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Sample records for spinel-type cobalt ruthenium

  1. Application of spinel-type cobalt chromite as a novel catalyst for combustion of chlorinated organic pollutants.

    PubMed

    Kim, D C; Ihm, S K

    2001-01-01

    Various chromium-containing catalysts were tested for the total oxidation of trichloroethylene (TCE) as a model reaction for the catalytic combustion of chlorinated organic pollutants. A spinel-type cobalt chromite (CoCr2O4) among others was proven to be a very promising catalyst showing higher activity and higher CO2 selectivity than traditional alumina supported chromia. Even if both Cr3+ and Cr6+ species were observed on the surface of CoCr2O4, the Cr6+ species was stable under reducing environment. The presence of Cr3+-Cr6+ pair sites and the effect of redox treatments on the activity were investigated to explain the nature of possible active sites for TCE decomposition. Higher selectivity to CO2 of CoCr2O4 was ascribed to the abundance of its Cr3+ species, together with its activity for water gas shift reaction.

  2. Spinel-type lithium cobalt oxide as a bifunctional electrocatalyst for the oxygen evolution and oxygen reduction reactions.

    PubMed

    Maiyalagan, Thandavarayan; Jarvis, Karalee A; Therese, Soosairaj; Ferreira, Paulo J; Manthiram, Arumugam

    2014-05-27

    Development of efficient, affordable electrocatalysts for the oxygen evolution reaction and the oxygen reduction reaction is critical for rechargeable metal-air batteries. Here we present lithium cobalt oxide, synthesized at 400 °C (designated as LT-LiCoO2) that adopts a lithiated spinel structure, as an inexpensive, efficient electrocatalyst for the oxygen evolution reaction. The catalytic activity of LT-LiCoO2 is higher than that of both spinel cobalt oxide and layered lithium cobalt oxide synthesized at 800 °C (designated as HT-LiCoO2) for the oxygen evolution reaction. Although LT-LiCoO2 exhibits poor activity for the oxygen reduction reaction, the chemically delithiated LT-Li1-xCoO2 samples exhibit a combination of high oxygen reduction reaction and oxygen evolution reaction activities, making the spinel-type LT-Li0,5CoO2 a potential bifunctional electrocatalyst for rechargeable metal-air batteries. The high activities of these delithiated compositions are attributed to the Co4O4 cubane subunits and a pinning of the Co(3+/4+):3d energy with the top of the O(2-):2p band.

  3. Adapting Ruthenium Sensitizers to Cobalt Electrolyte Systems.

    PubMed

    Amit Kumar, Sangeeta; Urbani, Maxence; Medel, María; Ince, Mine; González-Rodríguez, David; Chandiran, Aravind Kumar; Bhaskarwar, Ashok N; Torres, Tomás; Nazeeruddin, Md K; Grätzel, Michael

    2014-02-06

    In this work, we report the use of bulky substitutions in a new heteroleptic ruthenium(II) bipyridine complex, Ru(NCS)2LL', coded TT-230 to obtain high open-circuit potential in a dye-sensitized solar cell (where L is a bipyridine ligand appended with two cyclopenta(2,1-b;3,4-bA)dithiophene moieties, and L' = 4,4,'-dicarboxylic acid 2,2'-bipyridine). The electrolytes based on cobalt complexes have shown significant advantages in terms of attainable open-circuit potential compared to the standard iodide/tri-iodide redox mediators. These merits of the cobalt complexes were previously realized with a porphyrin sensitizer, achieving a VOC greater than 1 V in DSC. However, with conventional Ru(II)-polypyridyl complexes such as the C101 dye, similar increase in the VOC could not be attained due to the enhanced recombination. In this work, we have shown that the use of bulky substituents can prevent the back reaction of photogenerated electron and subsequently increase the open-circuit potential of the device. The recombination processes were investigated by transient photovoltage decay measurements.

  4. Development of a stable cobalt-ruthenium Fisher-Tropsch catalyst. Final report

    SciTech Connect

    Frame, R.R.; Gala, H.B.

    1995-02-01

    The reverse micelle catalyst preparation method has been used to prepare catalysts on four supports: magnesium oxide, carbon, alumina- titania and steamed Y zeolite. These catalysts were not as active as a reference catalyst prepared during previous contracts to Union Carbide Corp. This catalyst was supported on steamed Y zerolite support and was impregnated by a pore-filling method using a nonaqueous solvent. Additional catalysts were prepared via pore- filling impregnation of steamed Y zeolites. These catalysts had levels of cobalt two to three and a half times as high as the original Union Carbide catalyst. On a catalyst volume basis they were much more active than the previous catalyst; on an atom by atom basis the cobalt was about of the same activity, i.e., the high cobalt catalysts` cobalt atoms were not extensively covered over and deactivated by other cobalt atoms. The new, high activity, Y zerolite catalysts were not as stable as the earlier Union Carbide catalyst. However, stability enhancement of these catalysts should be possible, for instance, through adjustment of the quantity and/or type of trace metals present. A primary objective of this work was determination whether small amounts of ruthenium could enhance the activity of the cobalt F-T catalyst. The reverse micelle catalysts were not activated by ruthenium, indeed scanning transmission electronic microscopy (STEM) analysis provided some evidence that ruthenium was not present in the cobalt crystallites. Ruthenium did not seem to activate the high cobalt Y zeolite catalyst either, but additional experiments with Y zeolite-supported catalysts are required. Should ruthenium prove not to be an effective promoter under the simple catalyst activation procedure used in this work, more complex activation procedures have been reported which are claimed to enhance the cobalt/ruthenium interaction and result in activity promotion by ruthenium.

  5. Ligand Engineering for the Efficient Dye-Sensitized Solar Cells with Ruthenium Sensitizers and Cobalt Electrolytes.

    PubMed

    Aghazada, Sadig; Gao, Peng; Yella, Aswani; Marotta, Gabriele; Moehl, Thomas; Teuscher, Joël; Moser, Jacques-E; De Angelis, Filippo; Grätzel, Michael; Nazeeruddin, Mohammad Khaja

    2016-07-05

    Over the past 20 years, ruthenium(II)-based dyes have played a pivotal role in turning dye-sensitized solar cells (DSCs) into a mature technology for the third generation of photovoltaics. However, the classic I3(-)/I(-) redox couple limits the performance and application of this technique. Simply replacing the iodine-based redox couple by new types like cobalt(3+/2+) complexes was not successful because of the poor compatibility between the ruthenium(II) sensitizer and the cobalt redox species. To address this problem and achieve higher power conversion efficiencies (PCEs), we introduce here six new cyclometalated ruthenium(II)-based dyes developed through ligand engineering. We tested DSCs employing these ruthenium(II) complexes and achieved PCEs of up to 9.4% using cobalt(3+/2+)-based electrolytes, which is the record efficiency to date featuring a ruthenium-based dye. In view of the complicated liquid DSC system, the disagreement found between different characterizations enlightens us about the importance of the sensitizer loading on TiO2, which is a subtle but equally important factor in the electronic properties of the sensitizers.

  6. Chemical Mechanical Polishing of Ruthenium, Cobalt, and Black Diamond Films

    NASA Astrophysics Data System (ADS)

    Peethala, Brown Cornelius

    Ta/TaN bilayer serves as the diffusion barrier as well as the adhesion promoter between Cu and the dielectric in 32 nm technology devices. A key concern of future technology devices (<32 nm) for Cu interconnects is the extendibility of TaN/Ta/Cu-seed to sustain the diffusion barrier performance without forming voids and meeting the requirements of low resistivity. These are very challenging requirements for the Ta/TaN bilayer at a thickness of < 5 nm. Hence, ruthenium (Ru) and cobalt (Co), among these, are being considered for replacing Ta/TaN as barrier materials for Cu interconnects in future technology devices. Both are very attractive for reasons such as the capability of direct electroplating of Cu, lower resistivity and for a single layer (vs. a bilayer of Ta/TaN) to act as a barrier. During patterning, they need to be planarized using conventional chemical mechanical polishing (CMP) to achieve a planar surface. However, CMP of these new barrier materials requires novel slurry compositions that provide adequate selectivity towards Cu and dielectric films, and minimize galvanic corrosion. Apart from the application as a barrier, Ru also has been proposed as a lower electrode material in metal-insulator-metal capacitors where high (> 50 nm/min) Ru removal rates (RRs) are required and as a stop layer in magnetic recording head fabrication where low (< 1 nm/min) Ru RRs are desired. A Ru removal rate of ˜60 nm/min was achieved with a colloidal silica-based slurry at pH 9 using potassium periodate (KIO4) as the oxidizer. At this pH, toxic RuO4 does not form eliminating a major challenge in Ru CMP. This removal rate was obtained by increasing the solubility of KIO4 by adding potassium hydroxide (KOH). It was also determined that increased the ionic strength is not responsible for the observed increase in Ru removal rate. Benzotirazole (BTA) and ascorbic acid were added to the slurry to reduce the open circuit potential (Eoc) difference between Cu and Ru to ˜20 m

  7. Cobalt.

    PubMed

    Fowler, Joseph F

    2016-01-01

    Cobalt has been a recognized allergen capable of causing contact dermatitis for decades. Why, therefore, has it been named 2016 "Allergen of the Year"? Simply put, new information has come to light in the last few years regarding potential sources of exposure to this metallic substance. In addition to reviewing some background on our previous understanding of cobalt exposures, this article will highlight the recently recognized need to consider leather as a major site of cobalt and the visual cues suggesting the presence of cobalt in jewelry. In addition, a chemical spot test for cobalt now allows us to better identify its presence in suspect materials.

  8. Cobalt

    SciTech Connect

    1993-02-01

    Cobalt is typical a by- or co-product with copper or nickel. The average crustal abundance of cobalt is 23 pans per million. Cobalt-containing minerals include cobaltite, skutterudite, and linnaeite. Due to the diversity of cobalt deposits, several techniques are used to extract the ore. The copper/cobalt-bearing ores of Zaire are extracted by open pit and underground methods. In Zambia, similar deposits are mined using modified sublevel, and cut-and-fill underground stoping methods. The sulfide and oxide ore concentrates mined in Zaire are roasted and leached in sulfuric acid. Copper is subsequently recovered by electrolysis, and cobalt is precipitated in the form of a hydrate. Finally, the hydrate is dissolved in acid and cobalt is recovered by electrolysis.

  9. In situ synthesis of binary cobalt-ruthenium nanofiber alloy counter electrode for electrolyte-free cadmium sulfide quantum dot solar cells

    NASA Astrophysics Data System (ADS)

    Du, Nan; Ren, Lei; Sun, Weifu; Jin, Xiao; Zhao, Qing; Cheng, Yuanyuan; Wei, Taihuei; Li, Qinghua

    2015-06-01

    A facile, low-cost and low-temperature fabrication approach of counter electrode is essential for pursuing robust photovoltaic devices. Herein, we develop a hydrothermal in situ growth of Cobalt-Ruthenium (Co-Ru) alloy nanofiber electrode for quantum dot solar cell (QDSC) applications. Colloidal CdS QDs with tunable absorption band edge are synthesized and used as light absorber. After optimizing the QDs with the highest photoluminescence quantum yield accompanied by considerable solar light absorption ability, QDSC based on Co-Ru alloy electrode delivers a much higher power conversion efficiency than its counterparts, i.e., either pure Co or Ru metal electrodes. In detail, Co-Ru alloy electrode exhibits high specific area, excellent electrical behavior, intimate interface contact, and good stability, thus leading to notable improved device performances. The impressive robust function of Co-Ru alloy with simple manufacturing procedure highlights its potential applications in robust QDSCs.

  10. Cobalt

    SciTech Connect

    Fox, G.J.

    1994-12-01

    Traditionally, cobalt has been well-known for its chemical uses, including pigments used in ceramic glazes that create the popular cobalt blue color derived from cobalt aluminate. Because of its diverse physical properties, the element is linked to many other applications, including superalloys, permanent magnets, and chemical catalysts. Cobalt 60, a radioisotope of cobalt, continues to be a contributor to the success of high-technology advancements, including innovations in medical treatments. Typically a by-product of copper and nickel production, significant cobalt reserves are found in only a few countries. The African countries of Zaire and Zambia, as well as Canada, are leading cobalt producers. Although the USA is the world's largest consumer, accounting for about one-third of total consumption, it has no domestic production and relies solely upon foreign imports to satisfy demand. The world market has been plagued with the effects of economic and political factors throughout the years, and consequently, price instability has been common. Presently, supply and demand are moving toward a closer balance, and lower market prices are expected within the next year.

  11. Porous nanoarchitectures of spinel-type transition metal oxides for electrochemical energy storage systems.

    PubMed

    Park, Min-Sik; Kim, Jeonghun; Kim, Ki Jae; Lee, Jong-Won; Kim, Jung Ho; Yamauchi, Yusuke

    2015-12-14

    Transition metal oxides possessing two kinds of metals (denoted as AxB3-xO4, which is generally defined as a spinel structure; A, B = Co, Ni, Zn, Mn, Fe, etc.), with stoichiometric or even non-stoichiometric compositions, have recently attracted great interest in electrochemical energy storage systems (ESSs). The spinel-type transition metal oxides exhibit outstanding electrochemical activity and stability, and thus, they can play a key role in realising cost-effective and environmentally friendly ESSs. Moreover, porous nanoarchitectures can offer a large number of electrochemically active sites and, at the same time, facilitate transport of charge carriers (electrons and ions) during energy storage reactions. In the design of spinel-type transition metal oxides for energy storage applications, therefore, nanostructural engineering is one of the most essential approaches to achieving high electrochemical performance in ESSs. In this perspective, we introduce spinel-type transition metal oxides with various transition metals and present recent research advances in material design of spinel-type transition metal oxides with tunable architectures (shape, porosity, and size) and compositions on the micro- and nano-scale. Furthermore, their technological applications as electrode materials for next-generation ESSs, including metal-air batteries, lithium-ion batteries, and supercapacitors, are discussed.

  12. In-vitro and in-vivo characterization of ruthenium-bleomycin compared to cobalt- and copper-bleomycin

    SciTech Connect

    Shao, H.S.; Meinken, G.E.; Srivastava, S.C.; Slosman, D.; Sacker, D.F.; Som, P.; Brill, A.B.

    1986-01-01

    Bleomycin (BLM) has undergone extensive investigation both as a cancer chemotherapeutic agent, and as a carrier for radionuclides for tumor imaging. The available methods or the radionuclides used, however, have had limited effectiveness. Although labeling of BLM with /sup 103/Ru has been reported earlier, we carried out a study to develop a more reproducible method of labeling particularly for use with Brookhaven Linac Isotope Producer produced /sup 97/Ru. Ruthenium-97 has favorable physical properties that make it ideal for imaging applications: decay by electron capture; ..gamma.. 216 keV, 85%; t/sub 1/2/ 2.9 d. A novel method based on the reduction of Ru/sup 3 +/ to Ru/sup 2 +/ using stannous chloride was investigated for labeling BLM with /sup 97/Ru and/or /sup 103/Ru. In-vitro and in vivo comparisons of the product(s) with /sup 57/Co and /sup 67/Cu-labeled BLM were also carried out. 4 refs., 3 tabs.

  13. Decomposition of spinel-type nickel chromium indium sulfides -- X-ray powder structure determination

    SciTech Connect

    Lutz, H.D.; Kringe, C.; Mohn, K.; Stingl, T.

    1998-03-01

    The phase diagram of the quaternary system NiCr{sub 2}S{sub 4}-NiIn{sub 2}S{sub 4}-Cr{sub 2}S{sub 3}-In{sub 2}S{sub 3} has been studied at 873 and 1,223 K by X-ray powder structure determination of quenched samples. At high temperatures, spinel-type Ni{sub y}(Cr{sub 2{minus}2x}In{sub 2x}){sub 1{minus}y}S{sub 3{minus}2y} solid solutions are formed in a large range of composition (y:0--0.5, x:03--1). At temperatures below 1,183 K, these solid solutions decompose to Cr-rich and In-rich spinel-type sulfides, whereby nickel is enriched in the Cr-rich compounds. The decomposition of the spinel-type sulfides is greatly retarded, even at temperatures about 900 K, due to both thermodynamic and kinetic reasons. The cation distribution established corresponds to a site preference as Cr{sup 3+} > Ni{sup 2+} > In{sup 3+} at the octahedral 16d site and {open_square} (vacancies) > In{sup 3+} > Ni{sup 2+} at the tetrahedral 8a site of the spinel structure. The metal-sulfur distances of the solid solutions refined are compared with those calculated from characteristic metal-sulfur distances in close-packed structures, taking into account the site occupation established. For the respective indium-sulfur distances, the following improved values are recommended: In{sub tet}-S = 247.1 pm; In{sub oct}-S = 260.6 pm.

  14. RECOVERY OF RUTHENIUM VALUES

    DOEpatents

    Grummitt, W.E.; Hardwick, W.H.

    1961-01-01

    A process is given for the recovery of ruthenium from its aqueous solutions by oxidizing the ruthenium to the octavalent state and subsequently extracting the ruthenium into a halogen-substituted liquid paraffin.

  15. Colloidal Synthesis of Bipolar Off-Stoichiometric Gallium Iron Oxide Spinel-Type Nanocrystals with Near-IR Plasmon Resonance.

    PubMed

    Urso, Carmine; Barawi, Mariam; Gaspari, Roberto; Sirigu, Gianluca; Kriegel, Ilka; Zavelani-Rossi, Margherita; Scotognella, Francesco; Manca, Michele; Prato, Mirko; De Trizio, Luca; Manna, Liberato

    2017-01-25

    We report the colloidal synthesis of ∼5.5 nm inverse spinel-type oxide Ga2FeO4 (GFO) nanocrystals (NCs) with control over the gallium and iron content. As recently theoretically predicted, some classes of spinel-type oxide materials can be intrinsically doped by means of structural disorder and/or change in stoichiometry. Here we show that, indeed, while stoichiometric Ga2FeO4 NCs are intrinsic small bandgap semiconductors, off-stoichiometric GFO NCs, produced under either Fe-rich or Ga-rich conditions, behave as degenerately doped semiconductors. As a consequence of the generation of free carriers, both Fe-rich and Ga-rich GFO NCs exhibit a localized surface plasmon resonance in the near-infrared at ∼1000 nm, as confirmed by our pump-probe absorption measurements. Noteworthy, the photoelectrochemical characterization of our GFO NCs reveal that the majority carriers are holes in Fe-rich samples, and electrons in Ga-rich ones, highlighting the bipolar nature of this material. The behavior of such off-stoichiometric NCs was explained by our density functional theory calculations as follows: the substitution of Ga(3+) by Fe(2+) ions, occurring in Fe-rich conditions, can generate free holes (p-type doping), while the replacement of Fe(2+) by Ga(3+) cations, taking place in Ga-rich samples, produces free electrons (n-type doping). These findings underscore the potential relevance of spinel-type oxides as p-type transparent conductive oxides and as plasmonic semiconductors.

  16. Radiochemistry of ruthenium

    SciTech Connect

    Schulz, W W; Metcalf, S G; Barney, G S

    1984-06-01

    Information on ruthenium is presented. Topics include the following; isotopes and nuclear properties of ruthenium; review of the chemistry of ruthenium including metal and alloys, compounds of ruthenium, and solution chemistry; separation methods including volatilization of RuO{sub 4}, precipitation and coprecipitation, solvent extraction, chromatographic techniques, and analysis for radioruthenium. 445 refs., 7 figs., 23 tabs.

  17. Crystal structure of spinel-type Li0.64Fe2.15Ge0.21O4

    PubMed Central

    Redhammer, Günther J.; Tippelt, Gerold

    2016-01-01

    Spinel-type Li0.64Fe2.15Ge0.21O4, lithium diiron(III) germanium tetra­oxide, has been formed as a by-product during flux growth of an Li–Fe–Ge pyroxene-type material. In the title compound, lithium is ordered on the octa­hedral B sites, while Ge4+ orders onto the tetra­hedral A sites, and iron distributes over both the octa­hedral and tetra­hedral sites, and is in the trivalent state as determined from Mössbauer spectroscopy. The oxygen parameter u is 0.2543; thus, the spinel is close to having an ideal cubic closed packing of the O atoms. The title spinel is compared with other Li- and Ge-containing spinels. PMID:27375876

  18. Comparison effects and electron spin resonance studies of α-Fe2O4 spinel type ferrite nanoparticles.

    PubMed

    Bayrakdar, H; Yalçın, O; Cengiz, U; Özüm, S; Anigi, E; Topel, O

    2014-11-11

    α-Fe2O4 spinel type ferrite nanoparticles have been synthesized by cetyltrimethylammonium bromide (CTAB) and ethylenediaminetetraacetic acid (EDTA) assisted hydrothermal route by using NaOH solution. Electron spin resonance (ESR/EPR) measurements of α-Fe2O4 nanoparticles have been performed by a conventional x-band spectrometer at room temperature. The comparison effect of nanoparticles prepared by using CTAB and EDTA in different α-doping on the structural and morphological properties have been investigated in detail. The effect of EDTA-assisted synthesis for α-Fe2O4 nanoparticles are refined, and thus the spectroscopic g-factor are detected by using ESR signals. These samples can be considered as great benefits for magnetic recording media, electromagnetic and drug delivery applications.

  19. Crystal structure of spinel-type Li0.64Fe2.15Ge0.21O4.

    PubMed

    Redhammer, Günther J; Tippelt, Gerold

    2016-04-01

    Spinel-type Li0.64Fe2.15Ge0.21O4, lithium diiron(III) germanium tetra-oxide, has been formed as a by-product during flux growth of an Li-Fe-Ge pyroxene-type material. In the title compound, lithium is ordered on the octa-hedral B sites, while Ge(4+) orders onto the tetra-hedral A sites, and iron distributes over both the octa-hedral and tetra-hedral sites, and is in the trivalent state as determined from Mössbauer spectroscopy. The oxygen parameter u is 0.2543; thus, the spinel is close to having an ideal cubic closed packing of the O atoms. The title spinel is compared with other Li- and Ge-containing spinels.

  20. Effect of Heat-Treatment and Composition on Structure and Luminescence Properties of Spinel-Type Solid Solution Nanocrystals.

    PubMed

    Sakoda, Kazuki; Hirano, Masanori

    2015-08-01

    The compositional dependence of the structure and properties of spinel-type solid solutions, Zn(A,Ga)2O4 was investigated by comparison with samples hydrothermally prepared and those after heat treatment at 1000 °C in air. Nanocrystalline spinel-type solid solutions in the whole composition range in the ZnAl2O4-ZnGa2O4 system were directly formed from the aqueous precursor solutions of ZnSO4, Al(NO3)3 and Ga(NO3)3 under hydrothermal conditions at 180 °C for 5 h in the presence of tetramethylammonium hydroxide. The incorporation of aluminum into the lattice, Zn(AlxGa1-x)2O4, resulted in lower crystallinity of the spinel. The relationship between the lattice parameter of as-prepared samples and the Al atomic ratio in the spinel composition was slightly apart from the ideal linear relationship that was obtained in the samples after heat treatment at 1000 °C. The optical band gap of both as-prepared solid solutions and those heat treated linearly increased from 4.1~4.2 to 5.25 eV by the incorporation of aluminum ion into the lattice, Zn(AlxGa1-x)2O4. Two main broad-band emission spectra centered at around 360 and 430 nm in the range of 300-600 nm were observed in the spinel solid solutions under excitation at 270 nm, thought their broad-band emission spectra and their peak wavelengths subtly changed depending on the composition and heat treatment.

  1. Metals fact sheet: Ruthenium

    SciTech Connect

    1996-06-01

    Ruthenium, named after Ruthenia, a province in Western Russia, was discovered in 1827 by Osann in placer ores from Russia`s Ural mountains. A minor platinum group metal (PGM), Ruthenium was the last of the PGMs to be isolated. In 1844, Klaus prepared the first 6 grams of pure ruthenium metal.

  2. Ferromagnetic-phase transition in the spinel-type CuCr{sub 2}Te{sub 4}

    SciTech Connect

    Suzuyama, Takeshi; Awaka, Junji; Yamamoto, Hiroki; Ebisu, Shuji; Ito, Masakazu; Suzuki, Takashi; Nakama, Takao; Yagasaki, Katsuma; Nagata, Shoichi . E-mail: naga-sho@mmm.muroran-it.ac.jp

    2006-01-15

    Ferromagnetic-phase transition in spinel-type CuCr{sub 2}Te{sub 4} has been clearly observed. CuCr{sub 2}Te{sub 4} is a telluride-spinel with the lattice constant a=11.134A, which has been synthesized successfully. The heat capacity exhibits a sharp peak due to the ferromagnetic-phase transition with the Curie temperature T{sub C}=326K. This value of T{sub C} corresponds exactly to that of the negative peak of dM/dT in low field of 1.0Oe. The magnetic susceptibility shows the Curie-Weiss behavior between 380 and 650K with the effective magnetic moment {mu}{sub eff}=4.14{mu}{sub B}/Cr-ion and the Weiss constant {theta}=+357K. The low temperature magnetization indicates the spin-wave excitations, where the existence of first term of Bloch T{sup 3/2} law and the next T{sup 5/2} term are verified experimentally. This spin-wave excitation is detected up to approximately 250K which is a fairly high temperature.

  3. Electrochemical Synthesis of Spinel Type ZnCo2O4 Electrodes for Use as Oxygen Evolution Reaction Catalysts.

    PubMed

    Kim, Tae Woo; Woo, Myong A; Regis, Morrisa; Choi, Kyoung-Shin

    2014-07-03

    A new electrochemical synthesis route was developed to prepare spinel-type ZnCo2O4 and Co3O4 as high quality thin film-type electrodes for use as electrocatalysts for oxygen evolution reaction (OER). Whereas Co3O4 contains Co(2+) in the tetrahedral sites and Co(3+) in the octahedral sites in the spinel structure, ZnCo2O4 contains only Co(3+) in the octahedral sites; Co(2+) in the tetrahedral sites is replaced by Zn(2+). Therefore, by comparing the catalytic properties of ZnCo2O4 and Co3O4 electrodes prepared with comparable surface morphologies and thicknesses, it was possible to examine whether Co(2+) in Co3O4 is catalytically active for OER. The electrocatalytic properties of ZnCo2O4 and Co3O4 for OER in both 1 M KOH (pH 13.8) and 0.1 M phosphate buffer (pH 7) solutions were investigated and compared. The results suggest that the Co(2+) in Co3O4 is not catalytically critical for OER and ZnCo2O4 can be a more economical and environmentally benign replacement for Co3O4 as an OER catalyst.

  4. Synthesis of ruthenium hydride

    NASA Astrophysics Data System (ADS)

    Kuzovnikov, M. A.; Tkacz, M.

    2016-02-01

    Ruthenium hydride was synthesized at a hydrogen pressure of about 14 GPa in a diamond-anvil cell. Energy-dispersive x-ray diffraction was used to monitor the ruthenium crystal structure as a function of hydrogen pressure up to 30 GPa. The hydride formation was accompanied by phase transition from the original hcp structure of the pristine metal to the fcc structure. Our results confirmed the theoretical prediction of ruthenium hydride formation under hydrogen pressure. The standard Gibbs free energy of the ruthenium hydride formation reaction was calculated assuming the pressure of decomposition as the equilibrium pressure.

  5. meta-C-H Bromination on Purine Bases by Heterogeneous Ruthenium Catalysis.

    PubMed

    Warratz, Svenja; Burns, David J; Zhu, Cuiju; Korvorapun, Korkit; Rogge, Torben; Scholz, Julius; Jooss, Christian; Gelman, Dmitri; Ackermann, Lutz

    2017-02-01

    Methods for positionally selective remote C-H functionalizations are in high demand. Herein, we disclose the first heterogeneous ruthenium catalyst for meta-selective C-H functionalizations, which enabled remote halogenations with excellent site selectivity and ample scope. The versatile heterogeneous Ru@SiO2 catalyst was broadly applicable and could be easily recovered and reused, which set the stage for the direct fluorescent labeling of purines. In contrast to palladium, rhodium, iridium, or cobalt complexes, solely the ruthenium catalysis manifold provided access to meta-halogenated purine derivatives, illustrating the unique power of ruthenium C-H activation catalysis.

  6. SOLVENT EXTRACTION OF RUTHENIUM

    DOEpatents

    Hyman, H.H.; Leader, G.R.

    1959-07-14

    The separation of rathenium from aqueous solutions by solvent extraction is described. According to the invention, a nitrite selected from the group consisting of alkali nitrite and alkaline earth nitrite in an equimolecular quantity with regard to the quantity of rathenium present is added to an aqueous solution containing ruthenium tetrantrate to form a ruthenium complex. Adding an organic solvent such as ethyl ether to the resulting mixture selectively extracts the rathenium complex.

  7. A general method of fabricating flexible spinel-type oxide/reduced graphene oxide nanocomposite aerogels as advanced anodes for lithium-ion batteries.

    PubMed

    Zeng, Guobo; Shi, Nan; Hess, Michael; Chen, Xi; Cheng, Wei; Fan, Tongxiang; Niederberger, Markus

    2015-04-28

    High-capacity anode materials for lithium ion batteries (LIBs), such as spinel-type metal oxides, generally suffer from poor Li(+) and e(-) conductivities. Their drastic crystal structure and volume changes, as a result of the conversion reaction mechanism with Li, severely impede the high-rate and cyclability performance toward their practical application. In this article, we present a general and facile approach to fabricate flexible spinel-type oxide/reduced graphene oxide (rGO) composite aerogels as binder-free anodes where the spinel nanoparticles (NPs) are integrated in an interconnected rGO network. Benefiting from the hierarchical porosity, conductive network and mechanical stability constructed by interpenetrated rGO layers, and from the pillar effect of NPs in between rGO sheets, the hybrid system synergistically enhances the intrinsic properties of each component, yet is robust and flexible. Consequently, the spinel/rGO composite aerogels demonstrate greatly enhanced rate capability and long-term stability without obvious capacity fading for 1000 cycles at high rates of up to 4.5 A g(-1) in the case of CoFe2O4. This electrode design can successfully be applied to several other spinel ferrites such as MnFe2O4, Fe3O4, NiFe2O4 or Co3O4, all of which lead to excellent electrochemical performances.

  8. Enzyme mimics of spinel-type Co(x)Ni(1-x)Fe2O4 magnetic nanomaterial for eletroctrocatalytic oxidation of hydrogen peroxide.

    PubMed

    Luo, Liqiang; Zhang, Yuting; Li, Fang; Si, Xiaojing; Ding, Yaping; Deng, Dongmei; Wang, Tianlin

    2013-07-25

    A series of spinel-type Co(x)Ni(1-x)Fe2O4 (x=0, 0.2, 0.4, 0.5, 0.6, 0.8, 1.0) magnetic nanomaterials were solvothermally synthesized as enzyme mimics for the eletroctrocatalytic oxidation of H2O2. X-ray diffraction and scanning electron microscope were employed to characterize the composition, structure and morphology of the material. The electrochemical properties of spinel-type Co(x)Ni(1-x)Fe2O4 with different (Co/Ni) molar ratio toward H2O2 oxidation were investigated, and the results demonstrated that Co0.5Ni0.5Fe2O4 modified carbon paste electrode (Co0.5Ni0.5Fe2O4/CPE) possessed the best electrocatalytic activity for H2O2 oxidation. Under optimum conditions, the calibration curve for H2O2 determination on Co0.5Ni0.5Fe2O4/CPE was linear in a wide range of 1.0×10(-8)-1.0×10(-3)M with low detection limit of 3.0×10(-9)M (S/N=3). The proposed Co0.5Ni0.5Fe2O4/CPE was also applied to the determination of H2O2 in commercial toothpastes with satisfactory results, indicating that Co(x)Ni(1-x)Fe2O4 is a promising hydrogen peroxidase mimics for the detection of H2O2.

  9. Cobalt poisoning

    MedlinePlus

    ... the wear and tear of some cobalt/chromium metal-on-metal hip implants. This type of implant is an ... hip socket that is created by fitting a metal ball into a metal cup. Sometimes, metal particles ( ...

  10. RUTHENIUM DECONTAMINATION METHOD

    DOEpatents

    Gresky, A.T.

    1960-07-19

    A liquid-liquid extraction method of separating uranium from fission products is given. A small amount of a low molecular weight ketone is added to an acidic aqueous solution containing neutron-irradiated uranium and its associated fission products. The resulting solution is digested and then contacted with an organic liquid that extracts uranium values. The purpose of the step of digesting the aqueous solution in the presence of the ketone is to suppress the extractability of ruthenium.

  11. Optimization of reaction conditions in selective oxidation of styrene over fine crystallite spinel-type CaFe{sub 2}O{sub 4} complex oxide catalyst

    SciTech Connect

    Pardeshi, Satish K.; Pawar, Ravindra Y.

    2010-05-15

    The CaFe{sub 2}O{sub 4} spinel-type catalyst was synthesized by citrate gel method and well characterized by thermogravimetric analysis, atomic absorption spectroscopy, Fourier-transform infrared spectroscopy, X-ray diffraction and transmission electron microscopy. The crystallization temperature of the spinel particle prepared by citrate gel method was 600 {sup o}C which was lower than that of ferrite prepared by other methods. CaFe{sub 2}O{sub 4} catalysts prepared by citrate gel method show better activity for styrene oxidation in the presence of dilute H{sub 2}O{sub 2} (30%) as an oxidizing agent. In this reaction the oxidative cleavage of carbon-carbon double bond of styrene takes place selectively with 38 {+-} 2 mol% conversion. The major product of the reaction is benzaldehyde up to 91 {+-} 2 mol% and minor product phenyl acetaldehyde up to 9 {+-} 2 mol%, respectively. The products obtained in the styrene oxidation reaction were analyzed by gas chromatography and mass spectroscopy. The influence of the catalyst, reaction time, temperature, amount of catalyst, styrene/H{sub 2}O{sub 2} molar ratio and solvents on the conversion and product distribution were studied.

  12. Cobalt superalloy

    SciTech Connect

    Crook, P.

    1983-11-15

    Disclosed is a cobalt-base superalloy containing about 32% cobalt, 8% nickel, 26.5% chromium, 2.5% tungsten, 5% niobium, about 1% each manganese and silicon, about 0.4% carbon, and the balance about 23% iron plus incidental impurities and modifiers normally found in alloys of this class. The alloy is readily processed in the form of wrought products, castings, metal powder and all forms of welding and hardfacing materials. The outstanding characteristics of the new alloy include the resistance to cavitation erosion and galling, low cost and minimal use of strategic metals.

  13. Magnetic properties of the spinel-type Cu(Cr{sub 1-x}Hf{sub x}){sub 2}S{sub 4}

    SciTech Connect

    Kariya, F.; Ebina, K.; Hasegawa, K.; Koshimizu, K.; Wuritunasitu, B.; Hondou, K.; Ebisu, S.; Nagata, S.

    2009-08-15

    The spinel sulphide CuCr{sub 2}S{sub 4} is a metallic ferromagnet with a Curie temperature T{sub c}{approx_equal}380K, while CuHf{sub 2}S{sub 4} has no magnetic anomaly. Magnetic properties of the quaternary spinel-type Cu(Cr{sub 1-x}Hf{sub x}){sub 2}S{sub 4} system have been studied. With increasing x the ferromagnetic properties are weakened gradually from a predominant ferromagnetic, a spin-glass, finally to a simple paramagnetic behavior. For the composition of x{approx_equal}0.50, a re-entrant spin-glass phase could emerge, even though the Curie temperature is ill-defined as a ferromagnetic phase boundary. Specimens with x>=0.90 remain paramagnetic down to 4.2 K. A spin crossover phenomenon is found around 160 K in the specimens of x=0.50-0.70. A step-like anomaly is manifestly detected in the magnetization, which corresponds with the change of the spin state. This crossover indicates that the spin state converts from high temperature S=2 into low temperature S=3/2 states. In the ordered states in T<160K, the magnetic moment originates from only Cr{sup 3+} ions. - Spin crossover phenomenon in Cu(Cr{sub 1-x}Hf{sub x}){sub 2}S{sub 4}. A step-like anomaly is found around 160 K for x=0.50, 0.60, and 0.70 in the magnetization as a function of temperature. The inset shows the enlargement data for x=0.60. This crossover indicates that the spin state changes from high temperature S=2 to low temperature S=3/2 states.

  14. Spinel-type manganese ferrite (MnFe2O4) microspheres: A novel affinity probe for selective and fast enrichment of phosphopeptides.

    PubMed

    Long, Xing-Yu; Li, Jia-Yuan; Sheng, Dong; Lian, Hong-Zhen

    2017-05-01

    The spinel-type magnetic manganese ferrite (MnFe2O4) microspheres synthesized by simple solvothermal method were used as a novel adsorbent for selective enrichment and effective isolation of phosphopeptides. The uniform MnFe2O4 magnetic affinity microspheres (MAMSs) had a narrow particle size distribution between 250 and 260nm, and displayed superparamagnetism with a saturation magnetization value of 67.0emu/g. Comprehensively, the possible formation mechanism of MnFe2O4 microspheres with ferric and manganous sources as dual precursors was elucidated by comparison with those of Fe3O4 nanoparticles and MnOOH nanosheets respectively with either ferric or manganous source as single precursor. It was suggested that the spherical or sheet nanostructures could be achieved via secondary recrystallization or Ostwald ripening. The MnFe2O4 MAMSs probe exhibited excellent dispersibility in aqueous solution, and rapid magnetic separation within 15s, as well as good reusability. More importantly, MnFe2O4 was highly selective for phosphopeptides because of the strong coordination interaction between metal ions (Fe(3+) and Mn(2+)) and phosphate groups of phosphopeptdies. This high specificity was demonstrated by effectively enriching phosphopeptides from digest mixture of β-casein and bovine serum albumin (BSA) with high content of non-phosphopeptides, and embodied further in phosphopeptides enrichment from non-fat milk digests and human serum. Consequently, the prepared MnFe2O4 affinity materials are expected to possess great potential in phosphoproteome research.

  15. Moderated ruthenium fischer-tropsch synthesis catalyst

    DOEpatents

    Abrevaya, Hayim

    1991-01-01

    The subject Fischer-Tropsch catalyst comprises moderated ruthenium on an inorganic oxide support. The preferred moderator is silicon. Preferably the moderator is effectively positioned in relationship to ruthenium particles through simultaneous placement on the support using reverse micelle impregnation.

  16. SEPARATION OF RUTHENIUM FROM AQUEOUS SOLUTIONS

    DOEpatents

    Callis, C.F.; Moore, R.L.

    1959-09-01

    >The separation of ruthenium from aqueous solutions containing uranium plutonium, ruthenium, and fission products is described. The separation is accomplished by providing a nitric acid solution of plutonium, uranium, ruthenium, and fission products, oxidizing plutonium to the hexavalent state with sodium dichromate, contacting the solution with a water-immiscible organic solvent, such as hexone, to extract plutonyl, uranyl, ruthenium, and fission products, reducing with sodium ferrite the plutonyl in the solvent phase to trivalent plutonium, reextracting from the solvent phase the trivalent plutonium, ruthenium, and some fission products with an aqueous solution containing a salting out agent, introducing ozone into the aqueous acid solution to oxidize plutonium to the hexavalent state and ruthenium to ruthenium tetraoxide, and volatizing off the ruthenium tetraoxide.

  17. SEPARATION OF RUTHENIUM FROM AQUEOUS SOLUTIONS

    DOEpatents

    Beederman, M.; Vogler, S.; Hyman, H.H.

    1959-07-14

    The separation of rathenium from a rathenium containing aqueous solution is described. The separation is accomplished by adding sodium nitrite, silver nitrate and ozone to the ruthenium containing aqueous solution to form ruthenium tetroxide and ihen volatilizing off the ruthenium tetroxide.

  18. Characterization And Dissolution Properties Of Ruthenium Oxides

    EPA Science Inventory

    Ruthenium oxides (RuO2•1.10H2O and RuO2) have been synthesized by forced hydrolysis and oxidation of ruthenium chloride. The resulting materials were extensively characterized to determine the crystallinity, surface area, and ruthenium oxidation ...

  19. Influence of the presence of ruthenium on the activity and stability of Co-Mg-Al-based catalysts in CO2 reforming of methane for syngas production.

    PubMed

    Gennequin, Cédric; Hany, Sara; Tidahy, Haingomalala Lucette; Aouad, Samer; Estephane, Jane; Aboukaïs, Antoine; Abi-Aad, Edmond

    2016-11-01

    Hydrogen production by methane dry reforming is an important yet challenging process. A performing catalyst will favor the thermodynamic equilibrium while ensuring good hydrogen selectivity. We hereby report the synthesis of Co x Mg6-x Al2 (with x = 2 and 6) mixed oxide catalysts synthesized via hydrotalcite precursors and the synthesis of a ruthenium-based catalyst on a cobalt, magnesium, and aluminum mixed oxide supports Ru/Co x Mg6-x Al2 (with x = 2 and 6). The impregnation of ruthenium on the hydrotalcites was performed in two ways: by impregnation on the dried hydrotalcite and by memory effect on hydrotalcite calcined at 500 °C. The deposition of ruthenium by memory effect of the magnesium and cobalt support allows the generation of both metallic and basic sites which provides an active and stable catalyst for the dry reforming reaction of methane.

  20. Synthesis and Characterization of Cobalt Substituted Zinc Ferrite Nanoparticles by Microwave Combustion Method.

    PubMed

    Sundararajan, M; Kennedy, L John; Vijaya, J Judith

    2015-09-01

    Pure and cobalt doped zinc ferrites were prepared by microwave combustion method using L-arginine as a fuel. The prepared samples were characterized by various instrumental techniques such as X-ray powder diffractometry, high resolution scanning electron microscopy (HR-SEM), energy dispersive X-ray analysis, Fourier transformed infrared (FT-IR) spectroscopy, photoluminescence spectroscopy and UV-Visible diffuse reflectance spectroscopy. Vibrating sample magnetometry at room temperature was recorded to study the magnetic behavior of the samples. X-ray analysis confirmed the formation of zinc ferrites normal spinel-type structure with an average crystallite sizes in the range, 25.69 nm to 35.68 nm. The lattice parameters decreased as cobalt fraction was increased. The HR-SEM images showed nanoparticles are agglomerated. The estimated band gap energy value was found to decrease with an increase in cobalt content (1.87 to 1.62 eV). Broad visible emissions are observed in the photoluminescence spectra. A gradual increase in the coercivity and saturation magnetization (M(s)) were noted at relatively higher cobalt doping fractions.

  1. Ruthenium complexes as antimicrobial agents.

    PubMed

    Li, Fangfei; Collins, J Grant; Keene, F Richard

    2015-04-21

    One of the major advances in medical science has been the development of antimicrobials; however, a consequence of their widespread use has been the emergence of drug-resistant populations of microorganisms. There is clearly a need for the development of new antimicrobials--but more importantly, there is the need for the development of new classes of antimicrobials, rather than drugs based upon analogues of known scaffolds. Due to the success of the platinum anticancer agents, there has been considerable interest in the development of therapeutic agents based upon other transition metals--and in particular ruthenium(II/III) complexes, due to their well known interaction with DNA. There have been many studies of the anticancer properties and cellular localisation of a range of ruthenium complexes in eukaryotic cells over the last decade. However, only very recently has there been significant interest in their antimicrobial properties. This review highlights the types of ruthenium complexes that have exhibited significant antimicrobial activity and discusses the relationship between chemical structure and biological processing--including site(s) of intracellular accumulation--of the ruthenium complexes in both bacterial and eukaryotic cells.

  2. Carbon deposition in the Bosch process with ruthenium and ruthenium-iron alloy catalysts. M.S. Thesis. Final Report, Jan. 1981 - Jul. 1982

    NASA Technical Reports Server (NTRS)

    Manning, M. P.; Reid, R. C.; Sophonpanich, C.

    1982-01-01

    The effectiveness of ruthenium and the alloys 50Ru50Fe and 33Ru67Fe as alternatives to iron, nickel, and cobalt catalysts in recovering oxygen from metabolic carbon dioxide was investigated. Carbon deposition boundaries over the unsupported alloys are reported. Experiments were also carried out over 50Ru50Fe and 97Ru3Fe3 catalysts supported on gamma-alumina to determine their performance in the synthesis of low molecular weight olefins. High production of ethylene and propylene would be beneficial for an improvement of an overall Bosch process, as a gas phase containing high olefin content would enhance carbon deposition in a Bosch reactor.

  3. Cobalt free maraging steel

    SciTech Connect

    Floreen, S.

    1984-04-17

    The subject invention is directed to ferrous-base alloys, particularly to a cobalt-free maraging steel of novel chemistry characterized by a desired combination of strength and toughness, notwithstanding that cobalt is non-essential.

  4. Nitric oxide-releasing ruthenium nanoparticles.

    PubMed

    Ho, Chi-Ming; Liao, Kai-Jun; Lok, Chun-Nam; Che, Chi-Ming

    2011-10-14

    Nitric oxide-releasing ruthenium nanoparticles were synthesized by the reaction of alkanethiolate-protected ruthenium nanoparticles with tert-butyl nitrite ((t)BuONO), and their water-soluble derivatives are able to deliver NO to proteins such as reduced myoglobin upon light irradiation in aqueous media.

  5. IR-doped ruthenium oxide catalyst for oxygen evolution

    NASA Technical Reports Server (NTRS)

    Valdez, Thomas I. (Inventor); Narayanan, Sekharipuram R. (Inventor)

    2012-01-01

    A method for preparing a metal-doped ruthenium oxide material by heating a mixture of a doping metal and a source of ruthenium under an inert atmosphere. In some embodiments, the doping metal is in the form of iridium black or lead powder, and the source of ruthenium is a powdered ruthenium oxide. An iridium-doped or lead-doped ruthenium oxide material can perform as an oxygen evolution catalyst and can be fabricated into electrodes for electrolysis cells.

  6. One-dimensional manganese-cobalt oxide nanofibres as bi-functional cathode catalysts for rechargeable metal-air batteries

    PubMed Central

    Jung, Kyu-Nam; Hwang, Soo Min; Park, Min-Sik; Kim, Ki Jae; Kim, Jae-Geun; Dou, Shi Xue; Kim, Jung Ho; Lee, Jong-Won

    2015-01-01

    Rechargeable metal-air batteries are considered a promising energy storage solution owing to their high theoretical energy density. The major obstacles to realising this technology include the slow kinetics of oxygen reduction and evolution on the cathode (air electrode) upon battery discharging and charging, respectively. Here, we report non-precious metal oxide catalysts based on spinel-type manganese-cobalt oxide nanofibres fabricated by an electrospinning technique. The spinel oxide nanofibres exhibit high catalytic activity towards both oxygen reduction and evolution in an alkaline electrolyte. When incorporated as cathode catalysts in Zn-air batteries, the fibrous spinel oxides considerably reduce the discharge-charge voltage gaps (improve the round-trip efficiency) in comparison to the catalyst-free cathode. Moreover, the nanofibre catalysts remain stable over the course of repeated discharge-charge cycling; however, carbon corrosion in the catalyst/carbon composite cathode degrades the cycling performance of the batteries. PMID:25563733

  7. One-dimensional manganese-cobalt oxide nanofibres as bi-functional cathode catalysts for rechargeable metal-air batteries

    NASA Astrophysics Data System (ADS)

    Jung, Kyu-Nam; Hwang, Soo Min; Park, Min-Sik; Kim, Ki Jae; Kim, Jae-Geun; Dou, Shi Xue; Kim, Jung Ho; Lee, Jong-Won

    2015-01-01

    Rechargeable metal-air batteries are considered a promising energy storage solution owing to their high theoretical energy density. The major obstacles to realising this technology include the slow kinetics of oxygen reduction and evolution on the cathode (air electrode) upon battery discharging and charging, respectively. Here, we report non-precious metal oxide catalysts based on spinel-type manganese-cobalt oxide nanofibres fabricated by an electrospinning technique. The spinel oxide nanofibres exhibit high catalytic activity towards both oxygen reduction and evolution in an alkaline electrolyte. When incorporated as cathode catalysts in Zn-air batteries, the fibrous spinel oxides considerably reduce the discharge-charge voltage gaps (improve the round-trip efficiency) in comparison to the catalyst-free cathode. Moreover, the nanofibre catalysts remain stable over the course of repeated discharge-charge cycling; however, carbon corrosion in the catalyst/carbon composite cathode degrades the cycling performance of the batteries.

  8. Substrate selectivity in the low temperature atomic layer deposition of cobalt metal films from bis(1,4-di-tert-butyl-1,3-diazadienyl)cobalt and formic acid.

    PubMed

    Kerrigan, Marissa M; Klesko, Joseph P; Rupich, Sara M; Dezelah, Charles L; Kanjolia, Ravindra K; Chabal, Yves J; Winter, Charles H

    2017-02-07

    The initial stages of cobalt metal growth by atomic layer deposition are described using the precursors bis(1,4-di-tert-butyl-1,3-diazadienyl)cobalt and formic acid. Ruthenium, platinum, copper, Si(100), Si-H, SiO2, and carbon-doped oxide substrates were used with a growth temperature of 180 °C. On platinum and copper, plots of thickness versus number of growth cycles were linear between 25 and 250 cycles, with growth rates of 0.98 Å/cycle. By contrast, growth on ruthenium showed a delay of up to 250 cycles before a normal growth rate was obtained. No films were observed after 25 and 50 cycles. Between 100 and 150 cycles, a rapid growth rate of ∼1.6 Å/cycle was observed, which suggests that a chemical vapor deposition-like growth occurs until the ruthenium surface is covered with ∼10 nm of cobalt metal. Atomic force microscopy showed smooth, continuous cobalt metal films on platinum after 150 cycles, with an rms surface roughness of 0.6 nm. Films grown on copper gave rms surface roughnesses of 1.1-2.4 nm after 150 cycles. Films grown on ruthenium, platinum, and copper showed resistivities of <20 μΩ cm after 250 cycles and had values close to those of the uncoated substrates at ≤150 cycles. X-ray photoelectron spectroscopy of films grown with 150 cycles on a platinum substrate showed surface oxidation of the cobalt, with cobalt metal underneath. Analogous analysis of a film grown with 150 cycles on a copper substrate showed cobalt oxide throughout the film. No film growth was observed after 1000 cycles on Si(100), Si-H, and carbon-doped oxide substrates. Growth on thermal SiO2 substrates gave ∼35 nm thick layers of cobalt(ii) formate after ≥500 cycles. Inherently selective deposition of cobalt on metallic substrates over Si(100), Si-H, and carbon-doped oxide was observed from 160 °C to 200 °C. Particle deposition occurred on carbon-doped oxide substrates at 220 °C.

  9. Substrate selectivity in the low temperature atomic layer deposition of cobalt metal films from bis(1,4-di-tert-butyl-1,3-diazadienyl)cobalt and formic acid

    NASA Astrophysics Data System (ADS)

    Kerrigan, Marissa M.; Klesko, Joseph P.; Rupich, Sara M.; Dezelah, Charles L.; Kanjolia, Ravindra K.; Chabal, Yves J.; Winter, Charles H.

    2017-02-01

    The initial stages of cobalt metal growth by atomic layer deposition are described using the precursors bis(1,4-di-tert-butyl-1,3-diazadienyl)cobalt and formic acid. Ruthenium, platinum, copper, Si(100), Si-H, SiO2, and carbon-doped oxide substrates were used with a growth temperature of 180 °C. On platinum and copper, plots of thickness versus number of growth cycles were linear between 25 and 250 cycles, with growth rates of 0.98 Å/cycle. By contrast, growth on ruthenium showed a delay of up to 250 cycles before a normal growth rate was obtained. No films were observed after 25 and 50 cycles. Between 100 and 150 cycles, a rapid growth rate of ˜1.6 Å/cycle was observed, which suggests that a chemical vapor deposition-like growth occurs until the ruthenium surface is covered with ˜10 nm of cobalt metal. Atomic force microscopy showed smooth, continuous cobalt metal films on platinum after 150 cycles, with an rms surface roughness of 0.6 nm. Films grown on copper gave rms surface roughnesses of 1.1-2.4 nm after 150 cycles. Films grown on ruthenium, platinum, and copper showed resistivities of <20 μ Ω cm after 250 cycles and had values close to those of the uncoated substrates at ≤150 cycles. X-ray photoelectron spectroscopy of films grown with 150 cycles on a platinum substrate showed surface oxidation of the cobalt, with cobalt metal underneath. Analogous analysis of a film grown with 150 cycles on a copper substrate showed cobalt oxide throughout the film. No film growth was observed after 1000 cycles on Si(100), Si-H, and carbon-doped oxide substrates. Growth on thermal SiO2 substrates gave ˜35 nm thick layers of cobalt(ii) formate after ≥500 cycles. Inherently selective deposition of cobalt on metallic substrates over Si(100), Si-H, and carbon-doped oxide was observed from 160 °C to 200 °C. Particle deposition occurred on carbon-doped oxide substrates at 220 °C.

  10. Electronic Transitions of Ruthenium Monoxide

    NASA Astrophysics Data System (ADS)

    Wang, Na; Ng, Y. W.; Cheung, A. S.-C.

    2013-06-01

    The electronic transition spectrum of ruthenium monoxide (RuO) molecule in the spectral region between 545nm to 640nm has been recorded and analyzed using laser ablation/reaction free-jet expansion and laser induced fluorescence spectroscopy. The RuO molecule was produced by reacting laser- ablated ruthenium atoms with N_{2}O seeded in argon. Nine vibrational bands were recorded and they are identified to be belonging to four electronic transition systems, namely the [18.1]Ω = 4 - X^{5} Δ_4 transition, [16.0]^{5} Φ_5 - X^{5} Δ_4 transition, [18.1]Ω = 3 - X^{5} Δ_3, and [15.8] ^{5} Φ_4 - X^{5} Δ_3 transition. RuO has been determined to have a X^{5} Δ_4 ground state. A least squares fit of the measured rotational lines yielded molecular constants for the ground and the low-lying electronic states. A molecular orbital energy level diagram has been used to help with the assignment of the observed electronic states.

  11. Luminescent tetrametallic complexes of ruthenium

    SciTech Connect

    Murphy, W.R. Jr.; Brewer, K.J.; Gettliffe, G.; Petersen, J.D. )

    1989-01-11

    Tetrametallic complexes constructed around the metal core Ru(dpp){sub 3}{sup 2+} (where dpp = 2,3-bis(2-pyridyl)pyrazine) have been prepared and characterized. The complexes, which have the general formula Ru((dpp)ML{sub 2}){sub 3}{sup n+}, where ML{sub 2} = Ru{sup II}(bpy){sub 2} (n = 8), Ru{sup II}(phen){sub 2} (n = 8), and Ru{sup II}(tpy)Cl (n = 5) and bpy = 2,2{prime}-bipyridine, phen = 1,10-phenanthroline, and tpy = 2,2{prime}:6{prime},2{double prime}-terpyridine, are prepared from the reaction of Ru(dpp){sub 3}{sup 2+} with ML{sub 2}Cl{sub 2} in ethanol/water. The tetrametallic complexes luminesce at room temperature in acetonitrile with emissions characteristic of a single ruthenium center with excited-state lifetimes in the 100-ns range. Electrochemically, the most facile reductions occur at the dpp ligand, and the lower energy oxidation is a single peak associated with the three peripheral ruthenium centers. 13 refs., 1 fig., 2 tabs.

  12. Lead-ruthenium pyrochlores as oxygen electrocatalysts

    NASA Technical Reports Server (NTRS)

    Anderson, E. B.; Taylor, E. J.; Moniz, G. A.

