serve as potential photoactive materials as indicated from their characteristic fluorescence properties. The second harmonic generation (SHG efficiency of the ligands was found to have considerable effect compared to that of urea and KDP.

  9. The future of/for vanadium.

    Science.gov (United States)

    Rehder, Dieter

    2013-09-07

    Vanadium compounds are stored or employed by several groups of bacterial and eukaryotic organisms. Two types of vanadium-dependent enzymes have so far been characterised: vanadate-dependent haloperoxidases from fungi, lichens, marine macroalgae and Streptomyces bacteria, and vanadium nitrogenases in proteo- and cyanobacteria. Several bacterial strains can employ vanadate(V) as an external electron acceptor in respiration, reducing vanadate to VO(2+) and thus contributing to the mineralisation of vanadium and to the detoxification of vanadate-contaminated water. Amanita mushrooms and many sea squirts accumulate vanadium, without the importance of this practise being well understood. Further, the analogy between vanadate and phosphate implicates an interference of vanadate with metabolic processes involving phosphate, suggesting a regulatory role for vanadate in most if not all organisms, including humans, but also hinting at toxic effects at unphysiologically high vanadate concentrations. The antidiabetic effect of vanadium compounds is probably related to the phosphate-vanadate antagonism, as is the potentiality of vanadate in the amelioration of cardiovascular affliction. The anti-cancer action of vanadium compounds and their in vitro activity towards the protozoa causing amoebiasis, leishmaniasis and Chagas' disease again may be rooted in the intervention of vanadate with the activity of phosphatases and kinases. In addition, most likely the ability of vanadate(V) and oxidovanadium(IV) to regulate the cellular production of reactive oxygen species comes in, thus influencing cellular signalling. Future developments of vanadium chemistry are likely to emphasize topics related to biological, environmental and medicinal aspects. Condensation of monovanadate results in the formation of oligovanadates, polyvanadates and finally colloidal and solid vanadium oxides that, in part, convey bio-mimetic functions comparable to those of simple vanadate, including its catalytic

  10. DISLOCATION DYNAMICS IN VANADIUM - A NUCLEAR-MAGNETIC-RESONANCE AND TRANSMISSION ELECTRON-MICROSCOPIC STUDY

    NARCIS (Netherlands)

    CHRISTIAN, A; KANERT, O; DEHOSSON, JTM

    1990-01-01

    Pulsed nuclear magnetic resonance proved to be a complementary new technique for the study of moving dislocations in b.c.c. metals. From the motion induced part of the spin-lattice relaxation rate the mean jump distance of mobile dislocations has been measured in Vanadium as a function of

  11. Ab initio study of spin-dependent transport in carbon nanotubes with iron and vanadium adatoms

    DEFF Research Database (Denmark)

    Fürst, Joachim Alexander; Brandbyge, Mads; Jauho, Antti-Pekka

    2008-01-01

    We present an ab initio study of spin-dependent transport in armchair carbon nanotubes with transition metal adsorbates: iron or vanadium. The method based on density functional theory and nonequilibrium Green's functions is used to compute the electronic structure and zero-bias conductance. The ...

  12. Removal of heavy metal Cu(II) in simulated aquaculture wastewater by modified palygorskite.

    Science.gov (United States)

    Cao, Jia-Shun; Wang, Cheng; Fang, Fang; Lin, Jun-Xiong

    2016-12-01

    Palygorskite (PAL) is a good heavy metal adsorbent due to its high surface area, low cost, and environmentally compatibility. But the natural PAL has limited its adsorption capacity and selectivity. In this study, a cost-effective and readily-generated absorbent, l-threonine-modified palygorskite (L-PAL), was used and its performance for Cu(II) removal in simulated aquaculture wastewater was evaluated. After preparation, L-PAL was characterized by using Fourier transform infrared spectroscopy, scanning electron microscope, energy dispersive X-ray spectroscopy, X-ray diffractometer, X-ray photoelectron spectroscopy, transmission electron microscopy and thermogravimetric analysis. The impacts of pH, adsorbent dosage, contact time, and initial Cu(II) concentration on the adsorption capacity of L-PAL were examined. The Cu(II) adsorption capacity on L-PAL was enhanced almost 10 times than that of raw PAL. The adsorption isotherms of Cu(II) fit the Langmuir isotherms, and the adsorption kinetics was dominated by the pseudo-second-order model. The thermodynamic parameters at four temperatures were calculated, which indicated that the adsorption was spontaneous and endothermic. The adsorption mechanism involves complexation, chelation, electrostatic attraction, and micro-precipitation. Furthermore, L-PAL is shown to have a high regeneration capacity. These results indicate that L-PAL is a cheap and promising absorbent for Cu(II) removal and hold potential to be used for aquaculture wastewater treatment. Copyright © 2016 Elsevier Ltd. All rights reserved.

  13. Application of factorial designs and Doehlert matrix in optimization of experimentalvariabl es associated with the preconcentration and determination of vanadium and copper in seawater by inductively coupled plasma optical emission spectrometry

    OpenAIRE

    Ferreira, Sergio Luis Costa; Queiroz, Adriana Santana; Fernandes, Marcelo Santiago; Hilda Costa dos Santos, Talma

    2002-01-01

    p. 1939–1950 In the present paper a procedure for preconcentration and determination of vanadium and copper in seawater using inductively coupled plasma optical emission spectrometry (ICP OES) is proposed, which is based on solid-phase extraction of vanadium (IV), vanadium (V) and copper (II) ions as 1-(2-pyridylazo)-2-naphthol (PAN) complexes by active carbon. The optimization process was carried out using two-level full factorials and Doehlert matrix designs. Four variables (PA...

  14. Model investigations for vanadium-protein interactions: vanadium(III) compounds with dipeptides and their oxovanadium(IV) analogues.

    Science.gov (United States)

    Tasiopoulos, Anastasios J; Tolis, Evangelos J; Tsangaris, John M; Evangelou, Angelos; Woollins, DerekJ; Slawin, Alexandra M Z; Pessoa, Costa; Correia, Isabel; Kabanos, Themistoklis A

    2002-04-01

    The reaction of VCl(3) with 1,10-phenanthroline and a series of dipeptides (H(2)dip), having aliphatic as well as aromatic side chains, in methyl alcohol and in the presence of triethylamine affords vanadium(III) compounds of the general formula [V(III)(dip)(MeOH)(phen)]Cl. Aerial oxidation/hydrolysis of the vanadium(III) species gives their oxovanadium(IV) analogues of the general formula [V(IV)O(dip)(phen)]. X-ray crystallographic characterization of the [V(IV)O(dip)(phen)] compounds (where dip(2-)=Gly- L-Ala, Gly- L-Val and Gly- L-Phe) revealed that the vanadium atom possesses a severely distorted octahedral coordination and is ligated to a tridentate dip(2-) ligand at the N(amine) atom, the deprotonated N(peptide) atom and one of the O(carboxylate) atoms, as well as an oxo group and two phenanthroline nitrogen atoms. Circular dichroism characterization of the V(III)/V(IV)O(2+)-dipeptide compounds revealed a strong signal for the V(IV)O(2+) species in the visible range of the spectrum, with a characteristic pattern which may be exploited to identify the N(am), N(pep) and O(car) ligation of a peptide or a protein to V(IV)O(2+) center, and a weak Cotton effect of opposite sign to their vanadium(III) analogues. The visible spectra of the V(III)-dipeptide compounds revealed two d-d bands with high intensity, thus indicating that the covalency of the metal-donor atoms is significant, i.e. the vanadium d orbitals are significantly mixed with the ligand orbitals, and this is confirmed by the low values of their Racah B parameters. The high-intensity band of the V(IV)O(2+)-dipeptide compounds at approximately 460 nm implies also a strong covalency of the metal with the equatorial donor atoms and this was supported by the EPR spectra of these compounds. Moreover, the V(III)/V(IV)O(2+)-dipeptide complexes were characterized by EPR and IR spectroscopies as well as conductivity and magnetic susceptibility measurements.

  15. Lattice-Symmetry-Driven Phase Competition in Vanadium Dioxide

    Energy Technology Data Exchange (ETDEWEB)

    Tselev, Alexander [ORNL; Luk' yanchuk, Prof. Igor A. [University of Picardie Jules Verne, Amiens, France; Ivanov, Ilia N [ORNL; Budai, John D [ORNL; Tischler, Jonathan Zachary [ORNL; Strelcov, Evgheni [Southern Illinois University; Kolmakov, Andrei [Southern Illinois University; Kalinin, Sergei V [ORNL

    2011-01-01

    We performed group-theoretical analysis of the symmetry relationships between lattice structures of R, M1, M2, and T phases of vanadium dioxide in the frameworks of the general Ginzburg-Landau phase transition theory. The analysis leads to a conclusion that the competition between the lower-symmetry phases M1, M2, and T in the metal-insulator transition is pure symmetry driven, since all the three phases correspond to different directions of the same multi-component structural order parameter. Therefore, the lower-symmetry phases can be stabilized in respect to each other by small perturbations such as doping or stress.

  16. Ethylene oligomerization in metal-organic frameworks bearing nickel(ii) 2,2'-bipyridine complexes.

    Science.gov (United States)

    Gonzalez, Miguel I; Oktawiec, Julia; Long, Jeffrey R

    2017-09-08

    The metal-organic frameworks Zr6O4(OH)4(bpydc)6 (1; bpydc(2-) = 2,2'-bipyridine-5,5'-dicarboxylate) and Zr6O4(OH)4(bpydc)0.84(bpdc)5.16 (2; bpdc(2-) = biphenyl-4,4'-dicarboxylate) were readily metalated with Ni(DME)Br2 (DME = dimethoxyethane) to produce the corresponding metalated frameworks 1(NiBr2)6 and 2(NiBr2)0.84. Both nickel(ii)-containing frameworks catalyze the oligomerization of ethylene in the presence of Et2AlCl. In these systems, the pore environment around the active nickel sites significantly influences their selectivity for formation of oligomers over polymer. Specifically, the single-crystal structure of 1(NiBr2)5.64 reveals that surrounding metal-linker complexes enforce a steric environment on each nickel site that causes polymer formation to become favorable. Minimizing this steric congestion by isolating the nickel(ii) bipyridine complexes in the mixed-linker framework 2(NiBr2)0.84 markedly improves both the catalytic activity and selectivity for oligomers. Furthermore, both frameworks give product mixtures that are enriched in shorter olefins (C4-10), leading to deviations from the expected Schulz-Flory distribution of oligomers. Although these deviations indicate possible pore confinement effects on selectivity, control experiments using the nickel-treated biphenyl framework Zr6O4(OH)4(bpdc)6(NiBr2)0.14 (3(NiBr2)0.14) reveal that they likely arise at least in part from the presence of nickel species that are not ligated by bipyridine within 1(NiBr2)5.64 and 2(NiBr2)0.84.

  17. A porous Cu(II) metal-organic framework: Synthesis, crystal structure and gas adsorption properties

    Science.gov (United States)

    Li, Wu-Wu; Guo, Ying; Zhang, Wei-Hong

    2017-09-01

    Presented here is a new porous Cu(II) metal-organic framework, namely [Cu(tdc)(H2O)]n·n(DMA) (1 H2tdc = thiophene-2,5-dicarboxylic acid, DMA = N,N‧-dimethylacetamide), which was obtained by the self-assembly reaction of CuCl2 and H2tdc under solvothermal conditions. Single crystal X-ray diffraction analysis revealed that compound 1 features a 3D porous framework based on 1D chain structure subunits, and the 1D rhombohedral channels are occupied by the lattice DMA molecules. Gas adsorption studies reveal that this desolvated sample exhibit high uptake capacity for light hydrocarbons.

  18. The Cooling Ability Study on CO2 and O2 Mixed Injection in Vanadium Extraction Process

    Science.gov (United States)

    Li, Pengcheng; Wang, Yu; Du, Wei-Tong; Wen, Gang

    Carbon dioxide could be utilized as a weak oxidant and a kind of coolant to oxidize elements, meanwhile, helping control the temperature during the converter vanadium extraction process. However, the optimum content of CO2 and the cooling effect of CO2 at low content have not been reported. In this study, experimental research based on the influence of different CO2 contents from 0% to 25% injected to the vanadium-containing hot metal was carried out, as well as contrast experiments of O2-N2 mixed blowing. The results indicated that the optimum content of CO2 was 15%. Under the optimum condition, the oxidation of [C] was the lowest and the oxidation rate of [V] was 96.9%, while the temperature was also lower than the O2-N2 mixed blowing. This paper provide a potential property for utilizing CO2 during the converter vanadium extraction process.

  19. Enhancing the Electronic Conductivity of Vanadium-tellurite Glasses by Tuning the Redox State

    DEFF Research Database (Denmark)

    Kjeldsen, Jonas; Yue, Yuanzheng

    Transition metal oxides are used in a variety of electronic purposes, e.g., vanadium tellurite as cathode material in high-power demanding batteries. By tuning the redox state of vanadium, it is possible to achieve a lower internal resistance within the entire battery unit, thus a higher capacity....... In this work we vary the redox state of a given vanadium tellurite system by performing post heat-treatment in controlled atmosphere. This process is in theory not limited only to varying electronic conductivity, but also varying the glass structure, and hence, changing properties of the glasses, e.g, thermal...... and mechanical properties. Finally we give insight into the relation between the redox state and electronic conductivity....

  20. Production of high-purity vanadium, chromium and titanium for use in low activation materials

    Science.gov (United States)

    Murphy, D.; Butterworth, G. J.

    1992-09-01

    The presence of radiologically potent tramp elements must be strictly controlled if the intrinsic low activation properties of alloys based on vanadium and chromium are to be fully realized. In this study the incidence of critical impurity elements in commercial sources of vanadium, chromium and titanium metals and precursor compounds is investigated using techniques for trace element analysis. Maximum permitted concentrations corresponding to the attainment of the “hands-on” dose rate limit of 25 μSvh-1 after 100 yr cooling of first wall material were adopted as target values. Chromium and titanium from commercial sources are able to satisfy the purity target. Commercially available vanadium may contain unacceptable levels of Mo, Ag, Nb or Co and additional purification steps designed to remove these impurities are described.

  1. ESR study of deoxygenated and oxidated forms of vanadium(4) porphyrins

    Energy Technology Data Exchange (ETDEWEB)

    Selyutin, G.E.; Shklyaev, A.A. (AN SSSR, Krasnoyarsk. Inst. Khimii i Khimicheskoj Tekhnologii)

    1982-01-01

    Halogenated and oxidated forms of porphyrins of oxovanadium VOP (ethioporphyrin-EP and tetraphenylporphyrin) with different halides are studied using the ESR method. In reactions of vanadylporphyrins with metal halides deoxygenation of vanadyl ion is realized and octahedral complex of dihalogenovanadium (4) of porphyrin (P) are formed and at the intermediate stage bimetal complex of vanadiumporphyrin with halide is formed, in which halide cation is bonded by means of the bridge oxygen atom with vanadium ion. In dihalide complexes VX/sub 2//sup -/P for vanadium (4) ion a regular octahedral surrounding is realized and the axis of tetragonal distortion can be oriented both in perpendicular and lay in porphyrin plane. The oxidated forms, formed during oxidation in the presence of halides, present dihalide vanadium (4) complexes with mono- and dication of porphyrin ligand.

  2. Protection against vanadium-induced testicular toxicity by testosterone propionate in rats.

    Science.gov (United States)

    Chandra, Amar K; Ghosh, Rituparna; Chatterjee, Aparajita; Sarkar, Mahitosh

    2010-07-01

    Vanadium is a well recognized industrial hazard known to adversely affect male reproductive functions. The intricate mechanistic aspects of this metal and the role of oxidative stress in the deterioration of testicular functions are investigated in the current study. The experiment also focused on the effects of testosterone propionate in testicular and sperm functions in the rat intoxicated with vanadate. Vanadium exposure resulted in a more prominent spermatogenic arrest and consistently abolished the conversion of round to mature spermatids along with decreased epididymal sperm number and increased percentage of abnormal sperm. This is followed by a precipitous decline in the level of serum testosterone and gonadotropins and consequently the testicular steroidogenic and antioxidant enzymes were inhibited. Vanadium induces degeneration in the genital organs of rats and exhibits high indices of lipid oxidative damage. In response to exogenous testosterone propionate (TP) administration, spermatogonial cell populations remained suppressed, while the spermatogenesis was restored quantitatively. In contrast, the hormone treatment had no effect on the dramatically decreased serum FSH level after vanadate treatment. Moreover, TP could ameliorate the toxicity, as indicated by decreased testicular lipid peroxidation with marginal but significant increase in the activities of all the measured enzymes following vanadate-treatment. Taken together all these studies establish that vanadium is a testicular toxicant that perturbs the male reproductive system adversely. However, hormone replacement therapy by testosterone propionate may provide partial protection. The results suggest the feasibility of using endocrine regimens to impede deleterious effects of vanadium on the male reproductive system.

  3. Interaction of vanadium and phosphorus in chicks.

    Science.gov (United States)

    Hill, C H

    1994-12-01

    Studies were carried out to determine the effect of dietary vanadium on chicks fed phosphorus deficient and control diets. Vanadium at 50 mg/kg of diet decreased growth of both control and deficient chicks. The high mortality among the phosphorus deficient chicks was significantly alleviated by the presence of vanadium. The increased relative ventricular weights found among the deficient chicks was also alleviated by the presence of dietary vanadium. Vanadium fed at 10 or 20 mg/kg diet did not reduce growth rate but significantly reduced mortality among chicks fed the deficient diet and decreased the relative ventricle weights. Time course studies revealed that chicks are hatched with high relative ventricular weights (.83% of body wt) and remain at that level among chicks fed the phosphorus deficient diet. The addition of vanadium or phosphate to the diet resulted in a progressive decrease in relative ventricular weights. The inclusion of vanadium in the diet resulted in increased serum phosphorus levels among the deficient chicks that may be related to the decrease in mortality and relative ventricle weights.

  4. Metals from the ritual site of Shaitanskoye Ozero II (Sverdlovsk Oblast, Russia

    Directory of Open Access Journals (Sweden)

    Nikolaevna Korochkova, Olga

    2010-12-01

    Full Text Available The present article describes materials from the ritual site of Shaitanskoye Ozero II, Sverdlovsk Oblast. Few excavations carried out at the site measuring less than 240 sq. m in size, yielded more than 160 bronze artifacts: utensils, weapons, rolled copper ornaments, and abundant smelting and casting waste. Apart from Seima-Turbino (celts and laminar knives and Eurasian types (daggers with cast hilts, truncated knives with guards, fluted bracelets and rings, several metal artifacts were revealed manufactured in the style of the Samus-Kizhirovo tradition. Bronze artifacts, stone knives and scrapers, and numerous arrowheads are accompanied by ceramics of the Koptyaki type. Metals use mainly a copper-tin alloy. This assemblage is shown to be relevant to the local tradition of metalworking, which, in this particular region, was comparatively ancient having been left uninterrupted by the rapid migrations of the Seima-Turbino people. In addition, the assemblage indicates the sources from which post-Seima artifacts reached the Alakul people. These artifacts may also have been linked with a large metalworking center located in the Middle Urals.

    Este artículo describe los materiales del sitio ritual de Shaitanskoye Ozero II, Provincia de Sverdlovsk. Las reducidas excavaciones emprendidas en el lugar con superficie inferior a los 240 m2 han entregado más de 160 objetos de bronce: utensilios, armas, adornos en espiral de cobre y abundantes residuos de la fusión y el trabajo del metal. Además de tipos Seima-Turbino (hachas tubulares y cuchillos planos y Euroasiáticos (puñales de mango fundido, cuchillos con empuñadura de lengüeta, brazaletes y anillos acanalados, varios artefactos metálicos resultaron manufacturados según el estilo de la tradición Samus-Kizhirovo. Los artefactos de bronce, los líticos (cuchillos, raspadores y numerosas puntas de flecha están acompañados por cerámicos de tipo Koptyaki. El metal es

  5. Geometric constraints on phase coexistence in vanadium dioxide single crystals.

    Science.gov (United States)

    McGahan, Christina; Gamage, Sampath; Liang, Jiran; Cross, Brendan; Marvel, Robert E; Haglund, Richard F; Abate, Yohannes

    2017-02-24

    The appearance of stripe phases is a characteristic signature of strongly correlated quantum materials, and its origin in phase-changing materials has only recently been recognized as the result of the delicate balance between atomic and mesoscopic materials properties. A vanadium dioxide (VO2) single crystal is one such strongly correlated material with stripe phases. Infrared nano-imaging on low-aspect-ratio, single-crystal VO2 microbeams decorated with resonant plasmonic nanoantennas reveals a novel herringbone pattern of coexisting metallic and insulating domains intercepted and altered by ferroelastic domains, unlike previous reports on high-aspect-ratio VO2 crystals where the coexisting metal/insulator domains appear as alternating stripe phases perpendicular to the growth axis. The metallic domains nucleate below the crystal surface and grow towards the surface with increasing temperature as suggested by the near-field plasmonic response of the gold nanorod antennas.

  6. Synthesis, spectroscopic characterization, DFT optimization and biological activities of Schiff bases and their metal (II) complexes

    Science.gov (United States)

    Rauf, Abdur; Shah, Afzal; Munawar, Khurram Shahzad; Khan, Abdul Aziz; Abbasi, Rashda; Yameen, Muhammad Arfat; Khan, Asad Muhammad; Khan, Abdur Rahman; Qureshi, Irfan Zia; Kraatz, Heinz-Bernhard; Zia-ur-Rehman

    2017-10-01

    A Novel Schiff base, 3-(((4-chlorophenyl)imino)methyl)benzene-1,2-diol (HL1) was successfully synthesized along with a structurally similar Schiff base 3-(((4-bromophenyl)imino)methyl)benzene-1,2-diol (HL2). Both the Schiff bases were used to synthesize their zinc (II) and cobalt (II) complexes. These compounds were characterized by FTIR, 1H NMR, 13C NMR and elemental analysis. Metal complexes were confirmed by TGA. Crystals of Schiff bases were also characterized by X-ray analysis and experimental parameters were found in line with the theoretical parameters. Quantum mechanical approach was also used to fine useful structural parameters and to ensure the geometry of metal complexes. The photometric behaviors of all the synthesized compounds were investigated in a wide pH range using BR buffers. The appearance of isosbestic points indicated the existence of Schiff bases in more than one isomeric form. Moreover, these compounds were screened for enzyme inhibition; antibacterial, cytotoxic and in vivo antidiabetic activities and compounds were found active against one or other activity. Results indicate that ZnL22 is a good inhibitor of alkaline phosphatase enzyme and possess highest potential against diabetes, blood cholesterol level and cancer cells. This effort just provides preliminary data for some biological properties. Further investigations are required to precisely determine mechanistic pathways of their use towards drug development.

  7. Vanadium Bioleaching Behavior by Acidithiobacillus ferrooxidans from a Vanadium-Bearing Shale

    Directory of Open Access Journals (Sweden)

    Dunpei Wei

    2018-01-01

    Full Text Available This study investigated bioleaching behavior of vanadium from a vanadium-bearing shale using Acidithiobacillus ferrooxidans (A. ferrooxidans. Results showed a maximum recovery of 62% vanadium in 1.2-day bioleaching, which was 22.45% higher than the controls. Then, the vanadium leaching efficiency decreased significantly, only 24% of that was obtained on the tenth day. The vanadium extraction in 1.2 days was mainly attributed to the dissolution of vanadium in free oxides of shale. Fe3+ produced by A. ferrooxidans promoted the dissolution process. X-ray diffraction (XRD patterns of the leached residues confirmed the generation of jarosite. SEM-EDS analysis of the residues indicated that jarosite adsorbed on the shale and inhibited the further dissolution of vanadium. The relevance of V, Fe, S, O was quite good in the energy disperse X-ray spectrometry (EDS element mapping of jarosite, and acid-washing of the jarosite resulted in 31.6% of the vanadium in the precipitates desorption, indicating that the decrease of vanadium leaching efficiency in bioleaching process was caused by both adsorption and co-precipitation with jarosite.

  8. Two polymeric metal complexes based on polycarbazole containing complexes of 8-hydroxyquinoline with Zn(II) and Ni(II) in the backbone: Synthesis, characterization and photovoltaic applications

    Energy Technology Data Exchange (ETDEWEB)

    Deng Jinyan; Guo Lihui; Xiu Qian; Zhang Lirong; Wen Gaojun [Key Laboratory of Environmentally Friendly Chemistry and Applications of Ministry of Education, Xiangtan University, College of Chemistry, Xiangtan, Hunan 411105 (China); Zhong Chaofan, E-mail: zhongcf798@yahoo.com.cn [Key Laboratory of Environmentally Friendly Chemistry and Applications of Ministry of Education, Xiangtan University, College of Chemistry, Xiangtan, Hunan 411105 (China)

    2012-03-15

    Highlights: Black-Right-Pointing-Pointer We have synthesized two photosensitizers of D-{pi}-A polymeric metal complexes. Black-Right-Pointing-Pointer The polymeric metal complexes possess excellent thermal stability and good open-circuit voltages. Black-Right-Pointing-Pointer The application of the photosensitizers in dye-sensitized solar cells was investigated. Black-Right-Pointing-Pointer The polymeric metal complex containing d{sup 10} Zn(II) exhibited better device performance than that containing low spin d{sup 8} Ni(II). - Abstract: Two novel polymeric metal complexes PZn(Q){sub 2}-C and PNi(Q){sub 2}-C based on polycarbazole containing complexes of 8-hydroxyquinoline with Zn(II) and Ni(II) were synthesized and applied in dye-sensitized solar cells (DSSCs) as photosensitizers. They possess moderate thermal stability and good open-circuit voltages, and the power conversion efficiency of them reached to 1.11% and 0.45%, respectively, under simulated AM 1.5 G solar irradiation (100 mW cm{sup -2}), which shows a new strategy to design photosensitizers for DSSCs.

  9. Carbazole-based N4-donor Schiff base macrocycles: obtained metal free and as Cu(ii) and Ni(ii) complexes.

    Science.gov (United States)

    Malthus, Stuart J; Wilson, Rajni K; Vikas Aggarwal, A; Cameron, Scott A; Larsen, David S; Brooker, Sally

    2017-03-07

    The very different multi-step routes to the closely related pair of diformyl-carbazole head units, 1,8-diformyl-3,6-di-tert-butyl-9H-carbazole (1tBu) and 1,8-diformyl-9H-carbazole (1H), are detailed and compared. The first examples of Schiff base macrocycles derived from diformyl-carbazole head units are reported. Specifically, the direct cyclisation of 1tBu or 1H with diethylenetriamine gives the two metal-free [1 + 1] Schiff base macrocycles HLH and HLtBu in high yields. Four carbazole-based macrocyclic complexes, [Cu(II)L(OH2)]OAc and [Ni(II)L]OAc, where L = LH or LtBu, were accessed either by metallation of these macrocycles, or by metal templated reaction of the macrocycle components. [Cu(II)LtBu(OH2)]OAc·0.5(Ether) and [NiLH]OAc·EtOH, were structurally characterised, confirming the nickel(ii) complexes are square planar (both show diamagnetic NMR spectra) and that the copper(ii) complexes are square pyramidal with a water molecule bound in the axial site. Like porphyrins, both of these N4-donor macrocycles, which differ only in the R group present at the 3 and 6 positions (H or tBu), impose a strong ligand field.

  10. Mesoporous Vanadium Nitride Synthesized by Chemical Routes

    National Research Council Canada - National Science Library

    Mishra, Pragnya P; Theerthagiri, J; Panda, Rabi N

    2014-01-01

    Nanocrystalline vanadium nitride (VN) materials are synthesized by two different routes, namely, the urea route and the ammonia route, using various V2O5 precursors obtained by citric acid–based sol–gel method...

  11. Mn Oxide Biogenesis and Metal Sequestration in the Presence of Co (II) and Cu (II) By Bacillus SG-1 Bacterial Spores

    Energy Technology Data Exchange (ETDEWEB)

    Bayat, N

    2004-02-05

    Mn oxides play an important role in degrading contaminants and cycling nutrients in soils and natural waters. The process in which Mn (II) oxidizes to form MnO, is slow; however, Bacillus SG-1 bacterial spores can catalyze the process and allow it to proceed up to five orders of magnitude faster. This experiment explored the affects of co-ion metal concentrations on Biogenic Mn oxide production and their ability to sequester metal cations. Spore solutions were prepared with different ratios of Metal (II): Mn (II) added over a three-week period; this was done separately for Co (II) and Cu (II). The copper solutions were analyzed with ICP/AES to check for the amount of copper and manganese left in solution after biogenic MnO, production. ICP/AES was used to analyze the ratio of Co: Mn in spores where Co was the co-ion metal. Observations showed very little dissolved Cu and Mn exist in solutions with low copper concentrations, but a large amount of Cu and Mn were left in solutions where higher Cu concentrations were used. This shows that high Cu concentration inhibits biogenic Mn oxide production and Cu sequestration. For the experiments with Co as the co-ion metal, it was observed that the ratio of Co: Mn in the spores is relatively similar to the ratios added; however, an exception to this rule was experiments where high concentrations of Co were used. The inconsistency in Co: Mn ratios at high Co concentrations showed that high Co concentrations also inhibit biogenic Mn oxide production.

  12. A novel method to remove chromium, vanadium and ammonium from vanadium industrial wastewater using a byproduct of magnesium-based wet flue gas desulfurization.

    Science.gov (United States)

    Fang, Dean; Zhang, Xuefei; Dong, Mengge; Xue, Xiangxin

    2017-08-15

    A novel treatment for chromium, vanadium and ammonium from vanadium industrial wastewater using a byproduct of magnesium-based wet flue gas desulfurization is investigated. In the present study, the byproduct is used as a reductant for chromium and vanadium removal by chemical precipitation, and the residual magnesium ion can also be used to remove ammonium in the present of phosphate by struvite crystallization. Besides, the effects of main operational parameters (reaction pH, byproduct dosage and reaction time) on the heavy metal removal and ammonium removal (reaction pH, Mg(2+):NH4(+):PO4(3-) molar ratio and reaction time) are investigated, and the reaction mechanism for this treatment technology is also proposed. Under the optimal conditions, the residual concentrations of chromium(IV), total chromium and vanadium are 0.046mg/L, 0.468mg/L and 0.06mg/L, respectively. The removal efficiency of ammonium is 95.72% and the residual concentrations of ammonium and phosphorus are 137.12mg/L and 5.49mg/L, respectively. Additionally, the precipitations are characterized using X-ray diffraction (XRD), fourier transform infrared spectroscopy (FT-IR), scanning electron microscope-energy dispersive spectrometer (SEM-EDS) and thermogravimetry differential scanning calorimetry (TG-DSC), respectively. Finally, a resource utilization method of the precipitation sludge from this technology is also presented. Copyright © 2017 Elsevier B.V. All rights reserved.

  13. Vertical Administration of Vanadium through Lactation Induces ...

    African Journals Online (AJOL)

    The work investigated the protective role of vitamin E on vanadium induced neurotoxicity. Three adult female rats were divided into three groups, A-C with each dam and her pups forming a group. Group A served as control. The dam in Group B was given 3mg/kg b.w./day of vanadium from PND 1 while the Group C dam ...

  14. Studies on metal-organic frameworks of Cu(II) with isophthalate linkers for hydrogen storage.

    Science.gov (United States)

    Yan, Yong; Yang, Sihai; Blake, Alexander J; Schröder, Martin

    2014-02-18

    Hydrogen (H2) is a promising alternative energy carrier because of its environmental benefits, high energy density, and abundance. However, development of a practical storage system to enable the "Hydrogen Economy" remains a huge challenge. Metal-organic frameworks (MOFs) are an important class of crystalline coordination polymers constructed by bridging metal centers with organic linkers. MOFs show promise for H2 storage owing to their high surface area and tuneable properties. In this Account, we summarize our research on novel porous materials with enhanced H2 storage properties and describe frameworks derived from 3,5-substituted dicarboxylates (isophthalates) that serve as versatile molecular building blocks for the construction of a range of interesting coordination polymers with Cu(II) ions. We synthesized a series of materials by connecting linear tetracarboxylate linkers to {Cu(II)2} paddlewheel moieties. These materials exhibit high structural stability and permanent porosity. Varying the organic linker modulates the pore size, geometry, and functionality to control the overall H2 adsorption. Our top-performing material in this series has a H2 storage capacity of 77.8 mg g(-1) at 77 K, 60 bar. H2 adsorption at low, medium, and high pressures correlates with the isosteric heat of adsorption, surface area, and pore volume, respectively. Another series, using tribranched C3-symmetric hexacarboxylate ligands with Cu(II), gives highly porous (3,24)-connected frameworks incorporating {Cu(II)2} paddlewheels. Increasing the length of the hexacarboxylate struts directly tunes the porosity of the resultant material from micro- to mesoporosity. These materials show exceptionally high H2 uptakes owing to their high surface area and pore volume. The first member of this family reported adsorbs 111 mg g(-1) of H2, or 55.9 g L(-1), at 77 K, 77 bar, while at 77 K, 1 bar, the material adsorbs 2.3 wt % H2. We and others have since achieved enhanced H2 adsorption in these

  15. A plasmid containing the human metallothionein II gene can function as an antibody-assisted electrophoretic biosensor for heavy metals.

    Science.gov (United States)

    Wooten, Dennis C; Starr, Clarise R; Lyon, Wanda J

    2016-01-01

    Different forms of heavy metals affect biochemical systems in characteristic ways that cannot be detected with typical metal analysis methods like atomic absorption spectrometry. Further, using living systems to analyze interaction of heavy metals with biochemical systems can be laborious and unreliable. To generate a reliable easy-to-use biologically-based biosensor system, the entire human metallothionein-II (MT-II) gene was incorporated into a plasmid (pUC57-MT) easily replicated in Escherichia coli. In this system, a commercial polyclonal antibody raised against human metal-responsive transcription factor-1 protein (MTF-1 protein) could modify the electrophoretic migration patterns (i.e. cause specific decreases in agarose gel electrophoretic mobility) of the plasmid in the presence or absence of heavy metals other than zinc (Zn). In the study here, heavy metals, MTF-1 protein, and polyclonal anti-MTF-1 antibody were used to assess pUC57-MT plasmid antibody-assisted electrophoretic mobility. Anti-MTF-1 antibody bound both MTF-1 protein and pUC57-MT plasmid in a non-competitive fashion such that it could be used to differentiate specific heavy metal binding. The results showed that antibody-inhibited plasmid migration was heavy metal level-dependent. Zinc caused a unique mobility shift pattern opposite to that of other metals tested, i.e. Zn blocked the antibody ability to inhibit plasmid migration, despite a greatly increased affinity for DNA by the antibody when Zn was present. The Zn effect was reversed/modified by adding MTF-1 protein. Additionally, antibody inhibition of plasmid mobility was resistant to heat pre-treatment and trypsinization, indicating absence of residual DNA extraction-resistant bacterial DNA binding proteins. DNA binding by anti-DNA antibodies may be commonly enhanced by xenobiotic heavy metals and elevated levels of Zn, thus making them potentially effective tools for assessment of heavy metal bioavailability in aqueous solutions and

  16. Comparison of hypoglycemic activity and toxicity of vanadium (IV) and vanadium (V) absorbed in fermented mushroom of Coprinus comatus.

    Science.gov (United States)

    Ma, Zhaoji; Fu, Qin

    2009-12-01

    This study was designed to evaluate the effect and toxicity of administration of vanadium (IV, V) absorbed by Coprinus comatus (VACC) on alloxan-induced and sucrosefed hyperglycemic mice, respectively. The blood glucose, lipid profile, and the organ masses of the mice were analyzed. After the mice were administered with VACC, the blood glucose and the lipid profile of hyperglycemic mice decreased, irrespective of the VACC produced by vanadium (IV) or vanadium (V). However, the organ masses of the mice were significantly different after the mice were treated with vanadium (IV) and vanadium (V) 9 weeks later. The results indicate both vanadium (IV) and vanadium (V) absorbed in C. comatus have hypoglycemic activity on hyperglycemic mice. However, vanadium (IV) absorbed in C. comatus is less toxic to mice than vanadium (V).

  17. Vanadium speciation by chromatographic separation of V(IV) and V ...

    African Journals Online (AJOL)

    A new method for vanadium speciation has been developed. The method is based on chromatographic separation of vanadium(IV) and vanadium(V) in acidic medium followed by the determination with ICP-OES. Vanadium species exist in acidic solution (pH < 3) as VO2+ for vanadium(IV) and VO2 + for vanadium(V).

  18. 77 FR 46712 - Ferrovanadium and Nitrided Vanadium From the Russian Federation: Negative Final Determination of...

    Science.gov (United States)

    2012-08-06

    ... are vanadium additives other than ferrovanadium and nitrided vanadium, such as vanadium-aluminum master alloys, vanadium chemicals, vanadium waste and scrap, vanadium-bearing raw materials, such as slag... the processing performed in the United States represents a small proportion of the value of the...

  19. Vanadium in landscape components of western Transbaikalia

    Science.gov (United States)

    Kashin, V. K.

    2017-10-01

    Vanadium in soil-forming rocks, soils, and vegetation of forest-steppe, steppe, and dry-steppe landscapes of Transbaikalia has been studied. The mean element contents in rocks and soils are equal to its mean natural abundances (clarke values). The content of vanadium in soils is strictly determined by its content in parent materials; its dependence on the vanadium concentration in plants and on the soil pH and humus is less pronounced. With respect to the coefficient of biological uptake by plants, vanadium is assigned to the group of elements of slight accumulation (0.10-0.33) on mineral soils and of moderate accumulation (1.1-1.5) on peat bog soils. The mean vanadium concentration in steppe, meadow, and cultivated vegetation exceeds the norm for animals by 1.7-2.6 times but does not rich toxic levels. Vanadium uptake by plants is most intensive in meadow cenoses and is less intensive in dry-steppe cenoses.

  20. Development of analytical techniques of vanadium isotope in seawater

    Science.gov (United States)

    Huang, T.; Owens, J. D.; Sarafian, A.; Sen, I. S.; Huang, K. F.; Blusztajn, J.; Nielsen, S.

    2015-12-01

    Vanadium (V) is a transition metal with isotopes of 50V and 51V, and oxidation states of +2, +3, +4 and +5. The average concentration in seawater is 1.9 ppb, which results in a marine residence time of ~50 kyrs. Its various oxidation states make it a potential tool for investigating redox conditions in the ocean and sediments due to redox related changes in the valance state of vanadium. In turn, chemical equilibrium between different oxidation states of V will likely cause isotopic fractionation that can potentially be utilized to quantify past ocean redox states. In order to apply V isotopes as a paleo-redox tracer, it is required that we know the isotopic composition of seawater and the relation to marine sources and sinks of V. We developed a novel method for pre-concentrating V and measuring the isotope ratio in seawater samples. In our method, we used four ion exchange chromatography columns to separate vanadium from seawater matrix elements, in particular titanium and chromium, which both have an isobaric interference on 50V. The first column uses the NOBIAS resin, which effectively separates V and other transition metals from the majority of seawater matrix. Subsequent columns are identical to those utilized when separating V from silicate samples (Nielsen et al, Geostand. Geoanal. Res., 2011). The isotopic composition of the purified V is measured using a Thermo Scientific Neptune multiple collector inductively coupled plasma mass spectrometer (MC-ICP-MS) in medium resolution mode. This setup resolves all molecular interferences from masses 49, 50, 51, 52 and 53 including S-O species on mass 50. To test the new method, we spiked an open ocean seawater sample from the Bermuda Atlantic Time Series (BATS) station with 10-25 μg of Alfa Aesar vanadium solution, which has an isotopic composition of δ51V = 0 [where δ51V = 1000 × [(51V/50Vsample - 51V/50VAA)/51V/50VAA]. The average of six spiked samples is -0.03±0.19‰, which is within error of the true

  1. Vanadium recovery from oil fly ash by leaching, precipitation and solvent extraction processes.

    Science.gov (United States)

    Navarro, R; Guzman, J; Saucedo, I; Revilla, J; Guibal, E

    2007-01-01

    In order to reduce the environmental impact due to land disposal of oil fly ash from power plants and to valorize this waste material, the removal of vanadium was investigated using leaching processes (acidic and alkaline treatments), followed by a second step of metal recovery from leachates involving either solvent extraction or selective precipitation. Despite a lower leaching efficiency (compared to sulfuric acid), sodium hydroxide was selected for vanadium leaching since it is more selective for vanadium (versus other transition metals). Precipitation was preferred to solvent extraction for the second step in the treatment since: (a) it is more selective; enabling complete recovery of vanadate from the leachate in the form of pure ammonium vanadate; and (b) stripping of the loaded organic phase (in the solvent extraction process) was not efficient. Precipitation was performed in a two-step procedure: (a) aluminum was first precipitated at pH 8; (b) then ammonium chloride was added at pH 5 to bring about vanadium precipitation.

  2. Selenium, Vanadium, and Chromium as Micronutrients to Improve Metabolic Syndrome.

    Science.gov (United States)

    Panchal, Sunil K; Wanyonyi, Stephen; Brown, Lindsay

    2017-03-01

    Trace metals play an important role in the proper functioning of carbohydrate and lipid metabolism. Some of the trace metals are thus essential for maintaining homeostasis, while deficiency of these trace metals can cause disorders with metabolic and physiological imbalances. This article concentrates on three trace metals (selenium, vanadium, and chromium) that may play crucial roles in controlling blood glucose concentrations possibly through their insulin-mimetic effects. For these trace metals, the level of evidence available for their health effects as supplements is weak. Thus, their potential is not fully exploited for the target of metabolic syndrome, a constellation that increases the risk for cardiovascular disease and type 2 diabetes. Given that the prevalence of metabolic syndrome is increasing throughout the world, a simpler option of interventions with food supplemented with well-studied trace metals could serve as an answer to this problem. The oxidation state and coordination chemistry play crucial roles in defining the responses to these trace metals, so further research is warranted to understand fully their metabolic and cardiovascular effects in human metabolic syndrome.

  3. Nearby Spiral Galaxy Globular Cluster Systems. II. Globular Cluster Metallicities in NGC 300

    Science.gov (United States)

    Nantais, Julie B.; Huchra, John P.; Barmby, Pauline; Olsen, Knut A. G.

    2010-03-01

    We present new metallicity estimates for globular cluster (GC) candidates in the Sd spiral NGC 300, one of the nearest spiral galaxies outside the Local Group. We have obtained optical spectroscopy for 44 Sculptor Group GC candidates with the Boller and Chivens (B&C) spectrograph on the Baade Telescope at Las Campanas Observatory. There are two GCs in NGC 253 and 12 objects in NGC 300 with globular-cluster-like spectral features, nine of which have radial velocities above 0 km s-1. The remaining three, due to their radial velocities being below the expected 95% confidence limit for velocities of NGC 300 halo objects, are flagged as possible foreground stars. The non-cluster-like candidates included 13 stars, 15 galaxies, and an H II region. One GC, four galaxies, two stars, and the H II region from our sample were identified in archival Hubble Space Telescope images. For the GCs, we measure spectral indices and estimate metallicities using an empirical calibration based on Milky Way GCs. The GCs of NGC 300 appear similar to those of the Milky Way. Excluding possible stars and including clusters from the literature, the GC system (GCS) has a velocity dispersion of 68 km s-1 and has no clear evidence of rotation. The mean metallicity for our full cluster sample plus one literature object is [Fe/H] = -0.94, lying above the relationship between mean GC metallicity and overall galaxy luminosity. Excluding the three low-velocity candidates, we obtain a mean [Fe/H] = -0.98, still higher than expected, raising the possibility of significant foreground star contamination even in this sample. Visual confirmation of genuine GCs using high-resolution space-based imagery could greatly reduce the potential problem of interlopers in small samples of GCSs in low-radial-velocity galaxies. Data for this project were obtained at the Baade 6.5 m telescope, Las Campanas Observatory, Chile. This publication makes use of data products from the Two Micron All Sky Survey, which is a joint

  4. MODIFICATION OF KELUD VOLCANIC ASH 2014 AS SELECTIVE ADSORBENT MATERIAL FOR COPPER(II METAL ION

    Directory of Open Access Journals (Sweden)

    Susila Kristianingrum

    2017-01-01

      This research aims to prepare an adsorbent from Kelud volcanic ash for better Cu(II adsorption efficiency than Kiesel gel 60G E'Merck. Adsorbent synthesis was done by dissolving 6 grams of volcanic ash activated 700oC 4 hours and washed with HCl 0.1 M into 200 ml of 3M sodium hydroxide with stirring and heating of 100 °C for 1 hour. The filtrate sodium silicate was then neutralized using sulfuric acid. The mixture was allowed to stand for 24 hours then filtered and washed with aquaDM, then dried and crushed. The procedure is repeated for nitric acid, acetic acid and formic acid with a contact time of 24 hours. The products were then characterized using FTIR and XRD, subsequently determined acidity, moisture content, and tested for its adsorption of the ion Cu (II with AAS. The results showed that the type of acid that produced highest rendemen is AK-H2SO4-3M ie 36.93%, acidity of the adsorbent silica gel synthesized similar to Kiesel gel 60G E'Merck ie adsorbent AK-CH3COOH-3M and the water content of the silica gel adsorbent synthesized similar to Kiesel gel 60G E'Merck ie adsorbent AK-H2SO4-2 M. The character of the functional groups of silica gel synthesized all have similarities with Kiesel gel 60G E'Merck as a comparison. Qualitative analysis by XRD for all modified adsorbent showed a dominant peak of SiO2 except adsorbent AK-H2SO4 amorphous and chemical bonds with FTIR indicates that it has formed a bond of Si-O-Si and Si-OH. The optimum adsorption efficiency of the metal ions Cu(II obtained from AK-H2SO4-5M adsorbent that is equal to 93.2617% and the optimum adsorption capacity of the Cu(II metal ions was obtained from the adsorbent AK-CH3COOH-3M is equal to 2.4919 mg/ g.   Keywords: adsorbents, silica gel, adsorption, kelud volcanic ash

  5. Interactions of Penicillium griseofulvum with inorganic and organic substrates: vanadium, lead and hexachlorocyclohexane

    Science.gov (United States)

    Ceci, Andrea; Pierro, Lucia; Riccardi, Carmela; Maggi, Oriana; Pinzari, Flavia; Gadd, Geoffrey Michael; Petrangeli Papini, Marco; Persiani, Anna Maria

    2015-04-01

    Soil is an essential and non-renewable resource for human beings and ecosystems. In recent years, anthropogenic activities mainly related to hydrocarbon fuel combustion, mining and industrial activities have increased the levels of vanadium in the environment, raising concern over its spread. Vanadium may be essential for some bacteria and fungi, but can have toxic effects at high concentrations. The pesticide lindane or γ-hexachlorocyclohexane (γ-HCH) and another two isomers of hexachlorocyclohexane (HCH), α-HCH, and β-HCH, were included as persistent organic pollutants in the Stockholm Convention in 2008, and their worldwide spread and toxic effects on organisms are severe environmental problems. Fungi play important roles in soil and can survive in high concentrations of toxic elements and pesticides by possessing mechanisms for the degradation, utilization and transformation of organic and inorganic substrates. The transformation of potentially toxic elements (PTEs), and degradation of chlorinated pesticides and other persistent organic pollutants may provide environmentally-friendly and economical approaches for environmental management and restoration. In this work, we have investigated the tolerance of a soil fungal species, Penicillum griseofulvum, to different hexachlorocyclohexane (HCH) isomers, α-HCH, β-HCH, δ-HCH and γ-HCH or lindane, and two PTEs, vanadium and lead in relation to growth responses and biotransformation. P. griseofulvum was isolated from soils with high levels of PTEs (including vanadium and lead), and HCH residues. P. griseofulvum was able to tolerate vanadium concentrations up to 5 mM, combinations of 2.5 mM vanadium and lead compounds, and was able to grow in the presence of a 4 mg L-1 mixture of α-HCH, β-HCH, δ-HCH and γ-HCH, and degrade these substrates. Tolerance mechanisms may explain the occurrence of fungi in polluted habitats: their roles in the biotransformation of metals and persistent organic pollutants may

  6. Nickel(II) oxide nanostructure derived from metal-organic frameworks and its adsorption capability

    Science.gov (United States)

    Ru, Shuai; Xu, Lina; Xiao, Hongping; Li, Xinhua

    2016-11-01

    Nanosized nickel(II) oxide (NiO) was obtained by oxidation of ([(Ni2(nic)4(H2O)] n , nic = nicotinic acid), a metal-organic framework (MOF), at 350 °C. Nanosized NiO assembled to form block NiO having a mesoporous structure similar to the porous structure of activated carbon block. This bulk NiO exhibits excellent adsorbing capability, with 100% higher adsorption capacities than the [(Ni2(nic)4(H2O)] n MOF towards toluene and water steam; therefore, it can find potential application in gas adsorption. Moreover, this bulk NiO can be synthesized using a facile, environment-friendly, and cost-effective method, and exhibits excellent hydrothermal stability, which is not commonly observed for MOFs.

  7. Direct Synthesis of 7 nm Thick Zinc(II)-Benzimidazole-Acetate Metal-Organic Framework Nanosheets

    Energy Technology Data Exchange (ETDEWEB)

    Xue, Feng; Kumar, Prashant; Xu, Wenqian; Mkhoyan, K. Andre; Tsapatsis, Michael

    2018-01-09

    Two-dimensional metal-organic frameworks (MOFs) are promising candidates for high performance gas sepa-ration membranes. Currently, MOF nanosheets are mostly fabricated through delamination of layered MOFs, which often re-sults in a low yield of intact free-standing nanosheets. In this work, we present a direct synthesis method for zinc(II)-benzimidazole-acetate (Zn(Bim)OAc) MOF nanosheets. The obtained nanosheets have a lateral dimension of 600 nm when synthesized at room temperature. By adjusting the synthesis temperature, the morphology of obtained nanosheets can be readily tuned from nanosheets to nanobelts. A thickness of 7 nm is determined for Zn(Bim)OAc using high-angle annular dark-field scanning transmission electron microscopy, which makes these nanosheets promising building blocks of gas sepa-ration membranes.

  8. Theoretical study of heavy metal Cd, Cu, Hg, and Ni(II) adsorption on the kaolinite(0 0 1) surface

    Science.gov (United States)

    Zhao, Jian; He, Man-Chao

    2014-10-01

    Heavy metal pollution is currently of great concern because it has been recognized as a potential threat to air, water, and soil. Adsorption was one of the most popular methods for the removal of heavy metal. The adsorption of heavy metal Cd, Cu, Hg, and Ni(II) atoms on the hydroxylated (0 0 1) surface of kaolinite was investigated using density-functional theory within the generalized gradient approximation and a supercell approach. The coverage dependence of the adsorption structures and energetics were systematically studied for a wide range of coverage Θ [from 0.11 to 1.0 monolayers (ML)] and adsorption sites. The most stable among all possible adsorption sites for Cd(II) atom was the two-fold bridge site followed by the one-fold top site, and the top site was the most favorite adsorption site for Cu and Ni(II) atoms, while the three-fold hollow site was the most stable adsorption site for Hg(II) atom followed by the two-fold bridge site. The adsorption energy increases with the coverage for Cd, Cu, and Hg(II) atoms, thus indicating the higher stability of surface adsorption and a tendency to the formation of adsorbate islands (clusters) with increasing the coverage. However, the adsorption energy of Ni(II) atoms decreases when increasing the coverage. The adsorption capabilities of the kaolinite clay for the heavy metal atoms were in the order of Ni > Cu > Cd > Hg(II). The other properties of the Cd, Cu, Hg, and Ni(II)/kaolinite(0 0 1) system including the different charge distribution, the lattice relaxation, and the electronic density of states were also studied and discussed in detail.