    1990-01-01

    An investigation of lead-ruthenium pyrochlores of the structure Pb2(Ru/2-x/Pb/x/) O7-y for use as oxygen electrocatalysts in alkaline media is discussed. Lead-ruthenium pyrochlore mixed metal oxides were prepared and characterized by X-ray diffraction, BET surface area, dry powder conductivity, and chemical stability. Gas diffusion electrodes were developed specifically for the lead-ruthenium pyrochlore materials. Also investigated were the effects of varying electrode fabrication parameters on the oxygen reduction performance of the lead-ruthenium pyrochlore electrocatalyst. Long-term stability performance was also evaluated. The oxygen reduction performance of the pyrochlore electrocatalyst is considerably higher than that of the state-of-the-art gold-platinum alloy electrocatalyst currently used by NASA. Furthermore, the pyrochlore electrocatalysts are attractive candidates for high-performance pressurized alkaline fuel cells.

  13. Platinum-ruthenium-nickel fuel cell electrocatalyst

    DOEpatents

    Gorer, Alexander

    2005-07-26

    A catalyst suitable for use in a fuel cell, especially as an anode catalyst, that contains platinum, ruthenium, and nickel, wherein the nickel is at a concentration that is less than about 10 atomic percent.

  14. Platinum-ruthenium-palladium fuel cell electrocatalyst

    DOEpatents

    Gorer, Alexander

    2006-02-07

    A catalyst suitable for use in a fuel cell, especially as an anode catalyst, that contains platinum at a concentration that is between about 20 and about 60 atomic percent, ruthenium at a concentration that is between about 20 and about 60 atomic percent, palladium at a concentration that is between about 5 and about 45 atomic percent, and having an atomic ratio of platinum to ruthenium that is between about 0.7 and about 1.2. Alternatively, the catalyst may contain platinum at a concentration that is between about 25 and about 50 atomic percent, ruthenium at a concentration that is between about 25 and about 55 atomic percent, palladium at a concentration that is between about 5 and about 45 atomic percent, and having a difference between the concentrations of ruthenium and platinum that is no greater than about 20 atomic percent.

  15. Ruthenium Sesquisilicide: A Promising Thermoelectric Material

    NASA Technical Reports Server (NTRS)

    Vining, Cronin B.

    1993-01-01

    Report describes experimental investigation of thermoelectric properties of ruthenium sesquisilicide (RU2Si3). Suggests suitably doped Ru2Si3 could have thermoelectric figures of merit two or more times as large as SiGe.

  16. Marine cobalt resources

    USGS Publications Warehouse

    Manheim, F. T.

    1986-01-01

    Ferromanganese oxides in the open oceans are more enriched in cobalt than any other widely distributed sediments or rocks. Concentrations of cobalt exceed 1 percent in ferromanganese crusts on seamounts, ocean ridges, and other raised areas of the ocean. The cobalt-rich crusts may be the slowest growing of any earth material, accumulating one molecular layer every 1 to 3 months. Attention has been drawn to crusts as potential resources because they contain cobalt, manganese, and platinum, three of the four priority strategic metals for the United States. Moreover, unlike abyssal nodules, whose recovery is complicated by their dominant location in international waters, some of the most cobalt-rich crusts occur within the exclusive economic zone of the United States and other nations. Environmental impact statements for crust exploitation are under current development by the Department of the Interior.

  17. Samarium/Cobalt Magnets

    NASA Technical Reports Server (NTRS)

    Das, D.; Kumar, K.; Frost, R.; Chang, C.

    1985-01-01

    Intrinsic magnetic coercivities of samarium cobalt magnets made to approach theoretical limit of 350 kA/m by carefully eliminating oxygen from finished magnet by hot isostatic pressing (HIP). HIP process viable alternative to currently used sintering process.

  18. Cationic ruthenium alkylidene catalysts bearing phosphine ligands.

    PubMed

    Endo, Koji; Grubbs, Robert H

    2016-02-28

    The discovery of highly active catalysts and the success of ionic liquid immobilized systems have accelerated attention to a new class of cationic metathesis catalysts. We herein report the facile syntheses of cationic ruthenium catalysts bearing bulky phosphine ligands. Simple ligand exchange using silver(i) salts of non-coordinating or weakly coordinating anions provided either PPh3 or chelating Ph2P(CH2)nPPh2 (n = 2 or 3) ligated cationic catalysts. The structures of these newly reported catalysts feature unique geometries caused by ligation of the bulky phosphine ligands. Their activities and selectivities in standard metathesis reactions were also investigated. These cationic ruthenium alkylidene catalysts reported here showed moderate activity and very similar stereoselectivity when compared to the second generation ruthenium dichloride catalyst in ring-closing metathesis, cross metathesis, and ring-opening metathesis polymerization assays.

  19. Photonastic effects in ruthenium sulfoxide polymers

    NASA Astrophysics Data System (ADS)

    Rack, Jeffrey J.; Livshits, Maksim Y.; Shin, Jisoo

    2016-09-01

    We have established that film morphology and laser induced heating from dye absorption are important parameters in the creation of new photonastic materials. Photonastic is defined as regular, repeatable movement in a pre-programmed direction following exposure to light. This work builds upon the development of photonastic polymers of ruthenium sulfoxide complexes, where the action of bending is ascribed to phototriggered isomerization of a sulfoxide ligand in a ruthenium coordination complex that is covalently attached to polynorbornene. The bending is analyzed in terms of a bilayer cantilever model.

  20. Bis(Dioxolene)(Bipyridine)Ruthenium Redox Series

    DTIC Science & Technology

    1988-07-11

    reactions with isosbestic points were generally observed in these redox processes. The electronic spectra of 02, 01, S, RI and R2 are shown Tor the (1...oOFFICE OF NAVAL RESEARCH Contract NOOOl4-84-G-0201 Task No. 0051-865 Technical Report *23 Bis(Dioxolene)(Bipyridine)Ruthenium Redox Series By...Classit’.’-tion) Bix(Dioxolene)(Bipyridine)Ruthenium Redox Series 12 PERSON4AL AUTHOR(S) A.B. P. Lever*, Pamela R. &uburn, Elaine S. Dodsworth, Masa-A

  1. Mercury-based cobalt magnetic fluids and cobalt nanoparticles

    NASA Astrophysics Data System (ADS)

    Massart, R.; Rasolonjatovo, B.; Neveu, S.; Cabuil, V.

    2007-01-01

    This paper describes the synthesis of a magnetic and conducting liquid consisting of cobalt nanoparticles dispersed in mercury. The magnetic nanoparticles are obtained in one step by the electroreduction of a cobalt(II) solution on mercury. These particles are then extracted using an organic solution of surfactant in order to obtain a ferrofluid based on cobalt nanoparticles.

  2. Catalysis: Cobalt gets in shape

    NASA Astrophysics Data System (ADS)

    Claeys, Michael

    2016-10-01

    Solid cobalt-based catalysts are used commercially to convert carbon monoxide and hydrogen into synthetic fuels. It emerges that much more valuable chemicals can be produced by using a different form of cobalt catalyst. See Letter p.84

  3. Evolution from a ferromagnetic to a spin-glass regime in the spinel-type Cu(Cr{sub 1-x}Ti{sub x}){sub 2}S{sub 4}

    SciTech Connect

    Kariya, Fumihiro; Ebisu, Shuji; Nagata, Shoichi

    2009-03-15

    Successive changes from ferromagnetic, re-entrant mixed, to spin-glass regime have been manifestly found with increasing Ti-composition x in the quaternary spinel-type Cu(Cr{sub 1-x}Ti{sub x}){sub 2}S{sub 4} system. The Curie temperature T{sub c} decreases steeply with increasing x and this transition becomes ill-defined around x=0.47. Two distinct transitions appear below T{sub c} over the range x=0.40-0.47. Coexistence of the ferromagnetism and spin-glass order would be observed below the Gabay and Toulouse transition (T{sub GT}), owing to freezing of the transverse-spin components without changing of the ferromagnetic order parameter. Finally, at a yet lower temperature de Almeida-Thouless transition (T{sub AT}), the longitudinal-spin component freezes randomly at which an irreversibility arises between zero-field-cooled (ZFC) and field-cooled (FC) magnetizations. Over the range of 0.47{<=}x{<=}0.85, a cusp of the ZFC magnetization is seen at T{sub g} like conventional spin-glass. Specimens with x{>=}0.90 remain paramagnetic down to 2.0 K. A magnetic phase diagram between T versus x has been obtained experimentally. The values of the multicritical point in 100 Oe is detected to be x=0.47 and T=7.40K. The low-field magnetization and the phase diagram are satisfactorily explained by the theory of Gabay and Toulouse on the basis of Heisenberg isotropic vector spin model rather than the Ising spin model. - An enlargement of the magnetic phase diagram for Cu(Cr{sub 1-x}Ti{sub x}){sub 2}S{sub 4} at a constant field of 100 Oe over the range of 0.40{<=}x{<=}0.70. The curves give a guide to the eye: para, paramagnetic; ferro, ferromagnetic; SGI, spin-glass I (GT-phase), and SGII: spin-glass II (AT-phase). Three characteristic temperatures of T{sub c},T{sub GT}, and T{sub AT} merge into 7.40 K at x=0.47 in H=100 Oe. This is a multicritical point.

  4. Thermodynamic properties of gaseous ruthenium species.

    PubMed

    Miradji, Faoulat; Souvi, Sidi; Cantrel, Laurent; Louis, Florent; Vallet, Valérie

    2015-05-21

    The review of thermodynamic data of ruthenium oxides reveals large uncertainties in some of the standard enthalpies of formation, motivating the use of high-level relativistic correlated quantum chemical methods to reduce the level of discrepancies. The reaction energies leading to the formation of ruthenium oxides RuO, RuO2, RuO3, and RuO4 have been calculated for a series of reactions. The combination of different quantum chemical methods has been investigated [DFT, CASSCF, MRCI, CASPT2, CCSD(T)] in order to predict the geometrical parameters, the energetics including electronic correlation and spin-orbit coupling. The most suitable method for ruthenium compounds is the use of TPSSh-5%HF for geometry optimization, followed by CCSD(T) with complete basis set (CBS) extrapolations for the calculation of the total electronic energies. SO-CASSCF seems to be accurate enough to estimate spin-orbit coupling contributions to the ground-state electronic energies. This methodology yields very accurate standard enthalpies of formations of all species, which are either in excellent agreement with the most reliable experimental data or provide an improved estimate for the others. These new data will be implemented in the thermodynamical databases that are used by the ASTEC code (accident source term evaluation code) to build models of ruthenium chemistry behavior in severe nuclear accident conditions. The paper also discusses the nature of the chemical bonds both from molecular orbital and topological view points.

  5. Ruthenium-Ruthenium-Bonded [Bis{corrolato-ruthenium(III)}](n) (n=0, +1, -1) Complexes: Model Compounds for the Photosynthetic Special Pair.

    PubMed

    Sinha, Woormileela; Sommer, Michael G; Hettmanczyk, Lara; Patra, Bratati; Filippou, Vasileios; Sarkar, Biprajit; Kar, Sanjib

    2017-02-16

    We present herein the synthesis of three new bis(corrolato-ruthenium(III)) complexes containing unsupported Ru-Ru bonds and their characterization in different redox states. The (1) H NMR spectra of the bis(corrolato-ruthenium(III)) complexes displayed "normal" chemical shifts and the compounds proved to be EPR-silent. Crystallographic characterization of the dimers indicated Ru-Ru distances of 2.175 Å, consistent with a triple bond between the two ruthenium centers. All of the synthesized complexes undergo two successive reversible oxidations and a single reversible reduction. A combination of UV/Vis/NIR/EPR spectroelectrochemical studies and DFT calculations established the redox state distributions in these ruthenium-ruthenium-bonded dimers. Whereas reduction of the dimers is metal-based and leads to metal-metal-bonded mixed-valent Ru(II) -Ru(III) species, one-electron oxidation largely retains the Ru(III) -Ru(III) situation with the generation of metal-bound corrolato radicals. The present study thus concerns the first UV/Vis/NIR/EPR spectroelectrochemical characterization and DFT calculations of ruthenium-ruthenium-bonded rotationally ordered corrole dimers. The mean plane separation between the two corrole units in these dimers is around 3.543 Å, which is in close agreement to that in the "special pair" in chlorophyll. Oxidation of these ruthenium-ruthenium-bonded dimers gives rise to two new electronic absorption bands in the NIR region (similar to those of the special pair), which have apparently not been mentioned/observed in earlier reports on ruthenium-ruthenium-bonded corrole dimers. These bands mainly originate from inter-corrole transitions.

  6. One-pot solvothermal synthesis of novel cobalt salicylaldimine-urea complexes: A new approach to Co3O4 nanoparticles

    NASA Astrophysics Data System (ADS)

    Nassar, M. Y.; Mohamed, T. Y.; Ahmed, I. S.

    2013-10-01

    Three novel Cobalt salicylaldimine-urea complexes {[CoxLy(H2O)n]Clz; where, L = 1,3-bis(salicylaldehydimine)urea Schiff base; x, y = 1 or 2; n = 2 or 8; z = 0 or 2} were synthesized by one-pot solvothermal treatment of methanolic solutions of urea, salicylaldehyde, and cobalt chloride at 120 °C for 3 h. Subsequently, normal spinel-type Co3O4 nanoparticles, with an average crystallite size in the range 22-38 nm, were easily produced via thermal decomposition of the synthesized complexes at 400 °C for 2 h. The synthesized compounds were characterized by elemental analysis, thermal analysis (TG-DTA/DTG), X-ray powder diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), UV-Vis spectroscopy, transmission electron microscopy (TEM) and EI mass spectroscopy. Investigation of the optical properties of the produced cobalt oxide, using UV-Vis spectroscopy, confirmed its semiconducting properties by revealing two optical band gabs in the range of 1.42-1.50 and 1.83-1.95 eV.

  7. The biokinetics of ruthenium in the human body.

    PubMed

    Leggett, R W

    2012-03-01

    The International Commission on Radiological Protection (ICRP) is updating its biokinetic and dosimetric models for workers and subsequently will revisit its models for members of the public. This paper summarises the biokinetic database for ruthenium and proposes a new biokinetic model for systemic ruthenium. In contrast to the ICRP's current model, the proposed model depicts recycling of ruthenium between tissues and blood and a non-uniform distribution of systemic ruthenium. The paper also points out inconsistencies between the ICRP's respiratory model for RuO(4) vapour and reported data, and inconsistencies between the ICRP's default gastrointestinal (GI) uptake value and data for some forms of ruthenium. Dosimetric implications of the proposed systemic model and the findings for inhaled RuO(4) vapour and GI uptake of ruthenium are examined.

  8. Coordination Complexes of Cobalt.

    ERIC Educational Resources Information Center

    Williams, Gregory M.; And Others

    1989-01-01

    Described is an experiment involving the synthesis and spectral studies of cobalt complexes that not only give general chemistry students an introduction to inorganic synthesis but allows them to conduct a systematic study on the effect of different ligands on absorption spectra. Background information, procedures, and experimental results are…

  9. Halogenation of cobalt dicarbollide

    DOEpatents

    Hurlburt, P.K.; Abney, K.D.; Kinkead, S.A.

    1997-05-20

    A method for selectively adding chlorine, bromine, or iodine to cobalt dicarbollide anions by means of electrophilic substitution reactions. Halogens are added only to the B10 and B10{prime} positions of the anion. The process involves use of hypohalous acid or N-halosuccinimide or gaseous chlorine in the presence of iron. 1 fig.

  10. Halogenation of cobalt dicarbollide

    DOEpatents

    Hurlburt, Paul K.; Abney, Kent D.; Kinkead, Scott A.

    1997-01-01

    A method for selectively adding chlorine, bromine, or iodine to cobalt dicarbollide anions by means of electrophilic substitution reactions. Halogens are added only to the B10 and B10' positions of the anion. The process involves use of hypohalous acid or N-halosuccinimide or gaseous chlorine in the presence of iron.

  11. Transient photocyclization in ruthenium(ii) polypyridine complexes of indolamines.

    PubMed

    Carrone, G; Zayat, L; Slep, L D; Etchenique, R

    2017-01-18

    Ruthenium polypyridine complexes have proved to be useful caging groups for visible-light photodelivery of biomolecules. In most photoreactions, one ligand is expelled upon irradiation, yielding ruthenium mono-aqua complexes and no other photoproduct. In this work we show that a long-lived transient photoproduct is generated when the ruthenium complexes involve indolamines. The spatial conformation of this species is compatible with a cyclic structure that contains both the amine and the normally non-coordinating aromatic ring coordinated to the ruthenium center.

  12. OMCVD of cobalt and cobalt silicide

    NASA Astrophysics Data System (ADS)

    Dormans, G. J. M.; Meekes, G. J. B. M.; Staring, E. G. J.

    1991-11-01

    Cobalt and cobalt silicide layers were deposited by OMCVD using the Co precursors Co(C 5H 5) 2, Co 2(CO) 8, Co(C 5H 5)(CO) 2 and CoCF 3(CO) 4, and the Si precursors SiH 4 and Si 2H 6. Strongly textured (111)-β Co layers were grown from Co(C 5H 5) 2, Co(C 5H 5)(CO) 2 and CoCF 3(CO) 4 at temperatures above 300°C in H 2 at atmospheric pressure. Growth from Co(C 5H 5) 2 is inhibited on Si substrates. For temperatures ≥600°C the Co layers deposited from Co(C 5H 5)(CO) 2 react with the Si(100) substrate to form CoSi 2(00 l) aligned with the substrate orientation. Co 2(CO) 8 gives amorphous Co between 200 and 300°C. The upper temperature is set by the occurrence of homogeneous gas-phase reactions at atmospheric reactor pressure. Cobalt silicide layers can be grown from CO 2(CO) 8 and (di)silane at temperatures between 200 and 400°C. The Co/Si ratio in the layers decreases with increasing temperature and is independent of the gas-phase Co/Si ratio. Stoichiometric CoSi 2 is obtained at ~ 300°C. Both Co(C 5H 5) 2 and Co(C 5H 5)(CO) 2 react with (di)silane, leading to the incorporation of carbon in the layer. The Co/Si ration and the carbon content in the layers are practically independent of the deposition conditions. With CoCF 3(CO) 4 no contamination-free silicide could be grown. The carbon incorporation with Co(C 5H 5) 2 and Co(C 5H 5)(CO) 2 can be avoided by a pulsed growth method in which the Co precursor and the Si precursor are introduced alternately into the reactor. With Co(C 5H 5) 2 the growth is then inhibited on Si substrates.

  13. Phase and composition controllable synthesis of cobalt manganese spinel nanoparticles towards efficient oxygen electrocatalysis

    PubMed Central

    Li, Chun; Han, Xiaopeng; Cheng, Fangyi; Hu, Yuxiang; Chen, Chengcheng; Chen, Jun

    2015-01-01

    Spinel-type oxides are technologically important in many fields, including electronics, magnetism, catalysis and electrochemical energy storage and conversion. Typically, these materials are prepared by conventional ceramic routes that are energy consuming and offer limited control over shape and size. Moreover, for mixed-metal oxide spinels (for example, CoxMn3−xO4), the crystallographic phase sensitively correlates with the metal ratio, posing great challenges to synthesize active product with simultaneously tuned phase and composition. Here we report a general synthesis of ultrasmall cobalt manganese spinels with tailored structural symmetry and composition through facile solution-based oxidation–precipitation and insertion–crystallization process at modest condition. As an example application, the nanocrystalline spinels catalyse the oxygen reduction/evolution reactions, showing phase and composition co-dependent performance. Furthermore, the mild synthetic strategy allows the formation of homogeneous and strongly coupled spinel/carbon nanocomposites, which exhibit comparable activity but superior durability to Pt/C and serve as efficient catalysts to build rechargeable Zn–air and Li–air batteries. PMID:26040417

  14. Phase and composition controllable synthesis of cobalt manganese spinel nanoparticles towards efficient oxygen electrocatalysis

    NASA Astrophysics Data System (ADS)

    Li, Chun; Han, Xiaopeng; Cheng, Fangyi; Hu, Yuxiang; Chen, Chengcheng; Chen, Jun

    2015-06-01

    Spinel-type oxides are technologically important in many fields, including electronics, magnetism, catalysis and electrochemical energy storage and conversion. Typically, these materials are prepared by conventional ceramic routes that are energy consuming and offer limited control over shape and size. Moreover, for mixed-metal oxide spinels (for example, CoxMn3-xO4), the crystallographic phase sensitively correlates with the metal ratio, posing great challenges to synthesize active product with simultaneously tuned phase and composition. Here we report a general synthesis of ultrasmall cobalt manganese spinels with tailored structural symmetry and composition through facile solution-based oxidation-precipitation and insertion-crystallization process at modest condition. As an example application, the nanocrystalline spinels catalyse the oxygen reduction/evolution reactions, showing phase and composition co-dependent performance. Furthermore, the mild synthetic strategy allows the formation of homogeneous and strongly coupled spinel/carbon nanocomposites, which exhibit comparable activity but superior durability to Pt/C and serve as efficient catalysts to build rechargeable Zn-air and Li-air batteries.

  15. Cobalt sorption in silica-pillared clays.

    PubMed

    Sampieri, A; Fetter, G; Bosch, P; Bulbulian, S

    2006-01-03

    Silicon pillared samples were prepared following conventional and microwave irradiation methods. The samples were characterized and tested in cobalt sorption. Ethylenediammine was added before cobalt addition to improve the amount of cobalt retained. The amount of cobalt introduced in the original clay in the presence of ethylenediammine was the highest. In calcined pillared clays the cobalt retention with ethylenediammine was lower (ca. 40%). In all cases the presence of ethylenediammine increased twice the amount of cobalt sorption measured for aqueous solutions.

  16. Bioaccessibility testing of cobalt compounds.

    PubMed

    Stopford, Woodhall; Turner, John; Cappellini, Danielle; Brock, Tom

    2003-08-01

    Testing of metal compounds for solubility in artificial fluids has been used for many years to assist determining human health risk from exposure to specific compounds of concern. In lieu of obtaining bioavailability data from samples of urine, blood, or other tissues, these studies measured solubility of compounds in various artificial fluids as a surrogate for bioavailability. In this context, the measurement of metal "bioaccessibility" can be used as an in vitro substitute for measuring metal bioavailability. Bioaccessibility can be defined as a value representing the availability of metal for absorption when dissolved in in vitro surrogates of body fluids or juices. The aim of this study was to measure and compare the bioaccessibility of selected cobalt compounds in artificial human tissue fluids and human serum. A second aim was to initiate studies to experimentally validate an in vitro methodology that would provide a conservative estimate of cobalt bioavailability in the assessment of dose from human exposure to various species of cobalt compounds. This study evaluated the bioaccessibility of cobalt(II) from 11 selected cobalt compounds and an alloy in 2 physical forms in 5 surrogate human tissue fluids and human serum. Four (4) separate extraction times were used up to 72 hours. The effect of variables such as pH, dissolution time, and mass-ion effect on cobalt bioaccessibility were assessed as well. We found that the species of cobalt compound as well as the physico-chemical properties of the surrogate fluids, especially pH, had a major impact on cobalt solubility. Cobalt salts such as cobalt(II) sulfate heptahydrate were highly soluble, whereas cobalt alloys used in medical implants and cobalt aluminate spinels used as pigments, showed minimal dissolution over the period of the assay.

  17. Cobalt ion-containing epoxies

    NASA Technical Reports Server (NTRS)

    Stoakley, D. M.; St.clair, A. K.

    1983-01-01

    Varying concentrations of an organometallic cobalt complex were added to an epoxy system currently used by the aerospace industry as a composite matrix resin. Methods for combining cobalt (III) acetylacetonate with a tetraglycidyl 4,4 prime - diaminodiphenylmethane-based epoxy were investigated. The effects of increasing cobalt ion concentration on the epoxy cure were demonstrated by epoxy gel times and differential scanning calorimetry cure exotherms. Analysis on cured cobalt-containing epoxy castings included determination of glass transition temperatures by thermomechanical analysis, thermooxidative stabilities by thermogravimetric analysis, and densities in a density gradient column. Flexural strength and stiffness were also measured on the neat resin castings.

  18. Fischer-Tropsch synthesis process employing a moderated ruthenium catalyst

    DOEpatents

    Abrevaya, H.

    1990-07-31

    A Fischer-Tropsch type process produces hydrocarbons from carbon monoxide and hydrogen using a novel catalyst comprising moderated ruthenium on an inorganic oxide support. The preferred moderator is silicon. Preferably the moderator is effectively positioned in relationship to ruthenium particles through simultaneous placement on the support using reverse micelle impregnation. 1 fig.

  19. Fischer-Tropsch synthesis process employing a moderated ruthenium catalyst

    DOEpatents

    Abrevaya, Hayim

    1990-01-01

    A Fischer-Tropsch type process produces hydrocarbons from carbon monoxide and hydrogen using a novel catalyst comprising moderated ruthenium on an inorganic oxide support. The preferred moderator is silicon. Preferably the moderator is effectively positioned in relationship to ruthenium particles through simultaneous placement on the support using reverse micelle impregnation.

  20. The biokinetics of ruthenium in the human body

    SciTech Connect

    Leggett, Richard Wayne

    2011-01-01

    The biokinetics of ruthenium (Ru) in the human body is of interest due mainly to the potential for occupational or environmental exposure to 106Ru (T1/2 = 373.6 d) and 103Ru (T1/2 = 39.3 d), which typically represent a significant portion of the fission products in a reactor inventory. During reactor operations or nuclear fuel reprocessing these ruthenium isotopes may be present as ruthenium tetroxide (RuO4) vapor, a highly mobile form of ruthenium that has been involved in a number of cases of accidental exposure to 106Ru or 103Ru. This paper summarizes the biokinetic database for ruthenium and proposes a new respiratory model for inhaled RuO4 vapor, a new biokinetic for systemic (absorbed) ruthenium, and material-specific gastrointestinal absorption fractions for ruthenium. The proposed respiratory model for RuO4 differs from the current ICRP model mainly in that it depicts slower clearance of deposited activity from the respiratory tract and lower absorption to blood than depicted in the current ICRP model. The proposed systemic biokinetic model depicts more realistic paths of movement of absorbed ruthenium in the body than the current ICRP model and, in contrast to the present model, a less uniform distribution of systemic activity. Implications of the proposed models with regard to inhalation and ingestion dose coefficients for 106Ru are examined.

  1. Side-on bound diazene and hydrazine complexes of ruthenium.

    PubMed

    Field, Leslie D; Li, Hsiu L; Dalgarno, Scott J

    2010-07-05

    The reaction of cis-[RuCl(2)(PP)(2)] (PP = depe, dmpe) with hydrazine afforded end-on bound ruthenium(II) hydrazine complexes. Treatment of the hydrazine complexes with strong base afforded the side-on bound ruthenium(0) diazene complexes cis-[Ru(eta(2)-NH=NH)(PP)(2)]. Treatment of cis-[Ru(eta(2)-NH=NH)(depe)(2)] with weak acid under chloride-free conditions afforded the side-on bound hydrazine complex cis-[Ru(eta(2)-N(2)H(4))(depe)(2)](2+). These are the first reported side-on bound diazene and hydrazine complexes of ruthenium, and they have been characterized by NMR spectroscopy ((1)H, (31)P, (15)N) and by X-ray crystallography. The interconversion between the ruthenium diazene and the ruthenium hydrazine by acid-base treatment was reversible.

  2. Application of ruthenium catalyzed oxidation of [tris(2-aminoethyl)amine] in trace determination of ruthenium in environmental water samples

    NASA Astrophysics Data System (ADS)

    Prasad, Surendra; Naik, Radhey M.; Srivastava, Abhishek

    2008-10-01

    The ruthenium catalyzed oxidation of tris(2-aminoethyl)amine (TREN) by hexacyanoferrate(III) has been utilized for the development of a new and sensitive catalytic kinetic method (CKM) for the determination of ruthenium(III). The reaction was followed spectrophotometrically by the decrease in absorbance at 420 nm ( λmax of [Fe(CN) 6] 3-). The CKM developed utilizes fixed time procedure under optimum reaction conditions where the change in absorbance (Δ At) versus ruthenium(III) concentrations is plotted. The calibration curve recommended for the method is linear in the concentration range 10.11-252.67 ng ml -1 with very good accuracy and reproducibility and a maximum error 2.20%. The detection limits of the method for ruthenium(III) corresponding to 10, 15 and 20 min are 8.02, 5.03 and 3.15 ng ml -1, respectively. The ruthenium(III) has also been determined in the presence of several other interfering and non-interfering cations and anions and no foreign ions interfered in the determination of ruthenium(III) up to five-fold higher concentration of the foreign ions tested. The method is highly sensitive, selective and stable. It has successfully been applied for the determination of trace ruthenium(III) in some synthetic and environmental water samples. A review of most of the published catalytic kinetic and some other important methods for the determination of ruthenium has also been presented.

  3. Ruthenium / aerogel nanocomposits via Atomic Layer Deposition

    SciTech Connect

    Biener, J; Baumann, T F; Wang, Y; Nelson, E J; Kucheyev, S O; Hamza, A V; Kemell, M; Ritala, M; Leskela, M

    2006-08-28

    We present a general approach to prepare metal/aerogel nanocomposites via template directed atomic layer deposition (ALD). In particular, we used a Ru ALD process consisting of alternating exposures to bis(cyclopentadienyl)ruthenium (RuCp{sub 2}) and air at 350 C to deposit metallic Ru nanoparticles on the internal surfaces of carbon and silica aerogels. The process does not affect the morphology of the aerogel template and offers excellent control over metal loading by simply adjusting the number of ALD cycles. We also discuss the limitations of our ALD approach, and suggest ways to overcome these.

  4. Interaction of ruthenium red with Ca2(+)-binding proteins

    SciTech Connect

    Charuk, J.H.; Pirraglia, C.A.; Reithmeier, R.A. )

    1990-07-01

    The interaction of ruthenium red, ((NH3)5Ru-O-Ru(NH3)4-O-Ru(NH3)5)Cl6.4H2O, with various Ca2(+)-binding proteins was studied. Ruthenium red inhibited Ca2+ binding to the sarcoplasmic reticulum protein, calsequestrin, immobilized on Sepharose 4B. Furthermore, ruthenium red bound to calsequestrin with high affinity (Kd = 0.7 microM; Bmax = 218 nmol/mg protein). The dye stained calsequestrin in sodium dodecyl sulfate-polyacrylamide gels or on nitrocellulose paper and was displaced by Ca2+ (Ki = 1.4 mM). The specificity of ruthenium red staining of several Ca2(+)-binding proteins was investigated by comparison with two other detection methods, 45Ca2+ autoradiography and the Stains-all reaction. Ruthenium red bound to the same proteins detected by the 45Ca2+ overlay technique. Ruthenium red stained both the erythrocyte Band 3 anion transporter and the Ca2(+)-ATPase of skeletal muscle sarcoplasmic reticulum. Ruthenium red also stained the EF hand conformation Ca2(+)-binding proteins, calmodulin, troponin C, and S-100. This inorganic dye provides a simple, rapid method for detecting various types of Ca2(+)-binding proteins following electrophoresis.

  5. Impregnated ruthenium on magnetite as a recyclable catalyst for the N-alkylation of amines, sulfonamides, sulfinamides, and nitroarenes using alcohols as electrophiles by a hydrogen autotransfer process.

    PubMed

    Cano, Rafael; Ramón, Diego J; Yus, Miguel

    2011-07-15

    Various impregnated metallic salts on magnetite have been prepared, including cobalt, nickel, copper, ruthenium, and palladium salts, as well as a bimetallic palladium-copper derivative. Impregnated ruthenium catalyst is a versatile, inexpensive, and simple system for the selective N-monoalkylation of amino derivatives with poor nucleophilic character, such as aromatic and heteroaromatic amines, sulfonamides, sulfinamides, and nitroarenes, using in all cases alcohols as the initial source of the electrophile, through a hydrogen autotransfer process. In the case of sulfinamides, this is the first time that these amino compounds have been alkylated following this strategy, allowing the use of chiral sulfinamides and secondary alcohols to give the alkylated compound with a diastereomeric ratio of 92:8. In these cases, after alkylation, a simple acid deprotection gave the expected primary amines in good yields. The ruthenium catalyst is quite sensitive, and small modifications of the reaction medium can change the final product. The alkylation of amines using potassium hydroxide renders the N-monoalkylated amines, and the same protocol using sodium hydroxide yields the related imines. The catalyst can be easily removed by a simple magnet and can be reused up to ten times, showing the same activity.

  6. Building Indenylidene-Ruthenium Catalysts for Metathesis Transformations

    NASA Astrophysics Data System (ADS)

    Clavier, Hervé; Nolan, Steven P.

    Ruthenium-mediated olefin metathesis has emerged as an indispensable tool in organic synthesis for the formation carbon-carbon double bonds, attested by the large number of applications for natural product synthesis. Among the numerous catalysts developed to mediate olefin metathesis transformations, ruthenium-indenylidene complexes are robust and powerful pre-catalysts. The discovery of this catalyst category was slightly muddled due to a first mis-assignment of the compound structure. This report provides an overview of the synthetic routes for the construction of the indenylidene pattern in ruthenium complexes. The parameters relating to the indenylidene moiety construction will be discussed as well as the mechanism of this formation

  7. PROCESS FOR DECONTAMINATING THORIUM AND URANIUM WITH RESPECT TO RUTHENIUM

    DOEpatents

    Meservey, A.A.; Rainey, R.H.

    1959-10-20

    The control of ruthenium extraction in solvent-extraction processing of neutron-irradiated thorium is presented. Ruthenium is rendered organic-insoluble by the provision of sulfite or bisulfite ions in the aqueous feed solution. As a result the ruthenium remains in the aqueous phase along with other fission product and protactinium values, thorium and uranium values being extracted into the organic phase. This process is particularly applicable to the use of a nitrate-ion-deficient aqueous feed solution and to the use of tributyl phosphate as the organic extractant.

  8. Characteristics and reactivity of ruthenium-oxo complexes.

    PubMed

    Ishizuka, Tomoya; Kotani, Hiroaki; Kojima, Takahiko

    2016-11-14

    In this perspective, we have surveyed the synthetic procedure, characteristics, and reactivity of high-valent ruthenium-oxo complexes. The ruthenium-oxo complexes have served as ideal species to elucidate the characteristics of metal-oxo complexes in terms of not only geometrical and electronic structures but also oxidation reactivity and mechanisms of oxidation reactions. Due to the high stability and excellent reversibility of redox processes, ruthenium-oxo complexes have provided significant mechanistic insights into the oxidation of organic compounds including alcohols, alkenes, and alkanes and also water on the basis of detailed kinetic analysis.

  9. Ruthenium-containing bond coats for thermal barrier coating systems

    NASA Astrophysics Data System (ADS)

    Tryon, B.; Cao, F.; Murphy, K. S.; Levi, C. G.; Pollock, T. M.

    2006-01-01

    Bond coats for zirconia-based thermal barrier coating systems applied to nickel-based superalloys are typically composed of the B2 NiAl phase. Since RuAl has the same B2 crystal structure but a melting point 400°C higher than NiAl, ruthenium-modified aluminide bond coats could provide improved system temperature capability. Creep experiments on ternary Al-Ni-Ru alloys demonstrate greatly improved creep properties with increasing ruthenium content. Processing paths for ruthenium-modified NiAl-based bond coatings have been established within the bounds of commercially available coating systems. The oxidation resistance of ruthenium-modified bond coats during thermal cycling has been examined, and potential thermal barrier coating system implications are discussed.

  10. Splitting water with cobalt.

    PubMed

    Artero, Vincent; Chavarot-Kerlidou, Murielle; Fontecave, Marc

    2011-08-01

    The future of energy supply depends on innovative breakthroughs regarding the design of cheap, sustainable, and efficient systems for the conversion and storage of renewable energy sources, such as solar energy. The production of hydrogen, a fuel with remarkable properties, through sunlight-driven water splitting appears to be a promising and appealing solution. While the active sites of enzymes involved in the overall water-splitting process in natural systems, namely hydrogenases and photosystem II, use iron, nickel, and manganese ions, cobalt has emerged in the past five years as the most versatile non-noble metal for the development of synthetic H(2)- and O(2)-evolving catalysts. Such catalysts can be further coupled with photosensitizers to generate photocatalytic systems for light-induced hydrogen evolution from water.

  11. Cobalt: for strength and color

    USGS Publications Warehouse

    Boland, Maeve A.; Kropschot, S.J.

    2011-01-01

    Cobalt is a shiny, gray, brittle metal that is best known for creating an intense blue color in glass and paints. It is frequently used in the manufacture of rechargeable batteries and to create alloys that maintain their strength at high temperatures. It is also one of the essential trace elements (or "micronutrients") that humans and many other living creatures require for good health. Cobalt is an important component in many aerospace, defense, and medical applications and is a key element in many clean energy technologies. The name cobalt comes from the German word kobold, meaning goblin. It was given this name by medieval miners who believed that troublesome goblins replaced the valuable metals in their ore with a substance that emitted poisonous fumes when smelted. The Swedish chemist Georg Brandt isolated metallic cobalt-the first new metal to be discovered since ancient times-in about 1735 and identified some of its valuable properties.

  12. Nonproductive events in ring-closing metathesis using ruthenium catalysts.

    PubMed

    Stewart, Ian C; Keitz, Benjamin K; Kuhn, Kevin M; Thomas, Renee M; Grubbs, Robert H

    2010-06-30

    The relative TONs of productive and nonproductive metathesis reactions of diethyl diallylmalonate are compared for eight different ruthenium-based catalysts. Nonproductive cross metathesis is proposed to involve a chain-carrying ruthenium methylidene. A second more-challenging substrate (dimethyl allylmethylallylmalonate) that forms a trisubstituted olefin product is used to further delineate the effect of catalyst structure on the relative efficiencies of these processes. A steric model is proposed to explain the observed trends.

  13. Nickel/ruthenium catalyst and method for aqueous phase reactions

    DOEpatents

    Elliott, Douglas C.; Sealock, John L.

    1998-01-01

    A method of hydrogenation using a catalyst in the form of a plurality of porous particles wherein each particle is a support having nickel metal catalytic phase or reduced nickel deposited thereon in a first dispersed phase and an additional ruthenium metal deposited onto the support in a second dispersed phase. The additional ruthenium metal is effective in retarding or reducing agglomeration or sintering of the nickel metal catalytic phase thereby increasing the life time of the catalyst during hydrogenation reactions.

  14. Structural evolution of small ruthenium cluster anions

    SciTech Connect

    Waldt, Eugen; Hehn, Anna-Sophia; Ahlrichs, Reinhart; Kappes, Manfred M.; Schooss, Detlef

    2015-01-14

    The structures of ruthenium cluster anions have been investigated using a combination of trapped ion electron diffraction and density functional theory computations in the size range from eight to twenty atoms. In this size range, three different structural motifs are found: Ru{sub 8}{sup −}–Ru{sub 12}{sup −} have simple cubic structures, Ru{sub 13}{sup −}–Ru{sub 16}{sup −} form double layered hexagonal structures, and larger clusters form close packed motifs. For Ru{sub 17}{sup −}, we find hexagonal close packed stacking, whereas octahedral structures occur for Ru{sub 18}{sup −}–Ru{sub 20}{sup −}. Our calculations also predict simple cubic structures for the smaller clusters Ru{sub 4}{sup −}–Ru{sub 7}{sup −}, which were not accessible to electron diffraction measurements.

  15. A promising new thermoelectric material - Ruthenium silicide

    NASA Technical Reports Server (NTRS)

    Vining, Cronin B.; Mccormack, Joseph A.; Zoltan, Andrew; Zoltan, Leslie D.

    1991-01-01

    Experimental and theoretical efforts directed toward increasing thermoelectric figure of merit values by a factor of 2 or 3 have been encouraging in several respects. An accurate and detailed theoretical model developed for n-type silicon-germanium (SiGe) indicates that ZT values several times higher than currently available are expected under certain conditions. These new, high ZT materials are expected to be significantly different from SiGe, but not unreasonably so. Several promising candidate materials have been identified which may meet the conditions required by theory. One such candidate, ruthenium silicide, currently under development at JPL, has been estimated to have the potential to exhibit figure of merit values 4 times higher than conventional SiGe materials. Recent results are summarized.

  16. Lightening up Ruthenium Complexes to Fight Cancer?

    PubMed

    Mari, Cristina; Gasser, Gilles

    2015-01-01

    In medicine, light is used in a medical treatment called photodynamic therapy (PDT) to treat some types of cancer and skin diseases. This technique generally allows for reduced side effects compared to traditional chemotherapy. However, PDT is not fully effective on hypoxic tumors (i.e. lacking oxygen). To overcome this important drawback, photoactivated chemotherapy (PACT) agents have been designed to obtain light-mediated cancer cell death via an oxygen-independent mechanism. Ruthenium complexes have already been and are currently deeply explored as traditional anticancer agents. However, as reported in this short review article, such compounds can also bring novel opportunities in the field of light-mediated cancer treatment. Herein, we report on our findings in the optimization of Ru(II) polypyridyl complexes as PDT and PACT agents for the potential treatment of cancer and, interestingly, also of bacterial infections.

  17. Nuclear targets of photodynamic tridentate ruthenium complexes.

    PubMed

    Zhao, Ran; Hammitt, Richard; Thummel, Randolph P; Liu, Yao; Turro, Claudia; Snapka, Robert M

    2009-12-28

    Octahedral ruthenium complexes, capable of photodynamic singlet oxygen production at near 100% efficiency, were shown to cause light-dependent covalent crosslinking of p53 and PCNA subunits in mammalian cells and cell lysates. Azide, a singlet oxygen quencher, greatly reduced the p53 photocrosslinking, consistent with the idea that singlet oxygen is the reactive oxygen species involved in p53 photocrosslinking. A photodynamically inactive ruthenium complex, [Ru(tpy)(2)](2+) (tpy = [2,2';6',2'']-terpyridine), had no effect on p53 or PCNA photocrosslinking. Photodynamic damage to p53 has particular relevance since p53 status is an important determinant of phototoxicity and the effectiveness of photodynamic cancer therapy. The two photodynamic complexes studied, [Ru(tpy)(pydppn)](2+), where pydppn = (3-(pyrid-2'-yl)-4,5,9,16-tetraaza-dibenzo[a,c]naphthacene, and [Ru(pydppn)(2)](2+), differed in their efficiency of p53 and PCNA photocrosslinking in cells, but showed similar efficiency of photocrosslinking in cell lysates, suggesting that they differ in their ability to enter cells. Photocrosslinking of PCNA by [Ru(tpy)(pydppn)](2+) increased linearly with concentration, time of uptake, or light exposure. Both [Ru(tpy)(pydppn)](2+) and [Ru(pydppn)(2)](2+) caused photodynamic protein-DNA crosslinking in cells, but [Ru(tpy)(pydppn)](2+) was more efficient. The efficiency of photodynamic protein-DNA crosslinking by [Ru(tpy)(pydppn)](2+) in cells increased with increasing levels of photodynamic damage. Photodynamic damage by [Ru(tpy)(pydppn)](2+) caused inhibition of DNA replication in a classical biphasic response, suggesting that DNA damage signaling and cell cycle checkpoint pathways were still operative after significant damage to nuclear proteins.

  18. Antimicrobial ruthenium complex coating on the surface of titanium alloy. High efficiency anticorrosion protection of ruthenium complex.

    PubMed

    El-Gamel, Nadia E A; Fekry, Amany M

    2015-08-01

    A ruthenium complex was prepared and structurally characterized using various techniques. Antibacterial and antifungal activities of ruthenium complex were evaluated. High significant antimicrobial activity against Escherichia coli, Staphylococcus aureus and Candida albicans was recorded. Minor cytotoxicity records were reported at the highest concentration level using MTT assay. The influence of Cu(II), Cr(III), Fe(III) and Ru(III) metal ions of salen Schiff base on the corrosion resistance of Ti-alloy in 0.5M HCl was studied. In vitro corrosion resistance was investigated using electrochemical impedance spectroscopy (EIS) measurements and confirmed by surface examination via scanning electron microscope (SEM) technique. Both impedance and phase angle maximum (θ(max)) values were at maximum in the case of the ruthenium complex with promising antibacterial and antifungal activities. The surface film created by the ruthenium complex was highly resistant against attack or deterioration by bacteria. The EIS study showed high impedance values for the ruthenium complex with increasing exposure time up to 8 days. SEM images showed uniform distribution and adsorption of Ru(III) ions on Ti-alloy surface. The ruthenium complex, as a model of organic-inorganic hybrid complex, offered new prospects with desired properties in industrial and medical applications.

  19. Iridium-Doped Ruthenium Oxide Catalyst for Oxygen Evolution

    NASA Technical Reports Server (NTRS)

    Valdez, Thomas I.; Narayan, Sri R.; Billings, Keith J.

    2011-01-01

    NASA requires a durable and efficient catalyst for the electrolysis of water in a polymer-electrolyte-membrane (PEM) cell. Ruthenium oxide in a slightly reduced form is known to be a very efficient catalyst for the anodic oxidation of water to oxygen, but it degrades rapidly, reducing efficiency. To combat this tendency of ruthenium oxide to change oxidation states, it is combined with iridium, which has a tendency to stabilize ruthenium oxide at oxygen evolution potentials. The novel oxygen evolution catalyst was fabricated under flowing argon in order to allow the iridium to preferentially react with oxygen from the ruthenium oxide, and not oxygen from the environment. Nanoparticulate iridium black and anhydrous ruthenium oxide are weighed out and mixed to 5 18 atomic percent. They are then heat treated at 300 C under flowing argon (in order to create an inert environment) for a minimum of 14 hours. This temperature was chosen because it is approximately the creep temperature of ruthenium oxide, and is below the sintering temperature of both materials. In general, the temperature should always be below the sintering temperature of both materials. The iridium- doped ruthenium oxide catalyst is then fabricated into a PEM-based membrane- electrode assembly (MEA), and then mounted into test cells. The result is an electrolyzer system that can sustain electrolysis at twice the current density, and at the same efficiency as commercial catalysts in the range of 100-200 mA/sq cm. At 200 mA/sq cm, this new system operates at an efficiency of 85 percent, which is 2 percent greater than commercially available catalysts. Testing has shown that this material is as stable as commercially available oxygen evolution catalysts. This means that this new catalyst can be used to regenerate fuel cell systems in space, and as a hydrogen generator on Earth.

  20. Kinetics and Photochemistry of Ruthenium Bisbipyridine Diacetonitrile Complexes: An Interdisciplinary Inorganic and Physical Chemistry Laboratory Exercise

    ERIC Educational Resources Information Center

    Rapp, Teresa L.; Phillips, Susan R.; Dmochowski, Ivan J.

    2016-01-01

    The study of ruthenium polypyridyl complexes can be widely applied across disciplines in the undergraduate curriculum. Ruthenium photochemistry has advanced many fields including dye-sensitized solar cells, photoredox catalysis, lightdriven water oxidation, and biological electron transfer. Equally promising are ruthenium polypyridyl complexes…

  1. Controlling the misuse of cobalt in horses.

    PubMed

    Ho, Emmie N M; Chan, George H M; Wan, Terence S M; Curl, Peter; Riggs, Christopher M; Hurley, Michael J; Sykes, David

    2015-01-01

    Cobalt is a well-established inducer of hypoxia-like responses, which can cause gene modulation at the hypoxia inducible factor pathway to induce erythropoietin transcription. Cobalt salts are orally active, inexpensive, and easily accessible. It is an attractive blood doping agent for enhancing aerobic performance. Indeed, recent intelligence and investigations have confirmed cobalt was being abused in equine sports. In this paper, population surveys of total cobalt in raceday samples were conducted using inductively coupled plasma mass spectrometry (ICP-MS). Urinary threshold of 75 ng/mL and plasma threshold of 2 ng/mL could be proposed for the control of cobalt misuse in raceday or in-competition samples. Results from administration trials with cobalt-containing supplements showed that common supplements could elevate urinary and plasma cobalt levels above the proposed thresholds within 24 h of administration. It would therefore be necessary to ban the use of cobalt-containing supplements on raceday as well as on the day before racing in order to implement and enforce the proposed thresholds. Since the abuse with huge quantities of cobalt salts can be done during training while the use of legitimate cobalt-containing supplements are also allowed, different urinary and plasma cobalt thresholds would be required to control cobalt abuse in non-raceday or out-of-competition samples. This could be achieved by setting the thresholds above the maximum urinary and plasma cobalt concentrations observed or anticipated from the normal use of legitimate cobalt-containing supplements. Urinary threshold of 2000 ng/mL and plasma threshold of 10 ng/mL were thus proposed for the control of cobalt abuse in non-raceday or out-of-competition samples.

  2. Cobalt(II) and Cobalt(III) Coordination Compounds.

    ERIC Educational Resources Information Center

    Thomas, Nicholas C.; And Others

    1989-01-01

    Presents a laboratory experiment which illustrates the formation of tris(phenanthroline)cobalt complexes in the 2+ and 3+ oxidation states, the effect of coordination on reactions of the ligand, and the use of a ligand displacement reaction in recovering the transformed ligand. Uses IR, UV-VIS, conductivity, and NMR. (MVL)

  3. Ruthenium Catalysis in the Synthesis of Six-Membered Heterocycles

    NASA Astrophysics Data System (ADS)

    Zhang, Min

    Owing to the cost-effectiveness and versatility of ruthenium in catalysis, the utilization of ruthenium for developing atom and step-economic methodologies, allowing for the synthesis of six-membered heterocycles, is of particular importance in synthetic chemistry because of the important value of such compounds employed in discovering biologically and pharmacologically active compositions, the preparation of novel materials with specific functions, etc. This chapter highlights the recent 15 years' advances on ruthenium-catalyzed synthesis of six-membered heterocycles, with particular focus on the related approaches and mechanistic basis, which includes the synthesis of N-heterocycles, O-heterocycles, N,O-heterocycles, and other type of heteroatom-heterocycles.

  4. Determination of oxygen diffusion kinetics during thin film ruthenium oxidation

    NASA Astrophysics Data System (ADS)

    Coloma Ribera, R.; van de Kruijs, R. W. E.; Yakshin, A. E.; Bijkerk, F.

    2015-08-01

    In situ X-ray reflectivity was used to reveal oxygen diffusion kinetics for thermal oxidation of polycrystalline ruthenium thin films and accurate determination of activation energies for this process. Diffusion rates in nanometer thin RuO2 films were found to show Arrhenius behaviour. However, a gradual decrease in diffusion rates was observed with oxide growth, with the activation energy increasing from about 2.1 to 2.4 eV. Further exploration of the Arrhenius pre-exponential factor for diffusion process revealed that oxidation of polycrystalline ruthenium joins the class of materials that obey the Meyer-Neldel rule.

  5. Nickel/ruthenium catalyst and method for aqueous phase reactions

    DOEpatents

    Elliott, D.C.; Sealock, J.L.

    1998-09-29

    A method of hydrogenation is described using a catalyst in the form of a plurality of porous particles wherein each particle is a support having nickel metal catalytic phase or reduced nickel deposited thereon in a first dispersed phase and an additional ruthenium metal deposited onto the support in a second dispersed phase. The additional ruthenium metal is effective in retarding or reducing agglomeration or sintering of the nickel metal catalytic phase thereby increasing the life time of the catalyst during hydrogenation reactions. 2 figs.

  6. Determination of oxygen diffusion kinetics during thin film ruthenium oxidation

    SciTech Connect

    Coloma Ribera, R. Kruijs, R. W. E. van de; Yakshin, A. E.; Bijkerk, F.

    2015-08-07

    In situ X-ray reflectivity was used to reveal oxygen diffusion kinetics for thermal oxidation of polycrystalline ruthenium thin films and accurate determination of activation energies for this process. Diffusion rates in nanometer thin RuO{sub 2} films were found to show Arrhenius behaviour. However, a gradual decrease in diffusion rates was observed with oxide growth, with the activation energy increasing from about 2.1 to 2.4 eV. Further exploration of the Arrhenius pre-exponential factor for diffusion process revealed that oxidation of polycrystalline ruthenium joins the class of materials that obey the Meyer-Neldel rule.

  7. Cosine (Cobalt Silicide Growth Through Nitrogen-Induced Epitaxy) Process For Epitaxial Cobalt Silicide Formation For High Performance Sha

    DOEpatents

    Lim, Chong Wee; Shin, Chan Soo; Gall, Daniel; Petrov, Ivan Georgiev; Greene, Joseph E.

    2004-09-28

    A method for forming an epitaxial cobalt silicide layer on a MOS device includes sputter depositing cobalt in an ambient to form a first layer of cobalt suicide on a gate and source/drain regions of the MOS device. Subsequently, cobalt is sputter deposited again in an ambient of argon to increase the thickness of the cobalt silicide layer to a second thickness.

  8. Polytypic transformations during the thermal decomposition of cobalt hydroxide and cobalt hydroxynitrate

    SciTech Connect

    Ramesh, Thimmasandra Narayan

    2010-06-15

    The isothermal decomposition of cobalt hydroxide and cobalt hydroxynitrate at different intervals of temperature leads to the formation of Co{sub 3}O{sub 4}. The phase evolution during the decomposition process was monitored using powder X-ray diffraction. The transformation of cobalt hydroxide to cobalt oxide occurs via three phase mixture while cobalt hydroxynitrate to cobalt oxide occurs through a two phase mixture. The nature of the sample and its preparation method controls the decomposition mechanism. The comparison of topotactical relationship between the precursors to the decomposed product has been reported in relation to polytypism. - Graphical abstract: Isothermal thermal decomposition studies of cobalt hydroxide and cobalt hydroxynitrate at different intervals of temperature show the metastable phase formed prior to Co{sub 3}O{sub 4} phase.

  9. On the cobalt and cobalt oxide electrodeposition from a glyceline deep eutectic solvent.

    PubMed

    Sakita, Alan M P; Della Noce, Rodrigo; Fugivara, Cecílio S; Benedetti, Assis V

    2016-09-14

    The electrodeposition of cobalt and cobalt oxides from a glyceline deep eutectic solvent is reported. Cyclic voltammetry, chronoamperometry, scanning electron microscopy, and Raman spectroscopy are employed to study the Co deposition processes. Surface analysis reveals that metallic cobalt is deposited at potentials less negative than the current peak potential whereas cobalt oxides are detected and electrochemically observed when the deposition is done at more negative potentials. i-t transients are analyzed by applying the Scharifker and Hills (SH) theoretical model. It is concluded that cobalt deposition occurs via a progressive nucleation and growth mechanism for concentrations higher than 0.05 mol L(-1) cobalt ions. For concentrations ≤0.025 mol L(-1) cobalt ions and low overpotentials, the mechanism changes to instantaneous nucleation. The im-tm relationships of the SH model are used to determine the values of the kinetic parameters and the cobalt ion diffusion coefficient.