  9. Allergy to orthopedic metal implants - a prospective study.

    Science.gov (United States)

    Kręcisz, Beata; Kieć-Świerczyńska, Marta; Chomiczewska-Skóra, Dorota

    2012-09-01

    Evaluation of the allergenic properties of the metal knee or hip joint implants 24 months post surgery and assessment of the relation between allergy to metals and metal implants failure. The study was conducted in two stages. Stage I (pre-implantation) - 60 patients scheduled for arthroplasty surgery. Personal interview, dermatological examination and patch testing with 0.5% potassium dichromate, 1.0% cobalt chloride, 5.0% nickel sulfate, 2.0% copper sulfate, 2.0% palladium chloride, 100% aluminum, 1% vanadium chloride, 5% vanadium, 10% titanium oxide, 5% molybdenum and 1% ammonium molybdate tetrahydrate were performed. Stage II (post-surgery) - 48 subjects participated in the same procedures as those conducted in Stage I. Stage I - symptoms of "metal dermatitis" were found in 21.7% of the subjects: 27.9% of the females, 5.9% of the males. Positive patch test results were found in 21.7% of the participants, namely to: nickel (20.0%); palladium (13.3%); cobalt (10.0%); and chromium (5.9%). The allergy to metals was confirmed by patch testing in 84.6% of the subjects with a history of metal dermatitis. Stage II - 10.4% of the participants complained about implant intolerance, 4.2% of the examined persons reported skin lesions. Contact allergy to metals was found in 25.0% of the patients: nickel 20.8%, palladium 10.4%, cobalt 16.7%, chromium 8.3%, vanadium 2.1% Positive post-surgery patch tests results were observed in 10.4% of the patients. The statistical analysis of the pre- and post-surgery patch tests results showed that chromium and cobalt can be allergenic in implants. Metal orthopedic implants may be the primary cause of allergies. that may lead to implant failure. Patch tests screening should be obligatory prior to providing implants to patients reporting symptoms of metal dermatitis. People with confirmed allergies to metals should be provided with implants free from allergenic metals.

  10. Multiobjective Optimization for Fixture Locating Layout of Sheet Metal Part Using SVR and NSGA-II

    Directory of Open Access Journals (Sweden)

    Yuan Yang

    2017-01-01

    Full Text Available Fixture plays a significant role in determining the sheet metal part (SMP spatial position and restraining its excessive deformation in many manufacturing operations. However, it is still a difficult task to design and optimize SMP fixture locating layout at present because there exist multiple conflicting objectives and excessive computational cost of finite element analysis (FEA during the optimization process. To this end, a new multiobjective optimization method for SMP fixture locating layout is proposed in this paper based on the support vector regression (SVR surrogate model and the elitist nondominated sorting genetic algorithm (NSGA-II. By using ABAQUS™ Python script interface, a parametric FEA model is established. And the fixture locating layout is treated as design variables, while the overall deformation and maximum deformation of SMP under external forces are as the multiple objective functions. First, a limited number of training and testing samples are generated by combining Latin hypercube design (LHD with FEA. Second, two SVR prediction models corresponding to the multiple objectives are established by learning from the limited training samples and are integrated as the multiobjective optimization surrogate model. Third, NSGA-II is applied to determine the Pareto optimal solutions of SMP fixture locating layout. Finally, a multiobjective optimization for fixture locating layout of an aircraft fuselage skin case is conducted to illustrate and verify the proposed method.

  11. Iron diminishes the in vitro biological effect of vanadium.

    Science.gov (United States)

    Mechanistic pathways underlying inflammatory injury following exposures to vanadium-containing compounds are not defined. We tested the postulate that the in vitro biological effect of vanadium results from its impact on iron homeostasis. Human bronchial epithelial (HBE) cells ex...

  12. Synthesis and characterization of transition metal 2,6-pyridinedicarboxylic acid derivatives, interactions of Cu(II) and Ni(II) complexes with DNA in vitro

    Science.gov (United States)

    Khan, Sadaf; Nami, Shahab A. A.; Siddiqi, K. S.; Husain, Eram; Naseem, Imrana

    2009-03-01

    Mononuclear complexes M(L)Cl 2 where M = Mn(II), Fe(II), Co(II), Ni(II) and Cu(II) and (L = N,N-diethylpiperazinyl,2,6-pyridinedicarboxylate), have been synthesized and characterized by elemental analysis, FT-IR, 1H NMR spectroscopy, UV-vis, magnetic moment, TGA/DSC, cyclic voltammetry and conductivity measurement data. The spectral data suggests that the dipicolinic acid acts as a bidentate ligand and is coordinated to the metal ion through the carboxylate oxygen. The cyclic voltammogram for Cu(L)Cl 2 complex was found to display two reversible Cu(II)/Cu(I) and Cu(II)/Cu(III) redox couple. The ligand exhibits a two-step thermolytic pattern while the complexes decompose in three stages respectively. An octahedral geometry has been proposed for both the complexes. The investigation of the interaction of the complexes with calf thymus DNA has been performed with absorption spectroscopy and fluorescence quenching experiments, which showed that the complexes are avid binders of calf thymus DNA. Also the interaction of the Cu(II) and Ni(II) complexes with plasmid DNA (pUC 19) was studied using agarose gel electrophoresis. The results revealed that these complexes can act as effective DNA cleaving agents resulting in the nicked form of DNA (pUC 19) under physiological conditions. The gel was run both in the absence and presence of an oxidizing agent (H 2O 2). The ligand and its complexes have also been screened against microbes in order to study their antibacterial action. The results revealed that the Cu(II) complex has activity comparable with the reference drugs gentamycin and flucanzole.

  13. Mutational analysis of divalent metal ion binding in the active site of class II α-mannosidase from sulfolobus solfataricus

    DEFF Research Database (Denmark)

    Hansen, Dennis K.; Webb, Helen; Nielsen, Jonas Willum

    2015-01-01

    Mutational analysis of Sulfolobus solfataricus class II α-mannosidase was focused on side chains that interact with the hydroxyls of the-1 mannosyl of the substrate (Asp-534) or form ligands to the active site divalent metal ion (His-228 and His-533) judged from crystal structures of homologous...

  14. Two luminescent Zn(II) metal-organic frameworks for exceptionally selective detection of picric acid explosives.

    Science.gov (United States)

    Shi, Zhi-Qiang; Guo, Zi-Jian; Zheng, He-Gen

    2015-05-14

    Two luminescent Zn(II) metal-organic frameworks were prepared from a π-conjugated thiophene-containing carboxylic acid ligand. These two MOFs show strong luminescene and their luminescence could be quenched by a series of nitroaromatic explosives. Importantly, they exhibit very highly sensitive and selective detection of picric acid compared to other nitroaromatic explosives.

  15. Rapid and specific luminescence sensing of Cu(ii) ions with a porphyrinic metal-organic framework.

    Science.gov (United States)

    Li, Linnan; Shen, Sensen; Lin, Ruoyun; Bai, Yu; Liu, Huwei

    2017-09-05

    We herein present a porphyrinic metal-organic framework (MOF) as a highly sensitive fluorescent probe targeting Cu(ii) ions with a fast response. The well-isolated nature of porphyrin moieties within the framework greatly enable accessible recognition sites, which leads to an outstanding detection limit performance of 67 nM among MOF-based materials.

  16. 77 FR 51825 - Ferrovanadium and Nitrided Vanadium From Russia

    Science.gov (United States)

    2012-08-27

    ... COMMISSION Ferrovanadium and Nitrided Vanadium From Russia Determination On the basis of the record \\1... antidumping duty order on ferrovanadium and nitrided vanadium from Russia would not be likely to lead to... contained in USITC Publication 4345 (August 2012), entitled Ferrovanadium and Nitrided Vanadium from Russia...

  17. Determination of Leachable Vanadium (V) in Sediment | Mampuru ...

    African Journals Online (AJOL)

    A method for speciation of vanadium in solid samples was developed for quantification of vanadium(+5) in solid samples of sediment Certified Reference Materials (CRM) PACS-2 and MESS-3 (Trace Elements in Sediments) of known total vanadium content. The method relies on a classical analytical chemistry procedure ...

  18. Improved recovery of trace amounts of gold (III), palladium (II) and platinum (IV) from large amounts of associated base metals using anion-exchange resins.

    Science.gov (United States)

    Matsubara, I; Takeda, Y; Ishida, K

    2000-02-01

    The adsorption and desorption behaviors of gold (III), palladium (II) and platinum (IV) were surveyed in column chromatographic systems consisting of one of the conventional anion-exchange resins of large ion-exchange capacity and dilute thiourea solutions. The noble metals were strongly adsorbed on the anion-exchange resins from dilute hydrochloric acid, while most base metals did not show any marked adsorbability. These facts made it possible to separate the noble metals from a large quantity of base metals such as Ag (I), Al (III), Co (II), Cu (II), Fe (III), Mn (II), Ni (II), Pb (II), and Zn (II). Although it used to be very difficult to desorb the noble metals from the resins used, the difficulty was easily overcome by use of dilute thiourea solutions as an eluant. In the present study, as little as 1.00 microg of the respective noble metals was quantitatively separated and recovered from as much as ca. 10 mg of a number of metals on a small column by elution with a small amount of dilute thiourea solution. The present systems should be applicable to the separation, concentration and recovery of traces of the noble metals from a number of base metals coexisting in a more extended range of amounts and ratios.

  19. Breakdown of half-metallic ferromagnetism in zinc-blende II-V compounds: First-principles calculations

    Science.gov (United States)

    Li, Yun; Yu, Jaejun

    2008-10-01

    We investigated the electronic and magnetic properties of a series of zinc-blend II-V compounds by carrying out density-functional theory calculations including spin-orbit couplings. Contrary to the case of CaN and CaP, the half-metallic characteristics of the II-V compounds such as CaBi were found to be destroyed. Our analysis of the valence-band structures of CaAs, CaSb, and CaBi revealed a critical role of the spin-orbit coupling interactions on the exchange-split band structure, thereby leading to breakdown of the half-metallic ferromagnetism for the systems with heavier group V elements in the zinc-blend II-V compounds.

  20. The removal of toxic metals from liquid effluents by ion exchange resins. Part II: cadmium(II/ sulphate/Lewatit TP260

    Directory of Open Access Journals (Sweden)

    Alguacil, F. J.

    2002-10-01

    Full Text Available The adsorption of cadmium (II, from aqueous sulphate solutions, on Lewatit TP260 resin has been investigated in batch equilibrium experiments. The influence of pH and temperature on metal adsorption capacity have also been examined. The kinetic performance of the resin has been assesed and the results have been correlated by the pore diffusion model. The resin has been used in mini-columns to study its performance under dynamics conditions. The desorption of metal ion is achieved using sulphuric acid (0.25M and 0.5M.

    Se estudia la adsorción de cadmio(II, de disoluciones en medio sulfato, sobre la resina Lewatit TP260. La adsorción del metal se ha investigado en función del pH, la temperatura y el tiempo de contacto con la resina. Los estudios cinéticos permiten correlacionar el proceso de intercambio iónico con el modelo de difusión en poro. Se ha empleado el sistema en mini columnas para evaluar el comportamiento de la resina bajo condiciones dinámicas. La desorción del metal se lleva a cabo con disoluciones de ácido sulfúrico (0,25M y 0,5M.

  1. The role of vanadium haloperoxidases in the formation of volatile brominated compounds and their impact on the environment

    NARCIS (Netherlands)

    Wever, R.; van der Horst, M.A.

    2013-01-01

    Vanadium haloperoxidases differ strongly from heme peroxidases in substrate specificity and stability and in contrast to a heme group they contain the bare metal oxide vanadate as a prosthetic group. These enzymes specifically oxidize halides in the presence of hydrogen peroxide into hypohalous

  2. Vanadium(IV/V) speciation of pyridine-2,6-dicarboxylic acid and 4-hydroxy-pyridine-2,6-dicarboxylic acid complexes: potentiometry, EPR spectroscopy and comparison across oxidation states.

    Science.gov (United States)

    Jakusch, Tamás; Jin, Wenzheng; Yang, Luqin; Kiss, Tamás; Crans, Debbie C

    2003-05-01

    Evaluation of stability of vanadium(IV) and (V) complexes under similar conditions is critical for the interpretation and assessment of bioactivity of various vanadium species. Detailed understanding of the chemical properties of these complexes is necessary to explain differences observed their activity in biological systems. These studies are carried out to link the chemistry of both vanadium(IV) and (V) complexes of two ligands, 2,6-pyridinedicarboxylic acid (dipicolinic acid, H(2)dipic) and 4-hydroxy-2,6-pyridinedicarboxylic acid (H(2)dipic-OH). Solution speciation of the two 2,6-pyridinedicarboxylic acids with vanadium(IV) and vanadium(V) ions was determined by pH-potentiometry at I=0.2 M (KCl) ionic strength and at T=298 K. The stability and the metal affinities of the ligands were compared. Vanadium(V) complexes were found to form only tridentate coordinated 1:1 complexes, while vanadium(IV) formed complexes with both 1:1 and 1:2 stoichiometries. The formation constant reflects hindered coordination of a second ligand molecule, presumably because of the relatively small size of the metal ion. The most probable binding mode of the complexes was further explored using ambient and low temperature EPR spectroscopy for vanadium(IV) and 51V NMR spectroscopy for vanadium(V) systems. Upon complex formation the pyridinol-OH in position 4 deprotonates with pK approximately 3.7-4.1, which is approximately 6 orders of magnitude lower than that of the free ligand. The deprotonation enhances the ligand metal ion affinity compared to the parent ligand dipicolinic acid. In the light of the speciation and stability data of the metal complexes, the efficiency of the two ligands in transporting the metal ion in the two different oxidation states are assessed and discussed.

  3. Atomic layer deposition of VO{sub 2} films with Tetrakis-dimethyl-amino vanadium (IV) as vanadium precursor

    Energy Technology Data Exchange (ETDEWEB)

    Lv, Xinrui [Key Laboratory of Inorganic Coating Materials CAS, Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 201800 (China); University of Chinese Academy of Sciences, Beijing 100049 (China); Cao, Yunzhen, E-mail: yzhcao@mail.sic.ac.cn [Key Laboratory of Inorganic Coating Materials CAS, Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 201800 (China); Yan, Lu; Li, Ying; Song, Lixin [Key Laboratory of Inorganic Coating Materials CAS, Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 201800 (China)

    2017-02-28

    Highlights: • VO{sub 2} film was easily deposited by ALD using novel vanadium precursor V(NMe{sub 2}){sub 4}. • Deposition and annealing condition were systematically investigated. • Comparable transition properties of VO{sub 2} film on resistance and spectral transmittance were studied. - Abstract: VO{sub 2} thin films have been grown on Si(100) (VO{sub 2}/Si) and fused silica substrates (VO{sub 2}/SiO{sub 2}) by atomic layer deposition (ALD) using tetrakis-dimethyl-amino vanadium (IV) (TDMAV) as a novel vanadium precursor and water as reactant gas. The quartz crystal microbalance (QCM) measurement was performed to study the ALD process of VO{sub 2} thin film deposition, and a constant growth rate of about 0.95 Å/cycle was obtained at the temperature range of 150–200 °C. XRD measurement was performed to study the influence of deposition temperature and post-annealing condition on the crystallization of VO{sub 2} films, which indicated that the films deposited between 150 and 200 °C showed well crystallinity after annealing at 475 °C for 100 min in Ar atmosphere. XPS measurement verified that the vanadium oxidation state was 4+ for both as-deposited film and post-annealed VO{sub 2}/Si film. AFM was applied to study the surface morphology of VO{sub 2}/Si films, which showed a dense polycrystalline film with roughness of about 1 nm. The resistance of VO{sub 2}/Si films deposited between 150 °C and 200 °C as a function of temperature showed similar semiconductor-to-metal transition (SMT) characters with the transition temperature for heating branch (T{sub c,h}) of about 72 °C, a hysteresis width of about 10 °C and the resistance change of two orders of magnitude. The increase of T{sub c,h} compared with the bulk VO{sub 2} (68 °C) may be attributed to the tensile stress along the c-axis in the film. Transmittance measurement of VO{sub 2}/SiO{sub 2} films showed typical thermochromic property with a NIR switching efficiency of above 50% at 2 μm across

  4. An extraction-chromogenic system for vanadium(IV,V based on 2,3-dihydroxynaphtahlene

    Directory of Open Access Journals (Sweden)

    Gavazov Kiril B.

    2016-10-01

    Full Text Available A liquid-liquid extraction-chromogenic system for vanadium(IV, V containing 2,3-dihydroxynaphtahlene (DN, 2,3,5-triphenyl-2H-tetrazolium chloride (TTC, water and chloroform was studied in detail. When the vanadium is in the oxidation state of IV, the extracted species are aggregates containing three 1:2:1 (V:DN:TTC ion-pair units composed of triphenyltetrazolium cations (TT+ and chelate anions {[VIVO(DN(DNH]− (I and/or [VIV(OH(DN2]− (II}. When the initial oxidation state of vanadium is V and the DN concentration is high, vanadium(V is reduced by DN to a lower oxidation state, V(IV. However, at low DN concentration, vanadium(V can enter the organic phase as a part of an ion-pair consisting of TT+ and [VVO2(DN]− (III. The ground-state equilibrium geometries of the anions I, II, and III were optimized by quantum chemical calculations using BLYP/6-31++G⋆. The following characteristics were determined under the optimum conditions for VIV extraction: absorption maximum λmax = 333 nm, molar absorptivity ε333= 2.1x104 dm3 mol−1 cm−1, Sandell’s sensitivity SS = 2.4 ng cm−2, and fraction extracted E = 98%. The conditional extraction constant was calculated by two independent methods. The calibration graph was linear in the range 0.1-3.1 μg cm−3 (R2=0.9994 and the limit of detection was 0.03 μg cm−3.

  5. Bipolar resistive switching in room temperature grown disordered vanadium oxide thin-film devices

    Science.gov (United States)

    Wong, Franklin J.; Sriram, Tirunelveli S.; Smith, Brian R.; Ramanathan, Shriram

    2013-09-01

    We demonstrate bipolar switching with high OFF/ON resistance ratios (>104) in Pt/vanadium oxide/Cu structures deposited entirely at room temperature. The SET (RESET) process occurs when negative (positive) bias is applied to the top Cu electrode. The vanadium oxide (VOx) films are amorphous and close to the vanadium pentoxide stoichiometry. We also investigated Cu/VOx/W structures, reversing the position of the Cu electrode, and found the same polarity dependence with respect to the top and bottom electrodes, which suggests that the bipolar nature is linked to the VOx layer itself. Bipolar switching can be observed at 100 °C, indicating that it not due to a temperature-induced metal-insulator transition of a vanadium dioxide second phase. We discuss how ionic drift can lead to the bipolar electrical behavior of our junctions, similar to those observed in devices based on several other defective oxides. Such low-temperature processed oxide switches could be of relevance to back-end or package integration processing schemes.

  6. Influence of titanium and vanadium on the hydrogen transport through amorphous alumina films

    Energy Technology Data Exchange (ETDEWEB)

    Palsson, G.K. [Department of Physics, Uppsala University, Box 530, S-751 21 Uppsala (Sweden); Wang, Y.T. [Department of Physics, Uppsala University, Box 530, S-751 21 Uppsala (Sweden); Azofeifa, D. [Centro de Investigacion en Ciencia e Ingenieria de Materiales and Escuela de Fisica, Universidad de Costa Rica, San Jose (Costa Rica); Raanaei, H. [Department of Physics, Uppsala University, Box 530, S-751 21 Uppsala (Sweden); Department of Physics, Persian Gulf University, Bushehr 75168 (Iran, Islamic Republic of); Sahlberg, M. [Department of Materials Chemistry, Uppsala University, Box 538, S-751 21 Uppsala (Sweden); Hjoervarsson, B. [Department of Physics, Uppsala University, Box 530, S-751 21 Uppsala (Sweden)

    2010-04-02

    The influence of titanium and vanadium on the hydrogen transport rate through thin amorphous alumina films is addressed. Only small changes in the transport rate are observed when the Al{sub 2}O{sub 3} are covered with titanium or vanadium. This is in stark contrast to results with a Pd overlayer, which enhances the transport by an order of magnitude. Similarly, when titanium is embedded into the alumina the transport rate is faster than for the covered case but still slower than the undoped reference. Embedding vanadium in the alumina does not yield an increase in uptake rate compared to the vanadium covered oxide layers. These results add to the understanding of the hydrogen uptake of oxidized metals, especially the alanates, where the addition of titanium has been found to significantly enhance the rate of hydrogen uptake. The current findings eliminate two possible routes for the catalysis of alanates by Ti, namely dissociation and effective diffusion short-cuts formed by Ti. Finally, no photocatalytic enhancement was noticed on the titanium covered samples.

  7. Simultaneous oxidation of EDTA and reduction of metal ions in mixed Cu(II)/Fe(III)-EDTA system by TiO2 photocatalysis.

    Science.gov (United States)

    Park, Eun-Hee; Jung, Jinho; Chung, Hung-Ho

    2006-06-01

    Both the photooxidation of EDTA and the photoreduction of metal ions in metal-EDTA systems were investigated. EDTA oxidation by TiO(2) photocatalysis occurred sequentially as Cu(II)-EDTA>Cu(II)/Fe(III)-EDTA>Fe(III)-EDTA. For Cu(II)-EDTA, EDTA was completely decomposed after only 60min of irradiation. The rate of EDTA decomposition was directly correlated with the initial Cu(II) concentration in the case of a mixed Cu(II)/Fe(III)-EDTA system. The metal ions in a single metal-EDTA complex were removed following significant decomposition of EDTA. For a mixed Cu(II)/Fe(III)-EDTA system, however, no copper was removed whereas almost all of the iron was removed. The iron and copper species deposited on the TiO(2) surface were identified via EPR and XPS as mixed FeO/Fe(3)O(4) and Cu(0)/Cu(2)O, respectively.

  8. Peripherally and non-peripherally tetra-benzothiazole substituted metal-free zinc (II) and lead (II) phthalocyanines: Synthesis, characterization, and investigation of photophysical and photochemical properties

    Science.gov (United States)

    Demirbaş, Ümit; Göl, Cem; Barut, Burak; Bayrak, Rıza; Durmuş, Mahmut; Kantekin, Halit; Değirmencioğlu, İsmail

    2017-02-01

    In this study, novel phthalonitrile compounds bearing 2-methylbenzo[d]thiazol-5-yloxy groups (4 and 5) and their peripherally and non-peripherally tetra-substituted metal-free (6 and 7), zinc (II) (8 and 9), and lead (II) (10 and 11) phthalocyanine derivatives were synthesized and characterized for the first time. These novel compounds showed extremely good solubility in most common organic solvents. The novel phthalocyanine compounds presented excellent results from photophysical and photochemical examinations in DMF solution. Especially, the singlet oxygen quantum yield (ΦΔ) values of the substituted zinc (II) phthalocyanines indicate that these compounds have significant potential as photosensitizers in cancer treatment by the photodynamic therapy (PDT) technique. The fluorescence quenching behaviour of these novel phthalocyanine compounds by 1,4-benzoquinone (BQ) was also examined in DMF solution.

  9. Transition metal complexes of neocryptolepine analogues. Part I: Synthesis, spectroscopic characterization, and invitro anticancer activity of copper(II) complexes

    Science.gov (United States)

    Emam, Sanaa Moustafa; El Sayed, Ibrahim El Tantawy; Nassar, Nagla

    2015-03-01

    New generation of copper(II) complexes with aminoalkylaminoneocryptolepine as bidentate ligands has been synthesized and it is characterized by elemental analyses, magnetic moment, spectra (IR, UV-Vis, 1H NMR and ESR) and thermal studies. The IR data suggest the coordination modes for ligands which behave as a bidentate with copper(II) ion. Based on the elemental analysis, magnetic studies, electronic and ESR data, binuclear square planar geometry was proposed for complexes 7a, 7b, square pyramidal for 9a, 9b and octahedral for 8a, 8b, 10a, 10b. The molar conductance in DMF solution indicates that all complexes are electrolyte except 7a and 7b. The ESR spectra of solid copper(II) complexes in powder form showed an axial symmetry with 2B1g as a ground state and hyperfine structure. The thermal stability and degradation of the ligands and their metal complexes were studied employing DTA and TG methods. The metal-free ligands and their copper(II) complexes were tested for their in vitro anticancer activity against human colon carcinoma (HT-29). The results showed that the synthesized copper(II) complexes exhibited higher anticancer activity than their free ligands. Of all the studied copper(II) complexes, the bromo-substituted complex 9b exhibited high anticancer activity at low micromolar inhibitory concentrations (IC50 = 0.58 μM), compared to the other complexes and the free ligands.

  10. Influence of Environmental Factors and Relationships between Vanadium, Chromium, and Calcium in Human Bone

    OpenAIRE

    Natalia Lanocha-Arendarczyk; Kosik-Bogacka, Danuta I.; Elzbieta Kalisinska; Sebastian Sokolowski; Lukasz Kolodziej; Halina Budis; Krzysztof Safranow; Karolina Kot; Zaneta Ciosek; Natalia Tomska; Katarzyna Galant

    2016-01-01

    The aim of this study was to investigate the impact of environmental factors on the concentrations of vanadium (V), chromium (Cr), and calcium (Ca) and to examine the synergistic or antagonistic relationships between these metals, in cartilage (C), cortical bone (CB), and spongy bone (SB) samples obtained following hip joint surgery on patients with osteoarthritis in NW Poland. We found significantly higher concentrations of V and Cr in spongy bone in patients who consumed game meat and also ...

  11. Metal based biologically active compounds: Design, synthesis, DNA binding and antidiabetic activity of 6-methyl-3-formyl chromone derived hydrazones and their metal (II) complexes.

    Science.gov (United States)

    Philip, Jessica Elizabeth; Shahid, Muhammad; Prathapachandra Kurup, M R; Velayudhan, Mohanan Puzhavoorparambil

    2017-10-01

    Two chromone hydrazone ligands HL 1 and HL 2 were synthesized and characterized by elemental analyses, IR, 1 H NMR & 13 C NMR, electronic absorption and mass spectra. The reactions of the chromone hydrazones with transition metals such as Ni, Cu, and Zn (II) salts of acetate afforded mononuclear metal complexes. Characterization and structure elucidation of the prepared chromone hydrazone metal (II) complexes were done by elemental, IR, electronic, EPR spectra and thermo gravimetric analyses as well as conductivity and magnetic susceptibility measurements. The spectroscopic data showed that the ligand acts as a mono basic bidentate with coordination sites are azomethine nitrogen and hydrazonic oxygen, and they exhibited distorted geometry. The biological studies involved antidiabetic activity i.e. enzyme inhibition of α-amylase and α-glucosidase, Calf Thymus - DNA (CT-DNA) interaction and molecular docking. Potential capacity of synthesized compounds to inhibit the α-amylase and α-glucosidase activity was assayed whereas DNA interaction studies were carried out with the help UV-Vis absorption titration and viscosity method. The docking studies of chromone hydrazones show that they are minor groove binders. Complexes were found to be good DNA - intercalates. Chromone hydrazones and its transition metal complexes have shown comparable antidiabetic activity with a standard drug acarbose. Copyright © 2017 Elsevier B.V. All rights reserved.

  12. Liquid Metallic Hydrogen II. A Critical Assessment of Current and Primordial Helium Levels in the Sun

    Directory of Open Access Journals (Sweden)

    Robitaille P.-M.

    2013-04-01

    lar winds which, though highly variable, provide a wealth of data. Evaluations of pr imordial helium levels based on 1 the spectroscopic study of H-II regions and 2 microwav e anisotropy data, re- main highly questionable. Current helium levels, both with in the stars (Robitaille J. C. and Robitaille P.-M. Liquid Metallic Hydrogen III. Interca lation and Lattice Exclusion versus Gravitational Settling, and Their Consequences Rel ative to Internal Structure, Surface Activity, and Solar Winds in the Sun. Progr. Phys. , 2013, v. 2, in press and the universe at large, appear to be overstated. A careful con sideration of available ob- servational data suggests that helium abundances are consi derably lower than currently believed.

  13. Syntheses, structural characterization and spectroscopic studies of cadmium(II)-metal(II) cyanide complexes with 4-(2-aminoethyl)pyridine

    Science.gov (United States)

    Karaağaç, Dursun; Kürkçüoğlu, Güneş Süheyla; Şenyel, Mustafa; Hökelek, Tuncer

    2017-02-01

    Three new cadmium(II)-metal(II) cyanide complexes, [Cd(4aepy)2(H2O)2][Ni(CN)4] (1), [Cd(4aepy)2(H2O)2][Pd(CN)4] (2) and [Cd(4aepy)2(H2O)2][Pt(CN)4] (3) [4aepy = 4-(2-aminoethyl)pyridine], have been synthesized and characterized by elemental, thermal, FT-IR and Raman spectral analyses. The crystal structures of 1 and 2 have been determined by single crystal X-ray diffraction technique, in which they crystallize in the monoclinic system and C2/c space group. The M(II) [M(II) = Ni(II), Pd(II) and Pt(II)] ions are coordinated with the carbon atoms of the four cyanide groups in the square planar geometries and the [M(CN)4]2- ions act as counter ions. The Cd(II) ions display an N4O2 coordination sphere with a distorted octahedral geometry, the nitrogen donors belonging to four molecules of the organic 4aepy that act as unidentate ligands and two oxygen atoms from aqua ligands. 3D supramolecular structures of 1 and 2 were occurred by M⋯π and hydrogen bonding (Nsbnd H⋯N and Osbnd H⋯N) interactions. Vibrational assignments of all the observed bands were given and the spectral properties were also supported the crystal structures of the complexes. A possible decompositions of the complexes were investigated in the temperature range 30-800 °C in the static atmosphere.

  14. Lithium, Vanadium and Chromium Uptake Ability of Brassica juncea from Lithium Mine Tailings.

    Science.gov (United States)

    Elektorowicz, M; Keropian, Z

    2015-01-01

    The potential for phytoremediation and phytostabilization of lithium in lieu with vanadium and chromium on a formulated acidic heterogeneous growth media engineered around lithium mine tailings, was investigated in four phases: (1) overall efficiency of the removal of the three metals, (2) bioaccumulation ratios of the three metals, (3) overall relative growth rate, and (4) translocation index of the three metals in the physiology of the hyperaccumulator plant. A pot study was conducted to assess the suitability of Brassica juncea (Indian mustard) in a phytoremediation process whereby it was lingered for eighty-six days under homogeneous growth conditions and irrigated bidaily with organic fertilizer amended with LiCl. A post harvest data analysis was achieved through ashing and the implementation of cold digestion procedure in a concentrated hydrochloric acidic matrix. In physiological efficiency parameters, the hyperaccumulator plant was twice as able to phytostabilize chromium and four times was able to phytostabilize vanadium in comparison to lithium. Moreover, it was extremely efficient in translocating and accumulating lithium inside its upper physiological sites, more so than chromium and vanadium, thereby demonstrating Indian mustard, as a hyperaccumulator plant, for phytoextraction and phytostabilization in an acidic heterogeneous rhizosphere, with an extremely low relative growth rate.

  15. Establishing human heart chromium, cobalt and vanadium concentrations by inductively coupled plasma mass spectrometry.

    Science.gov (United States)

    Day, Patrick L; Eckdahl, Steven J; Maleszewski, Joseph J; Wright, Thomas C; Murray, David L

    2017-05-01

    Chromium, cobalt, and vanadium are used in metallic joint prosthesis. Case studies have associated elevated heart tissue cobalt concentrations with myocardial injury. To document the long term heart metal ion concentrations, a validated inductively coupled plasma mass spectroscopy (ICP-MS) method was needed. The method utilized a closed-vessel microwave digestion system to digest the samples. An ICP-MS method utilizing Universal Cell Technology was used to determine our target analyte concentrations. Accuracy was verified using reference materials. Precision, sensitivity, recovery and linearity studies were performed. This method was used to establish a reference range for a non-implant containing cohort of 80 autopsy human heart tissues RESULTS: This method demonstrated an analytic measurement range of 0.5-100ng/mL for each element. Accuracy was within ±10% of target value for each element. Within-run precision for each element was below 20% CV. The chromium, vanadium and cobalt concentrations (mean±SD) were 0.1523±0.2157μg/g, 0.0094±0.0211μg/g and 0.1039±0.1305μg/g respectively in 80 non-implant containing human heart tissue samples. This method provides acceptable recovery of the chromium, cobalt and vanadium in heart tissue; allowing assessment of the effects of metallic joint prosthesis on myocardial health. Copyright © 2017 Elsevier GmbH. All rights reserved.

  16. System Assessment of Carbon Dioxide Used as Gas Oxidant and Coolant in Vanadium-Extraction Converter

    Science.gov (United States)

    Du, Wei Tong; Wang, Yu; Liang, Xiao Ping

    2017-10-01

    With the aim of reducing carbon dioxide (CO2) emissions and of using waste resources in steel plants, the use of CO2 as a gas oxidant and coolant in the converter to increase productivity and energy efficiency was investigated in this study. Experiments were performed in combination with thermodynamic theory on vanadium-extraction with CO2 and oxygen (O2) mixed injections. The results indicate that the temperature of the hot metal bath decreased as the amount of CO2 introduced into O2 increased. At an injection of 85 vol.% O2 and 15 vol.% CO2, approximately 12% of additional carbon was retained in the hot metal. Moreover, the content of vanadium trioxide in the slag was higher. In addition, the O2 consumption per ton of hot metal was reduced by 8.5% and additional chemical energy was recovered by the controlled injection of CO2 into the converter. Therefore, using CO2 as a gas coolant was conducive to vanadium extraction, and O2 consumption was reduced.

  17. Global biogeochemical cycle of vanadium.

    Science.gov (United States)

    Schlesinger, William H; Klein, Emily M; Vengosh, Avner

    2017-12-26

    Synthesizing published data, we provide a quantitative summary of the global biogeochemical cycle of vanadium (V), including both human-derived and natural fluxes. Through mining of V ores (130 × 109 g V/y) and extraction and combustion of fossil fuels (600 × 109 g V/y), humans are the predominant force in the geochemical cycle of V at Earth's surface. Human emissions of V to the atmosphere are now likely to exceed background emissions by as much as a factor of 1.7, and, presumably, we have altered the deposition of V from the atmosphere by a similar amount. Excessive V in air and water has potential, but poorly documented, consequences for human health. Much of the atmospheric flux probably derives from emissions from the combustion of fossil fuels, but the magnitude of this flux depends on the type of fuel, with relatively low emissions from coal and higher contributions from heavy crude oils, tar sands bitumen, and petroleum coke. Increasing interest in petroleum derived from unconventional deposits is likely to lead to greater emissions of V to the atmosphere in the near future. Our analysis further suggests that the flux of V in rivers has been incremented by about 15% from human activities. Overall, the budget of dissolved V in the oceans is remarkably well balanced-with about 40 × 109 g V/y to 50 × 109 g V/y inputs and outputs, and a mean residence time for dissolved V in seawater of about 130,000 y with respect to inputs from rivers.

  18. Vanadium bioavailability in soils amended with blast furnace slag

    Energy Technology Data Exchange (ETDEWEB)

    Larsson, Maja A., E-mail: maja.larsson@slu.se [Department of Soil and Environment, Swedish University of Agricultural Sciences, P.O. Box 7014, 750 07 Uppsala (Sweden); Baken, Stijn, E-mail: stijn.baken@ees.kuleuven.be [Department of Earth and Environmental Sciences, Leuven University, Kasteelpark Arenberg 20 bus 2459, 3001 Leuven (Belgium); Smolders, Erik, E-mail: erik.smolders@ees.kuleuven.be [Department of Earth and Environmental Sciences, Leuven University, Kasteelpark Arenberg 20 bus 2459, 3001 Leuven (Belgium); Cubadda, Francesco, E-mail: francesco.cubadda@iss.it [Department of Food Safety and Veterinary Public Health, Istituto Superiore di Sanità, Viale Regina Elena 299, Rome 00161 (Italy); Gustafsson, Jon Petter, E-mail: jon-petter.gustafsson@slu.se [Department of Soil and Environment, Swedish University of Agricultural Sciences, P.O. Box 7014, 750 07 Uppsala (Sweden); Division of Land and Water Resources Engineering, KTH Royal Institute of Technology, Brinellvägen 28, 100 44 Stockholm (Sweden)

    2015-10-15

    Blast furnace (BF) slags are commonly applied as soil amendments and in road fill material. In Sweden they are also naturally high in vanadium. The aim of this study was to assess the vanadium bioavailability in BF slags when applied to soil. Two soils were amended with up to 29% BF slag (containing 800 mg V kg{sup −1}) and equilibrated outdoors for 10 months before conducting a barley shoot growth assay. Additional soil samples were spiked with dissolved vanadate(V) for which assays were conducted two weeks (freshly spiked) and 10 months (aged) after spiking. The BF slag vanadium was dominated by vanadium(III) as shown by V K-edge XANES spectroscopy. In contrast, results obtained by HPLC-ICP-MS showed that vanadium(V), the most toxic vanadium species, was predominant in the soil solution. Barley shoot growth was not affected by the BF slag additions. This was likely due to limited dissolution of vanadium from the BF slag, preventing an increase of dissolved vanadium above toxic thresholds. The difference in vanadium bioavailability among treatments was explained by the vanadium concentration in the soil solution. It was concluded that the vanadium in BF slag is sparingly available. These findings should be of importance in environmental risk assessment.

  19. Antibacterial, antifungal and in vitro antileukaemia activity of metal complexes with thiosemicarbazones

    Science.gov (United States)

    Pahontu, Elena; Julea, Felicia; Rosu, Tudor; Purcarea, Victor; Chumakov, Yurie; Petrenco, Petru; Gulea, Aurelian

    2015-01-01

    1-phenyl-3-methyl-4-benzoyl-5-pyrazolone 4-ethyl-thiosemicarbazone (HL) and its copper(II), vanadium(V) and nickel(II) complexes: [Cu(L)(Cl)]·C2H5OH·(1), [Cu(L)2]·H2O (2), [Cu(L)(Br)]·H2O·CH3OH (3), [Cu(L)(NO3)]·2C2H5OH (4), [VO2(L)]·2H2O (5), [Ni(L)2]·H2O (6), were synthesized and characterized. The ligand has been characterized by elemental analyses, IR, 1H NMR and 13C NMR spectroscopy. The tridentate nature of the ligand is evident from the IR spectra. The copper(II), vanadium(V) and nickel(II) complexes have been characterized by different physico-chemical techniques such as molar conductivity, magnetic susceptibility measurements and electronic, infrared and electron paramagnetic resonance spectral studies. The structures of the ligand and its copper(II) (2, 4), and vanadium(V) (5) complexes have been determined by single-crystal X-ray diffraction. The composition of the coordination polyhedron of the central atom in 2, 4 and 5 is different. The tetrahedral coordination geometry of Cu was found in complex 2 while in complex 4, it is square planar, in complex 5 the coordination polyhedron of the central ion is distorted square pyramid. The in vitro antibacterial activity of the complexes against Escherichia coli, Salmonella abony, Staphylococcus aureus, Bacillus cereus and the antifungal activity against Candida albicans strains was higher for the metal complexes than for free ligand. The effect of the free ligand and its metal complexes on the proliferation of HL-60 cells was tested. PMID:25708540

  20. Fractal structures in two-metal electrodeposition systems II: Cu and Zn

    Science.gov (United States)

    Nakouzi, Elias; Sultan, Rabih

    2012-06-01

    In this second part of our study on fractal co-electrochemical deposition, we investigate the Cu-Zn system. Macroscopic and microscopic inspection shows a sensitive dependence of the morphology of the final pattern on initial concentrations. The pattern is seen to undergo a transition from classical dendrites to randomly ramified deposits, with each slight increase in [Cu2+]0, while [Zn2+]0 is maintained constant. The variational trends in chemical composition, growth velocity, and fractal dimension with increasing [Cu2+]0 are analyzed. The latter is seen to generally increase with copper (II) ion concentration. In contrast, the growth rate of the deposits is seen to decrease with increasing concentration of Cu2+ ions. A new probe of dense ramified morphology, the pattern density, is introduced and seen to increase with [Cu2+]0. XRD measurements reveal that the observed properties correlate with the birth of copper-rich nuclei, which disrupt the crystalline anisotropy of the two-metal alloy.

  1. Radial velocities and metallicities from infrared Ca ii triplet spectroscopy of open clusters. II. Berkeley 23, King 1, NGC 559, NGC 6603, and NGC 7245

    Science.gov (United States)

    Carrera, R.; Casamiquela, L.; Ospina, N.; Balaguer-Núñez, L.; Jordi, C.; Monteagudo, L.

    2015-06-01

    Context. Open clusters are key to studying the formation and evolution of the Galactic disc. However, there is a deficiency of radial velocity and chemical abundance determinations for open clusters in the literature. Aims: We intend to increase the number of determinations of radial velocities and metallicities from spectroscopy for open clusters. Methods: We acquired medium-resolution spectra (R ~ 8000) in the infrared region Ca ii triplet lines (~8500 Å) for several stars in five open clusters with the long-slit IDS spectrograph on the 2.5 m Isaac Newton Telescope (Roque de los Muchachos Observatory, Spain). Radial velocities were obtained by cross-correlation fitting techniques. The relationships available in the literature between the strength of infrared Ca ii lines and metallicity were also used to derive the metallicity for each cluster. Results: We obtain ⟨Vr⟩ = 48.6 ± 3.4, -58.4 ± 6.8, 26.0 ± 4.3, and -65.3 ± 3.2 km s-1 for Berkeley 23, NGC 559, NGC 6603, and NGC 7245, respectively. We found [ Fe/H ] = -0.25 ± 0.14 and -0.15 ± 0.18 for NGC 559 and NGC 7245, respectively. Berkeley 23 has low metallicity, [ Fe/H ] = -0.42 ± 0.13, which is similar to other open clusters in the outskirts of the Galactic disc. In contrast, we derived high metallicity ([ Fe/H ] = +0.43 ± 0.15) for NGC 6603, which places this system among the most metal-rich known open clusters. To our knowledge, this is the first determination of radial velocities and metallicities from spectroscopy for these clusters, except NGC 6603, for which radial velocities had been previously determined. We have also analysed ten stars in the line of sight to King 1. Because of the large dispersion obtained in both radial velocity and metallicity, we cannot be sure that we have sampled true cluster members. Based on observations made with the 2.5 m Isaac Newton Telescope operated on the island of La Palma by the Isaac Newton Group in the Spanish Observatorio del Roque de los Muchachos of the

  2. Gas tungsten arc welding of vanadium alloys with impurity control

    Science.gov (United States)

    Grossbeck, M. L.; King, J. F.; Nagasaka, T.; David, S. A.

    2002-12-01

    Gas tungsten arc welding in vanadium alloys is controlled by interstitial impurities. Techniques have been developed to weld V-4Cr-4Ti in a high-purity argon atmosphere resulting in a DBTT of -20 °C. The atmosphere was controlled by a Zr-Al getter which is activated at high temperature to obtain a clean surface then cooled and allowed to absorb hydrogen and oxygen impurities. Through the use of low-oxygen base metal and high-purity weld filler wire, a DBTT of -145 °C was obtained. Experiments using electron beam welding have shown that grain size also has an important effect on weld ductility. Introduction of nitrogen and yttrium has been used to study their effect on grain size. Using a combination of atmosphere control, alloy purity control, and grain size control, it is anticipated that V-Cr-Ti alloys will be weldable in field conditions.

  3. Tc anisotropy and phase separation in strained Vanadium Dioxide films

    Science.gov (United States)

    Liu, Mengkun; Wagner, Martin; Abreu, Elsa; Kittiwatanakul, Salinporn; McLeod, Alexander; Goldflam, Michael; Fei, Zhe; Dai, Siyuan; Fogler, Michael; Lu, Jiwei; Wolf, Stuart; Averitt, Richard; Basov, D. N.

    2013-03-01

    We report Infrared near field study on strain induced transition temperature (Tc) anisotropy in vanadium dioxide (VO2) films via direct visualization of a spontaneous structural and electronic phase separation. The films are epitaxially grown on [110]R or [100]R TiO2 substrates and exhibit large uniaxial strain. By mapping the film topography with AFM and electronic percolation with Infrared scattering scanning near-field optical microscopy, a temperature dependent electron-lattice correlation can be clearly observed. Our work sheds a new light onto the nature of the Tc anomaly in metal-insulator transition and leads to the possibility of controlling the material's properties through strain induced phase separation.

  4. [Study on solid phase extraction and spectrophotometric determination of vanadium in environmental samples with 2-(2-quinolinylazo)-1,3-dihydroxidebenzene].

    Science.gov (United States)

    Cui, Yongchun; Zhang, Xiaoman; Zhai, Ping; Hu, Qiufen; Yin, Jiayuan; Yang, Guangyu

    2004-09-01

    Based on the color reaction of 2-(2-quinolinylazo)-1,3-dihydroxidebenzene (QADHB) with vanadium (v) and the solid phase extraction of its colored complex with C18 cartridge, a new method for the determination of vanadium was studied. In the presence of CTMAB and citric acid-sodium hydroxide buffer solution (pH 3.5) medium. QADHB reacts with vanadium(II) to form a stable 2:1 complex. The colored complex was extracted by C18 cartridge and eluted the retained chelate from cartridge with ethanol (containing 2% of acetic acid), then can be determined by spectrophotometry at 552 nm. Beer's law is obeyed in range of 0-1.0 mg/l. This method can be applied to the determination of vanadium in environmental samples with good results.

  5. Stability of rhombohedral phases in vanadium at high-pressure and high-temperature: first-principles investigations

    CERN Document Server

    Wang, Yi X; Chen, Xiang R; Geng, Hua Y

    2016-01-01

    The pressure-induced transition of vanadium from BCC to rhombohedral structures is unique and intriguing among transition metals. In this work, the stability of these phases is revisited by using density functional theory. At finite temperatures, a novel transition of rhombohedral phases back to BCC phase induced by thermal electrons is discovered. This reentrant transition is found not driven by phonons, instead it is the electronic entropy that stabilizes the latter phase, which is totally out of expectation. Parallel to this transition, we find a peculiar and strong increase of the shear modulus C44 with increasing temperature. It is counter-intuitive in the sense that it suggests an unusual harding mechanism of vanadium by temperature. With these stability analyses, the high-pressure and finite-temperature phase diagram of vanadium is proposed. Furthermore, the dependence of the stability of RH phases on the Fermi energy and chemical environment is investigated. The results demonstrate that the position o...

  6. Synthesis, spectroscopic characterization, DFT calculations and biological evaluation of benzothiazole derivative bearing Mn(II) and Ni(II) metal ions

    Science.gov (United States)

    El-Gamel, Nadia E. A.; Ali, Korany A.

    2017-11-01

    N-(benzo[d]thiazol-2-yl)-3-oxo-3-phenylpropanamide ligand and its Nickel and Manganese complexes have been synthesized and characterized by elemental and thermal analyses, IR, diffuse reflectance, mass and UV-Vis spectra, molar conductance and magnetic moment measurements. The decomposition mechanism and thermal stability of the investigated complexes are interpreted in terms of their structures. The thermal behaviour of the complexes has been studied and different thermodynamic parameters are calculated using Coats-Redfern method. N-(benzo[d]thiazol-2-yl)-3-oxo-3-phenylpropanamide is a neutral bidentate ligand coordinating metal ions via thiazole ring nitrogen and amide carbonyl O forming high spin octahedral complexes with Mn(II) (2) and distorted square planar in case of Ni(II) (1). Natural bond orbital analysis and geometry optimization were carried out at DFT/B3LYP/6-31G(d) level of theory for the ligand and the mentioned complexes. Ab inito computations at the HF/6-31G(d) level of the theory is conducted in order to detect any probability of a hydrogen bond formation in the ligand. The dipole moment of the Ni(II) and Mn(II) complexes is recorded to be 9.69 and 7.39 Debye, respectively, indicating that the complexes are more polarized than the ligand 2.39 Debye. The in vitro biological activity of the metal chelates is screened against the Gram-positive bacteria (Staphylococcus aureus) and Gram-negative bacteria (Escherichia coli), fungus (Aspergillus flavus, Candida albicans). Ni(II) complexes displayed the highest activity against Candida albicans and Staphylococcus aureus with MIC values of 13, 30 μg/cm3, respectively.

  7. Extraction of vanadium from vanadium slag by high pressure oxidative acid leaching

    Science.gov (United States)

    Zhang, Guo-quan; Zhang, Ting-an; Lü, Guo-zhi; Zhang, Ying; Liu, Yan; Liu, Zhuo-lin

    2015-01-01

    To extract vanadium in an environment friendly manner, this study focuses on the process of leaching vanadium from vanadium slag by high pressure oxidative acid leaching. Characterizations of the raw slag, mineralogy transformation, and the form of leach residues were made by X-ray diffraction, scanning electron microscopy, and energy dispersive X-ray spectroscopy. The result shows that the vanadium slag is composed of major phases of fayalite, titanomagnetite, and spinel. During the high pressure oxidative acid leaching process, the fayalite and spinel phases are gradually decomposed by sulfuric acid, causing the release of vanadium and iron in the solution. Meanwhile, unreacted silicon and titanium are enriched in the leach residues. With the initial concentration of sulfuric acid at 250 g·L-1, a leaching temperature of 140°C, a leaching time of 50 min, a liquid-solid ratio of 10:1 mL·g-1, and oxygen pressure at 0.2 MPa, the leaching rate of vanadium reaches 97.69%.

  8. Hazardous waste to materials: recovery of molybdenum and vanadium from acidic leach liquor of spent hydroprocessing catalyst using alamine 308.