  10. Study on volatilization mechanism of ruthenium tetroxide from nitrosyl ruthenium nitrate by using mass spectrometer

    NASA Astrophysics Data System (ADS)

    Kato, Tetsuya; Usami, Tsuyoshi; Tsukada, Takeshi; Shibata, Yuki; Kodama, Takashi

    2016-10-01

    In a cooling malfunction accident of a high-level liquid waste (HLLW) tank, behavior of ruthenium (Ru) attracts much attention, since Ru could be oxidized to a volatile chemical form in the boiling and drying of HLLW, and part of radioactive Ru can potentially be released to the environment. In this study, nitrosyl Ru nitrate (Ru(NO)(NO3)3) dissolved in nitric acid (HNO3), which is commonly contained in a simulated HLLW, was dried and heated up to 723 K, and the evolved gas was introduced into a mass spectrometer. The well-known volatile species, ruthenium tetroxide (RuO4) was detected in a temperature range between 390 K and 500 K with the peak top around 440 K. Various gases such as HNO3, nitrogen dioxide (NO2), nitrogen monoxide (NO) also evolved due to evaporation of the nitric acid and decomposition of the nitrate ions. The ion current of RuO4 seems to increase with the increasing decomposition of nitrate, while the evaporation of HNO3 decreases. More volatilization of RuO4 was observed from the HNO3 solution containing not only Ru(NO)(NO3)3 but also cerium nitrate (Ce(NO3)3·6H2O) which was added for extra supply of nitrate ion, compared with that from the HNO3 solution containing only Ru(NO)(NO3)3. These experimental results suggest that Ru could be oxidized to form RuO4 by the nitrate ion as well as HNO3.

  11. Ruthenium-catalyzed C–H activation of thioxanthones

    PubMed Central

    Wagner, Danny

    2015-01-01

    Summary Thioxanthones – being readily available in one step from thiosalicylic acid and arenes – were used in ruthenium-catalyzed C–H-activation reaction to produce 1-mono- or 1,8-disubstituted thioxanthones in good to excellent yields. Scope and limitation of this reaction are presented. PMID:25977717

  12. Molecular Models of Ruthenium(II) Organometallic Complexes

    ERIC Educational Resources Information Center

    Coleman, William F.

    2007-01-01

    This article presents the featured molecules for the month of March, which appear in the paper by Ozerov, Fafard, and Hoffman, and which are related to the study of the reactions of a number of "piano stool" complexes of ruthenium(II). The synthesis of compound 2a offers students an alternative to the preparation of ferrocene if they are only…

  13. Improvement of ruthenium based decarboxylation of carboxylic acids

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The removal of oxygen atoms from biobased carboxylic acids is an attractive route to provide the drop in replacement feedstocks that industry needs to continue to provide high performance products. Through the use of ruthenium catalysis, an efficient method where this process can be accomplished on ...

  14. PRECIPITATION OF ZIRCONIUM, NIOBIUM, AND RUTHENIUM FROM AQUEOUS SOLUTIONS

    DOEpatents

    Wilson, A.S.

    1958-08-12

    An improvement on the"head end process" for decontaminating dissolver solutions of their Zr, Ni. and Ru values. The process consists in adding a water soluble symmetrical dialkyl ketone. e.g. acetone, before the formation of the manganese dioxide precipitate. The effect is that upon digestion, the ruthenium oxide does not volatilize, but is carried on the manganese dioxide precipitate.

  15. A new approach to synthesize supported ruthenium phosphides for hydrodesulfurization

    SciTech Connect

    Wang, Qingfang; Wang, Zhiqiang; Yin, Xiaoqian; Zhou, Linxi; Zhang, Minghui

    2016-02-15

    Highlights: • We bring out a new method to synthesize noble metal phosphides at low temperature. • Both RuP and Ru{sub 2}P were synthesized using triphenylphosphine as phosphorus sources. • Ru{sub 2}P was the better active phase for HDS than RuP and metal Ru. • RuP/SiO{sub 2} prepared by new method had better HDS activity to that by TPR method. - Abstract: Supported noble metal ruthenium phosphides were synthesized by one-step H{sub 2}-thermal treatment method using triphenylphosphine (TPP) as phosphorus sources at low temperatures. Two phosphides RuP and Ru{sub 2}P can be prepared by this method via varying the molar ratio of metal salt and TPP. The as-prepared phosphides were characterized by X-ray powder diffraction (XRD), low-temperature N{sub 2} adsorption, CO chemisorption and transmission electronic microscopy (TEM). The supported ruthenium phosphides prepared by new method and conventional method together with contradistinctive metallic ruthenium were evaluated in hydrodesulfurization (HDS) of dibenzothiophene (DBT). The catalytic results showed that metal-rich Ru{sub 2}P was the better active phase for HDS than RuP and metal Ru. Besides this, ruthenium phosphide catalyst prepared by new method exhibited superior HDS activity to that prepared by conventional method.

  16. Parameters governing ruthenium sawhorse-based decarboxylation of oleic acid

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Ruthenium-catalyzed decarboxylation of 9-cisoctadecenoic is a path to produce biobased olefins. Here, a mechanistic study of this reaction was undertaken utilizing a closed reaction system and a pressure reactor. The proposed mechanism of an isomerization followed by a decarboxylation reaction was c...

  17. Arsenate Adsorption On Ruthenium Oxides: A Spectroscopic And Kinetic Investigation

    EPA Science Inventory

    Arsenate adsorption on amorphous (RuO2•1.1H2O) and crystalline (RuO2) ruthenium oxides was evaluated using spectroscopic and kinetic methods to elucidate the adsorption mechanism. Extended X-ray absorption fine structure spectroscopy (EXAFS) was ...

  18. Molecular dinitrogen complexes of ruthenium(II) porphyrins

    SciTech Connect

    Camenzind, M.J.; James, B.R.; Dolphin, D.; Sparapany, J.W.; Ibers, J.A.

    1988-08-24

    The existence of both mono- and bis(nitrogen) complexes of ruthenium have been previously established. Details on a series of complexes are presented herein, and results of an x-ray crystallographic study of Ru(TMP) (THF) (N/sub 2/) are reported. 30 references, 4 tables.

  19. Ruthenium-catalyzed tertiary amine formation from nitroarenes and alcohols.

    PubMed

    Feng, Chao; Liu, Yong; Peng, Shengming; Shuai, Qi; Deng, Guojun; Li, Chao-Jun

    2010-11-05

    A highly selective ruthenium-catalyzed C-N bond formation was developed by using the hydrogen-borrowing strategy. Various tertiary amines were obtained efficiently from nitroarenes and primary alcohols. The reaction tolerates a wide range of functionalities. A tentative mechanism was proposed for this direct amination reaction of alcohols with nitroarenes.

  20. Ruthenium red-induced bundling of bacterial cell division protein, FtsZ.

    PubMed

    Santra, Manas Kumar; Beuria, Tushar K; Banerjee, Abhijit; Panda, Dulal

    2004-06-18

    The assembly of FtsZ plays a major role in bacterial cell division, and it is thought that the assembly dynamics of FtsZ is a finely regulated process. Here, we show that ruthenium red is able to modulate FtsZ assembly in vitro. In contrast to the inhibitory effects of ruthenium red on microtubule polymerization, we found that a substoichiometric concentration of ruthenium red strongly increased the light-scattering signal of FtsZ assembly. Further, sedimentable polymer mass was increased by 1.5- and 2-fold in the presence of 2 and 10 microm ruthenium red, respectively. In addition, ruthenium red strongly reduced the GTPase activity and prevented dilution-induced disassembly of FtsZ polymers. Electron microscopic analysis showed that 4-10 microm of ruthenium red produced thick bundles of FtsZ polymers. The significant increase in the light-scattering signal and pelletable polymer mass in the presence of ruthenium red seemed to be due to the bundling of FtsZ protofilaments into larger polymers rather than the actual increase in the level of polymeric FtsZ. Furthermore, ruthenium red was found to copolymerize with FtsZ, and the copolymerization of substoichiometric amounts of ruthenium red with FtsZ polymers promoted cooperative assembly of FtsZ that produced large bundles. Calcium inhibited the binding of ruthenium red to FtsZ. However, a concentration of calcium 1000-fold higher than that of ruthenium red was required to produce similar effects on FtsZ assembly. Ruthenium red strongly modulated FtsZ polymerization, suggesting the presence of an important regulatory site on FtsZ and suggesting that a natural ligand, which mimics the action of ruthenium red, may regulate the assembly of FtsZ in bacteria.

  1. Cobalt-Base Alloy Gun Barrel Study

    DTIC Science & Technology

    2014-07-01

    Cobalt -Base Alloy Gun Barrel Study by William S. de Rosset and Jonathan S. Montgomery ARL-RP-0491 July 2014 A reprint...21005-5069 ARL-RP-0491 July 2014 Cobalt -Base Alloy Gun Barrel Study William S. de Rosset and Jonathan S. Montgomery Weapons and Materials...DATE (DD-MM-YYYY) July 2014 2. REPORT TYPE Reprint 3. DATES COVERED (From - To) October–November 2013 4. TITLE AND SUBTITLE Cobalt -Base Alloy

  2. Mineral resource of the month: cobalt

    USGS Publications Warehouse

    Shedd, Kim B.

    2009-01-01

    Cobalt is a metal used in numerous commercial, industrial and military applications. On a global basis, the leading use of cobalt is in rechargeable lithium-ion, nickel-cadmium and nickel-metal hydride battery electrodes. Cobalt use has grown rapidly since the early 1990s, with the development of new battery technologies and an increase in demand for portable electronics such as cell phones, laptop computers and cordless power tools.

  3. [Neurotoxic effects of cobalt: an open question].

    PubMed

    Catalani, S; Apostoli, P

    2011-01-01

    Increased cobalt levels have been associated with neurological diseases (hand tremor, incoordination, cognitive decline, depression, vertigo, hearing loss and visual changes) in addition to "classic" and known cardiac diseases (arrhythmias and cardiomyopathies) and allergic or endocrine symptoms. Cobalt neurotoxicity is reported in isolated cases: old occupational or iatrogenic exposures and more recent releases of metallic ions by prosthesis. The studies of these cases have revealed a typical symptomatology of cobalt probably due to its ability to induce oxidative stress and mitochondrial alterations.

  4. Cobalt-catalyzed C-H borylation.

    PubMed

    Obligacion, Jennifer V; Semproni, Scott P; Chirik, Paul J

    2014-03-19

    A family of pincer-ligated cobalt complexes has been synthesized and are active for the catalytic C-H borylation of heterocycles and arenes. The cobalt catalysts operate with high activity and under mild conditions and do not require excess borane reagents. Up to 5000 turnovers for methyl furan-2-carboxylate have been observed at ambient temperature with 0.02 mol % catalyst loadings. A catalytic cycle that relies on a cobalt(I)-(III) redox couple is proposed.

  5. Solution for Depositing an Electroless Cobalt Alloy.

    DTIC Science & Technology

    SOLUTIONS(MIXTURES), *ELECTROLESS PLATING), (*PATENTS, ELECTROLESS PLATING), (*COBALT ALLOYS, ELECTROLESS PLATING), ADDITIVES, SODIUM COMPOUNDS... TUNGSTATES , POTASSIUM COMPOUNDS, NICKEL COMPOUNDS, SULFATES, THIOUREA, MAGNETIC PROPERTIES

  6. Oxidation of low cobalt alloys

    NASA Technical Reports Server (NTRS)

    Barrett, C. A.

    1982-01-01

    Four high temperature alloys: U-700, Mar M-247, Waspaloy and PM/HIP U-700 were modified with various cobalt levels ranging from 0 percent to their nominal commercial levels. The alloys were then tested in cyclic oxidation in static air at temperatures ranging from 1000 to 1150 C at times from 500 to 100 1 hour cycles. Specific weight change with time and X-ray diffraction analyses of the oxidized samples were used to evaluate the alloys. The alloys tend to be either Al2O3/aluminate spinel or Cr2O3/chromite spinel formers depending on the Cr/Al ratio in the alloy. Waspaloy with a ratio of 15:1 is a strong Cr2O3 former while this U-700 with a ratio of 3.33:1 tends to form mostly Cr2O3 while Mar M-247 with a ratio of 1.53:1 is a strong Al2O3 former. The best cyclic oxidation resistance is associated with the Al2O3 formers. The cobalt levels appear to have little effect on the oxidation resistance of the Al2O3/aluminate spinel formers while any tendency to form Cr2O3 is accelerated with increased cobalt levels and leads to increased oxidation attack.

  7. A Metal-Organic Framework Derived Porous Cobalt Manganese Oxide Bifunctional Electrocatalyst for Hybrid Na-Air/Seawater Batteries.

    PubMed

    Abirami, Mari; Hwang, Soo Min; Yang, Juchan; Senthilkumar, Sirugaloor Thangavel; Kim, Junsoo; Go, Woo-Seok; Senthilkumar, Baskar; Song, Hyun-Kon; Kim, Youngsik

    2016-12-07

    Spinel-structured transition metal oxides are promising non-precious-metal electrocatalysts for oxygen electrocatalysis in rechargeable metal-air batteries. We applied porous cobalt manganese oxide (CMO) nanocubes as the cathode electrocatalyst in rechargeable seawater batteries, which are a hybrid-type Na-air battery with an open-structured cathode and a seawater catholyte. The porous CMO nanocubes were synthesized by the pyrolysis of a Prussian blue analogue, Mn3[Co(CN)6]2·nH2O, during air-annealing, which generated numerous pores between the final spinel-type CMO nanoparticles. The porous CMO electrocatalyst improved the redox reactions, such as the oxygen evolution/reduction reactions, at the cathode in the seawater batteries. The battery that used CMO displayed a voltage gap of ∼0.53 V, relatively small compared to that of the batteries employing commercial Pt/C (∼0.64 V) and Ir/C (∼0.73 V) nanoparticles and without any catalyst (∼1.05 V) at the initial cycle. This improved performance was due to the large surface area (catalytically active sites) and the high oxidation states of the randomly distributed Co and Mn cations in the CMO. Using a hard carbon anode, the Na-metal-free seawater battery exhibited a good cycle performance with an average discharge voltage of ∼2.7 V and a discharge capacity of ∼190 mAh g(-1)hard carbon during 100 cycles (energy efficiencies of 74-79%).

  8. Spectroscopic investigation on the interaction of ruthenium complexes with tumor specific lectin, jacalin

    NASA Astrophysics Data System (ADS)

    Ayaz Ahmed, Khan Behlol; Reshma, Elamvazhuthi; Mariappan, Mariappan; Anbazhagan, Veerappan

    2015-02-01

    Several ruthenium complexes are regarded as anticancer agents and considered as an alternative to the widely used platinum complexes. Owing to the preferential interaction of jacalin with tumor-associated T-antigen, we report the interaction of jacalin with four ruthenium complex namely, tris(1,10-phenanthroline)ruthenium(II)chloride, bis(1,10-phenanthroline)(N-[1,10]phenanthrolin-5-yl-pyrenylmethanimine)ruthenium(II)chloride, bis(1,10-phenanthroline)(dipyrido[3,2-a:2‧,3‧-c]-phenazine)ruthenium(II)chloride, bis(1,10-phenanthroline)(11-(9-acridinyl)dipyrido[3,2-a:2‧,3‧-c]phenazine)ruthenium(II) chloride. Fluorescence spectroscopic analysis revealed that the ruthenium complexes strongly quenched the intrinsic fluorescence of jacalin through a static quenching procedure, and a non-radiative energy transfer occurred within the molecules. Association constants obtained for the interaction of different ruthenium complexes with jacalin are in the order of 105 M-1, which is in the same range as those obtained for the interaction of lectin with carbohydrate and hydrophobic ligand. Each subunit of the tetrameric jacalin binds one ruthenium complex, and the stoichiometry is found to be unaffected by the presence of the specific sugar, galactose. In addition, agglutination activity of jacalin is largely unaffected by the presence of the ruthenium complexes, indicating that the binding sites for the carbohydrate and the ruthenium complexes are different. These results suggest that the development of lectin-ruthenium complex conjugate would be feasible to target malignant cells in chemo-therapeutics.

  9. Synthesis of PVP-stabilized ruthenium colloids with low boiling point alcohols.

    PubMed

    Zhang, Yuqing; Yu, Jiulong; Niu, Haijun; Liu, Hanfan

    2007-09-15

    A route to the preparation of poly(N-vinyl-2-pyrrolidone) (PVP)-stabilized ruthenium colloids by refluxing ruthenium(III) chloride in low boiling point alcohols was developed. Deep purple colloids with shuttle-like ruthenium particles were also synthesized. XPS measurement verified the nanoparticles were in the metallic state. The morphology of metal nanoparticles was characterized by UV-visible absorption spectrophotometry, TEM and XRD.

  10. Spectroscopic investigation on the interaction of ruthenium complexes with tumor specific lectin, jacalin.

    PubMed

    Ayaz Ahmed, Khan Behlol; Reshma, Elamvazhuthi; Mariappan, Mariappan; Anbazhagan, Veerappan

    2015-02-25

    Several ruthenium complexes are regarded as anticancer agents and considered as an alternative to the widely used platinum complexes. Owing to the preferential interaction of jacalin with tumor-associated T-antigen, we report the interaction of jacalin with four ruthenium complex namely, tris(1,10-phenanthroline)ruthenium(II)chloride, bis(1,10-phenanthroline)(N-[1,10]phenanthrolin-5-yl-pyrenylmethanimine)ruthenium(II)chloride, bis(1,10-phenanthroline)(dipyrido[3,2-a:2',3'-c]-phenazine)ruthenium(II)chloride, bis(1,10-phenanthroline)(11-(9-acridinyl)dipyrido[3,2-a:2',3'-c]phenazine)ruthenium(II) chloride. Fluorescence spectroscopic analysis revealed that the ruthenium complexes strongly quenched the intrinsic fluorescence of jacalin through a static quenching procedure, and a non-radiative energy transfer occurred within the molecules. Association constants obtained for the interaction of different ruthenium complexes with jacalin are in the order of 10(5) M(-1), which is in the same range as those obtained for the interaction of lectin with carbohydrate and hydrophobic ligand. Each subunit of the tetrameric jacalin binds one ruthenium complex, and the stoichiometry is found to be unaffected by the presence of the specific sugar, galactose. In addition, agglutination activity of jacalin is largely unaffected by the presence of the ruthenium complexes, indicating that the binding sites for the carbohydrate and the ruthenium complexes are different. These results suggest that the development of lectin-ruthenium complex conjugate would be feasible to target malignant cells in chemo-therapeutics.

  11. Effect of Nitrogen Post-Doping on a Commercial Platinum-Ruthenium/Carbon Anode Catalyst

    DTIC Science & Technology

    2014-02-15

    is unlimited. Effect of nitrogen post-doping on a commercial platinum– ruthenium /carbon anode catalyst The views, opinions and/or findings contained in...ABSTRACT Effect of nitrogen post-doping on a commercial platinum– ruthenium /carbon anode catalyst Report Title This work investigates the effects of...performance of available best-in-class commercial catalysts. Effect of nitrogen post-doping on a commercial platinum– ruthenium /carbon anode catalyst Approved

  12. Thermodynamic data bases for multivalent elements: An example for ruthenium

    SciTech Connect

    Rard, J.A.

    1987-11-01

    A careful consideration and understanding of fundamental chemistry, thermodynamics, and kinetics is absolutely essential when modeling predominance regions and solubility behavior of elements that exhibit a wide range of valence states. Examples of this are given using the ruthenium-water system at 298.15 K, for which a critically assessed thermochemical data base is available. Ruthenium exhibits the widest range of known aqueous solution valence states. Known solid anhydrous binary oxides of ruthenium are crystalline RuO/sub 2/, RuO/sub 4/, and possibly RuO/sub 3/ (thin film), and known hydroxides/hydrated oxides (all amorphous) are Ru(OH)/sub 3/ . H/sub 2/O, RuO/sub 2/ . 2H/sub 2/O, RuO/sub 2/ . H/sub 2/O, and a poorly characterized Ru(V) hydrous oxide. Although the other oxides, hydroxides, and hydrous oxides are generally obtained as precipitates from aqueous solutions, they are thermodynamically unstable with regard to RuO/sub 2/(cr) formation. Characterized aqueous species of ruthenium include RuO/sub 4/ (which slowly oxidizes water and which dissociates as a weak acid), RuO/sub 4//sup -/ and RuO/sub 4//sup 2 -/ (which probably contain lesser amounts of RuO/sub 3/(OH)/sub 2//sup -/ and RuO/sub 3/(OH)/sub 2//sup 2 -/, respectively, and other species), Ru(OH)/sub 2//sup 2 +/, Ru/sub 4/(OH)/sub 12//sup 4 +/, Ru(OH)/sub 4/, Ru/sup 3 +/, Ru(OH)/sup 2 +/, Ru(OH)/sub 2//sup +/, Ru/sup 2 +/, and some hydroxytetramers with formal ruthenium valences of 3.75 greater than or equal to Z greater than or equal to 2.0. Potential pH diagrams of the predominance regions change significantly with concentration due to polymerization/depolymerization reactions. Failure to consider the known chemistry of ruthenium can yield large differences in predicted solubilities.

  13. Electrochemical capacitor performance of hydrous ruthenium oxide/mesoporous carbon composite electrodes

    NASA Astrophysics Data System (ADS)

    Jang, Jong H.; Han, Sangjin; Hyeon, Taeghwan; Oh, Seung M.

    Ruthenium/carbon composite materials are prepared by impregnating ruthenium(III) acetylacetonate into a mesoporous carbon (average pore diameter=12 mn, pore volume=3.6 cm 3 g -1) and then heat treatment at 320 °C for 2 h under an argon atmosphere. The metallic ruthenium nanoparticles are converted to pseudo-capacitive hydrous ruthenium oxide by electrochemical oxidation at 0.75 V (versus SCE) for 2 h in 2.0 M H 2SO 4. The specific capacitance of the composite electrodes, which is the sum of the double-layer capacitance of mesoporous carbon and the pseudo-capacitance of hydrous ruthenium oxide, reaches 243 F g -1 with heavy loading. As the loading is increased, however, the degree of ruthenium utilization for a pseudo-capacitor becomes poorer, presumably due to a limited conversion to the hydrous oxide form. The rate capability of composite electrodes also decreases with increase in ruthenium loading, due to an increase in both the equivalent series resistance (ESR) and the overall capacitance value. The ESR enlargement is caused mainly an increase in the electrolyte resistance within pores which, in turn, results from a pore narrowing with ruthenium loading Hindered ionic motion in narrowed pores can explain this feature. An increase in the RC time constant with ruthenium loading is further verified by ac impedance measurements.

  14. Surface and sub-surface thermal oxidation of thin ruthenium films

    NASA Astrophysics Data System (ADS)

    Coloma Ribera, R.; van de Kruijs, R. W. E.; Kokke, S.; Zoethout, E.; Yakshin, A. E.; Bijkerk, F.

    2014-09-01

    A mixed 2D (film) and 3D (nano-column) growth of ruthenium oxide has been experimentally observed for thermally oxidized polycrystalline ruthenium thin films. Furthermore, in situ x-ray reflectivity upon annealing allowed the detection of 2D film growth as two separate layers consisting of low density and high density oxides. Nano-columns grow at the surface of the low density oxide layer, with the growth rate being limited by diffusion of ruthenium through the formed oxide film. Simultaneously, with the growth of the columns, sub-surface high density oxide continues to grow limited by diffusion of oxygen or ruthenium through the oxide film.

  15. Surface and sub-surface thermal oxidation of thin ruthenium films

    SciTech Connect

    Coloma Ribera, R.; Kruijs, R. W. E. van de; Yakshin, A. E.; Bijkerk, F.; Kokke, S.; Zoethout, E.

    2014-09-29

    A mixed 2D (film) and 3D (nano-column) growth of ruthenium oxide has been experimentally observed for thermally oxidized polycrystalline ruthenium thin films. Furthermore, in situ x-ray reflectivity upon annealing allowed the detection of 2D film growth as two separate layers consisting of low density and high density oxides. Nano-columns grow at the surface of the low density oxide layer, with the growth rate being limited by diffusion of ruthenium through the formed oxide film. Simultaneously, with the growth of the columns, sub-surface high density oxide continues to grow limited by diffusion of oxygen or ruthenium through the oxide film.

  16. CuAAC click reactions for the design of multifunctional luminescent ruthenium complexes.

    PubMed

    Zabarska, Natalia; Stumper, Anne; Rau, Sven

    2016-02-14

    CuAAC (Cu(i) catalyzed azide-alkyne cycloaddition) click chemistry has emerged as a versatile tool in the development of photoactive ruthenium complexes with multilateral potential applicability. In this contribution we discuss possible synthetic approaches towards CuAAC reactions with ruthenium(ii) polypyridine complexes and their differences with respect to possible applications. We focus on two main application possibilities of the click-coupled ruthenium assemblies. New results within the development of ruthenium based photosensitizers for the field of renewable energy supply, i.e. DSSCs (dye-sensitized solar cells) and artificial photocatalysis for the production of hydrogen, or for anticancer photodynamic therapeutic applications are reviewed.

  17. Inhalation cancer risk assessment of cobalt metal.

    PubMed

    Suh, Mina; Thompson, Chad M; Brorby, Gregory P; Mittal, Liz; Proctor, Deborah M

    2016-08-01

    Cobalt compounds (metal, salts, hard metals, oxides, and alloys) are used widely in various industrial, medical and military applications. Chronic inhalation exposure to cobalt metal and cobalt sulfate has caused lung cancer in rats and mice, as well as systemic tumors in rats. Cobalt compounds are listed as probable or possible human carcinogens by some agencies, and there is a need for quantitative cancer toxicity criteria. The U.S. Environmental Protection Agency has derived a provisional inhalation unit risk (IUR) of 0.009 per μg/m(3) based on a chronic inhalation study of soluble cobalt sulfate heptahydrate; however, a recent 2-year cancer bioassay affords the opportunity to derive IURs specifically for cobalt metal. The mechanistic data support that the carcinogenic mode of action (MOA) is likely to involve oxidative stress, and thus, non-linear/threshold mechanisms. However, the lack of a detailed MOA and use of high, toxic exposure concentrations in the bioassay (≥1.25 mg/m(3)) preclude derivation of a reference concentration (RfC) protective of cancer. Several analyses resulted in an IUR of 0.003 per μg/m(3) for cobalt metal, which is ∼3-fold less potent than the provisional IUR. Future research should focus on establishing the exposure-response for key precursor events to improve cobalt metal risk assessment.

  18. Cobalt Reduction Guidelines, Revision 1. Final report

    SciTech Connect

    Not Available

    1993-12-01

    This report, which updates and supersedes an earlier report (EPRI NP-6737) on the same subject, describes methods for establishing a program to identify nuclear power plant valves with high-cobalt hardfacing that are potential significant contributors to the cobalt inventory that is irradiated in the reactor core. The resulting radioactive cobalt isotope, cobalt-60, is a major contributor to plant radiation levels and therefore occupational doses received by plant operational and maintenance personnel. A methodology to determine whether hardfacing is actually required on specific valves is also described as is the physical, mechanical and wear properties of high-cobalt and potential replacement cobalt-free hardfacing and trim alloys. Discussions are presented of the general and specific design requirements for valve hardfacing in nuclear service. Current world-wide nuclear utility experience with cobalt-free hardfacing alloys is described. The regulatory and industry code issues related to replacing and/or changing valve hardfacing materials are discussed. The actions and responsibilities of utility management in implementing an effective cobalt-reduction program are also delineated.

  19. Serum cobalt in children with essential hypertension.

    PubMed

    Nicoloff, G; Angelova, M; Christova, I; Nikolov, A; Alexiev, A

    2006-01-01

    The effect of cobalt on the cardiovascular system is one of many aspects of cobalt metabolism in humans. Elastin and collagen are the main proteins of the vascular wall. The aims of this study were: 1) to determine serum cobalt concentrations in children with hypertension; and 2) to study the correlation between serum cobalt and some biological markers of the extracellular matrix of the vascular wall, i.e., anti-elastin and anti-collagen type IV antibodies. Patients showed statistically significant higher levels of systolic and diastolic blood pressure, and significantly lower serum cobalt concentrations, than controls. Children with hypertension showed significantly higher levels of total cholesterol (P = 0.0003) and collagen type IV IgM (P = 0.04). Collagen type IV IgG levels (P = 0.027) were lower than in controls. Serum cobalt in patients showed a correlation with systolic blood pressure (r = -0.44, P = 0.05), elastin IgM (r = 0.60, P = 0.007), and collagen type IV IgG (r = -0.46, P = 0.04). Our data suggest the existence of a correlation between changes in levels of serum cobalt, total cholesterol, anti-collagen type IV antibodies, and essential hypertension in children. This is the first study of serum cobalt in children with essential hypertension.

  20. Preparation, stability, and photoreactivity of thiolato ruthenium polypyridyl complexes: Can cysteine derivatives protect ruthenium-based anticancer complexes?

    PubMed

    van Rixel, Vincent H S; Busemann, Anja; Göttle, Adrien J; Bonnet, Sylvestre

    2015-09-01

    Ruthenium polypyridyl complexes may act as light-activatable anticancer prodrugs provided that they are protected by well-coordinated ligands that i) prevent coordination of other biomolecules to the metal center in the dark and ii) can be removed by visible light irradiation. In this paper, the use of monodentate thiol ligands RSH as light-cleavable protecting groups for the ruthenium complex [Ru(tpy)(bpy)(OH2)](PF6)2 ([1](PF6)2; tpy=2,2';6',2″-terpyridine, bpy=2,2'-bypyridine), is investigated. The reaction of [1](2+) with RSH=H2Cys (L-cysteine), H2Acys (N-acetyl-L-cysteine), and HAcysMe (N-acetyl-L-cysteine methyl ester), is studied by UV-visible spectroscopy, NMR spectroscopy, and mass spectrometry. Coordination of the monodentate thiol ligands to the ruthenium complex takes place upon heating to 353 K, but full conversion to the protected complex [Ru(tpy)(bpy)(SR)]PF6 is only possible when a large excess of ligand is used. Isolation and characterization of the two new thiolato complexes [Ru(tpy)(bpy)(κS-HCys)]PF6 ([2]PF6) and [Ru(tpy)(bpy)(κS-HAcys)]PF6 ([3]PF6) is reported. [3]PF6 shows a metal-to-ligand charge-transfer absorption band that is red shifted (λmax=492 nm in water) compared to its methionine analogue [Ru(tpy)(bpy)(κS-HAmet)](Cl)2 ([5](Cl)2, λmax=452 nm; HAmet=N-acetyl-methionine). In the dark the thiolate ligand coordinated to ruthenium is oxidized even by traces of oxygen, which first leads to the sulfenato, sulfinato, and disulfide ruthenium complexes, and finally to the formation of the aqua complex [1](2+). [3]PF6 showed slow photosubstitution of the thiolate ligand by water under blue light irradiation, together with faster photooxidation of the thiolate ligand compared to dark conditions. The use of thiol vs. thioether monodentate ligands is discussed for the protection of anticancer ruthenium-based prodrugs.

  1. Cobalt Derivatives as Promising Therapeutic Agents

    PubMed Central

    Heffern, Marie C.; Yamamoto, Natsuho; Holbrook, Robert J.; Eckermann, Amanda L.; Meade, Thomas J.

    2013-01-01

    Inorganic complexes are versatile platforms for the development of potent and selective pharmaceutical agents. Cobalt possesses a diverse array of properties that can be manipulated to yield promising drug candidates. Investigations into the mechanism of cobalt therapeutic agents can provide valuable insight into the physicochemical properties that can be harnessed for drug development. This review presents examples of bioactive cobalt complexes with special attention to their mechanisms of action. Specifically, cobalt complexes that elicit biological effects through protein inhibition, modification of drug activity, and bioreductive activation are discussed. Insights gained from these examples reveal features of cobalt that can be rationally tuned to produce therapeutics with high specificity and improved efficacy for the biomolecule or pathway of interest. PMID:23270779

  2. Hydrogen and oxygen adsorption stoichiometries on silica supported ruthenium nanoparticles

    SciTech Connect

    Berthoud, Romain; Delichere, Pierre; Gajan, David; Lukens, Wayne; Pelzer, Katrin; Basset, Jean-Marie; Candy, Jean-Pierre; Coperet, Christophe

    2008-12-01

    Treatment under H{sub 2} at 300 C of Ru(COD)(COT) dispersed on silica yields 2 nm ruthenium nanoparticles, [Ru{sub p}/SiO{sub 2}], according to EXAFS, HRTEM and XPS. H{sub 2} adsorption measurements on [Ru{sub p}/SiO{sub 2}] in the absence of O{sub 2} show that Ru particles adsorb up to ca. 2 H per surface ruthenium atoms (2H/Ru{sub s}) on various samples; this technique can therefore be used to measure the dispersion of Ru particles. In contrast, O{sub 2} adsorption on [Ru{sub p}/SiO{sub 2}] leads to a partial oxidation of the bulk at 25 C, to RuO{sub 2} at 200 C and to sintering upon further reduction under H{sub 2}, showing that O{sub 2} adsorption cannot be used to measure the dispersion of Ru particles.

  3. Complex of transferrin with ruthenium for medical applications

    DOEpatents

    Richards, Powell; Srivastava, Suresh C.; Meinken, George E.

    1984-05-15

    A novel Ruthenium-transferrin complex, prepared by reacting iron-free human transferrin dissolved in a sodium acetate solution at pH 7 with ruthenium by heating at about 40.degree. C. for about 2 hours, and purifying said complex by means of gel chromotography with pH 7 sodium acetate as eluent. The mono- or di-metal complex produced can be used in nuclear medicine in the diagnosis and/or treatment of tumors and abscesses. Comparative results with Ga-67-citrate, which is the most widely used tumor-localizing agent in nuclear medicine, indicate increased sensitivity of detection and greater tumor uptake with the Ru-transferrin complex.

  4. Complex of transferrin with ruthenium for medical applications

    DOEpatents

    Richards, P.; Srivastava, S.C.; Meinken, G.E.

    1984-05-15

    A novel ruthenium-transferrin complex is disclosed which is prepared by reacting iron-free human transferrin dissolved in a sodium acetate solution at pH 7 with ruthenium by heating at about 40 C for about 2 hours. The complex is purified by means of gel chromotography with pH 7 sodium acetate as eluent. The mono- or di-metal complex produced can be used in nuclear medicine in the diagnosis and/or treatment of tumors and abscesses. Comparative results with Ga-67-citrate, which is the most widely used tumor-localizing agent in nuclear medicine, indicate increased sensitivity of detection and greater tumor uptake with the Ru-transferrin complex. No Drawings

  5. Arsenate adsorption on ruthenium oxides: A spectroscopic and kinetic investigation

    SciTech Connect

    Luxton, Todd P.; Eick, Matthew J.; Scheckel, Kirk G.

    2008-12-08

    Arsenate adsorption on amorphous (RuO{sub 2} {center_dot} 1.1H{sub 2}O) and crystalline (RuO{sub 2}) ruthenium oxides was evaluated using spectroscopic and kinetic methods to elucidate the adsorption mechanism. Extended X-ray absorption fine structure spectroscopy (EXAFS) was used to determine the local coordination environment of adsorbed arsenate. Additionally, pressure-jump (p-jump) relaxation spectroscopy was used to investigate the kinetics of arsenate adsorption/desorption on ruthenium oxides. Chemical relaxations resulting from the induced pressure change were monitored via electrical conductivity detection. EXAFS data were collected for two initial arsenate solution concentrations, 3 and 33 mM at pH 5. The collected spectra indicated a similar coordination environment for arsenate adsorbed to RuO{sub 2} {center_dot} 1.1H{sub 2}O for both arsenate concentrations. In contrast the EXAFS spectra of RuO{sub 2} indicated differences in the local coordination environments for the crystalline material with increasing arsenate concentration. Data analysis indicated that both mono- and bidentate surfaces complexes were present on both RuO{sub 2} {center_dot} 1.1H{sub 2}O and RuO{sub 2}. Relaxation spectra from the pressure-jump experiments of both ruthenium oxides resulted in a double relaxation event. Based on the relaxation spectra, a two step reaction mechanism for arsenate adsorption is proposed resulting in the formation of a bidentate surface complex. Analysis of the kinetic and spectroscopic data suggested that while there were two relaxation events, arsenate adsorbed to ruthenium oxide surfaces through both mono- and bidentate surface complexes.

  6. Characteristics of a promising new thermoelectric material - Ruthenium silicide

    NASA Technical Reports Server (NTRS)

    Ohta, Toshitaka; Vining, Cronin B.; Allevato, Camillo E.

    1991-01-01

    A preliminary study on arc-melted samples has indicated that ruthenium silicide has the potential to obtain figure-of-merit values four times higher than that of conventional silicon-germanium material. In order to realize the high figure-of-merit values, high-quality crystal from the melt is needed. A Bridgman-like method has been employed and has realized much better crystals than arc-melted ones.

  7. The Mystery of the Electronic Spectrum of Ruthenium Monophosphide

    NASA Astrophysics Data System (ADS)

    Adam, Allan G.; Christensen, Ryan M.; Dore, Jacob M.; Konder, Ricarda M.; Tokaryk, Dennis W.

    2016-06-01

    Using PH3 as a reactant gas and ruthenium as the target metal in the UNB laser ablation spectrometer, the ruthenium monophosphide molecule (RuP) has been detected. Dispersed fluorescence experiments have been performed to determine ground state vibrational frequencies and the presence of any low-lying electronic states. Rotationally resolved spectra of two vibrational bands at 577nm and 592nm have been taken; the bands have been identified as 1-0 and 0-0 bands based on isotopic shifts. Ruthenium has seven stable isotopes and rotational transitions have been observed for six of the RuP isotopologues. RuP is isoelectronic to RuN so it is expected that RuP will have a 2Σ+ ground state and low resolution spectra indicated a likely 2Σ+ - 2Σ+ electronic transition. Further investigation has led us to believe we are observing a 2Π - 2Σ+ transition but mysteriously some important rotational branches are missing. It is hoped that new data to be recorded on a second electronic system we have observed at 535nm will help shed light on this mystery.

  8. Electrochemical deposition of conducting ruthenium oxide films from solution

    SciTech Connect

    Anderson, D.P.; Warren, L.F.

    1984-02-01

    In the last decade, ruthenium oxide, RuO /sub x/ (x less than or equal to 2), has been used extensively as the active anode electrocatalyst constituent for Cl/sub 2/ and O/sub 2/ evolution reactions, in chlorate production, and in metal electrowinning from mixed chloride-sulfate solutions. More recently, this material has been incorporated in several light-induced water electrolysis schemes and apparently possesses the ability to inhibit CdS photocorrosion by acting as a hole scavenger. The numerous applications for this catalyst material certainly warrant further studies of its electrochemical properties on a variety of substrates, e.g., semiconductors. The lack of a simple technique for controlled deposition of ruthenium oxide onto conducting substrates prompted us to investigate an electrochemical approach to this problem. We describe here a new way to electrochemically deposit conducting films of hydrated ruthenium oxide from an aqueous solution of the benzeneruthenium (II)aqua complex. The films slowly dissolve in aqueous electrolytes upon potential cycling, yet appear to be catalytic with regards to water oxidation.

  9. Thin film ruthenium microstructures for transition edge sensors

    NASA Astrophysics Data System (ADS)

    Ilin, A. S.; Cohn, I. A.; Vystavkin, A. N.; Kovalenko, A. G.

    2016-12-01

    The superconducting properties of ruthenium (Ru) thin films and microstructures are investigated. The microstructures are used as transition edge sensors (TES), working at He-3 evaporation cryostats' temperatures. Ruthenium is substantially inert, and the critical temperature Tc for bulk Ru samples is known from state of art to be 0.40-0.51 K. We investigated magnetron sputtered Ru thin films with thicknesses 13-300 nm on a Si substrate and electron lithography fabricated TES samples, based on the thin-film Ru microstructures. It has been found, that the Tc for the Ru thin films is 0.55-0.70 K, and the width of the transition region is 1-5 mK, and for the Ru TES Tc = 0.55 and ΔT = 4 mK. Furthermore, it was established that lithography process had no significant influence on the properties of the TES samples, so we were able to get consistent properties for several fabrication sessions. Therefore ruthenium is concluded to be a desirable material for transition edge sensors working at He-3 cryostats' temperatures.

  10. Exposure to cobalt in the production of cobalt and cobalt compounds and its effect on the heart

    PubMed Central

    Linna, A; Oksa, P; Groundstroem, K; Halkosaari, M; Palmroos, P; Huikko, S; Uitti, J

    2004-01-01

    Aims: To investigate whether exposure to cobalt in cobalt plants has any measurable effect on the cardiovascular system. Methods: Occupational, cross sectional study, using a self administered questionnaire, blood pressure measurement, electrocardiography, and laboratory tests in which 203 male workers with at least one year of exposure to cobalt and 94 unexposed controls participated. Echocardiography was performed on a subset of 122 most highly exposed cobalt workers, of which 109 were analysed, and on 60 controls, of which 57 were analysed. Analysis of covariance and a multiple regression analysis were used to evaluate the data. Results: Two of the echocardiography parameters measured were associated with cobalt exposure. In the higher exposure group the left ventricular isovolumic relaxation time (mean 53.3, 49.1, and 49.7 ms in the high exposure, low exposure, and control groups respectively) and the deceleration time of the velocity of the early rapid filling wave (mean 194.3, 180.5, and 171.7 ms for those in the high exposure, low exposure, and control groups respectively) were prolonged, indicating altered left ventricular relaxation and early filling. Conclusion: Cumulative exposure to cobalt was found to be associated with the results of Doppler echocardiography measurements, indicating altered diastole. This finding supports the hypothesis that cobalt accumulation in the myocardium could affect myocardial function. Whether this finding has clinical implications remains to be evaluated. PMID:15477280

  11. Vibrational Spectroscopic Studies of Hydrogen, Carbon-Monoxide and Thiophene Adsorption on Ruthenium-Sulfide and Sulfided Ruthenium Catalysts.

    NASA Astrophysics Data System (ADS)

    Heise, William Herbert

    The "working surface" of ruthenium hydrodesulfurization (HDS) catalysts has been modeled by preadsorption of sulfur, carbon and carbon plus sulfur on Ru(0001). Adsorption and decomposition of thiophene over these surfaces have been investigated using TDS/TPRS, XPS and EELS. Thiophene is proposed to decompose via a three-step mechanism involving: (i) initial thiophene cracking at 120 K yielding surface sulfur and hydrocarbon species, (ii) hydrogen desorption near 230 K providing additional decomposition ensembles and (iii) continued decomposition to form "metallocycle -like" intermediates which retain EELS features similar to thiophene. Preadsorbed carbon or carbon plus sulfur are not as effective for passivation of the surface toward metallocycle formation as preadsorbed sulfur alone. This result is attributed to the fact that carbon deposited from butadiene annealed and decomposed at 700 K forms islands, while sulfur establishes a well-ordered superlattice on the surface. The decrease in metallocycle formation with increasing poison levels appears to explain HDS selectivity and specific activity trends observed in our laboratory from mildly sulfided (10% H_2S/H_2 , 673 K, 2h) ruthenium catalysts retaining submonolayers of sulfur. Incoherent inelastic neutron scattering (IINS) has been used to characterize hydrogen adsorption sites on ruthenium sulfide. Hydrogen resides on sulfur anions to form SH groups, yielding two non-degenerate bending modes at 600 and 710 cm^{-1}. Complementary hydrogen adsorption and H_2/D _2 exchange data suggest that the active sites for hydrogen adsorption may be coordinatively unsaturated S-S anion pairs. Comparison of CO adsorption on sulfided Ru/Al _2O_3 to sulfur precovered Ru(0001) reveals an adsorption site related to edge/corner atoms directly perturbed by sulfur, consistent with previous kinetic studies demonstrating higher specific activity for thiophene HDS over smaller ruthenium crystallites.

  12. Ruthenium-Catalyzed Ammonia Borane Dehydrogenation: Mechanism and Utility.

    PubMed

    Zhang, Xingyue; Kam, Lisa; Trerise, Ryan; Williams, Travis J

    2017-01-17

    One of the greatest challenges in using H2 as a fuel source is finding a safe, efficient, and inexpensive method for its storage. Ammonia borane (AB) is a solid hydrogen storage material that has garnered attention for its high hydrogen weight density (19.6 wt %) and ease of handling and transport. Hydrogen release from ammonia borane is mediated by either hydrolysis, thus giving borate products that are difficult to rereduce, or direct dehydrogenation. Catalytic AB dehydrogenation has thus been a popular topic in recent years, motivated both by applications in hydrogen storage and main group synthetic chemistry. This Account is a complete description of work from our laboratory in ruthenium-catalyzed ammonia borane dehydrogenation over the last 6 years, beginning with the Shvo catalyst and resulting ultimately in the development of optimized, leading catalysts for efficient hydrogen release. We have studied AB dehydrogenation with Shvo's catalyst extensively and generated a detailed understanding of the role that borazine, a dehydrogenation product, plays in the reaction: it is a poison for both Shvo's catalyst and PEM fuel cells. Through independent syntheses of Shvo derivatives, we found a protective mechanism wherein catalyst deactivation by borazine is prevented by coordination of a ligand that might otherwise be a catalytic poison. These studies showed how a bidentate N-N ligand can transform the Shvo into a more reactive species for AB dehydrogenation that minimizes accumulation of borazine. Simultaneously, we designed novel ruthenium catalysts that contain a Lewis acidic boron to replace the Shvo -OH proton, thus offering more flexibility to optimize hydrogen release and take on more general problems in hydride abstraction. Our scorpionate-ligated ruthenium species (12) is a best-of-class catalyst for homogeneous dehydrogenation of ammonia borane in terms of its extent of hydrogen release (4.6 wt %), air tolerance, and reusability. Moreover, a synthetically

  13. Advances in cobalt complexes as anticancer agents.

    PubMed

    Munteanu, Catherine R; Suntharalingam, Kogularamanan

    2015-08-21

    The evolution of resistance to traditional platinum-based anticancer drugs has compelled researchers to investigate the cytostatic properties of alternative transition metal-based compounds. The anticancer potential of cobalt complexes has been extensively studied over the last three decades, and much time has been devoted to understanding their mechanisms of action. This perspective catalogues the development of antiproliferative cobalt complexes, and provides an in depth analysis of their mode of action. Early studies on simple cobalt coordination complexes, Schiff base complexes, and cobalt-carbonyl clusters will be documented. The physiologically relevant redox properties of cobalt will be highlighted and the role this plays in the preparation of hypoxia selective prodrugs and imaging agents will be discussed. The use of cobalt-containing cobalamin as a cancer specific delivery agent for cytotoxins will also be described. The work summarised in this perspective shows that the biochemical and biophysical properties of cobalt-containing compounds can be fine-tuned to produce new generations of anticancer agents with clinically relevant efficacies.

  14. Thermochemistry of Ruthenium Oxyhydroxide Species and Their Impact on Volatile Speciations in Severe Nuclear Accident Conditions.

    PubMed

    Miradji, Faoulat; Virot, François; Souvi, Sidi; Cantrel, Laurent; Louis, Florent; Vallet, Valérie

    2016-02-04

    Literature thermodynamic data of ruthenium oxyhydroxides reveal large uncertainties in some of the standard enthalpies of formation, motivating the use of high-level relativistic correlated quantum chemical methods to reduce the level of discrepancies. Reaction energies leading to the formation of all possible oxyhydroxide species RuOx(OH)y(H2O)z have been calculated for a series of reactions combining DFT (TPSSh-5%HF) geometries and partition functions, CCSD(T) energies extrapolated to the complete basis set limits. The highly accurate ab initio thermodynamic data were used as input data of thermodynamic equilibrium computations to derive the speciation of gaseous ruthenium species in the temperature, pressure and concentration conditions of severe nuclear accidents occurring in pressurized water reactors. At temperatures lower than 1000 K, gaseous ruthenium tetraoxide is the dominating species, between 1000 and 2000 K ruthenium trioxide becomes preponderant, whereas at higher temperatures gaseous ruthenium oxide, dioxide and even Ru in gaseous phase are formed. Although earlier studies predicted the formation of oxyhydroxides in significant quantities, the use of highly accurate ab initio thermodynamic data for ruthenium gaseous species leads to a more reliable inventory of gaseous ruthenium species in which gaseous oxyhydroxide ruthenium molecules are formed only in negligible amounts.

  15. Ruthenium catalyzed synthesis of 2,3-unsaturated C-glycosides from glycals.

    PubMed

    Srinivas, Batthula; Reddy, Thurpu Raghavender; Kashyap, Sudhir

    2015-04-10

    A highly efficient and convenient C-glycosylation method was developed using ruthenium(III) chloride for the synthesis of 2,3-unsaturated C-glycosides. Various nucleophiles such as allyl trimethylsilane, triethylsilane, trimethylsilyl cyanide, trimethylsilyl azide and heterocycles such as thiophene and furan reacted smoothly with glycals in the presence of catalytic amount of ruthenium trichloride under mild reaction conditions.

  16. Magnetic Silica-Supported Ruthenium Nanoparticles: An Efficient Catalyst for Transfer Hydrogenation of Carbonyl Compounds

    EPA Science Inventory

    One-pot synthesis of ruthenium nanoparticles on magnetic silica is described which involve the in situ generation of magnetic silica (Fe3O4@ SiO2) and ruthenium nano particles immobilization; the hydration of nitriles and transfer hydrogenation of carbonyl compounds occurs in hi...

  17. Ruthenium on chitosan: A recyclable heterogeneous catalyst for aqueous hydration of nitriles to amides

    EPA Science Inventory

    Ruthenium has been immobilized over chitosan by simply stirring an aqueous suspension of chitosan in water with ruthenium chloride and has been utilized for the oxidation of nitriles to amides; the hydration of nitriles occurs in high yield and excellent selectivity, which procee...

  18. Cobalt - poly(amido amine) superparamagnetic nanocomposites.

    PubMed

    Atwater, James E; Akse, James R; Holtsnider, John T

    2008-06-30

    Metallic cobalt-dendrimer nanocomposites were prepared using generation 5 Poly(amido amine) dendrimers with primary amino termini. Cobalt loading of ~38 atoms per dendrimer was determined by atomic absorption spectrophotometry. Magnetic properties of the cobalt-dendrimer nanocomposites were investigated across the temperature range from 2-300 K by SQUID magnetometry. Magnetization as a function of temperature and applied field strength was studied in zero field cooled samples. Magnetization-demagnetization curves (hysteresis loops) were also acquired at temperatures between 10 - 300 K. These results clearly indicate superparamagnetism for the nanocomposites with a characteristic blocking temperature of ~50 K.

  19. Cobalt - poly(amido amine) superparamagnetic nanocomposites

    PubMed Central

    Atwater, James E.; Akse, James R.; Holtsnider, John T.

    2010-01-01

    Metallic cobalt-dendrimer nanocomposites were prepared using generation 5 Poly(amido amine) dendrimers with primary amino termini. Cobalt loading of ~38 atoms per dendrimer was determined by atomic absorption spectrophotometry. Magnetic properties of the cobalt-dendrimer nanocomposites were investigated across the temperature range from 2–300 K by SQUID magnetometry. Magnetization as a function of temperature and applied field strength was studied in zero field cooled samples. Magnetization-demagnetization curves (hysteresis loops) were also acquired at temperatures between 10 – 300 K. These results clearly indicate superparamagnetism for the nanocomposites with a characteristic blocking temperature of ~50 K. PMID:20352068

  20. Cobalt-related defects in silicon

    NASA Astrophysics Data System (ADS)

    Gibbons, T. M.; Backlund, D. J.; Estreicher, S. K.

    2017-01-01

    Transition metals from the 3d series are unavoidable and unwanted contaminants in Si-based devices. Cobalt is one of the most poorly understood impurities with incomplete experimental information and few theoretical studies. In this contribution, the properties of interstitial cobalt (Coi) in Si and its interactions with the vacancy, self-interstitial, hydrogen, and substitutional boron are calculated using the first-principles tools. The stable configurations, gap levels, and binding energies are predicted. The activation energy for diffusing Coi is calculated with the nudged-elastic-band method and found to be slightly lower than that of interstitial copper and nickel. The binding energies and gap levels of the substitutional cobalt (Cos) and of the {Cos,H} and {Cos,H,H} complexes are close to the experimental data. The properties of the cobalt-boron pair are calculated.

  1. Bioextraction of cobalt from complex metal sulfides

    SciTech Connect

    Thompson, D.L.; Noah, K.S.; Wichlacz, P.L.; Torma, A.E.

    1993-05-01

    The present study has investigated the bioleachability of naturally occurring cobaltite and synthetic cobalt sulfides using 29 pedigree and ``wild type`` strains of Thiobacillus ferrooxidans. On the basis of a screening test, five strains of bacteria were selected for assessing the effects of leach parameters (pH, ferrous and ferric sulfates, ammonium sulfate, bipotassium hydrogen phosphate, and substrate concentrations) on cobalt extraction from Blackbird Mine ore and concentrate. The mechanisms of cobalt extraction were explained in terms of direct and indirect modes of bacterial activity, and the chemistry involved in these processes was identified. Using various size fractions of a high-grade cobaltite, the kinetic parameters of cobalt extraction were derived for the effect of specific surface area to be V{sub m} = 376 mg dm{sup {minus}3} h{sup {minus}1} and K 1.27 m{sup 2} g{sup {minus}1}.

  2. Bioextraction of cobalt from complex metal sulfides

    SciTech Connect

    Thompson, D.L.; Noah, K.S.; Wichlacz, P.L.; Torma, A.E.

    1993-01-01

    The present study has investigated the bioleachability of naturally occurring cobaltite and synthetic cobalt sulfides using 29 pedigree and wild type'' strains of Thiobacillus ferrooxidans. On the basis of a screening test, five strains of bacteria were selected for assessing the effects of leach parameters (pH, ferrous and ferric sulfates, ammonium sulfate, bipotassium hydrogen phosphate, and substrate concentrations) on cobalt extraction from Blackbird Mine ore and concentrate. The mechanisms of cobalt extraction were explained in terms of direct and indirect modes of bacterial activity, and the chemistry involved in these processes was identified. Using various size fractions of a high-grade cobaltite, the kinetic parameters of cobalt extraction were derived for the effect of specific surface area to be V[sub m] = 376 mg dm[sup [minus]3] h[sup [minus]1] and K 1.27 m[sup 2] g[sup [minus]1].

  3. 40 CFR 415.650 - Applicability; description of the cobalt salts production subcategory.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... cobalt salts production subcategory. 415.650 Section 415.650 Protection of Environment ENVIRONMENTAL... SOURCE CATEGORY Cobalt Salts Production Subcategory § 415.650 Applicability; description of the cobalt... cobalt salts....

  4. 40 CFR 415.650 - Applicability; description of the cobalt salts production subcategory.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... cobalt salts production subcategory. 415.650 Section 415.650 Protection of Environment ENVIRONMENTAL... SOURCE CATEGORY Cobalt Salts Production Subcategory § 415.650 Applicability; description of the cobalt... cobalt salts....

  5. 40 CFR 415.650 - Applicability; description of the cobalt salts production subcategory.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... cobalt salts production subcategory. 415.650 Section 415.650 Protection of Environment ENVIRONMENTAL... SOURCE CATEGORY Cobalt Salts Production Subcategory § 415.650 Applicability; description of the cobalt... cobalt salts....

  6. 40 CFR 415.650 - Applicability; description of the cobalt salts production subcategory.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... cobalt salts production subcategory. 415.650 Section 415.650 Protection of Environment ENVIRONMENTAL... SOURCE CATEGORY Cobalt Salts Production Subcategory § 415.650 Applicability; description of the cobalt... cobalt salts....

  7. 40 CFR 415.650 - Applicability; description of the cobalt salts production subcategory.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... cobalt salts production subcategory. 415.650 Section 415.650 Protection of Environment ENVIRONMENTAL... SOURCE CATEGORY Cobalt Salts Production Subcategory § 415.650 Applicability; description of the cobalt... cobalt salts....