    Science.gov (United States)

    Sahu, K K; Agrawal, Archana; Mishra, D

    2013-08-15

    Recovery of valuable materials/metals from waste goes hand in hand with environmental protection. This paper deals with the development of a process for the recovery of metals such as Mo, V, Ni, Al from spent hydroprocessing catalyst which may otherwise cause a nuisance if dumped untreated. A detailed study on the separation of molybdenum and vanadium from the leach solution of spent hydroprocessing catalyst of composition: 27.15% MoO₃, 1.7% V₂O₅, 3.75% NiO, 54.3% Al₂O₃, 2.3% SiO₂ and 10.4% LOI is reported in this paper. The catalyst was subjected to roasting under oxidizing atmosphere at a temperature of about 550 °C and leaching in dilute sulphuric acid to dissolve molybdenum, vanadium, nickel and part of aluminium. Metals from the leach solution were separated by solvent extraction. Both molybdenum and vanadium were selectively extracted with a suitable organic solvent leaving nickel and dissolved aluminium in the raffinate. Various parameters such as initial pH of the aqueous feed, organic to aqueous ratio (O:A), solvent concentration etc. were optimized for the complete extraction and recovery of Mo and V. Molybdenum and vanadium from the loaded organic were stripped by ammonia solution. They were recovered as their corresponding ammonium salt by selective precipitation, and were further calcined to get the corresponding oxides in pure form. Copyright © 2013 Elsevier Ltd. All rights reserved.

  9. Recovery of Vanadium from a High Ca/V Ratio Vanadium Slag Using Sodium Roasting and Ammonia Leaching

    Science.gov (United States)

    Xu, Song; Long, Mujun; Chen, Dengfu; Fan, Helin; Chen, Yuting; Sun, Xue

    In order to seek an effective extraction process for vanadium, the recovery of vanadium from a high Ca/V ratio vanadium slag was studied by sodium roasting and ammonia leaching. In the present paper, the oxidation and leaching process of vanadium slag was investigated by X-ray diffraction (XRD), scanning electron microscopy and energy dispersive X-ray spectrometry (SEM/EDS) techniques. The effects of ammonium carbonate concentration, leaching temperature and leaching time on the leaching ratio of vanadium were discussed. As indicated in the experimental result, the optimal (NH4)2CO3 concentration was 120g/L, leaching temperature was 60°C and leaching time was 20 min. Approximately 92% of the vanadium was recovered under the optimal conditions. Furthermore, by means of X-ray diffraction analysis, the phase transformations of the vanadium slag during roasting and leaching processes were analyzed and discussed.

  10. Effect of municipal and industrial wastewater effluents on the Chromium and Vanadium residues in muscle tissue of Cyprinionm acrostomum and Chondrostoma regium fish in Kermanshah Gharasou River (2013

    Directory of Open Access Journals (Sweden)

    M Pirsaheb

    2015-02-01

    Full Text Available Nowadays, the entrance of heavy metals in the aquatic environment is an important and also a global environmental concern due to the indiscriminate discharging of various industrial wastewaters, which cause accumulation of heavy metals in body of aquatic animals including fishes. The present study aimed to evaluate the amount of Chromium and Vanadium in muscle tissue of Chondrostoma regium and Cyprinion macrostomum fish in Kermanshah Gharasou River in 2013. For sampling eight different places were chosen along the river and according to places of discharging municipal and industrial wastewaters. A total of 10 samples were collected from each place and all samples were analyzed for determination of Chromium and Vanadium metals using atomic absorption spectrophotometer. Based on results, mean concentrations of Chromium and Vanadium in muscle tissue of investigating different species among all places were significantly different (P

  11. Multisensor system for determination of polyoxometalates containing vanadium at its different oxidation states.

    Science.gov (United States)

    Rudnitskaya, Alisa; Evtuguin, Dmitry V; Gamelas, Jose A F; Legin, Andrey

    2007-04-30

    The electronic tongue (ET) multisensor system has been employed for the detection of metal-oxygen cluster anions (polyoxometalates) containing vanadium (IV/V) atoms. Sensitivity of a variety of potentiometric chemical sensors with plasticized polyvinyl chloride and chalcogenide glass membranes was evaluated with respect to vanadyl/vanadate ions, decavanadate and a series of Keggin-type polyoxometalates (POM) such as alpha-[SiW(11)V(IV)O(40)](6-), alpha-[SiW(11)V(V)O(40)](5-), alpha-[BW(11)V(IV)O(40)](7-), alpha-[BW(11)V(V)O(40)](6-), alpha-[PW(11)V(IV)O(40)](5-) and alpha-[PW(12-n)V(n)(V)O(40)]((3+n)-) (n=1, 2, 3). Sensor's responses to vanadium complexes were evaluated in the pH range of 2.4-6.5 and a set of sensors appropriate for detecting a variety of vanadium species was selected. Such sensor array was able to distinguish different vanadium complexes allowing their simultaneous quantification in binary (V(IV)/V(V)) mixtures. The vanillyl alcohol oxidation with alpha-[SiW(11)V(V)O(40)](5-) was monitored using ET to evaluate the capacity of proposed analytic system to detect simultaneously V(IV)/V(V) in POM under dynamic equilibrium. ET was demonstrated to be a promising tool for the discrimination and quantification of vanadium-containing POMs at different oxidation states. In particular, such a system could represent a significant interest for the mechanistic studies of redox reactions with POMs.

  12. A functionalized surface modification with vanadium nanoparticles of various valences against implant-associated bloodstream infection.

    Science.gov (United States)

    Wang, Jiaxing; Zhou, Huaijuan; Guo, Geyong; Cheng, Tao; Peng, Xiaochun; Mao, Xin; Li, Jinhua; Zhang, Xianlong

    2017-01-01

    Bloodstream infection, especially with implants involved, is an often life-threatening condition with high mortality rates, imposing a heavy burden on patients and medical systems. Herein, we firstly deposited homogeneous vanadium metal, V2O3, VO2, and V2O5 nanofilms on quartz glass by magnetron sputtering. Using these platforms, we further investigated the potential antimicrobial efficiency of these nano-VOx films and the interactions of human erythrocytes and bacteria (methicillin-resistant Staphylococcus aureus and Pseudomonas aeruginosa) with our samples in a novel cell-bacteria coculture model. It was demonstrated that these nano-VOx precipitated favorable antibacterial activity on both bacteria, especially on S. aureus, and this effect increased with higher vanadium valence. A possible mechanism accountable for these results might be elevated levels of vanadium-induced intracellular reactive oxygen species. More importantly, based on hemolysis assays, our nano-VOx films were found to be able to kill prokaryotic cells but were not toxic to mammalian cells, holding the potential for the prevention of implant-related hematogenous infections. As far as we know, this is the first report wherein such nano-VOx films have assisted human erythrocytes to combat bacteria in a valence-dependent manner. Additionally, vanadium ions were released from these nano-VOx films in a sustained manner, and low-valence films possessed better biocompatibility with human fibroblasts. This work may provide new insights for biomedical applications of inorganic vanadium compounds and attract growing attention in this field. From the perspective of surface modification and functionalization, this study holds promise to avail the prophylaxis of bloodstream infections involving implantable biomedical devices.

  13. Photophysical Studies of Ru(II)tris(2,2`-bipyridine) Confined within a Zn(II)-Trimesic Acid Polyhedral Metal-Organic Framework

    Energy Technology Data Exchange (ETDEWEB)

    Larsen, Randy W; Wojtas, Lukasz [USF

    2012-10-25

    The ability to confine photoactive catalysts within metal-organic framework (MOF) materials affords the opportunity to expand the functional diversity of these materials into solar based applications. Here, the confinement of Ru(II)tris(2,2'-bipyridine) (RuBpy) by a MOF material derived from Zn(II) ions and trimesic acid (hereafter, USF2) is examined. Although the encapsulated RuBpy could not be crystallographically resolved within the MOF framework, the photophysical properties of the complex are characteristic of confinement including extended triplet metal-to-ligand (3MLCT) lifetime (τethanol = 614 ns and {τUSF2 = 1.2 μs at 25 °C) and a slight hypsochromic shift in the steady-state emission spectrum relative to RuBpy in ethanol. The extended lifetime is attributed to a deactivation of a nonradiative 3dd that is antibonding with respect to the Ru(II)-bipyridine due to a confined molecular environment. These results represent one of the first examples of RuBpy encapsulation and photophysical characterization within a polyhedral MOF material.

  14. Vanadium in marine mussels and algae.

    Science.gov (United States)

    Sperling, K R; Bahr, B; Ott, J

    2000-01-01

    A method is presented which is sensitive enough for the determination of vanadium (V) in marine organisms such as mussels and algae. It was sufficiently checked by a reference material and it was applied to V determination in blue mussels and brown algae from the German Bight.

  15. Lithium insertion in sputtered vanadium oxide film

    DEFF Research Database (Denmark)

    West, K.; Zachau-Christiansen, B.; Skaarup, S.V.

    1992-01-01

    were oxygen deficient compared to V2O5. Films prepared in pure argon were reduced to V(4) or lower. The vanadium oxide films were tested in solid-state lithium cells. Films sputtered in oxygen showed electrochemical properties similar to crystalline V2O5. The main differences are a decreased capacity...

  16. Geochemistry of vanadium (V) in Chinese coals.

    Science.gov (United States)

    Liu, Yuan; Liu, Guijian; Qu, Qinyuan; Qi, Cuicui; Sun, Ruoyu; Liu, Houqi

    2017-10-01

    Vanadium in coals may have potential environmental and economic impacts. However, comprehensive knowledge of the geochemistry of V in coals is lacking. In this study, abundances, distribution and modes of occurrence of V are reviewed by compiling >2900 reported Chinese coal samples. With coal reserves in individual provinces as the weighting factors, V in Chinese coals is estimated to have an average abundance of 35.81 μg/g. Large variation of V concentration is observed in Chinese coals of different regions, coal-forming periods, and maturation ranks. According to the concentration coefficient of V in coals from individual provinces, three regions are divided across Chinese coal deposits. Vanadium in Chinese coals is probably influenced by sediment source and sedimentary environment, supplemented by late-stage hydrothermal fluids. Specifically, hydrothermal fluids have relatively more significant effect on the enrichment of V in local coal seams. Vanadium in coals is commonly associated with aluminosilicate minerals and organic matter, and the modes of V occurrence in coal depend on coal-forming environment and coal rank. The Chinese V emission inventory during coal combustion is estimated to be 4906 mt in 2014, accounting for 50.55 % of global emission. Vanadium emissions by electric power plants are the largest contributor.

  17. Temperature dependence of thermal conductivity of vanadium ...

    Indian Academy of Sciences (India)

    Unknown

    . Cryogenic Engineering .... Thermal conductivity of vanadium substituted BPSCCO system. 441 trical resistivity as well as the small decrease ..... G, Marre D, Putti M and Siri A S 1997 Physica C273 314. Chawlek J M, Uher C, Whitaker J F and ...

  18. Catalytic determination of vanadium in water

    Science.gov (United States)

    Fishman, M. J.; Skougstad, M.W.

    1964-01-01

    A rapid, accurate, and sensitive spectrophotometric method for the quantitative determination of trace amounts of vanadium in water is based on the catalytic effect of vanadium on the rate of oxidation of gallic acid by persulfate in acid solution. Under given conditions of concentrations of reactants, temperature, and reaction time, the extent of oxidation of gallic acid is proportional to the concentration of vanadium present. Vanadium is determined by measuring the absorbance of the sample at 415 m?? and comparison with standard solutions treated in an identical manner. Concentrations in the range of from 0.1 to 8.0 ??g. per liter may be determined with a standard deviation of 0.2 or less. By reducing the reaction time, the method may be extended to cover the range from 1 to 100 ??g. with a standard deviation of 0.8 or less. Several substances interfere, including chloride above 100 p.p.m., and bromide and iodide in much lower concentrations. Interference from the halides is eliminated or minimized by the addition of mercuric nitrate solution. Most other substances do not interfere at the concentration levels at which they commonly occur in natural waters.

  19. Role of vanadium in Bi-2223 ceramics

    Indian Academy of Sciences (India)

    Home; Journals; Pramana – Journal of Physics; Volume 54; Issue 2. Role of vanadium in Bi-2223 ceramics. D R Mishra ... higher magnetization scattering at the Cu site. The results were explained keeping in mind the liquid phase mechanism behind the formation of the 2223 phase and the possibility of magnetic scattering.

  20. The ternary system: silicon-uranium-vanadium

    Energy Technology Data Exchange (ETDEWEB)

    Noel, Henri [Laboratoire de Chimie du Solide et Materiaux, UMR-CNRS 6226, Universite de Rennes I, Avenue du General Leclerc, F-35042 Rennes, Cedex (France); Rogl, Peter Franz, E-mail: peter.franz.rogl@univie.ac.a [Institute of Physical Chemistry, University of Vienna, A-1090 Wien, Waehringerstrasse 42 (Austria)

    2010-09-01

    Phase equilibria in the system Si-U-V were established at 1100 {sup o}C by optical microscopy, EMPA and X-ray diffraction. Two ternary compounds were observed, U{sub 2}V{sub 3}Si{sub 4} and (U{sub 1-x}V{sub x}){sub 5}Si{sub 3}, for which the crystal structures were elucidated by X-ray powder data refinement and found to be isotypic with the monoclinic U{sub 2}Mo{sub 3}Si{sub 4}-type (space group P2{sub 1}/c; a = 0.6821(3), b = 0.6820(4), c = 0.6735(3) nm, {beta} = 109.77(1){sup o}) and the tetragonal W{sub 5}Si{sub 3}-type (space group I4/mcm, a = 1.06825(2), c = 0.52764(2) nm), respectively. (U{sub 1-x}V{sub x}){sub 5}Si{sub 3} appears at 1100 {sup o}C without any significant homogeneity region at x {approx} 0.2 resulting in a formula U{sub 4}VSi{sub 3} which corresponds to a fully ordered atom arrangement. DTA experiments clearly show decomposition of this phase above 1206 {sup o}C revealing a two-phase region U{sub 3}Si{sub 2} + V{sub 3}Si. At 1100 {sup o}C U{sub 4}VSi{sub 3} is in equilibrium with V{sub 3}Si, V{sub 5}Si{sub 3}, U{sub 3}Si{sub 2} and U(V). At 800 {sup o}C U{sub 4}VSi{sub 3} forms one vertex of the tie-triangle to U{sub 3}Si and V{sub 3}Si. Due to the rather high thermodynamic stability of V{sub 3}Si and the corresponding tie-lines V{sub 3}Si + liquid at 1100 {sup o}C and V{sub 3}Si + U(V) below 925 {sup o}C, no compatibility exists between U{sub 3}Si or U{sub 3}Si{sub 2} and vanadium metal.

  1. Biological low pH Mn(II) oxidation in a manganese deposit influenced by metal-rich groundwater

    Science.gov (United States)

    Bohu, Tsing; Akob, Denise M.; Abratis, Michael; Lazar, Cassandre S.; Küsel, Kirsten

    2016-01-01

    The mechanisms, key organisms, and geochemical significance of biological low-pH Mn(II) oxidation are largely unexplored. Here, we investigated the structure of indigenous Mn(II)-oxidizing microbial communities in a secondary subsurface Mn oxide deposit influenced by acidic (pH 4.8) metal-rich groundwater in a former uranium mining area. Microbial diversity was highest in the Mn deposit compared to the adjacent soil layers and included the majority of known Mn(II)-oxidizing bacteria (MOB) and two genera of known Mn(II)-oxidizing fungi (MOF). Electron X-ray microanalysis showed that romanechite [(Ba,H2O)2(Mn4+,Mn3+)5O10] was conspicuously enriched in the deposit. Canonical correspondence analysis revealed that certain fungal, bacterial, and archaeal groups were firmly associated with the autochthonous Mn oxides. Eight MOB within the Proteobacteria, Actinobacteria, and Bacteroidetes and one MOF strain belonging to Ascomycota were isolated at pH 5.5 or 7.2 from the acidic Mn deposit. Soil-groundwater microcosms demonstrated 2.5-fold-faster Mn(II) depletion in the Mn deposit than adjacent soil layers. No depletion was observed in the abiotic controls, suggesting that biological contribution is the main driver for Mn(II) oxidation at low pH. The composition and species specificity of the native low-pH Mn(II) oxidizers were highly adapted to in situ conditions, and these organisms may play a central role in the fundamental biogeochemical processes (e.g., metal natural attenuation) occurring in the acidic, oligotrophic, and metalliferous subsoil ecosystems.

  2. Effects of thermal aging on the microstructure of Type-II boundaries in dissimilar metal weld joints

    Energy Technology Data Exchange (ETDEWEB)

    Yoo, Seung Chang; Choi, Kyoung Joon [School of Mechanical and Nuclear Engineering, Ulsan National Institute of Science and Technology (UNIST), 100 Banyeon-ri, Eonyang-eup, Ulju-gun, Ulsan 689-798 (Korea, Republic of); Bahn, Chi Bum [School of Mechanical Engineering, Pusan National University, 63-gil, Geumjeong-Gu, Pusan 609-735 (Korea, Republic of); Kim, Si Hoon; Kim, Ju Young [School of Materials Science and Engineering, Ulsan National Institute of Science and Technology (UNIST), 100 Banyeon-ri, Eonyang-eup, Ulju-gun, Ulsan 689-798 (Korea, Republic of); Kim, Ji Hyun, E-mail: kimjh@unist.ac.kr [School of Mechanical and Nuclear Engineering, Ulsan National Institute of Science and Technology (UNIST), 100 Banyeon-ri, Eonyang-eup, Ulju-gun, Ulsan 689-798 (Korea, Republic of)

    2015-04-15

    In order to investigate the effects of long-term thermal aging on the microstructural evolution of Type-II boundary regions in the weld metal of Alloy 152, a representative dissimilar metal weld was fabricated from Alloy 690, Alloy 152, and A533 Gr.B. This mock-up was thermally aged at 450 °C to accelerate the effects of thermal aging in a nuclear power plant operation condition (320 °C). The microstructure of the Type-II boundary region of the weld root, which is parallel to and within 100 μm of the fusion boundary and known to be more susceptible to material degradation, was then characterized after different aging times using a scanning electron microscope equipped with an energy dispersive X-ray spectroscope for micro-compositional analysis, electron backscattered diffraction detector for grain and grain boundary orientation analysis, and a nanoindenter for measurement of mechanical properties. Through this, it was found that a steep compositional gradient and high grain average misorientation is created in the narrow zone between the Type-II and fusion boundaries, while the concentration of chromium and number of low-angle grain boundaries increases with aging time. A high average hardness was also observed in the same region of the dissimilar metal welds, with hardness peaking with thermal aging simulating an operational time of 15 years.

  3. Effects of thermal aging on the microstructure of Type-II boundaries in dissimilar metal weld joints

    Science.gov (United States)

    Yoo, Seung Chang; Choi, Kyoung Joon; Bahn, Chi Bum; Kim, Si Hoon; Kim, Ju Young; Kim, Ji Hyun

    2015-04-01

    In order to investigate the effects of long-term thermal aging on the microstructural evolution of Type-II boundary regions in the weld metal of Alloy 152, a representative dissimilar metal weld was fabricated from Alloy 690, Alloy 152, and A533 Gr.B. This mock-up was thermally aged at 450 °C to accelerate the effects of thermal aging in a nuclear power plant operation condition (320 °C). The microstructure of the Type-II boundary region of the weld root, which is parallel to and within 100 μm of the fusion boundary and known to be more susceptible to material degradation, was then characterized after different aging times using a scanning electron microscope equipped with an energy dispersive X-ray spectroscope for micro-compositional analysis, electron backscattered diffraction detector for grain and grain boundary orientation analysis, and a nanoindenter for measurement of mechanical properties. Through this, it was found that a steep compositional gradient and high grain average misorientation is created in the narrow zone between the Type-II and fusion boundaries, while the concentration of chromium and number of low-angle grain boundaries increases with aging time. A high average hardness was also observed in the same region of the dissimilar metal welds, with hardness peaking with thermal aging simulating an operational time of 15 years.

  4. Some new nano-sized Fe(II), Cd(II) and Zn(II) Schiff base complexes as precursor for metal oxides: Sonochemical synthesis, characterization, DNA interaction, in vitro antimicrobial and anticancer activities.

    Science.gov (United States)

    Abdel-Rahman, Laila H; Abu-Dief, Ahmed M; El-Khatib, Rafat M; Abdel-Fatah, Shimaa Mahdy

    2016-12-01

    The complexes of Fe(II), Cd(II) and Zn(II) with Schiff base derived from 2-amino-3-hydroxypyridine and 3-methoxysalicylaldehyde have been prepared. Melting points, decomposition temperatures, Elemental analyses, TGA, conductance measurements, infrared (IR) and UV-Visible spectrophotometric studies were utilized in characterizing the compounds. The UV-Visible spectrophotometric analysis revealed 1:1 (metal-ligand) stoichiometry for the three complexes. In addition to, the prepared complexes have been used as precursors for preparing their corresponding metal oxides nanoparticles via thermal decomposition. The structures of the nano-sized complexes and their metal oxides were characterized by X-ray powder diffraction and transmittance electron microscopy. Moreover, the prepared Schiff base ligand, its complexes and their corresponding nano-sized metal oxides have been screened in vitro for their antibacterial activity against three bacteria, gram-positive (Microccus luteus) and gram-negative (Escherichia coli, Serratia marcescence) and three strains of fungus. The metal chelates were shown to possess more antimicrobial activity than the free Schiff-base chelate and their nano-sized metal oxides have the highest activity. The binding behaviors of the complexes to calf thymus DNA have been investigated by absorption spectra, viscosity mensuration and gel electrophoresis. The DNA binding constants reveal that all these complexes interact with DNA through intercalative binding mode. Furthermore, the cytotoxic activity of the prepared Schiff base complexes on human colon carcinoma cells, (HCT-116 cell line) and hepatic cellular carcinoma cells, (HepG-2) showed potent cytotoxicity effect against growth of carcinoma cells compared to the clinically used Vinblastine standard. Copyright © 2016 Elsevier Inc. All rights reserved.

  5. Investigation of Explosively Driven Fragmentation of Metals - Two Dimensional Fracture and Fragmentation of Metal Shells: Progress Report II

    Energy Technology Data Exchange (ETDEWEB)

    Grady, D

    2003-02-01

    High explosive enclosed by a metal case qualitatively describes an essential component of high energy systems of importance to the Department of Energy. Detonation of the high explosive causes intense transient pressure loading of the metal following arrival of normal or obliquely incident explosive detonation wave. Subsequent expansion and deformation of the metal case leads to eventual rupture and the opening of fractures and fissures. Details of the rupture process are critical to performance of the system. Consequently, it is essential that the material and kinematic issues governing the processes of dynamic loading and subsequent failure of an explosive-metal case component within a functioning system be adequately understood. Among the reasons are to quantify existing performance, characterize potential degradation of performance resulting from system aging, and optimizing or maintaining system performance through implementation of structural or material changes. The physical and engineering issues underlying this dynamic response and failure phenomena are not adequately understood. The purpose of the present program is to identify the key issues and develop theoretical, computational and experimental models needed to achieve a satisfactory theoretical and analysis framework for analysis of metal case failure in the explosive environment. Specific tasks within the present program include: (1) Models and theories currently being pursued based on physical principles of both the statistical fragmentation concepts of Mott and the energy-based concept of others show promise of providing the analytic and computational methodology capable of predicting explosion-induced fracture and fragmentation of metal components. Experimental studies initiated in the earlier effort offer promise to provide critical test data for validation. The present task shall involve the further refinement and development of the dynamic failure and fragmentation models and theories, and the

  6. Preliminary screening of Ni(II metal tolerance and dye-decolorizing by Nocardiopsis sp. SD8

    Directory of Open Access Journals (Sweden)

    Ramasamy Thangaraj

    2016-04-01

    Full Text Available Objective: To reveal the screening of metal tolerance and dye-decolorizing of Nocardiopsis sp. Methods: NiSO4 and Congo red dye were used for evaluating the metal tolerance and dyedecolorizing of the randomly selected actinobacterial isolates. Results: Nocardiopsis sp. SD8 showed a better efficiency in Ni(II tolerance, though a longer lag phase was observed for this microorganism grown for 7 days in integrated mismatch negativity. Interestingly, we also found that Nocardiopsis sp. SD8 had dye-decolorizing, hemolytic, lipase and protease activity. Conclusions: The present results revealed the bioremediation of metal resistant and diverse properties of Nocardiopsis sp. SD8 and further investigations are needed to extract and identify the potent molecule.

  7. Flame atomic absorption spectrometric determination of heavy metals in aqueous solution and surface water preceded by co-precipitation procedure with copper(II) 8-hydroxyquinoline

    Science.gov (United States)

    Ipeaiyeda, Ayodele Rotimi; Ayoade, Abisayo Ruth

    2017-12-01

    Co-precipitation procedure has widely been employed for preconcentration and separation of metal ions from the matrices of environmental samples. This is simply due to its simplicity, low consumption of separating solvent and short duration for analysis. Various organic ligands have been used for this purpose. However, there is dearth of information on the application of 8-hydroxyquinoline (8-HQ) as ligand and Cu(II) as carrier element. The use of Cu(II) is desirable because there is no contamination and background adsorption interference. Therefore, the objective of this study was to use 8-HQ in the presence of Cu(II) for coprecipitation of Cd(II), Co(II), Cr(III), Ni(II) and Pb(II) from standard solutions and surface water prior to their determinations by flame atomic absorption spectrometry (FAAS). The effects of pH, sample volume, amount of 8-HQ and Cu(II) and interfering ions on the recoveries of metal ions from standard solutions were monitored using FAAS. The water samples were treated with 8-HQ under the optimum experimental conditions and metal concentrations were determined by FAAS. The metal concentrations in water samples not treated with 8-HQ were also determined. The optimum recovery values for metal ions were higher than 85.0%. The concentrations (mg/L) of Co(II), Ni(II), Cr(III), and Pb(II) in water samples treated with 8-HQ were 0.014 ± 0.002, 0.03 ± 0.01, 0.04 ± 0.02 and 0.05 ± 0.02, respectively. These concentrations and those obtained without coprecipitation technique were significantly different. Coprecipitation procedure using 8-HQ as ligand and Cu(II) as carrier element enhanced the preconcentration and separation of metal ions from the matrix of water sample.

  8. Flame atomic absorption spectrometric determination of heavy metals in aqueous solution and surface water preceded by co-precipitation procedure with copper(II) 8-hydroxyquinoline

    Science.gov (United States)

    Ipeaiyeda, Ayodele Rotimi; Ayoade, Abisayo Ruth

    2017-07-01

    Co-precipitation procedure has widely been employed for preconcentration and separation of metal ions from the matrices of environmental samples. This is simply due to its simplicity, low consumption of separating solvent and short duration for analysis. Various organic ligands have been used for this purpose. However, there is dearth of information on the application of 8-hydroxyquinoline (8-HQ) as ligand and Cu(II) as carrier element. The use of Cu(II) is desirable because there is no contamination and background adsorption interference. Therefore, the objective of this study was to use 8-HQ in the presence of Cu(II) for coprecipitation of Cd(II), Co(II), Cr(III), Ni(II) and Pb(II) from standard solutions and surface water prior to their determinations by flame atomic absorption spectrometry (FAAS). The effects of pH, sample volume, amount of 8-HQ and Cu(II) and interfering ions on the recoveries of metal ions from standard solutions were monitored using FAAS. The water samples were treated with 8-HQ under the optimum experimental conditions and metal concentrations were determined by FAAS. The metal concentrations in water samples not treated with 8-HQ were also determined. The optimum recovery values for metal ions were higher than 85.0%. The concentrations (mg/L) of Co(II), Ni(II), Cr(III), and Pb(II) in water samples treated with 8-HQ were 0.014 ± 0.002, 0.03 ± 0.01, 0.04 ± 0.02 and 0.05 ± 0.02, respectively. These concentrations and those obtained without coprecipitation technique were significantly different. Coprecipitation procedure using 8-HQ as ligand and Cu(II) as carrier element enhanced the preconcentration and separation of metal ions from the matrix of water sample.

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

    Science.gov (United States)

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

    2017-09-01

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

  10. Simultaneous first order derivative spectrophotometric determination of vanadium and zirconium in alloy steels and minerals.

    Science.gov (United States)

    Varghese, Anitha; George, Louis

    2012-09-01

    A simple, selective and sensitive spectrophotometric method has been developed for the individual and simultaneous determination of trace amounts of vanadium(V) and zirconium(IV) in acetic acid medium using a newly synthesised reagent diacetylmonoxime salicyloylhydrazone (DMSH), without any prior separation. The molar absorptivity and Sandell's sensitivity of the coloured species are 1.30 x 10(4) and 1.82 x 10(4) L mol(-1)cm(-1) and 3.9 and 2.5 ng cm(-2) for V(V) and Zr(IV), respectively. Beer's law is obeyed between 0.26-2.80 and 0.30-3.20 μg mL(-1) concentration of vanadium (V) and zirconium (IV) at 405 and 380 nm respectively. The stoichiometry of the complex was found to be 1:1 (metal:ligand) for V(V) and 1:2 for Zr(IV) complexes. These metal ions interfere with the determination of each other in zero order spectrophotometry. The first derivative spectra of these complexes permitted a simultaneous determination of V(V) and Zr(IV) at zero crossing wavelengths of 445 nm and 405 nm, respectively. The optimum conditions for maximum colour development and other analytical parameters were evaluated. The proposed method has been successfully applied for the determination of zirconium and vanadium in standard alloy steel samples, mineral and soil samples. Copyright © 2012 Elsevier B.V. All rights reserved.

  11. Electrochemiluminescent immunosensing of prostate-specific antigen based on silver nanoparticles-doped Pb (II) metal-organic framework.

    Science.gov (United States)

    Ma, Hongmin; Li, Xiaojian; Yan, Tao; Li, Yan; Zhang, Yong; Wu, Dan; Wei, Qin; Du, Bin

    2016-05-15

    In this work, silver nanoparticles-doped Pb (II) metal-organic framework (Ag-MOF) was prepared and exploited as a luminescence probe for the development of label-free electrochemiluminescence (ECL) immunosensing scheme for prostate-specific antigen (PSA). The β-cyclodextrin based MOF, Pb-β-cyclodextrin (Pb(II)-β-CD) shows excellent ECL behavior and unexpected reducing capacity towards silver ions. Silver nanoparticles could massively form on the surface of Pb(II)-β-CD (Ag@Pb(II)-β-CD) without use any additional reducing agent, while the ECL behavior of Pb(II)-β-CD still was well retained. The Ag@Pb(II)-β-CD was used as a substrate material to modify glass carbon electrodes and formed a sensing platform for the fabricating ECL immunosensor. The presence of silver nanoparticles enables the facile immobilization of capturing antibody of PSA. The specific binding of PSA onto the electrode surface induces the decrease of ECL signals. A linear range of 0.001-50 ng mL(-1) with a detection limit of 0.34 pg mL(-1) (S/N=3) was obtained after the optimization of experimental conditions. This simply fabricated immunosensor exhibits good stability, accuracy and acceptable reproducibility, which suggesting its potential applications in clinical diagnostics. Copyright © 2015 Elsevier B.V. All rights reserved.

  12. BIOASSAY STUDIES OF METAL(II) COMPLEXES OF 2,2'-(ETHANE ...

    African Journals Online (AJOL)

    Preferred Customer

    ABSTRACT. Ni(II), Cu(II) and Zn(II) coordination compounds with modified diammine 2,2'-(ethane-1,2- diyldiimino)diacetic acid (EDDA) were prepared and characterized. Coordination complexes of the EDDA were characterized by physical measurements including elemental analysis, IR, UV-Visible, magnetic ...

  13. Hydride Reactivity of Ni-II-X-Ni-II Entities : Mixed-Valent Hydrido Complexes and Reversible Metal Reduction

    NARCIS (Netherlands)

    Gehring, Henrike; Metzinger, Ramona; Herwig, Christian; Intemann, Julia; Harder, Sjoerd; Limberg, Christian

    After the lithiation of PYR-H2 (PYR2-=[{NC(Me)C(H)C(Me)NC6H3(iPr)2}2(C5H3N)]2-), which is the precursor of an expanded beta-diketiminato ligand system with two binding pockets, its reaction with [NiBr2(dme)] led to a dinuclear nickel(II)bromide complex, [(PYR)Ni(mu-Br)NiBr] (1). The bridging bromide

  14. Phase-selective vanadium dioxide (VO{sub 2}) nanostructured thin films by pulsed laser deposition

    Energy Technology Data Exchange (ETDEWEB)

    Masina, B. N., E-mail: BMasina@csir.co.za, E-mail: slafane@cdta.dz [CSIR-National Laser Centre, PO BOX 395, Pretoria 0001 (South Africa); School of Physics, University of KwaZulu-Natal, Private Bag X54001, Durban 4000 (South Africa); Lafane, S., E-mail: BMasina@csir.co.za, E-mail: slafane@cdta.dz; Abdelli-Messaci, S.; Kerdja, T. [Division des Milieux Ionisés et Laser, Centre de Développement des Technologies Avancées, Cité du 20 Août 1956, BP 17, Baba Hassen (Algeria); Wu, L. [CSIR-National Laser Centre, PO BOX 395, Pretoria 0001 (South Africa); Akande, A. A.; Mwakikunga, B. [DST/CSIR National Centre for Nano-Structured Materials, PO BOX 395, Pretoria 0001 (South Africa); Forbes, A. [School of Physics, University of the Witwatersrand, Private Bag 3, Wits 2050, Johannesburg (South Africa)

    2015-10-28

    Thin films of monoclinic nanostructured vanadium dioxide are notoriously difficult to produce in a selective manner. To date, post-annealing, after pulsed laser deposition (PLD), has been used to revert the crystal phase or to remove impurities, and non-glass substrates have been employed, thus reducing the efficacy of the transparency switching. Here, we overcome these limitations in PLD by optimizing a laser-ablation and deposition process through optical imaging of the laser-induced plasma. We report high quality monoclinic rutile-type vanadium dioxide (VO{sub 2}) (M1) nanoparticles without post-annealing, and on a glass substrate. Our samples demonstrate a reversible metal-to-insulator transition at ∼43 °C, without any doping, paving the way to switchable transparency in optical materials at room temperature.

  15. Speciation of vanadium in Chinese cabbage (Brassica rapa L.) and soils in response to different levels of vanadium in soils and cabbage growth.

    Science.gov (United States)

    Tian, Liyan; Yang, Jinyan; Alewell, Christine; Huang, Jen-How

    2014-09-01

    This study highlights the accumulation and speciation of vanadium in Chinese cabbage (Brassica rapa L.) in relation to the speciation of soil vanadium with pot experiments at 122-622mgVkg(-1) by spiking NH4VO3. Cabbage planting decreased the bioavailable and residual vanadium based on sequential extraction, leading to enrichment of oxalate-extractable vanadium in soils. The biomass production increased with increasing concentrations of soil vanadium from 122 to 372mgVkg(-1), probably due to the increasing nitrogen availability and low vanadium availability in our soils with a consequent low vanadium toxicity. Although the concentrations of root vanadium (14.4-24.9mgVkg(-1)) related positively with soil vanadium, the bio-dilution alleviated the increase of leaf vanadium (2.1-2.7mgVkg(-1)). The predominance of vanadium(IV) in leaves (∼60-80% of total vanadium) indicates bio-reduction of vanadium in Chinese cabbage, since the mobile vanadium in oxic soils was usually pentavalent. Approximately 15-20% of the leaf vanadium was associated with recalcitrant leaf tissues. The majority of leaf vanadium was water and ethanol extractable, which is considered mobile and may cause more toxic effects on Chinese cabbage. Copyright © 2014 Elsevier Ltd. All rights reserved.

  16. Tris(pyridinealdoximato)metal complexes as ligands for the synthesis of asymmetric heterodinuclear Cr(III)M species [M = Zn(II), Cu(II), Ni(II), Fe(II), Mn(II), Cr(II), Co(III)]: a magneto-structural study.

    Science.gov (United States)

    Ross, S; Weyhermüller, T; Bill, E; Wieghardt, K; Chaudhuri, P

    2001-12-17

    Reactions of the LCr(III) unit with an in situ prepared M(PyA)(3)(n-) ion, where L represents 1,4,7-trimethyl-1,4,7-triazacyclononane and PyA(-) is the monoanion of pyridine-2-aldoxime, yield heterodinuclear complexes of general formula [LCr(III)(PyA)(3)M](2+/3+) as perchlorate salts, where M = Cr(II) (1), Mn(II) (2), low-spin Fe(II) (3), Ni(II) (4), Cu(II) (5), Zn(II) (6), and low-spin Co(III) (7). These compounds contain three oximato anions as bridging ligands. The hexadentate ligand with the identical donor atoms, tris(2-aldoximato-6-pyridyl)phosphine, P(PyA)(3), has been employed to prepare a second Cr(III)Ni(II) species 8, whose magnetic properties differ significantly from those of 4. Complexes 1-8 have been characterized on the basis of elemental analysis, mass spectrometry, IR, UV-vis, Mössbauer, and EPR spectroscopies, and variable-temperature (2-295 K) magnetic susceptibility measurements. They are isostructural in the sense that they all contain a terminal Cr(III) ion in a distorted octahedral environment, CrN(3)O(3), and a second six-coordinated metal ion M in a mostly trigonal prismatic MN(6) geometry. The crystal structures of the perchlorate salts of 2-5, 7, and 8 have been determined by X-ray crystallography at 100 K. The structures consist of mixed-metal Cr(III)M(II) and Cr(III)Co(III) complexes with a geometry in which two pseudooctahedral polyhedra are joined by three oximato (=N-O(-)) groups, with an intramolecular Cr.M(Co) distance in the range of 3.4-3.7 A. The cyclic voltammograms of the complexes reveal ligand oxidation and reduction processes, and in addition, metal-centered oxidation processes have been observed. X-band EPR spectroscopy has been used to establish the electronic ground state of the heterodinuclear complexes. Analysis of the susceptibility data indicates the presence of weak exchange interactions, both ferro- and antiferromagnetic, between the paramagnetic centers. A qualitative rationale on the basis of the Goodenough

  17. Optimal Location of Vanadium in Muscovite and Its Geometrical and Electronic Properties by DFT Calculation

    OpenAIRE

    Qiushi Zheng; Yimin Zhang; Tao Liu; Jing Huang; Nannan Xue; Qihua Shi

    2017-01-01

    Vanadium-bearing muscovite is the most valuable component of stone coal, which is a unique source of vanadium manufacture in China. Numbers of experimental studies have been carried out to destroy the carrier muscovite’s structure for efficient extraction of vanadium. Hence, the vanadium location is necessary for exploring the essence of vanadium extraction. Although most infer that vanadium may substitute for trivalent aluminium (Al) as the isomorphism in muscovite for the similar atomic rad...

  18. Soil-adjusted sorption isotherms for arsenic(V) and vanadium(V)

    Science.gov (United States)

    Rückamp, Daniel; Utermann, Jens; Florian Stange, Claus

    2017-04-01

    The sorption characteristic of a soil is usually determined by fitting a sorption isotherm model to laboratory data. However, such sorption isotherms are only valid for the studied soil and cannot be transferred to other soils. For this reason, a soil-adjusted sorption isotherm can be calculated by using the data of several soils. Such soil-adjusted sorption isotherms exist for cationic heavy metals, but are lacking for heavy metal oxyanions. Hence, the aim of this study is to establish soil-adjusted sorption isotherms for the oxyanions arsenate (arsenic(V)) and vanadate (vanadium(V)). For the laboratory experiment, 119 soils (samples from top- and subsoils) typical for Germany were chosen. The batch experiments were conducted with six concentrations of arsenic(V) and vanadium(V), respectively. By using the laboratory data, sorption isotherms for each soil were derived. Then, the soil-adjusted sorption isotherms were calculated by non-linear regression of the sorption isotherms with additional soil parameters. The results indicated a correlation between the sorption strength and oxalate-extractable iron, organic carbon, clay, and electrical conductivity for both, arsenic and vanadium. However, organic carbon had a negative regression coefficient. As total organic carbon was correlated with dissolved organic carbon; we attribute this observation to an effect of higher amounts of dissolved organic substances. We conclude that these soil-adjusted sorption isotherms can be used to assess the potential of soils to adsorb arsenic(V) and vanadium(V) without performing time-consuming sorption experiments.

  19. Synthesis, Crystal Structure, and Luminescent Properties of New Zinc(II and Cadmium(II Metal-Organic Frameworks Based on Flexible Bis(imidazol-1-ylalkane Ligands

    Directory of Open Access Journals (Sweden)

    Marina Barsukova

    2016-10-01

    Full Text Available New metal-organic frameworks (MOFs based on zinc and cadmium ions, terephthalic acid, and flexible ligands 1,5-bis(imidazol-1-ylpentane or 1,6-bis(imidazol-1-ylhexane were prepared and characterized by X-ray diffraction, thermorgavimetric analysis and IR spectroscopy. The imidazolyl ligands were prepared by a new robust procedure involving the reaction between imidazole and 1,5-dibromopentane or 1,6-dibromohexane in a superbasic medium (KOH in DMSO. MOFs based on 1,5-bis(imidazol-1-ylpentane had diamond topology (dia and are triply interpenetrated. Ligands with longer spacer 1,6-bis(imidazol-1-ylhexane, terephthalate ions and zinc(II ions formed five-fold interpenetrated metal-organic framework also with dia topology, while cadmium(II ions with the same ligands formed eight-connected uninodal net with a very rare self-penetrated topological type ilc and a point symbol 424.5.63. The influence of the chemical composition of MOFs on their photoluminescent properties is investigated and discussed in detail.

  20. Two Dawson-templated three-dimensional metal-organic frameworks based on oxalate-bridged binuclear cobalt(II)/Nickel(II) SBUs and Bpy linkers.

    Science.gov (United States)

    Zhao, Xinyu; Liang, Dadong; Liu, Shuxia; Sun, Chunyan; Cao, Ruige; Gao, Chaoying; Ren, Yuanhang; Su, Zhongmin

    2008-08-18

    The Dawson anion P 2W 18O 62 (6-) has been used as a noncoordinating polyoxoanion template for the construction of two metal-organic frameworks, namely, [M 2(bpy) 3(H 2O) 2(ox)][P 2W 18O 62]2(H 2-bpy). nH 2O (M = Co(II), n = 3 ( 1); M = Ni(II), n = 2 ( 2)) (bpy = 4,4'-bipyridine; ox = C 2O 4 (2-)). Single-crystal X-ray analysis reveals that both of the structures exhibit 3D host frameworks constructed from the oxalate-bridged binuclear superoctahedron secondary building units (SBUs) and bpy linkers and the voids of which are occupied by Dawson anions, guest bpy, and water molecules. Magnetic studies reveal that there are antiferromagnetic exchange interactions among the transition-metal centers in compounds 1 and 2. Furthermore, a compound 1-modified carbon paste electrode ( 1-CPE) displays good electrocatalytic activity toward the reduction of nitrite.

  1. Extraction of Vanadium from Vanadium Slag Via Non-salt Roasting and Ammonium Oxalate Leaching

    Science.gov (United States)

    Li, Meng; Du, Hao; Zheng, Shili; Wang, Shaona; Zhang, Yang; Liu, Biao; Dreisinger, David Bruce; Zhang, Yi

    2017-10-01

    A clean method featuring non-salt roasting followed by (NH4)2C2O4 leaching to recover vanadium from vanadium slag was proposed. The carcinogenic Cr6+ compounds and exhaust gases were avoided, and the water generated from vanadate precipitation may be recycled and reused in this new leaching process. The leaching residues may be easily used by a blast furnace. Moreover, (NH4)2C2O4 solution was used as a leaching medium to avoid expensive and complicated ammonium controlling operations as a result of the stability of (NH4)2C2O4 at a high temperature. The transformation mechanisms of vanadium- and chromium-bearing phases were systematically investigated by x-ray diffraction analysis and scanning electron microscopy with energy-disperse x-ray spectrometry, respectively. In addition, the effects of oxygen concentration, roasting temperature, and holding time on vanadium recovery were investigated. Finally, the effects of leaching variables on the vanadium leaching rate were also examined.

  2. Discrepancy between theory and measurement of superconducting vanadium

    Science.gov (United States)

    Zheng, X. H.; Walmsley, D. G.

    2015-08-01

    We have extracted consistent phonon dispersion information out of rather inconsistent vanadium X-ray scattering data from synchrotron and vacuum tube sources. With this and a new theoretical approach we have made firm predictions for the tunnelling conductance of superconducting vanadium; it is in unusually poor agreement with experimentally measured values. We argue that the problem lies in the experimental measurement rather than the theory. The preparation of a suitable high quality tunnel barrier on vanadium represents an outstanding challenge.

  3. Modified lithium vanadium oxide electrode materials products and methods

    Science.gov (United States)

    Thackeray, Michael M.; Kahaian, Arthur J.; Visser, Donald R.; Dees, Dennis W.; Benedek, Roy

    1999-12-21

    A method of improving certain vanadium oxide formulations is presented. The method concerns fluorine doping formulations having a nominal formula of LiV.sub.3 O.sub.8. Preferred average formulations are provided wherein the average oxidation state of the vanadium is at least 4.6. Herein preferred fluorine doped vanadium oxide materials, electrodes using such materials, and batteries including at least one electrode therein comprising such materials are provided.

  4. Trends in metal-biradical exchange interaction for first-row M(II)(nitronyl nitroxide-semiquinone) complexes.

    Science.gov (United States)

    Shultz, David A; Vostrikova, Kira E; Bodnar, Scot H; Koo, Hyun-Joo; Whangbo, Myung-Hwan; Kirk, Martin L; Depperman, Ezra C; Kampf, Jeff W

    2003-02-12

    We report molecular structures and temperature-dependent magnetic susceptibility data for several new metal complexes of heterospin triplet ground-state biradical ligands. The ligands are comprised of both nitronyl-nitroxide (NN) and semiquinone (SQ) spin carriers. Five compounds are five-coordinate M(II) complexes (M = Mn, Co, Ni, Cu, and Zn), and one is a six-coordinate Ni(II) complex. Five compounds were structurally characterized. During copper complex formation a reaction with methanol occurs to form a unique methoxy-substituted SQ ring. Variable-temperature magnetic susceptibility studies are consistent with strong intraligand (NN-SQ and NN-PhSQ) ferromagnetic exchange coupling. For the five-coordinate Mn, Co, and Ni complexes, the S = 1 ligand is antiferromagnetically coupled to the metal. For both the five-coordinate Cu complex and the six-coordinate Ni complex, the ligand is ferromagnetically coupled to the metal spins in accordance with orbital symmetry arguments. Despite the low molecular symmetries, the predicted trend in metal-ligand exchange interactions is supported by spin dimer analysis based on extended Hückel calculations. For (NN-SQ)NiTp(Cum,Me)() (Tp(Cum,Me)() = hydro-tris(3-cumenyl-5-methylpyrazolyl)borate), an antisymmetric exchange term was required for the best fit of the magnetic susceptibility data. Antisymmetric exchange was less important for the other complexes due to inherently smaller Deltag. Finally, it is shown that intraligand exchange coupling is of paramount importance in stabilizing high-spin states of mixed metal-biradical complexes.

  5. XAS study of vanadium in fluid cracking catalysts

    Science.gov (United States)

    Woolery, G. L.; Chin, A. A.; Kirker, G. W.; Huss, A.

    1989-06-01

    X-ray absorption spectroscopy was used to investigate the oxidation state and local environment of vanadium in Fluid Catalytic Cracking (FCC) catalysts as a function of processing and deactivation conditions. Our results suggest that oxidation of vanadium to V+5 alone is not solely responsible for catalyst deactivation but that other factors such as vanadium location and mobility play a significant role in catalyst performance. Basic alkaline earth oxide passivators such as MgO were found to interact strongly with vanadium during the regeneration period leading to formation of a magnesium vanadate compound.

  6. Chemical speciation of vanadium in coal bottom Ash

    Energy Technology Data Exchange (ETDEWEB)

    Aydin, Firat; Aydin, Isil; Hamamci, Candan [Science Faculty, Chemistry Department, Dicle University, Diyarbakir (Turkey); Saydut, Abdurrahman [Engineering Faculty, Mining Engineering Department, Dicle University, Diyarbakir (Turkey); Gunduz, Beniz [Science Faculty, Chemistry Department, Selcuk University, Konya (Turkey)

    2012-04-15

    Chemical speciation of vanadium is important to understand the true nature of this element in the environment as well as its biochemical pathways. Sample pretreatment, preparation, and chemical speciation methods were applied for vanadium in coal bottom ash here. Two-stage microwave acid digestion was used to preparation of samples. Determination of vanadium was performed using inductively coupled plasma-optical emission spectrometry (ICP-OES). Speciation of vanadium was carried out using a seven-step sequential extraction procedure of the coal bottom ash each releasing species of vanadium: Water soluble, exchangeable, carbonate, reducible, oxidizable, sulfide, and residual fractions. Total vanadium concentration in the coal bottom ash is 701 mg kg{sup -1} d.w. The most abundant form of vanadium in coal bottom ash is residual fraction of vanadium (196 mg kg{sup -1} d.w.). Relative abundances of the remaining vanadium fractions in coal bottom ash are as follows: Reducible (176 mg kg{sup -1} d.w.) > sulfide (176 mg kg{sup -1} d.w.) > carbonate (85 mg kg{sup -1} d.w.) > oxidizable (50 mg kg{sup -1} d.w.) > water soluble (10.6 mg kg{sup -1} d.w.) > exchangeable (9.0 mg kg{sup -1} d.w.). (Copyright copyright 2012 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  7. Adsorption of Azo-Dye Orange II from Aqueous Solutions Using a Metal-Organic Framework Material: Iron- Benzenetricarboxylate.

    Science.gov (United States)

    García, Elizabeth Rojas; Medina, Ricardo López; Lozano, Marcos May; Hernández Pérez, Isaías; Valero, Maria J; Franco, Ana M Maubert

    2014-12-12

    A Metal-Organic Framework (MOF), iron-benzenetricarboxylate (Fe(BTC)), has been studied for the adsorptive removal of azo-dye Orange II from aqueous solutions, where the effect of various parameters was tested and isotherm and kinetic models were suggested. The adsorption capacities of Fe(BTC) were much higher than those of an activated carbon. The experimental data can be best described by the Langmuir isotherm model (R² > 0.997) and revealed the ability of Fe(BTC) to adsorb 435 mg of Orange II per gram of adsorbent at the optimal conditions. The kinetics of Orange II adsorption followed a pseudo-second-order kinetic model, indicating the coexistence of physisorption and chemisorption, with intra-particle diffusion being the rate controlling step. The thermodynamic study revealed that the adsorption of Orange II was feasible, spontaneous and exothermic process (-25.53 kJ·mol-1). The high recovery of the dye showed that Fe(BTC) can be employed as an effective and reusable adsorbent for the removal of Orange II from aqueous solutions and showed the economic interest of this adsorbent material for environmental purposes.