  8. Role of cobalt in nickel base superalloys

    NASA Technical Reports Server (NTRS)

    Jarrett, R.; Barefoot, J.; Tien, J.; Sanchez, J.

    1982-01-01

    The effect of cobalt or substituting for cobalt on the mechanical properties of nickel-based superalloys is discussed. Waspaloy, UDIMET 700, and NIMONIC 115, which are representative of Ni-Cr-Co-Al-Ti-Mo superalloys having different gamma prime contents which are strengthened by a heavily alloyed matrix, coherent gamma prime precipitates, and carbides at the grain boundaries. Microstructure and in situ and extracted phase STEM micro-analysis were used to evaluate the three alloys.

  9. Nickel acts as an adjuvant during cobalt sensitization.

    PubMed

    Bonefeld, Charlotte Menné; Nielsen, Morten Milek; Vennegaard, Marie T; Johansen, Jeanne Duus; Geisler, Carsten; Thyssen, Jacob P

    2015-03-01

    Metal allergy is the most frequent form of contact allergy with nickel and cobalt being the main culprits. Typically, exposure comes from metal-alloys where nickel and cobalt co-exist. Importantly, very little is known about how co-exposure to nickel and cobalt affects the immune system. We investigated these effects by using a recently developed mouse model. Mice were epicutaneously sensitized with i) nickel alone, ii) nickel in the presence of cobalt, iii) cobalt alone, or iv) cobalt in the presence of nickel, and then followed by challenge with either nickel or cobalt alone. We found that sensitization with nickel alone induced more local inflammation than cobalt alone as measured by increased ear-swelling. Furthermore, the presence of nickel during sensitization to cobalt led to a stronger challenge response to cobalt as seen by increased ear-swelling and increased B and T cell responses in the draining lymph nodes compared to mice sensitized with cobalt alone. In contrast, the presence of cobalt during nickel sensitization only induced an increased CD8(+) T cell proliferation during challenge to nickel. Thus, the presence of nickel during cobalt sensitization potentiated the challenge response against cobalt more than the presence of cobalt during sensitization to nickel affected the challenge response against nickel. Taken together, our study demonstrates that sensitization with a mixture of nickel and cobalt leads to an increased immune response to both nickel and cobalt, especially to cobalt, and furthermore that the adjuvant effect appears to correlate with the inflammatory properties of the allergen.

  10. Intolerability of cobalt salt as erythropoietic agent.

    PubMed

    Ebert, Bastian; Jelkmann, Wolfgang

    2014-03-01

    Unfair athletes seek ways to stimulate erythropoiesis, because the mass of haemoglobin is a critical factor in aerobic sports. Here, the potential misuse of cobalt deserves special attention. Cobalt ions (Co(2+) ) stabilize the hypoxia-inducible transcription factors (HIFs) that increase the expression of the erythropoietin (Epo) gene. Co(2+) is orally active, easy to obtain, and inexpensive. However, its intake can bear risks to health. To elaborate this issue, a review of the pertinent literature was retrieved by a search with the keywords 'anaemia', 'cobalt', 'cobalt chloride', 'erythropoiesis', 'erythropoietin', 'Epo', 'side-effects' and 'treatment', amongst others. In earlier years, cobalt chloride was administered at daily doses of 25 to 300 mg for use as an anti-anaemic agent. Co(2+) therapy proved effective in stimulating erythropoiesis in both non-renal and renal anaemia, yet there were also serious medical adverse effects. The intake of inorganic cobalt can cause severe organ damage, concerning primarily the gastrointestinal tract, the thyroid, the heart and the sensory systems. These insights should keep athletes off taking Co(2+) to stimulate erythropoiesis.

  11. COBALT COMPOUNDS AS ANTIDOTES FOR HYDROCYANIC ACID.

    PubMed

    EVANS, C L

    1964-12-01

    The antidotal potency of a cobalt salt (acetate), of dicobalt edetate, of hydroxocobalamin and of cobinamide against hydrocyanic acid was examined mainly on mice and rabbits. All the compounds were active antidotes for up to twice the LD50; under some conditions for larger doses. The most successful was cobalt acetate for rabbits (5xLD50), which was effective at a molar cyanide/cobalt (CN/Co) ratio of 5, but had as a side-effect intense purgation. Hydroxocobalamin was irregular in action, but on the whole was most effective for mice (4.5xLD50 at a molar ratio of 1), and had no apparent side effects. Dicobalt edetate, at molar ratios of up to 2, was more effective for rabbits (3xLD50) than for mice (2xLD50), but had fewer side effects than cobalt acetate. The effect of thiosulphate was to augment the efficacy of dicobalt edetate and, in mice, that of hydroxocobalamin; but, apparently, in rabbits, to reduce that of hydroxocobalamin. Cobinamide, at a molar ratio of 1, was slightly more effective than hydroxocobalamin on rabbits and also less irregular in its action. Cobalt acetate by mouth was effective against orally administered hydrocyanic acid. The oxygen uptake of the body, reduced by cyanide, is rapidly reinstated when one of the cobalt antidotes has been successfully administered.

  12. Gas-phase chemistry of ruthenium and rhodium carbonyl complexes.

    PubMed

    Cao, Shiwei; Wang, Yang; Qin, Zhi; Fan, Fangli; Haba, Hiromitsu; Komori, Yukiko; Wu, Xiaolei; Tan, Cunmin; Zhang, Xin

    2016-01-07

    Short-lived ruthenium and rhodium isotopes were produced from a (252)Cf spontaneous fission (SF) source. Their volatile carbonyl complexes were formed in gas-phase reactions in situ with the carbon-monoxide containing gas. A gas-jet system was employed to transport the volatile carbonyls from the recoil chamber to the chemical separation apparatus. The gas-phase chemical behaviors of these carbonyl complexes were studied using an online low temperature isothermal chromatography (IC) technique. Long IC columns made up of FEP Teflon were used to obtain the chemical information of the high-volatile Ru and Rh carbonyls. By excluding the influence of precursor effects, short-lived isotopes of (109-110)Ru and (111-112)Rh were used to represent the chemical behaviours of Ru and Rh carbonyls. Relative chemical yields of about 75% and 20% were measured for Ru(CO)5 and Rh(CO)4, respectively, relative to the yields of KCl aerosols transported in Ar gas. The adsorption enthalpies of ruthenium and rhodium carbonyl complexes on a Teflon surface were determined to be around ΔHads = -33(+1)(-2) kJ mol(-1) and -36(+2)(-1) kJ mol(-1), respectively, by fitting the breakthrough curves of the corresponding carbonyl complexes with a Monte Carlo simulation program. Different from Mo and Tc carbonyls, a small amount of oxygen gas was found to be not effective for the chemical yields of ruthenium and rhodium carbonyl complexes. The general chemical behaviors of short-lived carbonyl complexes of group VI-IX elements were discussed, which can be used in the future study on the gas-phase chemistry of superheavy elements - Bh, Hs, and Mt carbonyls.

  13. Graphene-Ruthenium(II) complex composites for sensitive ECL immunosensors.

    PubMed

    Xiao, Fang-Nan; Wang, Min; Wang, Feng-Bin; Xia, Xing-Hua

    2014-02-26

    Non-covalent modification method has been proven as an effective strategy for enhancing the chemical properties of graphene while the structure and electronic properties of graphene can be retained. This work describes a novel strategy to fabricate a solid-state electrochemiluminescent (ECL) immunosensor based on ruthenium(II) complex/3,4,9,10-perylenetetracarboxylic acid (PTCA)/graphene nanocomposites (Ru-PTCA/G) for sensitive detection of α-fetoprotein (AFP). It is found that immobilization of PTCA and reduction of GO can be simultaneously achieved in one-pot synthesis method under alkaline condition and moderate temperature, forming PTCA/G nanocomposites. Further covalent attachment of ruthenium(II) complex to the PTCA assembled on graphene sheets produces the functional Ru-PTCA/G nanocomposites which show good electrochemical activity and ca. 21 times higher luminescence quantum efficiency than the adsorbed derivative ruthenium(II) complex. The Ru-PTCA/G nanocomposites based solid-state ECL sensor exhibits high stability toward the determination of tripropylamine (TPA) coreactant. In addition, a new ECL immunosensor based on steric hindrance effect is fabricated by cross-linking α-fetoprotein antibody (anti-AFP) with chitosan covered on Ru-PTCA/G composites modified electrode for detection of cancer biomarker AFP. This ECL immunosensor shows an extremely sensitive response to AFP in a linear range of 5 pg·mL(-1) -10 ng·mL(-1) with a detection limit of 0.2 pg·mL(-1) . The present approach is effective for various molecules immobilization and may become a promising technique for biomolecular detection.

  14. Antiparasitic activities of novel ruthenium/lapachol complexes.

    PubMed

    Barbosa, Marília I F; Corrêa, Rodrigo S; de Oliveira, Katia Mara; Rodrigues, Claudia; Ellena, Javier; Nascimento, Otaciro R; Rocha, Vinícius P C; Nonato, Fabiana R; Macedo, Taís S; Barbosa-Filho, José Maria; Soares, Milena B P; Batista, Alzir A

    2014-07-01

    The present study describes the synthesis, characterization, antileishmanial and antiplasmodial activities of novel diimine/(2,2'-bipyridine (bipy), 1,10-phenanthroline (phen), 4,4'-methylbipyridine (Me-bipy) and 4,4'-methoxybipyridine (MeO-bipy)/phosphine/ruthenium(II) complexes containing lapachol (Lap, 2-hydroxy-3-(3-33 methyl-2-buthenyl)-1,4-naphthoquinone) as bidentate ligand. The [Ru(Lap)(PPh3)2(bipy)]PF6 (1), [Ru(Lap)(PPh3)2(Me-bipy)]PF6 (2), [Ru(Lap)(PPh3)2(MeO-bipy)]PF6(3) and[Ru(Lap)(PPh3)2(phen)]PF6 (4) complexes, PPh3=triphenylphospine, were synthesized from the reactions of cis-[RuCl2(PPh3)2(X-bipy)] or cis-[RuCl2(PPh3)2(phen)], with lapachol. The [RuCl2(Lap)(dppb)] (5) [dppb=1,4-bis(diphenylphosphine)butane] was synthesized from the mer-[RuCl3(dppb)(H2O)] complex. The complexes were characterized by elemental analysis, molar conductivity, infrared and UV-vis spectroscopy, (31)P{(1)H} and (1)H NMR, and cyclic voltammetry. The Ru(III) complex, [RuCl2(Lap)(dppb)], was also characterized by the EPR technique. The structure of the complexes [Ru(Lap)(PPh3)2(bipy)]PF6 and [RuCl2(Lap)(dppb)] was elucidated by X-ray diffraction. The evaluation of the antiparasitic activities of the complexes against Leishmania amazonensis and Plasmodium falciparum demonstrated that lapachol-ruthenium complexes are more potent than the free lapachol. The [RuCl2(Lap)(dppb)] complex is the most potent and selective antiparasitic compound among the five new ruthenium complexes studied in this work, exhibiting an activity comparable to the reference drugs.

  15. Threading of Binuclear Ruthenium Complex Through DNA Bases

    NASA Astrophysics Data System (ADS)

    Paramanathan, Thayaparan; Westerlund, Fredrik; McCauley, Micah; Lincoln, Per; Rouzina, Ioulia; Williams, Mark

    2009-03-01

    Due to steric constraints the dumb-bell shaped binuclear ruthenium complex can only intercalate DNA by threading, which requires local melting of the DNA to occur. By mechanically manipulating a single DNA molecule held with optical tweezers, we lower the barrier to threading compared to bulk experiments. Stretching single DNA molecules with different drug concentrations and holding a constant force allows the binding to reach equilibrium. We can obtain the equilibrium fractional ligand binding and length of DNA at saturation. Fitting these results yields quantitative measurements of the binding thermodynamics and kinetics. In addition, we obtain the minimum binding site size, which may be determined by either electrostatic repulsion or steric constraints.

  16. Chiral-auxiliary-mediated asymmetric synthesis of ruthenium polypyridyl complexes.

    PubMed

    Gong, Lei; Wenzel, Marianne; Meggers, Eric

    2013-11-19

    An octahedral metal complex with 6 different monodentate ligands can form 15 diastereomers as pairs of enantiomers. As a result, the elaborate stereochemistry of octahedral coordination geometries provides tremendous opportunities in the fields of catalysis, the materials sciences, and the life sciences. The demand for enantiomerically pure coordination complexes for tasks related to the selective molecular recognition of biomacromolecules led us to develop synthetic methods to control the absolute stereochemistry at octahedral metal centers. A few years ago our laboratory therefore embarked on a project exploring new and general synthetic strategies for the asymmetric synthesis of inert octahedral transition metal complexes. We initially used the example of thermally inert ruthenium polypyridyl complexes and developed a family of chiral bidentate ligands, including salicyloxazolines, (mercaptophenyl)oxazolines, sulfinylphenols, N-acetylsulfinamides, a phosphinohydroxybinaphthyl, and even the amino acid proline to serve as chiral auxiliaries for asymmetric coordination chemistry. All these chiral auxiliaries strongly coordinate to ruthenium(II) in a bidentate, deprotonated fashion, allowing them to control the absolute metal-centered configuration in the course of subsequent ligand exchange reactions. Finally, we can remove them from the metal without any loss of chiral information and without leaving a chemical trace. A key feature of these chiral auxiliary ligands is their switchable binding strength. A chelate effect ensures that the chiral ligands coordinate very tightly to the metal center, placing their carbon-based, sulfur-based, or axial chirality in a well-defined position close to the metal center to efficiently establish the absolute metal-centered configuration. At the same time a coordinating phenolate, carboximidate, carboxylate, or thiophenolate moiety makes the coordination reversible by weakening the binding strength through protonation or

  17. Ruthenium Behavior at Phase Separation of Borosilicate Glass-12259

    SciTech Connect

    Enokida, Youichi; Sawada, Kayo

    2012-07-01

    The Rokkasho reprocessing plant (RRP) located in Aomori, Japan, vitrifies high level waste (HLW) into a borosilicate glass. The HLW is generated from the reprocessing of spent fuel and contains ruthenium (Ru) and other platinum group metals (PGMs). Based on the recent consequences after a huge earthquake that occurred in Japan, a hypothetical blackout was postulated for the RRP to address additional safety analysis requirements. During a prolonged blackout, the borosilicate glass could phase separate due to cooling of the glass in the melter. The Ru present in the glass matrix could migrate into separate phases and impact the durability of the borosilicate glass. The durability of the glass is important for quality assurance and performance assessment of the vitrified HLW. A fundamental study was performed at an independent university to understand the impact of a prolonged blackout. Simulated HLW glasses were prepared for the RRP, and the Ru behavior in phase separated glasses was studied. The simulated HLW glasses contained nonradioactive elements and PGMs. The glass compositions were then altered to enhance the formation of the phase-separated glasses when subjected to thermal treatment at 700 deg. C for 24 hours. The synthesized simulated glasses contained 1.1 % Ru by weight as ruthenium dioxide (RuO{sub 2}). A portion of the RuO{sub 2} formed needle-shaped crystals in the glass specimens. After the thermal treatment, the glass specimen had separated into two phases. One of the two phases was a B{sub 2}O{sub 3} rich phase, and the other phase was a SiO{sub 2} rich phase. The majority of the chemical species in the B{sub 2}O{sub 3} rich phase was leached away with the Material Characterization Center-3 (MCC-3) protocol standardized by the Pacific Northwest National Laboratory using an aqueous low-concentrated nitric acid solution, but the leaching of the Ru fraction was very limited; less than 1% of the original Ru content. The Ru leaching was much less than

  18. Progress in doping of ruthenium silicide (Ru2Si3)

    NASA Technical Reports Server (NTRS)

    Vining, C. B.; Allevato, C. E.

    1992-01-01

    Ruthenium silicide is currently under development as a promising thermoelectric material suitable for space power applications. Key to realizing the potentially high figure of merit values of this material is the development of appropriate doping techniques. In this study, manganese and iridium have been identified as useful p- and n-type dopants, respectively. Resistivity values have been reduced by more than 3 orders of magnitude. Anomalous Hall effect results, however, complicate interpretation of some of the results and further effort is required to achieve optimum doping levels.

  19. Microscopic Understanding of Fischer-Tropsch Synthesis on Ruthenium

    SciTech Connect

    Chavez, Donna L.

    2014-10-01

    Total energy calculations and scanning tunneling microscope (STM) image simulations were conducted in an effort to interpret new experimental images of CO and H adsorbed on the closepacked surface of ruthenium metal. The images are remarkable in suggesting that the adsorbed species are intermixed, plausibly accounting for the superior catalytic activity of this metal in forming hydrocarbons. Insight was gained over the short duration of the project, but a more accurate method of simulating images will be required before contact between theory and experiment points to a final result.

  20. The solubility of hydrogen in rhodium, ruthenium, iridium and nickel.

    NASA Technical Reports Server (NTRS)

    Mclellan, R. B.; Oates, W. A.

    1973-01-01

    The temperature variation of the solubility of hydrogen in rhodium, ruthenium, iridium, and nickel in equilibrium with H2 gas at 1 atm pressure has been measured by a technique involving saturating the solvent metal with hydrogen, quenching, and analyzing in resultant solid solutions. The solubilities determined are small (atom fraction of H is in the range from 0.0005 to 0.00001, and the results are consistent with the simple quasi-regular model for dilute interstitial solid solutions. The relative partial enthalpy and excess entropy of the dissolved hydrogen atoms have been calculated from the solubility data and compared with well-known correlations between these quantities.

  1. Ruthenium-catalyzed selective monoamination of vicinal diols.

    PubMed

    Bähn, Sebastian; Tillack, Annegret; Imm, Sebastian; Mevius, Kathleen; Michalik, Dirk; Hollmann, Dirk; Neubert, Lorenz; Beller, Matthias

    2009-01-01

    The monoamination of vicinal diols in the presence of in situ generated ruthenium catalysts has been investigated. Among the various phosphines tested in combination with [Ru(3)(CO)(12)], N-phenyl-2-(dicyclohexyl-phosphanyl)pyrrole showed the best performance. After optimization of the reaction conditions this system was applied to different secondary amines and anilines as well as a number of vicinal diols. With the exception of ethylene glycol, monoamination of the vicinal diols occurred selectively and the corresponding amino alcohols were obtained in good yields, producing water as the only side product.

  2. Light-Activated Protein Inhibition through Photoinduced Electron Transfer of a Ruthenium(II)–Cobalt(III) Bimetallic Complex

    PubMed Central

    Holbrook, Robert J.; Weinberg, David J.; Peterson, Mark D.; Weiss, Emily A.; Meade, Thomas J.

    2015-01-01

    We describe a mechanism of light activation that initiates protein inhibitory action of a biologically inert Co(III) Schiff base (Co(III)-sb) complex. Photoinduced electron transfer (PET) occurs from a Ru(II) bipyridal complex to a covalently attached Co(III) complex and is gated by conformational changes that occur in tens of nanoseconds. Reduction of the Co(III)-sb by PET initiates displacement of the inert axial imidazole ligands, promoting coordination to active site histidines of α-thrombin. Upon exposure to 455 nm light, the rate of ligand exchange with 4-methylimidazole, a histidine mimic, increases by approximately 5-fold, as observed by NMR spectroscopy. Similarly, the rate of α-thrombin inhibition increases over 5-fold upon irradiation. These results convey a strategy for light activation of inorganic therapeutic agents through PET utilizing redox-active metal centers. PMID:25671465

  3. Light-activated protein inhibition through photoinduced electron transfer of a ruthenium(II)–cobalt(III) bimetallic complex

    DOE PAGES

    Holbrook, Robert J.; Weinberg, David J.; Peterson, Mark D.; ...

    2015-02-11

    In this paper, we describe a mechanism of light activation that initiates protein inhibitory action of a biologically inert Co(III) Schiff base (Co(III)-sb) complex. Photoinduced electron transfer (PET) occurs from a Ru(II) bipyridal complex to a covalently attached Co(III) complex and is gated by conformational changes that occur in tens of nanoseconds. Reduction of the Co(III)-sb by PET initiates displacement of the inert axial imidazole ligands, promoting coordination to active site histidines of α-thrombin. Upon exposure to 455 nm light, the rate of ligand exchange with 4-methylimidazole, a histidine mimic, increases by approximately 5-fold, as observed by NMR spectroscopy. Similarly,more » the rate of α-thrombin inhibition increases over 5-fold upon irradiation. Finally, these results convey a strategy for light activation of inorganic therapeutic agents through PET utilizing redox-active metal centers.« less

  4. Light-activated protein inhibition through photoinduced electron transfer of a ruthenium(II)–cobalt(III) bimetallic complex

    SciTech Connect

    Holbrook, Robert J.; Weinberg, David J.; Peterson, Mark D.; Weiss, Emily A.; Meade, Thomas J.

    2015-02-11

    In this paper, we describe a mechanism of light activation that initiates protein inhibitory action of a biologically inert Co(III) Schiff base (Co(III)-sb) complex. Photoinduced electron transfer (PET) occurs from a Ru(II) bipyridal complex to a covalently attached Co(III) complex and is gated by conformational changes that occur in tens of nanoseconds. Reduction of the Co(III)-sb by PET initiates displacement of the inert axial imidazole ligands, promoting coordination to active site histidines of α-thrombin. Upon exposure to 455 nm light, the rate of ligand exchange with 4-methylimidazole, a histidine mimic, increases by approximately 5-fold, as observed by NMR spectroscopy. Similarly, the rate of α-thrombin inhibition increases over 5-fold upon irradiation. Finally, these results convey a strategy for light activation of inorganic therapeutic agents through PET utilizing redox-active metal centers.

  5. Metalorganic Chemical Vapor Deposition of Ruthenium-Doped Diamond like Carbon Films

    NASA Technical Reports Server (NTRS)

    Sunkara, M. K.; Ueno, M.; Lian, G.; Dickey, E. C.

    2001-01-01

    We investigated metalorganic precursor deposition using a Microwave Electron Cyclotron Resonance (ECR) plasma for depositing metal-doped diamondlike carbon films. Specifically, the deposition of ruthenium doped diamondlike carbon films was investigated using the decomposition of a novel ruthenium precursor, Bis(ethylcyclopentadienyl)-ruthenium (Ru(C5H4C2H5)2). The ruthenium precursor was introduced close to the substrate stage. The substrate was independently biased using an applied RF power. Films were characterized using Fourier Transform Infrared Spectroscopy (FTIR), Transmission Electron Microscopy (TEM) and Four Point Probe. The conductivity of the films deposited using ruthenium precursor showed strong dependency on the deposition parameters such as pressure. Ruthenium doped sample showed the presence of diamond crystallites with an average size of approx. 3 nm while un-doped diamondlike carbon sample showed the presence of diamond crystallites with an average size of 11 nm. TEM results showed that ruthenium was atomically dispersed within the amorphous carbon network in the films.

  6. Ruthenium Complexes: An Emerging Ground to the Development of Metallopharmaceuticals for Cancer Therapy.

    PubMed

    Abid, Mohammad; Shamsi, Farheen; Azam, Amir

    2016-01-01

    GLOBOCAN 2012 estimates 14.1 million new cancer cases and 8.2 million cancer-related deaths worldwide. Cancer is rapidly becoming a major public health concern in India as well, with the number of new cancer cases anticipated to double within the next 20 years. The percentage of currently approved metallodrugs is very low, in contrast to the majority of drugs available as organic compounds. The search for alternative drugs to cisplatin, carboplatin and other derivatives is highly needed due to their severe side effects including nephrotoxicity and neurotoxicity. Ruthenium, among other transition metal complexes appears to be a possible candidate for cancer therapy in the near future. The most significant rationale is ruthenium's octahedral chemistry and greater propensity to undergo redox reactions. The hypoxic environment of tumors favors the reduction of inert ruthenium (III) to active ruthenium (II) which opens new prospects for the development of novel prodrugs. Although studies suggest that ruthenium complexes penetrate well within the tumor cells and bind effectively to DNA, its binding to proteins is not very well explained. Ruthenium complexes are presently receiving great attention in the fields of biological, pharmaceutical and medicinal chemistry as anticancer agents. This review poses a comprehensive overview of the studies on competent anticancer ruthenium complexes and the role of these metal complexes in relation to their anticancer properties as well as those under clinical trials.

  7. Calcium-assisted reduction of cobalt ferrite nanoparticles for nanostructured iron cobalt with enhanced magnetic performance

    NASA Astrophysics Data System (ADS)

    Qi, B.; Andrew, J. S.; Arnold, D. P.

    2017-03-01

    This paper demonstrates the potential of a calcium-assisted reduction process for synthesizing fine-grain ( 100 nm) metal alloys from metal oxide nanoparticles. To demonstrate the process, an iron cobalt alloy (Fe66Co34) is obtained by hydrogen annealing 7-nm cobalt ferrite (CoFe2O4) nanoparticles in the presence of calcium granules. The calcium serves as a strong reducing agent, promoting the phase transition from cobalt ferrite to a metallic iron cobalt alloy, while maintaining high crystallinity. Magnetic measurements demonstrate the annealing temperature is the dominant factor of tuning the grain size and magnetic properties. Annealing at 700 °C for 1 h maximizes the magnetic saturation, up to 2.4 T (235 emu/g), which matches that of bulk iron cobalt.

  8. Synergetic interactions improve cobalt leaching from lithium cobalt oxide in microbial fuel cells.

    PubMed

    Huang, Liping; Li, Tianchi; Liu, Chuan; Quan, Xie; Chen, Lijie; Wang, Aijie; Chen, Guohua

    2013-01-01

    Cobalt leaching from lithium cobalt oxide is a promising reduction process for recovery of cobalt and recycle of spent lithium ion batteries, but suffers from consumption of large amount of reductants and energy, and generation of excess secondary polluted sludge. Thus, effective and environmental friendly processes are needed to improve the existing process limitations. Here we reported microbial fuel cells (MFCs) to effectively reduce Co(III) in lithium cobalt oxide with concomitant energy generation. There was a synergetic interaction in MFCs, leading to a more rapid Co(III) leaching at a rate 3.4 times the sum of rates by conventional chemical processes and no-acid controls. External resistor, solid/liquid ratio, solution conductivity, pH and temperature affected system performance. This study provides a new process for recovery of cobalt and recycle of spent lithium ion batteries with concomitant energy generation from MFCs.

  9. Reduction of transition metal complexes by tris(bipyridyl)ruthenium(1+) ion, chromium(II) ion, and the 10-hydroxy-1-methylethyl radical

    SciTech Connect

    Connolly, P. II

    1985-01-01

    The kinetics and mechanisms of the reactions of photochemically generated tris(bipyridyl)ruthenium(1+) ion with various metal complexes were studied. The rates of reduction of some Co(III) complexes were at, or near, the diffusion controlled limit. Several rare earth ions, Eu/sup 3 +/, Yb/sup 3 +/, and Sm/sup 3 +/ were also reacted with the ruthenium(1+) complex. Yb/sup 3 +/ was reduced; however, the reaction was just above the limits of detection. Sm/sup 3 +/ was not reduced, in accord with the thermodynamics of the reaction. The reductions of some Cr(III) complexes, including pentaaquo(organo)chromium(2+) ions and pentaaquo(pyridine)chromium(3+) ions, were also studied. The reduction of the organochromium(2+) complexes proceeded at a rate that was similar to the Cr(H/sub 2/O)/sub 6//sup 3 +/ ion. The homogeneous catalytic production of H/sub 2/ from reduced metal halide solutions (M/sup 2 +/ = Cr/sup 2 +/, Eu/sup 2 +/, V/sup 2 +/) is presented. The catalyst is a cobalt(II) macrocyclic complex, Co(dmgBF/sub 2/)/sub 2/, which is reduced by the M/sup 2 +/ ions to form, ultimately, a hydridometal complex. This complex leads to the evolution of H/sub 2/ in the acidic solutions employed. The mechanism of the reaction is discussed in terms of the Michaelis-Menten scheme for enzyme catalysis. A photochemical method for the generation of 1-hydroxy-1-methylethyl radical for kinetic study is presented. This radical is reacted with BrCo(dmgH)/sub 2/ and ClCo(dmgH)/sub 2/ to produce the highly colored Co(dmgH)/sub 2/ complex, which serves as the indicator for the reaction.

  10. Amorphous thin film ruthenium oxide as an electrode material for electrochemical capacitors

    SciTech Connect

    Jow, T.R.; Zheng, J.P.

    1995-12-31

    Ruthenium oxide thin films of an amorphous phase were successfully prepared on a titanium (Ti) substrate at temperatures below 160 C. The sol-gel process using metal alkoxide precursor in nonaqueous solvents was used to prepare these films. The preliminary results showed that a specific capacitance of 430 F/g can be achieved for amorphous ruthenium oxide electrode in sulfuric acid. Films prepared by this method are compared with the films prepared by the thermal decomposition of the aqueous ruthenium chloride solution at temperatures above 300 C. The specific capacitance, the crystalline structure, and the surface morphology of these films as a function of the preparation temperature were also discussed.

  11. Recent advances in ruthenium complex-based light-driven water oxidation catalysts.

    PubMed

    Xue, Long-Xin; Meng, Ting-Ting; Yang, Wei; Wang, Ke-Zhi

    2015-11-01

    The light driven splitting of water is one of the most attractive approaches for direct conversion of solar energy into chemical energy in the future. Ruthenium complexes as the water oxidation catalysts (WOCs) and light sensitizers have attracted increasing attention, and have made a great progress. This mini-review highlights recent progress on ruthenium complex-based photochemical and photoelectrochemical water oxidation catalysts. The recent representative examples of these ruthenium complexes that are in homogeneous solution or immobilized on solid electrodes, are surveyed. In particular, special attention has been paid on the supramolecular dyads with photosensitizer and WOC being covalently hold together, and grafted onto the solid electrode.

  12. Arene-ruthenium(II) complexes with hydrophilic P-donor ligands: versatile catalysts in aqueous media.

    PubMed

    Crochet, Pascale; Cadierno, Victorio

    2014-09-07

    In the last few years there has been increasing interest in the use of water as a reaction medium for catalysis, and therefore in designing water-soluble transition-metal catalysts. Half-sandwich (η(6)-arene)-ruthenium(ii) complexes are a versatile and well-known family of ruthenium compounds that exhibit a rich catalytic and coordination chemistry. This Perspective article focuses on the catalytic applications in aqueous media of (η(6)-arene)-ruthenium(ii) complexes containing water-soluble phosphines, and related hydrophilic P-donor ligands.

  13. Cobalt: A vital element in the aircraft engine industry

    NASA Technical Reports Server (NTRS)

    Stephens, J. R.

    1981-01-01

    Recent trends in the United States consumption of cobalt indicate that superalloys for aircraft engine manufacture require increasing amounts of this strategic element. Superalloys consume a lion's share of total U.S. cobalt usage which was about 16 million pounds in 1980. In excess of 90 percent of the cobalt used in this country was imported, principally from the African countries of Zaire and Zambia. Early studies on the roles of cobalt as an alloying element in high temperature alloys concentrated on the simple Ni-Cr and Nimonic alloy series. The role of cobalt in current complex nickel base superalloys is not well defined and indeed, the need for the high concentration of cobalt in widely used nickel base superalloys is not firmly established. The current cobalt situation is reviewed as it applies to superalloys and the opportunities for research to reduce the consumption of cobalt in the aircraft engine industry are described.

  14. Characteristics of polyaniline cobalt supported catalysts for epoxidation reactions.

    PubMed

    Kowalski, Grzegorz; Pielichowski, Jan; Grzesik, Mirosław

    2014-01-01

    A study of polyaniline (PANI) doping with various cobalt compounds, that is, cobalt(II) chloride, cobalt(II) acetate, and cobalt(II) salen, is presented. The catalysts were prepared by depositing cobalt compounds onto the polymer surface. PANI powders containing cobalt ions were obtained by one- or two-step method suspending PANI in the following acetonitrile/acetic acid solution or acetonitrile and then acetic acid solution. Moreover different ratios of Co(II) : PANI were studied. Catalysts obtained with both methods and at all ratios were investigated using various techniques including AAS and XPS spectroscopy. The optimum conditions for preparation of PANI/Co catalysts were established. Catalytic activity of polyaniline cobalt(II) supported catalysts was tested in dec-1-ene epoxidation with molecular oxygen at room temperature. The relationship between the amount of cobalt species, measured with both AAS and XPS techniques, and the activity of PANI-Co catalysts has been established.

  15. Characteristics of Polyaniline Cobalt Supported Catalysts for Epoxidation Reactions

    PubMed Central

    Kowalski, Grzegorz; Pielichowski, Jan; Grzesik, Mirosław

    2014-01-01

    A study of polyaniline (PANI) doping with various cobalt compounds, that is, cobalt(II) chloride, cobalt(II) acetate, and cobalt(II) salen, is presented. The catalysts were prepared by depositing cobalt compounds onto the polymer surface. PANI powders containing cobalt ions were obtained by one- or two-step method suspending PANI in the following acetonitrile/acetic acid solution or acetonitrile and then acetic acid solution. Moreover different ratios of Co(II) : PANI were studied. Catalysts obtained with both methods and at all ratios were investigated using various techniques including AAS and XPS spectroscopy. The optimum conditions for preparation of PANI/Co catalysts were established. Catalytic activity of polyaniline cobalt(II) supported catalysts was tested in dec-1-ene epoxidation with molecular oxygen at room temperature. The relationship between the amount of cobalt species, measured with both AAS and XPS techniques, and the activity of PANI-Co catalysts has been established. PMID:24701183

  16. Cobalt induces oxidative stress in isolated liver mitochondria responsible for permeability transition and intrinsic apoptosis in hepatocyte primary cultures.

    PubMed

    Battaglia, Valentina; Compagnone, Alessandra; Bandino, Andrea; Bragadin, Marcantonio; Rossi, Carlo Alberto; Zanetti, Filippo; Colombatto, Sebastiano; Grillo, Maria Angelica; Toninello, Antonio

    2009-03-01

    It is well established that cobalt mediates the occurrence of oxidative stress which contributes to cell toxicity and death. However, the mechanisms of these effects are not fully understood. This investigation aimed at establishing if cobalt acts as an inducer of mitochondrial-mediated apoptosis and at clarifying the mechanism of this process. Cobalt, in the ionized species Co(2+), is able to induce the phenomenon of mitochondrial permeability transition (MPT) in rat liver mitochondria (RLM) with the opening of the transition pore. In fact, Co(2+) induces mitochondrial swelling, which is prevented by cyclosporin A and other typical MPT inhibitors such as Ca(2+) transport inhibitors and bongkrekic acid, as well as anti-oxidant agents. In parallel with mitochondrial swelling, Co(2+) also induces the collapse of electrical membrane potential. However in this case, cyclosporine A and the other MPT inhibitors (except ruthenium red and EGTA) only partially prevent DeltaPsi drop, suggesting that Co(2+) also has a proton leakage effect on the inner mitochondrial membrane. MPT induction is due to oxidative stress, as a result of generation by Co(2+) of the highly damaging hydroxyl radical, with the oxidation of sulfhydryl groups, glutathione and pyridine nucleotides. Co(2+) also induces the release of the pro-apoptotic factors, cytochrome c and AIF. Incubation of rat hepatocyte primary cultures with Co(2+) results in apoptosis induction with caspase activation and increased level of expression of HIF-1alpha. All these observations allow us to state that, in the presence of calcium, Co(2+) is an inducer of apoptosis triggered by mitochondrial oxidative stress.

  17. Synthesis of Samarium Cobalt Nanoblades

    SciTech Connect

    Darren M. Steele

    2010-08-25

    As new portable particle acceleration technologies become feasible the need for small high performance permanent magnets becomes critical. With particle accelerating cavities of a few microns, the photonic crystal fiber (PCF) candidate demands magnets of comparable size. To address this need, samarium cobalt (SmCo) nanoblades were attempted to be synthesized using the polyol process. Since it is preferable to have blades of 1-2 {micro}m in length, key parameters affecting size and morphology including method of stirring, reaction temperature, reaction time and addition of hydroxide were examined. Nanoparticles consisting of 70-200 nm spherical clusters with a 3-5 nm polyvinylpyrrolidone (PVP) coating were synthesized at 285 C and found to be ferromagnetic. Nanoblades of 25nm in length were observed at the surface of the nanoclusters and appeared to suggest agglomeration was occurring even with PVP employed. Morphology and size were characterized using a transmission electron microscope (TEM). Powder X-Ray Diffraction (XRD) analysis was conducted to determine composition but no supportive evidence for any particular SmCo phase has yet been observed.

  18. Platinum-ruthenium nanotubes and platinum-ruthenium coated copper nanowires as efficient catalysts for electro-oxidation of methanol

    SciTech Connect

    Zheng, Jie; Cullen, David A.; Forest, Robert V.; Wittkopf, Jarrid A.; Zhuang, Zhongbin; Zheng, Whenchao; Chen, Jingguang G.; Yan, Yushan

    2015-01-15

    The sluggish kinetics of methanol oxidation reaction (MOR) is a major barrier to the commercialization of direct methanol fuel cells (DMFCs). In this study, we report a facile synthesis of platinum–ruthenium nanotubes (PtRuNTs) and platinum–ruthenium-coated copper nanowires (PtRu/CuNWs) by galvanic displacement reaction using copper nanowires as a template. The PtRu compositional effect on MOR is investigated; the optimum Pt/Ru bulk atomic ratio is about 4 and surface atomic ratio about 1 for both PtRuNTs and PtRu/CuNWs. Enhanced specific MOR activities are observed on both PtRuNTs and PtRu/CuNWs compared with the benchmark commercial carbon-supported PtRu catalyst (PtRu/C, Hispec 12100). Finally, x-ray photoelectron spectroscopy (XPS) reveals a larger extent of electron transfer from Ru to Pt on PtRu/CuNWs, which may lead to a modification of the d-band center of Pt and consequently a weaker bonding of CO (the poisoning intermediate) on Pt and a higher MOR activity on PtRu/CuNWs.

  19. Platinum-ruthenium nanotubes and platinum-ruthenium coated copper nanowires as efficient catalysts for electro-oxidation of methanol

    DOE PAGES

    Zheng, Jie; Cullen, David A.; Forest, Robert V.; ...

    2015-01-15

    The sluggish kinetics of methanol oxidation reaction (MOR) is a major barrier to the commercialization of direct methanol fuel cells (DMFCs). In this study, we report a facile synthesis of platinum–ruthenium nanotubes (PtRuNTs) and platinum–ruthenium-coated copper nanowires (PtRu/CuNWs) by galvanic displacement reaction using copper nanowires as a template. The PtRu compositional effect on MOR is investigated; the optimum Pt/Ru bulk atomic ratio is about 4 and surface atomic ratio about 1 for both PtRuNTs and PtRu/CuNWs. Enhanced specific MOR activities are observed on both PtRuNTs and PtRu/CuNWs compared with the benchmark commercial carbon-supported PtRu catalyst (PtRu/C, Hispec 12100). Finally, x-raymore » photoelectron spectroscopy (XPS) reveals a larger extent of electron transfer from Ru to Pt on PtRu/CuNWs, which may lead to a modification of the d-band center of Pt and consequently a weaker bonding of CO (the poisoning intermediate) on Pt and a higher MOR activity on PtRu/CuNWs.« less

  20. Equilibrium phase boundary between hcp-cobalt and fcc-cobalt

    NASA Astrophysics Data System (ADS)

    Cynn, Hyunchae; Lipp, Magnus J.; Evans, William J.; Baer, Bruce J.

    In 2000 (Yoo et al., PRL), fcc-cobalt was reported as a new high pressure phase transforming from ambient hcp-cobalt starting at around 105 GPa and 300 K. Both cobalts coexist up to 150 GPa and thereafter only fcc-cobalt was found to be the only stable phase to 200 GPa. Our recent synchrotron x-ray diffraction data on cobalt are at odds with the previous interpretation. We will present our new finding and elaborate on our understanding in terms of the equilibrium phase boundary of cobalt. We will also compare our previous work on xenon (Cynn et al., 2001, PRL) with our new results on cobalt. This work performed under the auspices of the U.S. Department of Energy by Lawrence Livermore National Laboratory under Contract DE-AC52-07NA27344. Portions of this work were performed at HPCAT (Sector 16), APS, Argonne National Laboratory. HPCAT operations are supported by DOE-NNSA under Award No. DENA0001974 and DOE-BES under Award No. DE-FG02-99ER45775. The Advanced Photon Source is a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under Contract No. DE-AC02-06CH11357.

  1. 40 CFR 721.10201 - Cobalt lithium manganese nickel oxide.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Cobalt lithium manganese nickel oxide... Specific Chemical Substances § 721.10201 Cobalt lithium manganese nickel oxide. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as cobalt lithium...

  2. 40 CFR 721.10201 - Cobalt lithium manganese nickel oxide.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Cobalt lithium manganese nickel oxide... Specific Chemical Substances § 721.10201 Cobalt lithium manganese nickel oxide. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as cobalt lithium...

  3. 40 CFR 721.10201 - Cobalt lithium manganese nickel oxide.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Cobalt lithium manganese nickel oxide... Specific Chemical Substances § 721.10201 Cobalt lithium manganese nickel oxide. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as cobalt lithium...

  4. Palladium-cobalt particles as oxygen-reduction electrocatalysts

    DOEpatents

    Adzic, Radoslav; Huang, Tao

    2009-12-15

    The present invention relates to palladium-cobalt particles useful as oxygen-reducing electrocatalysts. The invention also relates to oxygen-reducing cathodes and fuel cells containing these palladium-cobalt particles. The invention additionally relates to methods for the production of electrical energy by using the palladium-cobalt particles of the invention.

  5. [Suppression of activity of Candida albicans proteinases by cobalt chloride].

    PubMed

    Kutyreva, M P; Mukhametzianova, A R; Ulakhovich, N A

    2012-01-01

    Influence of cobalt (II) chloride on the system of Candida albicans proteinase (SAP C. alb.) (both in solution and immobilized on a surface of nitrocellulose membranes) has been investigated. In solution cobalt chloride inactivated inducible but not constitute enzyme. In the heterogenous sytem proteolitical effect of the cobalt ion on inductible proteinase was also observed.

  6. Ruthenium carbonyl catalyst supported on ceric oxide for preparation of olefins from synthesis gas

    DOEpatents

    Pierantozzi, Ronald

    1985-01-01

    A catalyst comprising a ruthenium carbonyl compound deposited on a cerium oxide-containing support material provides for the selective synthesis of low molecular weight olefinic hydrocarbons from mixtures of hydrogen and carbon monoxide.

  7. Ruthenium or osmium complexes and their uses as catalysts for water oxidation

    DOEpatents

    Corbea, Javier Jesus Concepcion; Chen, Zoufeng; Jurss, Jonah Wesley; Templeton, Joseph L.; Hoertz, Paul; Meyer, Thomas J.

    2016-06-07

    The present invention provides ruthenium or osmium complexes and their uses as a catalyst for catalytic water oxidation. Another aspect of the invention provides an electrode and photo-electrochemical cells for electrolysis of water molecules.

  8. Preparation of olefins from synthesis gas using ruthenium supported on ceric oxide

    DOEpatents

    Pierantozzi, Ronald

    1985-01-01

    A catalyst comprising a ruthenium carbonyl compound deposited on a cerium oxide-containing support material provides for the selective synthesis of low molecular weight olefinic hydrocarbons from mixtures of hydrogen and carbon monoxide.

  9. Dendrimer-Encapsulated Ruthenium Nanoparticles as Catalysts for Lithium-O2 Batteries

    SciTech Connect

    Bhattacharya, Priyanka; Nasybulin, Eduard N.; Engelhard, Mark H.; Kovarik, Libor; Bowden, Mark E.; Li, Shari; Gaspar, Daniel J.; Xu, Wu; Zhang, Jiguang

    2014-12-01

    Dendrimer-encapsulated ruthenium nanoparticles (DEN-Ru) have been used as catalysts in lithium-O2 batteries for the first time. Results obtained from UV-vis spectroscopy, electron microscopy and X-ray photoelectron spectroscopy show that the nanoparticles synthesized by the dendrimer template method are ruthenium oxide instead of metallic ruthenium reported earlier by other groups. The DEN-Ru significantly improve the cycling stability of lithium (Li)-O2 batteries with carbon black electrodes and decrease the charging potential even at low catalyst loading. The monodispersity, porosity and large number of surface functionalities of the dendrimer template prevent the aggregation of the ruthenium nanoparticles making their entire surface area available for catalysis. The potential of using DEN-Ru as stand-alone cathode materials for Li-O2 batteries is also explored.

  10. Ruthenium or osmium complexes and their uses as catalysts for water oxidation

    SciTech Connect

    Concepcion Corbea, Javier Jesus; Chen, Zuofeng; Jurss, Jonah Wesley; Templeton, Joseph L; Hoertz, Paul; Meyer, Thomas J

    2014-10-28

    The present invention provides ruthenium or osmium complexes and their uses as a catalyst for catalytic water oxidation. Another aspect of the invention provides an electrode and photo-electrochemical cells for electrolysis of water molecules.

  11. Preparation of olefins from synthesis gas using ruthenium supported on ceric oxide

    DOEpatents

    Pierantozzi, R.

    1985-04-09

    A catalyst comprising a ruthenium carbonyl compound deposited on a cerium oxide-containing support material provides for the selective synthesis of low molecular weight olefinic hydrocarbons from mixtures of hydrogen and carbon monoxide.

  12. Ruthenium carbonyl catalyst supported on ceric oxide for preparation of olefins from synthesis gas

    DOEpatents

    Pierantozzi, R.

    1985-04-02

    A catalyst comprising a ruthenium carbonyl compound deposited on a cerium oxide-containing support material provides for the selective synthesis of low molecular weight olefinic hydrocarbons from mixtures of hydrogen and carbon monoxide.

  13. Ruthenium or osmium complexes and their uses as catalysts for water oxidation

    SciTech Connect

    Corbea, Javier Jesus Concepcion; Chen, Zuofeng; Jurss, Jonah Wesley; Templeton, Joseph L.; Hoertz, Paul; Meyer, Thomas J.

    2013-09-03

    The present invention provides ruthenium or osmium complexes and their uses as a catalyst for catalytic water oxidation. Another aspect of the invention provides an electrode and photo-electrochemical cells for electrolysis of water molecules.

  14. Platinum-ruthenium-palladium alloys for use as a fuel cell catalyst

    DOEpatents

    Gorer, Alexander

    2002-01-01

    A noble metal alloy composition for a fuel cell catalyst, a ternary alloy composition containing platinum, ruthenium and palladium. The alloy shows increased activity as compared to well-known catalysts.

  15. Ruthenium complexes containing bis-benzimidazole derivatives as a new class of apoptosis inducers.

    PubMed

    Li, Linlin; Wong, Yum-Shing; Chen, Tianfeng; Fan, Cundong; Zheng, Wenjie

    2012-01-28

    A series of ruthenium complexes containing bis-benzimidazole derivatives have been synthesized and identified as able to target mitochondria and induce caspase-dependent apoptosis in cancer cells through superoxide overproduction.

  16. Characterization of Palladium and Ruthenium after Reaction with Tetraphenylborate and Mercury

    SciTech Connect

    Duff, M.C.

    2001-09-11

    This report documents a second series of X-ray fine structure and chemical analyses to examine the form that Pd - and, to a lesser extent, ruthenium (Ru) - takes in simulated high-level slurries containing TPB salts.

  17. A novel ruthenium(II)-cobaloxime supramolecular complex for photocatalytic H2 evolution: Synthesis, characterisation, and mechanistic studies

    PubMed Central

    Cropek, Donald M.; Metz, Anja; Müller, Astrid M.; Gray, Harry B.; Horne, Toyketa; Horton, Dorothy C.; Poluektov, Oleg; Tiede, David M.; Weber, Ralph T.; Jarrett, William L.; Phillips, Joshua D.

    2012-01-01

    We report the synthesis and characterization of novel mixed-metal binuclear ruthenium(II)-cobalt(II) photocatalysts for hydrogen evolution in acidic acetonitrile. First, 2-(2′-pyridyl)benzothiazole (pbt), 1, was reacted with RuCl3·xH2O to produce [Ru(pbt)2Cl2] ·0.25CH3COCH3, 2, which was then reacted with 1,10-phenanthroline-5,6-dione (phendione), 3 in order to produce [Ru(pbt)2(phendione)](PF6)2·4H2O, 4. Compound 4 was then reacted with 4-pyridinecarboxaldehyde in order to produce [Ru(pbt)2(L-pyr)](PF6)2·9.5H2O, 5 (where L-pyr = (4-pyridine)oxazolo[4,5-f]phenanthroline). Compound 5 was then reacted with [Co(dmgBF2)2(H2O)2] (where dmgBF2 = difluorboryldimethylglyoximate) in order to produce the mixed-metal binuclear complex, [Ru(pbt)2(L-pyr)Co(dmgBF2)2(H2O)](PF6)2·11H2O·1.5CH3COCH3, 6. [Ru(Me2bpy)2(L-pyr)Co(dmgBF2)2(OH2)](PF6)2, 7 (where Me2bpy = 1,10-phenanthroline, 4,4′-dimethyl-2,2′-bipyridine) and [Ru(phen)2(L-pyr)Co(dmgBF2)2(OH2)](PF6)2, 8 were also synthesised. All complexes were characterized by elemental analysis, UV-visible absorption, 11B, 19F, and 59Co NMR, ESR spectroscopy, and cyclic voltammetry, where appropriate. Photocatalytic studies carried out in acidified acetonitrile demonstrated constant hydrogen generation longer than a 42 hour period as detected by gas chromatography. Time resolved spectroscopic measurements were performed on compound 6, which proved an intramolecular electron transfer from an excited Ru(II) metal centre to the Co(II) metal centre via the bridging L-pyr ligand. This resulted in the formation of a cobalt(I)-containing species that is essential for the production of H2 gas in the presence of H+ ions. A proposed mechanism for the generation of hydrogen is presented. PMID:23001132

  18. A novel ruthenium(II)-cobaloxime supramolecular complex for photocatalytic H2 evolution: synthesis, characterisation and mechanistic studies.

    PubMed

    Cropek, Donald M; Metz, Anja; Müller, Astrid M; Gray, Harry B; Horne, Toyketa; Horton, Dorothy C; Poluektov, Oleg; Tiede, David M; Weber, Ralph T; Jarrett, William L; Phillips, Joshua D; Holder, Alvin A

    2012-11-14

    We report the synthesis and characterization of novel mixed-metal binuclear ruthenium(II)-cobalt(II) photocatalysts for hydrogen evolution in acidic acetonitrile. First, 2-(2'-pyridyl)benzothiazole (pbt), 1, was reacted with RuCl(3)·xH(2)O to produce [Ru(pbt)(2)Cl(2)]·0.25CH(3)COCH(3), 2, which was then reacted with 1,10-phenanthroline-5,6-dione (phendione), 3, in order to produce [Ru(pbt)(2)(phendione)](PF(6))(2)·4H(2)O, 4. Compound 4 was then reacted with 4-pyridinecarboxaldehyde in order to produce [Ru(pbt)(2)(L-pyr)](PF(6))(2)·9.5H(2)O, 5 (where L-pyr = (4-pyridine)oxazolo[4,5-f]phenanthroline). Compound 5 was then reacted with [Co(dmgBF(2))(2)(H(2)O)(2)] (where dmgBF(2) = difluoroboryldimethylglyoximato) in order to produce the mixed-metal binuclear complex, [Ru(pbt)(2)(L-pyr)Co(dmgBF(2))(2)(H(2)O)](PF(6))(2)·11H(2)O·1.5CH(3)COCH(3), 6. [Ru(Me(2)bpy)(2)(L-pyr)Co(dmgBF(2))(2)(OH(2))](PF(6))(2), 7 (where Me(2)bpy = 1,10-phenanthroline, 4,4'-dimethyl-2,2'-bipyridine) and [Ru(phen)(2)(L-pyr)Co(dmgBF(2))(2)(OH(2))](PF(6))(2), 8 were also synthesised. All complexes were characterized by elemental analysis, ESI MS, HRMS, UV-visible absorption, (11)B, (19)F, and (59)Co NMR, ESR spectroscopy, and cyclic voltammetry, where appropriate. Photocatalytic studies carried out in acidified acetonitrile demonstrated constant hydrogen generation longer than a 42 hour period as detected by gas chromatography. Time resolved spectroscopic measurements were performed on compound 6, which proved an intramolecular electron transfer from an excited Ru(II) metal centre to the Co(II) metal centre via the bridging L-pyr ligand. This resulted in the formation of a cobalt(I)-containing species that is essential for the production of H(2) gas in the presence of H(+) ions. A proposed mechanism for the generation of hydrogen is presented.

  19. The cytotoxicity and genotoxicity of soluble and particulate cobalt in human lung epithelial cells.

    PubMed

    Xie, Hong; Smith, Leah J; Holmes, Amie L; Zheng, Tongzhang; Pierce Wise, John

    2016-05-01

    Cobalt is a toxic metal used in various industrial applications leading to adverse lung effects by inhalation. Cobalt is considered a possible human carcinogen with the lung being a primary target. However, few studies have considered cobalt-induced toxicity in human lung cells, especially normal lung epithelial cells. Therefore, in this study, we sought to determine the cytotoxicity and genotoxicity of particulate and soluble cobalt in normal primary human lung epithelial cells. Cobalt oxide and cobalt chloride were used as representative particulate and soluble cobalt compounds, respectively. Exposure to both particulate and soluble cobalt induced a concentration-dependent increase in cytotoxicity, genotoxicity, and intracellular cobalt ion levels. Based on intracellular cobalt ion levels, we found that soluble and particulate cobalt induced similar cytotoxicity while soluble cobalt was more genotoxic than particulate cobalt. These data indicate that cobalt compounds are cytotoxic and genotoxic to human lung epithelial cells.

  20. Controlled cobalt doping in biogenic magnetite nanoparticles

    PubMed Central

    Byrne, J. M.; Coker, V. S.; Moise, S.; Wincott, P. L.; Vaughan, D. J.; Tuna, F.; Arenholz, E.; van der Laan, G.; Pattrick, R. A. D.; Lloyd, J. R.; Telling, N. D.

    2013-01-01

    Cobalt-doped magnetite (CoxFe3 −xO4) nanoparticles have been produced through the microbial reduction of cobalt–iron oxyhydroxide by the bacterium Geobacter sulfurreducens. The materials produced, as measured by superconducting quantum interference device magnetometry, X-ray magnetic circular dichroism, Mössbauer spectroscopy, etc., show dramatic increases in coercivity with increasing cobalt content without a major decrease in overall saturation magnetization. Structural and magnetization analyses reveal a reduction in particle size to less than 4 nm at the highest Co content, combined with an increase in the effective anisotropy of the magnetic nanoparticles. The potential use of these biogenic nanoparticles in aqueous suspensions for magnetic hyperthermia applications is demonstrated. Further analysis of the distribution of cations within the ferrite spinel indicates that the cobalt is predominantly incorporated in octahedral coordination, achieved by the substitution of Fe2+ site with Co2+, with up to 17 per cent Co substituted into tetrahedral sites. PMID:23594814

  1. Nickel cobalt phosphorous low stress electroplating

    NASA Technical Reports Server (NTRS)

    Engelhaupt, Darell E. (Inventor); Ramsey, Brian D. (Inventor)

    2002-01-01

    An electrolytic plating process is provided for electrodepositing a nickel or nickel cobalt alloy which contains at least about 2% to 25% by atomic volume of phosphorous. The process solutions contains nickel and optionally cobalt sulfate, hypophosphorous acid or a salt thereof, boric acid or a salt thereof, a monodentate organic acid or a salt thereof, and a multidentate organic acid or a salt thereof. The pH of the plating bath is from about 3.0 to about 4.5. An electroplating process is also provided which includes electroplating from the bath a nickel or nickel cobalt phosphorous alloy. This process can achieve a deposit with high microyield of at least about 84 kg/mm.sup.2 (120 ksi) and a density lower than pure nickel of about 8.0 gm/cc. This process can be used to plate a deposit of essentially zero stress at plating temperatures from ambient to 70.degree. C.