  8. Adsorption of Azo-Dye Orange II from Aqueous Solutions Using a Metal-Organic Framework Material: Iron- Benzenetricarboxylate

    Directory of Open Access Journals (Sweden)

    Elizabeth Rojas García

    2014-12-01

    Full Text Available A Metal-Organic Framework (MOF, iron-benzenetricarboxylate (Fe(BTC, has been studied for the adsorptive removal of azo-dye Orange II from aqueous solutions, where the effect of various parameters was tested and isotherm and kinetic models were suggested. The adsorption capacities of Fe(BTC were much higher than those of an activated carbon. The experimental data can be best described by the Langmuir isotherm model (R2 > 0.997 and revealed the ability of Fe(BTC to adsorb 435 mg of Orange II per gram of adsorbent at the optimal conditions. The kinetics of Orange II adsorption followed a pseudo-second-order kinetic model, indicating the coexistence of physisorption and chemisorption, with intra-particle diffusion being the rate controlling step. The thermodynamic study revealed that the adsorption of Orange II was feasible, spontaneous and exothermic process (−25.53 kJ·mol−1. The high recovery of the dye showed that Fe(BTC can be employed as an effective and reusable adsorbent for the removal of Orange II from aqueous solutions and showed the economic interest of this adsorbent material for environmental purposes.

  9. Microadditions of boron and vanadium in ADI

    Directory of Open Access Journals (Sweden)

    Rzychoń T.

    2007-01-01

    Full Text Available In the second part of the study, describing the role of vanadium and boron microadditions in the process of structure formation in heavy-walled castings made from ADI, the results of own investigations were presented. Within this study two series of melts of the ductile iron were made, introducing microadditions of the above mentioned elements to both unalloyed ductile iron and the ductile iron containing high levels of nickel and copper (the composition typical of ADI. Melts were conducted with iron-nickel-magnesium master alloy. Thermal analysis of the solidification process of the cast keel blocks was conducted, the heat treatment of the alloys was carried out, and then the effect of the introduced additions of boron and vanadium on the hardenability of the investigated cast iron was examined and evaluated.

  10. Vanadium in fuel oil - a new solution

    Energy Technology Data Exchange (ETDEWEB)

    Czech, N. [Siemens, Muelheim (Germany); Finckh, H. [Siemens, Erlangen (Germany)

    1998-11-01

    Hot corrosion of the hot-gas-path components due to vanadium contamination is one of the hazards associated with heavy residual oil combustion in heavy-duty gas turbines. This economically attractive oil combustion process has benefited from the recently developed vanadium inhibition technique, which is currently being tested at the Valladolid 220 MWe combined cycle plant in Mexico. The method uses atomization of a dilute aqueous solution of Epsom salt (MgSO{sub 7},7H{sub 2}O) into very small droplets which are then injected onto the flame where intensive mixing takes place. The successful use of this new technique promises extended operating periods between cleanup operations, and cost reductions from the use of inexpensive materials, as well as the ability to operate advanced gas turbines on difficult fuels, not previously feasible. (UK)

  11. Irradiation creep of vanadium-base alloys

    Energy Technology Data Exchange (ETDEWEB)

    Tsai, H.; Billone, M.C.; Strain, R.V.; Smith, D.L. [Argonne National Lab., IL (United States); Matsui, H. [Tohoku Univ. (Japan)

    1998-03-01

    A study of irradiation creep in vanadium-base alloys is underway with experiments in the Advanced Test Reactor (ATR) and the High Flux Isotope Reactor (HFIR) in the United States. Test specimens are thin-wall sealed tubes with internal pressure loading. The results from the initial ATR irradiation at low temperature (200--300 C) to a neutron damage level of 4.7 dpa show creep rates ranging from {approx}0 to 1.2 {times} 10{sup {minus}5}/dpa/MPa for a 500-kg heat of V-4Cr-4Ti alloy. These rates were generally lower than reported from a previous experiment in BR-10. Because both the attained neutron damage levels and the creep strains were low in the present study, however, these creep rates should be regarded as only preliminary. Substantially more testing is required before a data base on irradiation creep of vanadium alloys can be developed and used with confidence.

  12. Nearby supernova host galaxies from the CALIFA survey. II. Supernova environmental metallicity

    NARCIS (Netherlands)

    Galbany, L.; Stanishev, V.; Mourão, A. M.; Rodrigues, M.; Flores, H.; Walcher, C. J.; Sánchez, S. F.; García-Benito, R.; Mast, D.; Badenes, C.; González Delgado, R. M.; Kehrig, C.; Lyubenova, M.; Marino, R. A.; Mollá, M.; Meidt, S.; Pérez, E.; van de Ven, G.; Vílchez, J. M.

    2016-01-01

    The metallicity of a supernova progenitor, together with its mass, is one of the main parameters that can rule the progenitor's fate. We present the second study of nearby supernova (SN) host galaxies (0.005 ⊙) > 10 dex) by targeted searches. We neither found evidence that the metallicity at the SN

  13. Microadditions of boron and vanadium in ADI

    OpenAIRE

    Rzychoń T.; Kiełbus A.; Szala J.

    2007-01-01

    In the second part of the study, describing the role of vanadium and boron microadditions in the process of structure formation in heavy-walled castings made from ADI, the results of own investigations were presented. Within this study two series of melts of the ductile iron were made, introducing microadditions of the above mentioned elements to both unalloyed ductile iron and the ductile iron containing high levels of nickel and copper (the composition typical of ADI). Melts were conducted ...

  14. Controlled synthesis and electrochemical properties of vanadium ...

    Indian Academy of Sciences (India)

    Vanadium oxides (V3O7.H2O and VO2) with different morphologies have been selectively synthesized by a facile hydrothermal approach using glucose as the reducing and structure-directing reagent. The as-obtained V3O7.H2O nanobelts have a length up to several tens of micrometers, width of about 60–150 nm and ...

  15. Determination of Leachable Vanadium (V) in Sediment

    African Journals Online (AJOL)

    NICO

    USA) were used for the filtration of sample solutions. RESEARCH ... were transferred to a Teflon beaker and treated on a hot plate at about 110 °C ... Table 1 Thermal programme for the determination of vanadium using. ET-AAS. Step. Temperature/°C. Ramp/s–1. Hold/s–1. Internal gas flow/mL min–1. 1. 120. 1. 10. 250. 2.

  16. Characterization of vanadium flow battery. Revised

    Energy Technology Data Exchange (ETDEWEB)

    Bindner, H.; Ekman, C.; Gehrke, O.; Isleifsson, F.

    2011-02-15

    This report summarizes the work done at Risoe-DTU testing a vanadium flow battery as part of the project ''Characterisation of Vanadium Batteries'' (ForskEl project 6555) with the partners PA Energy A/S and OI Electric A/S under the Danish PSO energy research program. A 15kW/120kWh vanadium battery has been installed as part of the distributed energy systems experimental facility, SYSLAB, at Risoe DTU. A test programme has been carried out to get hands-on experience with the technology, to characterize the battery from a power system point of view and to assess it with respect to integration of wind energy in the Danish power system. The battery has been in operation for 18 months. During time of operation the battery has not shown signs of degradation of performance. It has a round-trip efficiency at full load of approximately 60% (depending on temperature and SOC). The sources of the losses are power conversion in cell stacks/electrolyte, power converter, and auxiliary power consumption from pumps and controller. The efficiency was not influenced by the cycling of the battery. The response time for the battery is limited at 20kW/s by the ramp rate of the power converter. The battery can thus provide power and frequency support for the power system. The battery was operated together with a 11kW stall-regulated Gaia wind turbine to smooth the output of the wind turbine and during the tests the battery proved capable of firming the output of the wind turbine. Vanadium battery is a potential technology for storage based services to the power system provided investment and O and M cost are low enough and long term operation is documented. (Author)

  17. Synthesis, characterization and investigation of electrochemical and spectroelectrochemical properties of peripherally tetra 4-phenylthiazole-2-thiol substituted metal-free, zinc(II), copper(II) and cobalt(II) phthalocyanines

    Science.gov (United States)

    Demirbaş, Ümit; Akçay, Hakkı Türker; Koca, Atıf; Kantekin, Halit

    2017-08-01

    In this study novel peripherally tetra 4-phenylthiazole-2-thiol substituted metal-free phthalocyanine (4) and its zinc(II) (5), copper(II) (6) and cobalt(II) (7) derivatives were synthesized and characterized by a combination of various spectroscopic techniques such as FT-IR, 1H-NMR, UV-vis and MALDI-TOF mass. Electrochemical characterizations of metallo-phthalocyanine complexes were conducted by voltammetric and in situ spectroelectrochemical measurements. CoIIPc went [CoIIPc-2]/[CoIPc-2]1-, [CoIPc-2]1-/[CoIPc-3]2-, [CoIPc-3]2-/[CoIPc-4]3- and [CoIIPc-2]/[CoIIPc-2]1+ reduction and oxidation processes respectively. Differently ZnIIPc only showed four ligand-based reductions and two ligand based oxidation processes.

  18. Pb(II) and Hg(II) binding to $\\textit{de novo}$ designed proteins studied by $^{204m}$Pb- and $^{199m}$Hg-Perturbed Angular Correlation of $\\gamma$-rays (PAC) spectroscopy : Clues to heavy metal toxicity

    CERN Multimedia

    2002-01-01

    $\\textit{De novo}$ design of proteins combined with PAC spectroscopy offers a unique and powerful approach to the study of fundamental chemistry of heavy metal-protein interactions, and thus of the mechanisms underlying heavy metal toxicity. In this project we focus on Pb(II) and Hg(II) binding to designed three stranded coiled coil proteins with one or two binding sites, mimicking a variety of naturally occurring thiolate-rich metal ion binding sites in proteins. The $^{204m}$Pb- and $^{199m}$Hg-PAC experiments will complement data already recorded with EXAFS, NMR, UV-Vis and CD spectroscopies.

  19. Vanadium proton exchange membrane water electrolyser

    Science.gov (United States)

    Noack, Jens; Roznyatovskaya, Nataliya; Pinkwart, Karsten; Tübke, Jens

    2017-05-01

    In order to reverse the reactions of vanadium oxygen fuel cells and to regenerate vanadium redox flow battery electrolytes that have been oxidised by atmospheric oxygen, a vanadium proton exchange membrane water electrolyser was set up and investigated. Using an existing cell with a commercial and iridium-based catalyst coated membrane, it was possible to fully reduce V3.5+ and V3+ solutions to V2+ with the formation of oxygen and with coulomb efficiencies of over 96%. The cell achieved a maximum current density of 75 mA/cm2 during this process and was limited by the proximity of the V(III) reduction to the hydrogen evolution reaction. Due to the specific reaction mechanisms of V(IV) and V(III) ions, V(III) solutions were reduced with an energy efficiency of 61%, making this process nearly twice as energy efficient as the reduction of V(IV) to V(III). Polarisation curves and electrochemical impedance spectroscopy were used to further investigate the losses of half-cell reactions and to find ways of further increasing efficiency and performance levels.

  20. Vanadium oxide/polypyrrole aerogel nanocomposites

    Energy Technology Data Exchange (ETDEWEB)

    Dave, B.C.; Dunn, B.S.; Wong, H.P. [Univ. of California, Los Angeles, CA (United States). Dept. of Materials Science and Engineering; Leroux, F.; Nazar, L.F. [Univ. of Waterloo, Ontario (Canada). Dept. of Chemistry

    1996-12-31

    Vanadium pentoxide/polypyrrole aerogel (ARG) nanocomposites were prepared by hydrolysis of VO(OC{sub 3}H{sub 7}){sub 3} using pyrrole/water/acetone mixtures. Monolithic green-black gels with polypyrrole/V ratios ranging from 0.15 to 1.0 resulted from simultaneously polymerization of the pyrrole and vanadium alkoxide precursors. Supercritical drying yielded high surface (150--200 m{sup 2}/g) aerogels, of sufficient mechanical integrity to allow them to be cut without fracturing. TEM studies of the aerogels show that they are comprised of fibers similar to that of V{sub 2}O{sub 5} ARG`s, but with a much shorter chain length. Evidence from IR that the inorganic and organic components strongly interact leads them to propose that this impedes the vanadium condensation process. The result is ARG`s that exhibit decreased electronic conductivity with increasing polymer content. Despite the unexpected deleterious effect of the conductive polymer on the bulk conductivity, at low polymer content, the nanocomposite materials show enhanced electrochemical properties for Li insertion compared to the pristine aerogel.

  1. Selective extraction of histidine derivatives by metal affinity with a copper(II)-chelating ligand complex in an aqueous two-phase system.

    Science.gov (United States)

    Oshima, Tatsuya; Oshima, Chinatsu; Baba, Yoshinari

    2015-05-15

    Affinity extraction based on the interaction between a target molecule and a specific affinity ligand offers a novel separation system for biomolecules in an aqueous two-phase system, however, most of affinity ligands are expensive. In the present study, metal affinity extraction of histidine (His) derivatives using a complex between Cu(II) and a commercially available chelating ligand was studied in a poly(ethylene glycol) (PEG)/Li2SO4 ATPS. Alizarin complexone (3-[N,N-bis(carboxymethyl)amino methyl]-1,2-dihydroxy anthraquinone, AC) was selected as the chelating ligand because of the good extractability of Cu(II) into the upper PEG-rich phase. On the basis of coordinate bonding with Cu(II), the extraction of His in the presence of the Cu(II)-AC complex under neutral condition was 73%, which was much higher than that under Cu(II) free condition (13%). Among a series of divalent transition metal ions (Cu(II), Ni(II), Co(II), and Zn(II)), Cu(II) was the most effective for the extraction of His. Derivatives of His were selectively extracted in the presence of many other amino acids because of the specificity of the interaction between Cu(II) and imidazole group of His. Extracted His was quantitatively stripped from the Cu(II)-AC complex using competitive complexation with agents such as iminodiacetic acid and imidazole. Copyright © 2015 Elsevier B.V. All rights reserved.

  2. An extraction process to recover vanadium from low-grade vanadium-bearing titanomagnetite.

    Science.gov (United States)

    Chen, Desheng; Zhao, Hongxin; Hu, Guoping; Qi, Tao; Yu, Hongdong; Zhang, Guozhi; Wang, Lina; Wang, Weijing

    2015-08-30

    An extraction process to recover vanadium from low-grade vanadium-bearing titanomagnetite was developed. In this study, a mixed solvent system of di(2-ethylhexyl) phosphate (D2EHPA) and tri-n-butyl phosphate (TBP) diluted with kerosene was used for the selective extraction of vanadium from a hydrochloric acid leaching solution that contained low vanadium concentration with high concentrations of iron and impurities of Ca, Mg, and Al. In the extraction process, the initial solution pH and the phase ratio had considerable functions in the extraction of vanadium from the hydrochloric acid leaching solution. Under optimal extraction conditions (i.e., 30-40°C for 10min, 1:3 phase ratio (O/A), 20% D2EHPA concentration (v/v), and 0-0.8 initial solution pH), 99.4% vanadium and only 4.2% iron were extracted by the three-stage counter-current extraction process. In the stripping process with H2SO4 as the stripping agent and under optimal stripping conditions (i.e., 20% H2SO4 concentration, 5:1 phase ratio (O/A), 20min stripping time, and 40°C stripping temperature), 99.6% vanadium and only 5.4% iron were stripped by the three-stage counter-current stripping process. The stripping solution contained 40.16g/LV2O5,0.691g/L Fe, 0.007g/L TiO2, 0.006g/L SiO2 and 0.247g/L CaO. A V2O5 product with a purity of 99.12% V2O5 and only 0.026% Fe was obtained after the oxidation, precipitation, and calcination processes. The total vanadium recovered from the hydrochloric acid leaching solution was 85.5%. Copyright © 2015 Elsevier B.V. All rights reserved.

  3. Method of producing microporous joints in metal bodies

    Science.gov (United States)

    Danko, Joseph C.

    1982-01-01

    Tungsten is placed in contact with either molybdenum, tantalum, niobium, vanadium, rhenium, or other metal of atoms having a different diffusion coefficient than tungsten. The metals are heated so that the atoms having the higher diffusion coefficient migrate to the metal having the lower diffusion rate, leaving voids in the higher diffusion coefficient metal. Heating is continued until the voids are interconnected.

  4. Alginate and Algal-Based Beads for the Sorption of Metal Cations: Cu(II and Pb(II

    Directory of Open Access Journals (Sweden)

    Shengye Wang

    2016-09-01

    Full Text Available Alginate and algal-biomass (Laminaria digitata beads were prepared by homogeneous Ca ionotropic gelation. In addition, glutaraldehyde-crosslinked poly (ethyleneimine (PEI was incorporated into algal beads. The three sorbents were characterized by scanning electron microscopy (SEM coupled with energy dispersive X-ray analysis (EDX: the sorption occurs in the whole mass of the sorbents. Sorption experiments were conducted to evaluate the impact of pH, sorption isotherms, and uptake kinetics. A special attention was paid to the effect of drying (air-drying vs. freeze-drying on the mass transfer properties. For alginate, freeze drying is required for maintaining the porosity of the hydrogel, while for algal-based sorbents the swelling of the material minimizes the impact of the drying procedure. The maximum sorption capacities observed from experiments were 415, 296 and 218 mg Pb g−1 and 112, 77 and 67 mg Cu g−1 for alginate, algal and algal/PEI beads respectively. Though the sorption capacities of algal-beads decreased slightly (compared to alginate beads, the greener and cheaper one-pot synthesis of algal beads makes this sorbent more competitive for environmental applications. PEI in algal beads decreases the sorption properties in the case of the sorption of metal cations under selected experimental conditions.

  5. An improved method of preparation of nanoparticular metal oxide catalysts

    DEFF Research Database (Denmark)

    2014-01-01

    The present invention concerns an improved method of preparation of nanoparticular vanadium oxide/anatase titania catalysts having a narrow particle size distribution. In particular, the invention concerns preparation of nanoparticular vanadium oxide/anatase titania catalyst precursors comprising...... combustible crystallization seeds upon which the catalyst metal oxide is coprecipitated with the carrier metal oxide, which crystallization seeds are removed by combustion in a final calcining step....

  6. Cobalt, manganese, nickel, and vanadium derivatives of the cyclic 48-tungsto-8-phosphate [H(7)P(8)W(48)O(184)](33-).

    Science.gov (United States)

    Bassil, Bassem S; Ibrahim, Masooma; Mal, Sib Sankar; Suchopar, Andreas; Biboum, Rosa Ngo; Keita, Bineta; Nadjo, Louis; Nellutla, Saritha; van Tol, Johan; Dalal, Naresh S; Kortz, Ulrich

    2010-06-07

    The cobalt(II) containing tungstophosphate [Co(4)(H(2)O)(16)P(8)W(48)O(184)](32-) (1) has been synthesized by addition of Co(2+) ions to an aqueous solution of [H(7)P(8)W(48)O(184)](33-) (P(8)W(48)) and characterized by single-crystal XRD, IR, and UV-vis spectroscopy, elemental analysis, electrochemistry, and magnetochemistry. The novel polyanion 1 is a derivative of the superlacunary P(8)W(48) with four cobalt(II) ions coordinated to the rim of the central cavity and two additional cobalt(II) ions linked on the outside bridging neighboring polyanions. Using similar synthetic procedures, but adding a few drops of H(2)O(2), we isolated the manganese(II) derivative [Mn(4)(H(2)O)(16)(P(8)W(48)O(184))(WO(2)(H(2)O)(2))(2)](28-) (2) and its nickel(II) analogue [Ni(4)(H(2)O)(16)(P(8)W(48)O(184))(WO(2)(H(2)O)(2))(2)](28-) (3). Both polyanions have picked up two equivalents of tungsten resulting in the unprecedented {P(8)W(50)} host framework. We also made the vanadium(V) derivative [(VO(2))(4)(P(8)W(48)O(184))](36-) (4), with four tetrahedral vanadate groups grafted to the P(8)W(48) host. The voltammetric patterns associated with the W-centers in polyanions 1, 2, and 4 display enough distinct features allowing for a qualitative classification according to relative basicity of the reduced polyanions: 2 > P(8)W(48) > 1 > 4. The electrochemistry of 1 offers a new example for detection of the Co(2+) centers in a multicobalt containing polyanion. During a study of the Mn(2+) centers of 2 at pH 5, a film deposition is observed. The vanadium(V) centers of 4 are well-behaved in a pH 0.33 medium. Temperature and magnetic field dependence of the magnetic moment of 1-3 were performed on a SQUID magnetometer over the temperature range 1.8-250 K and field range 0-7 T. The results are consistent with the model of noninteracting 3d metal ions. Variable temperature (4-295 K) and variable frequency (34-413 GHz) EPR measurements support the magnetic susceptibility results. The zero

  7. Synthesis and Characterization of 2-(Hydroxyimino-1-(phenylpropylidenethiocarbonohydrazide and its Metal Complexes with Co(II, Ni(II and Cu(II Ions

    Directory of Open Access Journals (Sweden)

    A. Venkatchallam

    2009-01-01

    Full Text Available Synthesis and characterization of 2-(hydroxyimino-1-(phenyl propylidene thiocarbonohydrazide (called ‘HPTCHOPD’ was studied. The synthesized compound having the molecular formula C10H13N5OS, where in isonitrosopropiophenone is reacted with thiocarbonohydrazide in presence of sodium acetate in ethanol-water mixture. The yield which is comprises effecting the reaction in the presence of sodium acetate. Also the present work report a process for producing metal complexes having the formula ML2 and (ML2 Cl, wherein M is the divalent metal cation, like cobalt (Co+2, nickel (Ni+2 and copper (Cu+2. The compound HPTCHOPD is admixed with a basic divalent compound that is halide, mainly chloride of Co+2, Ni+2 and Cu+2 in presence of methanol-water mixture. The metal complexes so produced are characterized on the basis of spectral, elemental and magnetic analysis; reveal interesting geometries and bonding features. The data suggested square planar geometry for Co+2 complex, a distorted tetrahedral/square planar-octahedral geometry for Ni+2 complex and a bridged structure for Cu+2 complex.

  8. Applications of RIGAKU Dmax Rapid II micro-X-ray diffractometer in the analysis of archaeological metal objects

    Science.gov (United States)

    Mozgai, Viktória; Szabó, Máté; Bajnóczi, Bernadett; Weiszburg, Tamás G.; Fórizs, István; Mráv, Zsolt; Tóth, Mária

    2017-04-01

    During material analysis of archaeological metal objects, especially their inlays or corrosion products, not only microstructure and chemical composition, but mineralogical composition is necessary to be determined. X-ray powder diffraction (XRD) is a widely-used method to specify the mineralogical composition. However, when sampling is not or limitedly allowed due to e.g. the high value of the object, the conventional XRD analysis can hardly be used. Laboratory micro-XRD instruments provide good alternatives, like the RIGAKU Dmax Rapid II micro-X-ray diffractometer, which is a unique combination of a MicroMax-003 third generation microfocus, sealed tube X-ray generator and a curved 'image plate' detector. With this instrument it is possible to measure as small as 10 µm area in diameter on the object. Here we present case studies for the application of the micro-XRD technique in the study of archaeological metal objects. In the first case niello inlay of a Late Roman silver augur staff was analysed. Due to the high value of the object, since it is the only piece known from the Roman Empire, only non-destructive analyses were allowed. To reconstruct the preparation of the niello, SEM-EDX analysis was performed on the niello inlays to characterise their chemical composition and microstructure. Two types of niello are present: a homogeneous, silver sulphide niello (acanthite) and an inhomogeneous silver-copper sulphide niello (exsolution of acanthite and jalpaite or jalpaite and stromeyerite). The micro-X-ray diffractometer was used to verify the mineralogical composition of the niello, supposed on the base of SEM results. In the second case corrosion products of a Late Roman copper cauldron with uncertain provenance were examined, since they may hold clues about the burial conditions (pH, Eh, etc.) of the object. A layer by layer analysis was performed in cross sections of small metal samples by using electron microprobe and micro-X-ray diffractometer. The results

  9. Lithium-vanadium advanced blanket development. ITER final report on U.S. contribution: Task T219/T220

    Energy Technology Data Exchange (ETDEWEB)

    Smith, D.L.; Mattas, R.F. [comps.

    1997-07-01

    The objective of this task is to develop the required data base and demonstrate the performance of a liquid lithium-vanadium advanced blanket design. The task has two main activities related to vanadium structural material and liquid lithium system developments. The vanadium alloy development activity included four subtasks: (1.1) baseline mechanical properties of non irradiated base metal and weld metal joints; (1.2) compatibility with liquid lithium; (1.3) material irradiation tests; and (1.4) development of material manufacturing and joining methods. The lithium blanket technology activity included four subtasks: (2.1) electrical insulation development and testing for liquid metal systems; (2.2) MHD pressure drop and heat transfer study for self-cooled liquid metal systems; (2.3) chemistry of liquid lithium; and (2.4) design, fabrication and testing of ITER relevant size blanket mockups. A summary of the progress and results obtained during the period 1995 and 1996 in each of the subtask areas is presented in this report.

  10. A porous Cd(II) metal-organic framework with high adsorption selectivity for CO2 over CH4

    Science.gov (United States)

    Zhu, Chunlan

    2017-05-01

    Metal-organic frameworks (MOFs) have attracted a lot of attention in recent decades. We applied a semi-rigid four-carboxylic acid linker to assemble with Cd(II) ions to generate a novel microporous Cd(II) MOF material. Single crystal X-ray diffraction study reveals the different two dimension (2D) layers can be further packed together with an AB fashion by hydrogen bonds (O4sbnd H4⋯O7 = 1.863 Å) to construct a three dimension (3D) supermolecular architecture. The resulting sample can be synthesized under solvothermal reactions successfully, which exhibits high selectivity adsorption of CO2 over CH4 at room temperature. In addition, the obtained sample was characterized by thermal gravimetric analyses (TGA), Fourier-transform infrared spectra (FT-IR), elemental analysis (CHN) and powder X-ray diffraction (PXRD).

  11. Studies on Metal-Organic Frameworks of Cu(II) with Isophthalate Linkers for Hydrogen Storage

    OpenAIRE

    Yan, Yong; Yang, Sihai; Blake, Alexander J.; Schröder, Martin

    2014-01-01

    Hydrogen (H2) is a promising alternative energy carrier due to its environmental benefits, high energy density and its abundance. However, development of a practical storage system to enable the “Hydrogen Economy” remains a huge challenge. Metal-organic frameworks (MOFs) are an important class of crystalline coordination polymers constructed by bridging metal centers with organic linkers, and show promise for H2 storage due to their high surface area and tuneable properties. We summarize our ...

  12. In situ electrical resistivity measurements of vanadium thin films performed in vacuum during different annealing cycles

    Science.gov (United States)

    Pedrosa, Paulo; Cote, Jean-Marc; Martin, Nicolas; Arab Pour Yazdi, Mohammad; Billard, Alain

    2017-02-01

    The present study describes a sputtering and in situ vacuum electrical resistivity setup that allows a more efficient sputtering-oxidation coupling process for the fabrication of oxide compounds like vanadium dioxide, VO2. After the sputtering deposition of pure V thin films, the proposed setup enables the sample holder to be transferred from the sputtering to the in situ annealing + resistivity chamber without venting the whole system. The thermal oxidation of the V films was studied by implementing two different temperature cycles up to 550 °C, both in air (using a different resistivity setup) and vacuum conditions. Main results show that the proposed system is able to accurately follow the different temperature setpoints, presenting clean and low-noise resistivity curves. Furthermore, it is possible to identify the formation of different vanadium oxide phases in air, taking into account the distinct temperature cycles used. The metallic-like electrical properties of the annealed coatings are maintained in vacuum whereas those heated in air produce a vanadium oxide phase mixture.

  13. Spectral characterization, electrochemical and anticancer studies on some metal(II) complexes containing tridentate quinoxaline Schiff base.

    Science.gov (United States)

    Chellaian, Justin Dhanaraj; Johnson, Jijo

    2014-06-05

    Co(II), Ni(II), Cu(II) and Zn(II) complexes of a tridentate ONO donor Schiff base ligand derived from 3-(2-aminoethylamino)quinoxalin-2(1H)-one were synthesized. The ligand and its metal complexes were characterized using elemental analysis, molar conductance, IR, (1)H NMR, mass, magnetic susceptibility, electronic spectra and ESR spectral studies. Electrochemical behavior of the synthesized compounds was studied using cyclic voltammetry. The grain size of the synthesized compounds was determined by powder XRD. The Schiff base and its complexes have been screened for their antimicrobial activities against the bacterial species E. coli, K. pneumoniae, P. aeruginosa and S. aureus; fungal species include, A. niger, and C. albicans by disc diffusion method. The results show that the complexes have higher activity than the free ligand. The interaction of the complexes with calf thymus DNA (CT DNA) has been investigated by electronic absorption method. Furthermore, the DNA cleavage activity of the complexes was studied using agarose gel electrophoresis. In vitro anticancer studies of the ligand and its complexes using MTT assay was also done. Copyright © 2014 Elsevier B.V. All rights reserved.

  14. Photolytic Release of Dissolved Vanadium and Copper from Resuspended Coastal Marine Sediments

    Science.gov (United States)

    Skrabal, S. A.; Hammaker, S. N.; McBurney, A. W.; Avery, G. B., Jr.; Kieber, R. J.; Mead, R. N.

    2016-02-01

    Sunlight photolysis engenders release of dissolved vanadium (V), copper (Cu), and dissolved organic carbon (DOC) from a wide variety of resuspendable coastal marine sediments. Net photoreleases after 6 h of simulated sunlight were as high as 12 nM for Cu and as high as 15 nM for V. Release of Cu significantly correlated with sediment Cu. Photoreleased Cu (but not V) correlated with sediment Fe content, suggesting that photoreduction of Fe oxide carrier phases may be an important photoproduction mechanism for Cu. Longer term experiments showed continued release of metals that were not immediately readsorbed back onto sediments after 24 h of irradiation suggesting that photoproduced metals persist in the dissolved phase and are not immediately scavenged onto particles. Experiments utilizing differing total suspended sediment (TSS) levels show that, although higher TSS causes more photoproduction of Cu and V, the amount produced per mass of sediment is greatest at the lowest TSS. Vanadium photoproduction increased in Macondo oil-amended sediments compared to controls after a one-month incubation period suggesting that the oil may be a source of this metal to the water column. These results imply that photoproduction is an unrecognized source of the micronutrient metals Cu and V to coastal waters.

  15. Fragility–structure–conductivity relations in vanadium tellurite glass

    DEFF Research Database (Denmark)

    Kjeldsen, Jonas; Yue, Yuanzheng; Rodrigues, Ana Candida Martins

    the ability to intercalate lithium-ions, it is a candidate as cathode material. Here, we investigate the correlation between liquid fragility, structure and electronic conductivity in a series of vanadium-tellurite glasses with varying vanadium concentration. We measure dynamic and thermodynamic fragility...

  16. Combined effect of vanadium and nickel on lipid peroxidation and ...

    African Journals Online (AJOL)

    use

    2011-12-12

    Dec 12, 2011 ... Signs of toxicity were observed following treatment with vanadium, not nickel nor combined vanadium and .... Kazakhstan. Animal treatment. Outbred 3-month-old male albino rats, weighing between 230 to. 235 g (mean) at the beginning of experiment, were obtained from ..... Vitamin E supplementation.

  17. Lorentz-violating type-II Dirac fermions in transition metal dichalcogenide PtTe2.

    Science.gov (United States)

    Yan, Mingzhe; Huang, Huaqing; Zhang, Kenan; Wang, Eryin; Yao, Wei; Deng, Ke; Wan, Guoliang; Zhang, Hongyun; Arita, Masashi; Yang, Haitao; Sun, Zhe; Yao, Hong; Wu, Yang; Fan, Shoushan; Duan, Wenhui; Zhou, Shuyun

    2017-08-15

    Topological semimetals have recently attracted extensive research interests as host materials to condensed matter physics counterparts of Dirac and Weyl fermions originally proposed in high energy physics. Although Lorentz invariance is required in high energy physics, it is not necessarily obeyed in condensed matter physics, and thus Lorentz-violating type-II Weyl/Dirac fermions could be realized in topological semimetals. The recent realization of type-II Weyl fermions raises the question whether their spin-degenerate counterpart-type-II Dirac fermions-can be experimentally realized too. Here, we report the experimental evidence of type-II Dirac fermions in bulk stoichiometric PtTe2 single crystal. Angle-resolved photoemission spectroscopy measurements and first-principles calculations reveal a pair of strongly tilted Dirac cones along the Γ-A direction, confirming PtTe2 as a type-II Dirac semimetal. Our results provide opportunities for investigating novel quantum phenomena (e.g., anisotropic magneto-transport) and topological phase transition.Whether the spin-degenerate counterpart of Lorentz-violating Weyl fermions, the Dirac fermions, can be realized remains as an open question. Here, Yan et al. report experimental evidence of such type-II Dirac fermions in bulk PtTe2 single crystal with a pair of strongly tilted Dirac cones.

  18. In situ reactive zone with modified Mg(OH)2 for remediation of heavy metal polluted groundwater: Immobilization and interaction of Cr(III), Pb(II) and Cd(II)

    Science.gov (United States)

    Dong, Jun; Li, Bowen; Bao, Qiburi

    2017-04-01

    Mg(OH)2 dissolves slowly and can provide a long-term source of alkalinity, thus a promising alternative reagent for the in situ remediation of heavy metal polluted groundwater. However, the application of Mg(OH)2 on in situ reactive zone (IRZ) for heavy metal polluted groundwater has never been investigated. In this study, the behaviors of heavy metals in a Mg(OH)2 IRZ were monitored for 45 d. The heavy metals show a sequential precipitation by modified Mg(OH)2 due to the difference of Ksp. Column tests were conducted to investigate the temporal and spatial distribution of heavy metals in Mg(OH)2 IRZ and evaluate the stabilization effect for multi-heavy metal polluted groundwater. Experimental results indicate that there exist interactions between different heavy metals, and their zoning distribution is attributed either to the competitive adsorption onto porous media (control column) or to the sequential precipitation of heavy metal ions (IRZ column). In contrast with the control column, heavy metal contaminated area in Mg(OH)2 IRZ significantly shrinks. According to the chemical speciation analysis, when water containing Pb(II), Cd(II) and Cr(III) flows through Mg(OH)2 IRZ, exchangeable fraction of total concentration significantly reduce and the proportion of carbonate and Fe/Mn oxides fraction increase, indicating the decrease of their mobility and toxicity.

  19. VizieR Online Data Catalog: On the metallicity of open clusters. II. (Heiter+, 2014)

    Science.gov (United States)

    Heiter, U.; Soubiran, C.; Netopil, M.; Paunzen, E.

    2013-11-01

    In Table 1 we list the basic information for each star and each metallicity determination in the starting sample, which should be sufficient to extract the corresponding atmospheric parameters from the PASTEL catalogue. Table 4 lists the weighted mean metallicities for each OC and each paper, which were computed using the metallicities from the references in Table 1. For the weights we used the inverse square of the individual errors quoted by the authors. Table 4 also gives the ranges of effective temperature (Teff) and surface gravity (logg) of the stars corresponding to each paper. After removing all determinations with Teff outside the range 4400 to 6500K and with logg<2.0, we constructed a list of recommended cluster metallicities, which we call the final high-resolution sample. The weighted mean metallicities for each cluster in the final sample are given in Table 11, and the individual determinations included in the final sample are identified in Table 1 (first column). (3 data files).

  20. Switching adhesion forces by crossing the metal–insulator transition in Magnéli-type vanadium oxide crystals

    Directory of Open Access Journals (Sweden)

    Bert Stegemann

    2011-01-01

    Full Text Available Magnéli-type vanadium oxides form the homologous series VnO2n-1 and exhibit a temperature-induced, reversible metal–insulator first order phase transition (MIT. We studied the change of the adhesion force across the transition temperature between the cleavage planes of various vanadium oxide Magnéli phases (n = 3 … 7 and spherical titanium atomic force microscope (AFM tips by systematic force–distance measurements with a variable-temperature AFM under ultrahigh vacuum conditions (UHV. The results show, for all investigated samples, that crossing the transition temperatures leads to a distinct change of the adhesion force. Low adhesion corresponds consistently to the metallic state. Accordingly, the ability to modify the electronic structure of the vanadium Magnéli phases while maintaining composition, stoichiometry and crystallographic integrity, allows for relating frictional and electronic material properties at the nano scale. This behavior makes the vanadium Magnéli phases interesting candidates for technology, e.g., as intelligent devices or coatings where switching of adhesion or friction is desired.

  1. Vanadium and vanadium nitride thin films grown by high power impulse magnetron sputtering

    Science.gov (United States)

    Hajihoseini, H.; Gudmundsson, J. T.

    2017-12-01

    Thin vanadium and vanadium nitride films were grown on SiO2 by non-reactive and reactive high power impulse magnetron sputtering (HiPIMS), respectively. The film properties were compared to films grown by conventional dc magnetron sputtering (dcMS) at similar conditions. We explored the influence of the stationary magnetic confinement field strength on the film properties and the process parameters. The deposition rate is much lower for non-reactive sputtering by HiPIMS than for dcMS. Furthermore, for both dcMS and HiPIMS the deposition rate is lower for strong magnetic confinement. Structural characterization was carried out using x-ray diffraction and reflection methods as well as atomic force microscopy and scanning electron microscope. Both dcMS and HiPIMS grown vanadium films are polycrystalline with similar grain size regardless of magnetic field strength. For dcMS grown vanadium films the surface roughness is higher when a strong magnetic field is used. For both non-reactive growth of vanadium and reactive growth of vanadium nitride the HiPIMS process produces denser films with lower surface roughness than dcMS does. Lowering the magnetic field strength increases the deposition rate significantly for reactive HiPIMS while it increases only slightly in the reactive dcMS case. The films grown by HiPIMS with strong magnetic confinement exhibit higher density and lower roughness. We find that the operating pressure, growth temperature, discharge voltage and film thickness has influence on the properties of HiPIMS grown vanadium nitride films. The films are denser when grown at high temperature, high discharge voltage and low pressure. The density of those films is lower for thicker films and thicker films consist of larger grain size. For all the films explored, higher density coincides with lower surface roughness. Thus, the deposition method, magnetic field strength, growth temperature, discharge voltage, film thickness and growth pressure have a significant

  2. Gas adsorption and structural diversity in a family of Cu(II) pyridyl-isophthalate metal-organic framework materials

    Science.gov (United States)

    Gould, Jamie A.; Athwal, Harprit Singh; Blake, Alexander J.; Lewis, William; Hubberstey, Peter; Champness, Neil R.; Schröder, Martin

    2017-01-01

    A family of Cu(II)-based metal-organic frameworks (MOFs) has been synthesized using three pyridyl-isophthalate ligands, H2L1 (4'-(pyridin-4-yl)biphenyl-3,5-dicarboxylic acid), H2L2 (4''-(pyridin-4-yl)-1,1':4',1''-terphenyl-3,5-dicarboxylic acid) and H2L3 (5-[4-(pyridin-4-yl)naphthalen-1-yl]benzene-1,3-dicarboxylic acid). Although in each case the pyridyl-isophthalate ligands adopt the same pseudo-octahedral [Cu2(O2CR)4N2] paddlewheel coordination modes, the resulting frameworks are structurally diverse, particularly in the case of the complex of Cu(II) with H2L3, which leads to three distinct supramolecular isomers, each derived from Kagomé and square nets. In contrast to [Cu(L2)] and the isomers of [Cu(L3)], [Cu(L1)] exhibits permanent porosity. Thus, the gas adsorption properties of [Cu(L1)] were investigated with N2, CO2 and H2, and the material exhibits an isosteric heat of adsorption competitive with leading MOF sorbents for CO2. [Cu(L1)] displays high H2 adsorption, with the density in the pores approaching that of liquid H2. This article is part of the themed issue 'Coordination polymers and metal-organic frameworks: materials by design'.

  3. 40 CFR 440.30 - Applicability; description of the uranium, radium and vanadium ores subcategory.

    Science.gov (United States)

    2010-07-01

    ... for the extraction of uranium, radium and vanadium. Only vanadium byproduct production from uranium... uranium, radium and vanadium ores subcategory. 440.30 Section 440.30 Protection of Environment... SOURCE CATEGORY Uranium, Radium and Vanadium Ores Subcategory § 440.30 Applicability; description of the...

  4. Ecological Risk Assessment of a Metal-Contaminated Area in the Tropics. Tier II: Detailed Assessment

    Science.gov (United States)

    Niemeyer, Júlia Carina; Moreira-Santos, Matilde; Ribeiro, Rui; Rutgers, Michiel; Nogueira, Marco Antonio; da Silva, Eduardo Mendes; Sousa, José Paulo

    2015-01-01

    This study presents data on the detailed evaluation (tier 2) of a site-specific ecological risk assessment (ssERA) in a former smelter area contaminated with metals (Santo Amaro, Bahia, Brazil). Combining information from three lines of evidence (LoE), chemical (ChemLoE), ecotoxicological (EcotoxLoE) and ecological (EcoLoE), in the Triad approach, integrated risk values were calculated to rank sites and confirm the potential risk disclosed with tier 1. Risk values were calculated for the habitat and for the retention functions in each sampling point. Habitat function included the ChemLoE calculated from total metal concentrations. The EcotoxLoE was based on reproduction tests with terrestrial invertebrates (Folsomia candida, Enchytraeus crypticus, Eisenia andrei), shoot length and plant biomass (Avena sativa, Brassica rapa). For the EcoLoE, ecological parameters (microbial parameters, soil invertebrate community, litter breakdown) were used to derive risk values. Retention function included the ChemLoE, calculated from extractable metal concentrations, and the EcotoxLoE based on eluate tests with aquatic organisms (Daphnia magna reproduction and Pseudokirchneriella subcapitata growth). Results related to the habitat function indicated that the metal residues are sufficient to cause risk to biota, while the low metal levels in extracts and the general lack of toxicity in aquatic tests indicated a high soil retention capacity in most sampling points. Integrated risk of tier 2 showed the same trend of tier 1, suggesting the need to proceed with remediation actions. The high risk levels were related to direct toxicity to organisms and indirect effects, such as failure in the establishment of vegetation and the consequent loss of habitat quality for microorganisms and soil fauna. This study shed some light on the selection of tools for the tier 2 of an ssERA in tropical metal-contaminated sites, focusing on ecological receptors at risk and using available chemical

  5. Ecological Risk Assessment of a Metal-Contaminated Area in the Tropics. Tier II: Detailed Assessment.

    Directory of Open Access Journals (Sweden)

    Júlia Carina Niemeyer

    Full Text Available This study presents data on the detailed evaluation (tier 2 of a site-specific ecological risk assessment (ssERA in a former smelter area contaminated with metals (Santo Amaro, Bahia, Brazil. Combining information from three lines of evidence (LoE, chemical (ChemLoE, ecotoxicological (EcotoxLoE and ecological (EcoLoE, in the Triad approach, integrated risk values were calculated to rank sites and confirm the potential risk disclosed with tier 1. Risk values were calculated for the habitat and for the retention functions in each sampling point. Habitat function included the ChemLoE calculated from total metal concentrations. The EcotoxLoE was based on reproduction tests with terrestrial invertebrates (Folsomia candida, Enchytraeus crypticus, Eisenia andrei, shoot length and plant biomass (Avena sativa, Brassica rapa. For the EcoLoE, ecological parameters (microbial parameters, soil invertebrate community, litter breakdown were used to derive risk values. Retention function included the ChemLoE, calculated from extractable metal concentrations, and the EcotoxLoE based on eluate tests with aquatic organisms (Daphnia magna reproduction and Pseudokirchneriella subcapitata growth. Results related to the habitat function indicated that the metal residues are sufficient to cause risk to biota, while the low metal levels in extracts and the general lack of toxicity in aquatic tests indicated a high soil retention capacity in most sampling points. Integrated risk of tier 2 showed the same trend of tier 1, suggesting the need to proceed with remediation actions. The high risk levels were related to direct toxicity to organisms and indirect effects, such as failure in the establishment of vegetation and the consequent loss of habitat quality for microorganisms and soil fauna. This study shed some light on the selection of tools for the tier 2 of an ssERA in tropical metal-contaminated sites, focusing on ecological receptors at risk and using available

  6. Conceptual chemistry approach towards the support effect in supported vanadium oxides: valence bond calculations on the ionicity of vanadium catalysts

    NARCIS (Netherlands)

    Fievez, T.; De Proft, F.; Geerlings, P.; Weckhuysen, B.M.; Havenith, R.W.A.

    2011-01-01

    The concept of bond ionicity, obtained via a valence bond analysis, is invoked in the interpretation of the catalytic activity of supported vanadium oxides, in analogy with previous work conducted within the framework of conceptual DFT. For a set of model clusters representing the vanadium oxide

  7. Conceptual chemistry approach towards the support effect in supported vanadium oxides : Valence bond calculations on the ionicity of vanadium catalysts

    NARCIS (Netherlands)

    Fievez, Tim; De Proft, Frank; Geerlings, Paul; Weckhuysen, Bert M.; Havenith, Remco W. A.

    2011-01-01

    The concept of bond ionicity, obtained via a valence bond analysis, is invoked in the interpretation of the catalytic activity of supported vanadium oxides, in analogy with previous work conducted within the framework of conceptual DFT. For a set of model clusters representing the vanadium oxide

  8. Mesoporous tungsten oxynitride as electrocatalyst for promoting redox reactions of vanadium redox couple and performance of vanadium redox flow battery

    Science.gov (United States)

    Lee, Wonmi; Jo, Changshin; Youk, Sol; Shin, Hun Yong; Lee, Jinwoo; Chung, Yongjin; Kwon, Yongchai

    2018-01-01

    For enhancing the performance of vanadium redox flow battery (VRFB), a sluggish reaction rate issue of V2+/V3+ redox couple evaluated as the rate determining reaction should be addressed. For doing that, mesoporous tungsten oxide (m-WO3) and oxyniride (m-WON) structures are proposed as the novel catalysts, while m-WON is gained by NH3 heat treatment of m-WO3. Their specific surface area, crystal structure, surface morphology and component analysis are measured using BET, XRD, TEM and XPS, while their catalytic activity for V2+/V3+ redox reaction is electrochemically examined. As a result, the m-WON shows higher peak current, smaller peak potential difference, higher electron transfer rate constant and lower charge transfer resistance than other catalysts, like the m-WO3, WO3 nanoparticle and mesoporous carbon, proving that it is superior catalyst. Regarding the charge-discharge curve tests, the VRFB single cell employing the m-WON demonstrates high voltage and energy efficiencies, high specific capacity and low capacity loss rate. The excellent results of m-WON are due to the reasons like (i) reduced energy band gap, (ii) reaction familiar surface functional groups and (ii) greater electronegativity.

  9. Local impacts of coal mines and power plants across Canada. II. Metals, organics and toxicity in sediments

    Energy Technology Data Exchange (ETDEWEB)

    Cheam, V.; Reynoldson, T.; Garbai, G.; Rajkumar, J.; Milani, D. [Environment of Canada, Burlington, ON (Canada). National Water Research Institute

    2000-07-01

    A Canada-wide survey was undertaken to study local impacts of coal mines and coal-fired electrical generating stations. The first part dealt with thallium in waters and sediments. This, Part II, deals with metals and organics in sediments as well as sediment toxicity to four different organisms. Several elevated metal and PAH concentrations as well as high toxicity (based on biological sediment guidelines) were observed compared to uncontaminated sites. Based on Ontario's sediment guidelines, most of the studied sediments fell in the 'marginally to significantly polluted' category of sediment quality, although two belonged to the 'grossly polluted' class due to the extremely high concentrations of some metals. The observed diversity of PAHs and near-unity carbon preference indices indicate non-biological origins of the studied sediments. In this initial study, four different organisms, Chironomus riparius, Hyalella azteca, Hexagenia spp. (Hexagenia limbata) and Tubifex tubifex were used to determine sediment toxicity, which showed 50% of the tested sites were highly stressed.

  10. DFT/TD-DFT study on spectroscopic properties of zinc(II, nickel(II, and palladium(II metal complexes with a thiourea derivative

    Directory of Open Access Journals (Sweden)

    Wang Xin

    2016-01-01

    Full Text Available The geometries, electronic structures, and spectral properties of three metal complexes Zn(C10H12N3OS2 (1, Ni(C10H12N3OS2 (2, and Pd(C10H12N3OS2 (3 with N-(2-pyridinylmorpholine-4-carbothioamide as a ligand are investigated by means of DFT (density functional theory and TD-DFT (time-dependent density functional theory methods. Complex 1 is a distorted tetrahedral geometry, while complexes 2 and 3 present a distorted square-planar coordination environment. In the simulated range, the spectrum of complex 1 has five obvious absorption peaks and one of them has the strongest intensity. The latter two complexes have one more absorption peak and shoulder peak with the similar intensity. Moreover, the strongest peaks of complexes 2.

  11. Hydrothermal Synthesis of Nanostructured Vanadium Oxides

    Directory of Open Access Journals (Sweden)

    Jacques Livage

    2010-08-01

    Full Text Available A wide range of vanadium oxides have been obtained via the hydrothermal treatment of aqueous V(V solutions. They exhibit a large variety of nanostructures ranging from molecular clusters to 1D and 2D layered compounds. Nanotubes are obtained via a self-rolling process while amazing morphologies such as nano-spheres, nano-flowers and even nano-urchins are formed via the self-assembling of nano-particles. This paper provides some correlation between the molecular structure of precursors in the solution and the nanostructure of the solid phases obtained by hydrothermal treatment.

  12. Two different zinc(II)-aqua complexes held up by a metal-oxide ...

    Indian Academy of Sciences (India)

    WINTEC

    1. Introduction. Polyoxometalate (POM), a metal-oxide-based clus- ter, has attracted considerable research interest in recent years because of its applications in diverse areas, such as, biomedical chemistry, catalysis, magne- tism, sorption properties, etc. 1. One of the recent advances in POM chemistry is to synthesize inor-.

  13. Mixed ligand two dimensional Cd(ii)/Ni(ii) metal organic frameworks containing dicarboxylate and tripodal N-donor ligands: Cd(ii) MOF is an efficient luminescent sensor for detection of picric acid in aqueous media.

    Science.gov (United States)

    Rachuri, Yadagiri; Parmar, Bhavesh; Bisht, Kamal Kumar; Suresh, Eringathodi

    2016-05-04

    Two dimensional metal organic frameworks (MOFs) [Cd(5-BrIP)(TIB)]n () and [Ni2(5-BrIP)2(TIB)2]n (), involving the aromatic polycarboxylate ligand 5-bromo isophthalic acid (H2BrIP), flexible tripodal ligand 1,3,5-tris(imidazol-1-ylmethyl)benzene (TIB) and Cd(ii)/Ni(ii) metal nodes have been synthesized by different methods. These compounds were characterized by various analytical methods, and variable temperature X-ray diffraction data showed thermal stability of both MOFs up to 350 °C. Phase purity as well as water stability of the MOFs were established by powder X-ray diffraction, and the structural diversity of the compounds were investigated by single-crystal X-ray diffraction. Both the MOFs are mixed ligand 2D nets, and the topology of the network can be described as a binodal 3,5-c connected net with 3,5L2 topology having the point symbol {4(2)·6(7)·8}{4(2)·6}. Sensing of picric acid [2,4,6-trinitrophenol, TNP] by luminescence quenching among a large range of nitroanalytes in aqueous phase by the Cd(ii) luminescent MOF (LMOF) were been investigated. Structural studies on 1 : 1 co-crystals () of TIB and TNP were carried out. The selective and sensitive fluorescence quenching response of towards electron-deficient TNP over other nitro analytes in aqueous phase was demonstrated by fluorescence quenching titration. Concomitant occurrence of electron transfer/energy transfer processes and electrostatic interaction favours the selective sensing of TNP. A Cd(ii) LMOF ()-coated paper strip that we developed demonstrated fast and selective response to TNP, by the complete quenching of the blue fluorescence upon excitation of the paper strip at 365 nm radiation in its presence.

  14. A high-performance catalyst support for methanol oxidation with graphene and vanadium carbonitride.

    Science.gov (United States)

    Huang, Taizhong; Mao, Shun; Zhou, Guihua; Zhang, Zhaoliang; Wen, Zhenhai; Huang, Xingkang; Ci, Suqin; Chen, Junhong

    2015-01-28

    In this study, a graphene-vanadium carbonitride (G-V(C, N)) hybrid is reported as a novel support for the Pt catalyst in methanol oxidation. The catalytic activity of the Pt/G-V(C, N) hybrid for methanol oxidation is greatly enhanced compared with that of a commercial Pt/C catalyst with carbon black as the catalyst support. The outstanding catalytic activity of the Pt/G-V(C, N) catalyst suggests the potential of using graphene-metal carbonitride as the catalyst support in fuel cells.

  15. Tunable optical antennas enabled by the phase transition in vanadium dioxide.

    Science.gov (United States)

    Earl, Stuart K; James, Timothy D; Davis, Timothy J; McCallum, Jeffrey C; Marvel, Robert E; Haglund, Richard F; Roberts, Ann

    2013-11-04

    Optical antennas, subwavelength metallic structures resonating at visible frequencies, are a relatively new branch of antenna technology being applied in science, technology and medicine. Dynamically tuning the resonances of these antennas would increase their range of application and offer potential increases in plasmonic device efficiencies. Silver nanoantenna arrays were fabricated on a thin film of the phase change material vanadium dioxide (VO(2)) and the resonant wavelength of these arrays was modulated by increasing the temperature of the substrate above the critical temperature (approximately 68 °C). Depending on the array, wavelength modulation of up to 110 nm was observed.

  16. Thermolysis of Half-Sandwich Vanadium(V) Imido Complexes to Generate Vanadium(III) Imido Species via a Vanadium(IV) Intermediate

    NARCIS (Netherlands)

    Batinas, Aurora A.; Dam, Jeroen; Meetsma, Auke; Hessen, Bart; Bouwkamp, Marco W.

    2010-01-01

    Thermolysis of half-sandwich vanadium imido complexes Cp(RN)V(i-Pr(2)N)Me (R = p-Tol, 1a; R = t-Bu, 1b) results in a mixture of products, including vanadium(IV) dimers [CpVMe](2)(mu-RN)(2), i-Pr(2)NH, i-PrNCMe(2), CH(4), and one or more paramagnetic species. In the presence of dmpe (dmpe =

  17. Crystal growth, characterization and theoretical studies of alkaline earth metal-doped tetrakis(thiourea)nickel(II) chloride

    Science.gov (United States)

    Agilandeshwari, R.; Muthu, K.; Meenatchi, V.; Meena, K.; Rajasekar, M.; Aditya Prasad, A.; Meenakshisundaram, SP.

    2015-02-01

    The influence of Sr(II)-doping on the properties of tetrakis(thiourea)nickel(II) chloride (TTNC) has been described. The reduction in the intensity observed in powder X-ray diffraction of doped specimen and slight shifts in vibrational frequencies of doped specimens confirm the lattice stress as a result of doping. Surface morphological changes due to doping of the Sr(II) are observed by scanning electron microscopy. The incorporation of metal into the host crystal lattice was confirmed by energy dispersive X-ray spectroscopy. Lattice parameters are determined by single crystal XRD analysis. The thermogravimetric and differential thermal analysis studies reveal the purity of the materials and no decomposition is observed up to the melting point. The nonlinear optical properties of the doped and undoped specimens were studied. Theoretical calculations were performed using the Density functional theory (DFT) method with B3LYP/LANL2DZ as the basis set. The molecular geometry and vibrational frequencies of TTNC in the ground state were calculated and the observed structural parameters of TTNC are compared with parameters obtained from single crystal X-ray studies. The atomic charge distributions are obtained by Mulliken charge population analysis. The first-order molecular hyperpolarizability, polarizability and dipole moment were derived.

  18. Orange peel essential oil as component of a metal sensor for lead (II ...

    African Journals Online (AJOL)

    Orange (Citrus sinensis) peel, a waste material was used as source of essential oil that served as component of a sensor that detects the presence of lead (II) ions in aqueous solutions. The prepared sensor was investigated in evaluating its potential as a substitute for commercially available working electrodes.

  19. Heavy Metals (Mg, Mn, Ni and Sn contamination in Soil Samples of Ahvaz II Industrial Estate of Iran in 2013

    Directory of Open Access Journals (Sweden)

    Soheil l Sobhanardakani

    2016-04-01

    Full Text Available Background & Aims of the Study: Due to the rapid industrial development in Khuzestan province of Iran during recent years, this study was performed to analyze the variation of metals concentrations (Mg, Mn, Ni, and Sn in soil samples of Ahvaz II Industrial estate during the spring season of 2013. Materials & Methods: In this experimental study, 27 topsoil samples were collected from nine stations. The intensity of the soil contamination was evaluated, using a contamination factor (Cf and geo-accumulation index (I-geo. Results:  The mean soil concentrations (in mg kg-1 (dry weight were in ranged within 870-1144 (Mg, 188-300 (Mn, 93-199 (Ni and 9-15 (Sn. The data indicated that the I-geo value for all metals falls in class ‘1’. Also the Cf value for Mg and Mn falls in class ‘0’, the Cf value for Sn falls in class ‘1’ and the Cf value for Ni falls in the classes of ‘1’ and ‘2’. The result of the Pearson correlation showed that there were significant positive associations between all metals. Conclusions: According to the results which were achieved by a cluster analysis, there were significant positive associations among all metals based on Pearson correlation coefficient, especially between Ni and Sn; also both of them with Mn. Because the Ni originates from oil sources it can be resulted that Mn and Sn originate from oil sources, too. Therefore, industrial activities and exploitation of oil reservoirs are the main cause of pollution in that area. Also, it can be concluded that, with increasing the distance from the source of pollution, the accumulation of contaminants in the soil samples decreased.

  20. Pareto-Lognormal Modeling of Known and Unknown Metal Resources. II. Method Refinement and Further Applications

    Energy Technology Data Exchange (ETDEWEB)

    Agterberg, Frits, E-mail: agterber@nrcan.gc.ca [Geological Survey of Canada (Canada)

    2017-07-01

    Pareto-lognormal modeling of worldwide metal deposit size–frequency distributions was proposed in an earlier paper (Agterberg in Nat Resour 26:3–20, 2017). In the current paper, the approach is applied to four metals (Cu, Zn, Au and Ag) and a number of model improvements are described and illustrated in detail for copper and gold. The new approach has become possible because of the very large inventory of worldwide metal deposit data recently published by Patiño Douce (Nat Resour 25:97–124, 2016c). Worldwide metal deposits for Cu, Zn and Ag follow basic lognormal size–frequency distributions that form straight lines on lognormal Q–Q plots. Au deposits show a departure from the straight-line model in the vicinity of their median size. Both largest and smallest deposits for the four metals taken as examples exhibit hyperbolic size–frequency relations and their Pareto coefficients are determined by fitting straight lines on log rank–log size plots. As originally pointed out by Patiño Douce (Nat Resour Res 25:365–387, 2016d), the upper Pareto tail cannot be distinguished clearly from the tail of what would be a secondary lognormal distribution. The method previously used in Agterberg (2017) for fitting the bridge function separating the largest deposit size–frequency Pareto tail from the basic lognormal is significantly improved in this paper. A new method is presented for estimating the approximate deposit size value at which the upper tail Pareto comes into effect. Although a theoretical explanation of the proposed Pareto-lognormal distribution model is not a required condition for its applicability, it is shown that existing double Pareto-lognormal models based on Brownian motion generalizations of the multiplicative central limit theorem are not applicable to worldwide metal deposits. Neither are various upper tail frequency amplification models in their present form. Although a physicochemical explanation remains possible, it is argued that

  1. Stability Constants of Mixed Ligand Complexes of Transition Metal(II Ions with Salicylidene-4-methoxyaniline as Primary Ligand and 5-Bromosalicylidene-4-nitroaniline as Secondary Ligand

    Directory of Open Access Journals (Sweden)

    N. G. Nadkarni

    2011-01-01

    Full Text Available Binary and ternary complexes of the type M-Y and M-X-Y [M = Mn(II, Ni(II, Cu(II and Zn(II; X = salicylidene-4-methoxyaniline and Y=5-bromosalicylidene-4-nitroaniline] have been examined pH-metrically at 27±0.5 °C and at constant ionic strength, μ= 0.1 M (KCl in 75 : 25(v/v 1,4-dioxne-water medium. The stability constants for binary (M-Y and ternary (M-X-Y systems were calculated. The relative stability (Δ log KT values of the ternary complexes with corresponding binary complexes for all the metal(II ions in the present study found to be negative indicating that ternary 1:1:1 (M-X-Y complexes are less stable than binary 1:1 (M-Y complexes. In the ternary system studied, the order of stability constants of mixed ligand complexes with respect to the metal ions was found to be Cu(II > NI(II > Mn(II > Zn(II; which is same as in the corresponding binary (M-Y systems.

  2. Synthesis and Characterization of a New Bidentate Ligand 5-Substituted-(2-methyl-5-nitro-1-imidazomethyl-1,3,4-oxadiazole-2-thione and its Metal Complexes of Ag(I, Cu(II and Zn(II

    Directory of Open Access Journals (Sweden)

    Shabbir A. A. Kazi

    2011-01-01

    Full Text Available A new ligand (2-methyl-5-nitro-1-imidazomethyl-1,3,4-oxadiazole-2-thione (L and its Ag(I,Cu(II and Zn(II complexes were synthesized. The authenticity of the ligand and its transition metal complexes were established by elemental analyses, conductance and magnetic susceptibility measurements, as well as spectroscopic (IR, 1H NMR, electronic, mass and ESR and thermal studies. The IR spectral studies revealed the existence thiol-thione tautamerism in the ligand molecule. The magnetic and electronic spectral studies suggest an octahedral geometry for Cu(II and Zn(II complexes. The ligand acts as a bidentate coordinating through the N-3 nitrogen and the exocyclic sulfur atoms of oxadiazole rings. Antimicrobial screening of the ligand and its metal complexes were determined against the bacteria Escherichia coli and Salmonella paratyphiA.

  3. Solid solution formation between vanadium(V) and tungsten(V) oxide phosphate

    Energy Technology Data Exchange (ETDEWEB)

    Roy, Subrata Chandra; Glaum, Robert [Institut fuer Anorganische Chemie, Rheinische Friedrich-Wilhelms-Universitaet Bonn (Germany); Abdullin, Dinar; Schiemann, Olav [Institut fuer Physikalische und Theoretische Chemie, Rheinische Friedrich-Wilhelms-Universitaet Bonn (Germany); Bac, Nguyen Quang; Lii, Kwang-Hwa [Department of Chemistry, National Central University, Jhongli, Taiwan (China)

    2014-08-15

    The solid solutions (V{sub 1-x}W{sub x})OPO{sub 4} with β-VOPO{sub 4} structure type (0.0 ≤ x ≤ 0.01) and α{sub II}-VOPO{sub 4} structure type (0.04 ≤ x ≤ 0.26) were obtained from mixtures of V{sup V}OPO{sub 4} and W{sup V}OPO{sub 4} by conventional solid state reactions and by solution combustion synthesis. Single crystals of up to 3 mm edge length were obtained by chemical vapor transport (CVT) (800 → 700 C, Cl{sub 2} as a transporting agent). Single crystal structure refinements of crystals at x = 0.10 [a = 6.0503(2) Aa, c = 4.3618(4) Aa, R{sub 1} = 0.021, wR{sub 2} = 0.058, 21 parameters, 344 independent reflections] and x = 0.26 [a = 6.0979(2) Aa, c = 4.2995(1) Aa, R{sub 1} = 0.030, wR{sub 2} = 0.081, 21 parameters, 346 independent reflections] confirm the α{sub II}-VOPO{sub 4} structure type (P4/n, Z = 2) with mixed occupancy V/W for the metal site. Due to the specific redox behavior of W{sup 5+} and V{sup 5+}, solid solutions (V{sub 1-x}W{sub x})OPO{sub 4} should be formulated as (V{sup IV}{sub x}V{sup V}{sub 1-2x}W{sup VI}{sub x})OPO{sub 4}. The valence states of vanadium and tungsten are confirmed by XPS measurements. V{sup 4+} with d{sup 1} configuration was identified by EPR spectroscopy and magnetic measurements. Electronic spectra of the solid solutions show the IVCT(V{sup 4+} → V{sup 5+}) and the LMCT(O{sup 2-} → V{sup 5+}). (V{sub 0.74}W{sub 0.26})OPO{sub 4} powders exhibit semi-conducting behavior (E{sub g} = 0.7 eV). (Copyright copyright 2014 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  4. Analysis of metal-matrix composite structures. I - Micromechanics constitutive theory. II - Laminate analyses

    Science.gov (United States)

    Arenburg, R. T.; Reddy, J. N.

    1991-01-01

    The micromechanical constitutive theory is used to examine the nonlinear behavior of continuous-fiber-reinforced metal-matrix composite structures. Effective lamina constitutive relations based on the Abouli micromechanics theory are presented. The inelastic matrix behavior is modeled by the unified viscoplasticity theory of Bodner and Partom. The laminate constitutive relations are incorporated into a first-order deformation plate theory. The resulting boundary value problem is solved by utilizing the finite element method. Attention is also given to computational aspects of the numerical solution, including the temporal integration of the inelastic strains and the spatial integration of bending moments. Numerical results the nonlinear response of metal matrix composites subjected to extensional and bending loads are presented.

  5. On Phonons in Simple Metals II. Calculated Dispersion Curves In Aluminium

    Energy Technology Data Exchange (ETDEWEB)

    Johnson, R. [AB Atomenergi, Nykoeping (Sweden); Westin, A. [Dept. of Theore tical Physics, Univ. of Uppsala, Uppsala (Sweden)

    1969-07-15

    The real part of the dynamical matrix, derived earlier in a weak local potential ion-electron interaction model of the metal, is investigated in the case of aluminium. It is shown that the free electron, or Lindhard, dielectric function leads to a picture of the metal which is inconsistent with the dHvA observations of the Fermi surface. By adjusting one parameter, however, the experimental phonon frequencies are reproduced satisfactorily. Even some simple structure in the derivative d{omega}/dq can be reproduced in this way. Although corrections to the Lindhard dielectric matrix give no essential contributions to the dynamical matrix, the first order corrections, which are the most important, can explain the observed Fermi surface. Much of the observed structure in the phonon dispersion curves seems also to be due to these non-diagonal terms in the dielectric matrix.

  6. Metal vapors in gas tungsten arcs: part ii. theoretical calculations of transport properties

    Science.gov (United States)

    Dunn, G. J.; Eagar, T. W.

    1986-10-01

    Theoretical calculations of gas tungsten arc transport properties have revealed that small amounts of low ionization potential elements such as aluminum or calcium do not have as great an effect on the electrical and thermal conductivities as has been previously reported, if the presence of other metal vapors such as iron or manganese is also considered. It is therefore concluded that the effects of minor elements on arc properties may be less important than has previously been believed in explaining the variable penetration often associated with minor element additions to the base metal, and that weld pool convection effects such as surface tension modifications are probably more important. However, the effects of vapors emitted by the tungsten electrode may have a great effect on arc properties, as the shielding gas is otherwise free of contaminants in the upper regions of the arc.

  7. SYNTHESIS OF METAL-ORGANIC (COMPLEXES COMPOUNDS COPPER(II-IMIDAZOLE FOR ANTIVIRAL HIV CANDIDATE

    Directory of Open Access Journals (Sweden)

    Teguh Hari Sucipto

    2016-01-01

    Full Text Available The human immunodeficiency virus (HIV is viruses known as rotaviruses. Potential target for therapeutic is reverse transcriptase (RT, possesses an RNA dependent DNA polymerase, DNA-dependent DNA polymerase and ribonuclease H fuctions. Imidazoles have high anti-HIV inhibitory activity, some derivates of imidazole reported drugs. 8-chloro-2,3-dihydroimidazole[1,2-b] [1,4,2]benzodithiazine-5,5-dioxides and 9-chloro-2,3,4-trihydropyri-mido[1,2-b][1,4,2]benzodithi-azine-6,6-dioxides. This compounds succesfully identified anti-HIV activity. Copper is a bio-essential element and copper complexes have been extensively utilized in metal mediated DNA cleavage for the generation of activated oxygen species. It has been reported that teraaza macrocyclic copper coordination compounds have anti-HIV activities. Studies have shown that these macrocyclic complexes can react with DNA in different binding fashions and exhibit effective nuclease activities. Complex compounds are compounds in which there is an atom that acts as the central atom and trotter group of molecules that can be either neutral or charged ions. Application a metal-organic (complex compounds, especially copper metal and derivates of imidazole. So, in this study can explore new anti-HIV candidate.

  8. On the regiospecificity of vanadium bromoperoxidase.

    Science.gov (United States)

    Martinez, J S; Carroll, G L; Tschirret-Guth, R A; Altenhoff, G; Little, R D; Butler, A

    2001-04-11

    Vanadium haloperoxidase enzymes catalyze the oxidation of halide ions by hydrogen peroxide, producing an oxidized intermediate, which can halogenate an organic substrate or react with a second equivalent of hydrogen peroxide to produce dioxygen. Haloperoxidases are thought to be involved in the biogenesis of halogenated natural products isolated from marine organisms, including indoles and terpenes, of which many are selectively oxidized or halogenated. Little has been shown concerning the ability of the marine haloperoxidases to catalyze regioselective reactions. Here we report the regiospecific bromoperoxidative oxidation of 1,3-di-tert-butylindole by V-BrPO from the marine algae Ascophyllum nodosum and Corallina officinalis. Both enzymes catalyze the regiospecific oxidation of 1,3-di-tert-butylindole in a reaction requiring both H(2)O(2) and Br(-) as substrates, but which produce the unbrominated 1,3-di-tert-butyl-2-indolinone product exclusively, in near quantitative yield (i.e. one H(2)O(2) consumed per product). By contrast, reactions with the controlled addition of aqueous bromine solution (HOBr = Br(2) = Br(3)(-)) produce three monobromo and one dibromo-2-indolinone products, all of which differ from the V-BrPO-catalyzed product. Further, reactivities of 1,3-di-tert-butyl-2-indolinone with both aqueous bromine and V-BrPO differ significantly and shed light onto the possible nature of the oxidizing intermediate. This is the first example of a regiospecific bromination by a vanadium haloperoxidase and further extends their usefulness as catalysts.

  9. Polymerization of Ethylene Catalyzed by Vanadium(III Complexes

    Directory of Open Access Journals (Sweden)

    Hamdi Ali Elagab

    2017-07-01

    Full Text Available Thirty five  complexes of 1,2- bis(benzimidazole, benzothiazole and benzoxazolebenzene,  1,2-bis(benzimidazole, benzothiazole and benzoxazole-4-methyl-benzene, 1,2-bis  (benzimidazole, benzothiazole and benzoxazole4-bromobenzene, 1, 2-bis(benzimidazole, benzothiazole and benzoxazole 4- chlorobenzene,  and 2, 6-bis(benzimidazole, benzothiazole and benzoxazole pyridine compounds with V (III metal centers were synthesized, characterized, activated with methylalumoxane (MAO and then tested for catalytic ethylene polymerization. The catalysts generally show moderate to good activities compared to the benchmark catalyst Cp2ZrCl2. The activities of the various catalysts were found to be function of the hetero atoms in the ligand frameworks and also strongly influenced by the bridging unit of the ligand. The highest activity was obtained with 36 / MAO (442 kg PE / mol cat. h. The produced polyethylenes showed high molecular weights (up to 2.7 × 106 g/mol and broad molecular weight distributions (PD = 1.4 - 16.6. Thermal analysis of polyethylenes produced with vanadium complexes revealed that the catalyst systems were capable to produce high density polyethylenes with melting temperatures > 135 °C and crystallization temperatures range from 117-120 °C with high degree of crystallinity. DOI: http://dx.doi.org/10.17807/orbital.v9i3.985 

  10. Determination of Ni(II) in metal alloys by spectrophotometry UV-Vis using dopasemiquinone

    OpenAIRE

    Wagner José Barreto; Sonia Regina Giancoli Barreto; Ieda Spacino Scarminio; Dílson Norio Ishikawa; Miriam de Fátima Soares; Marcus Vinícius Brás de Proença

    2010-01-01

    A spectrophotometric method was proposed for Ni(II) determination in alloys using a dopa-semiquinone (L-1) to form [Ni(II)(L1-)3]1-, ε = 9.3 x 10³ L mol-1 cm-1. The optimal conditions for the determination were: wavelength 590 nm, temperature 25 °C, reaction time 45 min and pH 7.5. The Beer's law was obeyed for nickel from 3.33 x 10-5 to 1.78 x 10-4 mol L-1. The method was applied to complex samples, such as inox, nickel-titanium and cobalt-chromium alloys. A study of the potential inter...

  11. Determination of Ni(II in metal alloys by spectrophotometry UV-Vis using dopasemiquinone

    Directory of Open Access Journals (Sweden)

    Wagner José Barreto

    2010-01-01

    Full Text Available A spectrophotometric method was proposed for Ni(II determination in alloys using a dopa-semiquinone (L-1 to form [Ni(II(L1-3]1-, ε = 9.3 x 10³ L mol-1 cm-1. The optimal conditions for the determination were: wavelength 590 nm, temperature 25 °C, reaction time 45 min and pH 7.5. The Beer's law was obeyed for nickel from 3.33 x 10-5 to 1.78 x 10-4 mol L-1. The method was applied to complex samples, such as inox, nickel-titanium and cobalt-chromium alloys. A study of the potential interferents revealed that Mn was the major interferent. The limit of detection and quantification were 2.88 x 10-5 mol L-1 and 3.06 x 10-5 mol L-1, respectively.

  12. Synthesis and Luminescence Properties of New Metal-Organic Frameworks Based on Zinc(II) Ions and 2,5-Thiophendicarboxylate Ligands

    OpenAIRE

    Anna Lysova; Denis Samsonenko; Danil Dybtsev; Vladimir Fedin

    2017-01-01

    Six new metal-organic frameworks based on 2,5-thiophendicarboxylate (tdc2–) and zinc(II) ions were prepared in different reaction conditions, and their crystal structures were determined by XRD analysis. The compound [Zn(tdc)(dabco)(H2O)]∙DMF (1) is based on mononuclear Zn(II) ions connected by tdc2– and dabco linkers into square-grid layered nets. The compound [Zn3(tdc)3(dabco)2] (2) is a rare example of monocoordinated dabco ligands in the metal-organic framework chemistry. Its crystal stru...

  13. Determination of trace amounts of vanadium by UV-vis spectrophotometric after separation and preconcentration with modified natural clinoptilolite as a new sorbent.

    Science.gov (United States)

    Rostampour, Leila; Taher, Mohammad Ali

    2008-06-15

    Natural clinoptilolite was used as a sorbent material for solid phase extraction and preconcentration of vanadium. The clinoptilolite was first saturated with a cation such as nickel(II) and then modified with benzyldimethyltetradecyleammonium chloride (BDTA) for increasing sorption of 4-(2-pyridylazo)resorcinol (PAR). Vanadium-PAR complex was quantitatively retained on the sorbent by the column method at the pH range 6.2-7.0 at a flow rate of 1 mL min(-1). It was removed from the column with 5.0 mL of dimethylformamide solution at a flow rate of 0.8 mL min(-1) and determined by UV-vis spectrophotometry at lambda(max) = 550 nm. 0.031 microg of vanadium can be concentrated from 450 mL of aqueous sample (where detection limit as 0.07 ng mL(-1) with preconcentration factor of 90). Relative standard deviation for eight replicate determination of 5.0 microg of vanadium in final solution is 2.1%. The interference of number of anions and cations has been studied in detail to optimize the conditions and method was successfully applied for determination of all vanadium as V(IV) form in standard samples.

  14. Tetra- and octa-[4-(2-hydroxyethyl)phenoxy bearing novel metal-free and zinc(II) phthalocyanines: Synthesis, characterization and investigation of photophysicochemical properties

    Energy Technology Data Exchange (ETDEWEB)

    Köksoy, Baybars [Marmara University, Department of Chemistry, 34722 Kadıköy, Istanbul (Turkey); Durmuş, Mahmut [Gebze Technical University, Department of Chemistry, 41400 Gebze, Kocaeli (Turkey); Bulut, Mustafa, E-mail: mbulut@marmara.edu.tr [Marmara University, Department of Chemistry, 34722 Kadıköy, Istanbul (Turkey)

    2015-05-15

    In this study, four novel phthalonitriles (1–4) and their corresponding metal-free (5–8) and zinc(II) phthalocyanine derivatives (9–12) bearing 4-(hydroxyethyl)phenoxy groups were synthesized. These novel compounds were characterized by IR, elemental analyses, {sup 1}H-NMR, UV–vis, and MALDI-TOF spectral data. Furthermore, photophysical (fluorescence quantum yields and lifetimes) and photochemical properties (singlet oxygen generation and photodegradation quantum yields) of these phthalocyanines were investigated in dimethylsulfoxide. The studied zinc(II) phthalocyanines generated highly singlet oxygen which is very important for the photodynamic therapy (PDT) of cancer. The fluorescence quenching behaviour of the newly synthesized phthalocyanine compounds were also investigated using 1,4-benzoquinone. - Highlights: • Octa and tetra 4-(hydroxyethyl)phenoxy substituted metal-free and zinc(II) phthalocyanines. • Study of photophysicochemical properties of eight new phthalocyanines. • Highly singlet oxygen generation for novel zinc(II) phthalocyanine photosensitizers.

  15. Vanadium and nickel in petroleums of bituminous Tatar rocks

    Energy Technology Data Exchange (ETDEWEB)

    Aigistova, S.Kh.; Safiullina, G.Kh.; Sadykov, A.N.; Kharlamov, V.A.

    1984-01-01

    The vanadium and nickel contents of petroleum obtained from bituminous rock of Ashal'chinsk, Akhmat, Gorskii, Katerchinsk, Klinsk (Studeno-Klyuchev), West-Chumachkin, Mordovian-Karmal' and Pokrov deposits, was determined polarographically. The vanadium concentration range in these petroleums is 0.01-0.09 and nickel 0.009-0.05 wt.%. According to results previously obtained, vanadium and nickel contents in ordinary petroleum of this country are no higher than 0.010 and 0.0014 wt.%, respectively. 3 references, 1 table.

  16. Vanadium-base alloys for fusion reactor applications

    Energy Technology Data Exchange (ETDEWEB)

    Smith, D.L.; Loomis, B.A.; Diercks, D.R.

    1984-10-01

    Vanadium-base alloys offer potentially significant advantages over other candidate alloys as a structural material for fusion reactor first wall/blanket applications. Although the data base is more limited than that for the other leading candidate structural materials, viz., austenitic and ferritic steels, vanadium-base alloys exhibit several properties that make them particularly attractive for the fusion reactor environment. This paper presents a review of the structural material requirements, a summary of the materials data base for selected vanadium-base alloys, and a comparison of projected performance characteristics compared to other candidate alloys. Also, critical research and development (R and D) needs are defined.

  17. El vanadio, un elemento ambiguo Vanadium, an ambiguous element

    Directory of Open Access Journals (Sweden)

    Graciela Beatriz García

    2006-12-01

    Full Text Available El vanadio (V se encuentra en 68 minerales diferentes, en los combustibles derivados del petróleo y el carbón y se utiliza principalmente en la industria metalúrgica. Para los humanos, la principal fuente de exposición al V es la contaminación atmosférica producida por la quema de combustibles. En los animales se ha demostrado que algunos compuestos del V son hepatotóxicos, nefrotóxicos, neurotóxicos, carcinogénicos y que afectan a la reproducción y al desarrollo de los fetos y lactantes. Sin embargo, los efectos toxicológicos finales, motivo de preocupación para las personas son la genotoxicidad y la irritación de las vías respiratorias. Por otra parte, los compuestos del V han sido objeto de investigación como agentes que disminuyen los niveles séricos de glucosa, como antihipertensivos, como anorexígenos y como anticancerígenos. El V, de efectos biológicos notables, debe ser más estudiado con el fin de conocer los mecanismos de su acción biológica y para poder determinar tanto los riesgos a su exposición como sus posibles usos farmacológicos en beneficio humano.Vanadium (V occurs in about 68 minerals and in fossil fuels and it is mainly used in steel industry. Air pollution produced by oil and coal burning is the main exposure source for human beings. Reproductive and developmental toxicity, hepatotoxicity, nephrotoxicity, neurotoxicity and carcinogenicity have been found in some vanadium compound exposed animals. Nevertheless, the toxicological end-points of concern for humans are genotoxicity and respiratory tract irritation. On the other hand, V compounds have been studied as anti-diabetic, as antihypertensive, as anorexigen and as anti-carcinogenic. V, which has remarkable biological effects should be studied in order to elucidate its biological mechanisms and to determine either its expositional risks or its pharmacological properties for human benefit.

  18. A study of the coordination shell of aluminum(III) and magnesium(II) in model protein environments: thermodynamics of the complex formation and metal exchange reactions.

    Science.gov (United States)

    Rezabal, Elixabete; Mercero, Jose M; Lopez, Xabier; Ugalde, Jesus M

    2006-03-01

    Al(III) toxicity in living organisms is based on competition with other metal cations. Mg(II) is one of the most affected cations, since the size similarity dominates over the charge identity. The slow ligand exchange rates for Al(III) render the ion useless as a metal ion at the active sites of enzymes and provide a mechanism by which Al(III) inhibits Mg(II) dependent biochemical processes. Al(III) cation interactions with relevant bioligands have been studied in a protein-model environment in gas and aqueous phases using density functional theory methods. The protein model consists of the metal cation bound to two chosen bioligands (functional groups of the amino acid side chains, one of them being always an acetate) and water molecules interacting with the cation to complete its first coordination shell. Analogous Mg(II) complexes are calculated and compared with the Al(III) ones. Formation energies of the complexes are calculated in both phases and magnesium/aluminum exchange energies evaluated. The effect of different dielectric media is also analyzed. The presence of an acetate ligand in the binding site is found to promote both, complex formation and metal exchange reactions. In addition, buried binding sites (with low dielectric constant) of the protein favor metal exchange, whereas fully solvated environments of high dielectric constant require the presence of two anionic ligands for metal exchange to occur.

  19. Atomic absorption techniques for determining vanadium and nickel in crude oil

    Energy Technology Data Exchange (ETDEWEB)

    Grizzle, P.L.; Wilson, C.A.; Ferrero, E.P.; Coleman, H.J.

    1977-05-01

    Four different techniques for sample preparation were evaluated for determining vanadium and nickel in crude oils by atomic absorption (AA) spectroscopy: (1) The flame-analyzed dilution method which consists of direct-flame AA analysis after diluting the sample with a suitable organic solvent; (2) the flame-analyzed, wet-ashing method in which the sample is combusted and the residue is then dissolved before flame analysis; (3) the flameless, dilution method which involves flameless AA analysis of the sample following dilution with a suitable organic solvent; and (4) the direct, flameless method in which the crude oil or residue is directly analyzed by flameless AA. The flame-analyzed dilution method yielded erratic and inaccurate analytical results for samples of crude oils as well as for a residual sample containing standard amounts of vanadium and nickel; hence, it is unsatisfactory for oil-identification. Similarly, the direct, flameless method is unsatisfactory owing to the small concentration range available for analysis (less than approximately 15 ppM). Both the flame-analyzed, wet-ashing and flameless-dilution methods yield reliable and reproducible (better than 10%) quantitative data for nickel and vanadium in crude oils and crude oil residues. Results demonstrate that the error associated with the loss of volatile metal containing compounds upon wet-ashing is within the reproducibility of the technique. Although wet-ashing may be slightly more reproducible, the flameless-dilution method is much simpler and faster and is recommended as the better of the two procedures for routine determinations of trace metals for oil identification.

  20. The use of Apatite II™ to remove divalent metal ions zinc(II), lead(II), manganese(II) and iron(II) from water in passive treatment systems: column experiments

    OpenAIRE

    Oliva, José; de Pablo, Joan; Cortina, José Luis; Cama, Jordi; Ayora, Carlos

    2010-01-01

    The conventional passive treatments for remediation of acid mine drainage using calcite are not totally efficient in the removal of certain heavy metal ions. Although pH increases to 6–7 and promotes the precipitation of trivalent and some divalent metals as hydroxides and carbonates, the remaining concentrations of some divalent metals ions do not fulfill the environmental regulations. In this study, Apatite II™, a biogenic hydroxyapatite, is used as an alternative reactive material to remov...

  1. Metal(II) complexes synthesized based on quinoline-2,3-dicarboxylate as electrocatalysts for the degradation of methyl orange.

    Science.gov (United States)

    Gong, Yun; Zhang, Miao Miao; Qin, Jian Bo; Li, Jian; Meng, Jiang Ping; Lin, Jian Hua

    2014-06-14

    Based on quinoline-2,3-dicarboxylic acid (H2L), two metal(II) complexes formulated as MnL(phen)(H2O)·H2O (phen = 1,10-phenanthroline) (1) and Co(HL)2(PPA)·4H2O (PPA = N(1),N(4)-di(pyridin-4-yl)terephthalamide) (2) were synthesized and structurally characterized by single-crystal X-ray diffraction. Both complexes 1 and 2 exhibit one-dimensional (1D) chain-like structures, in which stable five-membered rings are observed. Different chains are linked by strong π-π stacking interactions into a three-dimensional (3D) supramolecular architecture. Both complexes can increase the degradation rate of methyl orange (MO), which is expected to be associated with their electrocatalytic activities for the H2 evolution reaction from water.

  2. Synthesis, characterization and biological relevance of some metal (II) complexes with oxygen, nitrogen and oxygen (ONO) donor Schiff base ligand derived from thiazole and 2-hydroxy-1-naphthaldehyde

    Science.gov (United States)

    Nagesh, G. Y.; Mruthyunjayaswamy, B. H. M.

    2015-04-01

    The novel Schiff base ligand 2-((2-hydroxynaphthalen-1-yl)methylene)-N-(4-phenylthiazol-2-yl)hydrazinecarboxamide (L) obtained by the condensation of N-(4-phenylthiazol-2-yl)hydrazinecarboxamide with 2-hydroxy-1-naphthaldehyde and its newly synthesized Cu(II), Co(II), Ni(II), Zn(II) and Cd(II) complexes have been characterized by microanalysis, molar conductance, IR, 1H NMR, ESI-mass, UV-Visible, TGA/DTA, ESR and powder X-ray diffraction data to explicate their structures. The IR results confirmed the tridentate binding of the ligand involving oxygen atom of amide carbonyl, azomethine nitrogen and naphthol oxygen. 1H NMR spectral data of the ligand (L) and its Zn(II) complex agreed well with the proposed structures. Thermogravimetric studies for Cu(II) and Ni(II) complexes indicated the presence of coordinated water molecules and the final product is the metal oxide. In order to appraise the effect of antimicrobial activity of metal ions upon chelation, the newly synthesized ligand and its metal complexes were screened for their antimicrobial activity by minimum inhibitory concentration (MIC) method. The DNA cleavage activities were studied using plasmid DNA pBR322 (Bangal re Genei, Bengaluru, Cat. No 105850) as a target molecule by agarose gel electrophoresis method. The brine shrimp bioassay was also carried out to study the in vitro cytotoxicity properties against Artemia salina. Furthermore, the antioxidant activity were determined in vitro by reduction of 1,1-diphenyl-2-picryl hydrazyl (DPPH). The ligand exhibited better in vitro-antioxidant activity than its metal complexes.

  3. Bright Metal-Poor Stars from the Hamburg/ESO Survey. II. A Chemodynamical Analysis

    Science.gov (United States)

    Beers, Timothy C.; Placco, Vinicius M.; Carollo, Daniela; Rossi, Silvia; Lee, Young Sun; Frebel, Anna; Norris, John E.; Dietz, Sarah; Masseron, Thomas

    2017-01-01

    We obtain estimates of stellar atmospheric parameters for a previously published sample of 1777 relatively bright (9Hamburg/ESO Survey. The original Frebel et al. analysis of these stars was able to derive estimates of [Fe/H] and [C/Fe] only for a subset of the sample, due to limitations in the methodology then available. A new spectroscopic analysis pipeline has been used to obtain estimates of {T}{eff}, {log} g, [Fe/H], and [C/Fe] for almost the entire data set. This sample is very local—about 90% of the stars are located within 0.5 kpc of the Sun. We consider the chemodynamical properties of these stars in concert with a similarly local sample of stars from a recent analysis of the Bidelman and MacConnell “weak metal” candidates by Beers et al. We use this combined sample to identify possible members of the halo stream of stars suggested by Helmi et al. and Chiba & Beers, as well as stars that may be associated with stripped debris from the putative parent dwarf of the globular cluster Omega Centauri, suggested to exist by previous authors. We identify a clear increase in the cumulative frequency of carbon-enhanced metal-poor (CEMP) stars with declining metallicity, as well as an increase in the fraction of CEMP stars with distance from the Galactic plane, consistent with previous results. We also identify a relatively large number of CEMP stars with kinematics consistent with the metal-weak thick-disk population, with possible implications for its origin.

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

    Science.gov (United States)

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

    2011-07-01

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

  5. Metal-line emission from the warm-hot intergalactic medium - II. Ultraviolet

    Science.gov (United States)

    Bertone, Serena; Schaye, Joop; Booth, C. M.; Dalla Vecchia, Claudio; Theuns, Tom; Wiersma, Robert P. C.

    2010-10-01

    Approximately half the baryons in the local Universe are thought to reside in the warm-hot intergalactic medium (WHIM), i.e. diffuse gas with temperatures in the range 105 ~103photons-1cm-2sr-1) comes from relatively dense (ρ > 102ρmean) and metal rich (Z >~ 0.1Zsolar) gas. As such, emission lines are highly biased tracers of the missing baryons and are not an optimal tool to close the baryon budget. However, they do provide a powerful means to detect the gas cooling on to or flowing out of galaxies and groups.

  6. Metallation of ethylenediamine based Schiff base with biologically active Cu(II), Ni(II) and Zn(II) ions: synthesis, spectroscopic characterization, electrochemical behaviour, DNA binding, photonuclease activity and in vitro antimicrobial efficacy.

    Science.gov (United States)

    Raman, N; Selvan, A; Sudharsan, S

    2011-09-01

    A new ligand [C28H20N6O8] (L2) has been synthesized by the condensation reaction of 3-hydroxy-4-nitrobenzaldehydenephenylhydrazine (L1) with diethyloxalate. This ligand L2 is allowed to react with bis(ethylenediamine)Cu(II)/Ni(II)/Zn(II) complexes. It affords [(L2)Cu(en)2]Cl2(1)/[(L2)Ni(en)2]Cl2(2)/[(L2)Zn(en)2]Cl2(3) complexes, respectively. These complexes (1-3) have been characterized by the spectral and analytical techniques. The interaction of these complexes with calf thymus (CT) DNA is characterized by the absorption spectra which exhibit a slight red shift with hypochromic effect. Electrochemical analyses and viscosity measurements have also been carried out to determine the mode of binding. The shift in ΔEp, E1/2 and Ipc values explores the interaction of CT DNA with the above metal complexes. The slight increase in the viscosity of CT DNA indicates that these complexes bind to CT DNA through a partial non-classical intercalative mode. Cleavage experiments using pBR322 DNA in presence of H2O2 indicate that these complexes behave as efficient artificial chemical nucleases in the order of 1>2>3. Moreover, the antibacterial and antifungal studies reveal that complex 1 is highly active against the bacterial and fungal growth. Copyright © 2011 Elsevier B.V. All rights reserved.

  7. A novel route for the removal of bodily heavy metal lead (II)

    Science.gov (United States)

    Huang, Weirong; Zhang, Penghua; Xu, Hui; Chang, Shengli; He, Yongju; Wang, Fei; Liang, Gaowei

    2015-09-01

    The lead ion concentration in bile is considerably higher than in blood, and bile is released into the alimentary tract. Thiol-modified SBA-15 administered orally can combine with lead ions in the alimentary tract. In this paper, the in vitro lead absorption of bile was investigated. This thiol-modified SBA-15 material was used in pharmacodynamics studies on rabbits. The result that the lead content in faeces was notably higher indicates that thiol-modified SBA-15 can efficiently remove lead. The mechanism could include the following: thiol-modified SBA-15 material cuts off the heavy metal lead recirculation in the process of bile enterohepatic circulation by chelating the lead in the alimentary tract, causing a certain proportion of lead to be removed by the thiol mesoporous material, and the lead is subsequently egested out of the body in faeces. The results indicate that this material might be a potential non-injection material for the removal bodily heavy metal lead in the alimentary tract. This material may also be a useful means of lead removal, especially for non-acute sub-poisoning symptoms.

  8. New, high-capacity alloys for hydrogen batteries. Vanadium alloys with microcurrent collecting function; Atarashii suiso denchiyo koyoryo gokin. Maikuro shuden kino wo sonaeta vanadium gokin

    Energy Technology Data Exchange (ETDEWEB)

    Sakai, T. [Osaka National Research Institute, Osaka (Japan)

    1996-05-01

    In an attempt to provide vanadium-base alloys with microcurrent collecting functions and corrosion resistance, their compositions and metallic microstructures are controlled. This leads to development of a new alloy for batteries, which shows an electrical capacity at least 1.5 times higher than that of the conventional rare-earth alloys. A detailed phase diagram of the V-Ti-Ni systems is drawn for hydrogen occluding, to determine the optimum composition. For the electrode characteristics of V3TiNix, the discharge characteristics are notably improved as Ni content increases. For the microstructures, Ni is scarcely dissolved in the base phase of V, withdraws Ti from the base phase, and separates out in the grain boundaries as a TiNi phase dissolving part of V, to form micronetworks. These phenomena are considered to impart the internal microcurrent collecting function to the vanadium alloy. The composition of V3TiNi0.56 shows an initial capacity of 400Ah/g or higher. 3 refs., 5 figs.

  9. Vanadium sulfides interwoven nanoflowers based on in-situ sulfurization of vanadium oxides octahedron on nickel foam for efficient hydrogen evolution

    Science.gov (United States)

    Rao, Yi; Zhang, Li-Ming; Shang, Xiao; Dong, Bin; Liu, Yan-Ru; Lu, Shan-Shan; Chi, Jing-Qi; Chai, Yong-Ming; Liu, Chen-Guang

    2017-11-01

    Novel vanadium sulfides interwoven nanoflowers supported on nickel foam (VO-S/NF) has been synthesized through a facile two-step access. Firstly, octahedron-structured vanadium oxides as precursor were anchored on the surface of NF (VO/NF) by a hydrothermal process. Secondly, in-situ sulfurization in H2S gas has been applied to prepare VO-S/NF. XRD shows that VO-S/NF sample is composed of mixture phases including VS and Ni3S2, implying the interface effect between VS and Ni3S2. SEM images demonstrate that octahedron-structured VO from VO/NF changed to VO-S interwoven nanoflowers on VO-S/NF, which are composed of vertical interwoven nanosheets. It can enlarge surface area to expose abundant active sites and facilitate mass and charge transportation. The electrochemical measurements display the enhanced HER activity of VO-S/NF requiring an overpotential of 165 mV to deliver 10 mA cm-2, which may be ascribed to the novel structure of VS interwoven nanosheets and the synergistic effect between VS and Ni3S2. Furthermore, VO-S/NF remains high HER activity for at least 10 h with excellent structural stability confirmed by post-HER characterization such as XRD, SEM and XPS. Therefore, it may provide a new way to design multiple transition metal sulfides-based electrocatalysts with unique nanostructure as well as interface effect for HER in alkaline.

  10. Enhancement of chitosan-graphene oxide SPR sensor with a multi-metallic layers of Au–Ag–Au nanostructure for lead(II) ion detection

    Energy Technology Data Exchange (ETDEWEB)

    Kamaruddin, Nur Hasiba [Department of Electric, Electronic and Systems Engineering, Faculty of Engineering and Built Environment, Universiti Kebangsaan Malaysia, 43600 UKM Bangi, Selangor (Malaysia); Bakar, Ahmad Ashrif A., E-mail: ashrif@ukm.edu.my [Department of Electric, Electronic and Systems Engineering, Faculty of Engineering and Built Environment, Universiti Kebangsaan Malaysia, 43600 UKM Bangi, Selangor (Malaysia); Yaacob, Mohd Hanif; Mahdi, Mohd Adzir [Wireless and Photonic Network Research Centre, Faculty of Engineering, Universiti Putra Malaysia, 43400 Serdang, Selangor (Malaysia); Zan, Mohd Saiful Dzulkefly [Department of Electric, Electronic and Systems Engineering, Faculty of Engineering and Built Environment, Universiti Kebangsaan Malaysia, 43600 UKM Bangi, Selangor (Malaysia); Shaari, Sahbudin [Institute of Microengineering and Nanoelectronics, Universiti Kebangsaan Malaysia, 43600 UKM Bangi, Selangor (Malaysia)

    2016-01-15

    Highlights: • Tri-metallic Au–Ag–Au CS-GO SPR sensor was fabricated for the first time. • The tri-metallic nanostructure provided an enhanced evanescent field. • Successful functionalization of the CS-GO sensing layer. • Superior performance for lead(II) ion detection. - Abstract: We demonstrate the enhancement of surface plasmon resonance (SPR) technique by implementing a multi-metallic layers of Au–Ag–Au nanostructure in the chitosan-graphene oxide (CS-GO) SPR sensor for lead(II) ion detection. The performance of the sensor is analyzed via SPR measurements, from which the sensitivity, signal-to-noise ratio and repeatability are determined. The nanostructure layers are characterized using field emission scanning electron microscopy (FESEM), atomic force microscopy (AFM), X-ray diffraction (XRD), Raman spectroscopy and X-ray photoelectron spectroscopy (XPS). We showed that the proposed structure has increased the shift in the SPR angle up to 3.5° within the range of 0.1–1 ppm due to the enhanced evanescent field at the sensing layer-analyte interface. This sensor also exhibits great repeatability which benefits from the stable multi-metallic nanostructure. The SNR value of 0.92 for 5 ppm lead(II) ion solution and reasonable linearity range up to that concentration shows that the tri-metallic CS-GO SPR sensor gives a good response towards the lead(II) ion solution. The CS-GO SPR sensor is also sensitive to at least a 10{sup −5} change in the refractive index. The results prove that our proposed tri-metallic CS-GO SPR sensor demonstrates a strong performance and reliability for lead(II) ion detection in accordance with the standardized lead safety level for wastewater.

  11. CFA-13 - a bifunctional perfluorinated metal-organic framework featuring active Cu(i) and Cu(ii) sites.

    Science.gov (United States)

    Fritzsche, J; Denysenko, D; Grzywa, M; Volkmer, D

    2017-11-07

    The synthesis and crystal structure of the mixed-valent perfluorinated metal-organic framework (Me2NH2)[CFA-13] (Coordination Framework Augsburg University-13), (Me2NH2)[CuCu(tfpc)4] (H2-tfpc = 3,5-bis(trifluoromethyl)-1H-pyrazole-4-carboxylic acid) is described. The copper-containing MOF crystallizes in the monoclinic crystal system within the space group P21/n (no. 14) and the unit cell parameters are as follows: a = 22.3887(19), b = 13.6888(8), c = 21.1804(13) Å, β = 90.495(3)°, V = 6491.0(8) Å3. (Me2NH2)[CFA-13] features a porous 3-D structure constructed from two types of secondary building units (SBUs). Besides novel trinuclear [Cu(pz)4]- coordination units, the network also exhibits Cu(ii) paddle-wheel SBUs. (Me2NH2)[CFA-13] is fully characterized by single crystal X-ray diffraction, thermogravimetric analysis, variable temperature powder X-ray diffraction, IR spectroscopy, photoluminescence, gas sorption measurements and pulse chemisorption experiments. M[CFA-13] (M = K+, Cs+) frameworks were prepared by postsynthetic exchange of interchannel dimethylammonium cations. Moreover, it was shown that CO molecules can be selectively bound at Cu(i) sites of [Cu(pz)4]- units, whereas Cu(ii) paddle-wheel units bind selectively NH3 molecules.

  12. Microporous Cd(II) metal-organic framework as fluorescent sensor for nitroaromatic explosives at the sub-ppm level

    Science.gov (United States)

    Wang, Xing-Po; Han, Lu-Lu; Wang, Zhi; Guo, Ling-Yu; Sun, Di

    2016-03-01

    A novel Cd(II) metal-organic framework (MOF) based on a rigid biphenyltetracarboxylic acid, [Cd4(bptc)2(DMA)4(H2O)2·4DMA] (1) was successfully synthesized under the solvothermal condition and characterized by single-crystal X-ray diffraction and further consolidated by elemental analyses, powder X-ray diffraction (PXRD), infrared spectra (IR) and luminescent measurements. Single crystal X-ray diffraction analysis reveals that compound 1 is 4-connected PtS (Point symbol: {42·84}) network based on [Cd2(COO)4] secondary building units (SBUs). Its inherent porous and emissive characteristics make them to be a suitable fluorescent probe to sense small solvents and nitroaromatic explosives. Compound 1 shows obviously solvent-dependent emissive behaviors, especially for acetone with very high fluorescence quenching effect. Moreover, compound 1 displays excellent sensing of nitroaromatic explosives at sub-ppm level, giving a detection limit of 0.43 ppm and 0.37 ppm for nitrobenzene (NB) and p-nitrotoluene (PNT), respectively. This shows this Cd(II) MOF can be used as fluorescence probe for the detection of nitroaromatic explosives.

  13. A new vanadium(V) persulfide complex: (NEt[sub 4])[VO(S[sub 2])[sub 2](bpy)

    Energy Technology Data Exchange (ETDEWEB)

    Castro, S.L.; Martin, J.D.; Christou, G. (Indiana Univ., Bloomington, IN (United States))

    1993-06-23

    Over the last several years, the authors have been investigating nonorganometallic vanadium/sulfide chemistry, concentrating on the higher metal oxidation states (III-V). They have found this area to be rich in structural types and reactivity characteristics. Together with related efforts by others, an impressive pool of complexes has now been made available spanning a variety of nuclearities and oxidation levels, including mixed valency. The authors' interest in this area stems from the conversion of crude oil vanadyl impurities to polymeric vanadium sulfides under the sulfur-rich conditions present during catalytic hydrodesulfurization and hydrodemetalation processes. A variety of discrete V/S species are probably forming as intermediates, and the characterization of V/S species thus becomes of relevance to the understanding of these transformations. The area of impact of the present work is vanadium persulfide chemistry. A number of V complexes of various metal nuclearities are now known that contain S[sub 2][sup 2[minus

  14. A GMOS-N IFU study of the central H ii region in the blue compact dwarf galaxy NGC 4449: kinematics, nebular metallicity and star formation

    Science.gov (United States)

    Kumari, Nimisha; James, Bethan L.; Irwin, Mike J.