  2. Rapid phase synthesis of nanocrystalline cobalt ferrite

    SciTech Connect

    Shanmugavel, T.; Raj, S. Gokul; Rajarajan, G.; Kumar, G. Ramesh

    2014-04-24

    Synthesis of single phase nanocrystalline Cobalt Ferrite (CoFe{sub 2}O{sub 4}) was achieved by single step autocombustion technique with the use of citric acid as a chelating agent in mono proportion with metal. Specimens prepared with this method showed significantly higher initial permeability's than with the conventional process. Single phase nanocrystalline cobalt ferrites were formed at very low temperature. Surface morphology identification were carried out by transmission electron microscopy (TEM) analysis. The average grain size and density at low temperature increased gradually with increasing the temperature. The single phase formation is confirmed through powder X-ray diffraction analysis. Magnetization measurements were obtained at room temperature by using a vibrating sample magnetometer (VSM), which showed that the calcined samples exhibited typical magnetic behaviors. Temperature dependent magnetization results showed improved behavior for the nanocrystalline form of cobalt ferrite when compared to the bulk nature of materials synthesized by other methods.

  3. Ruthenium on rutile catalyst, catalytic system, and method for aqueous phase hydrogenations

    DOEpatents

    Elliot, Douglas C.; Werpy, Todd A.; Wang, Yong; Frye, Jr., John G.

    2001-01-01

    An essentially nickel- and rhenium-free catalyst is described comprising ruthenium on a titania support where the titania is greater than 75% rutile. A catalytic system containing a nickel-free catalyst comprising ruthenium on a titania support where the titania is greater than 75% rutile, and a method using this catalyst in the hydrogenation of an organic compound in the aqueous phase is also described.

  4. 2-Nitroimidazole-ruthenium polypyridyl complex as a new conjugate for cancer treatment and visualization.

    PubMed

    Mazuryk, Olga; Maciuszek, Monika; Stochel, Grażyna; Suzenet, Franck; Brindell, Małgorzata

    2014-05-01

    A novel long-lifetime highly luminescent ruthenium polypyridyl complex containing 2-nitroimidazole moiety [Ru(dip)2(bpy-2-nitroIm)]Cl2 (dip=4,7-diphenyl-1,10-phenanthroline, bpy-2-nitroIm=4-[3-(2-nitro-1H-imidazol-1-yl)propyl]-2,2'-bipyridine) has been designed cancer treatment and imaging. The luminescence properties of the synthesized compound strongly depend on the oxygen concentration. Under oxygen-free conditions quantum yield of luminescence and the average lifetime of emission were found to be 0.034 and 1.9 μs, respectively, which is ca. three times higher in comparison to values obtained in air-equilibrated solution. The binding properties of the investigated ruthenium complex to human serum albumin have been studied and the apparent binding constant for the formation of the protein-ruthenium adduct was determined to be 1.1×10(5)M(-1). The quantum yield and the average lifetime of emission are greatly enhanced upon binding of ruthenium compound to the protein. The DNA binding studies revealed two distinguished binding modes which lead to a decrease in luminescence intensity of ruthenium complex up to 60% for [DNA]/[Ru]<2, and enhancement of emission for [DNA]/[Ru]>80. Preliminary biological studies confirmed fast and efficient accumulation of the ruthenium complex inside cells. Furthermore, the ruthenium complex was found to be relatively cytotoxic with LD50 of 12 and 13 μM for A549 and CT26 cell lines, respectively, under normoxic conditions. The retention and cellular uptake of ruthenium complex is enhanced under hypoxic conditions and its LD50 decreases to 8 μM for A549 cell line.

  5. Electron Transfer Studies of Ruthenium(II) Complexes with Biologically Important Phenolic Acids and Tyrosine.

    PubMed

    Rajeswari, Angusamy; Ramdass, Arumugam; Muthu Mareeswaran, Paulpandian; Rajagopal, Seenivasan

    2016-03-01

    The ruthenium(II) complexes having 2,2'-bipyridine and phenanthroline derivatives are synthesized and characterized. The photophysical properties of these complexes at pH 12.5 are studied. The electron transfer reaction of biologically important phenolic acids and tyrosine are studied using absorption, emission and transient absorption spectral techniques. Semiclassical theory is applied to calculate the rate of electron transfer between ruthenium(II) complexes and biologically important phenolic acids.

  6. Photochemical generation and kinetic studies of a putative porphyrin-ruthenium(V)-oxo species.

    PubMed

    Zhang, Rui; Vanover, Eric; Luo, Weilong; Newcomb, Martin

    2014-06-21

    Photo-disproportionation of a bis-porphyrin-diruthenium(IV) μ-oxo dimer gave a porphyrin-ruthenium(III) species and a putative porphyrin-ruthenium(V)-oxo species that can be detected and studied in real time via laser flash photolysis methods. As determined by its spectral and kinetic behavior, the same oxo transient was also formed by photolysis of a porphyrin-ruthenium(III) N-oxide adduct. Second-order rate constants for reactions with several substrates at 22 °C were determined; representative values of rate constants were kox = 6.6 × 10(3) M(-1) s(-1) for diphenylmethanol, kox = 2.5 × 10(3) M(-1) s(-1) for styrene, and kox = 1.8 × 10(3) M(-1) s(-1) for cyclohexene. The putative porphyrin-ruthenium(V)-oxo transient reacted 5-6 orders of magnitude faster than the corresponding trans-dioxoruthenium(VI) porphyrins, and the rate constants obtained in this work were similar to those of the corrole-iron(V)-oxo derivative. The high reactivity for the photochemically generated ruthenium-oxo species in comparison to other porphyrin-metal-oxo intermediates suggests that it is a true ruthenium(V)-oxo species.

  7. Phosphorescent ruthenium complexes with a nitroimidazole unit that image oxygen fluctuation in tumor tissue.

    PubMed

    Son, Aoi; Kawasaki, Atsushi; Hara, Daiki; Ito, Takeo; Tanabe, Kazuhito

    2015-02-02

    Understanding oxygen fluctuation in a cancerous tumor is important for effective treatment, especially during radiotherapy. In this paper, ruthenium complexes bearing a nitroimidazole group are shown to report the oxygen status in tumor tissue directly. The nitroimidazole group was known to be accumulated in hypoxic tumor tissues. On the other hand, the ruthenium complex showed strong phosphorescence around 600 nm. The emission of ruthenium is quenched instantaneously by molecular oxygen due to energy transfer between triplet states of oxygen and ruthenium complex, but the emission is then recovered by the removal of oxygen. Thus, we could observe oxygen fluctuation in tumor tissue in a real-time manner by monitoring the phosphorescence of the ruthenium complex. The versatility of the probe is demonstrated by monitoring oxygen fluctuation in living cells and tumor tissue planted in mice. The ruthenium complex promptly penetrated plasma membrane and accumulated in cells to emit its oxygen-dependent phosphorescence. In vivo experiments revealed that the oxygen level in tumor tissue seems to fluctuate at the sub-minute timescale.

  8. Corrosion Investigations of Ruthenium in Potassium Periodate Solutions Relevant for Chemical Mechanical Polishing

    NASA Astrophysics Data System (ADS)

    Cheng, Jie; Wang, Tongqing; Pan, Jinshan; Lu, Xinchun

    2016-08-01

    Ruthenium is the most promising material for the barrier layer used for the sub 14 nm technology node in integrated circuits manufacturing. Potassium periodate (KIO4)-based slurry is used in the chemical mechanical planarization (CMP) process of the barrier layer. However, the electrochemical and corrosion properties of ruthenium have not been investigated in such slurry. In this paper, the electrochemical and corrosion behaviors of ruthenium in KIO4 solutions were investigated under static conditions but at different pH values by potentiodynamic polarization and electrochemical impedance spectroscopy measurements, combined with surface chemical analysis using auger electron spectroscopy. Moreover, to study wear enhanced corrosion during CMP, tribocorrosion experiments were carried out to monitor the current density changes during and after mechanical scratching. The results show that at pH 6, ruthenium forms a relatively thick and heterogeneous surface film composed of RuO2·2H2O/RuO3, showing a high corrosion resistance and it exhibits a quick repassivation after mechanical scratching. At pH 4, ruthenium shows a passivation behavior with formation of a uniform and conductive oxide like RuO2·2H2O. It should be noted that there is a possible formation of RuO4 toxic gas under this condition, which should be avoided in the actual production. However, at pH 11, ruthenium exhibits no considerable passivity and the corrosion proceeds uniformly.

  9. Cation distributions on rapidly solidified cobalt ferrite

    NASA Technical Reports Server (NTRS)

    De Guire, Mark R.; Kalonji, Gretchen; O'Handley, Robert C.

    1990-01-01

    The cation distributions in two rapidly solidified cobalt ferrites have been determined using Moessbauer spectroscopy at 4.2 K in an 8-T magnetic field. The samples were obtained by gas atomization of a Co0-Fe2O3-P2O5 melt. The degree of cation disorder in both cases was greater than is obtainable by cooling unmelted cobalt ferrite. The more rapidly cooled sample exhibited a smaller departure from the equilibrium cation distribution than did the more slowly cooled sample. This result is explained on the basis of two competing effects of rapid solidification: high cooling rate of the solid, and large undercooling.

  10. Alterations of histone modifications by cobalt compounds

    PubMed Central

    Li, Qin; Ke, Qingdong; Costa, Max

    2009-01-01

    In the present study, we examined the effects of CoCl2 on multiple histone modifications at the global level. We found that in both human lung carcinoma A549 cells and human bronchial epithelial Beas-2B cells, exposure to CoCl2 (≥200 μM) for 24 h increased H3K4me3, H3K9me2, H3K9me3, H3K27me3, H3K36me3, uH2A and uH2B but decreased acetylation at histone H4 (AcH4). Further investigation demonstrated that in A549 cells, the increase in H3K4me3 and H3K27me3 by cobalt ions exposure was probably through enhancing histone methylation processes, as methionine-deficient medium blocked the induction of H3K4me3 and H3K27me3 by cobalt ions, whereas cobalt ions increased H3K9me3 and H3K36me3 by directly inhibiting JMJD2A demethylase activity in vitro, which was probably due to the competition of cobalt ions with iron for binding to the active site of JMJD2A. Furthermore, in vitro ubiquitination and deubiquitination assays revealed that the cobalt-induced histone H2A and H2B ubiquitination is the result of inhibition of deubiquitinating enzyme activity. Microarray data showed that exposed to 200 μM of CoCl2 for 24 h, A549 cells not only increased but also decreased expression of hundreds of genes involved in different cellular functions, including tumorigenesis. This study is the first to demonstrate that cobalt ions altered epigenetic homeostasis in cells. It also sheds light on the possible mechanisms involved in cobalt-induced alteration of histone modifications, which may lead to altered programs of gene expression and carcinogenesis since cobalt at higher concentrations is a known carcinogen. PMID:19376846

  11. International strategic minerals inventory summary report; cobalt

    USGS Publications Warehouse

    Crockett, R.N.; Chapman, G.R.; Forrest, M.D.

    1987-01-01

    Major world resources of cobalt are described in this summary report of information in the International Strategic Minerals Inventory {ISMI}. ISMI is a cooperative data-collection effort of earth-science and mineral-resource agencies in Australia, Canada, the Federal Republic of Germany, the Republic of South Africa, and the United States of America. This report, designed to be of benefit to policy analysts, contains two parts. Part I presents an overview of the resources and potential supply of cobalt on the basis of inventory information. Part II contains tables of some of the geologic information and mineral-resource and production data that were collected by ISMI participants.

  12. Effect of cobalt on the primary productivity of Spirulina platensis

    SciTech Connect

    Sharma, R.M.; Panigrahi, S.; Azeez, P.A.

    1987-10-01

    Cobalt, a micronutrient for biological organisms, is a metal of wide use. Main sources of Co to the environment are combustion of fossil fuels, smelters, cobalt processing facilities, sewage and industrial wastes. Atomic power plants and nuclear weapon detonations form an important source of radioisotopes of this metal to the environment. Cobalt has been included in the 14 toxic trace elements of critical importance from the point of view of environmental pollution and health hazards. Cobalt deficiency leads to diseases like stunted growth. At toxic level, Co inhibits heme biosynthesis and enzyme activities. The present study reports the effect of cobalt on biomass productivity of blue-green alga Spirulina platensis.

  13. A selective, long-lived deep-red emissive ruthenium(II) polypyridine complexes for the detection of BSA.

    PubMed

    Babu, Eththilu; Muthu Mareeswaran, Paulpandian; Singaravadivel, Subramanian; Bhuvaneswari, Jayaraman; Rajagopal, Seenivasan

    2014-09-15

    A selective, label free luminescence sensor for bovine serum albumin (BSA) is investigated using ruthenium(II) complexes over the other proteins. Interaction between BSA and ruthenium(II) complexes has been studied using absorption, emission, excited state lifetime and circular dichroism (CD) spectral techniques. The luminescence intensity of ruthenium(II) complexes (I and II), has enhanced at 602 and 613 nm with a large hypsochromic shift of 18 and 5 nm respectively upon addition of BSA. The mode of binding of ruthenium(II) complexes with BSA has analyzed using computational docking studies.

  14. Anticancer Activity and Modes of Action of (arene) ruthenium(II) Complexes Coordinated to C-, N-, and O-ligands.

    PubMed

    Biersack, Bernhard

    2016-01-01

    An overview of anticancer active (arene)ruthenium(II) complexes coordinated to period 2 element-based ligand systems, i.e., carbon-, nitrogen-, and oxygen-coordinated ligands, is provided in this mini-review. A bridge is forged from the large group of anticancer active ruthenium compounds with monodentate and chelating nitrogen ligands via complexes of O,O-chelating ligands to organometallic ruthenium derivatives coordinated to carbon. (Arene)ruthenium(II) complexes with reduced side-effects and enhanced efficacy against cancer are highlighted. Pertinent literature is covered up to 2014.

  15. Similar Biological Activities of Two Isostructural Ruthenium and Osmium Complexes

    SciTech Connect

    Maksimoska,J.; Williams, D.; Atilla-Gokcumen, G.; Smalley, K.; Carroll, P.; Webster, R.; Filippakopoulos, P.; Knapp, S.; Herlyn, M.; Meggers, E.

    2008-01-01

    In this study, we probe and verify the concept of designing unreactive bioactive metal complexes, in which the metal possesses a purely structural function, by investigating the consequences of replacing ruthenium in a bioactive half-sandwich kinase inhibitor scaffold by its heavier congener osmium. The two isostructural complexes are compared with respect to their anticancer properties in 1205?Lu melanoma cells, activation of the Wnt signaling pathway, IC50 values against the protein kinases GSK-3? and Pim-1, and binding modes to the protein kinase Pim-1 by protein crystallography. It was found that the two congeners display almost indistinguishable biological activities, which can be explained by their nearly identical three-dimensional structures and their identical mode of action as protein kinase inhibitors. This is a unique example in which the replacement of a metal in an anticancer scaffold by its heavier homologue does not alter its biological activity.

  16. Modulating the Anticancer Activity of Ruthenium(II)-Arene Complexes.

    PubMed

    Clavel, Catherine M; Păunescu, Emilia; Nowak-Sliwinska, Patrycja; Griffioen, Arjan W; Scopelliti, Rosario; Dyson, Paul J

    2015-04-23

    Following the identification of [Ru(η(6)-p-cymene)Cl2(1H,1H,2H,2H-perfluorodecyl-3-(pyridin-3-yl)propanoate)], a ruthenium(II)-arene complex with a perfluoroalkyl-modified ligand that displays remarkable in vitro cancer cell selectivity, a series of structurally related compounds were designed. In the new derivatives, the p-cymene ring and/or the chloride ligands are substituted by other ligands to modulate the steric bulk or aquation kinetics. The new compounds were evaluated in both in vitro (cytotoxicity and migration assays) and in vivo (chicken chorioallantoic membrane) models and were found to exhibit potent antivascular effects.

  17. Thermal conductivity of ruthenium aluminide (RuAl)

    SciTech Connect

    Anderson, S.A.; Lang, C.I.

    1998-01-06

    Ruthenium aluminide (RuAl) is an intermetallic compound which exhibits strength at high temperatures together with attractive room temperature toughness. This combination of properties makes it a promising material for use at higher temperatures than currently possible with conventional titanium and nickel based alloys. Although high temperature applications will demand a knowledge and understanding of the thermal properties of RuAl, no such information is available in the scientific literature. In this paper, measurements of the thermal conductivity of RuAl are reported for the first time. Although the electrical properties of RuAl have previously been investigated, further electrical resistivity measurements have been made, using the same samples used to measure thermal conductivity. This allows a direct, meaningful comparison of electrical and thermal conductivity data, offering insights into the thermal transport mechanisms in RuAl. Microstructure is shown to have a significant influence on thermal and electrical properties.

  18. Size Effect of Ruthenium Nanoparticles in Catalytic Carbon Monoxide Oxidation

    SciTech Connect

    Joo, Sang Hoon; Park, Jeong Y.; Renzas, J. Russell; Butcher, Derek R.; Huang, Wenyu; Somorjai, Gabor A.

    2010-04-04

    Carbon monoxide oxidation over ruthenium catalysts has shown an unusual catalytic behavior. Here we report a particle size effect on CO oxidation over Ru nanoparticle (NP) catalysts. Uniform Ru NPs with a tunable particle size from 2 to 6 nm were synthesized by a polyol reduction of Ru(acac){sub 3} precursor in the presence of poly(vinylpyrrolidone) stabilizer. The measurement of catalytic activity of CO oxidation over two-dimensional Ru NPs arrays under oxidizing reaction conditions (40 Torr CO and 100 Torr O{sub 2}) showed an activity dependence on the Ru NP size. The CO oxidation activity increases with NP size, and the 6 nm Ru NP catalyst shows 8-fold higher activity than the 2 nm catalysts. The results gained from this study will provide the scientific basis for future design of Ru-based oxidation catalysts.

  19. Platinum adlayered ruthenium nanoparticles, method for preparing, and uses thereof

    DOEpatents

    Tong, YuYe; Du, Bingchen

    2015-08-11

    A superior, industrially scalable one-pot ethylene glycol-based wet chemistry method to prepare platinum-adlayered ruthenium nanoparticles has been developed that offers an exquisite control of the platinum packing density of the adlayers and effectively prevents sintering of the nanoparticles during the deposition process. The wet chemistry based method for the controlled deposition of submonolayer platinum is advantageous in terms of processing and maximizing the use of platinum and can, in principle, be scaled up straightforwardly to an industrial level. The reactivity of the Pt(31)-Ru sample was about 150% higher than that of the industrial benchmark PtRu (1:1) alloy sample but with 3.5 times less platinum loading. Using the Pt(31)-Ru nanoparticles would lower the electrode material cost compared to using the industrial benchmark alloy nanoparticles for direct methanol fuel cell applications.

  20. Synthesis, characterization, and anticancer activity of ruthenium-pyrazole complexes.

    PubMed

    David, Solene; Perkins, Richard S; Fronczek, Frank R; Kasiri, Sahba; Mandal, Subhrangsu S; Srivastava, Radhey S

    2012-06-01

    A series of new water soluble Ru(III) pyrazole complexes mer-[RuCl(3)(DMSO-S)(pyz)(2)] 1, mer-[RuCl(3)(DMSO-S)(DMSO-O)(pyz)] 2, mer-[RuCl(3)(bpy)(dmpyz)] 3, and mer-[RuCl(3)(DMSO-S)(dmpyz)(2)] 4 (pyz=pyrazole; dmpyz=3,5-dimethylpyrazole, bpy=2,2'-bipyridine) have been synthesized and characterized by use of a combination of spectroscopy (IR and UV-visible), X-ray diffraction, and cyclic voltammetry. The molecular X-ray structure of all reported compounds (1-4) revealed distorted octahedral coordination around ruthenium. The cytotoxicity assay on human breast cancer cells (MCF7) demonstrated that compounds 1 and 4 affect cell viability, whereas compounds 2 and 3 do not show appreciable activity. The IC(50) values for 1 and 4 lie within the range of 71-32μM in MCF7 cells.

  1. Catalytic determination of ultratrace amounts of ruthenium with oscillopolarography monitoring

    SciTech Connect

    Jiang Zhi-Liang; Wang Li-Sheng )

    1993-09-01

    The single sweep oscillopolarographic behaviour of Rhodamine B in sulphuric acid medium was investigated. A novel, sensitive and selective catalytic method with oscillopolarography monitoring for the determination of ultratrace amounts of ruthenium was described, based on the catalytic effect of Ru(III) on the slow redox reaction occurring between Rhodamine B and potassium periodate in sulphuric acid medium at 25[degrees]C. Single sweep oscillopolarography is used to monitor the changes in concentration of Rhodamine B by means of the second derivative wave [minus]0.55 V vs. SCE. The determination range from 8.2x10[sup [minus]10] to 2.5x10[sup [minus]8] M Ru was obtained by the initial rate procedure. Influence of 30 foreign ions was considered. Ru in ore samples was analysed by this method, with satisfactory results.

  2. The cytotoxicity and genotoxicity of soluble and particulate cobalt in human lung fibroblast cells.

    PubMed

    Smith, Leah J; Holmes, Amie L; Kandpal, Sanjeev Kumar; Mason, Michael D; Zheng, Tongzhang; Wise, John Pierce

    2014-08-01

    Cobalt exposure is increasing as cobalt demand rises worldwide due to its use in enhancing rechargeable battery efficiency, super-alloys, and magnetic products. Cobalt is considered a possible human carcinogen with the lung being a primary target. However, few studies have considered cobalt-induced toxicity in human lung cells. Therefore, in this study, we sought to determine the cytotoxicity and genotoxicity of particulate and soluble cobalt in human lung cells. Cobalt oxide and cobalt chloride were used as representative particulate and soluble cobalt compounds, respectively. Exposure to both particulate and soluble cobalt induced a concentration-dependent increase in cytotoxicity, genotoxicity, and intracellular cobalt ion levels. Based on intracellular cobalt ion levels, we found that soluble cobalt was more cytotoxic than particulate cobalt while particulate and soluble cobalt induced similar levels of genotoxicity. However, soluble cobalt induced cell cycle arrest indicated by the lack of metaphases at much lower intracellular cobalt concentrations compared to cobalt oxide. Accordingly, we investigated the role of particle internalization in cobalt oxide-induced toxicity and found that particle-cell contact was necessary to induce cytotoxicity and genotoxicity after cobalt exposure. These data indicate that cobalt compounds are cytotoxic and genotoxic to human lung fibroblasts, and solubility plays a key role in cobalt-induced lung toxicity.

  3. Preparation of cobalt nanoparticles by hydrogen reduction of cobalt chloride in the gas phase

    SciTech Connect

    Jang, Hee Dong; Hwang, Dae Won; Kim, Dong Pyo; Kim, Heon Chang; Lee, Byung Yoon; Jeong, In Bum

    2004-01-03

    Cobalt nanoparticles were produced by the hydrogen reduction of cobalt chloride vapor in a multistage tubular aerosol flow reactor. Reaction zone temperature, preheating temperature, mole fractions of CoCl{sub 2} and H{sub 2}, and residence time were considered as key process variables for the control of particle size and size distribution. Ranging from 50 to 78 nm in average diameter, cobalt nanoparticles with narrow size distributions were synthesized throughout our experiments. All of the considered process variables affected the particle size and size distribution in the synthesis of cobalt nanoparticles. As the reaction zone temperature and the CoCl{sub 2} mole fraction increased, the average particle diameter increased. But the average particle diameter decreased as the residence time of reactants increased.

  4. Sintered diamond compacts using metallic cobalt binders

    NASA Technical Reports Server (NTRS)

    Libby, W. F.; Katzman, H.

    1972-01-01

    Method is developed for sintering diamond powder which uses metallic cobalt as binder. Present samples show maximum microhardness of over 3000 kg/sq mm on Knoop scale. Material may be used as hard surface coating or may compete with cubic boron nitride as abrasive grain.

  5. Magnetization dynamics of cobalt grown on graphene

    SciTech Connect

    Berger, A. J.; White, S. P.; Adur, R.; Pu, Y.; Hammel, P. C.; Amamou, W.; Kawakami, R. K.

    2014-05-07

    Ferromagnetic resonance (FMR) spin pumping is a rapidly growing field which has demonstrated promising results in a variety of material systems. This technique utilizes the resonant precession of magnetization in a ferromagnet to inject spin into an adjacent non-magnetic material. Spin pumping into graphene is attractive on account of its exceptional spin transport properties. This article reports on FMR characterization of cobalt grown on chemical vapor deposition graphene and examines the validity of linewidth broadening as an indicator of spin pumping. In comparison to cobalt samples without graphene, direct contact cobalt-on-graphene exhibits increased FMR linewidth—an often used signature of spin pumping. Similar results are obtained in Co/MgO/graphene structures, where a 1 nm MgO layer acts as a tunnel barrier. However, magnetometry, magnetic force microscopy, and Kerr microscopy measurements demonstrate increased magnetic disorder in cobalt grown on graphene, perhaps due to changes in the growth process and an increase in defects. This magnetic disorder may account for the observed linewidth enhancement due to effects such as two-magnon scattering or mosaicity. As such, it is not possible to conclude successful spin injection into graphene from FMR linewidth measurements alone.

  6. Evidence of Formation of Superdense Nonmagnetic Cobalt

    PubMed Central

    Banu, Nasrin; Singh, Surendra; Satpati, B.; Roy, A.; Basu, S.; Chakraborty, P.; Movva, Hema C. P.; Lauter, V.; Dev, B. N.

    2017-01-01

    Because of the presence of 3d transition metals in the Earth’s core, magnetism of these materials in their dense phases has been a topic of great interest. Theory predicts a dense face-centred-cubic phase of cobalt, which would be nonmagnetic. However, this dense nonmagnetic cobalt has not yet been observed. Recent investigations in thin film polycrystalline materials have shown the formation of compressive stress, which can increase the density of materials. We have discovered the existence of ultrathin superdense nonmagnetic cobalt layers in a polycrystalline cobalt thin film. The densities of these layers are about 1.2–1.4 times the normal density of Co. This has been revealed by X-ray reflectometry experiments, and corroborated by polarized neutron reflectometry (PNR) experiments. Transmission electron microscopy provides further evidence. The magnetic depth profile, obtained by PNR, shows that the superdense Co layers near the top of the film and at the film-substrate interface are nonmagnetic. The major part of the Co film has the usual density and magnetic moment. These results indicate the possibility of existence of nonmagnetic Co in the earth’s core under high pressure. PMID:28157186

  7. Evidence of Formation of Superdense Nonmagnetic Cobalt

    NASA Astrophysics Data System (ADS)

    Banu, Nasrin; Singh, Surendra; Satpati, B.; Roy, A.; Basu, S.; Chakraborty, P.; Movva, Hema C. P.; Lauter, V.; Dev, B. N.

    2017-02-01

    Because of the presence of 3d transition metals in the Earth’s core, magnetism of these materials in their dense phases has been a topic of great interest. Theory predicts a dense face-centred-cubic phase of cobalt, which would be nonmagnetic. However, this dense nonmagnetic cobalt has not yet been observed. Recent investigations in thin film polycrystalline materials have shown the formation of compressive stress, which can increase the density of materials. We have discovered the existence of ultrathin superdense nonmagnetic cobalt layers in a polycrystalline cobalt thin film. The densities of these layers are about 1.2–1.4 times the normal density of Co. This has been revealed by X-ray reflectometry experiments, and corroborated by polarized neutron reflectometry (PNR) experiments. Transmission electron microscopy provides further evidence. The magnetic depth profile, obtained by PNR, shows that the superdense Co layers near the top of the film and at the film-substrate interface are nonmagnetic. The major part of the Co film has the usual density and magnetic moment. These results indicate the possibility of existence of nonmagnetic Co in the earth’s core under high pressure.

  8. Localized comedo formation after cobalt irradiation

    SciTech Connect

    Myskowski, P.L.; Safai, B.

    1981-10-01

    Following Cobalt-60 irradiation for a left frontotemporal tumor, a 61-year-old woman developed comedones on the forehead. These changes responded to conventional acne therapy with retinoic acid. Multiple acneigenic factors were implicated in the pathogenesis of her lesions.

  9. Hardfacing with cobalt and nickel alloys

    SciTech Connect

    Wu, J.B.C. ); Redman, J. , Los Angles, CA )

    1994-09-01

    The use of cobalt or nickel alloys for added wear resistance was initiated in the early 1900s with the development of the cobalt-chromium-tungsten family of alloys. The cobalt alloys were called the Stellite'' because of their bright, shiny, nontarnished appearance. Further development and characterization of this alloy system established its usage in unlubricated metal-to-metal contact or erosion by high-velocity fluid or solid particulate impingement. Initially, the alloys were used as solid castings but later were applied by welding to tougher or more ductile substrates, hence the birth of the hardfacing industry. Many of the original Stellite compositions are still in use, but many others, including the nickel and iron alloys, have been developed for special applications or for use by newer application procedures. Examining the microstructural features and wear properties of these families of hardfacing alloys can help in choosing the right alloy for the job. Various cobalt and nickel alloys, their available product forms and the corresponding hardfacing methods, are reviewed in this article.

  10. Water splitting: Taking cobalt in isolation

    NASA Astrophysics Data System (ADS)

    Wang, Aiqin; Zhang, Tao

    2016-01-01

    The sustainable production of hydrogen is key to the delivery of clean energy in a hydrogen economy; however, lower-cost alternatives to platinum electrocatalysts are needed. Now, isolated, earth-abundant cobalt atoms dispersed over nitrogen-doped graphene are shown to efficiently electrolyse water to generate hydrogen.

  11. Sol-gel entrapped cobalt complex

    SciTech Connect

    Lima, Omar J. de; Papacidero, Andrea T.; Rocha, Lucas A.; Sacco, Herica C.; Nassar, Eduardo J.; Ciuffi, Katia J.; Bueno, Luciano A.; Messaddeq, Younes; Ribeiro, Sidney J.L

    2003-03-15

    This work describes optimized conditions for preparation of a cobalt complex entrapped in alumina amorphous materials in the form of powder. The hybrid materials, CoNHG, were obtained by a nonhydrolytic sol-gel route through condensation of aluminum chloride with diisopropylether in the presence of cobalt chloride. The materials were calcined at various temperatures. The presence of cobalt entrapped in the alumina matrix is confirmed by ultraviolet visible spectroscopy. The materials have been characterized by X-ray diffraction (XRD), surface area analysis, thermogravimetric analysis (TGA), differential thermal analyses (DTA) and transmission electron microscopy (TEM). The prepared alumina matrix materials are amorphous, even after heat treatment up to 750 deg. C. The XRD, TGA/DTA and TEM data support the increase of sample crystallization with increasing temperature. The specific surface area, pore size and pore diameter changed as a function of the heat treatment temperature employed. Different heat treatment temperatures result in materials with different compositions and structures, and influence their catalytic activity. The entrapped cobalt materials calcined at 750 deg. C efficiently catalyzed the epoxidation of (Z)-cyclooctene using iodozylbenzene as the oxygen donor.

  12. Aging effects on cobalt availability in soils.

    PubMed

    Wendling, Laura A; Kirby, Jason K; McLaughlin, Michael J

    2009-08-01

    Aging processes in soils can significantly affect the potential biological availability of introduced metals via incorporation into crystal lattices, diffusion into micropores, or formation of metal precipitates on the surfaces of soil minerals. Over time, metals in contact with the soil solid phase are less freely exchangeable with the soil solution and, hence, less available to soil biota. In the present study, the effects of aging on the fate and behavior of added divalent cobalt (Co2+) in a range of soils with varying physicochemical characteristics was assessed using isotope-exchange techniques, chemical extraction, and plant growth. Following addition to soil, the Co2+ salt rapidly partitioned to the soil solid phase. Particularly in soils with neutral to alkaline pH, a large percentage of the surface-bound Co was fixed in forms no longer in equilibrium with soil solution cobalt through aging reactions. Using techniques commonly applied to estimate metal bioavailability in soil, the lability (E values), plant availability (L values), and extractability of added Co2+ salts with the mild chemical extractants calcium chloride (CaCl2) and ammonium nitrate (NH4NO3) were observed to markedly decrease with time, particularly in soils with high pH or those containing appreciable quantities of iron/ manganese oxyhydroxide minerals. Results indicated rapid partitioning of added Co2+ into isotopically nonexchangeable pools, with more than 60% of the aging occurring within 15 d in most soils. Soil pH was the primary factor controlling the rate of cobalt aging and extent of exchangeability in the soils examined. Understanding the influence of long-term aging on cobalt availability in soils is necessary to accurately assess the potential risk associated with cobalt contamination of soil environments.

  13. The cytotoxicity and genotoxicity of soluble and particulate cobalt in human lung fibroblast cells

    SciTech Connect

    Smith, Leah J.; Holmes, Amie L.; Kandpal, Sanjeev Kumar; Mason, Michael D.; Zheng, Tongzhang; Wise, John Pierce

    2014-08-01

    Cobalt exposure is increasing as cobalt demand rises worldwide due to its use in enhancing rechargeable battery efficiency, super-alloys, and magnetic products. Cobalt is considered a possible human carcinogen with the lung being a primary target. However, few studies have considered cobalt-induced toxicity in human lung cells. Therefore, in this study, we sought to determine the cytotoxicity and genotoxicity of particulate and soluble cobalt in human lung cells. Cobalt oxide and cobalt chloride were used as representative particulate and soluble cobalt compounds, respectively. Exposure to both particulate and soluble cobalt induced a concentration-dependent increase in cytotoxicity, genotoxicity, and intracellular cobalt ion levels. Based on intracellular cobalt ion levels, we found that soluble cobalt was more cytotoxic than particulate cobalt while particulate and soluble cobalt induced similar levels of genotoxicity. However, soluble cobalt induced cell cycle arrest indicated by the lack of metaphases at much lower intracellular cobalt concentrations compared to cobalt oxide. Accordingly, we investigated the role of particle internalization in cobalt oxide-induced toxicity and found that particle-cell contact was necessary to induce cytotoxicity and genotoxicity after cobalt exposure. These data indicate that cobalt compounds are cytotoxic and genotoxic to human lung fibroblasts, and solubility plays a key role in cobalt-induced lung toxicity. - Highlights: • Particulate and soluble cobalt are cytotoxic and genotoxic to human lung cells. • Soluble cobalt induces more cytotoxicity compared to particulate cobalt. • Soluble and particulate cobalt induce similar levels of genotoxicity. • Particle-cell contact is required for particulate cobalt-induced toxicity.

  14. Structural basis and anticancer properties of ruthenium-based drug complexed with human serum albumin.

    PubMed

    Zhang, Yao; Ho, Andy; Yue, Jiping; Kong, Linlin; Zhou, Zuping; Wu, Xiaoyang; Yang, Feng; Liang, Hong

    2014-10-30

    Ruthenium-based anticancer complexes have become increasingly popular for study over the last two decades. Although ruthenium complexes are currently being investigated in clinical trials, there are still some difficulties with their delivery and associated side effects. Human serum albumin (HSA)-based delivery systems are promising for improving anticancer drug targeting and reducing negative side effects. However, there have been few studies regarding the HSA delivery system for metal-based anticancer compounds and no mention of its structural mechanism. Therefore, we studied the structure and anticancer properties of the ruthenium-based compound [RuCl5(ind)](2-) in complex with HSA. The structure revealed that [RuCl5(ind)](2-) has two binding sites in HSA. In the IB subdomain, [RuCl5(ind)](2-) binds to a new sub-site by coordinating with His-146. In the IIA subdomain, ruthenium (III) of [RuCl5(ind)](2-) binds to the hydrophobic cavity and forms coordination bonds by replacing chlorine atoms with the His-242 and Lys-199 residues of HSA. Interestingly, [RuCl5(ind)](2-), together with HSA, can enhance cytotoxicity by two to five times in cancer cells but has no effect on normal cells in vitro. Compared with unbound drug, the HSA-[RuCl5(ind)](2-) complex promotes MGC-803 cell apoptosis and also has a stronger capacity for cell cycle arrest at the G2 phase in MGC-803. In conclusion, this study will guide the rational design and development of ruthenium-containing or ruthenium-centered drugs and an HSA delivery system for ruthenium-based drugs.

  15. Design and development of novel MRI compatible zirconium- ruthenium alloys with ultralow magnetic susceptibility.

    PubMed

    Li, H F; Zhou, F Y; Li, L; Zheng, Y F

    2016-04-19

    In the present study, novel MRI compatible zirconium-ruthenium alloys with ultralow magnetic susceptibility were developed for biomedical and therapeutic devices under MRI diagnostics environments. The results demonstrated that alloying with ruthenium into pure zirconium would significantly increase the strength and hardness properties. The corrosion resistance of zirconium-ruthenium alloys increased significantly. High cell viability could be found and healthy cell morphology observed when culturing MG 63 osteoblast-like cells and L-929 fibroblast cells with zirconium-ruthenium alloys, whereas the hemolysis rates of zirconium-ruthenium alloys are <1%, much lower than 5%, the safe value for biomaterials according to ISO 10993-4 standard. Compared with conventional biomedical 316L stainless steel, Co-Cr alloys and Ti-based alloys, the magnetic susceptibilities of the zirconium-ruthenium alloys (1.25 × 10(-6) cm(3)·g(-1)-1.29 × 10(-6) cm(3)·g(-1) for zirconium-ruthenium alloys) are ultralow, about one-third that of Ti-based alloys (Ti-6Al-4V, ~3.5 × 10(-6) cm(3)·g(-1), CP Ti and Ti-6Al-7Nb, ~3.0 × 10(-6) cm(3)·g(-1)), and one-sixth that of Co-Cr alloys (Co-Cr-Mo, ~7.7 × 10(-6) cm(3)·g(-1)). Among the Zr-Ru alloy series, Zr-1Ru demonstrates enhanced mechanical properties, excellent corrosion resistance and cell viability with lowest magnetic susceptibility, and thus is the optimal Zr-Ru alloy system as therapeutic devices under MRI diagnostics environments.

  16. Design and development of novel MRI compatible zirconium- ruthenium alloys with ultralow magnetic susceptibility

    PubMed Central

    Li, H.F.; Zhou, F.Y.; Li, L.; Zheng, Y.F.

    2016-01-01

    In the present study, novel MRI compatible zirconium-ruthenium alloys with ultralow magnetic susceptibility were developed for biomedical and therapeutic devices under MRI diagnostics environments. The results demonstrated that alloying with ruthenium into pure zirconium would significantly increase the strength and hardness properties. The corrosion resistance of zirconium-ruthenium alloys increased significantly. High cell viability could be found and healthy cell morphology observed when culturing MG 63 osteoblast-like cells and L-929 fibroblast cells with zirconium-ruthenium alloys, whereas the hemolysis rates of zirconium-ruthenium alloys are <1%, much lower than 5%, the safe value for biomaterials according to ISO 10993-4 standard. Compared with conventional biomedical 316L stainless steel, Co–Cr alloys and Ti-based alloys, the magnetic susceptibilities of the zirconium-ruthenium alloys (1.25 × 10−6 cm3·g−1–1.29 × 10−6 cm3·g−1 for zirconium-ruthenium alloys) are ultralow, about one-third that of Ti-based alloys (Ti–6Al–4V, ~3.5 × 10−6 cm3·g−1, CP Ti and Ti–6Al–7Nb, ~3.0 × 10−6 cm3·g−1), and one-sixth that of Co–Cr alloys (Co–Cr–Mo, ~7.7 × 10−6 cm3·g−1). Among the Zr–Ru alloy series, Zr–1Ru demonstrates enhanced mechanical properties, excellent corrosion resistance and cell viability with lowest magnetic susceptibility, and thus is the optimal Zr–Ru alloy system as therapeutic devices under MRI diagnostics environments. PMID:27090955

  17. Design and development of novel MRI compatible zirconium- ruthenium alloys with ultralow magnetic susceptibility

    NASA Astrophysics Data System (ADS)

    Li, H. F.; Zhou, F. Y.; Li, L.; Zheng, Y. F.

    2016-04-01

    In the present study, novel MRI compatible zirconium-ruthenium alloys with ultralow magnetic susceptibility were developed for biomedical and therapeutic devices under MRI diagnostics environments. The results demonstrated that alloying with ruthenium into pure zirconium would significantly increase the strength and hardness properties. The corrosion resistance of zirconium-ruthenium alloys increased significantly. High cell viability could be found and healthy cell morphology observed when culturing MG 63 osteoblast-like cells and L-929 fibroblast cells with zirconium-ruthenium alloys, whereas the hemolysis rates of zirconium-ruthenium alloys are <1%, much lower than 5%, the safe value for biomaterials according to ISO 10993-4 standard. Compared with conventional biomedical 316L stainless steel, Co–Cr alloys and Ti-based alloys, the magnetic susceptibilities of the zirconium-ruthenium alloys (1.25 × 10‑6 cm3·g‑1–1.29 × 10‑6 cm3·g‑1 for zirconium-ruthenium alloys) are ultralow, about one-third that of Ti-based alloys (Ti–6Al–4V, ~3.5 × 10‑6 cm3·g‑1, CP Ti and Ti–6Al–7Nb, ~3.0 × 10‑6 cm3·g‑1), and one-sixth that of Co–Cr alloys (Co–Cr–Mo, ~7.7 × 10‑6 cm3·g‑1). Among the Zr–Ru alloy series, Zr–1Ru demonstrates enhanced mechanical properties, excellent corrosion resistance and cell viability with lowest magnetic susceptibility, and thus is the optimal Zr–Ru alloy system as therapeutic devices under MRI diagnostics environments.

  18. Sol-gel synthesis of hydrous ruthenium oxide nanonetworks from 1,2-epoxides

    SciTech Connect

    Walker, Jeremy; Bruce King, R.; Tannenbaum, Rina

    2007-08-15

    Hydrous ruthenium oxide (RuO{sub 2}.xH{sub 2}O) xerogels were synthesized through the addition of a 1,2-epoxide, propylene oxide, to commercial hydrated ruthenium chloride, 'RuCl{sub 3}.xH{sub 2}O,' in ethanol. After a blue-black monolithic gel formed in 4 h, the samples were allowed to age for 24 h and were dried in ambient conditions. The dried samples were then characterized by XPS, XRD, DTA and TGA. XPS showed the Ru(3d{sub 5/2}) peak at a binding energy of 281.7 eV, corresponding to that of hydrous ruthenium oxide. XRD data revealed the synthesized material as amorphous. Heating the sample in inert atmospheres caused the complete reduction of the oxide to the zero-valent state, whereas heating the sample in air resulted in both crystalline anhydrous RuO{sub 2} and zero-valent ruthenium, depending on the method of heating. DTA traces showed an endotherm ending at 150 deg. C, corresponding to the loss of coordinated water, as well as two higher temperature crystallization exotherms when the sample was heated in both inert and oxygen-rich atmospheres. TGA runs also confirmed the complete reduction of the hydrous oxide when heated in nitrogen below 270 deg. C and the formation of anhydrous ruthenium oxide when heated in air, confirming the XRD results. - Graphical abstract: Heating of hydrous ruthenium oxide, RuO{sub 2}.xH{sub 2}O, under an inert atmosphere, results in its complete reduction to the zero-valent state, whereas heating it in air results in both crystalline anhydrous RuO{sub 2} and zero-valent ruthenium, depending on the method of heating.

  19. Reducing the cobalt inventory in light water reactors

    SciTech Connect

    Ocken, H.

    1985-01-01

    Reducing the cobalt content of materials used in nuclear power plants is one approach to controlling the radiation fields responsible for occupational radiation exposure; corrosion of steam generator tubing is the primary source in pressurized water reactors (PWRs). Wear of the cobalt-base alloys used to hardface valves (especially feedwater regulator valves) and as pins and rollers in control blades are the primary boiling water reactor (BWR) sources. Routine valve maintenance can also be a significant source of cobalt. Wear, mechanical property, and corrosion measurements led to the selection of Nitronic-60/CFA and PH 13-8 Mo/Inconel X-750 as low-cobalt alloys for use as pin/roller combinations. These alloys are currently being tested in two commercial BWRs. Measurements show that Type 440C stainless steel wears less than the cobalt-base alloys in BWR feedwater regulator valves. Sliding wear tests performed at room temperature in simulated PWR water showed that Colmonoy 74 and 84, Deloro 40, and Vertx 4776 are attractive low-cobalt hardfacing alloys if the applied loads are less than or equal to103 MPa. The cobalt-base alloys performed best at high loads (207 MPa). Ongoing laboratory studies address the development and evaluation of cobalt-free iron-base hardfacing alloys and seek to improve the wear resistance of cobalt-base alloys by using lasers. Reducing cobalt impurity levels in core components that are periodically discharged should also help reduce radiation fields and disposal costs.

  20. Directional photoinduced electron transfer in paraquat silicate thin films containing entrapped ruthenium(II)-tris(bathophenanthroline-disulfonate).

    PubMed

    Trammell, Scott A; Tsoi, Stanislav; Martin, Brett; Melde, Brian J; Moore, Martin M; Dressick, Walter J

    2011-10-28

    We have demonstrated directional photoinduced electron transfer in paraquat silicate thin films containing entrapped ruthenium(II)-tris(bathophenanthroline-disulfonate (RuBPS). The films were made by electrochemically-induced hydrolysis of a silane analogue of paraquat with ruthenium(II)-tris(bathophenanthroline-disulfonate as its ion pair.

  1. A facile one-pot synthesis of ruthenium hydroxide nanoparticles on magnetic silica: Aqueous hydration of nitriles to amides

    EPA Science Inventory

    One-pot synthesis of ruthenium hydroxide nanoparticles on magnetic silica is described which involve the in situ generation of magnetic silica (Fe3O4@ SiO2) and ruthenium hydroxide immobilization; the hydration of nitriles occurs in high yield and excellent selectivity using this...

  2. Syntheses and Characterization of Ruthenium(II) Tetrakis(pyridine)complexes: An Advanced Coordination Chemistry Experiment or Mini-Project

    ERIC Educational Resources Information Center

    Coe, Benjamin J.

    2004-01-01

    An experiment for third-year undergraduate a student is designed which provides synthetic experience and qualitative interpretation of the spectroscopic properties of the ruthenium complexes. It involves the syntheses and characterization of several coordination complexes of ruthenium, the element found directly beneath iron in the middle of the…

  3. Effects of cobalt precursor on pyrolyzed carbon-supported cobalt-polypyrrole as electrocatalyst toward oxygen reduction reaction

    PubMed Central

    2013-01-01

    A series of non-precious metal electrocatalysts, namely pyrolyzed carbon-supported cobalt-polypyrrole, Co-PPy-TsOH/C, are synthesized with various cobalt precursors, including cobalt acetate, cobalt nitrate, cobalt oxalate, and cobalt chloride. The catalytic performance towards oxygen reduction reaction (ORR) is comparatively investigated with electrochemical techniques of cyclic voltammogram, rotating disk electrode and rotating ring-disk electrode. The results are analyzed and discussed employing physiochemical techniques of X-ray diffraction, transmission electron microscopy, Raman spectroscopy, X-ray photoelectron spectroscopy, inductively coupled plasma, elemental analysis, and extended X-ray absorption fine structure. It shows that the cobalt precursor plays an essential role on the synthesis process as well as microstructure and performance of the Co-PPy-TsOH/C catalysts towards ORR. Among the studied Co-PPy-TsOH/C catalysts, that prepared with cobalt acetate exhibits the best ORR performance. The crystallite/particle size of cobalt and its distribution as well as the graphitization degree of carbon in the catalyst greatly affects the catalytic performance of Co-PPy-TsOH/C towards ORR. Metallic cobalt is the main component in the active site in Co-PPy-TsOH/C for catalyzing ORR, but some other elements such as nitrogen are probably involved, too. PMID:24229351

  4. Quantitative study of ruthenium cross-over in direct methanol fuel cells during early operation hours

    NASA Astrophysics Data System (ADS)

    Schoekel, A.; Melke, J.; Bruns, M.; Wippermann, K.; Kuppler, F.; Roth, C.

    2016-01-01

    In direct methanol fuel cells (DMFC), ruthenium cross-over is an important degradation phenomenon. The loss of ruthenium from the anode, its transport through the membrane and its deposition onto the cathode are detrimental to the fuel cell performance and limit the fuel cell's lifetime. Here we present a quantitative study on the fraction of ruthenium being transferred from the anode to the cathode during early operation hours (0-100 h) of a DMFC. Already during fabrication of the MEA ruthenium is transferred to the cathode. In our pristine MEAs about 0.024 wt% Ru could be found in the cathode catalyst. The cell potential during operation seems to have only a minor influence on the dissolution process. In contrast, the operation time appears to be much more important. Our data hint at two dissolution processes: a fast process dominating the first hours of operation and a slower process, which is responsible for the ongoing ruthenium transfer during the fuel cell lifetime. After 2 h held at open circuit conditions the Ru content of the cathode side was 10 times higher than in the pristine MEA. In contrast, the slower process increased that amount only by a factor of two over the course of another 100 h.

  5. Transient Spectroscopic Characterization of the Genesis of a Ruthenium Complex Catalyst Supported on Zeolite Y

    SciTech Connect

    Ogino, Isao; Gates, Bruce C.

    2010-01-12

    A mononuclear ruthenium complex anchored to dealuminated zeolite HY, Ru(acac)(C{sub 2}H{sub 4}){sup 2+} (acac = acetylacetonate, C{sub 5}H{sub 7}O{sup 2}{sup -}), was characterized in flow reactors by transient infrared (IR) spectroscopy and Ru K edge X-ray absorption spectroscopy. The combined results show how the supported complex was converted into a form that catalyzes ethene conversion to butene. The formation of these species resulted from the removal of acac ligands from the ruthenium (as shown by IR and extended X-ray absorption fine structure (EXAFS) spectra) and the simultaneous decrease in the symmetry of the ruthenium complex, with the ruthenium remaining mononuclear and its oxidation state remaining essentially unchanged (as shown by EXAFS and X-ray absorption near-edge structure spectra). The removal of anionic acac ligands from the ruthenium was evidently compensated by the bonding of other anionic ligands, such as hydride from H2 in the feed stream, to form species suggested to be Ru(H)(C{sub 2}H{sub 4}){sub 2}{sup +}, which is coordinatively unsaturated and inferred to react with ethene, leading to the observed formation of butene in a catalytic process.

  6. Band Offsets of a Ruthenium Gate on Ultrathin High-k Oxide Films on Silicon

    SciTech Connect

    Rangan, S.; Bersch, W; Bartynski, R; Garfunkel, E; Vescovo, E

    2009-01-01

    Valence-band and conduction-band edges of ultrathin oxides and their shifts upon sequential metallization with ruthenium have been measured using synchrotron-radiation-excited x-ray, ultraviolet, and inverse photoemissions. From these techniques, the offsets between the valence-band and conduction-band edges of the oxides, and the ruthenium metal gate Fermi edge have been directly measured. In addition the core levels of the oxides and the ruthenium have been characterized. Upon deposition, Ru remains metallic and no chemical alteration of the underlying oxide gates, or interfacial SiO{sub 2} in the case of the high-? thin films, can be detected. However a clear shift of the band edges is measured for all samples due to the creation of an interface dipole at the ruthenium-oxide interface. Using the energy gap, the electron affinity of the oxides, and the ruthenium work function that have been directly measured on these samples, the experimental band offsets are compared to those predicted by the induced gap states model.

  7. Sol gel synthesis of hydrous ruthenium oxide nanonetworks from 1,2-epoxides

    NASA Astrophysics Data System (ADS)

    Walker, Jeremy; Bruce King, R.; Tannenbaum, Rina

    2007-08-01

    Hydrous ruthenium oxide (RuO 2· xH 2O) xerogels were synthesized through the addition of a 1,2-epoxide, propylene oxide, to commercial hydrated ruthenium chloride, "RuCl 3· xH 2O," in ethanol. After a blue-black monolithic gel formed in 4 h, the samples were allowed to age for 24 h and were dried in ambient conditions. The dried samples were then characterized by XPS, XRD, DTA and TGA. XPS showed the Ru(3 d5/2) peak at a binding energy of 281.7 eV, corresponding to that of hydrous ruthenium oxide. XRD data revealed the synthesized material as amorphous. Heating the sample in inert atmospheres caused the complete reduction of the oxide to the zero-valent state, whereas heating the sample in air resulted in both crystalline anhydrous RuO 2 and zero-valent ruthenium, depending on the method of heating. DTA traces showed an endotherm ending at 150 °C, corresponding to the loss of coordinated water, as well as two higher temperature crystallization exotherms when the sample was heated in both inert and oxygen-rich atmospheres. TGA runs also confirmed the complete reduction of the hydrous oxide when heated in nitrogen below 270 °C and the formation of anhydrous ruthenium oxide when heated in air, confirming the XRD results.

  8. Metal-metal interactions in linear tri-, penta-, hepta-, and nona-nuclear ruthenium string complexes.

    PubMed

    Niskanen, Mika; Hirva, Pipsa; Haukka, Matti

    2012-05-01

    Density functional theory (DFT) methodology was used to examine the structural properties of linear metal string complexes: [Ru(3)(dpa)(4)X(2)] (X = Cl(-), CN(-), NCS(-), dpa = dipyridylamine(-)), [Ru(5)(tpda)(4)Cl(2)], and hypothetical, not yet synthesized complexes [Ru(7)(tpta)(4)Cl(2)] and [Ru(9)(ppta)(4)Cl(2)] (tpda = tri-α-pyridyldiamine(2-), tpta = tetra-α-pyridyltriamine(3-), ppta = penta-α-pyridyltetraamine(4-)). Our specific focus was on the two longest structures and on comparison of the string complexes and unsupported ruthenium backboned chain complexes, which have weaker ruthenium-ruthenium interactions. The electronic structures were studied with the aid of visualized frontier molecular orbitals, and Bader's quantum theory of atoms in molecules (QTAIM) was used to study the interactions between ruthenium atoms. The electron density was found to be highest and distributed most evenly between the ruthenium atoms in the hypothetical [Ru(7)(tpta)(4)Cl(2)] and [Ru(9)(ppta)(4)Cl(2)] string complexes.

  9. Pulsed Laser Deposition of Nanoporous Cobalt Thin Films

    PubMed Central

    Jin, Chunming; Nori, Sudhakar; Wei, Wei; Aggarwal, Ravi; Kumar, Dhananjay; Narayan, Roger J.