    2017-10-01

    We use integral field spectroscopic (IFS) observations from the Gemini Multi-Object Spectrograph North (GMOS-N) to study the central H ii region in a nearby blue compact dwarf (BCD) galaxy NGC 4449. The IFS data enable us to explore the variation of physical and chemical conditions of the star-forming region and the surrounding gas on spatial scales as small as 5.5 pc. Our kinematical analysis shows possible signatures of shock ionization and shell structures in the surroundings of the star-forming region. The metallicity maps of the region, created using direct Te and indirect strong line methods (R23, O3N2 and N2), do not show any chemical variation. From the integrated spectrum of the central H ii region, we find a metallicity of 12 + log(O/H) = 7.88 ± 0.14 ({˜ }0.15^{+0.06}_{-0.04} Z⊙) using the direct method. Comparing the central H ii region metallicity derived here with those of H ii regions throughout this galaxy from previous studies, we find evidence of increasing metallicity with distance from the central nucleus. Such chemical inhomogeneities can be due to several mechanisms, including gas loss via supernova blowout, galactic winds or metal-poor gas accretion. However, we find that the localized area of decreased metallicity aligns spatially with the peak of star-forming activity in the galaxy, suggesting that gas accretion may be at play here. Spatially resolved IFS data for the entire galaxy are required to confirm the metallicity inhomogeneity found in this study and determine its possible cause.

  15. Vanadium - investigations on supply and demand of mineral raw materials

    Energy Technology Data Exchange (ETDEWEB)

    Eggert, P.; Kippenberger, C.; Kruszona, M.; Schmidt, H.; Wettig, E.

    1981-11-01

    Conclusions which are drawn in the latest report of the Federal Institute for Geosciences and Mineral Resources, Hanover, and the German Institute for Economic Research, Berlin, on the steel additive vanadium are presented.

  16. Method to Remove Uranium/Vanadium Contamination from Groundwater

    Energy Technology Data Exchange (ETDEWEB)

    Metzler, Donald R.; Morrison Stanley

    2004-07-27

    A process for removing uranium/vanadium-based contaminants from groundwater using a primary in-ground treatment media and a pretreatment media that chemically adjusts the groundwater contaminant to provide for optimum treatment by the primary treatment media.

  17. Exploring a novel approach to fabricate vanadium carbide ...

    Indian Academy of Sciences (India)

    -shell structure; composite materials; mesoporous material; solid-state reaction. ... A novel approach to the fabrication of vanadium carbide encapsulated into carbon nanotube (VC@C) core-shell structured composite by thermal treatment with ...

  18. Chromium, nickel and vanadium mobility in soils derived from fluvioglacial sands.

    Science.gov (United States)

    Agnieszka, Jeske; Barbara, Gworek

    2012-10-30

    The presented study was focused on soils developed from fluvioglacial sands from the Puszcza Borecka forest complex. The mobility of chromium, nickel and vanadium was evaluated with regard to litho- and pedogenic factors. The aim of the study was to determine with which soil constituents fractions of heavy metals are bound with particular attention drawn on the mobile fractions (F1+F2). Heavy metal fractions in the soils were determined using the sequential extraction method of Tessier et al. The purpose of sequential extraction methods to soil samples provides relevant information about possible toxicity when they are discharged into the soil environment. Chromium, nickel, and vanadium occurred predominantly in the fraction bound with iron and manganese oxides and in the residual fraction, thus showed low mobility. With regard to mobility, the elements studied can be arranged as follows: V

  19. Effect of Doping on Hydrogen Evolution Reaction of Vanadium Disulfide Monolayer

    Science.gov (United States)

    Qu, Yuanju; Pan, Hui; Kwok, Chi Tat; Wang, Zisheng

    2015-12-01

    As cheap and abundant materials, transitional metal dichalcogenide monolayers have attracted increasing interests for their application as catalysts in hydrogen production. In this work, the hydrogen evolution reduction of doped vanadium disulfide monolayers is investigated based on first-principles calculations. We find that the doping elements and concentration affect strongly the catalytic ability of the monolayer. We show that Ti-doping can efficiently reduce the Gibbs free energy of hydrogen adsorption in a wide range of hydrogen coverage. The catalytic ability of the monolayer at high hydrogen coverage can be improved by low Ti-density doping, while that at low hydrogen coverage is enhanced by moderate Ti-density doping. We further show that it is much easier to substitute the Ti atom to the V atom in the vanadium disulfide (VS2) monolayer than other transitional metal atoms considered here due to its lowest and negative formation energy. It is expected that the Ti-doped VS2 monolayer may be applicable in water electrolysis with improved efficiency.

  20. Structures and Spectroscopy Studies of Two M(II-Phosphonate Coordination Polymers Based on Alkaline Earth Metals (M = Ba, Mg

    Directory of Open Access Journals (Sweden)

    Kui-Rong Ma

    2013-01-01

    Full Text Available The two examples of alkaline-earth M(II-phosphonate coordination polymers, [Ba2(L(H2O9]·3H2O (1 and [Mg1.5(H2O9]·(L-H21.5·6H2O (2 (H4L = H2O3PCH2N(C4H8NCH2PO3H2, N,N′-piperazinebis(methylenephosphonic acid, (L-H2 = O3PH2CHN(C4H8NHCH2PO3 have been hydrothermally synthesized and characterized by elemental analysis, FT-IR, PXRD, TG-DSC, and single-crystal X-ray diffraction. Compound 1 possesses a 2D inorganic-organic alternate arrangement layer structure built from 1D inorganic chains through the piperazine bridge, in which the ligand L−4 shows two types of coordination modes reported rarely at the same time. In 1, both crystallographic distinct Ba(1 and Ba(2 ions adopt 8-coordination two caps and 9-coordination three caps triangular prism geometry structures, respectively. Compound 2 possesses a zero-dimensional mononuclear structure with two crystallographic distinct Mg(II ions. Free metal cations   [MgO6]n2+ and uncoordinated anions (L-H2n2- are joined together by static electric force. Results of photoluminescent measurement indicate three main emission bands centered at 300 nm, 378.5 nm, and 433 nm for 1 and 302 nm, 378 nm, and 434.5 nm for 2 (λex=235 nm, respectively. The high energy emissions could be derived from the intraligand π∗-n transition stations of H4L (310 nm and 382 nm, λex=235 nm, while the low energy emission (>400 nm of 1-2 may be due to the coordination effect with metal(II ions.

  1. A quasi-stationary numerical model of atomized metal droplets, II: Prediction and assessment

    DEFF Research Database (Denmark)

    Pryds, Nini H.; Hattel, Jesper Henri; Thorborg, Jesper

    1999-01-01

    A new model which extends previous studies and includes the interaction between enveloping gas and an array of droplets has been developed and presented in a previous paper. The model incorporates the probability density function of atomized metallic droplets into the heat transfer equations....... The main thrust of the model is that the gas temperature was not predetermined and calculated empirically but calculated numerically based on heat balance consideration. In this paper, the accuracy of the numerical model and the applicability of the model as a predictive tool have been investigated...... been illustrated.A comparison between the numerical model and the experimental results shows an excellent agreement and demonstrates the validity of the present model, e.g. the calculated gas temperature which has an important influence on the droplet solidification behaviour as well as the calculated...

  2. Structure, photoluminescent properties and photocatalytic activities of a new Cd(II) metal-organic framework.

    Science.gov (United States)

    Zhang, Cheng Yan; Ma, Wei Xing; Wang, Ming Yan; Yang, Xu Jie; Xu, Xing You

    2014-01-24

    A new metal-organic framework, [Cd(TDC)(bix)(H2O)]n (H2TDC = thiophene-2,5-dicarboxylic acid; bix = 1,4-bis(imidazol-1-ylmethyl)benzene), has been synthesized under hydrothermal conditions and structurally characterized by elemental analysis, infrared spectroscopy, thermogravimetric analysis, UV-vis and single X-ray diffraction. Cd-MOF is a 2D infinite layer framework, which is further interconnected by hydrogen-bond interactions leading to a 3D supramolecular architecture. The photoluminescent properties of the Cd-MOF were investigated and this compound shows intense fluorescent emissions in the solid state. In addition, it exhibits good photocatalytic activities for the degradation of methyl organic under UV light irradiation. Copyright © 2013 Elsevier B.V. All rights reserved.

  3. Metal-ion mutagenesis: conversion of a purple acid phosphatase from sweet potato to a neutral phosphatase with the formation of an unprecedented catalytically competent Mn(II)Mn(II) active site.

    Science.gov (United States)

    Mitić, Natasa; Noble, Christopher J; Gahan, Lawrence R; Hanson, Graeme R; Schenk, Gerhard

    2009-06-17

    The currently accepted paradigm is that the purple acid phosphatases (PAPs) require a heterovalent, dinuclear metal-ion center for catalysis. It is believed that this is an essential feature for these enzymes in order for them to operate under acidic conditions. A PAP from sweet potato is unusual in that it appears to have a specific requirement for manganese, forming a unique Fe(III)-mu-(O)-Mn(II) center under catalytically optimal conditions (Schenk et al. Proc. Natl. Acad. Sci. U.S.A. 2005, 102, 273). Herein, we demonstrate, with detailed electron paramagnetic resonance (EPR) spectroscopic and kinetic studies, that in this enzyme the chromophoric Fe(III) can be replaced by Mn(II), forming a catalytically active, unprecedented antiferromagnetically coupled homodivalent Mn(II)-mu-(H)OH-mu-carboxylato-Mn(II) center in a PAP. However, although the enzyme is still active, it no longer functions as an acid phosphatase, having optimal activity at neutral pH. Thus, PAPs may have evolved from distantly related divalent dinuclear metallohydrolases that operate under pH neutral conditions by stabilization of a trivalent-divalent metal-ion core. The present Mn(II)-Mn(II) system models these distant relatives, and the results herein make a significant contribution to our understanding of the role of the chromophoric metal ion as an activator of the nucleophile. In addition, the detailed analysis of strain broadened EPR spectra from exchange-coupled dinuclear Mn(II)-Mn(II) centers described herein provides the basis for the full interpretation of the EPR spectra from other dinuclear Mn metalloenzymes.

  4. Determination of heavy metals at sub-ppm levels in seawater and dialysis solutions by FAAS after tetrakis(pyridine)-nickel(II)bis(thiocyanate) coprecipitation.

    Science.gov (United States)

    Sahin, Uğur; Kartal, Senol; Ulgen, Ahmet

    2008-06-01

    A coprecipitation method has been developed for the determination of Cr(III), Mn(II), Fe(III), Co(II), Cu(II), Cd(II) and Pb(II) ions in aqueous samples by flame atomic absorption spectrometry (FAAS) with the combination of pyridine, nickel(II) as a carrier element and potassium thiocyanate as an auxiliary complexing agent. The obtained coprecipitates were dissolved with nitric acid and measured by FAAS. The coprecipitation conditions, such as the effect of the pH, amounts of nickel, pyridine and potassium thiocyanate, sample volume, and the standing time of the precipitate formation were examined in detail. It was found that the metal ions studied were quantitatively coprecipitated with tetrakis(pyridine)-nickel(II)bis(thiocyanate) precipitate (TP-Ni-BT) in the pH range of 9.0 - 10.5. The reliability of the results was evaluated by recovery tests, using synthetic seawater solutions spiked with the analyte metal ions. The obtained recoveries ranged from 96 to 101% for all of the metal ions investigated. The proposed method was validated by analyses of two certified reference materials (NIST SRM 2711 Montana soil and HPS Certified Waste Water Trace Metals Lot #D532205). It was also successfully applied to seawater and dialysis solution samples. The detection limits (n = 25, 3s) were in the range of 0.01-2.44 microg l(-1) for the studied elements and the relative standard deviations were < or =6%, which indicated that this method could fully satisfy the requirements for analysis of such samples as seawater and dialysis solution having high salt contents.

  5. High Performance Pillared Vanadium Oxide Cathode for Lithium Ion Batteries

    Science.gov (United States)

    2015-04-24

    Performance Pillared Vanadium Oxide Cathode for Lithium Ion Batteries Siu on Tung, Krista L. Hawthorne, Yi Ding, James Mainero, and Levi T. Thompson...Automotive Research Development and Engineering Center, Warren, MI 48387, USA Keywords: nanostructured materials, lithium ion batteries , cathode...2014 to 00-00-2015 4. TITLE AND SUBTITLE High Performance Pillared Vanadium Oxide Cathode for Lithium Ion Batteries 5a. CONTRACT NUMBER 5b. GRANT

  6. Enhancement of chitosan-graphene oxide SPR sensor with a multi-metallic layers of Au-Ag-Au nanostructure for lead(II) ion detection

    Science.gov (United States)

    Kamaruddin, Nur Hasiba; Bakar, Ahmad Ashrif A.; Yaacob, Mohd Hanif; Mahdi, Mohd Adzir; Zan, Mohd Saiful Dzulkefly; Shaari, Sahbudin

    2016-01-01

    We demonstrate the enhancement of surface plasmon resonance (SPR) technique by implementing a multi-metallic layers of Au-Ag-Au nanostructure in the chitosan-graphene oxide (CS-GO) SPR sensor for lead(II) ion detection. The performance of the sensor is analyzed via SPR measurements, from which the sensitivity, signal-to-noise ratio and repeatability are determined. The nanostructure layers are characterized using field emission scanning electron microscopy (FESEM), atomic force microscopy (AFM), X-ray diffraction (XRD), Raman spectroscopy and X-ray photoelectron spectroscopy (XPS). We showed that the proposed structure has increased the shift in the SPR angle up to 3.5° within the range of 0.1-1 ppm due to the enhanced evanescent field at the sensing layer-analyte interface. This sensor also exhibits great repeatability which benefits from the stable multi-metallic nanostructure. The SNR value of 0.92 for 5 ppm lead(II) ion solution and reasonable linearity range up to that concentration shows that the tri-metallic CS-GO SPR sensor gives a good response towards the lead(II) ion solution. The CS-GO SPR sensor is also sensitive to at least a 10-5 change in the refractive index. The results prove that our proposed tri-metallic CS-GO SPR sensor demonstrates a strong performance and reliability for lead(II) ion detection in accordance with the standardized lead safety level for wastewater.

  7. Design and generation of extended zeolitic metal-organic frameworks (ZMOFs): synthesis and crystal structures of zinc(II) imidazolate polymers with zeolitic topologies.

    Science.gov (United States)

    Tian, Yun-Qi; Zhao, Yu-Ming; Chen, Zhen-Xia; Zhang, Guang-Ning; Weng, Lin-Hong; Zhao, Dong-Yuan

    2007-01-01

    Attempts to create metal-organic frameworks (MOFs) with zeolitic topologies, metal (zinc(II) and cobalt(II)) imidazolates have repeatedly been used as the metal-organic motifs of inorganic silicate analogues. By modulating the synthetic strategy based on the solvothermal and liquid diffusion method, seven further MOFs (including at least three zeolitic MOFs) of zinc(II) imidazolates, [Zn(im)2.x G] (G=guest molecule, x=0.2-1) 1 a-7 a, have been successfully synthesized. Of these, 1 a-3 a are isostructural with the previously reported cobalt analogues 1 b-3 b, respectively, while 4 a-7 a are new members of the metal imidazolate MOF family. Complex 4 a exhibits a structure related to silicate CaAl2Si2O8 of CrB4 topology, but with a higher network symmetry; complex 5 a has a structure with zeolitic DFT topology that was discovered in zeolite-related materials of DAF-2, UCSB-3, and UCSB-3GaGe; complex 6 a demonstrates an unprecedented zeolite-like topology with one dimensional channels with 10-rings; and 7 a displays a structure of natural zeolite GIS (gismondine) topology. All of these polymorphous MOFs were created only by using certain solvents as structure-directing agents (SDAs). Further extensive metal-organic frameworks with zeolitic topologies can be envisaged if other solvents were to be used.

  8. Tackling capacity fading in vanadium flow batteries with amphoteric membranes

    Science.gov (United States)

    Oldenburg, Fabio J.; Schmidt, Thomas J.; Gubler, Lorenz

    2017-11-01

    Capacity fading and poor electrolyte utilization caused by electrolyte imbalance effects are major drawbacks for the commercialization of vanadium flow batteries (VFB). The influence of membrane type (cationic, anionic, amphoteric) on these effects is studied by determining the excess and net flux of each vanadium ion in an operating VFB assembled with a cation exchange membrane (CEM), Nafion® NR212, an anion exchange membrane (AEM), Fumatech FAP-450, and an amphoteric ion exchange membrane (AIEM) synthesized in-house. It is shown that the net vanadium flux, accompanied by water transport, is directed towards the positive side for the CEM and towards the negative side for the AEM. The content of cation and anion exchange groups in the AIEM is adjusted via radiation grafting to balance the vanadium flux between the two electrolyte sides. With the AIEM the net vanadium flux is significantly reduced and capacity fading due to electrolyte imbalances can be largely eliminated. The membrane's influence on electrolyte imbalance effects is characterized and quantified in one single charge-discharge cycle by analyzing the content of the four different vanadium species in the two electrolytes. The experimental data recorded herewith conclusively explains the electrolyte composition after 80 cycles.

  9. Towards the role of metal ions in the structural variability of proteins: CdII speciation of a metal ion binding loop motif

    DEFF Research Database (Denmark)

    Jancsó, Attila; Szunyogh, Dániel; Gyurcsik, Béla

    2011-01-01

    A de novo designed dodecapeptide (HS), inspired by the metal binding loops of metal-responsive transcriptional activators, was synthesized. The aim was to create a model system for structurally promiscuous and intrinsically unstructured proteins, and explore the effect of metal ions on their stru......A de novo designed dodecapeptide (HS), inspired by the metal binding loops of metal-responsive transcriptional activators, was synthesized. The aim was to create a model system for structurally promiscuous and intrinsically unstructured proteins, and explore the effect of metal ions...

  10. Next Generation Metallic Iron Nodule Technology in Electric Arc Steelmaking - Phase II

    Energy Technology Data Exchange (ETDEWEB)

    Donald R. Fosnacht; Iwao Iwasaki; Richard F. Kiesel; David J. Englund; David W. Hendrickson; Rodney L. Bleifuss

    2010-12-22

    The current trend in the steel industry is a gradual decline in conventional steelmaking from taconite pellets in blast furnaces, and an increasing number of alternative processes using metallic scrap iron, pig iron and metallized iron ore products. Currently, iron ores from Minnesota and Michigan are pelletized and shipped to the lower Great Lakes ports as blast furnace feed. The existing transportation system and infrastructure is geared to handling these bulk materials. In order to expand the opportunities for the existing iron ore mines beyond their blast furnace customer base, a new material is needed to satisfy the needs of the emerging steel industry while utilizing the existing infrastructure and materials handling. A recent commercial installation employing Kobe Steel’s ITmk3 process, was installed in Northeastern Minnesota. The basic process uses a moving hearth furnace to directly reduce iron oxides to metallic iron from a mixture of iron ore, coals and additives. The resulting products can be shipped using the existing infrastructure for use in various steelmaking processes. The technology reportedly saves energy by 30% over the current integrated steelmaking process and reduces emissions by more than 40%. A similar large-scale pilot plant campaign is also currently in progress using JFE Steel’s Hi-QIP process in Japan. The objective of this proposal is to build upon and improve the technology demonstrated by Kobe Steel and JFE, by further reducing cost, improving quality and creating added incentive for commercial development. This project expands previous research conducted at the University of Minnesota Duluth’s Natural Resources Research Institute and that reported by Kobe and JFE Steel. Three major issues have been identified and are addressed in this project for producing high-quality nodular reduced iron (NRI) at low cost: (1) reduce the processing temperature, (2) control the furnace gas atmosphere over the NRI, and (3) effectively use sub

  11. Localization of Vanabins, Vanadium-Binding Proteins, in the Blood Cells of the Vanadium-Rich Ascidian, Ascidia sydneiensis samea(Physiology)

    OpenAIRE

    Nobuo, Yamaguchi; Yuko, Amakawa; Hiroshi, Yamada; Tatsuya, Ueki; Hitoshi, Michibata; Marine Biological Laboratory, Graduate School of Science, Hiroshima University; Department of Neuroscience, Graduate School of Medicine and Dentistry, Okayama University; Molecular Physiology Laboratory, Department of Biological Science, Graduate School of Science, Hiroshima University

    2006-01-01

    Some species of the family Ascidiidae accumulate vanadium in concentrations in excess of 350mM, which is about 10^7-fold higher than the concentration of vanadium in seawater. In these species, signet ring cells with a single large vacuole in which vanadium ions are contained function as vanadium-accumulating cells. These have been termed vanadocytes. We recently isolated five vanadium-binding proteins, which we named Vanabinl, Vanabin2, Vanabin3, Vanabin4, and VanabinP, from vanadocytes of t...

  12. Nitrogen-Doped Carbon Nanotube/Graphite Felts as Advanced Electrode Materials for Vanadium Redox Flow Batteries.

    Science.gov (United States)

    Wang, Shuangyin; Zhao, Xinsheng; Cochell, Thomas; Manthiram, Arumugam

    2012-08-16

    Nitrogen-doped carbon nanotubes have been grown, for the first time, on graphite felt (N-CNT/GF) by a chemical vapor deposition approach and examined as an advanced electrode for vanadium redox flow batteries (VRFBs). The unique porous structure and nitrogen doping of N-CNT/GF with increased surface area enhances the battery performance significantly. The enriched porous structure of N-CNTs on graphite felt could potentially facilitate the diffusion of electrolyte, while the N-doping could significantly contribute to the enhanced electrode performance. Specifically, the N-doping (i) modifies the electronic properties of CNT and thereby alters the chemisorption characteristics of the vanadium ions, (ii) generates defect sites that are electrochemically more active, (iii) increases the oxygen species on CNT surface, which is a key factor influencing the VRFB performance, and (iv) makes the N-CNT electrochemically more accessible than the CNT.

  13. Monitoring pollution in River Mureş, Romania, part II: metal accumulation and histopathology in fish.

    Science.gov (United States)

    Triebskorn, Rita; Telcean, Ilie; Casper, Heidi; Farkas, Anna; Sandu, Cristina; Stan, Gheorghe; Colărescu, Ovidiu; Dori, Tiberiu; Köhler, Heinz-R

    2008-06-01

    As a part of an exposure and effect monitoring conducted along the river Mureş, Western Romania in 2004, the health status of two indigenous fish species, sneep (Chondrostoma nasus) and European chub (Leuciscus cephalus) was investigated upstream and downstream the city of Arad. In fish, histopathology was assessed in liver and gills, and heavy metals (cadmium, copper, lead and zinc) were analyzed in liver samples. In both fish species, histopathological reactions in the gills (epithelial lifting, focal proliferation of epithelial cells of primary and secondary lamellae and resulting fusion of secondary lamellae, hyperplasia and hypertrophy of mucous cells, focal inflammation and necrosis of epithelial cells) were most severe at the two sampling sites upstream Arad city, which were shown to be polluted by copper, cadmium, faecal coliforms and streptococci in a parallel study. At these two sites, also histopathology in the liver of L. cephalus was more prominent than at the two downstream sites. In C. nasus, symptoms in the liver (focal inflammation with lymphocytic infiltrations, macrophage aggregates and single cell necrosis) were also highly pronounced at the sampling site located directly downstream the municipal sewage treatment plant of Arad. With the exception of copper accumulation in L. cephalus caught at the most upstream sampling site, in both fish species cadmium and copper accumulation were exceptionally high and did not differ significantly between the four sampling sites.

  14. Application of Local Adsorbant From Southeast Sulawesi Clay Immobilized Saccharomyces Cerevisiae Bread’s Yeast Biomass for Adsorption Of Mn(Ii) Metal Ion

    Science.gov (United States)

    R, Halimahtussaddiyah; Mashuni; Budiarni

    2017-05-01

    Southeast Sulawesi has a great stock of clay. It is probably to use as a source of adsorbent. The adsorbent capacity of clay can be largered with teratment using bread’s yeast as biomass. At this research, study of analysis adsorption of Mn(II) metal ion on clay immobilized Saccharomyces cerevisiae bread’s yeast biomass adsorbent has been conducted. The aims of this research were to determine the effects of contact time, pH and concentration of Mn(II) metal ion and to determine the adsorption capacity of clay immobilized S. cerevisiae biomass for adsorbtion of Mn(II) metal ion. Activated clay was synthesized by reaction of clay with KMnO4, H2SO4 and HCl. S. cerevisiae biomass was result by bread’s yeast mashed. Immobilization of S. cerevisiae biomass into clay was done by mixing of ratio of S. cerevisiae bread’s yeast biomass and clay equal to 1:3 (mass of biomassa : mass of clay). The adsorption capacity was determined by using Freundlich and Langmuir adsorption isoterms. The results of FTIR spectrums showed that the functional groups of clay immobilized S. cerevisiae biomass were Si-OH (wave number 1643 cm-1), Si-O-Si (wave number 1033 cm-1), N-H (wave number 2337 cm-1), O-H (wave number 3441cm-1), and C-H (wave number 2931 cm-1). The result of adsorption capacity from Mn(II) metal ion of contact time optimum 120 minutes, pH optimun at 7 and concentration optimum 50 mg/L were 1,816 mg/g; 0,509 mg/g and 2,624mg/g respectively. The adsorption capacity of Mn(II) metal ion with ratio 1:3 (biomass : clay) was 0,1045 mg/g. Type of isothermal adsorption followed the Freunlich adsorption.

  15. Characterization of Cu(II) and Cd(II) resistance mechanisms in Sphingobium sp. PHE-SPH and Ochrobactrum sp. PHE-OCH and their potential application in the bioremediation of heavy metal-phenanthrene co-contaminated sites.

    Science.gov (United States)

    Chen, Chen; Lei, Wenrui; Lu, Min; Zhang, Jianan; Zhang, Zhou; Luo, Chunling; Chen, Yahua; Hong, Qing; Shen, Zhenguo

    2016-04-01

    Soil that is co-contaminated with heavy metals (HMs) and polycyclic aromatic hydrocarbons (PAHs) is difficult to bioremediate due to the ability of toxic metals to inhibit PAH degradation by bacteria. We demonstrated the resistance mechanisms to Cu(II) and Cd(II) of two newly isolated strains of Sphingobium sp. PHE-SPH and Ochrobactrum sp. PHE-OCH and further tested their potential application in the bioremediation of HM-phenanthrene (PhA) co-contaminated sites. The PHE-SPH and PHE-OCH strains tolerated 4.63 and 4.34 mM Cu(II) and also showed tolerance to 0.48 and 1.52 mM Cd(II), respectively. Diverse resistance patterns were detected between the two strains. In PHE-OCH cells, the maximum accumulation of Cu(II) occurred in the cell wall, while the maximum accumulation was in the cytoplasm of PHE-SPH cells. This resulted in a sudden suppression of growth in PHE-OCH and a gradual inhibition in PHE-SPH as the concentration of Cu(II) increased. Organic acid production was markedly higher in PHE-OCH than in PHE-SPH, which may also have a role in the resistance mechanisms, and contributes to the higher Cd(II) tolerance of PHE-OCH. The factors involved in the absorption of Cu(II) or Cd(II) in PHE-SPH and PHE-OCH were identified as proteins and carbohydrates by Fourier transform infrared (FT-IR) spectroscopy. Furthermore, both strains showed the ability to efficiently degrade PhA and maintained this high degradation efficiency under HM stress. The high tolerance to HMs and the PhA degradation capacity make Sphingobium sp. PHE-SPH and Ochrobactrum sp. PHE-OCH excellent candidate organisms for the bioremediation of HM-PhA co-contaminated sites.

  16. Application of factorial designs and Doehlert matrix in optimization of experimental variables associated with the preconcentration and determination of vanadium and copper in seawater by inductively coupled plasma optical emission spectrometry

    Science.gov (United States)

    Ferreira, Sérgio L. C.; Queiroz, Adriana S.; Fernandes, Marcelo S.; dos Santos, Hilda C.

    2002-12-01

    In the present paper a procedure for preconcentration and determination of vanadium and copper in seawater using inductively coupled plasma optical emission spectrometry (ICP OES) is proposed, which is based on solid-phase extraction of vanadium (IV), vanadium (V) and copper (II) ions as 1-(2-pyridylazo)-2-naphthol (PAN) complexes by active carbon. The optimization process was carried out using two-level full factorials and Doehlert matrix designs. Four variables (PAN mass, pH, active carbon mass and shaking time) were regarded as factors in the optimization. Results of the two-level full factorial design 2 4 with 16 runs for vanadium extraction, based on the variance analysis (ANOVA), demonstrated that the factors pH and active carbon mass, besides the interaction (pH×active carbon mass), are statistically significant. For copper, the ANOVA revealed that the factors PAN mass, pH and active carbon mass and the interactions (PAN mass×pH) and (pH×active carbon mass) are statistically significant. Doehlert designs were applied in order to determine the optimum conditions for extraction. The procedure proposed allowed the determination of vanadium and copper with detection limits (3σ/ S) of 73 and 94 ng l -1, respectively. The precision, calculated as relative standard deviation (R.S.D.), was 1.22 and 1.37% for 12.50 μg l -1 of vanadium and copper, respectively. The preconcentration factor was 80. The recovery achieved for determination of vanadium and copper in the presence of several cations demonstrated that this procedure improved the selectivity required for seawater analysis. The procedure was applied to the determination of vanadium and copper in seawater samples collected in Salvador City, Brazil. Results showed good agreement with other data reported in the literature.

  17. Synthesis and Structure of Vanadium Halide Complexes Containing Diphosphine Ligands with Pendant Amines

    Energy Technology Data Exchange (ETDEWEB)

    Egbert, Jonathan D.; Labios, Liezel A.; Darmon, Jonathan M.; Piro, Nicholas A.; Scott Kassel, W.; Mock, Michael T.

    2016-02-18

    A series of vanadium(III) diiodide complexes of the formula CpV(PRNR'PR)I2 (Cp = 5-C5H5; PRNR'PR = (R2PCH2)2N(R)), where R = Et, R = Me (1a), R = Ph (1b); R = Ph, R = Me (1c)) is reported. The corresponding vanadium(II) monoiodide complexes of the formula CpV(PRNR'PR)I, where R = Et, R = Me (2a), R = Ph (2b); R = Ph, R = Me (2c)) were prepared in THF by reduction of 1a-c with Zn powder. The paramagnetic complexes 1a-c and 2a-c are characterized by elemental analysis, 1H NMR spectroscopy, and by cyclic voltammetry for complexes 2b and 4b. Complexes 1c and 2a-c were also characterized in the single crystal by X-ray crystallography. We report the preparation of the vanadium(II) complexes CpV(PPh2NPh2)I (3) (PPh2NPh2 = 1,5-diphenyl-3,7-diphenyl-1,5-diaza-3,7-diphosphacyclooctane) and trans-[VCl2(PEtNMePEt)2] (4a) and trans-[VCl2(PEtNPhPEt)2] (4b). These complexes represent initial coordination chemistry of vanadium complexes with PRNR'PR and PPh2NPh2 diphosphine ligands, which contain a pendant amine in the second coordination sphere. This research was supported as part of the Center for Molecular Electrocatalysis, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences. Pacific Northwest National Laboratory is operated by Battelle for the U.S. Department of Energy.

  18. Comparison of Ultrasound-Assisted and Regular Leaching of Vanadium and Chromium from Roasted High Chromium Vanadium Slag

    Science.gov (United States)

    Wen, Jing; Jiang, Tao; Gao, Huiyang; Liu, Yajing; Zheng, Xiaole; Xue, Xiangxin

    2018-02-01

    Ultrasound-assisted leaching (UAL) was used for vanadium and chromium leaching from roasted material obtained by the calcification roasting of high-chromium-vanadium slag. UAL was compared with regular leaching. The effect of the leaching time and temperature, acid concentration, and liquid-solid ratio on the vanadium and chromium leaching behaviors was investigated. The UAL mechanism was determined from particle-size-distribution and microstructure analyses. UAL decreased the reaction time and leaching temperature significantly. Furthermore, 96.67% vanadium and less than 1% chromium were leached at 60°C for 60 min with 20% H2SO4 at a liquid-solid ratio of 8, which was higher than the maximum vanadium leaching rate of 90.89% obtained using regular leaching at 80°C for 120 min. Ultrasonic waves broke and dispersed the solid sample because of ultrasonic cavitation, which increased the contact area of the roasted sample and the leaching medium, the solid-liquid mass transfer, and the vanadium leaching rate.

  19. Fermi surface of the Weyl type-II metallic candidate WP2

    Science.gov (United States)

    Schönemann, R.; Aryal, N.; Zhou, Q.; Chiu, Y.-C.; Chen, K.-W.; Martin, T. J.; McCandless, G. T.; Chan, J. Y.; Manousakis, E.; Balicas, L.

    2017-09-01

    Weyl type-II fermions are massless quasiparticles that obey the Weyl equation and which are predicted to occur at the boundary between electron and hole pockets in certain semimetals, i.e., the (W,Mo )(Te ,P ) 2 compounds. Here, we present a study of the Fermi surface of WP2 via the Shubnikov-de Haas (SdH) effect. Compared to other semimetals, WP2 exhibits a very low residual resistivity, i.e., ρ0≃10 n Ω cm , which leads to perhaps the largest nonsaturating magnetoresistivity [ρ (H )] reported for any compound. For the samples displaying the smallest ρ0,ρ (H ) is observed to increase by a factor of 2.5 ×107% under μ0H =35 T at T =0.35 K. The angular dependence of the SdH frequencies is found to be in excellent agreement with the first-principles calculations when the electron and hole bands are shifted by 30 meV with respect to the Fermi level. This small discrepancy could have implications for the predicted topological character of this compound.

  20. Facile embedding of single vanadium atoms at the anatase TiO2(101) surface.

    Science.gov (United States)

    Koust, Stig; Arnarson, Logi; Moses, Poul G; Li, Zheshen; Beinik, Igor; Lauritsen, Jeppe V; Wendt, Stefan

    2017-04-05

    To understand the structure-reactivity relationships for mixed-metal oxide catalysts, well-defined systems are required. Mixtures of vanadia and titania (TiO 2 ) are of particular interest for application in heterogeneous catalysis, with TiO 2 often acting as the support. By utilizing high-resolution scanning tunneling microscopy, we studied the interaction of vanadium (V) with the anatase TiO 2 (101) surface in the sub-monolayer regime. At 80 K, metallic V nucleates into homogeneously distributed clusters onto the terraces with no preference for nucleation at the step edges. However, embedding of single V atoms into TiO 2 occurs following annealing at room temperature. In conjunction with X-ray photoelectron spectroscopy data and density functional theory calculations, we propose that monomeric V atoms occupy positions of regular surface Ti sites, i.e., Ti atoms are substituted by V atoms.

  1. Current-modulated optical properties of vanadium dioxide thin films in the phase transition region

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Shuyan; Kats, Mikhail A.; Cui, Yanjie; Zhou, You; Yao, Yu; Ramanathan, Shriram; Capasso, Federico, E-mail: capasso@seas.harvard.edu [School of Engineering and Applied Sciences, Harvard University, Cambridge, Massachusetts 02138 (United States)

    2014-11-24

    Vanadium dioxide (VO{sub 2}) is a correlated electron material which undergoes an insulator-metal transition proximal to room temperature. The large change of optical properties across this phase transition is promising for tunable optical and optoelectronic devices especially at infrared frequencies. We demonstrate the ability to locally tune the optical properties on the micron scale through a simple design consisting of two electrodes patterned on a VO{sub 2} thin film. By current injection between the electrodes, a localized conducting path (metallic phase) can be formed within the insulating background. The width of the conducting path can be controlled by varying the applied current. Fourier transform infrared imaging shows that this current-modulated reflectance changes significantly over a distance on the order of the wavelength in the mid-infrared spectral range.

  2. A liquid metal-based structurally embedded vascular antenna: II. Multiobjective and parameterized design exploration

    Science.gov (United States)

    Hartl, D. J.; Frank, G. J.; Malak, R. J.; Baur, J. W.

    2017-02-01

    Research on the structurally embedded vascular antenna concept leverages past efforts on liquid metal (LM) reconfigurable electronics, microvascular composites, and structurally integrated and reconfigurable antennas. Such a concept has potential for reducing system weight or volume while simultaneously allowing in situ adjustment of resonant frequencies and/or changes in antenna directivity. This work considers a microvascular pattern embedded in a laminated composite and filled with LM. The conductive liquid provides radio frequency (RF) functionality while also allowing self-cooling. Models describing RF propagation and heat transfer, in addition to the structural effects of both the inclusion of channels and changes in temperature, were described in part 1 of this two-part work. In this part 2, the engineering models developed and demonstrated in part 1 toward the initial exploration of design trends are implemented into multiple optimization frameworks for more detailed design studies, one of which being novel and particularly applicable to this class of problem. The computational expense associated with the coupled multiphysical analysis of the structurally embedded LM transmitting antenna motivates the consideration of surrogate-based optimization methods. Both static and adaptive approaches are explored; it is shown that iteratively correcting the surrogate leads to more accurate optimized design predictions. The expected strong dependence of antenna performance on thermal environment motivates the consideration of a novel ‘parameterized’ optimization approach that simultaneously calculates whole families of optimal designs based on changes in design or operational variables generally beyond the control of the designer. The change in Pareto-optimal response with evolution in operating conditions is clearly demonstrated.

  3. Effects of gamma irradiations on reactive pulsed laser deposited vanadium dioxide thin films

    Science.gov (United States)

    Madiba, I. G.; Émond, N.; Chaker, M.; Thema, F. T.; Tadadjeu, S. I.; Muller, U.; Zolliker, P.; Braun, A.; Kotsedi, L.; Maaza, M.

    2017-07-01

    Vanadium oxide films are considered suitable coatings for various applications such as thermal protective coating of small spacecrafts because of their thermochromic properties. While in outer space, such coating will be exposed to cosmic radiations which include γ-rays. To study the effect of these γ-rays on the coating properties, we have deposited vanadium dioxide (VO2) films on silicon substrates and subjected them to extensive γ-irradiations with typical doses encountered in space missions. The prevalent crystallographic phase after irradiation remains the monoclinic VO2 phase but the films preferential orientation shifts to lower angles due to the presence of disordered regions caused by radiations. Raman spectroscopy measurements also evidences that the VO2 structure is slightly affected by gamma irradiation. Indeed, increasing the gamma rays dose locally alters the crystalline and electronic structures of the films by modifying the V-V inter-dimer distance, which in turns favours the presence of the VO2 metallic phase. From the XPS measurements of V2p and O1s core level spectra, an oxidation of vanadium from V4+ towards V5+ is revealed. The data also reveal a hydroxylation upon irradiation which is corroborated by the vanishing of a low oxidation state peak near the Fermi energy in the valence band. Our observations suggest that gamma radiations induce the formation of Frenkel pairs. Moreover, THz transmission measurements show that the long range structure of VO2 remains intact after irradiation whilst the electrical measurements evidence that the coating resistivity decreases with gamma irradiation and that their transition temperature is slightly reduced for high gamma ray doses. Even though gamma rays are only one of the sources of radiations that are encountered in space environment, these results are very promising with regards to the potential of integration of such VO2 films as a protective coating for spacecrafts.

  4. Spin Forming Aluminum Crew Module (CM) Metallic Aft Pressure Vessel Bulkhead (APVBH) - Phase II

    Science.gov (United States)

    Hoffman, Eric K.; Domack, Marcia S.; Torres, Pablo D.; McGill, Preston B.; Tayon, Wesley A.; Bennett, Jay E.; Murphy, Joseph T.

    2015-01-01

    The principal focus of this project was to assist the Multi-Purpose Crew Vehicle (MPCV) Program in developing a spin forming fabrication process for manufacture of the Orion crew module (CM) aft pressure vessel bulkhead. The spin forming process will enable a single piece aluminum (Al) alloy 2219 aft bulkhead resulting in the elimination of the current multiple piece welded construction, simplify CM fabrication, and lead to an enhanced design. Phase I (NASA TM-2014-218163 (1)) of this assessment explored spin forming the single-piece CM forward pressure vessel bulkhead. The Orion MPCV Program and Lockheed Martin (LM) recently made two critical decisions relative to the NESC Phase I work scope: (1) LM selected the spin forming process to manufacture a single-piece aft bulkhead for the Orion CM, and (2) the aft bulkhead will be manufactured from Al 2219. Based on the Program's new emphasis related to the spin forming process, the NESC was asked to conduct a Phase II assessment to assist in the LM manufacture of the aft bulkhead and to conduct a feasibility study into spin forming the Orion CM cone. This activity was approved on June 19, 2013. Dr. Robert Piascik, NASA Technical Fellow for Materials at the Langley Research Center (LaRC), was selected to lead this assessment. The project plan was approved by the NASA Engineering and Safety Center (NESC) Review Board (NRB) on July 18, 2013. The primary stakeholders for this assessment were the NASA and LM MPCV Program offices. Additional benefactors are commercial launch providers developing CM concepts.

  5. Metal-biradical chains from a high-spin ligand and bis(hexafluoroacetylacetonato)copper(II).

    Science.gov (United States)

    Rajadurai, Chandrasekar; Enkelmann, Volker; Ikorskii, Vladimir; Ovcharenko, Victor I; Baumgarten, Martin

    2006-11-27

    The synthesis, X-ray crystal structure, and magnetic studies of a rare example of organic/inorganic spin hybrid clusters extended in infinite ladder-type chain [Cu(C5F6HO2)2]7(C35H35N5O4)2 ([Cu(hfac)2]7(pyacbisNN)2, 2) formed by the reaction of a high spin nitronylnitroxide biradical C35H35N5O4 (pyacbisNN, 1) and bis(hexafluroacetylacetonate)copper(II) = Cu(hfac)2 are described. Single-crystal X-ray structure analysis revealed the triclinic P1 space group of 2 with the following parameters: a = 10.6191(4) A, b = 19.6384(7) A, c = 21.941(9) A, alpha = 107.111(7) degrees, beta = 95.107(8) degrees, gamma = 94.208(0) degrees , Z = 2. Each repeating unit in 2 carries a centrosymmetric cyclic six spin and a linear five spin cluster with four different copper coordination environments having octahedral and square planar geometries. These clusters are interconnected to form infinite chains which are running along the crystallographic b axis. The magnetic measurements show nearly paramagnetic behavior with very small variations over a large temperature range. The magnetic properties are thus result of complex competitions of many weak ferro- and antiferromagnetic interactions, which appear as small deviations from quite linear mu(eff) vs T dependence at low temperature. At high temperature (300-14 K), antiferromagnetic behavior dominates a little, while at very low temperature (14-2 K), a small increase of mu(eff) was observed. The magnetic susceptibility data are described by the Curie-Weiss law [chi = C/(T - theta)] with the optimal parameters C = 4.32 +/- 0.01 emuK/mol and theta = - 0.6 +/- 0.3 K, where C is the Curie constant and theta is the Weiss temperature.

  6. Four Mixed-Ligand Zn(II Three-Dimensional Metal-Organic Frameworks: Synthesis, Structural Diversity, and Photoluminescent Property

    Directory of Open Access Journals (Sweden)

    Chih-Chieh Wang

    2017-11-01

    Full Text Available Assemblies of four three-dimensional (3D mixed-ligand coordination polymers (CPs having formulas, {[Zn2(bdc2(4-bpdh]·C2H5OH·2H2O}n (1, [Zn(bdc(4-bpdh]n (2, {[Zn2(bdc2(4-bpdh2]·(4-bpdh}n (3, and {[Zn(bdc(4-bpdh]·C2H5OH}n (4 (bdc2− = dianion of 1,4-benzenedicarboxylic acid, 4-bpdh = 2,5-bis(4-pyridyl-3,4-diaza-2,4-hexadiene have been synthesized and structurally characterized by single-crystal X-ray diffraction method. Structural determination reveals that the coordination numbers (geometry of Zn(II ions in 1, 2, 3, and 4 are five (distorted square-pyramidal (SP, six (distorted octahedral (Oh, five (trigonal-bipyramidal (TBP, and four (tetrahedral (Td, respectively, and are bridged by 4-bpdh with bis-monodentate coordination mode and bdc2− ligands with bis-bidentate in 1, chelating/bidentate in 2, bis-monodentate and bis-bidentate in 3, and bis-monodentate in 4, to generate two-fold interpenetrating 3D cube-like metal-organic framework (MOF with pcu topology, non-interpenetrating 3D MOF, two-fold interpenetrating 3D rectangular-box-like MOF with pcu topology and five-fold interpenetrating diamondoid-like MOF with dia topology, respectively. These different intriguing architectures indicate that the coordination numbers and geometries of Zn(II ions, coordination modes of bdc2− ligand, and guest molecules play important roles in the construction of MOFs and the formation of the structural topologies and interpenetrations. Thermal stabilities, and photoluminescence study of 1–4 were also studied in detail. The complexes exhibit ligands based photoluminescence properties at room temperature.

  7. Investigation of iron(III) reduction and trace metal interferences in the determination of dissolved iron in seawater using flow injection with luminol chemiluminescence detection

    Energy Technology Data Exchange (ETDEWEB)

    Ussher, Simon J. [School of Earth, Ocean and Environmental Sciences (SEOES), University of Plymouth, Drake Circus, Plymouth PL4 8AA (United Kingdom); Milne, Angela [School of Earth, Ocean and Environmental Sciences (SEOES), University of Plymouth, Drake Circus, Plymouth PL4 8AA (United Kingdom); Department of Oceanography, Florida State University, Tallahassee, FL 32306-4320 (United States); Landing, William M. [Department of Oceanography, Florida State University, Tallahassee, FL 32306-4320 (United States); Attiq-ur-Rehman, Kakar [Department of Chemistry, University of Balochistan, Quetta (Pakistan); Seguret, Marie J.M.; Holland, Toby [School of Earth, Ocean and Environmental Sciences (SEOES), University of Plymouth, Drake Circus, Plymouth PL4 8AA (United Kingdom); Achterberg, Eric P. [National Oceanography Centre, University of Southampton, European Way, Southampton SO14 3ZH (United Kingdom); Nabi, Abdul [Department of Chemistry, University of Balochistan, Quetta (Pakistan); Worsfold, Paul J., E-mail: pworsfold@plymouth.ac.uk [School of Earth, Ocean and Environmental Sciences (SEOES), University of Plymouth, Drake Circus, Plymouth PL4 8AA (United Kingdom)

    2009-10-12

    A detailed investigation into the performance of two flow injection-chemiluminescence (FI-CL) manifolds (with and without a preconcentration column) for the determination of sub-nanomolar dissolved iron (Fe(II) + Fe(III)), following the reduction of Fe(III) by sulphite, in seawater is described. Kinetic experiments were conducted to examine the efficiency of reduction of inorganic Fe(III) with sulphite under different conditions and a rigorous study of the potential interference caused by other transition metals present in seawater was conducted. Using 100 {mu}M concentrations of sulphite a reduction time of 4 h was sufficient to quantitatively reduce Fe(III) in seawater. Under optimal conditions, cobalt(II) and vanadium(IV)/(III) were the major positive interferences and strategies for their removal are reported. Specifically, cobalt(II) was masked by the addition of dimethylglyoxime to the luminol solution and vanadium(IV) was removed by passing the sample through an 8-hydroxyquinoline column in a low pH carrier stream. Manganese(II) also interfered by suppression of the CL response but this was not significant at typical open ocean concentrations.

  8. X-ray absorption of Azotobacter vinelandii vanadium nitrogenase

    Energy Technology Data Exchange (ETDEWEB)

    George, G.N.; Coyle, C.L.; Hales, B.J.; Cramer, S.P.

    1988-06-08

    Evidence for the existence of a vanadium-containing nitrogenase has existed for more than half a century, but progress in understanding this enzyme has only come recently. In 1980, Bishop and co-workers proposed that an alternative nitrogen-fixing enzyme exists in Azotobacter vinelandii and subsequently proposed that vanadium was involved. In 1986, Robson et al. demonstrated clearly that the alternate nitrogenase from Azotobacter chroococcum, Acl*, contained vanadium instead of molybdenum. Hales et al. have shown the vanadium is also found in the Azotobacter vinelandii alternative component I, Avl'. The molybdenum and vanadium nitrogenase proteins are similar in many respects. Like the molybdenum enzyme, both Acl* and Avl' exhibit an EPR spectrum characteristic of a species with an S = 3/2 ground state; Avl' also contains the so-called P-clusters. Additionally Acl* has recently been shown to possess an N-methylformamide soluble cofactor, FeVco, analogous to the well-known iron-molybdenum cofactor FeMoco. Arber et al. have reported X-ray absorption spectra for the Acl* enzyme and interpreted the EXAFS as evidence for a V-Fe-S cluster. The local vanadium structure is proposed to resemble a recently synthesized cubane-like VFe/sub 3/S/sub 4/ cluster, and analogies are drawn with the EXAFS-derived structure reported for the molybdenum nitrogenases. The authors report herein an X-ray absorption spectroscopic study of A. vinelandii vanadium nitrogenase, Avl', which supports and extends the work of Arber et al.

  9. Vanadium-Catalyzed Enantioselective Desymmetrization of meso-Secondary Allylic Alcohols and Homoallylic Alcohols

    OpenAIRE

    Li, Zhi; Zhang, Wei; Hisashi Yamamoto, H.

    2008-01-01

    Vanadium-catalyzed epoxidation has extended substrate scope. In addition to various bis-allylic alcohols, bis-homoallylic alcohols can also be desymmetrized using our Vanadium-Bis-hydroxamic acid complexes.

  10. Hydrated and Solvated Tin(II) Ions in Solution and the Solid State, and a Coordination Chemistry Overview of the d10s2Metal Ions.

    Science.gov (United States)

    Persson, Ingmar; D'Angelo, Paola; Lundberg, Daniel

    2016-12-19

    The coordination chemistry of d 10 s 2 metal ions is strongly affected by an (at least partially) occupied d 10 s 2 metal ion-ligand atom antibonding orbital, which may cause a void in the coordination sphere due to repulsion between the electrons in the antibonding orbital on the metal ion and those on the ligands. The character of the formed d 10 s 2 metal ion-ligand atom bond plays an important role in the electron density in the antibonding orbital and thereby also in the coordination chemistry. The hydrated tin(II) ion, [Sn(H 2 O) 3 ] 2+ , and the trihydroxidostannate ion, [Sn(OH) 3 ] - , have very different mean Sn-O bond lengths (2.21 and 2.08 Å, respectively) and O-Sn-O angles (ca. 78 and 90°, respectively) both in the solid state and in solution. On increasing the covalency of the tin(II)-ligand bonds, the repulsion decreases and higher coordination numbers are obtained, as seen in the dimethylsulfoxide- and N,N-dimethylthioformamide-solvated tin(II) ions, both of which are five-coordinate with square-pyramidal structures. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Second-Coordination-Sphere Assisted Selective Colorimetric Turn-on Fluoride Sensing by a Mono-Metallic Co(II) Hexacarboxamide Cryptand Complex.

    Science.gov (United States)

    Stauber, Julia M; Alliger, Glen E; Nocera, Daniel G; Cummins, Christopher C

    2017-07-17

    The preparation of a selective turn-on colorimetric fluoride sensor was achieved through single cobalt(II) ion insertion into a macrobicyclic cryptand. Monometallic [Co(mBDCA-5t-H3)]- (1) and [Zn(mBDCA-5t-H3)]- (2) complexes were prepared in 74 and 84% yields, respectively. Structural characterization of 1 confirmed the presence of a proximal hydrogen-bonding network consisting of carboxamide N-H donors. The reaction of 1 with F- was accompanied by a distinct colorimetric turn-on response in mixed aqueous/organic media, and 1 was capable of selective fluoride sensing in the presence of large quantities of potentially competitive anions. Complex 1 represents a unique example of a fluoride sensor wherein selective F- binding takes place directly at a transition-metal center and induces a color change based upon metal-centered transitions. The metal(II) fluoride complexes [F⊂Co(mBDCA-5t-H3)]2- (3) and [F⊂Zn(mBDCA-5t-H3)]2- (4) were both fully characterized, including single crystal X-ray analyses. Fluoride binding is synergistic involving hydrogen-bond donors from the second-coordination sphere together with metal(II) ion complexation.

  12. Optical and electrochemical characteristics of ethylenediamine complexes of Pt(II) and Ir(III) with metalated 2-phenyl- and 2-naphthylbenzothiazole

    Science.gov (United States)

    Katlenok, E. A.; Balashev, K. P.

    2016-05-01

    The cyclometalated complexes [Pt(C^N)En]PF6 and [Ir(C^N)2En]PF6 ((C^N)- are deprotonated forms of 2-phenylbenzothiazole or 2-naphthylbenzothiazole and En is ethylenediamine) are studied by 1H NMR, IR, electronic absorption, and emission spectroscopy, as well as by voltammetry. Metalation of heterocyclic ligands leads to the formation of five-membered {M(C^N)} cycles in the composition of squareplanar Pt(II) complexes and octahedral Ir(III) complexes of the cis-C,C structure. A bathochromic shift of the metal-to-cyclometalated ligand charge transfer bands and a decrease in the potential difference between the single-electron waves of metal-centered oxidation and ligand-centered reduction of complexes upon substitution of 2-phenylbenzothiazole by 2-naphthylbenzothiazole and of Pt(II) by Ir(II) are shown. The phosphorescence of complexes in the visible region is assigned to the radiative transition from the metal-modified intraligand electronic excited state.

  13. A Cd(II)-based metal-organic framework as a luminance sensor to nitrobenzene and Tb(III) ion.

    Science.gov (United States)

    Qu, Xiang-Long; Gui, Di; Zheng, Xiao-Li; Li, Rui; Han, Hong-Liang; Li, Xia; Li, Pei-Zhou

    2016-04-28

    A Cd(II)-based metal-organic framework, [Cd2(DPDC)2(BTB)]∞ (Cd-MOF, DPDC = 2,2'-diphenyldicarboxylate and BTB = 1,4-bis(1,2,4-triazol-1-yl)butane) was successfully constructed via a hydrothermal reaction. Structural analysis shows that the synthesized Cd-MOF is a three-dimensional (3D) architecture crystallized in the hexagonal system with a chiral space group P61. Powder X-ray diffraction experiments and thermogravimetric analysis reveal that the constructed Cd-MOF has a high chemical and thermal stability. A study of additional mechanical properties indicates that it exhibits a moderate stiffness with the average values of Young's modulus (E) and H as 11.3(2) and 0.9(7) GPa, respectively. The luminescence properties of the Cd-MOF were further studied. The result shows that it could be an effective sensor to the organic nitrobenzene molecule via a strong quenching effect, and also to the inorganic Tb(III) ion by a strong green emission effect. Moreover, when loading bimetal ions (Eu(III) and Tb(III) into the Cd-MOF/methanol suspension, tunable visible luminescence can also be achieved by carefully adjusting the excitation wavelengths.

  14. Non-noble metal graphene oxide-copper (II) ions hybrid electrodes for electrocatalytic hydrogen evolution reaction

    KAUST Repository

    Muralikrishna, S.

    2015-08-25

    Non-noble metal and inexpensive graphene oxide-copper (II) ions (GO-Cu2+) hybrid catalysts have been explored for the hydrogen evolution reaction (HER). We were able to tune the binding abilities of GO toward the Cu2+ ions and hence their catalytic properties by altering the pH. We have utilized the oxygen functional moieties such as carboxylate, epoxide, and hydroxyl groups on the edge and basal planes of the GO for binding the Cu2+ ions through dative bonds. The GO-Cu2+ hybrid materials were characterized by cyclic voltammetry in sodium acetate buffer solution. The morphology of the hybrid GO-Cu2+ was characterized by atomic force microscopy. The GO-Cu2+ hybrid electrodes show good electrocatalytic activity for HER with low overpotential in acidic solution. The Tafel slope for the GO-Cu2+ hybrid electrode implies that the primary discharge step is the rate determining step and HER proceed with Volmer step. © 2015 American Institute of Chemical Engineers Environ Prog.

  15. The crystal structure of a class II fructose-1,6-bisphosphate aldolase shows a novel binuclear metal-binding active site embedded in a familiar fold.

    Science.gov (United States)

    Cooper, S J; Leonard, G A; McSweeney, S M; Thompson, A W; Naismith, J H; Qamar, S; Plater, A; Berry, A; Hunter, W N

    1996-11-15

    [corrected] Aldolases catalyze a variety of condensation and cleavage reactions, with exquisite control on the stereochemistry. These enzymes, therefore, are attractive catalysts for synthetic chemistry. There are two classes of aldolase: class I aldolases utilize Schiff base formation with an active-site lysine whilst class II enzymes require a divalent metal ion, in particular zinc. Fructose-1,6-bisphosphate aldolase (FBP-aldolase) is used in gluconeogenesis and glycolysis; the enzyme controls the condensation of dihydroxyacetone phosphate with glyceraldehyde-3-phosphate to yield fructose-1,6-bisphosphate. Structures are available for class I FBP-aldolases but there is a paucity of detail on the class II enzymes. Characterization is sought to enable a dissection of structure/activity relationships which may assist the construction of designed aldolases for use as biocatalysts in synthetic chemistry. The structure of the dimeric class II FBP-aldolase from Escherichia coli has been determined using data to 2.5 A resolution. The asymmetric unit is one subunit which presents a familiar fold, the (alpha/beta)8 barrel. The active centre, at the C-terminal end of the barrel, contains a novel bimetallic-binding site with two metal ions 6.2 A apart. One ion, the identity of which is not certain, is buried and may play a structural or activating role. The other metal ion is zinc and is positioned at the surface of the barrel to participate in catalysis. Comparison of the structure with a class II fuculose aldolase suggests that these enzymes may share a common mechanism. Nevertheless, the class II enzymes should be subdivided into two categories on consideration of subunit size and fold, quaternary structure and metal-ion binding sites.

  16. Vanadium uptake by biomass of Coprinus comatus and their effect on hyperglycemic mice.

    Science.gov (United States)

    Han, Chunchao; Cui, Bo; Wang, Yingzi

    2008-07-01

    The Vanadium uptake by Coprinus comatus and their co-effect on hyperglycemic mice were studied. By fermentation and AAS analysis, the optimal concentration of vanadium in medium was 0.4%, and the content of vanadium accumulated in the mycelia was 3,528.0 microg/g. At the concentration of 0.4%, the vanadium-associated toxicity was reduced, and its anti-diabetic effects were maintained.

  17. A Novel Eco-Friendly Vanadium Precipitation Method by Hydrothermal Hydrogen Reduction Technology

    OpenAIRE

    Guobin Zhang; Yimin Zhang; Shenxu Bao; Jing Huang; Liuhong Zhang

    2017-01-01

    In view of the serious pollution problems caused by the traditional vanadium precipitation process, the eco-friendly technology of hydrothermal hydrogen reduction was first applied to precipitate phase pure vanadium sesquioxide (V2O3) products from stripped pentavalent vanadium (V (V)) solution extracted from vanadium-bearing shale. Thermodynamic analysis demonstrate the method of hydrothermal hydrogen reduction is feasible for precipitating V2O3 from V (V) solution at a suitable pH range, an...

  18. Synthesis and Exploratory Catalysis of 3d Metals: Group-Transfer Reactions, and the Activation and Functionalization of Small Molecules Including Greenhouse Gases

    Energy Technology Data Exchange (ETDEWEB)

    Mindiola, Daniel J.

    2014-05-07

    Our work over the past three years has resulted in the development of electron rich and low-coordinate vanadium fragments, molecular nitrides of vanadium and parent imide systems of titanium, and the synthesis of phosphorus containing molecules of the 3d transition metal series. Likewise, with financial support from BES Division in DOE (DE-FG02-07ER15893), we now completed the full characterization of the first single molecular magnet (SMM) of Fe(III). We demonstrated that this monomeric form of Fe(III) has an unusual slow relaxation of the magnetization under zero applied field. To make matters more interesting, this system also undergoes a rare example of an intermediate to high-spin transition (an S = 3/2 to S = 5/2 transition). In 2010 we reported the synthesis of the first neutral and low-coordinate vanadium complexes having the terminal nitride functionality. We have now completed a full study to understand formation of the nitride ligand from the metastable azide precursor, and have also explored the reactivity of the nitride ligand in the context of incomplete and complete N-atom transfer. During the 2010-2013 period we also discovered a facile approach to assemble low-coordinate and low-valent vanadium(II) complexes and exploit their multielectron chemistry ranging from 1-3 electrons. Consequently, we can now access 3d ligand frameworks such as cyclo-P3 (and its corresponding radical anion), nitride radical anions and cations, low-coordinate vanadium oxo’s, and the first example of a vanadium thionitrosyl complex. A cis-divacant iron(IV) imido having some ligand centered radical has been also discovered, and we are in the process of elucidating its electronic structure (in particular the sign of zero field splitting and the origin of its magnitude), bonding and reactivity. We have also revisited some paramagnetic and classic metallocene compounds with S >1/2 ground states in order to understand their reactivity patterns and electronic structure. Lastly

  19. Synthesis and DNA binding studies of Ni(II), Co(II), Cu(II) and Zn(II) metal complexes of N 1,N 5-bis[pyridine-2-methylene]-thiocarbohydrazone Schiff-base ligand

    Science.gov (United States)

    Tiwari, A. D.; Mishra, A. K.; Mishra, S. B.; Mamba, B. B.; Maji, B.; Bhattacharya, S.

    2011-09-01

    The thiocarbohydrazone Schiff-base ligand with a nitrogen and sulphur donor was synthesized through condensation of pyridine-2-carbaldehyde and thiocarbohydrazide. Schiff-base ligands have the ability to conjugate with metal salts. A series of metal complexes with a general formula [MCl 2(H 2L)]· nH 2O (M dbnd Ni, Co, Cu and Zn) were synthesized by forming complexes of the N 1,N 5-bis[pyridine-2-methylene]-thiocarbohydrazone (H 2L) Schiff-base ligand. These metal complexes and ligand were characterized by using ultraviolet-visible (UV-Vis), Fourier Transform Infrared (FT-IR), 1H and 13C NMR spectroscopy and mass spectroscopy, physicochemical characterization, CHNS and conductivity. The biological activity of the synthesized ligand was investigated by using Escherichia coli DNA as target. The DNA interaction of the synthesized ligand and complexes on E. coli plasmid DNA was investigated in the aqueous medium by UV-Vis spectroscopy and the binding constant ( Kb) was calculated. The DNA binding studies showed that the metal complexes had an improved interaction due to trans-geometrical isomers of the complexes than ligand isomers in cis-positions.

  20. Metal-complexes as ligands to generate asymmetric homo- and heterodinuclear M(A)(III)M(B)(II) species: a magneto-structural and spectroscopic comparison of imidazole-N versus pyridine-N.

    Science.gov (United States)

    Biswas, Biplab; Salunke-Gawali, Sunita; Weyhermüller, Thomas; Bachler, Vinzenz; Bill, Eckhard; Chaudhuri, Phalguni

    2010-01-18

    Ten hetero- and homodinuclear M(A)(III)M(B)(III) complexes, 1-10, containing the metal centers Fe(III)Zn(II) (1), Fe(III)Cu(II) (2), Fe(III)Ni(II) (3), Fe(III)Fe(II) (4), Fe(III)Mn(II) (5), Cr(III)Ni(II) (6), Cr(III)Zn(II) (7), Ga(III)Ni(II) (8), Co(III)Fe(II) (9), and Mn(III)Mn(II) (10) are described. The tridentate ligation property of the divalent metal complexes tris(1-methylimidazole-2-aldoximato)metal(II) with three facially disposed pendent oxime O-atoms has been utilized to generate the said complexes. Complexes were characterized by various physical methods including MS, IR, UV-vis, Mossbauer and EPR spectroscopy, cyclic voltammetry (CV), variable-temperature (2-290 K) magnetic susceptibility, and X-ray diffraction techniques. Binuclear complexes 1-10 contain three oximato anions as bridging ligands and are isostructural in the sense that they all contain a metal(III) ion, LM(A)(III) (L = 1,4,7-trimethyl-1,4,7-triazacyclononane), in a distorted octahedral environment M(A)(III)N(3)O(3) and a second six-coordinated divalent metal ion, M(B)(II), in a trigonally distorted M(B)(II)N(6) geometry. A comparison of the cyclic voltammograms of the complexes with those of similar systems reveal both ligand-centered and metal-centered redox processes. Complexes 2, 3, 5, and 6 display antiferromagnetic exchange coupling of the neighboring metal centers in the order Fe(III)Mn(II) (5) III)Ni(II) (3) III)Cu(II) (2) whereas Fe(III)Ni(II) (3) > Cr(III)Ni(II) (6). On the contrary, complex 10, containing high-spin Mn(III) and Mn(II) centers, exhibits ferromagnetic coupling yielding a "high-spin" molecule with an S(t) = (9)/(2) ground state. X-band electron paramagnetic resonance (EPR) spectroscopy for 6, Cr(III)Ni(II) and 3, Fe(III)Ni(II) has been used to establish the electronic ground state in great detail and to complement the magnetic susceptibility measurements. Moreover, computational results have been included to compare the sigma-bonding character of the nitrogen lone

  1. A new sensitive electrochemical method for the determination of vanadium(IV) and vanadium(V) in Benfield sample.

    Science.gov (United States)

    Qureshi, Munawar Saeed; Mohd Yusoff, Abdull Rahim bin; Shah, Afzal; Nafady, Ayman; Sirajuddin

    2015-01-01

    Vanadium(IV) and vanadium(V) can be determined by using differential pulse cathodic stripping voltammetry technique (DPCSV). Cupferron (ammonium N-nitrosophenylhydroxylamine) was used as ligand to form complex compounds with vanadium ions in Britton-Robinson buffer (BRB) solution. At concentration lower than 1.0×10(-6) M, both V(IV) and V(V) cupferron complexes showed a single cathodic peak at -0.576 V in BRB of pH 4; thus V(IV) and V(V) ions cannot be differentiated at low concentration. However, the ionic species of vanadium can be differentiated at high concentration in the presence of cupferron. Parameters including pH of BRB solution, initial potential and accumulation potential were optimized. Under the optimized parameters, the limit of detection (LOD) was 0.09 nM, and the peak current was linear in the concentration range 0.01-0.9 µM total vanadium ions. The determination of V(IV) and V(V) ions was carried out at higher concentration in the sample using calibration plot method. At higher concentration range of 10-60 µM V(IV) and V(V) ions were determined with LOD of 1.2 and 1.1 µM, respectively. The developed method was successfully applied to 10,00,000 fold diluted Benfield sample and 0.6227 M total vanadium ions were determined. The determination of V(IV) and V(V) ions were also successfully carried out in artificial sample as well as Benfield sample (dilution factor, 10,000). The concentration of V(IV) and V(V) ions was 22.52 µM and 38.91 µM, respectively, giving total vanadium concentration of 0.6143 M in Benfield sample. Copyright © 2014 Elsevier B.V. All rights reserved.

  2. Stabilization of heavy metals on spent fluid catalytic cracking catalyst using marine clay.

    Science.gov (United States)

    Sun, D D; Tay, J H; Qian, C E; Lai, D

    2001-01-01

    Spent fluid catalytic cracking catalyst is a hazardous solid waste generated by petroleum refineries containing vanadium and nickel. The marine clay was used as a matrix to stabilize vanadium and nickel and produce bricks which were then fired at various temperatures. TCLP leaching tests indicated that stabilizing brick had low metal leaching, with a maximum of 6.4 mg/l for vanadium and 19.8 microg/l for nickel. Compressive strength of stabilizing brick was found to range between 20 N/mm2 and 47 N/mm2. It is believed that stabilization and encapsulation mechanisms are responsible for the stabilization of vanadium and nickel. Encapsulation is a process whereby the marine clay matrix forms a physical barrier around the heavy metals which are thus prevented from leaching out into the environment. Incorporation involves the formation of bonds between the marine clay matrix and the heavy metals which thus become incorporated in the clay microstructure.

  3. Gastroprotective effect of vanadium in rats - the roles of gastric acid ...

    African Journals Online (AJOL)

    Vanadium (various forms) has been proven to be beneficial in the treatment of certain diseases, especially diabetes. Reports have it that vanadium may protect the stomach from gastric ulcerogens such as ethanol and acid. This study was designed to investigate the probable mechanism Vanadium exerts its' ...

  4. Method for Vanadium Speciation in Aqueous Samples by HPLC-ICP ...

    African Journals Online (AJOL)

    Method for Vanadium Speciation in Aqueous Samples by HPLC-ICP-OES. M Hu, PP Coetzee. Abstract. A method for vanadium speciation is proposed. The method uses a low concentration eluent, 10 mmol L–1 EDTA and 14 mmol L–1 sodium carbonate, for the ion chromatographic separation of vanadium species at a ...

  5. Method for Vanadium Speciation in Aqueous Samples by HPLC-ICP ...

    African Journals Online (AJOL)

    NJD

    methods can only measure the total concentration of vanadium, or one of the two vanadium species, particularly V(V).4–6 Some two-step methods for the determination of the two vanadium species7–10 have been proposed by several groups. These methods normally measure one of the two species in one step, and in the.

  6. Chemistry, spectroscopy and the role of supported vanadium oxides in heterogeneous catalysis

    NARCIS (Netherlands)

    Weckhuysen, B.M.; Keller, D.E.

    2003-01-01

    Supported vanadium oxide catalysts are active in a wide range of applications. In this review, an overview is given of the current knowledge available about vanadium oxide-based catalysts. The review starts with the importance of vanadium in heterogeneous catalysis, a discussion of the molecular

  7. Vanadium Extraction from Refractory Stone Coal Using Novel Composite Additive

    Science.gov (United States)

    Cai, Z. L.; Zhang, Y. M.; Liu, T.; Huang, J.

    2015-11-01

    Based on the novel composite additive BaCO3/CaO for the vanadium extraction from the refractory stone coal, the vanadium leaching effect has been investigated and many technical conditions have also been optimized. The results indicated that an optimum vanadium leaching efficiency of 81.07% can be obtained under the conditions that the mass ratio of BaCO3 to CaO was 1:9 with the total proportion of the raw ore was 5 wt.%, the roasting temperature was 850°C, the roasting time was 2 h, the sulfuric acid concentration was 15% (v/v), the leaching temperature was 95°C, the liquid-to-solid ratio was 4 mL/g, and the leaching time was 3 h. Meanwhile, the vanadium leaching mechanisms demonstrated that the composite additive BaCO3/CaO can destroy the lattice structure of muscovite and phlogopite with the production of BaSi4O9 and Ca2Al2SiO7 during the roasting process, which can therefore facilitate the release and extraction of vanadium.

  8. Imaging of Vanadium in Microfossils: A New Potential Biosignature

    Science.gov (United States)

    Marshall, Craig P.; Marshall, Alison Olcott; Aitken, Jade B.; Lai, Barry; Vogt, Stefan; Breuer, Pierre; Steemans, Philippe; Lay, Peter A.

    2017-11-01

    The inability to unambiguously distinguish the biogenicity of microfossil-like structures in the ancient rock record is a fundamental predicament facing Archean paleobiologists and astrobiologists. Therefore, novel methods for discriminating biological from nonbiological chemistries of microfossil-like structures are of the utmost importance in the search for evidence of early life on Earth. This, too, is important for the search for life on Mars by in situ analyses via rovers or sample return missions for future analysis here on Earth. Here, we report the application of synchrotron X-ray fluorescence imaging of vanadium, within thermally altered organic-walled microfossils of bona fide biological origin. From our data, we demonstrate that vanadium is present within microfossils of undisputable biological origin. It is well known in the organic geochemistry literature that elements such as vanadium are enriched and contained within crude oils, asphalts, and black shales that have been formed by diagenesis of biological organic material. It has been demonstrated that the origin of vanadium is due to the diagenetic alteration of precursor chlorophyll and heme porphyrin pigment compounds from living organisms. We propose that, taken together, microfossil-like morphology, carbonaceous composition, and the presence of vanadium could be used in tandem as a biosignature to ascertain the biogenicity of putative microfossil-like structures.

  9. Simultaneous microbial reduction of vanadium (V) and chromium (VI) by Shewanella loihica PV-4.

    Science.gov (United States)

    Wang, Guangyu; Zhang, Baogang; Li, Shuang; Yang, Meng; Yin, Changcheng

    2017-03-01

    Toxic vanadium (V) and chromium (VI) often co-exist in wastewater from vanadium ore smelting and their reductions by bacterial strain Shewanella loihica PV-4 is realized simultaneously. After 27-d operation, 71.3% of V(V) and 91.2% of Cr(VI) were removed respectively, with citrate as organic carbon source. Enhancement of Cr(VI) bioreduction was observed with the suppressed V(V) reduction. V(IV) and Cr(III), the main reduction products, precipitated inside the organisms and attached on cell surfaces. Both membrane components containing cytochrome c and cytoplasmic fractions containing soluble proteins as well as NADH may contribute to these microbial reductions. Most Cr(VI) were reduced extracellularly and V(V) tended to be reduced through intracellular process, as revealed by mapping the microbial surface and a line scan across the cell, performed by scanning transmission electron microscopy. This study provides an efficient alternative for controlling combined pollution caused by these two metals based on microbial technology. Copyright © 2016 Elsevier Ltd. All rights reserved.

  10. Influence of doping on the properties of vanadium oxide gel films

    Energy Technology Data Exchange (ETDEWEB)

    Pergament, A L; Velichko, A A; Berezina, O Ya; Kazakova, E L; Kuldin, N A; Artyukhin, D V [Physics and Technology Department, Petrozavodsk State University, Petrozavodsk 185910 (Russian Federation)], E-mail: aperg@psu.karelia.ru

    2008-10-22

    The effect of doping with H and W on the properties of V{sub 2}O{sub 5} and VO{sub 2} derived from V{sub 2}O{sub 5} gel has been studied. It is shown that the treatment of V{sub 2}O{sub 5} in low-temperature RF hydrogen plasma for 1-10 min leads to either hydration of vanadium pentoxide or its reduction (depending on the treatment conditions) to lower vanadium oxides. For some samples, which are subject to plasma treatment in the discharge active zone, a non-ordinary temperature dependence of resistance, with a maximum at T{approx}100 K, is observed. For W-doped VO{sub 2} films, it is shown that substitution of V{sup 4+} with W{sup 6+} results in a decrease of the temperature of the metal-insulator transition. Also, it has been shown that the doping of initial films with {approx}3 at.% of W reduces the statistical scatter in the threshold parameters of the switching devices with S-shaped I-V characteristics on the basis of V{sub 2}O{sub 5} gel films. (fast track communication)

  11. Membrane development for vanadium redox flow batteries.

    Science.gov (United States)

    Schwenzer, Birgit; Zhang, Jianlu; Kim, Soowhan; Li, Liyu; Liu, Jun; Yang, Zhenguo

    2011-10-17

    Large-scale energy storage has become the main bottleneck for increasing the percentage of renewable energy in our electricity grids. Redox flow batteries are considered to be among the best options for electricity storage in the megawatt range and large demonstration systems have already been installed. Although the full technological potential of these systems has not been reached yet, currently the main problem hindering more widespread commercialization is the high cost of redox flow batteries. Nafion, as the preferred membrane material, is responsible for about 11% of the overall cost of a 1 MW/8 MWh system. Therefore, in recent years two main membrane related research threads have emerged: 1) chemical and physical modification of Nafion membranes to optimize their properties with regard to vanadium redox flow battery (VRFB) application; and 2) replacement of the Nafion membranes with different, less expensive materials. This review summarizes the underlying basic scientific issues associated with membrane use in VRFBs and presents an overview of membrane-related research approaches aimed at improving the efficiency of VRFBs and making the technology cost-competitive. Promising research strategies and materials are identified and suggestions are provided on how materials issues could be overcome.

  12. Kinetics and mechanism for reversible chloride transfer between mercury(II) and square-planar platinum(II) chloro ammine, aqua, and sulfoxide complexes. Stabilities, spectra, and reactivities of transient metal-metal bonded platinum-mercury adducts.

    Science.gov (United States)

    Gröning, O; Sargeson, A M; Deeth, R J; Elding, L I

    2000-09-18

    The Hg2+aq- and HgCl+aq-assisted aquations of [PtCl4]2- (1), [PtCl3(H2O)]- (2), cis-[PtCl2(H2O)2] (3), trans-[PtCl2(H2O)2] (4), [PtCl(H2O)3]+ (5), [PtCl3Me2SO]- (6), trans-[PtCl2(H2O)Me2SO] (7), cis-[PtCl(H2O)2Me2SO]+ (8), trans-[PtCl(H2O)2M32SO]+ (9), trans-[PtCl2(NH3)2] (10), and cis-[PtCl2(NH3)2] (11) have been studied at 25.0 degrees C in a 1.00 M HClO4 medium buffered with chloride, using stopped-flow and conventional spectrophotometry. Saturation kinetics and instantaneous, large UV/vis spectral changes on mixing solutions of platinum complex and mercury are ascribed to formation of transient adducts between Hg2+ and several of the platinum complexes. Depending on the limiting rate constants, these adducts are observed for a few milliseconds to a few minutes. Thermodynamic and kinetics data together with the UV/vis spectral changes and DFT calculations indicate that their structures are characterized by axial coordination of Hg to Pt with remarkably short metal-metal bonds. Stability constants for the Hg2+ adducts with complexes 1-6, 10, and 11 are (2.1 +/- 0.4) x 10(4), (8 +/- 1) x 10(2), 94 +/- 6, 13 +/- 2, 5 +/- 2, 60 +/- 6, 387 +/- 2, and 190 +/- 3 M-1, respectively, whereas adduct formation with the sulfoxide complexes 7-9 is too weak to be observed. For analogous platinum(II) complexes, the stabilities of the Pt-Hg adducts increase in the order sulfoxide < aqua < ammine complex, reflecting a sensitivity to the pi-acid strength of the Pt ligands. Rate constants for chloride transfer from HgCl+ and HgCl2 to complexes 1-11 have been determined. Second-order rate constants for activation by Hg2+ are practically the same as those for activation by HgCl+ for each of the platinum complexes studied, yet resolved contributions for Hg2+ and HgCl+ reveal that the latter does not form dinuclear adducts of any significant stability. The overall experimental evidence is consistent with a mechanism in which the accumulated Pt(II)-Hg2+ adducts are not reactive

  13. A model approach to vanadium involvement in crude oils and their refining. Progress report

    Energy Technology Data Exchange (ETDEWEB)

    Christou, G.

    1994-04-01

    Heavy crude oils contain a large amount of metal impurities, primarily vanadium species. These comprise both vanadyl porphyrins and vanadyl non-porphyrins. During hydrotreating of crude oils (reaction with H{sub 2} over a supported Mo/S catalyst at 350-- 450{degrees}C) for upgrading to usable products the V impurities are converted to insoluble V sulfides which help poison the fixed-bed Mo catalyst. Very little is known about the chemistry occurring at a detailed level; basically, it is known that initial impurities are vanadyl (VO){sup 2+}, i.e., V{sup IV} species, and that during the refining processes they are reduced and sulfided into polymers, i.e., the metal is reduced from V{sup IV} to {approximately} V{sup III}, the oxo is lost, the organic ligation is lost, and the metal is sulfided. In what order and in precisely what manner this overall transformation is occurring is not known. The essence of our research efforts is to develop vanadium chemistry of relevance to this area and to thereby provide fundamental information on the transformations occurring and that might prove useful in catalyst design. Our work has encompassed the study of the reactivity chemistry of [VO]{sup 2+} species and the formation and characterization of V/S aggregates under conditions designed to mimic those present under hydrotreating conditions. Thus, we are applying an Inorganic Model Approach to provide insights into the chemistry occurring during the refining process. Our emphasis has been on definitive characterization of products using a variety of physical techniques,including X-ray crystallography. Our work covers the following areas, each of which is described: studies in V/O{sup 2+} chemistry; V{sup III}/O chemistry; V/S complexes; and absorption of [VO]{sup 2+} groups on catalyst surfaces.

  14. Graphite furnace atomic absorption spectrometric detection of vanadium in water and food samples after solid phase extraction on multiwalled carbon nanotubes.

    Science.gov (United States)

    Wadhwa, Sham Kumar; Tuzen, Mustafa; Gul Kazi, Tasneem; Soylak, Mustafa

    2013-11-15

    Vanadium(V) ions as 8-hydroxyquinoline chelates were loaded on multiwalled carbon nanotubes (MWNTs) in a mini chromatographic column. Vanadium was determined by graphite furnace atomic absorption spectrometry (GFAAS). Various analytical parameters including pH of the working solutions, amounts of 8-hydroxyquinoline, eluent type, sample volume, and flow rates were investigated. The effects of matrix ions and some transition metals were also studied. The column can be reused 250 times without any loss in its sorption properties. The preconcentration factor was found as 100. Detection limit (3 s) and limit of quantification (10 s) for the vanadium in the optimal conditions were observed to be 0.012 µg L(-1) and 0.040 μg L(-1), respectively. The capacity of adsorption was 9.6 mg g(-1). Relative standard deviation (RSD) was found to be 5%. The validation of the method was confirmed by using NIST SRM 1515 Apple leaves, NIST SRM 1570a Spinach leaves and GBW 07605 Tea certified reference materials. The procedure was applied to the determination of vanadium in tap water and bottled drinking water samples. The procedure was also successfully applied to microwave digested food samples including black tea, coffee, tomato, cabbage, zucchini, apple and chicken samples. Copyright © 2013 Elsevier B.V. All rights reserved.

  15. Synthesis and characterization of near-IR absorbing metal-free and zinc(II phthalocyanines modified with aromatic azo groups

    Directory of Open Access Journals (Sweden)

    Mukaddes Özçeşmeci

    2015-05-01

    Full Text Available Metal-free and zinc(II phthalocyanine complexes bearing peripheral (E-4-((2-hydroxynaphthalen-1-yldiazenyl units have been synthesized. Novel phthalonitrile derivative required for the preparation of phthalocyanine complexes was prepared by coupling 4-aminophthalonitrile and 2-naphthol. The structures of these new compounds were characterized by using elemental analyses, proton nuclear magnetic resonance, fourier transform infrared spectroscopy, ultraviolet–visible spectroscopy, fluorescence spectroscopy and mass spectrometry. In the UV-Vis spectra a broad absorption band appears for phthalocyanine complexes at around 450–500 nm resulting from azo-group introduced onto the phthalocyanine ring. The photophysical properties of metal-free and zinc(II phthalocyanines were studied in tetrahydrofuran.

  16. Heavy Metals in Soils and Tomatoes Grown in Urban Fringe ...

    African Journals Online (AJOL)

    user

    Heavy metals are ubiquitous in the environment, as a result of both natural and anthropogenic activities, and humans are exposed to them through various pathways. (Wilson and Pyatt, 2007). Heavy metals like iron, tin, copper, manganese and vanadium occur naturally in the environment and could serve as plant nutrients.

  17. Direct Acid Leaching of Vanadium from Stone Coal

    Science.gov (United States)

    Zhang, Bo; Gao, Zhaoguo; Liu, Hongzhao; Wang, Wei; Cao, Yaohua

    2017-09-01

    This paper focused on optimizing the process conditions of direct acid leaching process to enhance the leaching efficiency of leaching vanadium from the stone coal. Orthogonal experiments and single factor experiments were conducted to investigate the effect of the influential factors of direct acid leaching on vanadium leaching ratio. The results showed that the vanadium leaching ratio reached the maximum value of 89.22 % under the optimal process conditions of CaF2 dosage 5 mass%, H2SO4 dosage 40 mass%, leaching temperature 95 °C and leaching time 10 h. Furthermore, the reaction mechanisms of the main influencing factors were analyzed. Finally, the two-stage counter-current leaching process was adopted to decrease the consumption of sulfuric acid and neutralizer, and the results indicated that the consumption of sulfuric acid decreased 12.50 % as well as neutralizer decreased 35.80 %.

  18. Vanadium-modified molecular sieves: preparation, characterization and catalysis

    Directory of Open Access Journals (Sweden)

    Ângela A. Teixeira-Neto

    2009-01-01

    Full Text Available Vanadium-containing molecular sieves are redox catalysts and are good candidates as substitutes for oxide-supported V2O5 in a number of reactions. These materials have the advantage of presenting better dispersion of vanadium species, as well as shape-selective properties and controllable acidities. They may be prepared by one-pot synthesis or by post-synthesis methods and a number of techniques such as diffuse reflectance UV-visible spectroscopy, 51V nuclear magnetic resonance and electron paramagnetic resonance, to name but a few, have been used to characterize these materials. In this review, methods of preparation of vanadium-modified molecular sieves, their characterization and applications in catalysis are discussed.

  19. Nickel( ii ) and copper( i , ii )-based metal-organic frameworks incorporating an extended tris-pyrazolate linker

    Energy Technology Data Exchange (ETDEWEB)

    Tăbăcaru, Aurel [Scuola di Scienze del Farmaco e dei Prodotti della Salute; Università di Camerino; 62032 Camerino, Italy; Department of Chemistry; Physics and Environment; Galli, Simona [Dipartimento di Scienza e Alta Tecnologia; Università dell' Insubria; 22100 Como, Italy; Pettinari, Claudio [Scuola di Scienze del Farmaco e dei Prodotti della Salute; Università di Camerino; 62032 Camerino, Italy; Masciocchi, Norberto [Dipartimento di Scienza e Alta Tecnologia; Università dell' Insubria; 22100 Como, Italy; McDonald, Thomas M. [Department of Chemistry; University of California, Berkeley; , USA; Long, Jeffrey R. [Department of Chemistry; University of California, Berkeley; , USA; Materials Science Division; Lawrence Berkeley National Laboratory

    2015-01-01

    The synthesis, thermal behavior, crystal structure and adsorption properties of two novel MOFs isolated by coupling Ni(ii) and Cu(ii) to the extended tris(pyrazolate) strut 1,3,5-tris((1H-pyrazol-4-yl)phenyl)benzene are reported.

  20. Metal-free and dicopper(II) complexes of Schiff base [2 + 2] macrocycles derived from 2,2'-iminobisbenzaldehyde: syntheses, structures, and electrochemistry.

    Science.gov (United States)

    Cameron, Scott A; Brooker, Sally

    2011-04-18

    Three new bis-terdentate Schiff base [2 + 2] macrocycles (H(2)L(Et), H(2)L(Pr), and H(2)L(Bu)) have been prepared in high yields by 1:1 condensation of 2,2'-iminobisbenzaldehyde with 1,2-diaminoethane, 1,3-diaminopropane, and 1,4-diaminobutane, respectively. Metalation of these macrocycles yields the corresponding dicopper(II) acetate (1, 2, and 3) and tetrafluoroborate (4, 5, and 6) complexes. The structures of H(2)L(Et), H(2)L(Pr), H(2)L(Bu), [Cu(II)(2)L(i)(OAc)(2)]·solvents (where i is Et, Pr or Bu) and [Cu(II)(2)L(Pr)(DMF)(4)] (BF(4))(2)·0.5H(2)O are reported. Intramolecular hydrogen bonding is a feature of the metal-free macrocycles. The copper(II) centers in [Cu(II)(2)L(i)(OAc)(2)]·solvents are four coordinate, and the macrocycles have U-shaped (Et, Bu) or stepped (Pr) conformations. Complex 5 crystallizes with two dimethylformamide (DMF) molecules bound per five coordinate copper(II) center. Electrochemical studies revealed ligand based oxidations for all of the macrocycles and complexes. Complexes 1 and 2 undergo two quasi-reversible oxidations in DCM which are associated with the deposition of a visible film on the electrode after multiple scans in this oxidative region, suggestive of electropolymerization. Complexes 4-6, studied in MeCN, have Cu(II) → Cu(I) redox potentials at more positive potentials than for 1-3.

  1. Preparation and Antimicrobial Screeningof Cu (II, Ni (II, Zn (II Cd (II Complexes

    Directory of Open Access Journals (Sweden)

    R. M. Desai

    2006-01-01

    Full Text Available The metal complexes of Ni(II, Cu(II, Zn(II Cd(II with organic ligands viz Hydrazine hydrate, 1,2-N,N'-Bisammonium thiocarbamoyl ethane and 1,4-N,N'-Bisammonium thiocarbamoyl benzene have been prepared. These ligands and metal complexes of dithiocarbamates were screened for their antimicrobial activity against various microbs.

  2. Synthesis, crystal structures and luminescent properties of zinc(II) metal-organic frameworks constructed from terpyridyl derivative ligand

    Science.gov (United States)

    Yang, Xiao-Le; Shangguan, Yi-Qing; Hu, Huai-Ming; Xu, Bing; Wang, Bao-Cheng; Xie, Juan; Yuan, Fei; Yang, Meng-Lin; Dong, Fa-Xin; Xue, Gang-Lin

    2014-08-01

    Five zinc(II) metal-organic frameworks, [Zn3(344-pytpy)2Cl6]n·n(H2O) (1), [Zn(344-pytpy)(ox)]n (2), [Zn2(344-pytpy)(bdc)2]n·1.5n(H2O) (3), [Zn2(344-pytpy)2 (sfdb)2]n·1.5n(H2O) (4) and [Zn3(344-pytpy)2(btc)2]n·2n(H2O) (5), (344-pytpy=4‧-(3-pyridyl)-4,2‧:6‧,4″-terpyridine, H2ox=oxalic acid, H2bdc=1,4-benzenedi-carboxylic acid, H2sfdb=4,4‧-sulfonyldibenzoic acid and H3btc=1,3,5-benzene-tricarboxylic acid) have been prepared by hydrothermal reactions. Compound 1 is a 1D chain structure, in which 344-pytpy ligand links three ZnII centers through three of terminal N-donors. Compound 2 is a 4-connected 3D framework with the dia topological net and the Schläfli symbol of 66. Compound 3 displays a unusual 3-fold interpenetrating 3D coordination network which exhibits a new intriguing (3,3,4)-connected topological net with the Schläfli symbol of (4.82)(4.85)(83). Compound 4 features a two-fold interpenetrating 4-connected 2D framework with the sql topological net and the Schläfli symbol of (44.62). Compound 5 is a new self-interpenetrating (3,3,4,4)-connected topological net with the Schläfli symbol of (6.82)2(62.82.10.12)(62.83.10)2(62.8)2. The luminescence properties of 1-5 have been investigated by emission spectra and they possess great thermal stabilities which can be stable up to around 400 °C.

  3. Low-temperature solution-processed hydrogen molybdenum and vanadium bronzes for an efficient hole-transport layer in organic electronics.

    Science.gov (United States)

    Xie, Fengxian; Choy, Wallace C H; Wang, Chuandao; Li, Xinchen; Zhang, Shaoqing; Hou, Jianhui

    2013-04-11

    A simple one-step method is reported to synthesize low-temperature solution-processed transition metal oxides (TMOs) of molybdenum oxide and vanadium oxide with oxygen vacancies for a good hole-transport layer (HTL). The oxygen vacancy plays an essential role for TMOs when they are employed as HTLs: TMO films with excess oxygen are highly undesirable for their application in organic electronics. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Research and development on vanadium alloys for fusion applications

    Energy Technology Data Exchange (ETDEWEB)

    Zinkle, S.J.; Rowcliffe, A.F. [Oak Ridge National Lab., TN (United States); Matsui, H.; Abe, K. [Tohoku Univ. (Japan); Smith, D.L. [Argonne National Lab., IL (United States); Osch, E. van [NERF, Petten (Netherlands); Kazakov, V.A. [RIAR, Dimitrovgrad (Russian Federation)

    1998-03-01

    The current status of research and development on unirradiated and irradiated V-Cr-Ti alloys intended for fusion reactor structural applications is reviewed, with particular emphasis on the flow and fracture behavior of neutron-irradiated vanadium alloys. Recent progress on fabrication, joining, oxidation behavior, and the development of insulator coatings is also summarized. Fabrication of large (>500 kg) heats of V-4Cr-4Ti with properties similar to previous small laboratory heats has now been demonstrated. Impressive advances in the joining of thick sections of vanadium alloys using GTA and electron beam welds have been achieved in the past two years, although further improvements are still needed.

  5. Macromolecular peroxo complexes of Vanadium (V) and ...

    Indian Academy of Sciences (India)

    Macromolecular metal complexes; peroxovanadates; peroxomolybdates; enzyme inhibitors; polymer-supported metal catalysts; bromoperoxidases. ... activity with phosphohydrolase enzyme vis-à-vis free peroxovanadium (pV) or peroxomolybdenum (pMo) complexes, and their activity in biomimetic oxidative bromination ...

  6. Absorption of hydrogen in vanadium, enhanced by ion bombardment; Ionenbeschussunterstuetzte Absorption des Wasserstoffs in Vanadium

    Energy Technology Data Exchange (ETDEWEB)

    Paulus, H.; Lammers, M. [Inst. fuer Technologie- und Wissenstransfer, Soest (Germany); Mueller, K.H. [Inst. fuer Technologie- und Wissenstransfer, Soest (Germany)]|[Paderborn Univ. (Gesamthochschule), Soest (Germany). Fachbereich 16 - Elektrische Energietechnik; Kiss, G.; Kemeny, Z. [Technical Univ. Budapest (Hungary)

    1998-12-31

    Prior to hydrogen implantation into vanadium, the vanadium specimen usually is exposed to an activation process and is then heated at 1 atm hydrogen to temperatures between 500 and 600 C, subsequently cooled down in several steps. Within this temperature range, hydrogen solubility increases with declining temperature. A decisive factor determining hydrogen absorption is the fact that at temperatures above 250 C, oxygen desorbs from the material surface and thus no longer inhibits hydrogen absorption. Therefore a different approach was chosen for the experiments reported: Hydrogen absorption under UHV conditions at room temperature. After the usual activation process, the vanadium surface was cleaned by 5 keV Ar{sup +} ion bombardment. Thus oxygen absorption at the specimen surface (and new reactions with oxygen from the remaining gas) could be avoided, or removed. By means of thermal desorption mass spectrometry (TDMS), hydrogen absorption as a function of argon ion dose was analysed. TDMS measurements performed for specimens treated by ion bombardment prior to H{sup 2} exposure showed two H{sup 2} desorption peaks, in contrast to the profiles measured with specimens not exposed to ion bombardment. It is assumed that the ion bombardment disturbs the crystal structure so that further sites for hydrogen absorption are produced. (orig./CB) [Deutsch] Bei der Beladung von Vandium mit Wasserstoff wird ueblicherweise die Probe nach einer Aktivierungsprozedur bei 1 atm Wasserstoff auf Temperaturen im Bereich von 500 bis 600 C hochgeheizt und danach schrittweise abgekuehlt. In diesem Temperaturbereich nimmt die Wasserstoffloeslichkeit mit abnehmender Temperatur zu. Entscheidend fuer die Beladung ist aber auch die Tatsache, dass bei Temperaturen groesser 250 C Sauerstoff von der Oberflaeche desorbiert und dadurch die Absorption von Wasserstoff nicht mehr blockieren kann. Im Rahmen der hier beschriebenen Untersuchungen sollte die Wasserstoffbeladung unter UHV-Bedingungen bei

  7. Three-dimensional modeling of ionized gas. II. Spectral energy distributions of massive and very massive stars in stationary and time-dependent modeling of the ionization of metals in H II regions

    Science.gov (United States)

    Weber, J. A.; Pauldrach, A. W. A.; Hoffmann, T. L.

    2015-11-01

    Context. H II regions play a crucial role in the measurement of the chemical composition of the interstellar medium and provide fundamental data about element abundances that constrain models of galactic chemical evolution. Discrepancies that still exist between observed emission line strengths and those predicted by nebular models can be partly attributed to the spectral energy distributions (SEDs) of the sources of ionizing radiation used in the models as well as to simplifying assumptions made in nebular modeling. Aims: One of the main influences on the nebular spectra is the metallicity, both nebular and stellar, which shows large variations even among nearby galaxies. Although nebular modeling often involves testing of different nebular metallicities against their influence on the predicted spectra, adequate grids of stellar atmospheres and realistic SEDs for different metallicities are still lacking. This is unfortunate because the influence of stellar metallicity on nebular line strength ratios, via its effect on the SEDs, is of similar importance as variations in the nebular metallicity. To overcome this deficiency we have computed a grid of model atmosphere SEDs for massive and very massive O-type stars covering a range of metallicities from significantly subsolar (0.1 Z⊙) to supersolar (2 Z⊙). Methods: The SEDs have been computed using a state-of-the-art model atmosphere code that takes into account the attenuation of the ionizing flux by the spectral lines of all important elements and the hydrodynamics of the radiatively driven winds and their influence on the SEDs. For the assessment of the SEDs in nebular simulations we have developed a (heretofore not available) 3D radiative transfer code that includes a time-dependent treatment of the metal ionization. Results: Using the SEDs in both 1D and 3D nebular models we explore the relative influence of stellar metallicity, gas metallicity, and inhomogeneity of the gas on the nebular ionization structure

  8. Optimal Location of Vanadium in Muscovite and Its Geometrical and Electronic Properties by DFT Calculation

    Directory of Open Access Journals (Sweden)

    Qiushi Zheng

    2017-02-01

    Full Text Available Vanadium-bearing muscovite is the most valuable component of stone coal, which is a unique source of vanadium manufacture in China. Numbers of experimental studies have been carried out to destroy the carrier muscovite’s structure for efficient extraction of vanadium. Hence, the vanadium location is necessary for exploring the essence of vanadium extraction. Although most infer that vanadium may substitute for trivalent aluminium (Al as the isomorphism in muscovite for the similar atomic radius, there is not enough experimental evidence and theoretical supports to accurately locate the vanadium site in muscovite. In this study, the muscovite model and optimal location of vanadium were calculated by density functional theory (DFT. We find that the vanadium prefers to substitute for the hexa-coordinated aluminum of muscovite for less deformation and lower substitution energy. Furthermore, the local geometry and relative electronic properties were calculated in detail. The basal theoretical research of muscovite contained with vanadium are reported for the first time. It will make a further influence on the technology development of vanadium extraction from stone coal.

  9. Mathematical modeling of cadmium(II) solvent extraction from neutral and acidic chloride media using Cyanex 923 extractant as a metal carrier.

    Science.gov (United States)

    Leopold, A A; Coll, M T; Fortuny, A; Rathore, N S; Sastre, A M

    2010-10-15

    This paper describes experimental work and the mathematical modeling of solvent extraction of cadmium(II) from neutral and acidic aqueous chloride media with a Cyanex 923 extractant in Exxol D-100. Solvent extraction experiments were carried out to analyze the influence of variations in the composition of the aqueous and organic phases on the efficiency of cadmium(II) extraction. In neutral and acidic chloride conditions, the extraction of cadmium(II) by the organophosphorous extractant Cyanex 923 (L) is based on the solvation mechanism of neutral H(n)CdCl((2+n)) species and the formation of H(n)CdCl((2+n))L(q) complexes in the organic phase, where n=0, 1, 2 and q=1, 2. The mathematical model of cadmium(II) extraction was derived from the mass balances and chemical equilibria involved in the separation system. The model was computed with the Matlab software. The equilibrium parameters for metal extraction, i.e. the stability constants of the aqueous Cd-Cl complexes, the formation constants of the acidic Cd-Cl species and the metal equilibrium extraction constants, were proposed. The optimized constants were appropriate, as there was good agreement when the model was fitted to the experimental data for each of the experiments. 2010 Elsevier B.V. All rights reserved.

  10. Vanadium Recovery from Oil Fly Ash by Carbon Removal and Roast-Leach Process

    Science.gov (United States)

    Jung, Myungwon; Mishra, Brajendra

    2017-11-01

    This research mainly focuses on the recovery of vanadium from oil fly ash by carbon removal and the roast-leach process. The oil fly ash contained about 85% unburned carbon and 2.2% vanadium by weight. A vanadium-enriched product was obtained after carbon removal, and the vanadium content of this product was 19% by weight. Next, the vanadium-enriched product was roasted with sodium carbonate to convert vanadium oxides to water-soluble sodium metavanadate. The roasted sample was leached with water at 60°C, and the extraction percentage of vanadium was about 92% by weight. Several analytical techniques, such as inductively coupled plasma atomic emission spectroscopy (ICP-AES), x-ray fluorescence (XRF), and thermogravimetric and differential thermal analysis (TG-DTA), were utilized for sample analyses. Thermodynamic modeling was also conducted with HSC chemistry software to explain the experimental results.

  11. Comparison of vanadium-rich activity of three species fungi of basidiomycetes.

    Science.gov (United States)

    Han, Chunchao; Cui, Bo; Qu, Jingran

    2009-03-01

    A comparison of vanadium-rich activity of three species fungi of Basidiomycetes, Ganoderma lucidum, Coprinus comatus, and Grifola frondosa, was studied. By fermentation and atomic absorption spectroscopy analysis, the biomass of G. lucidum and G. frondosa declined rapidly when the concentration of vanadium exceeded 0.3% but the biomass of C. comatus did not decline rapidly until the concentration of vanadium exceeded 0.4% and the content of vanadium accumulated in the mycelia was 3529.3 microg/g. After the mice were administered (intragastrically) with vanadium-rich C. comatus, the blood glucose of alloxan-induced hyperglycemic mice was decreased (p comatus to absorb vanadium and chose 0.4% as the optimal concentration of vanadium for the pharmacological works.

  12. THE INFLUENCE OF NIOBIUM ON THE ACIDITY AND STRUCTURE OF GAMMA-ALUMINA-SUPPORTED VANADIUM OXIDES

    Directory of Open Access Journals (Sweden)

    Sathler M.N.B.