    2013-01-01

    Nanoporous cobalt thin films were deposited on anodized aluminum oxide (AAO) membranes at room temperature using pulsed laser deposition. Scanning electron microscopy demonstrated that the nanoporous cobalt thin films retained the monodisperse pore size and high porosity of the anodized aluminum oxide substrates. Temperature- and field-dependent magnetic data obtained between 10 K and 350 K showed large hysteresis behavior in these materials. The increase of coercivity values was larger for nanoporous cobalt thin films than for multilayered cobalt/alumina thin films. The average diameter of the cobalt nanograins in the nanoporous cobalt thin films was estimated to be ~5 nm for blocking temperatures near room temperature. These results suggest that pulsed laser deposition may be used to fabricate nanoporous magnetic materials with unusual properties for biosensing, drug delivery, data storage, and other technological applications. PMID:19198344

  10. Cobalt metabolism and toxicology--a brief update.

    PubMed

    Simonsen, Lars Ole; Harbak, Henrik; Bennekou, Poul

    2012-08-15

    Cobalt metabolism and toxicology are summarized. The biological functions of cobalt are updated in the light of recent understanding of cobalt interference with the sensing in almost all animal cells of oxygen deficiency (hypoxia). Cobalt (Co(2+)) stabilizes the transcriptional activator hypoxia-inducible factor (HIF) and thus mimics hypoxia and stimulates erythropoietin (Epo) production, but probably also by the same mechanism induces a coordinated up-regulation of a number of adaptive responses to hypoxia, many with potential carcinogenic effects. This means on the other hand that cobalt (Co(2+)) also may have beneficial effects under conditions of tissue hypoxia, and possibly can represent an alternative to hypoxic preconditioning. Cobalt is acutely toxic in larger doses, and in mammalian in vitro test systems cobalt ions and cobalt metal are cytotoxic and induce apoptosis and at higher concentrations necrosis with inflammatory response. Cobalt metal and salts are also genotoxic, mainly caused by oxidative DNA damage by reactive oxygen species, perhaps combined with inhibition of DNA repair. Of note, the evidence for carcinogenicity of cobalt metal and cobalt sulfate is considered sufficient in experimental animals, but is as yet considered inadequate in humans. Interestingly, some of the toxic effects of cobalt (Co(2+)) have recently been proposed to be due to putative inhibition of Ca(2+) entry and Ca(2+)-signaling and competition with Ca(2+) for intracellular Ca(2+)-binding proteins. The tissue partitioning of cobalt (Co(2+)) and its time-dependence after administration of a single dose have been studied in man, but mainly in laboratory animals. Cobalt is accumulated primarily in liver, kidney, pancreas, and heart, with the relative content in skeleton and skeletal muscle increasing with time after cobalt administration. In man the renal excretion is initially rapid but decreasing over the first days, followed by a second, slow phase lasting several weeks

  11. 21 CFR 189.120 - Cobaltous salts and its derivatives.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 21 Food and Drugs 3 2011-04-01 2011-04-01 false Cobaltous salts and its derivatives. 189.120... Generally Prohibited From Direct Addition or Use as Human Food § 189.120 Cobaltous salts and its derivatives. (a) Cobaltous salts are the chemicals, CoC4H6O4, CoCl2, and CoSO4.They have been used in...

  12. 21 CFR 189.120 - Cobaltous salts and its derivatives.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Cobaltous salts and its derivatives. 189.120... Generally Prohibited From Direct Addition or Use as Human Food § 189.120 Cobaltous salts and its derivatives. (a) Cobaltous salts are the chemicals, CoC4H6O4, CoCl2, and CoSO4.They have been used in...

  13. 21 CFR 189.120 - Cobaltous salts and its derivatives.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... 21 Food and Drugs 3 2012-04-01 2012-04-01 false Cobaltous salts and its derivatives. 189.120... Generally Prohibited From Direct Addition or Use as Human Food § 189.120 Cobaltous salts and its derivatives. (a) Cobaltous salts are the chemicals, CoC4H6O4, CoCl2, and CoSO4.They have been used in...

  14. 21 CFR 189.120 - Cobaltous salts and its derivatives.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... 21 Food and Drugs 3 2013-04-01 2013-04-01 false Cobaltous salts and its derivatives. 189.120... Generally Prohibited From Direct Addition or Use as Human Food § 189.120 Cobaltous salts and its derivatives. (a) Cobaltous salts are the chemicals, CoC4H6O4, CoCl2, and CoSO4.They have been used in...

  15. Creep-fatigue of low cobalt superalloys

    NASA Technical Reports Server (NTRS)

    Halford, G. R.

    1982-01-01

    Testing for the low cycle fatigue and creep fatigue resistance of superalloys containing reduced amounts of cobalt is described. The test matrix employed involves a single high temperature appropriate for each alloy. A single total strain range, again appropriate to each alloy, is used in conducting strain controlled, low cycle, creep fatigue tests. The total strain range is based upon the level of straining that results in about 10,000 cycles to failure in a high frequency (0.5 Hz) continuous strain-cycling fatigue test. No creep is expected to occur in such a test. To bracket the influence of creep on the cyclic strain resistance, strain hold time tests with ore minute hold periods are introduced. One test per composition is conducted with the hold period in tension only, one in compression only, and one in both tension and compression. The test temperatures, alloys, and their cobalt compositions that are under study are given.

  16. Gamma europium- and cobalt-sources

    SciTech Connect

    Klochkov, E.P.; Risovany, V.D.; Ponomarenko, B.V.

    1993-12-31

    The double-purpose control rods of nuclear reactors were made in which the inserts containing cobalt and europium oxide with natural {sup 151}Eu and {sup 153}Eu content were used as an absorbing core. The mass content of europium oxide is to exceed 15% to provide for a necessary reactivity. Cobalt and europium radionuclides were shown to be accumulated during the reactor operation allowing the inserts to be used as gamma sources after unloading of control rods at large commercial plants for radiation processing of different materials. Shape, geometry and composition of inserts were optimized allowing their specific activity to be obtained above 2 x 10 Bq/g (about 60 Ci/g). The spectral activity and radiation resistance of gamma sources were studied.

  17. Cobalt contraction of vascular smooth muscle

    SciTech Connect

    Dominiczak, A.; Clyde, E.; Bohr, D. )

    1991-03-11

    Although it has been reported that cobalt causes contraction of vascular smooth muscle, the mechanism responsible for this contraction has not been defined. The authors studied these contractions in rat aortic rings. Concentration-response studies indicated that the threshold for contraction was 10{sup {minus}8}M, maximum contraction occurred at 3 {times} 10{sup 7}M and relaxation began at 10{sup {minus}6}M. No contraction occurred in a calcium-free physiological salt solution and the contraction was not inhibited by H-7, a protein kinase C inhibitor. The authors conclude the cobalt in low concentrations causes contraction by activating calcium channels and that in high concentrations it causes relaxation by inactivating these same channels.

  18. Are cobaltates conventional? An ARPES viewpoint

    SciTech Connect

    Hasan, M.Z. . E-mail: mzhasan@Princeton.edu; Qian, D.; Foo, M.L.; Cava, R.J.

    2006-07-15

    Recently discovered class of cobaltate superconductors (Na{sub 0.3}CoO{sub 2}.nH{sub 2}O) is a novel realization of interacting quantum electron system in a triangular network with low-energy degrees of freedom. We employ angle-resolved photoemission spectroscopy to study the quasiparticle parameters in the parent superconductors. Results reveal a large hole-like Fermi surface generated by the crossing of heavy quasiparticles. The measured quasiparticle parameters collectively suggest two orders of magnitude departure from the conventional weak coupling (such as Al) Bardeen-Cooper-Schrieffer electron dynamics paradigm and unveils cobaltates as a rather hidden class of relatively high temperature superconductors. These parameters also form the basis for a microscopic Hamiltonian of the system.

  19. High-Spin Cobalt Hydrides for Catalysis

    SciTech Connect

    Holland, Patrick L.

    2013-08-29

    Organometallic chemists have traditionally used catalysts with strong-field ligands that give low-spin complexes. However, complexes with a weak ligand field have weaker bonds and lower barriers to geometric changes, suggesting that they may lead to more rapid catalytic reactions. Developing our understanding of high-spin complexes requires the use of a broader range of spectroscopic techniques, but has the promise of changing the mechanism and/or selectivity of known catalytic reactions. These changes may enable the more efficient utilization of chemical resources. A special advantage of cobalt and iron catalysts is that the metals are more abundant and cheaper than those currently used for major industrial processes that convert unsaturated organic molecules and biofeedstocks into useful chemicals. This project specifically evaluated the potential of high-spin cobalt complexes for small-molecule reactions for bond rearrangement and cleavage reactions relevant to hydrocarbon transformations. We have learned that many of these reactions proceed through crossing to different spin states: for example, high-spin complexes can flip one electron spin to access a lower-energy reaction pathway for beta-hydride elimination. This reaction enables new, selective olefin isomerization catalysis. The high-spin cobalt complexes also cleave the C-O bond of CO2 and the C-F bonds of fluoroarenes. In each case, the detailed mechanism of the reaction has been determined. Importantly, we have discovered that the cobalt catalysts described here give distinctive selectivities that are better than known catalysts. These selectivities come from a synergy between supporting ligand design and electronic control of the spin-state crossing in the reactions.

  20. Cobalt Complexes as Antiviral and Antibacterial Agents

    DTIC Science & Technology

    2010-01-01

    keratitis, one of the major causes of blindness in industrial nations [9]. Studies using the CTC class of drugs were performed using a rabbit eye model...CTC-96 inhibits membrane fusion events preventing virus entry, CTC-96 inhibited plaque formation by VSV (vesicular stomatitis virus) and VZV...antibacterial properties of cobalt complexes have appeared in the literature, with Co(II) complexes being the most studied , presumably due to their

  1. Cobalt Ions Improve the Strength of Epoxy Resins

    NASA Technical Reports Server (NTRS)

    Stoakley, D. M.; St. Clair, A. K.

    1986-01-01

    Technique developed for improving mechanical strength of epoxy resins by adding cobalt ions in form of tris(acetylacetonato)cobalt (III) complex. Solid cast disks prepared from cobalt ion-containing epoxy resins tested for flexural strength and stiffness. Incorporation of cobalt ions into epoxies increased flexural strength of resins by 10 to 95 percent. Suitable resins for this technique include any liquid or solid TGMDA resins. Improved epoxy formulation proves useful as composite matrix resin, adhesive, or casting resin for applications on commercial and advanced aircraft.

  2. Update on the genotoxicity and carcinogenicity of cobalt compounds

    PubMed Central

    Lison, D; De Boeck, M; Verougstraete, V; Kirsch-Volders, M

    2001-01-01

    OBJECTIVE—To integrate recent understandings of the mechanisms of genotoxicity and carcinogenicity of the different cobalt compounds.
METHOD—A narrative review of the studies published since the last IARC assessment in 1991 (genotoxicity, experimental carcinogenesis, and epidemiology).
RESULTS—Two different mechanisms of genotoxicity, DNA breakage induced by cobalt metal and especially hard metal particles, and inhibition of DNA repair by cobalt (II) ions contribute to the carcinogenic potential of cobalt compounds. There is evidence that soluble cobalt (II) cations exert a genotoxic and carcinogenic activity in vitro and in vivo in experimental systems but evidence in humans is lacking. Experimental data indicate some evidence of a genotoxic potential for cobalt metal in vitro in human lymphocytes but there is no evidence available of a carcinogenic potential. There is evidence that hard metal particles exert a genotoxic and carcinogenic activity in vitro and in human studies, respectively. There is insufficient information for cobalt oxides and other compounds.
CONCLUSION—Although many areas of uncertainty remain, an assessment of the carcinogenicity of cobalt and its compounds requires a clear distinction between the different compounds of the element and needs to take into account the different mechanisms involved.


Keywords: cobalt; DNA breakage; inhibition of DNA repair PMID:11555681

  3. Highly efficient and robust molecular ruthenium catalysts for water oxidation.

    PubMed

    Duan, Lele; Araujo, Carlos Moyses; Ahlquist, Mårten S G; Sun, Licheng

    2012-09-25

    Water oxidation catalysts are essential components of light-driven water splitting systems, which could convert water to H(2) driven by solar radiation (H(2)O + hν → 1/2O(2) + H(2)). The oxidation of water (H(2)O → 1/2O(2) + 2H(+) + 2e(-)) provides protons and electrons for the production of dihydrogen (2H(+) + 2e(-) → H(2)), a clean-burning and high-capacity energy carrier. One of the obstacles now is the lack of effective and robust water oxidation catalysts. Aiming at developing robust molecular Ru-bda (H(2)bda = 2,2'-bipyridine-6,6'-dicarboxylic acid) water oxidation catalysts, we carried out density functional theory studies, correlated the robustness of catalysts against hydration with the highest occupied molecular orbital levels of a set of ligands, and successfully directed the synthesis of robust Ru-bda water oxidation catalysts. A series of mononuclear ruthenium complexes [Ru(bda)L(2)] (L = pyridazine, pyrimidine, and phthalazine) were subsequently synthesized and shown to effectively catalyze Ce(IV)-driven [Ce(IV) = Ce(NH(4))(2)(NO(3))(6)] water oxidation with high oxygen production rates up to 286 s(-1) and high turnover numbers up to 55,400.

  4. Sweetening ruthenium and osmium: organometallic arene complexes containing aspartame.

    PubMed

    Gray, Jennifer C; Habtemariam, Abraha; Winnig, Marcel; Meyerhof, Wolfgang; Sadler, Peter J

    2008-09-01

    The novel organometallic sandwich complexes [(eta(6)-p-cymene)Ru(eta(6)-aspartame)](OTf)(2) (1) (OTf = trifluoromethanesulfonate) and [(eta(6)-p-cymene)Os(eta(6)-aspartame)](OTf)(2) (2) incorporating the artificial sweetener aspartame have been synthesised and characterised. A number of properties of aspartame were found to be altered on binding to either metal. The pK(a) values of both the carboxyl and the amino groups of aspartame are lowered by between 0.35 and 0.57 pH units, causing partial deprotonation of the amino group at pH 7.4 (physiological pH). The rate of degradation of aspartame to 3,6-dioxo-5-phenylmethylpiperazine acetic acid (diketopiperazine) increased over threefold from 0.12 to 0.36 h(-1) for 1, and to 0.43 h(-1) for 2. Furthermore, the reduction potential of the ligand shifted from -1.133 to -0.619 V for 2. For the ruthenium complex 1 the process occurred in two steps, the first (at -0.38 V) within a biologically accessible range. This facilitates reactions with biological reductants such as ascorbate. Binding to and activation of the sweet taste receptor was not observed for these metal complexes up to concentrations of 1 mM. The factors which affect the ability of metal-bound aspartame to interact with the receptor site are discussed.

  5. Highly efficient and robust molecular ruthenium catalysts for water oxidation

    PubMed Central

    Duan, Lele; Araujo, Carlos Moyses; Ahlquist, Mårten S.G.; Sun, Licheng

    2012-01-01

    Water oxidation catalysts are essential components of light-driven water splitting systems, which could convert water to H2 driven by solar radiation (H2O + hν → 1/2O2 + H2). The oxidation of water (H2O → 1/2O2 + 2H+ + 2e-) provides protons and electrons for the production of dihydrogen (2H+ + 2e- → H2), a clean-burning and high-capacity energy carrier. One of the obstacles now is the lack of effective and robust water oxidation catalysts. Aiming at developing robust molecular Ru-bda (H2bda = 2,2′-bipyridine-6,6′-dicarboxylic acid) water oxidation catalysts, we carried out density functional theory studies, correlated the robustness of catalysts against hydration with the highest occupied molecular orbital levels of a set of ligands, and successfully directed the synthesis of robust Ru-bda water oxidation catalysts. A series of mononuclear ruthenium complexes [Ru(bda)L2] (L = pyridazine, pyrimidine, and phthalazine) were subsequently synthesized and shown to effectively catalyze CeIV-driven [CeIV = Ce(NH4)2(NO3)6] water oxidation with high oxygen production rates up to 286 s-1 and high turnover numbers up to 55,400. PMID:22753518

  6. Homobimetallic Ruthenium-N-Heterocyclic Carbene Complexes For Olefin Metathesis

    NASA Astrophysics Data System (ADS)

    Sauvage, Xavier; Demonceau, Albert; Delaude, Lionel

    In this chapter, the synthesis and catalytic activity towards olefin metathesis of homobimetallic ruthenium (Ru)-alkylidene, -cyclodiene or -arene complexes bearing phosphine or N-heterocyclic carbene (NHC) ligands are reviewed. Emphasis is placed on the last category of bimetallic compounds. Three representatives of this new type of molecular scaffold were investigated. Thus, [(p-cymene)Ru(m-Cl)3RuCl (h2-C2H4)(L)] complexes with L = PCy3 (15a), IMes (16a), or IMesCl2 (16b) were prepared. They served as catalyst precursors for cross-metathesis (CM) of various styrene derivatives. These experiments revealed the outstanding aptitude of complex 16a (and to a lesser extent of 16b) to catalyze olefin metathesis reactions. Contrary to monometallic Ru-arene complexes of the [RuCl2(p-cymene)(L)] type, the new homobimetallic species did not require the addition of a diazo compound nor visible light illumination to initiate the ring-opening metathesis of norbornene or cyclooctene. When diethyl 2,2-diallylmalonate and N,N-diallyltosylamide were exposed to 16a,b, a mixture of cycloisomerization and ring-closing metathesis (RCM) products was obtained in a nonselective way. Addition of phenylacetylene enhanced the metathetical activity while completely repressing the cycloisomerization process.

  7. Coordination of dibensothiophenes and corannulenes to organometallic ruthenium (II) fragments

    SciTech Connect

    Vecchi, Paul Anthony

    2005-01-01

    This dissertation contains five papers in the format required for journal publication which describe (in part) my research accomplishments as a graduate student at Iowa State University. This work can be broadly categorized as the binding of weakly-coordinating ligands to cationic organometallic ruthenium fragments, and consists of two main areas of study. Chapters 2-4 are investigations into factors that influence the binding of dibenzothiophenes to [Cp'Ru(CO)2(+ fragments, where Cp' = η5-C5H5 (Cp) and η5-C5Me5 (Cp*). Chapters 5 and 6 present the synthesis and structural characterization of complexes containing corannulene buckybowls that are η6-coordinated to [Cp*Ru(+ fragments. The first chapter contains a brief description of the difficulty in lowering sulfur levels in diesel fuel along with a review of corannulene derivatives and their metal complexes. After the final paper is a short summary of the work herein (Chapter 7). Each chapter is independent, and all equations, schemes, figures, tables, references, and appendices in this dissertation pertain only to the chapter in which they appear.

  8. Diverse ruthenium nitrides stabilized under pressure: a theoretical prediction

    PubMed Central

    Zhang, Yunkun; Wu, Lailei; Wan, Biao; Lin, Yangzheng; Hu, Qingyang; Zhao, Yan; Gao, Rui; Li, Zhiping; Zhang, Jingwu; Gou, Huiyang

    2016-01-01

    First-principles calculations were performed to understand the structural stability, synthesis routes, mechanical and electronic properties of diverse ruthenium nitrides. RuN with a new I-4m2 symmetry stabilized by pressure is found to be energetically preferred over the experimental NaCl-type and ZnS-type ones. The Pnnm-RuN2 is found to be stable above 1.1 GPa, in agreement with the experimental results. Specifically, new stoichiometries like RuN3 and RuN4 are proposed firstly to be thermodynamically stable, and the dynamical and mechanical stabilities of the newly predicted structures have been verified by checking their phonon spectra and elastic constants. A phase transition from P4/mmm-RuN4 to C2/c-RuN4 is also uncovered at 23.0 GPa. Drawn from bonding and band structure analysis, P4/mmm-RuN4 exhibits semi-metal-like behavior and becomes a semiconductor for the high-pressure C2/c-RuN4 phase. Meanwhile the P21/c-RuN3 shows metallic feature. Highly directional covalent N-N and Ru-N bonds are formed and dominating in N-enriched Ru nitrides, making them promising hard materials. PMID:27627856

  9. Ruthenium oxide modified nickel electrode for ascorbic acid detection.

    PubMed

    Lee, Yuan-Gee; Liao, Bo-Xuan; Weng, Yu-Ching

    2017-04-01

    Electrodes of ruthenium oxide modified nickel were prepared by a thermal decomposition method. The stoichiometry of the modifier, RuOx, was quantitatively determined to be a meta-stable phase, RuO5. The electrodes were employed to sense ascorbic acid in alkaline solution with a high sensitivity, 296 μAcm(-2) mM(-1), and good selectivity for eight kinds of disturbing reagents. We found that the ascorbic acid was oxidized irreversibly in solution. To match with the variation of the morphology, the sensitivity reached a maximum when the RuOx segregated with a nano-crystalline feature. We find that the substrate oxidized as the deposited RuOx grew thicker. The feature of the deposited RuOx changed from nano-particles to small islands resulting from the wetting effect of the substrate oxide, NiO; meanwhile the sensitivity decreased dramatically. The endurance of the RuOx/Ni electrode also showed a good performance after 38 days of successive test.

  10. Ruthenium olefin metathesis catalysts featuring unsymmetrical N-heterocyclic carbenes.

    PubMed

    Paradiso, Veronica; Bertolasi, Valerio; Costabile, Chiara; Grisi, Fabia

    2016-01-14

    New ruthenium Grubbs' and Hoveyda-Grubbs' second generation catalysts bearing N-alkyl/N-isopropylphenyl N-heterocyclic carbene (NHC) ligands with syn or anti backbone configuration were obtained and compared in model olefin metathesis reactions. Different catalytic efficiencies were observed depending on the size of the N-alkyl group (methyl or cyclohexyl) and on the backbone configuration. The presence of an N-cyclohexyl substituent determined the most significant reactivity differences between catalysts with syn or anti phenyl groups on the backbone. In particular, anti catalysts proved highly efficient, especially in the ring-closing metathesis (RCM) of encumbered diolefins, while syn catalysts showed low efficiency in the RCM of less hindered diolefins. This peculiar behavior, rationalized through DFT studies, was found to be related to the high propensity of these catalysts to give nonproductive metathesis events. Enantiopure anti catalysts were also tested in asymmetric metathesis reactions, where moderate enantioselectivities were observed. The steric and electronic properties of unsymmetrical NHCs with the N-cyclohexyl group were then evaluated using the corresponding rhodium complexes. While steric factors proved unimportant for both syn and anti NHCs, a major electron-donating character was found for the unsymmetrical NHC with anti phenyl substituents on the backbone.

  11. Water oxidation by Ruthenium complexes incorporating multifunctional biipyridyl diphosphonate ligands

    DOE PAGES

    Xie, Yan; Shaffer, David W.; Lewandowska-Andralojc, Anna; ...

    2016-05-11

    Here, we describe herein the synthesis and characterization of ruthenium complexes with multifunctional bipyridyl diphosphonate ligands as well as initial water oxidation studies. In these complexes, the phosphonate groups provide redox-potential leveling through charge compensation and σ donation to allow facile access to high oxidation states. These complexes display unique pH-dependent electrochemistry associated with deprotonation of the phosphonic acid groups. The position of these groups allows them to shuttle protons in and out of the catalytic site and reduce activation barriers. A mechanism for water oxidation by these catalysts is proposed on the basis of experimental results and DFT calculations.more » The unprecedented attack of water at a neutral six-coordinate [RuIV] center to yield an anionic seven-coordinate [RuIV–OH]– intermediate is one of the key steps of a single-site mechanism in which all species are anionic or neutral. These complexes are among the fastest single-site catalysts reported to date.« less

  12. Water oxidation by Ruthenium complexes incorporating multifunctional biipyridyl diphosphonate ligands

    SciTech Connect

    Xie, Yan; Shaffer, David W.; Lewandowska-Andralojc, Anna; Szalda, David J.; Concepcion, Javier J.

    2016-05-11

    Here, we describe herein the synthesis and characterization of ruthenium complexes with multifunctional bipyridyl diphosphonate ligands as well as initial water oxidation studies. In these complexes, the phosphonate groups provide redox-potential leveling through charge compensation and σ donation to allow facile access to high oxidation states. These complexes display unique pH-dependent electrochemistry associated with deprotonation of the phosphonic acid groups. The position of these groups allows them to shuttle protons in and out of the catalytic site and reduce activation barriers. A mechanism for water oxidation by these catalysts is proposed on the basis of experimental results and DFT calculations. The unprecedented attack of water at a neutral six-coordinate [RuIV] center to yield an anionic seven-coordinate [RuIV–OH] intermediate is one of the key steps of a single-site mechanism in which all species are anionic or neutral. These complexes are among the fastest single-site catalysts reported to date.

  13. Conduction electron g-factors in ruthenium and osmium from de Haas-van Alphen measurements

    NASA Astrophysics Data System (ADS)

    Startsev, V. E.; Coleridge, P. T.; Templeton, I. M.; Fawcett, E.; Muir, C.; Perz, J. M.

    1984-04-01

    Conduction electron g-factors have been deduced from de Haas-van Alphen line shapes in the hexagonal group VIII 4 d transition metal ruthenium and the electronically analogous 5 d metal osmium. The values for orbits normal to [0001] are 1.8±0.1 and 1.3±0.1 for the ellipsoids centered on the line LM in ruthenium and osmium, respectively, and 1.9±0.2 for the Γ-centered ellipsoid in ruthenium. The more marked suppression of the g-factor in osmium, where spin-orbit coupling is stronger, is consistent with recent theoretical studies of transition metal g-factor trends.

  14. Nonlinear optics and surface relief gratings in alkynyl-ruthenium complexes

    NASA Astrophysics Data System (ADS)

    Sahraoui, B.; Luc, J.; Meghea, A.; Czaplicki, R.; Fillaut, J.-L.; Migalska-Zalas, A.

    2009-02-01

    Generally, the organometallic complexes rich in carbon and containing π-conjugated chains are materials interesting for the study of electronic transfer processes. Currently, the ruthenium-acetylide organometallic complexes form part of the most studied organometallic compounds in nonlinear optics. In this work, we highlight the nonlinear optical properties and the photo-induced structure of new organometallic complexes containing a ruthenium-acetylide donor fragment able to compete with the strongest organic donors. We determine, using various experimental techniques (degenerate four-wave mixing, second and third harmonic generation), the influence of the functionalization of these molecular structures on the improvement of their second-and third-order nonlinear optical properties exploiting in particular the nature of the acceptor fragment and the π-conjugated transmitter. Also we present the dynamics of formation of photo-induced surface relief gratings using a transmission holographic technique and the atomic force microscopy on ruthenium-acetylide complexes containing an azobenzene fragment.

  15. TCP suppression in a ruthenium-bearing single-crystal nickel-based superalloy

    NASA Astrophysics Data System (ADS)

    Hobbs, R. A.; Zhang, L.; Rae, C. M. F.; Tin, S.

    2008-07-01

    Ruthenium suppresses the precipitation of deleterious topologically close-packed (TCP) phases in high refractory content single-crystal nickel-based superalloys. The effectiveness of ruthenium as a TCP suppressant appears to be the net effect of its limited solubility in the TCP phase, a lower density of structural growth ledges for atomic attachment at the TCP/matrix interface, and destabilization of the γ' phase at elevated temperatures. These characteristics combine to limit the growth rates of TCP precipitates and decrease the driving force for their precipitation. Destabilization of the γ' phase upon the addition of ruthenium is particularly potent due to the sensitivity of the rhenium content in the γ matrix to changes in the γ' volume fraction.

  16. Is matching ruthenium with dithiocarbamato ligands a potent chemotherapeutic weapon in oncology?

    PubMed

    Nardon, Chiara; Brustolin, Leonardo; Fregona, Dolores

    2016-01-01

    In the last years, several metal-based compounds have been designed and biologically investigated worldwide in order to obtain chemotherapeutics with a better toxicological profile and comparable or higher antiblastic activity than the clinically-established platinum-based drugs. In this context, researchers have addressed their attention to alternative nonplatinum derivatives able to maximize the anticancer activity of the new drugs and to minimize the side effects. Among them, a number of ruthenium complexes have been developed, including the compounds NAMI-A and KP1019, now in clinical trials. Here, we report the results collected so far for a particular class of ruthenium complexes - the ruthenium(II/III)-dithiocarbamates - which proved more potent than cisplatin in vitro, even at nanomolar concentrations, against a wide panel of human tumor cell lines.

  17. Hydrodefluorination of carbon-fluorine bonds by the synergistic action of a ruthenium-palladium catalyst.

    PubMed

    Sabater, Sara; Mata, Jose A; Peris, Eduardo

    2013-01-01

    Catalytic hydrodefluorination of organic molecules is a major organometallic challenge, owing to the strength of C-F sigma bonds, and it is a process with multiple industrial applications. Here we report a new heterodimetallic ruthenium-palladium complex based on a triazolyl-di-ylidene ligand. The complex is remarkably active in the hydrodefluorination of aromatic and aliphatic carbon-fluorine bonds under mild reaction conditions. We observe that both metals are required to promote the reaction process. The overall process implies that the palladium fragment facilitates the C-F activation, whereas the ruthenium centre allows the reduction of the substrate via transfer hydrogenation from isopropanol/sodium t-butoxide. The activity of this heterodimetallic complex is higher than that shown by a mixture of the related homodimetallic complexes of ruthenium and palladium, demonstrating the catalytic benefits of the heterodimetallic complex linked by a single-frame ligand.

  18. Rigid 5'-6-locked phenanthroline-derived nucleosides chelated to ruthenium and europium ions.

    PubMed

    Gislason, Kristmann; Sigurdsson, Snorri Th

    2013-01-01

    We describe complexes of ruthenium and europium with rigid, 5'-6-locked 1,10-phenanthroline-containing nucleosides. Both nucleosides were synthesized from condensation of 5-amino-2'-deoxycytidine with the corresponding diketone. The ruthenium nucleoside displayed fluorescence characteristic of polypyridine ruthenium complexes with a maximum at 616 nm and a quantum yield of 0.011. Binding of europium to the 1,10-phenanthroline-2,9-diacid moiety of the lanthanide binding nucleoside showed formation of a 1:1 complex with emission at 570-630 nm, whose emission was enhanced by addition of two phenanthroline ligands. The lanthanide-binding nucleoside was incorporated into DNA oligonucleotides and shown to selectively bind one equivalent of europium ions.

  19. Development of a Method for the Preparation of Ruthenium Indenylidene-Ether Olefin Metathesis Catalysts

    PubMed Central

    Jimenez, Leonel R.; Tolentino, Daniel R.; Gallon, Benjamin J.; Schrodi, Yann

    2012-01-01

    The reactions between several derivatives of 1-(3,5-dimethoxyphenyl)-prop-2-yn-1-ol and different ruthenium starting materials [i.e., RuCl2(PPh3)3 and RuCl2(pcymene)(L), where L is tricyclohexylphosphine di-t-butylmethylphosphine, dicyclohexylphenylphosphine, triisobutylphosphine, triisopropylphosphine, or tri-npropylphosphine] are described. Several of these reactions allow for the easy, in-situ and atom-economic preparation of olefin metathesis catalysts. Organic precursor 1-(3,5-dimethoxyphenyl)-1-phenyl-prop-2-yn-1-ol led to the formation of active ruthenium indenylidene-ether complexes, while 1-(3,5-dimethoxyphenyl)-prop-2-yn-1-ol and 1-(3,5-dimethoxyphenyl)-1-methyl-prop-2-yn-1-ol did not. It was also found that a bulky and strong σ-donor phosphine ligand was required to impart good catalytic activity to the new ruthenium complexes. PMID:22580400

  20. Hot corrosion of low cobalt alloys

    NASA Technical Reports Server (NTRS)

    Stearns, C. A.

    1982-01-01

    The hot corrosion attack susceptibility of various alloys as a function of strategic materials content are investigated. Preliminary results were obtained for two commercial alloys, UDIMET 700 and Mar-M 247, that were modified by varying the cobalt content. For both alloys the cobalt content was reduced in steps to zero. Nickel content was increased accordingly to make up for the reduced cobalt but all other constituents were held constant. Wedge bar test samples were produced by casting. The hot corrosion test consisted of cyclically exposing samples to the high velocity flow of combustion products from an air-fuel burner fueled with jet A-1 and seeded with a sodium chloride aqueous solution. The flow velocity was Mach 0.5 and the sodium level was maintained at 0.5 ppm in terms of fuel plus air. The test cycle consisted of holding the test samples at 900 C for 1 hour followed by 3 minutes in which the sample could cool to room temperature in an ambient temperature air stream.

  1. Dual-targeting organometallic ruthenium(II) anticancer complexes bearing EGFR-inhibiting 4-anilinoquinazoline ligands.

    PubMed

    Zhang, Yang; Zheng, Wei; Luo, Qun; Zhao, Yao; Zhang, Erlong; Liu, Suyan; Wang, Fuyi

    2015-08-07

    We have recently demonstrated that complexation with (η(6)-arene)Ru(II) fragments confers 4-anilinoquinazoline pharmacophores a higher potential for inducing cellular apoptosis while preserving the highly inhibitory activity of 4-anilinoquinazolines against EGFR and the reactivity of the ruthenium centre to 9-ethylguanine (Chem. Commun., 2013, 49, 10224-10226). Reported herein are the synthesis, characterisation and evaluation of the biological activity of a new series of ruthenium(ii) complexes of the type [(η(6)-arene)Ru(N,N-L)Cl]PF6 (arene = p-cymene, benzene, 2-phenylethanol or indane, L = 4-anilinoquinazolines). These organometallic ruthenium complexes undergo fast hydrolysis in aqueous solution. Intriguingly, the ligation of (arene)Ru(II) fragments with 4-anilinoquinazolines not only makes the target complexes excellent EGFR inhibitors, but also confers the complexes high affinity to bind to DNA minor grooves while maintaining their reactivity towards DNA bases, characterising them with dual-targeting properties. Molecular modelling studies reveal that the hydrolysis of these complexes is a favourable process which increases the affinity of the target complexes to bind to EGFR and DNA. In vitro biological activity assays show that most of this group of ruthenium complexes are selectively active inhibiting the EGF-stimulated growth of the HeLa cervical cancer cell line, and the most active complex [(η(6)-arene)Ru(N,N-L13)Cl]PF6 (, IC50 = 1.36 μM, = 4-(3'-chloro-4'-fluoroanilino)-6-(2-(2-aminoethyl)aminoethoxy)-7-methoxyquinazoline) is 29-fold more active than its analogue, [(η(6)-arene)Ru(N,N-ethylenediamine)Cl]PF6, and 21-fold more active than gefitinib, a well-known EGFR inhibitor in use clinically. These results highlight the strong promise to develop highly active ruthenium anticancer complexes by ligation of cytotoxic ruthenium pharmacophores with bioactive organic molecules.

  2. Ruthenium(III) catalyzed oxidation of sugar alcohols by dichloroisocyanuric acid—A kinetic study

    NASA Astrophysics Data System (ADS)

    Lakshman Kumar, Y.; Venkata Nadh, R.; Radhakrishnamurti, P. S.

    2016-02-01

    Kinetics of ruthenium(III) catalyzed oxidation of biologically important sugar alcohols (myo-inositol, D-sorbitol, and D-mannitol) by dichloroisocyanuric acid was carried out in aqueous acetic acid—perchloric medium. The reactions were found to be first order in case of oxidant and ruthenium(III). Zero order was observed with the concentrations of sorbitol and mannitol whereas, a positive fractional order was found in the case of inositol concentration. An inverse fractional order was observed with perchloric acid in oxidation of three substrates. Arrhenius parameters were calculated and a plausible mechanism was proposed.

  3. ECL performance of ruthenium tris-bipyridyl complexes covalently linked with phenothiazine through different bridge.

    PubMed

    Sun, Shiguo; Yang, Yang; Liu, Fengyu; Fan, Jiangli; Kehr, Jan; Sun, Licheng; Peng, Xiaojun

    2010-10-07

    Three ruthenium complexes 1a, 1b and 1c were synthesized, in which the phenothiazine moiety was covalently linked to the ruthenium complex through a 4 carbon chain and amide bond, respectively. The results demonstrate that one PTZ moiety is preferred to reach a good ECL performance, and the 4 carbon chain linked complex 1a exhibits the highest ECL enhancement (up to about 9 times), in comparison with the commonly utilized parent Ru(bpy)(3)(2+), permitting a lower detection limit of 1.0 x 10(-14) M with signal to noise of 3 for 20 mM DBAE at Au electrode.

  4. Biopolymer-supported ionic-liquid-phase ruthenium catalysts for olefin metathesis.

    PubMed

    Clousier, Nathalie; Filippi, Alexandra; Borré, Etienne; Guibal, Eric; Crévisy, Christophe; Caijo, Fréderic; Mauduit, Marc; Dez, Isabelle; Gaumont, Annie-Claude

    2014-04-01

    Original ruthenium supported ionic liquid phase (SILP) catalysts based on alginates as supports were developed for olefin metathesis reactions. The marine biopolymer, which fulfills most of the requisite properties for a support such as widespread abundance, insolubility in the majority of organic solvents, a high affinity for ionic liquids, high chemical stability, biodegradability, low cost, and easy processing, was impregnated by [bmim][PF6 ] containing an ionically tagged ruthenium catalyst. These biosourced catalysts show promising performances in ring-closing metathesis (RCM) and cross-metathesis (CM) reactions, with a high level of recyclability and reusability combined with a good reactivity.

  5. Proton-coupled electron transfer and multielectron oxidations in complexes of ruthenium and osmium

    SciTech Connect

    Dovletoglou, A.

    1992-01-01

    This doctoral research concerns the mechanism of proton-coupled electron transfer over an extended pH range. These processes between ruthenium and osmium complexes and hydroquinones have been studied using spectrophotometric methods and cyclic voltammetry. Elucidation of the mechanistic details has been attempted by using isotopic labelling, kinetic analysis, and numerical simulation of complex kinetic schemes. The coordination and redox chemistry of polypyridyl-acetylacetonato and -oxalato complexes of ruthenium and the role of ancillary ligands in defining the properties of Ru[sup IV]O complexes were explored. These studies represent the first attempt to probe possible 2e[sup [minus

  6. Enantiotopos-selective C-H oxygenation catalyzed by a supramolecular ruthenium complex.

    PubMed

    Frost, James R; Huber, Stefan M; Breitenlechner, Stefan; Bannwarth, Christoph; Bach, Thorsten

    2015-01-07

    Spirocyclic oxindoles undergo an enantioselective oxygenation reaction (nine examples; e.r. up to 97:3) upon catalysis by a chiral ruthenium porphyrin complex (1 mol %). The catalyst exhibits a lactam ring, which is responsible for substrate association through hydrogen bonds, and an active ruthenium center, which is in a defined spatial relationship to the oxygenation substrate. DFT calculations illustrate the perfect alignment of the active site with the reactive C-H bond and suggest--in line with the kinetic isotope effect--an oxygen rebound mechanism for the reaction.

  7. Bis(Cyclic Alkyl Amino Carbene) Ruthenium Complexes: A Versatile, Highly Efficient Tool for Olefin Metathesis.

    PubMed

    Gawin, Rafał; Kozakiewicz, Anna; Guńka, Piotr A; Dąbrowski, Paweł; Skowerski, Krzysztof

    2017-01-19

    The state-of-the-art in olefin metathesis is application of N-heterocyclic carbene (NHC)-containing ruthenium alkylidenes for the formation of internal C=C bonds and of cyclic alkyl amino carbene (CAAC)-containing ruthenium benzylidenes in the production of terminal olefins. A straightforward synthesis of bis(CAAC)Ru indenylidene complexes, which are highly effective in the formation of both terminal and internal C=C bonds at loadings as low as 1 ppm, is now reported.

  8. Selective ruthenium labeling of the tryptophan residue in the bee venom Peptide melittin.

    PubMed

    Perekalin, Dmitry S; Novikov, Valentin V; Pavlov, Alexander A; Ivanov, Igor A; Anisimova, Natalia Yu; Kopylov, Alexey N; Volkov, Dmitry S; Seregina, Irina F; Bolshov, Michail A; Kudinov, Alexander R

    2015-03-23

    Melittin is a membrane-active peptide from bee venom with promising antimicrobial and anticancer activity. Herein we report on a simple and selective method for labeling of the tryptophan residue in melittin by the organometallic fragment [(C5 H5 )Ru](+) in aqueous solution and in air. Ruthenium coordination does not disturb the secondary structure of the peptide (as verified by 2D NMR spectroscopy), but changes the pattern of its intermolecular interactions resulting in an 11-fold decrease of hemolytic activity. The high stability of the organometallic conjugate allowed the establishment of the biodistribution of the labeled melittin in mice by inductively coupled plasma MS analysis of ruthenium.

  9. Ruthenium(II)-catalyzed oxidative C-H alkenylations of sulfonic acids, sulfonyl chlorides and sulfonamides.

    PubMed

    Ma, Wenbo; Mei, Ruhuai; Tenti, Giammarco; Ackermann, Lutz

    2014-11-10

    Twofold C-H functionalization of aromatic sulfonic acids was achieved with an in situ generated ruthenium(II) catalyst. The optimized cross-dehydrogenative alkenylation protocol proved applicable to differently substituted arenes and a variety of alkenes, including vinyl arenes, sulfones, nitriles and ketones. The robustness of the ruthenium(II) catalyst was demonstrated by the chemoselective oxidative olefination of sulfonamides as well as sulfonyl chlorides. Mechanistic studies provided support for a reversible, acetate-assisted C-H ruthenation, along with a subsequent olefin insertion.

  10. Conductive polymers derived from iron, ruthenium, and osmium metalloporphyrins: The shish-kebab approach

    PubMed Central

    Collman, James P.; McDevitt, John T.; Yee, Gordon T.; Leidner, Charles R.; McCullough, Laughlin G.; Little, William A.; Torrance, Jerry B.

    1986-01-01

    The synthesis and characterization of pyrazine-bridged polymers of iron(II/III), ruthenium(II/III), and osmium(II/III) octaethylporphyrin (dubbed “shish-kebab” polymers) are presented. Optical and dc conductivity measurements reveal that the ruthenium and osmium polymers, when partially oxidized, are highly conductive. Electrochemical and ESR results are presented that indicate the existence of an interesting metal-centered conduction pathway. Unlike most of the previously reported porphyrinic molecular metals in which the conduction electrons are macrocyclic-based, electron transport in these materials proceeds exclusively along the metal-pyrazine backbone. PMID:16593717

  11. Bis(Cyclic Alkyl Amino Carbene) Ruthenium Complexes: A Versatile, Highly Efficient Tool for Olefin Metathesis

    PubMed Central

    Gawin, Rafał; Kozakiewicz, Anna; Guńka, Piotr A.; Dąbrowski, Paweł

    2016-01-01

    Abstract The state‐of‐the‐art in olefin metathesis is application of N‐heterocyclic carbene (NHC)‐containing ruthenium alkylidenes for the formation of internal C=C bonds and of cyclic alkyl amino carbene (CAAC)‐containing ruthenium benzylidenes in the production of terminal olefins. A straightforward synthesis of bis(CAAC)Ru indenylidene complexes, which are highly effective in the formation of both terminal and internal C=C bonds at loadings as low as 1 ppm, is now reported. PMID:27943616

  12. A ruthenium-based biomimetic hydrogen cluster for efficient photocatalytic hydrogen generation from formic acid.

    PubMed

    Chang, Chin-Hao; Chen, Mei-Hua; Du, Wan-Shan; Gliniak, Jacek; Lin, Jia-Hoa; Wu, Hsin-Hua; Chan, Hsin-Fang; Yu, Jen-Shiang K; Wu, Tung-Kung

    2015-04-20

    A ruthenium-based biomimetic hydrogen cluster, [Ru2 (CO)6 (μ-SCH2 CH2 CH2 S)] (1), has been synthesized and, in the presence of the P ligand tri(o-tolyl)phosphine, demonstrated efficient photocatalytic hydrogen generation from formic acid decomposition. Turnover frequencies (TOFs) of 5500 h(-1) and turnover numbers (TONs) over 24 700 were obtained with less than 50 ppm of the catalyst, thus representing the highest TOFs for ruthenium complexes as well as the best efficiency for photocatalytic hydrogen production from formic acid. Moreover, 1 showed high stability with no significant degradation of the photocatalyst observed after prolonged photoirradiation at 90 °C.

  13. Formation of C-C bonds via ruthenium-catalyzed transfer hydrogenation().

    PubMed

    Moran, Joseph; Krische, Michael J

    2012-01-01

    Ruthenium-catalyzed transfer hydrogenation of diverse π-unsaturated reactants in the presence of aldehydes provides products of carbonyl addition. Dehydrogenation of primary alcohols in the presence of the same π-unsaturated reactants provides identical products of carbonyl addition. In this way, carbonyl addition is achieved from the alcohol or aldehyde oxidation level in the absence of stoichiometric organometallic reagents or metallic reductants. In this account, the discovery of ruthenium-catalyzed C-C bond-forming transfer hydrogenations and the recent development of diastereo- and enantioselective variants are discussed.

  14. Characterization of ruthenium red-binding sites of the Ca(2+)-ATPase from sarcoplasmic reticulum and their interaction with Ca(2+)-binding sites.

    PubMed Central

    Corbalan-Garcia, S; Teruel, J A; Gomez-Fernandez, J C

    1992-01-01

    Sarcoplasmic reticulum Ca(2+)-ATPase has previously been shown to bind and dissociate two Ca2+ ions in a sequential mode. This behaviour is confirmed here by inducing sequential Ca2+ dissociation with Ruthenium Red. Ruthenium Red binds to sarcoplasmic reticulum vesicles (6 nmol/mg) with a Kd = 2 microM, producing biphasic kinetics of Ca2+ dissociation from the Ca(2+)-ATPase, decreasing the affinity for Ca2+ binding. Studies on the effect of Ca2+ on Ruthenium Red binding indicate that Ruthenium Red does not bind to the high-affinity Ca(2+)-binding sites, as suggested by the following observations: (i) micromolar concentrations of Ca2+ do not significantly alter Ruthenium Red binding to the sarcoplasmic reticulum; (ii) quenching of the fluorescence of fluorescein 5'-isothiocyanate (FITC) bound to Ca(2+)-ATPase by Ruthenium Red (resembling Ruthenium Red binding) is not prevented by micromolar concentrations of Ca2+; (iii) quenching of FITC fluorescence by Ca2+ binding to the high-affinity sites is achieved even though Ruthenium Red is bound to the Ca(2+)-ATPase; and (iv) micromolar Ca2+ concentrations prevent inhibition of the ATP-hydrolytic capability by dicyclohexylcarbodi-imide modification, but Ruthenium Red does not. However, micromolar concentrations of lanthanides (La3+ and Tb3+) and millimolar concentrations of bivalent cations (Ca2+ and Mg2+) inhibit Ruthenium Red binding as well as quenching of FITC-labelled Ca(2+)-ATPase fluorescence by Ruthenium Red. Studies of Ruthenium Red binding to tryptic fragments of Ca(2+)-ATPase, as demonstrated by ligand blotting, indicate that Ruthenium Red does not bind to the A1 subfragment. Our observations suggest that Ruthenium Red might bind to a cation-binding site in Ca(2+)-ATPase inducing fast release of the last bound Ca2+ by interactions between the sites. PMID:1280106

  15. Iron-, Cobalt-, and Nickel-Catalyzed Asymmetric Transfer Hydrogenation and Asymmetric Hydrogenation of Ketones.

    PubMed

    Li, Yan-Yun; Yu, Shen-Luan; Shen, Wei-Yi; Gao, Jing-Xing

    2015-09-15

    Chiral alcohols are important building blocks in the pharmaceutical and fine chemical industries. The enantioselective reduction of prochiral ketones catalyzed by transition metal complexes, especially asymmetric transfer hydrogenation (ATH) and asymmetric hydrogenation (AH), is one of the most efficient and practical methods for producing chiral alcohols. In both academic laboratories and industrial operations, catalysts based on noble metals such as ruthenium, rhodium, and iridium dominated the asymmetric reduction of ketones. However, the limited availability, high price, and toxicity of these critical metals demand their replacement with abundant, nonprecious, and biocommon metals. In this respect, the reactions catalyzed by first-row transition metals, which are more abundant and benign, have attracted more and more attention. As one of the most abundant metals on earth, iron is inexpensive, environmentally benign, and of low toxicity, and as such it is a fascinating alternative to the precious metals for catalysis and sustainable chemical manufacturing. However, iron catalysts have been undeveloped compared to other transition metals. Compared with the examples of iron-catalyzed asymmetric reduction, cobalt- and nickel-catalyzed ATH and AH of ketones are even seldom reported. In early 2004, we reported the first ATH of ketones with catalysts generated in situ from iron cluster complex and chiral PNNP ligand. Since then, we have devoted ourselves to the development of ATH and AH of ketones with iron, cobalt, and nickel catalysts containing novel chiral aminophosphine ligands. In our study, the iron catalyst containing chiral aminophosphine ligands, which are expected to control the stereochemistry at the metal atom, restrict the number of possible diastereoisomers, and effectively transfer chiral information, are successful catalysts for enantioselective reduction of ketones. Among these novel chiral aminophosphine ligands, 22-membered macrocycle P2N4

  16. Solvent extraction of cobalt from laterite-ammoniacal leach liquors

    SciTech Connect

    Nilsen, D.N.; Siemens, R.E.; Rhoads, S.C.

    1980-01-01

    The Bureau of Mines is developing a method to recover Ni, Co, and Cu from laterites containing less than 1.2% Ni and 0.25% Co. The method consists of the following basic unit operations: (1) reduction roasting, (2) leaching, (3) solvent extraction, and (4) electrowinning. The method reflects three Bureau of Mines objectives: (1) recovery of critical minerals that are domestically in short supply from low-grade domestic laterites, (2) lower processing energy requirements, and (3) solution recycling. This report deals with the extraction of cobalt and the preparation of a suitable cobalt electrolyte by solvent extraction from liquor produced by this method. Nickel and copper are coextracted with LIX64N from an ammoniacal ammonium sulfate leach liquor containing about 1.00 g/1 Ni, 0.30 g/1 Co, 0.03 g/1 Cu, and 0.02 g/1 Zn. Cobalt (III) in the nickel-copper barren raffinate is reduced to cobalt (II) with cobalt metal. Reduction of cobalt (III) to cobalt (II) greatly aids subsequent extraction. Commercially available XI-51 extracts about 94% of the cobalt from the treated raffinate in one stage in a laboratory mixer-settler continuous circuit. Ammonia loaded on the solvent is removed in two washing steps. About 94% of the cobalt then is stripped from the XI-51 in one stage with spent cobalt electrolyte containing about 77 g/1 Co and 18 g/1 sulfuric acid (H/sub 2/SO/sub 4/). Electrolytes containing less H/sub 2/SO/sub 4/ also may be used. Preliminary data indicate that coextracted zinc may be removed from pregnant cobalt electrolyte containing 3 g/1 or less H/sub 2/SO/sub 4/ with di-(2 ethylhexyl) phosphoric acid (D2EHPA).

  17. Cytotoxic and genotoxic effects of cis-tetraammine(oxalato)ruthenium(III) dithionate on the root meristem cells of Allium cepa.

    PubMed

    Pereira, Flávia de Castro; Vilanova-Costa, Cesar Augusto Sam Tiago; de Lima, Aliny Pereira; Ribeiro, Alessandra de Santana Braga Barbosa; da Silva, Hugo Delleon; Pavanin, Luiz Alfredo; Silveira-Lacerda, Elisângela de Paula

    2009-06-01

    Ruthenium complexes have attracted much attention as possible building blocks for new transition-metal-based antitumor agents. The present study examines the mitotoxic and clastogenic effects induced in the root tips of Allium cepa by cis-tetraammine(oxalato)ruthenium(III) dithionate {cis-[Ru(C(2)O(2))(NH(3))(4)](2)(S(2)O(6))} at different exposure durations and concentrations. Correlation tests were performed to determine the effects of the time of exposure and concentration of ruthenium complex on mitotic index (MI) and mitotic aberration index. A comparison of MI results of cis-[Ru(C(2)O(2))(NH(3))(4)](2)(S(2)O(6)) to those of lead nitrate reveals that the ruthenium complex demonstrates an average mitotic inhibition eightfold higher than lead, with the frequency of cellular abnormalities almost fourfold lower and mitotic aberration threefold lower. A. cepa root cells exposed to a range of ruthenium complex concentrations did not display significant clastogenic effects. Cis-tetraammine(oxalato)ruthenium(III) dithionate therefore exhibits a remarkable capacity to inhibit mitosis, perhaps by inhibiting DNA synthesis or blocking the cell cycle in the G2 phase. Further investigation of the mechanisms of action of this ruthenium complex will be important to define its clinical potential and to contribute to a novel and rational approach to developing a new metal-based drug with antitumor properties complementary to those exhibited by the drugs already in clinical use.

  18. Catalytic water oxidation by ruthenium(II) quaterpyridine (qpy) complexes: evidence for ruthenium(III) qpy-N,N'''-dioxide as the real catalysts.

    PubMed

    Liu, Yingying; Ng, Siu-Mui; Yiu, Shek-Man; Lam, William W Y; Wei, Xi-Guang; Lau, Kai-Chung; Lau, Tai-Chu

    2014-12-22

    Polypyridyl and related ligands have been widely used for the development of water oxidation catalysts. Supposedly these ligands are oxidation-resistant and can stabilize high-oxidation-state intermediates. In this work a series of ruthenium(II) complexes [Ru(qpy)(L)2 ](2+) (qpy=2,2':6',2'':6'',2'''-quaterpyridine; L=substituted pyridine) have been synthesized and found to catalyze Ce(IV) -driven water oxidation, with turnover numbers of up to 2100. However, these ruthenium complexes are found to function only as precatalysts; first, they have to be oxidized to the qpy-N,N'''-dioxide (ONNO) complexes [Ru(ONNO)(L)2 ](3+) which are the real catalysts for water oxidation.

  19. The role of cobalt on the creep of Waspaloy

    NASA Technical Reports Server (NTRS)

    Jarrett, R. N.; Chin, L.; Tien, J. K.

    1984-01-01

    Cobalt was systematically replaced with nickel in Waspaloy (which normally contains 13% Co) to determine the effects of cobalt on the creep behavior of this alloy. Effects of cobalt were found to be minimal on tensile strengths and microstructure. The creep resistance and the stress rupture resistance determined in the range from 704 to 760 C (1300 to 1400 C) were found to decrease as cobalt was removed from the standard alloy at all stresses and temperatures. Roughly a ten-fold drop in rupture life and a corresponding increase in minimum creep rate were found under all test conditions. Both the apparent creep activation energy and the matrix contribution to creep resistance were found to increase with cobalt. These creep effects are attributed to cobalt lowering the stacking fault energy of the alloy matrix. The creep resistance loss due to the removal of cobalt is shown to be restored by slightly increasing the gamma' volume fraction. Results are compared to a previous study on Udimet 700, a higher strength, higher gamma' volume fraction alloy with similar phase chemistry, in which cobalt did not affect creep resistance. An explanation for this difference in behavior based on interparticle spacing and cross-slip is presented.

  20. Comparative toxicity and carcinogenicity of soluble and insoluble cobalt compounds.

    PubMed

    Behl, Mamta; Stout, Matthew D; Herbert, Ronald A; Dill, Jeffrey A; Baker, Gregory L; Hayden, Barry K; Roycroft, Joseph H; Bucher, John R; Hooth, Michelle J

    2015-07-03

    Occupational exposure to cobalt is of widespread concern due to its use in a variety of industrial processes and the occurrence of occupational disease. Due to the lack of toxicity and carcinogenicity data following exposure to cobalt, and questions regarding bioavailability following exposure to different forms of cobalt, the NTP conducted two chronic inhalation exposure studies in rats and mice, one on soluble cobalt sulfate heptahydrate, and a more recent study on insoluble cobalt metal. Herein, we compare and contrast the toxicity profiles following whole-body inhalation exposures to these two forms of cobalt. In general, both forms were genotoxic in the Salmonella T98 strain in the absence of effects on micronuclei. The major sites of toxicity and carcinogenicity in both chronic inhalation studies were the respiratory tract in rats and mice, and the adrenal gland in rats. In addition, there were distinct sites of toxicity and carcinogenicity noted following exposure to cobalt metal. In rats, carcinogenicity was observed in the blood, and pancreas, and toxicity was observed in the testes of rats and mice. Taken together, these findings suggest that both forms of cobalt, soluble and insoluble, appear to be multi-site rodent carcinogens following inhalation exposure.