    1998-01-01

    Full Text Available Gamma-alumina-supported niobium oxide was used as a support for vanadium oxides. The influence of the addition of niobium oxide was studied by looking for changes in the structure and acid-base character of superficial species. Vanadium oxide was deposited using the continuous adsorption method; niobium oxide was impregnated using the incipient wetness method. The catalysts were characterized by XPS, UV-visible and IR spectroscopy. Catalytic tests were performed using propane oxidation reaction at 400oC. For coverage below the monolayer, both vanadium and niobium oxides were observed in slightly condensed superficial species. The presence of vanadium oxide on the support was found to increase the Lewis acidity and create some Bronsted acidity. Higher catalytic activity and selectivity for propene were associated with vanadium oxides. The presence of niobium did not contribute to the modification of the chemical properties of superficial vanadium but did decrease the adsorption of vanadium on the alumina.

  13. Vanadium Recovery from Oil Fly Ash by Carbon Removal and Roast-Leach Process

    Science.gov (United States)

    Jung, Myungwon; Mishra, Brajendra

    2018-02-01

    This research mainly focuses on the recovery of vanadium from oil fly ash by carbon removal and the roast-leach process. The oil fly ash contained about 85% unburned carbon and 2.2% vanadium by weight. A vanadium-enriched product was obtained after carbon removal, and the vanadium content of this product was 19% by weight. Next, the vanadium-enriched product was roasted with sodium carbonate to convert vanadium oxides to water-soluble sodium metavanadate. The roasted sample was leached with water at 60°C, and the extraction percentage of vanadium was about 92% by weight. Several analytical techniques, such as inductively coupled plasma atomic emission spectroscopy (ICP-AES), x-ray fluorescence (XRF), and thermogravimetric and differential thermal analysis (TG-DTA), were utilized for sample analyses. Thermodynamic modeling was also conducted with HSC chemistry software to explain the experimental results.

  14. The Content of Vanadium in the Egg of the Ascidian, Halocynthia roretzi and Its Changes during the Development

    OpenAIRE

    堀, 令司; 沼宮内, 隆晴; 道端, 斉; Reiji, Hori; Takaharu, Numakunai; Hitoshi, Michibata; 東北大学理学部付属浅虫臨海実験所; 富山大学理学部生物学教室; Asamushi marine biological station, Tohoku University; Biological Institute, Faculty of Science, University of Kanazawa

    1981-01-01

    The vanadium content of the egg and embryo of the ascidian, Halocynthia roretzi was determined by activation analysis. The content of vanadium in an egg remained unchanged during the cleavage. A remarkable increase in the amount of vanadium in the embryo was observed during metamorphosis. Vanadium content in the larva one year after spawning amounted to about 820,000 times of that of the unfertilized egg. The accumulation of vanadium by the ascidian was discussed in comparison with phosphorus.

  15. On the layer structure of vanadium pentoxide gels. Comment on `molecular dynamic simulation of the vanadium pentoxide gel host`

    Energy Technology Data Exchange (ETDEWEB)

    Yao, Takeshi [Department of Fundamental Energy Science, Graduate School of Energy Sciences, Kyoto University, Kyoto (Japan); Oka, Yoshio [Department of Natural Environment Sciences, Faculty of Integrated Human Studies, Kyoto University, Kyoto (Japan)

    1997-04-16

    A comment on the article entitled `molecular dynamic simulation of the vanadium pentoxide gel host` [J. Linde and J.O. Thomas, Solid State Ionics 85 (1996) 1] is presented concerning the model structure of the V{sub 2}O{sub 5} layer of vanadium pentoxide gels. The double-layer structure used in the simulation was derived from the crystalline V{sub 2}O{sub 5}. This model structure significantly differs from the double-sheet type determined by the X-ray Rietvelt method. The simulation should be recalculated based on the double-sheet type V{sub 2}O{sub 5} layer

  16. Effect of ZnO buffer layer on phase transition properties of vanadium dioxide thin films

    Science.gov (United States)

    Zhu, Huiqun; Li, Lekang; Li, Chunbo

    2016-03-01

    VO2 thin films were prepared on ZnO buffer layers by DC magnetron sputtering at room temperature using vanadium target and post annealing at 400 °C. The ZnO buffer layers with different thickness deposited on glass substrates by magnetron sputtering have a high visible and near infrared optical transmittance. The electrical resistivity and the phase transition properties of the VO2/ZnO composite thin films in terms of temperature were investigated. The results showed that the resistivity variation of VO2 thin film with ZnO buffer layer deposited for 35 min was 16 KΩ-cm. The VO2/ZnO composite thin films exhibit a reversible semiconductor-metal phase transition at 48 °C.

  17. Magnetic properties of vanadium doped CdTe: Ab initio calculations

    Energy Technology Data Exchange (ETDEWEB)

    Goumrhar, F. [Laboratory of Physics of High Energy, Modeling & Simulations (LPHE-MS), Faculty of Sciences, Mohammed V University of Rabat, Av. Ibn Batouta, B.P. 1014 Rabat (Morocco); Bahmad, L., E-mail: bahmad@fsr.ac.ma [Laboratory of Magnetism and High Energy Physics (LMPHE-URAC12), Faculty of Sciences, Mohammed V University of Rabat, Av. Ibn Batouta, B.P. 1014 Rabat (Morocco); Mounkachi, O. [Material and Nanomaterial Center, MAScIR Fondation, Rabat (Morocco); Benyoussef, A. [Laboratory of Magnetism and High Energy Physics (LMPHE-URAC12), Faculty of Sciences, Mohammed V University of Rabat, Av. Ibn Batouta, B.P. 1014 Rabat (Morocco); Material and Nanomaterial Center, MAScIR Fondation, Rabat (Morocco); Hassan II Academy of Sciences and Technology, Rabat (Morocco)

    2017-04-15

    In this paper, we are applying the ab initio calculations to study the magnetic properties of vanadium doped CdTe. This study is based on the Korringa–Kohn–Rostoker method (KKR) combined with the coherent potential approximation (CPA), within the local density approximation (LDA). This method is called KKR-CPA-LDA. We have calculated and plotted the density of states (DOS) in the energy diagram for different concentrations of dopants. We have also investigated the magnetic and half-metallic properties of this compound and shown the mechanism of exchange interaction. Moreover, we have estimated the Curie temperature T{sub c} for different concentrations. Finally, we have shown how the crystal field and the exchange splittings vary as a function of the concentrations.

  18. Highly Stable Aqueous Zinc-ion Storage Using Layered Calcium Vanadium Oxide Bronze Cathode

    KAUST Repository

    Xia, Chuan

    2018-02-12

    Cost-effective aqueous rechargeable batteries are attractive alternatives to non-aqueous cells for stationary grid energy storage. Among different aqueous cells, zinc-ion batteries (ZIBs), based on Zn2+ intercalation chemistry, stand out as they can employ high-capacity Zn metal as anode material. Herein, we report a layered calcium vanadium oxide bronze as cathode material for aqueous Zn batteries. For the storage of Zn2+ ions in aqueous electrolyte, we demonstrate that calcium based bronze structure can deliver a high capacity of 340 mAh g-1 at 0.2 C, good rate capability and very long cycling life (96% retention after 3000 cycles at 80 C). Further, we investigate the Zn2+ storage mechanism, and the corresponding electrochemical kinetics in this bronze cathode. Finally, we show that our Zn cell delivers an energy density of 267 Wh kg-1 at a power density of 53.4 W kg-1.

  19. Properties of electrochromic nickel-vanadium oxide films sputter-deposited from nonmagnetic alloy target

    Science.gov (United States)

    Avendano, Esteban; Azens, Andris; Niklasson, Gunnar A.

    2001-11-01

    In this study we investigate the structure, composition, diffusion coefficient, and electrochromic properties of nickel-vanadium oxide films as a function of deposition conditions. Polycrystalline films have been deposited by DC magnetron sputtering from a nonmagnetic target of Ni0.93V0.07 in an atmosphere of O2/Ar and Ar/O2/H2, with the gas flow ratios varied systematically to cover the range from nearly-metallic to overoxidized films. The results contradict the usual view that films deposited in O2/Ar are dark brown in their as-deposited state. While such films can easily be deposited, the optimum electrochromic properties have been observed at O2/Ar ratios giving nearly transparent films. Addition of hydrogen to the sputtering atmosphere improved cycling stability of the films. The diffusion coefficient has been determined by the Galvanostatic Intermittent Titration Technique (GITT).

  20. Effects of twin boundaries in vanadium nitride films subjected to tensile/compressive deformations

    Science.gov (United States)

    Fu, Tao; Peng, Xianghe; Huang, Cheng; Zhao, Yinbo; Weng, Shayuan; Chen, Xiang; Hu, Ning

    2017-12-01

    Two kinds of atoms can serve as the twin boundary (TB) atoms in a transition metal nitride (TMN). In this work, we performed molecular dynamics (MD) simulations for the responses of vanadium nitride (VN) films with different kinds of TB atoms (V or N) subjected to uniaxial tensile/compressive deformations, to investigate their effects and the tensile-compressive asymmetry. In compressive deformation, the migration of TBs with V atoms to that with N atoms contributes to softening, while the pile-up of dislocations at TBs contributes to strengthening. During tension, fractures occur at the TBs without distinct nucleation of dislocations, the nature of the brittle fracture, which does not result in any improvement of fracture toughness and critical stress. Different frictional effects, cutoff radii, asymmetrical tensile and compressive nature of the interatomic potential and different deformation mechanisms are responsible for the tension-compression asymmetry in VN.

  1. Tuning the conductivity of vanadium dioxide films by swift heavy ion irradiation

    Energy Technology Data Exchange (ETDEWEB)

    Ehrhardt, Paul; Hofsaess, Hans; Gehrke, Hans-Gregor [II. Physikalisches Institut, Fakultaet fuer Physik, Universitaet Goettingen, Friedrich-Hund-Platz 1, 37077 Goettingen (Germany); Krauser, Johann [Hochschule Harz, University of Applied Sciences, Friedrichstrasse 57-59, 38855 Wernigerode (Germany); Trautmann, Christina [Gesellschaft fuer Schwerionenforschung, Planckstrasse 1, 64291 Darmstadt (Germany); Ramanathan, Shriram [Harvard School of Engineering and Applied Sciences, Harvard University, Cambridge, MA 02138 (United States)

    2012-07-01

    We demonstrate the generation of a persistent conductivity increase in vanadium dioxide thin films by irradiation with swift heavy ions at room temperature. VO{sub 2} undergoes a temperature driven metal-insulator-transition (MIT) at 67 C. After the ion irradiation the conductivity of the films we observe a strong increase in conductivity below the transition temperature proportional to the ion fluence. This change in conductivity is persistent and remains after several cycles of heating. Low temperature measurements down to 15 K show no further MIT below room temperature. Although the conductivity increase after irradiation at such low fluences is due to single ion track effects, atomic force microscopy (AFM) measurements do not show surface hillocks, which are characteristic for ion tracks in other materials. AFM measurements with conducting tip give no evidence for conducting ion tracks but indicate the existence of conducting regions around poorly conducting ion tracks, possible due to stress generation.

  2. Development of Vanadium Phosphaate Catalysts for Methanol Production by Selective Oxidation of Methane.

    Energy Technology Data Exchange (ETDEWEB)

    McCormick, R.L.

    1997-10-01

    This DOE sponsored study of methane partial oxidation was initiated at Amax Research and Development in Golden, CO in October of 1993. Shortly thereafter the management of Amax closed this R&D facility and the PI moved to the Colorado School of Mines. The project was begun again after contract transfer via a novation agreement. Experimental work began with testing of vandyl pyrophosphate (VPO), a well known alkane selective oxidation catalyst. It was found that VPO was not a selective catalyst for methane conversion yielding primarily CO. However, promotion of VPO with Fe, Cr, and other first row transition metals led to measurable yields for formaldehyde, as noted in the summary table. Catalyst characterization studies indicated that the role of promoters was to stabilize some of the vanadium in the V{sup 5+} oxidation state rather than the V{sup 4+} state formally expected for (VO){sub 2}P{sub 2}O{sub 7}.

  3. Tunable Electrical Properties of Vanadium Oxide by Hydrogen-Plasma-Treated Atomic Layer Deposition

    Directory of Open Access Journals (Sweden)

    Helen Hejin Park

    2017-04-01

    Full Text Available In this study, a plasma-modified process was developed to control the electrical properties of atomic layer deposition (ALD-grown vanadium dioxide (VO2, which is potentially useful for applications such as resistive switching devices, bolometers, and plasmonic metamaterials. By inserting a plasma pulse with varying H2 gas flow into each ALD cycle, the insulator-to-metal transition (IMT temperature of postdeposition-annealed crystalline VO2 films was adjusted from 63 to 78 °C. Film analyses indicate that the tunability may arise from changes in grain boundaries, morphology, and compositional variation despite hydrogen not remaining in the annealed VO2 films. This growth method, which enables a systematic variation of the electronic behavior of VO2, provides capabilities beyond those of the conventional thermal ALD and plasma-enhanced ALD.

  4. Vanadium dioxide thin film with low phase transition temperature deposited on borosilicate glass substrate

    Energy Technology Data Exchange (ETDEWEB)

    Huang Zhangli; Chen Sihai, E-mail: cshai99@mail.hust.edu.cn; Wang Boqing; Huang Ying; Liu Nengfu; Xu Jin; Lai Jianjun

    2011-04-29

    A nanostructured vanadium dioxide (VO{sub 2}) thin film showing a low metal-insulator transition temperature of 30 {sup o}C has been fabricated through reactive ion beam sputtering followed by thermal annealing. The thin film was grown on borosilicate glass substrate at the temperature of 280 {sup o}C with a Si{sub 3}N{sub 4} buffer layer. Both scanning electron microscopy and atomic force microscopy images have been taken to investigate the configuration of VO{sub 2} thin film. The average height of the crystallite is 20 nm and the grain size ranges from 40 nm to 100 nm. The transmittance measured from low to high temperatures also reveals that the film possesses excellent switching property in infrared light at critical transition temperature, with switching efficiency of 52% at 2600 nm. This experiment paves the way of VO{sub 2} thin film's application in smart windows.

  5. Effect of quantum confinement on thermoelectric properties of vanadium dioxide nanofilms

    Science.gov (United States)

    Khan, G. R.; Ahmad, Bilal

    2017-12-01

    The quantum confinement effect on thermoelectric properties of pristine vanadium dioxide (VO2) nanofilms across semiconductor to metal phase transition (SMT) has been demonstrated by studying VO2 nanofilms of 15 nm thickness in comparison to microfilms of 290 nm thickness synthesized via inorganic sol-gel method casted on glass substrates by spin coating technique. The ebbing of phase transition temperature in nanofilms across SMT was consistent with the results obtained from resistance-temperature hysteresis contour during SMT dynamics of the nanofilms. The temperature dependent Hall and Seebeck measurements revealed that electrons were the charge carriers in the nanofilms and that the value of charge carrier concentration increased as much as 4 orders of magnitude while going across SMT which stood responsible almost entirely for resistance variations. The decline in carrier mobility and escalation in Seebeck coefficient in the low temperature semiconducting region were splendidly witnessed across SMT.

  6. Effects of Microwave Roasting on the Kinetics of Extracting Vanadium from Vanadium Slag

    Science.gov (United States)

    Zhang, Guoquan; Zhang, Ting-an; Lü, Guozhi; Zhang, Ying; Liu, Yan; Zhang, Weiguang

    2016-02-01

    The kinetics of extracting vanadium (V) from microwave-roasted (MR) vanadium slag (V-slag) with concentrated H2SO4 were investigated. The microwave irradiation experiments were performed in a modified microwave muffle furnace at temperatures ranging from 150°C to 750°C. The x-ray diffraction analysis indicated that the spinel phase of the V-slag is destroyed after 10 min of roasting. The phase composition of the V-slag was changed by the roasting process, and a new Fe2O3 phase appeared in the samples roasted at higher temperatures. Compared to the raw slag, the surface area, pore volume, and pore size of the MR slags were much lower. It was easier to leach V from the MR samples than the raw sample with the H2SO4 solution, and the leaching process was accelerated in the MR samples. When the V-slag was roasted at 150°C and 350°C (MR@150 and MR@350, respectively), the apparent activation energy was decreased from 77.65 kJ/mol to 68.42 kJ/mol and 66.68 kJ/mol, respectively. The process of leaching V from the raw and MR slags was controlled by both the surface chemical reactions and internal diffusion. The reaction orders of the raw, MR@150, and MR@350 V-slags, with respect to the H2SO4 concentration, were 1.23, 0.75, and 0.70, respectively.

  7. Biogenic vanadium in total suspended particulate matter from Cabo Frio upwelling region, Southeast, Brazil

    Science.gov (United States)

    Sella, Silvia M.; Neves, Alessandra F.; Moreira, Josino Costa; Silva-Filho, Emmanoel V.

    In this work total suspended particulate (TSP) was collected during a year, in two municipalities located in a coastal region of Rio de Janeiro State, Southeast, Brazil, from February 2004 to January 2005. Two sites were chosen: site 1 located in front of the sea and representative of sea salt spray influence; site 2 in a tall booth of a highway representing vehicle exhaust influence. Samples were collected in glass fibre filters using Hi-Vol samplers and stored. 1/8 of those loaded filters were cut and digested in a microwave oven. The extract obtained was used to determine metal Ca, Cu, Mo, Mn, Ti, V, Zn and K concentration in the atmosphere. The results showed that TSP levels in site 1 (23.1-659 μg m -3) was higher than in site 2 (24.5-55.6 μg m -3) due to marine aerosol which is responsible for particle emissions with higher diameter. Vanadium was the only element studied whose concentration were higher in site 1 (0.840-20.9 ng m -3) compared to site 2 (0.655-7.07 ng m -3). The highest vanadium concentrations in site 1 were obtained during upwelling events, with NE winds predominance at high speed, which indicates the influence of this phenomena in V presence in the atmosphere. Principal components analysis was able to identify atmospheric particulate sources distributed in four factors. In site 1, those factors explain 86.5% of total data variance and indicate two sources: continental and marine. In site 2, those factors explain 89.2% of total data variance and indicate that vehicle exhaust is the main metals source in the atmosphere.

  8. Chemiluminescent determination of vanadium(IV) using a cinchomeronic hydrazide-H{sub 2}O{sub 2} system and flow injection analysis

    Energy Technology Data Exchange (ETDEWEB)

    Pradana Perez, J.A. [Departamento de Ciencias Analiticas, Facultad de Ciencias, Universidad Nacional de Educacion a Distancia, c/Senda del Rey 9, 28040 Madrid (Spain); Alegria, J.S. Durand [Departamento de Ciencias Analiticas, Facultad de Ciencias, Universidad Nacional de Educacion a Distancia, c/Senda del Rey 9, 28040 Madrid (Spain); Hernando, P. Fernandez [Departamento de Ciencias Analiticas, Facultad de Ciencias, Universidad Nacional de Educacion a Distancia, c/Senda del Rey 9, 28040 Madrid (Spain)]. E-mail: pfhernando@ccia.uned.es; Sierra, A. Narros [Departamento de Ingenieria Quimica y del Medio Ambiente, Escuela Tecnica Superior de Ingenieros Industriales, Universidad Politecnica de Madrid, Madrid (Spain)

    2005-04-22

    This paper proposes a new chemiluminescent flow injection analysis (FIA) method for the determination of vanadium(IV) ions in aqueous media. The method is based on the chemiluminescent reaction that occurs between cinchomeronic hydrazide (CH) and hydrogen peroxide in a strongly alkaline medium, in which vanadium(IV) acts as a catalyst. The chemical and physical variables involved in the flow injection system are optimised using a modified simplex method. Vanadium ions can be detected in the 0.08 and 1.00 {mu}g mL{sup -1} range; the detection limit for a signal-to-noise ratio of 3 is 0.08 {mu}g mL{sup -1}. Great variations in the quantum yield were observed when cobalt(II), chromium(III), copper(II) and/or nickel(II) were present in the reaction medium. The proposed method is selective and simple, and can be successfully used to analyse water samples without the need for separation or preconcentration processes.

  9. Metals and metal compounds in carcinogenesis.

    Science.gov (United States)

    Desoize, Bernard

    2003-01-01

    Several metals and metal containing compounds are potent mutagens and carcinogens. The most often blamed are chromium, arsenic, nickel, vanadium, iron, copper and manganese. Although each of them has its own mechanism of action, it is believed that most of their mechanisms of action involve reactive oxygen species (ROS). Furthermore, nickel modulates gene expression by induction of DNA methylation and/or suppression of histone acetylation. Arsenic activity on cell metabolism is multiple; it seems that cell transformation is induced by long-term exposure to a low level of arsenic. The paradox of arsenic is that it has also a valuable therapeutic efficacy in cancer treatment. Manganese is known to cause DNA damage, although it does not represent a significant carcinogenic risk. Magnesium deficiency and iron excess are not exactly carcinogenetic, but certain concentrations of these metal ions are needed to prevent cancer.

  10. Electrochemical, linear optical, and nonlinear optical properties and interpretation by density functional theory calculations of (4-N,N-dimethylaminostyryl)-pyridinium pendant group associated with polypyridinic ligands and respective multifunctional metal complexes (Ru(II) or Zn(II)).

    Science.gov (United States)

    Dumur, Frédéric; Mayer, Cédric R; Hoang-Thi, Khuyen; Ledoux-Rak, Isabelle; Miomandre, Fabien; Clavier, Gilles; Dumas, Eddy; Méallet-Renault, Rachel; Frigoli, Michel; Zyss, Joseph; Sécheresse, Francis

    2009-09-07

    The synthesis, linear optical and nonlinear optical properties, as well as the electrochemical behavior of a series of pro-ligands containing the 4-(4-N,N-dimethylaminostyryl)-1-methyl pyridinium (DASP(+)) group as a push-pull moiety covalently linked to terpyridine or bipyridine as chelating ligands are reported in this full paper. The corresponding multifunctional Ru(II) and Zn(II) complexes were prepared and investigated. The structural, electronic, and optical properties of the pro-ligands and the ruthenium complexes were investigated using density functional theory (DFT) and time-dependent (TD) DFT calculations. A fairly good agreement was observed between the experimental and the calculated electronic spectra of the pro-ligands and their corresponding ruthenium complexes. A quenching of luminescence was evidenced in all ruthenium complexes compared with the free pro-ligands but even the terpyridine-functionalized metal complexes exhibited detectable luminescence at room temperature. Second order nonlinear optical (NLO) measurements were performed by Harmonic Light Scattering and the contribution of the DASP(+) moieties (and their relative ordering) and the metal-polypyridyl core need to be considered to explain the nonlinear optical properties of the metal complexes.

  11. The Henryville Bed of the New Albany shale: II. Comparison of the nickel and vanadyl porphyrins in the bitumen with those generated from the kerogen during simulated catagenesis

    Energy Technology Data Exchange (ETDEWEB)

    Berkel, G.J.V.; Filby, R.H. (Washington State Univ., Pullman (USA)); Quirke, J.M.E. (Florida International Univ., Miami (USA))

    1989-01-01

    The Ni(II) and VO(II) porphyrin distributions in the bitumen from the Henryville Bed of New Albany shale (Clark County, Indiana) are compared with those of porphyrins isolated from a single New Albany shale kerogen aliquot by five sequential pyrolyses (110-450C). Both the bitumen and the pyrolsates contained Ni(II) and VO(II) complexes of at least three skeletal types: deoxophylloerythroetioporphyrin (DPEP), etioporphyrin (etio), and tetrahydrobenzo-DPEP (THBD). Ni(II) Benzo-DPEP and VO(II) benzo-DPEP and VO(II) benzo type porphyrins were detected in the pyrolysates but not in the bitumen. It was concluded from a comparison of porphyrin distributions in the pyrolysates that porphyrins were liberated from the kerogen by enhanced solubilization and/or desorption into the solvent rather than by kerogen-porphyrin carbon-carbon bond cleavages. Substantial amounts of organically combined nickel and vanadium remain in the kerogen after pyrolysis and may comprise porphyrin and non-porphyrin complexes. The similarity of the porphyrins in the bitumen and the pyrolysis indicates that porphyrins in the bitumen were released as a result of kerogen maturation. The similarity of the Ni(II) etio and DPEP species to the corresponding VO(II) porphyrins indicates that both metal complexes had a common premetallation tetrapyrrole precursor and that this precursor may have been associated with the evolving kerogen.

  12. Vanadium, rubidium and potassium in Octopus vulgaris (Mollusca: Cephalopoda

    Directory of Open Access Journals (Sweden)

    Sónia Seixas

    2005-06-01

    Full Text Available The levels of vanadium, rubidium and potassium were determined in Octopus vulgaris caught during commercial fishing activities at three locations (Cascais, Santa Luzia and Viana do Castelo in Portugal in autumn and spring. We determined the concentration of these elements in digestive gland, branchial heart, gills, mantle and arms in males and females. At least five males and five females were assessed for each season/location combination. Elemental concentrations were determined by Particle Induced X-ray Emission (PIXE. Vanadium was detectable only in digestive gland and branchial heart samples. Its concentration was not correlated with total weight, total length or mantle length. There were no differences in concentrations of V, Rb and K between sexes. There were significant differences in vanadium concentrations in branchial hearts in autumn between samples from Viana do Castelo and those from the other two sites. We found a significant positive relationship between the concentration of vanadium and those of potassium and rubidium in branchial hearts. Branchial hearts appear to play an important role in decontamination of V.

  13. Novel hybrid materials based on the vanadium oxide nanobelts

    Energy Technology Data Exchange (ETDEWEB)

    Zabrodina, G.S., E-mail: kudgs@mail.ru [G.A. Razuvaev Institute of Organometallic Chemistry of Russian Academy of Sciences, Nizhny Novgorod 603950 (Russian Federation); Lobachevsky State University, Nizhny Novgorod 603950 (Russian Federation); Makarov, S.G.; Kremlev, K.V. [G.A. Razuvaev Institute of Organometallic Chemistry of Russian Academy of Sciences, Nizhny Novgorod 603950 (Russian Federation); Lobachevsky State University, Nizhny Novgorod 603950 (Russian Federation); Yunin, P.A.; Gusev, S.A. [Institute for Physics of Microstructures Russian Academy of Sciences, Nizhny Novgorod 603087 (Russian Federation); Kaverin, B.S.; Kaverina, L.B. [G.A. Razuvaev Institute of Organometallic Chemistry of Russian Academy of Sciences, Nizhny Novgorod 603950 (Russian Federation); Ketkov, S.Yu. [G.A. Razuvaev Institute of Organometallic Chemistry of Russian Academy of Sciences, Nizhny Novgorod 603950 (Russian Federation); Lobachevsky State University, Nizhny Novgorod 603950 (Russian Federation)

    2016-04-15

    Graphical abstract: - Highlights: • Flat and curved vanadium oxide nanobelts have been synthesized. • Hybrid material was prepared via decoration of flexible nanobelts with zinc phthalocyanine. • Investigations of the thermal stability, morphologies and structures were carried out. - Abstract: Novel hybrid materials based on zinc phthalocyanine and nanostructured vanadium oxides have attracted extensive attention for the development of academic research and innovative industrial applications such as flexible electronics, optical sensors and heterogeneous catalysts. Vanadium oxides nanobelts were synthesized via a hydrothermal treatment V{sub 2}O{sub 5}·nH{sub 2}O gel with surfactants (TBAB, CTAB) used as structure-directing agents, where CTAB – cetyltrimethylammonium bromide, TBAB – tetrabutylammonium bromide. Hybrid materials were prepared decoration of (CTA){sub 0.33}V{sub 2}O{sub 5} flexible nanobelts with cationic zinc phthalocyanine by the ion-exchange route. Investigations of the thermal stability, morphologies and structures of the (CTA){sub 0.33}V{sub 2}O{sub 5}, (TBA){sub 0.16}V{sub 2}O{sub 5} nanobelts and zinc phthalocyanine exchange product were carried out. The hybrid materials based on the nanostructured vanadium oxide and zinc phthalocyanine were tested as photocatalysts for oxidation of citronellol and 2-mercaptoethanol by dioxygen.

  14. Structural and catalytic properties of a novel vanadium containing ...

    Indian Academy of Sciences (India)

    Abstract. A novel vanadium containing solid core mesoporous silica shell catalyst was synthesized with different Si/V ratios by sol-gel method under neutral conditions. The synthesized materials were characterized by various techniques and gas phase diphenyl methane oxidation reaction. The mesoporosity combined with ...

  15. Halofunctionalization of alkenes by vanadium chloroperoxidase from Curvularia inaequalis

    NARCIS (Netherlands)

    Dong, J.; Fernandez Fueyo, E.; Li, Jingbo; Guo, Zheng; Renirie, Rokus; Wever, Ron; Hollmann, F.

    The vanadium-dependent chloroperoxidase from Curvularia inaequalis is a stable and efficient biocatalyst for the hydroxyhalogenation of a broad range of alkenes into halohydrins. Up to 1 200 000 TON with 69 s−1 TOF were observed for the biocatalyst. A bienzymatic cascade to yield epoxides as

  16. Combined effect of vanadium and nickel on lipid peroxidation and ...

    African Journals Online (AJOL)

    In this investigation, hepatorenal antioxidant effects of combined oral administration of ammonium metavanadate (AMV; 0.15 mg V/ml) and nickel sulfate (NS; 0.18 mg Ni/ml) in male albino rats over a 21- day period have been evaluated. After administration of vanadium, lipid peroxidation (LPO) increased significantly (p ...

  17. TWO LIGAND OXIDIO-VANADIUM(IV) COMPLEXES AS NOVEL ...

    African Journals Online (AJOL)

    TWO LIGAND OXIDIO-VANADIUM(IV) COMPLEXES AS NOVEL EFFICIENT. CATALYSTS IN MULTICOMPONENT REACTIONS FOR SYNTHESIS OF. TETRAHYDROBENZOPYRAN DERIVATIVES. Mehdi Abaszadeh1,2*, Mohammad Seifi3 and S. Yousef Ebrahimipour 4,5. 1Pharmaceutics Research Center, Institute of ...

  18. Neurotoxic profiles of vanadium when administered at the onset of ...

    African Journals Online (AJOL)

    Further “immune” assays revealed astrocytic activation (GFAP stain), demyelination (CNPase) and activated microglia (Iba1) due to vanadium which were ameliorated by the administration of vit E to the dams. The pups whose dams were administered with vit E alone showed signs of cellular degeneration which might be ...

  19. Electrochemical properties of dip-coated vanadium pentaoxide thin ...

    Indian Academy of Sciences (India)

    Home; Journals; Bulletin of Materials Science; Volume 39; Issue 6. Electrochemical properties of dip-coated vanadium pentaoxide thin films. R S INGOLE B J LOKHANDE. Volume 39 Issue 6 ... Author Affiliations. R S INGOLE1 B J LOKHANDE1. School of Physical Sciences, Solapur University, Solapur 413 255, India ...

  20. Excimer laser reactive deposition of vanadium nitride thin films

    Science.gov (United States)

    D'Anna, E.; Di Cristoforo, A.; Fernández, M.; Leggieri, G.; Luches, A.; Majni, G.; Mengucci, P.; Nanai, L.

    2002-01-01

    We report on the deposition of thin vanadium nitride films by ablating vanadium targets in low-pressure N 2 atmosphere, and on their characterization. The targets were vanadium foils (purity 99.8%). 3 in. Si(1 1 1) wafers were used as substrates. Film characteristics (composition and crystalline structure) were studied as a function of N 2 pressure (0.5-200 Pa), KrF laser fluence (4.5-19 J/cm 2), substrate temperature (20-750 °C) and target-to-substrate distance (30-70 mm). Vanadium nitride is already formed at low N 2 ambient pressures (1 Pa) and laser fluences (6 J/cm 2) on substrates at room temperature. At the N 2 pressures of 1-10 Pa, the prevalent phase is VN. At higher pressures (100 Pa) and at relatively high laser fluences (16-19 J/cm 2), the dominant phase is V 2N. The crystallinity of the films improves by increasing the substrate temperature. Well-crystallized films are obtained on substrates heated at 500 °C.

  1. A model approach to vanadium involvement in crude oil refining

    Energy Technology Data Exchange (ETDEWEB)

    1991-01-01

    The research during the last nine months has continued with the overall goal of developing V/S chemistry and has been concentrated on the two main areas of the project: the reactivity chemistry of vanadyl complexes, and the development of sulfide-bridged vanadium cluster chemistry. Significant new progress has been achieved in both these areas.

  2. Optical properties of zinc–vanadium glasses doped with samarium ...

    Indian Academy of Sciences (India)

    Zinc–vanadium glasses doped with samarium oxide having the chemical composition Sm2O3() ZnO(40-)V2O5(60) (where = 0.1–0.5 mol%) were prepared by melt quenching method. The density of these glasses was measured by Archimedes method; the corresponding molar volumes have also been calculated.

  3. Geochemical behaviour of vanadium in iron—titanium oxides

    NARCIS (Netherlands)

    Schuiling, R.D.; Feenstra, A.

    The following geochemical rules-of-thumb seem to hold for vanadium: 1. (1) Magnetites as a group have higher V contents than either hematites or ilmenites. 2. (2) In magnetite—hematite pairs, however, the hematite has the higher V content. 3. (3) In magnetite—ilmenite pairs, the magnetite

  4. Vanadium Effect on a Medium Carbon Forging Steel

    Directory of Open Access Journals (Sweden)

    Carlos Garcia-Mateo

    2016-05-01

    Full Text Available In the present work the influence of vanadium on the hardenability and the bainitic transformation of a medium carbon steel is analyzed. While V in solid solution enhances the former, it hardly affects bainitic transformation. The results also reveal an unexpected result, an increase of the prior austenite grain size as the V content increases.

  5. determination of vanadium in foods by atomic absorption spectrometry

    African Journals Online (AJOL)

    This paper presents an assessment of the level of vanadium in foods (Plantain, Musa spp; Yam, Discorea rotundata; and Maize, Zea mays) from ten popular market places in Lagos metropolis, Nigeria. Total acid leaching digestion method was employed and determination was by Flame Atomic Absorption ...

  6. Effects of Vanadium Pentoxide on the Histological and Sperm ...

    African Journals Online (AJOL)

    The pharmacological effects of intraperitoneal administration of different doses of vanadium pentoxide (V2O5) on the histological and sperm parameters of male guinea pigs were investigated. Also investigated were the effects of oral pretreatment with different doses of vitamin E (a known protein kinase C inhibitor) on the ...

  7. Partial Oxidation of n-Pentane over Vanadium Phosphorus Oxide ...

    African Journals Online (AJOL)

    The selective oxidation of n-pentane to value-added products, maleic anhydride or phthallic anhydride by vanadium phosphorus oxide loaded on hydroxyapatites as catalysts and oxygen as oxidant was investigated. Hydroxyapatite (HAp) and cobalthydroxyapatite (Co-HAp) were prepared by the co-precipitation method ...

  8. Role of vanadium in Keggin heteropoly molybdate supported on ...

    Indian Academy of Sciences (India)

    ated for oxidation of 1,2-benzenedimethanol using H2O2 and O2 as oxidants. .... C on oil bath. In the case of O2 as oxidant, reaction was conducted under O2 atmosphere. Progress of the reaction was monitored by using thin-layer chro- ... The role of vanadium in heteropoly molybdate catalysts for oxidation reactions. 469.

  9. Speciation of Chromium and Vanadium in Medicinal Plants

    African Journals Online (AJOL)

    NICOLAAS

    Results of the determination of water-soluble (hot water) Cr(VI) and V(V) concentrations ... tive and purging gas. 2.2. Quality Assurance. The analytical results for the determination of chromium and vanadium were validated through the analysis of certified refer- ... were filtered through 0.45 µm hydrophilic PVDF filter prior the.

  10. Organometalic carbosilane polymers containing vanadium and their preparation

    Science.gov (United States)

    Yajima, S.; Okamura, K.; Shishido, T.; Fukuda, K.

    1983-01-01

    The present invention concerns a new organometallic polymer material containing in part a vanadium-siloxane linkage (V-0-Si), which has excellent resistance to heat and oxidation and a high residue ratio after high temperature treatment in a non-oxidizing atmosphere, for example, nitrogen, argon, helium, ammonia, or hydrogen.

  11. Novel vanadium phosphate phases as catalysts for selective oxidation

    Indian Academy of Sciences (India)

    Unknown

    important vanadium phosphate phases used as selective oxidation catalysts, it has been observed that ... molybdenum oxides are the most widely used ones for the selective oxidation of alkanes. Amongst these the ... pentane to maleic and pthalic anhydride, and in the oxidative dehydrogenation of ethane, propane etc 4.

  12. Ni(II), Cu(II) and Zn(II)

    African Journals Online (AJOL)

    NICO

    2010-06-15

    Jun 15, 2010 ... physico-chemical techniques. A square planar geometry was suggested for Cu(II) and octahedral geometry proposed for Co(II),. Ni(II) and Zn(II). TG curves indicated that the complexes decompose in three to four steps. The presence of coordinated water in metal complexes was confirmed by thermal and ...

  13. Migratory Transmetalation in Diphenoxo-Bridged Cu(II)M(II) Complexes of a Dinucleating Macrocycle with N(amine)(2)O(2) and N(imine)(2)O(2) Metal-Binding Sites.

    Science.gov (United States)

    Yonemura, Masami; Matsumura, Yukiko; Furutachi, Hideki; Ohba, Masaaki; Okawa, Hisashi; Fenton, David E.

    1997-06-18

    A phenol-based heterodinucleating macrocycle (H(2)L), comprised of two 2-((methylamino)methyl)-6-(iminomethyl)-4-bromophenolate entities bridged by the -(CH(2))(2)- groups between amine nitrogens and by the -(CH(2))(3)- groups between imine nitrogens, displays dissimilar N(amine)(2)O(2) and N(imine)(2)O(2) metal-binding sites sharing the phenolic oxygens and is prepared as a Cu(II)Pb(II) complex [CuPb(L)](ClO(4))(2). An analogous complex [CuPb(L)(BzO)(dmf)]ClO(4) crystallizes in the triclinic space group P&onemacr;, (No. 2), with a = 13.998(2) Å, b = 15.568(2) Å, c = 8.699(2) Å, alpha = 95.32(1) degrees, beta = 92.23(1) degrees, gamma = 82.81(1) degrees, V = 1871.9(5) Å(3), and Z = 2. Refinements based on 3788 reflections with I > 3.00sigma(I) converged with R = 0.058 and R(w) = 0.069. The Cu(II) resides at the N(imine)(2)O(2) site and assumes a planar geometry. The Pb(II) resides at the N(amine)(2)O(2) site and assumes a seven-coordinate geometry by further addition of a dmf molecule and a bidentate benzoate group. The Cu--Pb separation, doubly bridged by the phenolic oxygens, is 3.466(2) Å. The reaction of [CuPb(L)](ClO(4))(2) with metal(II) sulfate salts provides Cu(II)M(II) complexes [CuM(L)](ClO(4))(2).nH(2)O (M = Mn (n = 2), Co (n = 2), Ni (n = 0), Cu (n = 0), Zn (n = 1)). The CuZn complex, [CuZn(L)(AcO)]ClO(4), crystallizes in the triclinic space group P&onemacr;, (No. 2), with a = 12.290(3) Å, b = 13.402(4) Å, c = 11.501(2) Å, alpha = 95.10(2) degrees, beta = 116.68(2) degrees, gamma = 112.00(2) degrees, V = 1491.8(9) Å(3), and Z = 2. Refinements based on 2497 reflections with I > 3.00sigma(I) converge with R = 0.046 and R(w) = 0.034. The Cu(II) is bound at the N(amine)(2)O(2) site and the Zn(II) is bound at the N(imine)(2)O(2) site with a Cu--Zn separation of 2.942(2) Å. Further, the acetate group bridges the two metal ions providing a five-coordinate geometry about both metal ions. The CuM complexes except for the CuZn complex show significant

  14. Androgenic alopecia is associated with less dietary soy, lower [corrected] blood vanadium and rs1160312 1 polymorphism in Taiwanese communities.

    Directory of Open Access Journals (Sweden)

    Ching-Huang Lai

    Full Text Available Although the genetic basis of androgenic alopecia has been clearly established, little is known about its non-genetic causes, such as environmental and lifestyle factors.This study investigated blood and urine heavy metals concentrations, environmental exposure factors, personal behaviors, dietary intakes and the genotypes of related susceptibility genes in patients with androgenic alopecia (AGA.Age, AGA level, residence area, work hours, sleep patterns, cigarette usage, alcohol consumption, betel nut usage, hair treatments, eating habits, body heavy metals concentrations and rs1998076, rs913063, rs1160312 and rs201571 SNP genotype data were collected from 354 men. Logistic regression analysis was performed to examine whether any of the factors displayed odds ratios (ORs indicating association with moderate to severe AGA (≥ IV. Subsequently, Hosmer-Lemeshow, Nagelkerke R(2 and accuracy tests were conducted to help establish an optimal model.Moderate to severe AGA was associated with the AA genotype of rs1160312 (22.50, 95% CI 3.99-126.83, blood vanadium concentration (0.02, 95% CI 0.01-0.04, and regular consumption of soy bean drinks (0.23, 95% CI 0.06-0.85, after adjustment for age. The results were corroborated by the Hosmer-Lemeshow test (P = 0.73, Nagelkerke R(2 (0.59, accuracy test (0.816 and area under the curve (AUC; 0.90, 0.847-0.951 analysis.Blood vanadium and frequent soy bean drink consumption may provide protect effects against AGA. Accordingly, blood vanadium concentrations, the AA genotype of rs1160312 and frequent consumption of soy bean drinks are associated with AGA.

  15. Simultaneous recovery of vanadium and nickel from power plant fly-ash: Optimization of parameters using response surface methodology

    Energy Technology Data Exchange (ETDEWEB)

    Nazari, E.; Rashchi, F., E-mail: rashchi@ut.ac.ir; Saba, M.; Mirazimi, S.M.J.

    2014-12-15

    Highlights: • Leaching of vanadium and nickel from fly ash (14.43% V and 5.19% Ni) in sulfuric acid was performed. • Optimization of leaching parameters was carried out using a response surface methodology. • Using optimum conditions, 94.28% V and 81.01% Ni “actual recovery” was obtained. - Abstract: Simultaneous recovery of vanadium (V) and nickel (Ni), which are classified as two of the most hazardous metal species from power plant heavy fuel fly-ash, was studied using a hydrometallurgical process consisting of acid leaching using sulfuric acid. Leaching parameters were investigated and optimized in order to maximize the recovery of both vanadium and nickel. The independent leaching parameters investigated were liquid to solid ratio (S/L) (5–12.5 wt.%), temperature (45–80 °C), sulfuric acid concentration (5–25 v/v%) and leaching time (1–5 h). Response surface methodology (RSM) was used to optimize the process parameters. The most effective parameter on the recovery of both elements was found to be temperature and the least effective was time for V and acid concentration for Ni. Based on the results, optimum condition for metals recovery (actual recovery of ca.94% for V and 81% for Ni) was determined to be solid to liquid ratio of 9.15 wt.%, temperature of 80 °C, sulfuric acid concentration of 19.47 v/v% and leaching time of 2 h. The maximum V and Ni predicted recovery of 91.34% and 80.26% was achieved.

  16. Androgenic Alopecia Is Associated with Less Dietary Soy, Higher Blood Vanadium and rs1160312 1 Polymorphism in Taiwanese Communities

    Science.gov (United States)

    Lai, Ching-Huang; Chu, Nain-Feng; Chang, Chi-Wen; Wang, Shu-Li; Yang, Hsin-Chou; Chu, Chi-Ming; Chang, Chu-Ting; Lin, Ming-Huang; Chien, Wu-Chien; Su, Sui-Lung; Chou, Yu-Ching; Chen, Kang-Hua; Wang, Wei-Ming; Liou, Saou-Hsing

    2013-01-01

    Background Although the genetic basis of androgenic alopecia has been clearly established, little is known about its non-genetic causes, such as environmental and lifestyle factors. Objective This study investigated blood and urine heavy metals concentrations, environmental exposure factors, personal behaviors, dietary intakes and the genotypes of related susceptibility genes in patients with androgenic alopecia (AGA). Design Age, AGA level, residence area, work hours, sleep patterns, cigarette usage, alcohol consumption, betel nut usage, hair treatments, eating habits, body heavy metals concentrations and rs1998076, rs913063, rs1160312 and rs201571 SNP genotype data were collected from 354 men. Logistic regression analysis was performed to examine whether any of the factors displayed odds ratios (ORs) indicating association with moderate to severe AGA (≧IV). Subsequently, Hosmer-Lemeshow, Nagelkerke R2 and accuracy tests were conducted to help establish an optimal model. Results Moderate to severe AGA was associated with the AA genotype of rs1160312 (22.50, 95% CI 3.99–126.83), blood vanadium concentration (0.02, 95% CI 0.01–0.04), and regular consumption of soy bean drinks (0.23, 95% CI 0.06–0.85), after adjustment for age. The results were corroborated by the Hosmer-Lemeshow test (P = 0.73), Nagelkerke R2 (0.59), accuracy test (0.816) and area under the curve (AUC; 0.90, 0.847–0.951) analysis. Conclusions Blood vanadium and frequent soy bean drink consumption may provide protect effects against AGA. Accordingly, blood vanadium concentrations, the AA genotype of rs1160312 and frequent consumption of soy bean drinks are associated with AGA. PMID:24386074

  17. Androgenic alopecia is associated with less dietary soy, lower [corrected] blood vanadium and rs1160312 1 polymorphism in Taiwanese communities.

    Science.gov (United States)

    Lai, Ching-Huang; Chu, Nain-Feng; Chang, Chi-Wen; Wang, Shu-Li; Yang, Hsin-Chou; Chu, Chi-Ming; Chang, Chu-Ting; Lin, Ming-Huang; Chien, Wu-Chien; Su, Sui-Lung; Chou, Yu-Ching; Chen, Kang-Hua; Wang, Wei-Ming; Liou, Saou-Hsing

    2013-01-01

    Although the genetic basis of androgenic alopecia has been clearly established, little is known about its non-genetic causes, such as environmental and lifestyle factors. This study investigated blood and urine heavy metals concentrations, environmental exposure factors, personal behaviors, dietary intakes and the genotypes of related susceptibility genes in patients with androgenic alopecia (AGA). Age, AGA level, residence area, work hours, sleep patterns, cigarette usage, alcohol consumption, betel nut usage, hair treatments, eating habits, body heavy metals concentrations and rs1998076, rs913063, rs1160312 and rs201571 SNP genotype data were collected from 354 men. Logistic regression analysis was performed to examine whether any of the factors displayed odds ratios (ORs) indicating association with moderate to severe AGA (≥ IV). Subsequently, Hosmer-Lemeshow, Nagelkerke R(2) and accuracy tests were conducted to help establish an optimal model. Moderate to severe AGA was associated with the AA genotype of rs1160312 (22.50, 95% CI 3.99-126.83), blood vanadium concentration (0.02, 95% CI 0.01-0.04), and regular consumption of soy bean drinks (0.23, 95% CI 0.06-0.85), after adjustment for age. The results were corroborated by the Hosmer-Lemeshow test (P = 0.73), Nagelkerke R(2) (0.59), accuracy test (0.816) and area under the curve (AUC; 0.90, 0.847-0.951) analysis. Blood vanadium and frequent soy bean drink consumption may provide protect effects against AGA. Accordingly, blood vanadium concentrations, the AA genotype of rs1160312 and frequent consumption of soy bean drinks are associated with AGA.

  18. Analysis of metals in asphaltenes of KU-46 by PIXE analysis; Analisis de metales en asfaltenos de crudo mexicano KU-46 por PIXE

    Energy Technology Data Exchange (ETDEWEB)

    Navidad G, P.; Pina L, L.I.; Lopez M, J.; Ramirez T, J.J.; Aspiazu F, J.A.; Romero G, E.T. [Gerencia de Ciencias Basicas, Instituto Nacional de Investigaciones Nucleares, A.P. 18-1027, 11801 Mexico D.F. (Mexico)

    2002-07-01

    The content of metals of the asphaltenes obtained from the KU-46 mexican crude with n-heptane was evaluated. The found metals in higher concentration are transition metals as well as the vanadium, nickel, copper and zinc. Moreover the sulfur in high concentrations was quantified. The metallic content of the asphaltenes revealed that the crude contains a lower quantity of metals unlike the vacuum residue previously analysed. (Author)

  19. Clinical assessment of class II resin-based composites versus preformed metal crowns performed on primary molars in patients at high risk of caries.

    Science.gov (United States)

    Alyahya, A; Khanum, A; Qudeimat, M

    2018-02-01

    To compare class II resin composite with preformed metal crowns (PMC) in the treatment of proximal dentinal caries in high caries-risk patients. The charts (270) of paediatric patients with proximal caries of their primary molars were reviewed. Success or failure of a procedure was assessed using the dental notes. Survival analysis was used to calculate the mean survival time (MST) for both procedures. The influence of variables on the mean survival time was investigated. A total of 593 class II resin composites and 243 PMCs were placed in patients ranging between 4-13 years of age. The failure percentage of class II resin composites was 22.6% with the majority having been due to recurrent caries, while the failure percentage of PMCs was 15.2% with the majority due to loss of the crown. There was no significant difference between the MST of class II resin composites and PMCs, 41.3 and 45.6 months respectively (p value = 0.06). In class II resin composites, mesial restorations were associated with lower MST compared to distal restorations (p-value composites and PMCs were comparable when performed on high caries-risk patients.

  20. A novel resource utilization of the calcium-based semi-dry flue gas desulfurization ash: As a reductant to remove chromium and vanadium from vanadium industrial wastewater.

    Science.gov (United States)

    Fang, Dean; Liao, Xiang; Zhang, Xuefei; Teng, Aijun; Xue, Xiangxin

    2018-01-15

    A novel resource utilization of the calcium-based semi-dry flue gas desulfurization ash is investigated. In the present study, the semi-dry desulfurization ash is used as a reductant for chromium and vanadium removal by chemical reduction precipitation, the byproduct gypsum and chromium-contained sludge are obtained. Besides, the effects of main operational parameters (reaction pH, desulfurization ash dosage and reaction time) on the heavy metal removal are investigated, and the main reaction mechanism for this treatment technology is also proposed. Under the optimal conditions, the residual concentrations of Cr(VI), total Cr and V are 0.163mg/L, 0.395mg/L and 0.155mg/L, respectively. Additionally, byproduct gypsum and chromium-contained sludge are characterized using X-ray diffraction (XRD), fourier transform infrared spectroscopy (FT-IR), scanning electron microscope-energy dispersive spectrometer (SEM-EDS) and thermogravimetry differential scanning calorimetry (TG-DSC), respectively. Finally, the resource utilization methods of the byproduct gypsum and chromium-contained sludge from this technology are also submitted. The byproduct gypsum can be utilized to produce hemihydrate calcium sulfate whisker, and the roasted heavy metal precipitation can be used as a primary chromium raw material (Cr2O3 content is about 83%). Copyright © 2017 Elsevier B.V. All rights reserved.