  1. Microwave Mapping Demonstration Using the Thermochromic Cobalt Chloride Equilibrium

    ERIC Educational Resources Information Center

    Nguyen, Vu D.; Birdwhistell, Kurt R.

    2014-01-01

    An update to the thermochromic cobalt(II) chloride equilibrium demonstration is described. Filter paper that has been saturated with aqueous cobalt(II) chloride is heated for seconds in a microwave oven, producing a color change. The resulting pink and blue map is used to colorfully demonstrate Le Châtelier's principle and to illuminate the…

  2. Effect of cobalt on Escherichia coli metabolism and metalloporphyrin formation.

    PubMed

    Majtan, Tomas; Frerman, Frank E; Kraus, Jan P

    2011-04-01

    Toxicity in Escherichia coli resulting from high concentrations of cobalt has been explained by competition of cobalt with iron in various metabolic processes including Fe-S cluster assembly, sulfur assimilation, production of free radicals and reduction of free thiol pool. Here we present another aspect of increased cobalt concentrations in the culture medium resulting in the production of cobalt protoporphyrin IX (CoPPIX), which was incorporated into heme proteins including membrane-bound cytochromes and an expressed human cystathionine beta-synthase (CBS). The presence of CoPPIX in cytochromes inhibited their electron transport capacity and resulted in a substantially decreased respiration. Bacterial cells adapted to the increased cobalt concentration by inducing a modified mixed acid fermentative pathway under aerobiosis. We capitalized on the ability of E. coli to insert cobalt into PPIX to carry out an expression of CoPPIX-substituted heme proteins. The level of CoPPIX-substitution increased with the number of passages of cells in a cobalt-containing medium. This approach is an inexpensive method to prepare cobalt-substituted heme proteins compared to in vitro enzyme reconstitution or in vivo replacement using metalloporphyrin heme analogs and seems to be especially suitable for complex heme proteins with an additional coenzyme, such as human CBS.

  3. Potential for cobalt recovery from lateritic ores in Europe

    NASA Astrophysics Data System (ADS)

    Herrington, R.

    2012-04-01

    Cobalt is one of the 'critical metals' identified under the EU Raw Materials Initiative. Annually the global mine production of cobalt is around 55,000 tonnes,with Europe's industries consuming around 30% of that figure. Currently Europe produces around 27 tonnes of cobalt from mines in Finland although new capacity is planned. Co-bearing nickel laterite ores being mined in Greece, Macedonia and Kosovo where the cobalt is currently not being recovered (ores have typical analyses of 0.055% Co and >1% Ni,). These ores are currently treated directly in pyrometallurgical plants to recover the contained nickel and this process means there is no separate cobalt product produced. Hydrometallurgical treatment of mineralogically suitable laterite ores can recover the cobalt; for example Cuba recovers 3,500 tonnes of cobalt from its laterite mining operations, which are of a similar scale to the current European operations. Implementation of hydrometallurgical techniques is in its infancy in Europe with one deposit in Turkey planning to use atmospheric heap leaching to recover nickel and copper from oxide-dominated ores. More widespread implementation of these methods to mineralogically suitable ore types could unlock the highly significant undeveloped resources (with metal contents >0.04% Co and >1% Ni), which have been defined throughout the Balkans eastwards into Turkey. At a conservative estimate, this region has the potential to supply up to 30% of the EU cobalt requirements.

  4. {sup 106}Ruthenium Plaque Therapy (RPT) for Retinoblastoma

    SciTech Connect

    Murakami, Naoya; Suzuki, Shigenobu; Ito, Yoshinori; Yoshimura, Ryoichi; Inaba, Koji; Kuroda, Yuki; Morota, Madoka; Mayahara, Hiroshi; Sakudo, Mototake; Wakita, Akihisa; Okamoto, Hiroyuki; Sumi, Minako; Kagami, Yoshikazu; Nakagawa, Keiichi; Ohtomo, Kuni; Itami, Jun

    2012-09-01

    Purpose: To evaluate the effectiveness of episcleral {sup 106}ruthenium plaque therapy (RPT) in the management of retinoblastoma. Methods and Materials: One hundred one RPTs were retrospectively analyzed that were performed in 90 eyes of 85 patients with retinoblastoma at National Cancer Center Hospital between 1998 and 2008. Each RPT had a corresponding tumor and 101 tumors were considered in the analysis of local control. Median follow-up length was 72.8 months. Median patient age at the RPT was 28 months. Median prescribed doses at reference depth and outer surface of the sclera were 47.4 Gy and 162.3 Gy, respectively. Results: Local control rate (LCR) and ocular retention rate (ORR) at 2 years were 33.7% and 58.7%, respectively. Unilateral disease, International Classification of Retinoblastoma group C or more advanced at the first presentation or at the time of RPT, vitreous and/or subretinal seeding, tumor size greater than 5 disc diameter (DD), reference depth greater than 5 mm, dose rate at reference depth lower than 0.7 Gy/hour, dose at the reference depth lower than 35 Gy, and (biologically effective dose with an {alpha}/{beta} ratio of 10 Gy) at the reference depth lower than 40 Gy{sub 10} were associated with unfavorable LCR. Two patients died of metastatic disease. Radiation complications included retinal detachment in 12 eyes (13.3%), proliferative retinopathy in 6 (6.7%), rubeosis iris in 2 (2.2%), and posterior subcapsular cataract in 23 (25.6%). Conclusion: RPT is an effective eye-preserving treatment for retinoblastoma.

  5. Unconventional magnetisation texture in graphene/cobalt hybrids

    PubMed Central

    Vu, A. D.; Coraux, J.; Chen, G.; N’Diaye, A. T.; Schmid, A. K.; Rougemaille, N.

    2016-01-01

    Magnetic domain structure and spin-dependent reflectivity measurements on cobalt thin films intercalated at the graphene/Ir(111) interface are investigated using spin-polarised low-energy electron microscopy. We find that graphene-covered cobalt films have surprising magnetic properties. Vectorial imaging of magnetic domains reveals an unusually gradual thickness-dependent spin reorientation transition, in which magnetisation rotates from out-of-the-film plane to the in-plane direction by less than 10° per cobalt monolayer. During this transition, cobalt films have a meandering spin texture, characterised by a complex, three-dimensional, wavy magnetisation pattern. In addition, spectroscopy measurements suggest that the electronic band structure of the unoccupied states is essentially spin-independent already a few electron-Volts above the vacuum level. These properties strikingly differ from those of pristine cobalt films and could open new prospects in surface magnetism. PMID:27114039

  6. A combined experimental and computational study on the cycloisomerization of 2-ethynylbiaryls catalyzed by dicationic arene ruthenium complexes.

    PubMed

    Yamamoto, Yoshihiko; Matsui, Kazuma; Shibuya, Masatoshi

    2015-05-04

    Ruthenium-catalyzed cycloisomerization of 2-ethynylbiaryls was investigated to identify an optimal ruthenium catalyst system. A combination of [η(6) -(p-cymene)RuCl2 (PR3 )] and two equivalents of AgPF6 effectively converted 2-ethynylbiphenyls into phenanthrenes in chlorobenzene at 120 °C over 20 h. Moreover, 2-ethynylheterobiaryls were found to be favorable substrates for this ruthenium catalysis, thus achieving the cycloisomerization of previously unused heterocyclic substrates. Moreover, several control experiments and DFT calculations of model complexes were performed to propose a plausible reaction mechanism.

  7. Amidines for versatile ruthenium(II)-catalyzed oxidative C-H activations with internal alkynes and acrylates.

    PubMed

    Li, Jie; John, Michael; Ackermann, Lutz

    2014-04-25

    Cationic ruthenium complexes derived from KPF6 or AgOAc enabled efficient oxidative CH functionalizations on aryl and heteroaryl amidines. Thus, oxidative annulations of diversely decorated internal alkynes provided expedient access to 1-aminoisoquinolines, while catalyzed C-H activations with substituted acrylates gave rise to structurally novel 1-iminoisoindolines. The powerful ruthenium(II) catalysts displayed a remarkably high site-, regio- and, chemoselectivity. Therefore, the catalytic system proved tolerant of a variety of important electrophilic functional groups. Detailed mechanistic studies provided strong support for the cationic ruthenium(II) catalysts to operate by a facile, reversible C-H activation.

  8. Ruthenium-catalyzed direct C-H amidation of arenes including weakly coordinating aromatic ketones.

    PubMed

    Kim, Jiyu; Kim, Jinwoo; Chang, Sukbok

    2013-06-03

    C-H activation: The ruthenium-catalyzed direct sp(2) C-H amidation of arenes by using sulfonyl azides as the amino source is presented (see scheme). A wide range of substrates were readily amidated including arenes bearing weakly coordinating groups. Synthetic utility of the thus obtained products was demonstrated in the preparation of biologically active heterocycles.

  9. Ruthenium-Catalyzed Synthesis of β-Hydroxyamides from β-Ketonitriles in Water.

    PubMed

    González-Fernández, Rebeca; Crochet, Pascale; Cadierno, Victorio

    2016-12-02

    An unprecedented hydration/transfer hydrogenation tandem process for the catalytic conversion of β-ketonitriles into synthetically useful β-hydroxyamides in water has been developed, making use of the ruthenium(II) complex [RuCl2(η(6)-p-cymene){P(4-C6H4F)2Cl}] in combination with sodium formate.

  10. Metalation dictates remote regioselectivity: ruthenium-catalyzed functionalization of meta C(Ar)-H Bonds.

    PubMed

    Juliá-Hernández, Francisco; Simonetti, Marco; Larrosa, Igor

    2013-10-25

    Remote control: The title reaction is effective for the sulfonation and alkylation of arenes bearing directing groups. Initial ortho metalation of the substrate forms an intermediate which does not evolve towards functionalization at the CM bond. Instead, the ruthenium catalyst acts as a strong electron-donating group, thus directing a remote electrophilic attack.

  11. Probing the structural evolution of ruthenium doped germanium clusters: Photoelectron spectroscopy and density functional theory calculations

    NASA Astrophysics Data System (ADS)

    Jin, Yuanyuan; Lu, Shengjie; Hermann, Andreas; Kuang, Xiaoyu; Zhang, Chuanzhao; Lu, Cheng; Xu, Hongguang; Zheng, Weijun

    2016-07-01

    We present a combined experimental and theoretical study of ruthenium doped germanium clusters, RuGen‑ (n = 3–12), and their corresponding neutral species. Photoelectron spectra of RuGen‑ clusters are measured at 266 nm. The vertical detachment energies (VDEs) and adiabatic detachment energies (ADEs) are obtained. Unbiased CALYPSO structure searches confirm the low-lying structures of anionic and neutral ruthenium doped germanium clusters in the size range of 3 ≤ n ≤ 12. Subsequent geometry optimizations using density functional theory (DFT) at PW91/LANL2DZ level are carried out to determine the relative stability and electronic properties of ruthenium doped germanium clusters. It is found that most of the anionic and neutral clusters have very similar global features. Although the global minimum structures of the anionic and neutral clusters are different, their respective geometries are observed as the low-lying isomers in either case. In addition, for n > 8, the Ru atom in RuGen‑/0 clusters is absorbed endohedrally in the Ge cage. The theoretically predicted vertical and adiabatic detachment energies are in good agreement with the experimental measurements. The excellent agreement between DFT calculations and experiment enables a comprehensive evaluation of the geometrical and electronic structures of ruthenium doped germanium clusters.

  12. SEPARATION OF URANYL AND RUTHENIUM VALUES BY THE TRIBUTYL PHOSPHATE EXTRACTION PROCESS

    DOEpatents

    Wilson, A.S.

    1961-05-01

    A process is given for separating uranyl values from ruthenium values contained in an aqueous 3 to 4 M nitric acid solution. After the addition of hydrogen peroxide to obtain a concentration of 0.3 M, the uranium is selectively extracted with kerosene-diluted tributyl phosphate.

  13. Synthesis, Anticancer Activity, and Genome Profiling of Thiazolo Arene Ruthenium Complexes.

    PubMed

    Grozav, Adriana; Balacescu, Ovidiu; Balacescu, Loredana; Cheminel, Thomas; Berindan-Neagoe, Ioana; Therrien, Bruno

    2015-11-12

    Sixteen hydrazinyl-thiazolo arene ruthenium complexes of the general formula [(η(6)-p-cymene)Ru(N,N'-hydrazinyl-thiazolo)Cl]Cl were synthesized. All complexes were tested in vitro for their antiproliferative activity on three tumor cell lines (HeLa, A2780, and A2780cisR) and on a noncancerous cell line (HFL-1). A superior cytotoxic activity of the ruthenium complexes as compared to cisplatin and oxaliplatin, on both cisplatin-sensitive and cisplatin resistant ovarian cancer cells, was observed. In addition, the biological activity of two selected derivatives was evaluated using microarray gene expression assay and ingenuity pathway analysis. p53 signaling was identified as an important pathway modulated by both arene ruthenium compounds. New activated molecules such as FAS, ZMAT3, PRMT2, BBC3/PUMA, and PDCD4, whose overexpressions are correlated with overcoming resistance to cisplatin therapy, were also identified as potential targets. Moreover, the arene ruthenium complexes can be used in association with cisplatin to prevent cisplatin resistance development and synergistically to induce cell death in ovarian cancer cells.

  14. Olefin Ring Closing Metathesis and Hydrosilylation Reaction in Aqueous Medium by Grubbs Second Generation Ruthenium Catalyst

    EPA Science Inventory

    The Grubbs second generation ruthenium catalyst was shown to catalyze various olefin ring closing metathesis and hydrosilylation reactions in aqueous medium. Reactions proceeded in pure water without any additives or co-solvents, in a short period of time. We found that inhomogen...

  15. Effects of ruthenium seed layer on the microstructure and spin dynamics of thin permalloy films

    SciTech Connect

    Jin Lichuan; Zhang Huaiwu; Tang Xiaoli; Bai Feiming; Zhong Zhiyong

    2013-02-07

    The spin dynamics and microstructure properties of a sputtered 12 nm Ni{sub 81}Fe{sub 19} thin film have been enhanced by the use of a ruthenium seed layer. Both the ferromagnetic resonance field and linewidth are enhanced dramatically as the thickness of ruthenium seed layer is increased. The surface anisotropy energy constant can also be largely tailored from 0.06 to 0.96 erg/cm{sup -2} by changing the seed layer thickness. The changes to the dynamics magnetization properties are caused by both ruthenium seed layer induced changes in the Ni{sub 81}Fe{sub 19} structure properties and surface topography properties. Roughness induced inhomogeneous linewidth broadening is also seen. The damping constant is highly tunable via the ruthenium thickness. This approach can be used to tailor both the structure and spin dynamic properties of thin Ni{sub 81}Fe{sub 19} films over a wide range. And it may benefit the applications of spin dynamics and spin current based devices.

  16. SORPTION OF ARSENATE AND ARSENITE ON A RUTHENIUM COMPOUND: A MACROSCOPIC AND MICROSCOPIC STUDY

    EPA Science Inventory

    Sorption of arsenate and arsenite was examined on a ruthenium compound using macroscopic and microscopic techniques. Batch sorption experiments at pH 4,5,6, 7 and 8 were employed to construct constant solid solution ratio isotherms (CSI). After equilibration at the appropriate pH...

  17. Investigation of Ruthenium Dissolution in Advanced Membrane Electrode Assemblies for Direct Methanol Based Fuel Cell Stacks

    NASA Technical Reports Server (NTRS)

    Valdez, Thomas I.; Firdosy, S.; Koel, B. E.; Narayanan, S. R.

    2005-01-01

    Dissolution of ruthenium was observed in the 80-cell stack. Duration testing was performed in single cell MEAs to determine the pathway of cell degradation. EDAX analysis on each of the single cell MEAs has shown that the Johnson Matthey commercial catalyst is stable in DMFC operation for 250 hours, no ruthenium dissolution was observed. Changes in the hydrophobicity of the cathode backing papers was minimum. Electrode polarization analysis revealed that the MEA performance loss is attributed to changes in the cathode catalyst layer. Ruthenium migration does not seem to occur during cell operation but can occur when methanol is absent from the anode compartment, the cathode compartment has access to air, and the cells in the stack are electrically connected to a load (Shunt Currents). The open-to-air cathode stack design allowed for: a) The MEAs to have continual access to oxygen; and b) The stack to sustain shunt currents. Ruthenium dissolution in a DMFC stack can be prevented by: a) Developing an internally manifolded stacks that seal reactant compartments when not in operation; b) Bringing the cell voltages to zero quickly when not in operation; and c) Limiting the total number of cells to 25 in an effort to limit shunt currents.

  18. Magnetically Recoverable Supported Ruthenium Catalyst for Hydrogenation of Alkynes and Transfer Hydrogenation of Carbonyl Compounds

    EPA Science Inventory

    A ruthenium (Ru) catalyst supported on magnetic nanoparticles (NiFe2O4) has been successfully synthesized and used for hydrogenation of alkynes at room temperature as well as transfer hydrogenation of a number of carbonyl compounds under microwave irradiation conditions. The cata...

  19. Synthesis and anticancer activity of carbosilane metallodendrimers based on arene ruthenium(ii) complexes.

    PubMed

    Maroto-Díaz, Marta; Elie, Benelita T; Gómez-Sal, Pilar; Pérez-Serrano, Jorge; Gómez, Rafael; Contel, María; Javier de la Mata, F

    2016-04-28

    A series of new organometallic carbosilane dendrimers (first and second generation) and the corresponding non-dendritic mononuclear based on ruthenium arene fragments are described. The metallodendrimers were prepared by reactions of the precursor [Ru(η(6)-p-cymene)Cl2]2 with carbosilane dendrimers functionalized with N-donor monodentate ligands such as NH2- and pyridine, or with N,O-, N,N-chelating imine ligands. While the dendrimer precursors are insoluble in DMSO or water, novel metallodendrimers are soluble in DMSO and some of them are even highly soluble in water. The molecular structure of the "Ru-NH2" mononuclear compound (zero generation) was determined by single-crystal X-ray crystallography. The cytotoxicity activity of these dendritic structures was evaluated in several human cancer cell lines and compared with that of the corresponding mononuclear ruthenium complexes. Most compounds display significant cytotoxic activities in the low micromolar range with the first generation ruthenium dendrimers being the most active compounds. The cell death type for selected compounds has been studied as well as their reactivity towards relevant biomolecules such as DNA, Human Serum Albumin (HSA) and Cathepsin-B. All the data point to a mode of action different from that of cisplatin for most complexes. First generation ruthenium dendrimers inhibit Cathepsin-B, which may suggest potential antimetastatic properties of these compounds.

  20. Inhibitory effects of NAMI-A-like ruthenium complexes on prion neuropeptide fibril formation.

    PubMed

    Wang, Xuesong; Zhu, Dengsen; Zhao, Cong; He, Lei; Du, Weihong

    2015-05-01

    Prion diseases are a group of infectious and fatal neurodegenerative disorders caused by the conformational conversion of a cellular prion protein (PrP) into its abnormal isoform PrP(Sc). PrP106-126 resembles PrP(Sc) in terms of physicochemical and biological characteristics and is used as a common model for the treatment of prion diseases. Inhibitory effects on fibril formation and neurotoxicity of the prion neuropeptide PrP106-126 have been investigated using metal complexes as potential inhibitors. Nevertheless, the binding mechanism between metal complexes and the peptide remains unclear. The present study is focused on the interaction of PrP106-126 with NAMI-A and NAMI-A-like ruthenium complexes, including KP418, KP1019, and KP1019-2. Results demonstrated that these ruthenium complexes could bind to PrP106-126 in a distinctive binding mode through electrostatic and hydrophobic interactions. NAMI-A-like ruthenium complexes can also effectively inhibit the aggregation and fibril formation of PrP106-126. The complex KP1019 demonstrated the optimal inhibitory ability upon peptide aggregation, and cytotoxicity because of its large aromatic ligand contribution. The studied complexes could also regulate the copper redox chemistry of PrP106-126 and effectually inhibit the formation of reactive oxygen species. Given these findings, ruthenium complexes with relatively low cellular toxicity may be used to develop potential pharmaceutical products against prion diseases.

  1. Investigation of ruthenium dioxide formation mechanisms in containment glass synthesized by liquid feed

    SciTech Connect

    Sawada, K.; Shimada, T.; Sako, N.; Enokida, Y.; Schuller, S.; Angeli, F.; Charpentier, T.

    2013-07-01

    The presenting paper focuses on the structural configuration of ruthenium in vitreous matrices with the objective of obtaining more insight into ruthenium incorporation and solubilization mechanisms in borosilicate glasses. To determine the structural effect of an increasing RuO{sub 2} in a borosilicate glass, a series of glass samples were selected from a benchmark composition. {sup 11}B NMR shows that the borate network is influenced by the presence of RuO{sub 2} in the glass: the addition of 2% RuO{sub 2} in a borosilicate glass led to a significant rise of BO{sub 4}. RuO{sub 2} precipitated in the glass does not seem to be the cause of this modification because when RuO{sub 2} increase there is no further change of BO{sub 4} fraction. This effect can be therefore attributed to RuO{sub 2} dissolved in the glass. RuO{sub 2} is known to have a very low solubility in borosilicate glasses (50 to 2000 ppm depending on the temperature, sodium concentration and conditions of synthesis). The link between the ruthenium and the borated network is not yet clearly identified, however, assumptions can be made such as the formation of Ru-O-B when a sufficient quantity of Ru is add (> 400 ppm). Ruthenium could play the role of silicon in increasing the possibility of bridging bond formation with boron coordination number IV.

  2. SORPTION OF LEAD ON A RUTHENIUM COMPOUND: A MACROSCOPIC AND MICROSCOPIC STUDY

    EPA Science Inventory

    The objective of this study was to elucidate the sorption mechanism of Pb on the high-affinity ruthenium compound with time at pH 6 employing batch methods and X-ray absorption fine structure (XAFS) and X-ray diffraction (XRD) spectroscopies. For the spectroscopic studies, Pb so...

  3. Method for producing electricity using a platinum-ruthenium-palladium catalyst in a fuel cell

    DOEpatents

    Gorer, Alexander

    2004-01-27

    A method for producing electricity using a fuel cell that utilizes a ternary alloy composition as a fuel cell catalyst, the ternary alloy composition containing platinum, ruthenium and palladium. The alloy shows increased activity as compared to well-known catalysts.

  4. Cytoxicity and apoptotic mechanism of ruthenium(II) amino acid complexes in sarcoma-180 tumor cells.

    PubMed

    Lima, Aliny Pereira; Pereira, Flávia Castro; Almeida, Marcio Aurelio Pinheiro; Mello, Francyelli Mariana Santos; Pires, Wanessa Carvalho; Pinto, Thallita Monteiro; Delella, Flávia Karina; Felisbino, Sérgio Luis; Moreno, Virtudes; Batista, Alzir Azevedo; de Paula Silveira-Lacerda, Elisângela

    2014-01-01

    Over the past several decades, much attention has been focused on ruthenium complexes in antitumor therapy. Ruthenium is a transition metal that possesses several advantages for rational antitumor drug design and biological applications. In the present study, five ruthenium complexes containing amino acids were studied in vitro to determine their biological activity against sarcoma-180 tumor cells. The cytotoxicity of the complexes was evaluated by an MTT assay, and their mechanism of action was investigated. The results demonstrated that the five complexes inhibited the growth of the S180 tumor cell line, with IC50 values ranging from 22.53 µM to 50.18 µM, and showed low cytotoxicity against normal L929 fibroblast cells. Flow cytometric analysis revealed that the [Ru(gly)(bipy)(dppb)]PF6 complex (2) inhibited the growth of the tumor cells by inducing apoptosis, as evidenced by an increased number of Annexin V-positive cells and G0/G1 phase cell cycle arrest. Further investigation showed that complex 2 caused a loss of mitochondrial membrane potential; activated caspases 3, caspase-8, and caspase-9 and caused a change in the mRNA expression levels of caspase 3, caspase-9 as well as the bax genes. The levels of the pro-apoptotic Bcl-2 family protein Bak were increased. Thus, we demonstrated that ruthenium amino acid complexes are promising drugs against S180 tumor cells, and we recommend further investigations of their role as chemotherapeutic agents for sarcomas.

  5. Selective nuclei accumulation of ruthenium(II) complex enantiomers that target G-quadruplex DNA.

    PubMed

    Sun, Dongdong; Liu, Yanan; Yu, Qianqian; Liu, Du; Zhou, Yanhui; Liu, Jie

    2015-09-01

    Different enantiomers exhibit large differences in their biological activity and/or toxicity, but they rarely involve the relationship of the agents for molecular and cellular imaging with the chiral structure of ruthenium complexes. Here, we report that an enantiomer of a polypyridyl ruthenium complex can selectively accumulate in the nucleus of HepG2 cells. Confocal laser scanning microscopy studies show that this phenomenon occurs via a non-endocytotic, but temperature-dependent, mechanism of cellular uptake in HepG2 cells. DNA oligonucleotides with repetitive tracts of guanine bases that can form G-quadruplex structures have aroused interest as therapeutic agents and as targets for anticancer drug design. Various biophysical techniques show that the Λ-enantiomer of ruthenium complexes can selectively stabilize human telomeric G-quadruplex DNA and has a strong preference for G-quadruplex over duplex DNA. Judged from the NMR results, we speculate that at higher 4:1 ligand/G-quadruplex stoichiometry, complex Λ-Ru is likely to bind with each groove of the tetraplex in a dimeric form or intercalate with the G-tetrad in the 3' terminal face and coexist with other modes. The molecular modeling analysis is in agreement with the NMR titrations performed in this investigation indicating that ruthenium complexes are actually characterized by a mixed binding mode. The results provide many opportunities for the development of novel agents for living cell-related studies.

  6. Recent Advances on Dark and Light-Activated Cytotoxity of Imidazole-Containing Ruthenium Complexes.

    PubMed

    Liu, Ping; Jia, Jia; Zhao, Yue; Wang, Ke-Zhi

    2016-01-01

    Imidazole derivatives have known to possess a diverse range of pharmacological activity. In particular, one of ruthenium-based derivatives, imidazolium [trans-RuCl4(1H-imidazole)(DMSOS)] (NAMI-A) which is now in clinical trials, opens a new avenue for developing promising ruthenium-based anticancer drugs alternative to Cisplatin. This mini-review overviews some representative examples of imidazole-containing ruthenium complexes (ICRCs) with in vitro anticancer activities. Special attention is paid on ICRCs with the activities more potent than Cisplatin, and their correlation with their DNA binding properties in the context of possible cancer chemotherapeutic applications. The ICRCs are divided into two main categories according to their dark and light activated cytotoxicity; the former case is further clarified into mononuclear complexes including tris(bidentate polypyridyl) ruthenium complexes and those containing monodentatively coordinative imidazole ligands as well as polynuclear complexes. The perspective, challenges and future efforts for investigations into ICRCs are pointed out or suggested.

  7. Investigation of Ruthenium Dissolution in Advanced Membrane Electrode Assemblies for Direct Methanol Based Fuel Cells Stacks

    NASA Technical Reports Server (NTRS)

    Valdez, T. I.; Firdosy, S.; Koel, B. E.; Narayanan, S. R.

    2005-01-01

    This viewgraph presentation gives a detailed review of the Direct Methanol Based Fuel Cell (DMFC) stack and investigates the Ruthenium that was found at the exit of the stack. The topics include: 1) Motivation; 2) Pathways for Cell Degradation; 3) Cell Duration Testing; 4) Duration Testing, MEA Analysis; and 5) Stack Degradation Analysis.

  8. A new designed hydrazine group-containing ruthenium complex used for catalytic hydrogenation of esters.

    PubMed

    Tan, Xuefeng; Wang, Qingli; Liu, Yuanhua; Wang, Fangyuan; Lv, Hui; Zhang, Xumu

    2015-08-07

    A hydrazine group-containing nitrogen-phosphine ligand and corresponding ruthenium complexes were synthesized. When these complexes were used for hydrogenation of esters, excellent performance was observed (TON up to 17, 200). A wide substrate scope was suitable for this catalytic system.

  9. Cis-Selective Ring-Opening Metathesis Polymerization with Ruthenium Catalysts

    PubMed Central

    Keitz, Benjamin K.; Fedorov, Alexey; Grubbs, Robert H.

    2012-01-01

    Using a C-H activated, ruthenium-based metathesis catalyst, the cis selective ROMP of several monocyclic alkenes, as well as norbornene and oxanorbornene-type monomers is reported. The cis content of the isolated polymers depended heavily on monomer structure and temperature. By lowering the temperature, cis content as high as 96% could be obtained. PMID:22239675

  10. Design of photoactive ruthenium complexes to study electron transfer and proton pumping in cytochrome oxidase.

    PubMed

    Durham, Bill; Millett, Francis

    2012-04-01

    This review describes the development and application of photoactive ruthenium complexes to study electron transfer and proton pumping reactions in cytochrome c oxidase (CcO). CcO uses four electrons from Cc to reduce O(2) to two waters, and pumps four protons across the membrane. The electron transfer reactions in cytochrome oxidase are very rapid, and cannot be resolved by stopped-flow mixing techniques. Methods have been developed to covalently attach a photoactive tris(bipyridine)ruthenium group [Ru(II)] to Cc to form Ru-39-Cc. Photoexcitation of Ru(II) to the excited state Ru(II*), a strong reductant, leads to rapid electron transfer to the ferric heme group in Cc, followed by electron transfer to Cu(A) in CcO with a rate constant of 60,000s(-1). Ruthenium kinetics and mutagenesis studies have been used to define the domain for the interaction between Cc and CcO. New ruthenium dimers have also been developed to rapidly inject electrons into Cu(A) of CcO with yields as high as 60%, allowing measurement of the kinetics of electron transfer and proton release at each step in the oxygen reduction mechanism.

  11. Ruthenium bipyridyl tethered porous organosilica: a versatile, durable and reusable heterogeneous photocatalyst.

    PubMed

    Jana, Avijit; Mondal, John; Borah, Parijat; Mondal, Sujan; Bhaumik, Asim; Zhao, Yanli

    2015-07-07

    A versatile heterogeneous photocatalysis protocol was developed by using ruthenium bipyridyl tethered porous organosilica (Ru-POS). The versatility of the Ru-POS catalyst in organo-photocatalysis was explored by (i) oxidative aromatization of Hantzsch ester, (ii) reductive dehalogenation of alkyl halides, and (iii) functional group interconversion (FGI) of alcohols to alkyl halides.

  12. Probing the structural evolution of ruthenium doped germanium clusters: Photoelectron spectroscopy and density functional theory calculations

    PubMed Central

    Jin, Yuanyuan; Lu, Shengjie; Hermann, Andreas; Kuang, Xiaoyu; Zhang, Chuanzhao; Lu, Cheng; Xu, Hongguang; Zheng, Weijun

    2016-01-01

    We present a combined experimental and theoretical study of ruthenium doped germanium clusters, RuGen− (n = 3–12), and their corresponding neutral species. Photoelectron spectra of RuGen− clusters are measured at 266 nm. The vertical detachment energies (VDEs) and adiabatic detachment energies (ADEs) are obtained. Unbiased CALYPSO structure searches confirm the low-lying structures of anionic and neutral ruthenium doped germanium clusters in the size range of 3 ≤ n ≤ 12. Subsequent geometry optimizations using density functional theory (DFT) at PW91/LANL2DZ level are carried out to determine the relative stability and electronic properties of ruthenium doped germanium clusters. It is found that most of the anionic and neutral clusters have very similar global features. Although the global minimum structures of the anionic and neutral clusters are different, their respective geometries are observed as the low-lying isomers in either case. In addition, for n > 8, the Ru atom in RuGen−/0 clusters is absorbed endohedrally in the Ge cage. The theoretically predicted vertical and adiabatic detachment energies are in good agreement with the experimental measurements. The excellent agreement between DFT calculations and experiment enables a comprehensive evaluation of the geometrical and electronic structures of ruthenium doped germanium clusters. PMID:27439955

  13. An improved ruthenium catalyst for the environmentally benign amination of primary and secondary alcohols.

    PubMed

    Hollmann, Dirk; Tillack, Annegret; Michalik, Dirk; Jackstell, Ralf; Beller, Matthias

    2007-03-05

    The N-alkylation of amines in the presence of different ruthenium catalysts generated in situ was investigated. Among the various catalysts tested, the combination of [Ru3(CO)12] and N-phenyl-2-(dicyclohexylphosphanyl)pyrrole showed the best performance. By applying this novel catalyst, a variety of functionalized alcohols and amines were converted into the corresponding secondary amines in high yield.

  14. Simultaneous determination of iron and ruthenium as ternary complexes by extractive second derivative spectrophotometry.

    PubMed

    Toral, M I; Richter, P; Tapia, A E; Hernández, J

    1999-08-23

    A highly sensitive and selective second derivative spectrophotometric method has been developed for the determination of ruthenium and iron in mixtures. The method is based on the formation of the binary complexes of iron and ruthenium with 4,7-diphenyl-1,10-phenanthroline (bathophenanthroline) in the presence of ethyleneglycol. These complexes are formed at pH 4.0-6.0 upon heating at 90 degrees C for 60 min. The ternary perchlorate complexes are then separated by liquid-liquid extraction. The extracts were evaluated directly by derivative spectrophotometric measurement, using the zero-crossing approach for determination of both analytes. Ruthenium and iron were thus determined in the ranges 9.6-450 and 16.3-280 ng/ml, respectively, in the presence of one another. The detection limits achieved (3sigma) were found to be 2.9 ng/ml of ruthenium and 4.9 ng/ml of iron. The relative standard deviations were in all instances less than 1.5%. The proposed method was applied to the determination of both analytes in synthetic mixtures.

  15. A GSH-activatable ruthenium(ii)-azo photosensitizer for two-photon photodynamic therapy.

    PubMed

    Zeng, Leli; Kuang, Shi; Li, Guanying; Jin, Chengzhi; Ji, Liangnian; Chao, Hui

    2017-02-07

    A glutathione (GSH)-activatable ruthenium(ii)-azo photosensitizer was prepared. The complex had low toxicity towards cells under dark conditions. It exhibited excellent phototoxicity under two-photon excitation (810 nm) and thus was developed as a two-photon photodynamic anticancer agent for cancer therapy.

  16. Cobalt ferrite nanoparticles under high pressure

    SciTech Connect

    Saccone, F. D.; Ferrari, S.; Grinblat, F.; Bilovol, V.; Errandonea, D.

    2015-08-21

    We report by the first time a high pressure X-ray diffraction and Raman spectroscopy study of cobalt ferrite (CoFe{sub 2}O{sub 4}) nanoparticles carried out at room temperature up to 17 GPa. In contrast with previous studies of nanoparticles, which proposed the transition pressure to be reduced from 20–27 GPa to 7.5–12.5 GPa (depending on particle size), we found that cobalt ferrite nanoparticles remain in the spinel structure up to the highest pressure covered by our experiments. In addition, we report the pressure dependence of the unit-cell parameter and Raman modes of the studied sample. We found that under quasi-hydrostatic conditions, the bulk modulus of the nanoparticles (B{sub 0} = 204 GPa) is considerably larger than the value previously reported for bulk CoFe{sub 2}O{sub 4} (B{sub 0} = 172 GPa). In addition, when the pressure medium becomes non-hydrostatic and deviatoric stresses affect the experiments, there is a noticeable decrease of the compressibility of the studied sample (B{sub 0} = 284 GPa). After decompression, the cobalt ferrite lattice parameter does not revert to its initial value, evidencing a unit cell contraction after pressure was removed. Finally, Raman spectroscopy provides information on the pressure dependence of all Raman-active modes and evidences that cation inversion is enhanced by pressure under non-hydrostatic conditions, being this effect not fully reversible.

  17. Microemulsion-mediated synthesis of cobalt (pure fcc and hexagonal phases) and cobalt-nickel alloy nanoparticles.

    PubMed

    Ahmed, Jahangeer; Sharma, Shudhanshu; Ramanujachary, Kandalam V; Lofland, Samuel E; Ganguli, Ashok K

    2009-08-15

    By choosing appropriate microemulsion systems, hexagonal cobalt (Co) and cobalt-nickel (1:1) alloy nanoparticles have been obtained with cetyltrimethylammonium bromide as a cationic surfactant at 500 degrees C. This method thus stabilizes the hcp cobalt even at sizes (<10 nm) at which normally fcc cobalt is predicted to be stable. On annealing the hcp cobalt nanoparticles in H(2) at 700 degrees C we could transform them to fcc cobalt nanoparticles. Microscopy studies show the formation of spherical nanoparticles of hexagonal and cubic forms of cobalt and Co-Ni (1:1) alloy nanoparticles with the average size of 4, 8 and 20 nm, respectively. Electrochemical studies show that the catalytic property towards oxygen evolution is dependent on the applied voltage. At low voltage (less than 0.65 V) the Co (hexagonal) nanoparticles are superior to the alloy (Co-Ni) nanoparticles while above this voltage the alloy nanoparticles are more efficient catalysts. The nanoparticles of cobalt (hcp and fcc) and alloy (Co-Ni) nanoparticles show ferromagnetism. The saturation magnetization of Co-Ni nanoparticles is reduced compared to the bulk possibly due to surface oxidation.

  18. Low-Cobalt Powder-Metallurgy Superalloy

    NASA Technical Reports Server (NTRS)

    Harf, F. H.

    1986-01-01

    Highly-stressed jet-engine parts made with less cobalt. Udimet 700* (or equivalent) is common nickel-based superalloy used in hot sections of jet engines for many years. This alloy, while normally used in wrought condition, also gas-atomized into prealloyed powder-metallurgy (PM) product. Product can be consolidated by hot isostatically pressing (HIPPM condition) and formed into parts such as turbine disk. Such jet-engine disks "see" both high stresses and temperatures to 1,400 degrees F (760 degrees C).

  19. Exafs data analysis of some cobalt complexes

    NASA Astrophysics Data System (ADS)

    Mishra, A.; Vibhute, Vishakha; Jain, Garima; Ninama, Samrath

    2012-05-01

    X-ray spectroscopy has assumed great significance with its increasing application in the different fields of physics like solid state physics, chemical physics, atomic physics, Plasma Physics and Astro physics etc.in present paper we obtained bond lengths of cobalt metal complexes using Levy's, LSS and Lytle methods and are compared by FEFFIT (Fitting of EXAFS by Fast Fourier Inverse Transform) method. Bond length basically known as radial distance between ligand and metal complexes. FEFFIT is computer program for calculating bond length obtained theoretical data of EXAFS.

  20. Cobalt-phosphate oxygen-evolving compound.

    PubMed

    Kanan, Matthew W; Surendranath, Yogesh; Nocera, Daniel G

    2009-01-01

    The utilization of solar energy on a large scale requires efficient storage. Solar-to-fuels has the capacity to meet large scale storage needs as demonstrated by natural photosynthesis. This process uses sunlight to rearrange the bonds of water to furnish O2 and an H2-equivalent. We present a tutorial review of our efforts to develop an amorphous cobalt-phosphate catalyst that oxidizes water to O2. The use of earth-abundant materials, operation in water at neutral pH, and the formation of the catalyst in situ captures functional elements of the oxygen evolving complex of Photosystem II.

  1. Cyanidotetra-kis-(trimethyl-phosphine)cobalt(I).

    PubMed

    Xu, Xiaofeng; Feng, Lei; Li, Xiaoyan

    2011-04-01

    The title compound, [Co(CN)(C(3)H(9)P)(4)], was obtained as a product of the reaction of [Co(PMe(3))(4)] with a molar equivalent of 2,6-difluoro-benzonitrile in diethyl ether. This compound is stable in the air for several hours, but rapidly decomposes at room temperature in solution. The cobalt(I) atom has s trigonal-bipyramidal coordination enviroment in which the cyano group and one of the PMe(3) groups are in the axial positions.

  2. Synthesis of lithium cobaltate in halide melts

    NASA Astrophysics Data System (ADS)

    Modenov, D. V.; Dokutovich, V. N.; Khokhlov, V. A.; Antonov, B. D.; Kochedykov, V. A.; Zakir'yanova, I. D.

    2013-02-01

    A new method for the synthesis of lithium cobaltate LiCoo2 in salt melts is proposed and tested. The method is based on the oxidation of halide ions with molecular oxygen in Li X-CoCl2 mixtures ( X = Cl, Br, I). The chemical and phase compositions of the prepared powders and the crystal structure of the synthesized compound are studied by Fourier transform infrared spectroscopy and X-ray diffraction analysis. The average size of LiCoO2 crystallites is estimated from the X-ray diffraction data.

  3. Nitrogen oxides storage catalysts containing cobalt

    DOEpatents

    Lauterbach, Jochen; Snively, Christopher M.; Vijay, Rohit; Hendershot, Reed; Feist, Ben

    2010-10-12

    Nitrogen oxides (NO.sub.x) storage catalysts comprising cobalt and barium with a lean NO.sub.x storage ratio of 1.3 or greater. The NO.sub.x storage catalysts can be used to reduce NO.sub.x emissions from diesel or gas combustion engines by contacting the catalysts with the exhaust gas from the engines. The NO.sub.x storage catalysts can be one of the active components of a catalytic converter, which is used to treat exhaust gas from such engines.

  4. Hot Corrosion of Cobalt-Base Alloys

    DTIC Science & Technology

    1975-06-01

    Cast Alloys : NASA VIA, B-1900, 713C and 738X", Report NASA TN D-7682, Lewis Research Center, Cleveland, Ohio, August 1974. 36. Giggins, C.S. and...resistance of cobalt-base and nickel-base alloys . The contract was accomplished under the technical direction of Dr. H. C. Graham of the Aerospace Research...Interpretation of Results 3. SODIUM SULFATE INDUCED HOT CORROSION OF Co-25Al AND Co-35Cr ALLOYS a. Introduction b. Experimental Co-25Al c. Experimental

  5. The Cytotoxicity and Genotoxicity of Particulate and Soluble Cobalt in Human Urothelial Cells.

    PubMed

    Speer, Rachel M; The, Therry; Xie, Hong; Liou, Louis; Adam, Rosalyn M; Wise, John Pierce

    2017-03-21

    Cobalt use is increasing particularly due to its use as one of the primary metals in cobalt-chromium-molybdenum (CoCrMo) metal-on-metal prosthetics. CoCrMo is a high-strength, wear-resistant alloy with reduced risk for prosthetic loosening and device fracture. More than 500,000 people receive hip implants each year in the USA which puts them at potential risk for exposure to metal ions and particles released by the prosthetic implants. Data show cobalt ions released from prosthetics reach the bloodstream and accumulate in the bladder. As patients with failed hip implants show increased urinary and blood cobalt levels, no studies have considered the effects of cobalt on human urothelial cells. Accordingly, we investigated the cytotoxic and genotoxic effects of particulate and soluble cobalt in urothelial cells. Exposure to both particulate and soluble cobalt resulted in a concentration-dependent increase in cytotoxicity, genotoxicity, and intracellular cobalt ions. Based on intracellular cobalt ion levels, we found, when compared to particulate cobalt, soluble cobalt was more cytotoxic, but induced similar levels of genotoxicity. Interestingly, at similar intracellular cobalt ion concentrations, soluble cobalt induced cell cycle arrest indicated by a lack of metaphases not observed after particulate cobalt treatment. These data indicate that cobalt compounds are cytotoxic and genotoxic to human urothelial cells and solubility may play a key role in cobalt-induced toxicity.

  6. Comparison of supplemental cobalt form on fibre digestion and cobalamin concentrations in cattle

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Cobalt is essential for rumen microbial metabolism to synthesize methane, acetate and methionine. It also serves as a structural component of vitamin B12, which functions as a coenzyme in energy metabolism. A study was conducted to determine if cobalt form (cobalt carbonate vs cobalt glucoheptonate...

  7. Mechanistic study of hydrogen transfer to imines from a hydroxycyclopentadienyl ruthenium hydride. Experimental support for a mechanism involving coordination of imine to ruthenium prior to hydrogen transfer.

    PubMed

    Samec, Joseph S M; Ell, Alida H; Aberg, Jenny B; Privalov, Timofei; Eriksson, Lars; Bäckvall, Jan-E

    2006-11-08

    Reaction of [2,3,4,5-Ph(4)(eta(5)-C(4)COH)Ru(CO)(2)H] (2) with different imines afforded ruthenium amine complexes at low temperatures. At higher temperatures in the presence of 2, the complexes decomposed to give [Ru(2)(CO)(4)(mu-H)(C(4)Ph(4)COHOCC(4)Ph(4))] (1) and free amine. Electron-rich imines gave ruthenium amine complexes with 2 at a lower temperature than did electron-deficient imines. The negligible deuterium isotope effect (k(RuHOH)/k(RuDOD) = 1.05) observed in the reaction of 2 with N-phenyl[1-(4-methoxyphenyl)ethylidene]amine (12) shows that neither hydride (RuH) nor proton (OH) is transferred to the imine in the rate-determining step. In the dehydrogenation of N-phenyl-1-phenylethylamine (4) to the corresponding imine 8 by [2,3,4,5-Ph(4)(eta(4)-C(4)CO)Ru(CO)(2)] (A), the kinetic isotope effects observed support a stepwise hydrogen transfer where the isotope effect for C-H cleavage (k(CHNH)/k(CDNH) = 3.24) is equal to the combined (C-H, N-H) isotope effect (k(CHNH)/k(CDND) = 3.26). Hydrogenation of N-methyl(1-phenylethylidene)amine (14) by 2 in the presence of the external amine trap N-methyl-1-(4-methoxyphenyl)ethylamine (16) afforded 90-100% of complex [2,3,4,5-Ph(4)(eta(4)-C(4)CO)]Ru(CO)(2)NH(CH(3))(CHPhCH(3)) (15), which is the complex between ruthenium and the amine newly generated from the imine. At -80 degrees C the reaction of hydride 2 with 4-BnNH-C(6)H(9)=NPh (18), with an internal amine trap, only afforded [2,3,4,5-Ph(4)(eta(4)-C(4)CO)](CO)(2)RuNH(Ph)(C(6)H(10)-4-NHBn) (19), where the ruthenium binds to the amine originating from the imine, showing that neither complex A nor the diamine is formed. Above -8 degrees C complex 19 rearranged to the thermodynamically more stable [Ph(4)(eta(4)-C(4)CO)](CO)(2)RuNH(Bn)(C(6)H(10)-4-NHPh) (20). These results are consistent with an inner sphere mechanism in which the substrate coordinates to ruthenium prior to hydrogen transfer and are difficult to explain with the outer sphere pathway previously

  8. The nature of unsupported uranium-ruthenium bonds: a combined experimental and theoretical study.

    PubMed

    Gardner, Benedict M; Patel, Dipti; Cornish, Andrew D; McMaster, Jonathan; Lewis, William; Blake, Alexander J; Liddle, Stephen T

    2011-09-26

    Four new uranium-ruthenium complexes, [(Tren(TMS))URu(η(5)-C(5)H(5))(CO)(2)] (9), [(Tren(DMSB))URu(η(5)-C(5)H(5))(CO)(2)] (10), [(Ts(Tolyl))(THF)URu(η(5)-C(5)H(5))(CO)(2)] (11), and [(Ts(Xylyl))(THF)URu(η(5)-C(5)H(5))(CO)(2)] (12) [Tren(TMS)=N(CH(2)CH(2)NSiMe(3))(3); Tren(DMSB)=N(CH(2)CH(2)NSiMe(2)tBu)(3)]; Ts(Tolyl)=HC(SiMe(2)NC(6)H(4)-4-Me)(3); Ts(Xylyl)=HC(SiMe(2)NC(6)H(3)-3,5-Me(2))(3)], were prepared by a salt-elimination strategy. Structural, spectroscopic, and computational analyses of 9-12 shows: i) the formation of unsupported uranium-ruthenium bonds with no isocarbonyl linkages in the solid state; ii) ruthenium-carbonyl backbonding in the [Ru(η(5)-C(5)H(5))(CO)(2)](-) ions that is tempered by polarization of charge within the ruthenium fragments towards uranium; iii) closed-shell uranium-ruthenium interactions that can be classified as predominantly ionic with little covalent character. Comparison of the calculated U-Ru bond interaction energies (BIEs) of 9-12 with the BIE of [(η(5)-C(5)H(5))(3)URu(η(5)-C(5)H(5))(CO)(2)], for which an experimentally determined U-Ru bond disruption enthalpy (BDE) has been reported, suggests BDEs of approximately 150 kJ mol(-1) for 9-12.

  9. Use of Ruthenium Photooxidation Techniques to Study Electron Transfer in the Cytochrome bc1 Complex

    PubMed Central

    Millett, Francis; Durham, Bill

    2009-01-01

    Ruthenium photooxidation methods are presented to study electron transfer between the cytochrome bc1 complex and cytochrome c, and within the cytochrome bc1 complex. Methods are described to prepare a ruthenium cytochrome c derivative, Ruz-39-Cc, by labeling the single sulfhydryl on yeast H39C;C102T iso-1-Cc with the reagent Ru(bpz)2(4-bromomethyl-4′-methylbipyridine). The ruthenium complex attached to Cys-39 on the opposite side of Cc from the heme crevice does not affect the interaction with cyt bc1. Laser excitation of reduced Ruz-39-Cc results in photooxidation of heme c within 1 μs with a yield of 20%. Flash photolysis of a 1:1 complex between reduced yeast cytochrome bc1 and Ruz-39-Cc leads to electron transfer from heme c1 to heme c with a rate constant of 1.4 × 104 s-1. Methods are described for the use of the ruthenium dimer, Ru2D, to photooxidize cyt c1 in the cytochrome bc1 complex within 1 μs with a yield of 20%. Electron transfer from the Rieske iron-sulfur center [2Fe2S] to cyt c1 was detected with a rate constant of 6 × 104 s-1 in R. sphaeroides cyt bc1 using this method. This electron transfer step is rate-limited by the rotation of the Rieske iron-sulfur protein in a conformational gating mechanism. This method provides critical information on the dynamics of rotation of the iron-sulfur protein (ISP) as it transfers electrons from QH2 in the Qo site to cyt c1 These ruthenium photooxidation methods can be used to measure many of the electron transfer reactions in cytochrome bc1 complexes from any source. PMID:19348884

  10. Identification of the structural determinants for anticancer activity of a ruthenium arene peptide conjugate.

    PubMed

    Meier, Samuel M; Novak, Maria; Kandioller, Wolfgang; Jakupec, Michael A; Arion, Vladimir B; Metzler-Nolte, Nils; Keppler, Bernhard K; Hartinger, Christian G

    2013-07-08

    Organometallic Ru(arene)-peptide bioconjugates with potent in vitro anticancer activity are rare. We have prepared a conjugate of a Ru(arene) complex with the neuropeptide [Leu(5)]-enkephalin. [Chlorido(η(6)-p-cymene)(5-oxo-κO-2-{(4-[(N-tyrosinyl-glycinyl-glycinyl-phenylalanyl-leucinyl-NH2)propanamido]-1H-1,2,3-triazol-1-yl)methyl}-4H-pyronato-κO)ruthenium(II)] (8) shows antiproliferative activity in human ovarian carcinoma cells with an IC50 value as low as 13 μM, whereas the peptide or the Ru moiety alone are hardly cytotoxic. The conjugation strategy for linking the Ru(cym) (cym=η(6)-p-cymene) moiety to the peptide involved N-terminal modification of an alkyne-[Leu(5)]-enkephalin with a 2-(azidomethyl)-5-hydroxy-4H-pyran-4-one linker, using Cu(I)-catalyzed alkyne-azide cycloaddition (CuAAC), and subsequent metallation with the Ru(cym) moiety. The ruthenium-bioconjugate was characterized by high resolution top-down electrospray ionization mass spectrometry (ESI-MS) with regard to peptide sequence, linker modification and metallation site. Notably, complete sequence coverage was obtained and the Ru(cym) moiety was confirmed to be coordinated to the pyronato linker. The ruthenium-bioconjugate was analyzed with respect to cytotoxicity-determining constituents, and through the bioconjugate models [{2-(azidomethyl)-5-oxo-κO-4H-pyronato-κO}chloride (η(6)-p-cymene)ruthenium(II)] (5) and [chlorido(η(6)-p-cymene){5-oxo-κO-2-([(4-(phenoxymethyl)-1H-1,2,3-triazol-1-yl]methyl)-4H-pyronato-κO}ruthenium(II)] (6) the Ru(cym) fragment with a triazole-carrying pyronato ligand was identified as the minimal unit required to achieve in vitro anticancer activity.

  11. Synthesis and reactivity of compounds containing ruthenium-carbon, -nitrogen, and -oxygen bonds

    SciTech Connect

    Hartwig, J.F.

    1990-12-01

    The products and mechanisms of the thermal reactions of several complexes of the general structure (PMe{sub 3}){sub 4}Ru(X)(Y) and (DMPM){sub 2}Ru(X)(Y) where X and Y are hydride, aryl, and benzyl groups, have been investigated. The mechanism of decomposition depends critically on the structure of the complex and the medium in which the thermolysis is carried out. The alkyl hydride complexes are do not react with alkane solvent, but undergo C-H activation processes with aromatic solvents by several different mechanisms. Thermolysis of (PMe{sub 3}){sub 4}Ru(Ph)(Me) or (PMe{sub 3}){sub 4}Ru(Ph){sub 2} leads to the ruthenium benzyne complex (PMe{sub 3}){sub 4}Ru({eta}{sup 2}-C{sub 6}H{sub 4}) (1) by a mechanism which involves reversible dissociation of phosphine. In many ways its chemistry is analogous to that of early rather than late organo transition metal complexes. The synthesis, structure, variable temperature NMR spectroscopy and reactivity of ruthenium complexes containing aryloxide or arylamide ligands are reported. These complexes undergo cleavage of a P-C bond in coordinated trimethylphosphine, insertion of CO and CO{sub 2} and hydrogenolysis. Mechanistic studies on these reactions are described. The generation of a series of reactive ruthenium complexes of the general formula (PMe{sub 3}){sub 4}Ru(R)(enolate) is reported. Most of these enolates have been shown to bind to the ruthenium center through the oxygen atom. Two of the enolate complexes 8 and 9 exist in equilibrium between the O- and C-bound forms. The reactions of these compounds are reported, including reactions to form oxygen-containing metallacycles. The structure and reactivity of these ruthenium metallacycles is reported, including their thermal chemistry and reactivity toward protic acids, electrophiles, carbon monoxide, hydrogen and trimethylsilane. 243 refs., 10 tabs.

  12. Photoinduced electron transfer in ruthenium(II)/Tin(IV) multiporphyrin arrays.

    PubMed

    Indelli, M Teresa; Chiorboli, Claudio; Ghirotti, Marco; Orlandi, Michele; Scandola, Franco; Kim, Hyun Jung; Kim, Hee-Joon

    2010-11-18

    The photophysical behavior of a series of heterometallic arrays made of a central Sn(IV) porphyrin connected, respectively, to two (SnRu(2)), four (SnRu(4)), or six (SnRu(6)) ruthenium porphyrin units has been studied in dichloromethane. Two different motifs connect the ruthenium porphyrin units to central tin porphyrin core, axial coordination via ditopic bridging ligands and/or coordination to peripheral pyridyl groups of the central porphyrin ring. A remarkable number of electron transfer processes (photoinduced charge separation and recombination processes) have been time-resolved using a combination of emission spectroscopy and fast (nanosecond) and ultrafast (femtosecond) absorption techniques. In these systems both types of molecular components can be selectively populated by light absorption. In all the arrays, the local excited states of these units (the tin porphyrin singlet excited state and the ruthenium porphyrin triplet state) are quenched by electron transfer leading to a charge-separated state where the ruthenium porphyrin unit is oxidized and the tin porphyrin unit is reduced. For each array, the two forward electron transfer processes, as well as the charge recombination process leading back to the ground state, have been kinetically resolved. The rate constants obey standard free-energy correlations with the forward processes lying in the normal free-energy regime and the back reactions in the Marcus inverted region. The comparison between the trimeric (SnRu(2)) and pentameric (SnRu(4)) arrays shows that all the electron transfer processes are faster in the latter than in the former system. This can be rationalized in terms of differences in electronic factors (due to the different connecting motifs) and driving force. In less polar solvents, such as toluene, the energy of the charge-separated states is substantially lifted, leading to a switch (from electron transfer to triplet energy transfer) in the deactivation mechanism of the excited

  13. Cataractogenesis after Cobalt-60 eye plaque radiotherapy

    SciTech Connect

    Kleineidam, M.; Augsburger, J.J. ); Hernandez, C.; Glennon, P.; Brady, L.W. )

    1993-07-15

    This study was designed to estimate the actuarial incidence of typical postirradiation cataracts and to identify prognostic factors related to their development in melanoma-containing eyes treated by Cobalt-60 plaque radiotherapy. A special interest was the impact of calculated radiation dose and dose-rate to the lens. The authors evaluated the actuarial occurrence of post-irradiation cataract in 365 patients with primary posterior uveal melanoma treated by Cobalt-60 plaque radiotherapy between 1976 and 1986. Only 22% (S.E. = 4.6%) of the patients who received a total dose of 6 to 20 Gy at the center of the lens developed a visually significant cataract attributable to the radiation within 5 years after treatment. Using multivariate Cox proportional hazards modeling, the authors identified thickness of the tumor, location of the tumor's anterior margin relative to the equatorward and the ora serrata, and diameter of the eye plaque used as the best combination of covariables for predicting length of time until development of cataract. Surprisingly, the dose of radiation delivered to the lens, which was strongly correlated to all of these covariables, was not a significant predictive factor in multivariate analysis. The results suggest that success of efforts to decrease the occurrence rate of post-irradiation cataracts by better treatment planning might be limited in patients with posterior uveal melanoma. 21 refs., 2 figs., 5 tabs.

  14. Laser Induced Fluorescence Spectroscopy of Cobalt Monoboride

    NASA Astrophysics Data System (ADS)

    Pang, H. F.; Ng, Y. W.; Cheung, A. S.-C.

    2011-06-01

    Laser induced fluorescence spectrum of cobalt monoboride (CoB) in the visible region between 465 and 560 nm has been observed. CoB molecule was produced by the reaction of laser ablated cobalt atom and diborane (B_2H_6) seeded in argon. Over twenty five vibronic bands have been recorded, and both Co10B and Co11B isotopic species have been observed and analyzed. Preliminary analysis of the rotational lines showed that the observed vibronic bands belong to two categories namely: the Ω' = 2 - Ω'' = 2 and the Ω' = 3 - Ω'' = 3 transitions, which indicated the ground state of CoB is consistent with an assignment of a ^3Δ_i state predicted from ab initio calculations. Unresolved hyperfine structure arising from the Co nucleus (I = 7/2) causes a broadening of spectral lines. This work represents the first experimental investigation of the spectrum of the CoB molecule. Financial support from the Research Grants Council of the Hong Kong Special Administrative Region, China (Project No. HKU 701008P) is gratefully acknowledged.

  15. Preparation and characterization of electrodeposited cobalt nanowires

    SciTech Connect

    Irshad, M. I. Mohamed, N. M.; Ahmad, F. Abdullah, M. Z.

    2014-10-24

    Electrochemical deposition technique has been used to deposit cobalt nanowires into the nano sized channels of Anodized Aluminium Oxide (AAO) templates. CoCl{sub 2}Ðœ‡6H2O salt solution was used, which was buffered with H{sub 3}BO{sub 3} and acidified by dilute H{sub 2}SO{sub 4} to increase the plating life and control pH of the solution. Thin film of copper around 150 nm thick on one side of AAO template coated by e-beam evaporation system served as cathode to create electrical contact. FESEM analysis shows that the as-deposited nanowires are highly aligned, parallel to one another and have high aspect ratio with a reasonably high pore-filing factor. The TEM results show that electrodeposited cobalt nanowires are crystalline in nature. The Hysteresis loop shows the magnetization properties for in and out of plane configuration. The in plane saturation magnetization (Ms) is lower than out of plane configuration because of the easy axis of magnetization is perpendicular to nanowire axis. These magnetic nanowires could be utilized for applications such as spintronic devices, high density magnetic storage, and magnetic sensor applications.

  16. Nanocomposites of magnetic cobalt nanoparticles and cellulose

    NASA Astrophysics Data System (ADS)

    Pirkkalainen, K.; Leppänen, K.; Vainio, U.; Webb, M. A.; Elbra, T.; Kohout, T.; Nykänen, A.; Ruokolainen, J.; Kotelnikova, N.; Serimaa, R.

    2008-10-01

    Polymeric matrices with stabilized metallic nanoparticles constitute an important class of nanostructured materials, because polymer technology allows fabrication of components with various electronic, magnetic and mechanical properties. The porous cellulose matrix has been shown to be a useful support material for platinum, palladium, silver, copper and nickel nanoparticles. In the present study, nanosized cobalt particles with enhanced magnetic properties were made by chemical reduction within a microcrystalline cellulose (MCC) matrix. Two different chemical reducers, NaBH4 and NaH2PO2, were used, and the so-formed nanoparticles were characterized with X-ray absorption spectroscopy, X-ray diffraction, scanning electron microscopy and transmission electron microscopy. These experimental techniques were used to gain insight into the effect of different synthesis routes on structural properties of the nanoparticles. Magnetic properties of the nanoparticles were studied using a vibrating sample magnetometer. Particles made via the NaBH4 reduction were amorphous Co-B or Co oxide composites with diminished ferromagnetic behaviour and particles made via the NaH2PO2 reduction were well-ordered ferromagnetic hcp cobalt nanocrystals.

  17. Ruthenium Catalyzed Reductive Coupling of Paraformaldehyde to Trifluoromethyl Allenes: CF3-Bearing All-Carbon Quaternary Centers

    PubMed Central

    Sam, Brannon; Montgomery, T. Patrick; Krische, Michael J.

    2013-01-01

    Trifluoromethyl substituted allenes engage in ruthenium catalyzed reductive couplings with paraformaldehyde to form products of hydrohydroxymethylation as single regioisomers. This method enables generation of CF3-bearing all-carbon quaternary stereocenters. PMID:23841678

  18. High contrast solid state electrochromic devices based on Ruthenium Purple nanocomposites fabricated by layer-by-layer assembly.

    PubMed

    Jain, Vaibhav; Sahoo, Rabindra; Jinschek, Joerg R; Montazami, Reza; Yochum, Hank M; Beyer, Fredrick L; Kumar, Anil; Heflin, James R

    2008-08-21

    Electrochromic Ruthenium Purple-polymer nanocomposite films, fabricated by multilayer assembly, were found to exhibit sub-second switching speed and the highest electrochromic contrast reported to date for any inorganic material.

  19. Ruthenium-catalyzed decarbonylative addition reaction of anhydrides with alkynes: a facile synthesis of isocoumarins and α-pyrones.

    PubMed

    Prakash, Rashmi; Shekarrao, Kommuri; Gogoi, Sanjib; Boruah, Romesh C

    2015-06-21

    A novel ruthenium catalyzed straightforward and efficient synthesis of isocoumarin and α-pyrone derivatives has been accomplished by the decarbonylative addition reaction of anhydrides with alkynes under thermal conditions.

  20. A simple synthetic route to obtain pure trans-ruthenium(II) complexes for dye-sensitized solar cell applications.

    PubMed

    Barolo, Claudia; Yum, Jun-Ho; Artuso, Emma; Barbero, Nadia; Di Censo, Davide; Lobello, Maria Grazia; Fantacci, Simona; De Angelis, Filippo; Grätzel, Michael; Nazeeruddin, Mohammed Khaja; Viscardi, Guido

    2013-11-01

    We report a facile synthetic route to obtain functionalized quaterpyridine ligand and its trans-dithiocyanato ruthenium complex, based on a microwave-assisted procedure. The ruthenium complex has been purified using a silica chromatographic column by protecting carboxylic acid groups as iso-butyl ester, which are subsequently hydrolyzed. The highly pure complex exhibits panchromatic response throughout the visible region. DFT/time-dependent DFT calculations have been performed on the ruthenium complex in solution and adsorbed onto TiO2 to analyze relative electronic and optical properties. The ruthenium complex endowed with the functionalized quaterpyridine ligand was used as a sensitizer in dye-sensitized solar cell yielding a short-circuit photocurrent density of more than 19 mA cm(-2) with a broad incident photon to current conversion efficiency spectra ranging from 400 to 900 nm, exceeding 80 % at 700 nm.

  1. Selective deposition of nanostructured ruthenium oxide using Tobacco mosaic virus for micro-supercapacitors in solid Nafion electrolyte

    NASA Astrophysics Data System (ADS)

    Gnerlich, Markus; Ben-Yoav, Hadar; Culver, James N.; Ketchum, Douglas R.; Ghodssi, Reza

    2015-10-01

    A three-dimensional micro-supercapacitor has been developed using a novel bottom-up assembly method combining genetically modified Tobacco mosaic virus (TMV-1Cys), photolithographically defined micropillars and selective deposition of ruthenium oxide on multi-metallic microelectrodes. The three-dimensional microelectrodes consist of a titanium nitride current collector with two functionalized areas: (1) gold coating on the active electrode area promotes TMV-1Cys adhesion, and (2) sacrificial nickel pads dissolve in ruthenium tetroxide plating solution to produce ruthenium oxide on all electrically connected areas. The microfabricated electrodes are arranged in an interdigitated pattern, and the capacitance per electrode has been measured as high as 203 mF cm-2 with solid Nafion electrolyte. The process integration of bio-templated ruthenium oxide with microfabricated electrodes and solid electrolyte is an important advance towards the energy storage needs of mass produced self-sufficient micro-devices.

  2. High temperature behavior of B2-based ruthenium aluminide systems

    NASA Astrophysics Data System (ADS)

    Cao, Fang

    Ru-modified NiAl-based bond coats have the potential to improve the durability of Superalloy-Thermal Barrier Coating systems (TBCs) for advanced gas turbine engines. A fundamental understanding of the high temperature mechanical behavior across the Ni-Al-Ru B2 phase field can provide direction for the development of these new bond coats for TBCs. The purpose of this study has been to describe the fundamental processes of creep deformation in single phase B2 Ru-Al-Ni ternary alloys which would form the basis for the bond coats. To accomplish this, five ternary alloys with compositions located within the B2 field across the NiAl-RuAl phase region were fabricated and investigated. Special emphasis was placed on characterizing creep deformation and describing the operative creep mechanisms in these alloys. At room temperature, brittle failure was observed in the Ni-rich alloys in compression, while improved strength and ductility were displayed in two Ru-rich ternary alloys at temperatures up to 700°C. Exceptional creep strength was observed in these alloys, as compared to other high melting temperature B2 intermetallics. A continuous increase of the melting temperature and creep resistance with the increasing of the Ru/Ni ratio in these alloys was observed. Post-creep dislocation analyses identified the presence of <100> and <110> edge dislocations in the Ni-rich alloys, while uniformly distributed jogged <100> screw dislocations predominated in the Ru-rich ternary alloys. A transition of the creep mechanism from viscous glide controlled to jogged screw motion in these Ru-Al-Ni ternary B2 alloys with increasing Ru/Ni ratio is demonstrated by the characteristics of the creep deformation process, stress change creep tests, post-creep dislocation analyses, and numerical modeling. Additionally, the knowledge of the cyclic oxidation behavior of ruthenium aluminide-based alloy is essential, as many high-temperature applications for which this intermetallic might be

  3. Red electroluminescence of ruthenium sensitizer functionalized by sulfonate anchoring groups.

    PubMed

    Shahroosvand, Hashem; Abbasi, Parisa; Mohajerani, Ezeddin; Janghouri, Mohammad

    2014-06-28

    We have synthesized five novel Ru(ii) phenanthroline complexes with an additional aryl sulfonate ligating substituent at the 5-position [Ru(L)(bpy)2](BF4)2 (1), [Ru(L)(bpy)(SCN)2] (2), [Ru(L)3](BF4)2 (3), [Ru(L)2(bpy)](BF4)2 (4) and [Ru(L)(BPhen)(SCN)2] (5) (where L = 6-one-[1,10]phenanthroline-5-ylamino)-3-hydroxynaphthalene 1-sulfonic, bpy = 2,2'-bipyridine, BPhen = 4,7-diphenyl-1,10-phenanthroline), as both photosensitizers for oxide semiconductor solar cells (DSSCs) and light emitting diodes (LEDs). The absorption and emission maxima of these complexes red shifted upon extending the conjugation of the phenanthroline ligand. Ru phenanthroline complexes exhibit broad metal to ligand charge transfer-centered electroluminescence (EL) with a maximum near 580 nm. Our results indicated that a particular structure (2) can be considered as both DSSC and OLED devices. The efficiency of the LED performance can be tuned by using a range of ligands. Device (2) has a luminance of 550 cd m(-2) and maximum efficiency of 0.9 cd A(-1) at 18 V, which are the highest values among the five devices. The turn-on voltage of this device is approximately 5 V. The role of auxiliary ligands in the photophysical properties of Ru complexes was investigated by DFT calculation. We have also studied photovoltaic properties of dye-sensitized nanocrystalline semiconductor solar cells based on Ru phenanthroline complexes and an iodine redox electrolyte. A solar energy to electricity conversion efficiency (η) of 0.67% was obtained for Ru complex (2) under standard AM 1.5 irradiation with a short-circuit photocurrent density (Jsc) of 2.46 mA cm(-2), an open-circuit photovoltage (Voc) of 0.6 V, and a fill factor (ff) of 40%, which are all among the highest values for ruthenium sulfonated anchoring groups reported so far. Monochromatic incident photon to current conversion efficiency was 23% at 475 nm. Photovoltaic studies clearly indicated dyes with two SCN substituents yielded a higher Jsc for the

  4. Separation and Recovery of Cobalt from Copper Leach Solutions

    NASA Astrophysics Data System (ADS)

    Jeffers, T. H.

    1985-01-01

    Significant amounts of cobalt, a strategic and critical metal, are present in readily accessible copper recycling leach solutions. However, cost-effective technology is not available to separate and recover the cobalt from this low-grade domestic source. The Bureau of Mines has developed a procedure using a chelating ion-exchange resin from Dow Chemical Co. to successfully extract cobalt from a pH 3.0 copper recycling solution containing only 30 mg/1 cobalt. Cyclic tests with the commercial resin XFS-4195 in 4-ft-high by 1-in.-diameter columns gave an average cobalt extraction of 95% when 65 bed volumes of solution were processed at a flow rate of 4 gpm/ft.2 Elution of the cobalt using a 50 g/l H2SO4 solution yielded an eluate containing 0.5 gli Co. Selective elution of the loaded resin and solvent extraction procedures using di-2-ethylhexyl phosphoric acid (D2EHPA) and Cyanex 272 removed the impurities and produced a cobalt sulfate solution containing 25 g/l Co.

  5. Cobalt ions induce chemokine secretion in primary human osteoblasts.

    PubMed

    Queally, J M; Devitt, B M; Butler, J S; Malizia, A P; Murray, D; Doran, P P; O'Byrne, J M

    2009-07-01

    Chemokines are major regulators of the inflammatory response and have been shown to play an important role in periprosthetic osteolysis. Titanium particles have previously been shown to induce IL-8 and MCP-1 secretion in osteoblasts. These chemokines result in the chemotaxis and activation of neutrophils and macrophages, respectively. Despite a resurgence in the use of cobalt-chromium-molybdenum alloys in metal-on-metal arthroplasty, cobalt and chromium ion toxicity in the periprosthetic area has been insufficiently studied. In this study we investigate the in vitro effect of cobalt ions on primary human osteoblast activity. We demonstrate that cobalt ions rapidly induce the protein secretion of IL-8 and MCP-1 in primary human osteoblasts. This elevated chemokine secretion is preceded by an increase in the transcription of the corresponding chemokine gene. Using a Transwell migration chemotaxis assay we also demonstrate that the chemokines secreted are capable of inducing neutrophil and macrophage migration. Furthermore, cobalt ions significantly inhibit osteoblast function as demonstrated by reduced alkaline phosphatase activity and calcium deposition. In aggregate these data demonstrate that cobalt ions can activate transcription of the chemokine genes IL-8 and MCP-1 in primary human osteoblasts. Cobalt ions are not benign and may play an important role in the pathogenesis of osteolysis by suppressing osteoblast function and stimulating the production and secretion of chemokines that attract inflammatory and osteoclastic cells to the periprosthetic area.

  6. Production of cobalt and nickel particles by hydrogen reduction

    NASA Astrophysics Data System (ADS)

    Forsman, J.; Tapper, U.; Auvinen, A.; Jokiniemi, J.

    2008-05-01

    Cobalt and nickel nanoparticles were produced by hydrogen reduction reaction from cobalt or nickel chloride precursor vapour in nitrogen carrier gas. This aerosol phase method to produce nanoparticles is a scalable one-step process. Two different setups were introduced in particle production: a batch type reactor and a continuously operated reactor. Common feature in these setups was hydrogen mixing in a vertical flow reactor. The process was monitored on-line for particle mass concentration and for gas phase chemical reactions. Tapered element oscillating microbalance measured the particle mass concentration and Fourier transform infrared spectroscopy was used to monitor relevant gas phase species. The produced cobalt and nickel particles were characterised using transmission electron microscopy and x-ray diffraction. The produced cobalt and nickel particles were crystalline with cubic fcc structure. Twinning was often observed in cobalt particles while nickel particles were mostly single crystals. The cobalt particles formed typically long agglomerates. No significant neck growth between the primary particles was observed. The primary particle size for cobalt and nickel was below 100 nm.

  7. High doses of cobalt induce optic and auditory neuropathy.

    PubMed

    Apostoli, Pietro; Catalani, Simona; Zaghini, Anna; Mariotti, Andrea; Poliani, Pietro Luigi; Vielmi, Valentina; Semeraro, Francesco; Duse, Sarah; Porzionato, Andrea; Macchi, Veronica; Padovani, Alessandro; Rizzetti, Maria Cristina; De Caro, Raffaele

    2013-09-01

    The adverse biological effects of continuous exposure to cobalt and chromium have been well defined. In the past, this toxicity was largely an industrial issue concerning workers exposed in occupational setting. Nevertheless, recent reports have described a specific toxicity mediated by the high levels of cobalt and chromium released by metallic prostheses, particularly in patients who had received hip implants. Clinical symptoms, including blindness, deafness and peripheral neuropathy, suggest a specific neurotropism. However, little is known about the neuropathological basis of this process, and experimental evidence is still lacking. We have investigated this issue in an experimental setting using New Zealand White rabbits treated with repeated intravenous injections of cobalt and chromium, alone or in combination. No evident clinical or pathological alterations were associated after chromium administration alone, despite its high levels in blood and tissue while cobalt-chromium and cobalt-treated rabbits showed clinical signs indicative of auditory and optic system toxicity. On histopathological examination, the animals showed severe retinal and cochlear ganglion cell depletion along with optic nerve damage and loss of sensory cochlear hair cells. Interestingly, the severity of the alterations was related to dosages and time of exposure. These data confirmed our previous observation of severe auditory and optic nerve toxicity in patients exposed to an abnormal release of cobalt and chromium from damaged hip prostheses. Moreover, we have identified the major element mediating neurotoxicity to be cobalt, although the molecular mechanisms mediating this toxicity still have to be defined.

  8. Selective catalytic reduction system and process for treating NOx emissions using a palladium and rhodium or ruthenium catalyst

    DOEpatents

    Sobolevskiy, Anatoly; Rossin, Joseph A.; Knapke, Michael J.

    2011-07-12

    A process for the catalytic reduction of nitrogen oxides (NOx) in a gas stream (29) in the presence of H.sub.2 is provided. The process comprises contacting the gas stream with a catalyst system (38) comprising zirconia-silica washcoat particles (41), a pre-sulfated zirconia binder (44), and a catalyst combination (40) comprising palladium and at least one of rhodium, ruthenium, or a mixture of ruthenium and rhodium.

  9. Cobalt catalysis involving π components in organic synthesis.

    PubMed

    Gandeepan, Parthasarathy; Cheng, Chien-Hong

    2015-04-21

    Over the last three decades, transition-metal-catalyzed organic transformations have been shown to be extremely important in organic synthesis. However, most of the successful reactions are associated with noble metals, which are generally toxic, expensive, and less abundant. Therefore, we have focused on catalysis using the abundant first-row transition metals, specifically cobalt. In this Account, we demonstrate the potential of cobalt catalysis in organic synthesis as revealed by our research. We have developed many useful catalytic systems using cobalt complexes. Overall, they can be classified into several broad types of reactions, specifically [2 + 2 + 2] and [2 + 2] cycloadditions; enyne reductive coupling; reductive [3 + 2] cycloaddition of alkynes/allenes with enones; reductive coupling of alkyl iodides with alkenes; addition of organoboronic acids to alkynes, alkenes, or aldehydes; carbocyclization of o-iodoaryl ketones/aldehydes with alkynes/electron-deficient alkenes; coupling of thiols with aryl and alkyl halides; enyne coupling; and C-H bond activation. Reactions relying on π components, specifically cycloaddition, reductive coupling, and enyne coupling, mostly afford products with excellent stereo- and regioselectivity and superior atom economy. We believe that these cobalt-catalyzed π-component coupling reactions proceed through five-membered cobaltacyclic intermediates formed by the oxidative cyclometalation of two coordinated π bonds of the substrates to the low-valent cobalt species. The high regio- and stereoselectivity of these reactions are achieved as a result of the electronic and steric effects of the π components. Mostly, electron-withdrawing groups and bulkier groups attached to the π bonds prefer to be placed near the cobalt center of the cobaltacycle. Most of these transformations proceed through low-valent cobalt complexes, which are conveniently generated in situ from air-stable Co(II) salts by Zn- or Mn-mediated reduction

  10. Divergent Reactivity via Cobalt Catalysis: An Epoxide Olefination.

    PubMed

    Jamieson, Megan L; Hume, Paul A; Furkert, Daniel P; Brimble, Margaret A

    2016-02-05

    Cobalt salts exert an unexpected and profound influence on the reactivity of epoxides with dimethylsulfoxonium methylide. In the presence of a cobalt catalyst, conditions for epoxide to an oxetane ring expansion instead deliver homoallylic alcohol products, corresponding to a two-carbon epoxide homologation/ring-opening tandem process. The observed reactivity change appears to be specifically due to cobalt salts and is broadly applicable to a variety of epoxides, retaining the initial stereochemistry. This transformation also provides operationally simple access to enantiopure homoallylic alcohols from chiral epoxides without use of organometallic reagents. Tandem epoxidation-homologation of aldehydes in a single step is also demonstrated.

  11. Cobalt-based particles formed upon electrocatalytic hydrogen production by a cobalt pyridine oxime complex.

    PubMed

    Ghachtouli, Sanae El; Guillot, Regis; Brisset, Francois; Aukauloo, Ally

    2013-12-01

    An open-coordination-sphere cobalt(III) oximato-based complex was designed as a putative catalyst for the hydrogen evolution reaction (HER). Electrochemical alteration in the presence of acid occurs, leading to the formation of cobalt-based particles that act as an efficient catalyst for HER at pH 7. The exact chemical nature of these particles is yet to be determined. This study thus raises interesting issues regarding the fate of molecular-based complexes designed for the HER, and points to the challenging task of identifying the real catalytic species. Moreover, understanding and rationalizing the alteration pathways can be seen as a new route to reach catalytic particulates.

  12. Ruthenium Red Colorimetric and Birefringent Staining of Amyloid-β Aggregates in Vitro and in Tg2576 Mice

    PubMed Central

    2012-01-01

    Alzheimer’s disease (AD) is a devastating neurodegenerative disease most notably characterized by the misfolding of amyloid-β (Aβ) into fibrils and its accumulation into plaques. In this Article, we utilize the affinity of Aβ fibrils to bind metal cations and subsequently imprint their chirality to bound molecules to develop novel imaging compounds for staining Aβ aggregates. Here, we investigate the cationic dye ruthenium red (ammoniated ruthenium oxychloride) that binds calcium-binding proteins, as a labeling agent for Aβ deposits. Ruthenium red stained amyloid plaques red under light microscopy, and exhibited birefringence under crossed polarizers when bound to Aβ plaques in brain tissue sections from the Tg2576 mouse model of AD. Staining of Aβ plaques was confirmed via staining of the same sections with the fluorescent amyloid binding dye Thioflavin S. In addition, it was confirmed that divalent cations such as calcium displace ruthenium red, consistent with a mechanism of binding by electrostatic interaction. We further characterized the interaction of ruthenium red with synthetic Aβ fibrils using independent biophysical techniques. Ruthenium red exhibited birefringence and induced circular dichroic bands at 540 nm upon binding to Aβ fibrils due to induced chirality. Thus, the chirality and cation binding properties of Aβ aggregates could be capitalized for the development of novel amyloid labeling methods, adding to the arsenal of AD imaging techniques and diagnostic tools. PMID:23509974

  13. Growth and characterization of CVD ruthenium and amorphous ruthenium-phosphorus alloy films for liner application in copper interconnect

    NASA Astrophysics Data System (ADS)

    Shin, Jinhong

    Copper interconnect requires liner materials that function as a diffusion barrier, a seed layer for electroplating, and an adhesion promoting layer. Ruthenium has been considered as a promising liner material, however it has been reported that Ru itself is not an effective Cu diffusion barrier due to its microstructure, which is polycrystalline with columnar grains. The screening study of Ru precursors revealed that all Ru films were polycrystalline with columnar structure, and, due to its strong 3D growth mode, a conformal and ultrathin Ru film was difficult to form, especially on high aspect ratio features. The microstructure of Ru films can be modified by incorporating P. Amorphous Ru(P) films are formed by chemical vapor deposition at 575 K using a single source precursor, cis-RuH2(P(CH3) 3)4, or dual sources, Ru3(CO)12 and P(CH3)3 or P(C6H5)3. The films contain Ru and P, which are in zero-valent states, and C as an impurity. Phosphorus dominantly affects the film microstructure, and incorporating >13% P resulted in amorphous Ru(P) films. Metastable Ru(P) remains amorphous after annealing at 675 K for 3 hr, and starts recrystallization at ˜775 K. The density of states analysis of the amorphous Ru(P) alloy illustrates metallic character of the films, and hybridization between Ru 4d and P 3p orbitals, which contributes to stabilizing the amorphous structure. Co-dosing P(CH) 3 with Ru3(CO)12 improves film step coverage, and the most conformal Ru(P) film is obtained with cis-RuH 2(P(CH3)3)4; a fully continuous 5 nm Ru(P) film is formed within 1 mum deep, 8:1 aspect ratio trenches. First principles density functional theory calculations illustrate degraded Cu/Ru adhesion by the presence of P at the interface, however, due to the strong Ru-Cu bonds, amorphous Ru(P) forms a stronger interface with Cu than Ta and TaN do. Cu diffusion studies at 575 K suggests improved barrier property of amorphous Ru(P) films over polycrystalline PVD Ru.

  14. Atomic layer deposition of ruthenium and ruthenium dioxide: New process development, fabrication of heterostructured nanoelectrodes, and applications in energy storage

    NASA Astrophysics Data System (ADS)

    Gregorczyk, Keith E.

    The ability to fabricate heterostructured nanomaterials with each layer of the structure having some specific function, i.e. energy storage, charge collection, etc., has recently attracted great interest. Of the techniques capable of this type of process, atomic layer deposition (ALD) remains unique due to its monolayer thickness control, extreme conformality, and wide variety of available materials. This work aims at using ALD to fabricate fully integrated heterostructured nanomaterials. To that end, two ALD processes, using a new and novel precursor, bis(2,6,6-trimethyl-cyclohexadienyl)ruthenium, were developed for Ru and RuO2 showing stable growth rates of 0.5 A/cycle and 0.4 A/cycle respectively. Both process are discussed and compared to similar processes reported in the literature. The Ru process is shown to have significantly lower nucleation while the RuO2 is the first fully characterized ALD process known. Using the fully developed RuO2 ALD process, thin film batteries were fabricated and tested in standard coin cell configurations. These cells showed high first cycle gravimetric capacities of ˜1400 mAh/g, which significantly degraded after ˜40 cycles. Rate performance was also studied and showed a decrease in 1st cycle capacity as a function of increased rate. These results represent the first reports of any RuO2 battery studied beyond 3 cycles. To understand the degradation mechanisms witnessed in the thin film studies in-situ TEM experiments were conducted. Single crystal RuO2 nanowires were grown using a vapor transport method. These nanowires were cycled inside a TEM using Li2O as an electrolyte and showed a ˜95% volume expansion after lithiation, ˜26% of which was irreversible. Furthermore, a chemical irreversibility was also witnessed, where the reaction products Ru and Li2O remain even after full delithiation. With these mechanisms in mind heterostructured nanowires were fabricated in an attempt to improve the cycling performance. Core/shell Ti

  15. Studies of the Codeposition of Cobalt Hydroxide and Nickel Hydroxide

    NASA Technical Reports Server (NTRS)

    Ho, C. H.; Murthy, M.; VanZee, J. W.

    1997-01-01

    Topics considered include: chemistry, experimental measurements, planar film model development, impregnation model development, results and conclusion. Also included: effect of cobalt concentration on deposition/loading; effect of current density on loading distribution.

  16. Cobalt Oxide Hollow Nanoparticles Derived by Bio-Templating

    NASA Technical Reports Server (NTRS)

    Kim, Jae-Woo; Choi, Sang H.; Lillehei, Peter T.; Chu, Sang-Hyon; King, Glen C.; Watt, Gerald D.

    2005-01-01

    We present here the first fabrication of hollow cobalt oxide nanoparticles produced by a protein-regulated site-specific reconstitution process in aqueous solution and describe the metal growth mechanism in the ferritin interior.

  17. Reaction of cobalt in SO2 atmospheric at elevated temperatures

    NASA Technical Reports Server (NTRS)

    Jacobson, N. S.; Worrell, W. L.

    1983-01-01

    The reaction rate of cobalt in SO2 argon environments was measured at 650 C, 700 C, 750 C and 800 C. Product scales consist primarily of an interconnected sulfide phase in an oxide matrix. At 700 C to 800 C a thin sulfide layer adjacent to the metal is also observed. At all temperatures, the rapid diffusion of cobalt outward through the interconnected sulfide appears to be important. At 650 C, the reaction rate slows dramatically after five minutes due to a change in the distribution of these sulfides. At 700 C and 750 C the reaction is primarily diffusion controlled values of diffusivity of cobalt (CoS) calculated from this work show favorable agreement with values of diffusivity of cobalt (CoS) calculated from previous sulfidation work. At 800 C, a surface step becomes rate limiting.

  18. Recovery of Silver and Cobalt from Laboratory Wastes.

    ERIC Educational Resources Information Center

    Foust, Donald F.

    1984-01-01

    Procedures for recovering silver and cobalt from laboratory wastes (including those resulting from student experiments) are presented. The procedures are generally applicable since only common, inexpensive laboratory reagents are needed. (JN)

  19. Battery related cobalt and REE flows in WEEE treatment.

    PubMed

    Sommer, P; Rotter, V S; Ueberschaar, M

    2015-11-01

    In batteries associated with waste electrical and electronic equipment (WEEE), battery systems can be found with a higher content of valuable and critical raw materials like cobalt and rare earth elements (REE) relative to the general mix of portable batteries. Based on a material flow model, this study estimates the flows of REE and cobalt associated to WEEE and the fate of these metals in the end-of-life systems. In 2011, approximately 40 Mg REE and 325 Mg cobalt were disposed of with WEEE-batteries. The end-of-life recycling rate for cobalt was 14%, for REE 0%. The volume of waste batteries can be expected to grow, but variation in the battery composition makes it difficult to forecast the future secondary raw material potential. Nevertheless, product specific treatment strategies ought to be implemented throughout the stages of the value chain.

  20. The Study of a Cobalt Complex--A Laboratory Project.

    ERIC Educational Resources Information Center

    Loehlin, James H.; And Others

    1982-01-01

    Describes an 8-week project involving the synthesis of cobalt compounds. Once synthesized, compounds are qualitatively and quantitatively analyzed. Background information, laboratory procedures, and results/discussion are provided for three project experiments. (Author/JN)

  1. Reaction of cobalt in SO2 atmospheres at elevated temperatures

    NASA Technical Reports Server (NTRS)

    Jacobson, N. S.; Worrell, W. L.

    1984-01-01

    The reaction rate of cobalt in SO2 argon environments was measured at 650 C, 700 C, 750 C and 800 C. Product scales consist primarily of an interconnected sulfide phase in an oxide matrix. At 700 C to 800 C, a thin sulfide layer adjacent to the metal is also observed. At all temperatures, the rapid diffusion of cobalt outward through the interconnected sulfide appears to be important. At 650 C, the reaction rate slows dramatically after five minutes due to a change in the distribution of these sulfides. At 700 C and 750 C, the reaction is primarily diffusion controlled; values of diffusivity of cobalt (CoS) calculated from this work show favorable agreement with values of diffusivity of cobalt (CoS) calculated from previous sulfidation work. At 800 C, a surface step becomes rate limiting. Previously announced in STAR as N83-35104

  2. Exposure to cobalt in the welding process with stellite.

    PubMed

    Ferri, F; Candela, S; Bedogni, L; Piccinini, R; Sala, O

    1994-06-30

    In some small factories producing moulds for ceramic tiles using a cobalt alloy (stellite), environmental and biological (CoU) monitoring was conducted for eight workers employed in gas-shielded arc (MAG) and oxy-acetylene welding processes. During oxy-acetylene braze-welding, the exposure to cobalt is very low as are urinary cobalt concentrations. On the other hand, during the MAG welding process, the exposure levels can exceed the TLV-TWA levels and correlated well with CoU at the end of a working shift. Two MAG welders followed for two consecutive weeks, showed different patterns of urinary cobalt excretion: under the same environmental conditions, the higher CoU was found in the worker with greater past exposure. This aspect needs further evaluation before adopting CoU as a current indicator of occupational exposure to the metal.

  3. 21 CFR 73.1015 - Chromium-cobalt-aluminum oxide.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ...), not more than 30 parts per million. Arsenic (as As), not more than 3 parts per million. Total oxides of aluminum, chromium, and cobalt not less than 97 percent. Lead and arsenic shall be determined...

  4. Segregation of Fischer-Tropsch reactants on cobalt nanoparticle surfaces.

    PubMed

    Lewis, E A; Le, D; Jewell, A D; Murphy, C J; Rahman, T S; Sykes, E C H

    2014-06-21

    Using scanning tunnelling microscopy, we have visualized the segregation of carbon monoxide and hydrogen, the two reactants in Fischer-Tropsch synthesis, on cobalt nanoparticles at catalytically relevant coverages. Density functional theory was used to interrogate the relevant energetics.

  5. Determination of traces of cobalt in soils: A field method

    USGS Publications Warehouse

    Almond, H.

    1953-01-01

    The growing use of geochemical prospecting methods in the search for ore deposits has led to the development of a field method for the determination of cobalt in soils. The determination is based on the fact that cobalt reacts with 2-nitroso-1-naphthol to yield a pink compound that is soluble in carbon tetrachloride. The carbon tetrachloride extract is shaken with dilute cyanide to complex interfering elements and to remove excess reagent. The cobalt content is estimated by comparing the pink color in the carbon tetrachloride with a standard series prepared from standard solutions. The cobalt 2-nitroso-1-naphtholate system in carbon tetrachloride follows Beer's law. As little as 1 p.p.m. can be determined in a 0.1-gram sample. The method is simple and fast and requires only simple equipment. More than 40 samples can be analyzed per man-day with an accuracy within 30% or better.

  6. Magnetic properties of cobalt ferrite synthesized by hydrothermal method

    NASA Astrophysics Data System (ADS)

    Allaedini, Ghazaleh; Tasirin, Siti Masrinda; Aminayi, Payam

    2015-05-01

    In this study, the magnetic properties of nanocrystalline cobalt ferrite synthesized via the hydrothermal method have been investigated. The structural properties of the produced powders were investigated using X-ray diffraction (XRD) and scanning electron microscopy (SEM). The observed XRD pattern confirmed the spinel/cubic structure of the prepared cobalt ferrite. The SEM pictures show that the simple hydrothermal method produces uniform sphere-shaped nanopowders. Moreover, infrared spectroscopy was used to confirm the formation of cobalt ferrite particles. Magnetic hysteresis was measured using a vibrating sample magnetometer in a maximum field of 10 kOe. The magnetization of the prepared nanoparticles was investigated, and the saturation magnetization ( M s), remanence ( M r), and coercivity ( H c) were derived from the hysteresis loops. The results revealed that the cobalt ferrite nanoparticles synthesized via the simple hydrothermal method exhibit superior magnetic properties.

  7. Nitrogen-doped carbon-supported cobalt-iron oxygen reduction catalyst

    SciTech Connect

    Zelenay, Piotr; Wu, Gang

    2014-04-29

    A Fe--Co hybrid catalyst for oxygen reaction reduction was prepared by a two part process. The first part involves reacting an ethyleneamine with a cobalt-containing precursor to form a cobalt-containing complex, combining the cobalt-containing complex with an electroconductive carbon supporting material, heating the cobalt-containing complex and carbon supporting material under conditions suitable to convert the cobalt-containing complex and carbon supporting material into a cobalt-containing catalyst support. The second part of the process involves polymerizing an aniline in the presence of said cobalt-containing catalyst support and an iron-containing compound under conditions suitable to form a supported, cobalt-containing, iron-bound polyaniline species, and subjecting said supported, cobalt-containing, iron bound polyaniline species to conditions suitable for producing a Fe--Co hybrid catalyst.

  8. Cobalt and antimony: genotoxicity and carcinogenicity.

    PubMed

    De Boeck, Marlies; Kirsch-Volders, Micheline; Lison, Dominique

    2003-12-10

    The purpose of this review is to summarise the data concerning genotoxicity and carcinogenicity of Co and Sb. Both metals have multiple industrial and/or therapeutical applications, depending on the considered species. Cobalt is used for the production of alloys and hard metal (cemented carbide), diamond polishing, drying agents, pigments and catalysts. Occupational exposure to cobalt may result in adverse health effects in different organs or tissues. Antimony trioxide is primarily used as a flame retardant in rubber, plastics, pigments, adhesives, textiles, and paper. Antimony potassium tartrate has been used worldwide as an anti-shistosomal drug. Pentavalent antimony compounds have been used for the treatment of leishmaniasis. Co(II) ions are genotoxic in vitro and in vivo, and carcinogenic in rodents. Co metal is genotoxic in vitro. Hard metal dust, of which occupational exposure is linked to an increased lung cancer risk, is proven to be genotoxic in vitro and in vivo. Possibly, production of active oxygen species and/or DNA repair inhibition are mechanisms involved. Given the recently provided proof for in vitro and in vivo genotoxic potential of hard metal dust, the mechanistic evidence of elevated production of active oxygen species and the epidemiological data on increased cancer risk, it may be advisable to consider the possibility of a new evaluation by IARC. Both trivalent and pentavalent antimony compounds are generally negative in non-mammalian genotoxicity tests, while mammalian test systems usually give positive results for Sb(III) and negative results for Sb(V) compounds. Assessment of the in vivo potential of Sb2O3 to induce chromosome aberrations (CA) gave conflicting results. Animal carcinogenicity data were concluded sufficient for Sb2O3 by IARC. Human carcinogenicity data is difficult to evaluate given the frequent co-exposure to arsenic. Possible mechanisms of action, including potential to produce active oxygen species and to interfere with

  9. The Development and Study of Surface Bound Ruthenium Organometallic Complexes

    NASA Astrophysics Data System (ADS)

    Abbott, Geoffrey Reuben

    The focus of this project has been on the use of mono-diimine ruthenium organometallic complexes, of the general structure [H(Ru)(CO)(L)2(L') 2][PF6] (L=PPh3, DPPENE and L'=Bpy, DcBpy, MBpyC, Phen, AminoPhen) bound to surfaces as luminescent probes. Both biological and inorganic/organic hybrid surfaces have been studied. The complexes were characterized both bound and unbound using standard analytical techniques such as NMR, IR and X-ray crystallography, as well as through several photophysical methods as well. Initially the study focused on how the photophyscial properties of the complexes were affected by incorporation into biological membranes. It was found that by conjugating the probes to a more rigid cholesterol moiety that luminescence was conserved, compared to conjugation with a far more flexible lipid moiety, where luminescence was either lost or reduced. Both the cholesterol and lipid conjugates were able to insert into a lipid membrane, and in the more rigid environment some of the lipid conjugates regained some of their luminescence, but often blue shifted and reduced, depending on the conjugation site. Silica Polyamine Composites (SPCs) were a hybrid material developed in the Rosenberg Lab as useful metal separation materials, that could be easily modified, and had several benefits over current commercially available polymers, or inorganic materials. These SPCs also provided an opportunity for the development of a heterogeneous platform for luminescent complexes as either catalysts or sensors. Upon binding of the luminescent Ru complexes to the surface no loss, or major change in luminescence was seen, however, when bound to the rigid surface a significant increase in excited state lifetime was measured. It is likely that through binding and interacting with the surface that the complexes lost non-radiative decay pathways, resulting in the increase in lifetime, however, these interactions do not seem to affect the energy level of the MLCT band in a

  10. Use of phosphate for separation of cobalt from iron

    USGS Publications Warehouse

    North, V.; Wells, R.C.

    1942-01-01

    The well-known tendency of cobalt to be retained by the iron-alumina precipitate produced by ammonia has generally been ascribed to a specific adsorption by the large surface of this gelatinous precipitate. Whatever its cause, it can be overcome by precipitating the iron as phosphate at a pH of 3.5. The precipitate is easily filterable and practically all the cobalt passes into the filtrate.

  11. Annealing effects on microstrain of cobalt oxide nanoparticles

    SciTech Connect

    Deotale, Anjali Jain Nandedkar, R. V.; Sinha, A. K.; Singh, M. N.; Upadhyay, Anuj

    2014-04-24

    Cobalt oxide nanoparticles in different phases have been synthesized using ash supported method. The effect of isochronal annealing on micro-strain of cobalt oxide nanoparticles has been studied. The lattice strain contribution to the x-ray diffraction line broadening in the nanoparticles was analyzed using Williamson Hall (W-H) plot. It is observed that micro-strain was released at higher annealing temperature.

  12. Synthesis and structural characterization of polyaniline/cobalt chloride composites

    NASA Astrophysics Data System (ADS)

    Asha, Goyal, Sneh Lata; Kishore, Nawal

    2016-05-01

    Polyaniline (PANI) and PANI /cobalt chloride composites were synthesized by in situ chemical oxidative polymerization of aniline with CoCl2.6H2O using ammonium peroxidisulphate as an oxidant. These composites were characterized by X-ray diffraction (XRD) and Scanning electron microscopy (SEM). The XRD study reveals that both PANI and composites are amorphous. The XRD and SEM results confirm the presence of cobalt chloride in the composites.

  13. ESR ST study of hydroxyl radical generation in wet peroxide system catalyzed by heterogeneous ruthenium.

    PubMed

    Rokhina, Ekaterina V; Golovina, Elena A; As, Henk van; Virkutyte, Jurate

    2009-09-01

    Ru-based catalysts gained popularity because of their applicability for a variety of processes, including carbon monoxide oxidation, wet air catalytic oxidation and wastewater treatment. The focus of a current study was generation of hydroxyl radicals in the wet peroxide system catalyzed by heterogeneous ruthenium, spin-trapped by DEPMPO and DIPPMPO by means of electron spin resonance spin-trapping technique (ESR ST). The mechanism of free radicals formation was proposed via direct cleavage of hydrogen peroxide over ruthenium active sites. The chemical reactions occurring in the system were introduced according to the experimental results. Also, radical production rate was assessed based on concentration changes of species involved in the bulk liquid phase oxidation.

  14. Ruthenium-containing P450 inhibitors for dual enzyme inhibition and DNA damage.

    PubMed

    Zamora, Ana; Denning, Catherine A; Heidary, David K; Wachter, Erin; Nease, Leona A; Ruiz, José; Glazer, Edith C

    2017-02-14

    Cytochrome P450s are key players in drug metabolism, and overexpression in tumors is associated with significant resistance to many medicinal agents. Consequently, inhibition of P450s could serve as a strategy to restore drug efficacy. However, the widespread expression of P450s throughout the human body and the critical roles they play in various biosynthetic pathways motivates the development of P450 inhibitors capable of controlled local administration. Ruthenium complexes containing P450 inhibitors as ligands were synthesized in order to develop pro-drugs that can be triggered to release the inhibitors in a spatially and temporally controlled fashion. Upon light activation the compounds release ligands that directly bind and inhibit P450 enzymes, while the ruthenium center is able to directly damage DNA.

  15. Enantiomeric separations of ruthenium (II) polypyridyl complexes using HPLC with cyclofructan chiral stationary phases.

    PubMed

    Shu, Yang; Breitbach, Zachary S; Dissanayake, Milan K; Perera, Sirantha; Aslan, Joseph M; Alatrash, Nagham; MacDonnell, Frederick M; Armstrong, Daniel W

    2015-01-01

    The enantiomeric separation of 21 ruthenium (II) polypyridyl complexes was achieved with a novel class of cyclofructan-based chiral stationary phases (CSPs) in the polar organic mode. Aromatic derivatives on the chiral selectors proved to be essential for enantioselectivity. The R-napthylethyl carbamate functionalized cyclofructan 6 (LARIHC CF6-RN) column proved to be the most effective overall, while the dimethylphenyl carbamate cyclofructan 7 (LARIHC CF7-DMP) showed complementary selectivity. A combination of acid and base additives was necessary for optimal separations. The retention factor vs. acetonitrile/methanol ratio plot showed a U-shaped retention curve, indicating that different interactions take place at different polar organic solvent compositions. The separation results indicated that π-π interactions, steric effects, and hydrogen bonding contribute to the enantiomeric separation of ruthenium (II) polypyridyl complexes with cyclofructan chiral stationary phases in the polar organic mode.

  16. Experimental Investigation of the Kinetics of a Ruthenium-Catalyzed Deconstruction of Lignin Model Compounds

    SciTech Connect

    Bu, L.; Nimlos, M. R.; Shirts, M. R.; Himmel, M. E.; Crowley, M. F.; Beckham, G. T.

    2012-01-01

    Lignin is a major component of plant cell walls that is typically underutilized in selective conversion strategies for renewable fuels and chemicals. The mechanisms by which thermal and catalytic treatments deconstruct lignin remain elusive. In this work, we have investigated the kinetics of the catalytic deconstruction of lignin model compounds using a ruthenium catalyst reported by Bergman et al. in 2010. A series of investigations using NMR spectroscopy and GC/MS will be presented. In addition, we propose detailed mechanisms for lignin depolymerization with ruthenium catalysts. We have also used DFT to compute transition state geometries of catalytic cycle intermediates and compare the values determined computationally with those observed experimentally. Ultimately, our objective is to apply our methods to the design of new homogeneous and heterogeneous catalysts for the effective deconstruction and valorization of lignin.

  17. Ruthenium(II) polypyridyl complex as inhibitor of acetylcholinesterase and Aβ aggregation.

    PubMed

    Vyas, Nilima A; Bhat, Satish S; Kumbhar, Avinash S; Sonawane, Uddhavesh B; Jani, Vinod; Joshi, Rajendra R; Ramteke, Shefali N; Kulkarni, Prasad P; Joshi, Bimba

    2014-03-21

    Two ruthenium(II) polypyridyl complexes [Ru(phen)3](2+) (1) and [Ru(phen)2(bxbg)](2+) (2) (where phen = 1,10 phenanthroline, bxbg = bis(o-xylene)bipyridine glycoluril) have been evaluated for acetylcholinesterase (AChE) and Amyloid-β peptide (Aβ) aggregation inhibition. Complex 2 exhibits higher potency of AChE inhibition and kinetics and molecular modeling studies indicate that ancillary ligand plays significant role in inhibitory potency exhibited by complex 2. The inhibitory effect of these complexes on Aβ (1-40) aggregation is investigated using Thioflavin T fluorescence and Transmission Electron Microscopy. Both complexes efficiently inhibit Aβ (1-40) aggregation and are negligibly toxic to human neuroblastoma cells. This is the first demonstration that ruthenium(II) polypyridyl complexes simultaneously inhibit AChE and Aβ aggregation.

  18. Phosphine Supported Ruthenium Nanoparticle Catalyzed Synthesis of Substituted Pyrazines and Imidazoles from α-Diketones.

    PubMed

    Ganji, Prasad; van Leeuwen, Piet W N M

    2017-02-03

    A new methodology has been developed for the synthesis of highly substituted nitrogen heterocycles such as pyrazines and imidazoles starting from α-diketones using phosphine supported ruthenium nanoparticles (RuNPs) as catalysts. Ruthenium nanoparticles Ru1-Ru4 supported with different phosphines such as dbdocphos, dppp, DPEphos, and Xantphos are screened, of which Ru1 and Ru4 are found to be the most active. Interestingly, aryl-substituted and alkyl-substituted α-diketones produced different products: namely, pyrazine and imidazoles, respectively. This reaction methodology has been applied to the synthesis of a key intermediate (2m) of the marine cytotoxic natural product Dragmacidin B and an estrogen receptor (2l). This work represents the first examples of pyrazines prepared by RuNPs.

  19. Complex of transferrin with ruthenium for medical applications. [Ru 97, Ru 103

    DOEpatents

    Richards, P.; Srivastava, S.C.; Meinken, G.E.

    1980-11-03

    A novel Ruthenium-transferrin complex, prepared by reacting iron-free human transferrin dissolved in a sodium acetate solution at pH 7 with ruthenium by heating at about 40/sup 0/C for about 2 hours, and purifying said complex by means of gel chromatography with pH 7 sodium acetate as eluent. The mono- or di-metal complex produced can be used in nuclear medicine in the diagnosis and/or treatment of tumors and abscesses. Comparitive results with Ga-67-citrate, which is the most widely used tumor-localizing agent in nuclear medicine, indicate increased sensitivity of detection and greater tumor uptake with the Ru-transferrin complex.

  20. Ruthenium dioxide as cathode material for hydrogen evolution in hydroxide and chlorate solutions

    SciTech Connect

    Cornell, A.; Simonsson, D. . Dept. of Applied Electrochemistry and Corrosion Science)

    1993-11-01

    Ruthenium dioxide as electrocatalyst on an activated cathode for chlorate production was investigated with respect to its activity towards hydrogen evolution, hypochlorite reduction, and chlorate reduction, respectively. Investigations were made in the presence, as well as in the absence, of a chromium hydroxide film in 1M NaOH and in typical chlorate electrolyte. Low overvoltages for hydrogen evolution were found and, at technical current densities, an effect of catalyst coating thickness. Commercial DSA electrodes with RuO[sub 2] as the active compound were tested as cathodes and were less active but more stable than the coatings produced by the authors. Hypochlorite and chlorate were reduced in the absence of chromate, chlorate reduction being fast on ruthenium dioxide compared to the other electrode materials and by far the dominating cathodic reaction in chlorate electrolyte without chromate and hypochlorite at 70 C, 3 kA/m[sup 2].

  1. Optimization of process parameters for ruthenium nanoparticles synthesis by (w/o) reverse microemulsion

    NASA Astrophysics Data System (ADS)

    Nandanwar, S. U.; Barad, J.; Nandwani, S.; Chakraborty, M.

    2015-03-01

    Taguchi OA factorial design method was used to identify the several factors that might affect the particle size of ruthenium nanoparticles prepared by the mixing of two reactive microemulsions. In the present work, the objective of evaluating the factors influencing the particle size had been improvised by studying two qualitative factors viz., effect of different reducing agents and effect of different co-surfactants. Using orthogonal experimental design and analysis technique, the system performance could be analyzed with more objective conclusion through only a small number of simulation experiments. Analysis of variance was carried out to identify the significant factors affecting the response and the best possible factor level combination was determined through. It was found that the formation of ruthenium nanoparticles, microemulsions were greatly influenced by the type of reducing agent used in the technique followed by water-to-surfactant molar ratio.

  2. Determination of ruthenium in pharmaceutical compounds by graphite furnace atomic absorption spectroscopy.

    PubMed

    Jia, Xiujuan; Wang, Tiebang; Bu, Xiaodong; Tu, Qiang; Spencer, Sandra

    2006-04-11

    A graphite furnace atomic absorption (GFAA) spectrometric method for the determination of ruthenium (Rh) in solid and liquid pharmaceutical compounds has been developed. Samples are dissolved or diluted in dimethyl sulfoxide (DMSO) without any other treatment before they were analyzed by GFAA with a carefully designed heating program to avoid pre-atomization signal loss and to achieve suitable sensitivity. Various inorganic and organic solvents were tested and compared and DMSO was found to be the most suitable. In addition, ruthenium was found to be stable in DMSO for at least 5 days. Spike recoveries ranged from 81 to 100% and the limit of quantitation (LOQ) was determined to be 0.5 microg g(-1) for solid samples or 0.005 microg ml(-1) for liquid samples based a 100-fold dilution. The same set of samples was also analyzed by ICP-MS with a different sample preparation method, and excellent agreement was achieved.

  3. Effects of cobalt in nickel-base superalloys

    NASA Technical Reports Server (NTRS)

    Tien, J. K.; Jarrett, R. N.

    1983-01-01

    The role of cobalt in a representative wrought nickel-base superalloy was determined. The results show cobalt affecting the solubility of elements in the gamma matrix, resulting in enhanced gamma' volume fraction, in the stabilization of MC-type carbides, and in the stabilization of sigma phase. In the particular alloy studied, these microstructural and microchemistry changes are insufficient in extent to impact on tensile strength, yield strength, and in the ductilities. Depending on the heat treatment, creep and stress rupture resistance can be cobalt sensitive. In the coarse grain, fully solutioned and aged condition, all of the alloy's 17% cobalt can be replaced by nickel without deleteriously affecting this resistance. In the fine grain, partially solutioned and aged condition, this resistance is deleteriously affected only when one-half or more of the initial cobalt content is removed. The structure and property results are discussed with respect to existing theories and with respect to other recent and earlier findings on the impact of cobalt, if any, on the performance of nickel-base superalloys.

  4. The biokinetics of inorganic cobalt in the human body.

    PubMed

    Leggett, R W

    2008-01-25

    This paper reviews information on the biological behavior of inorganic cobalt in humans and laboratory animals and proposes a model of the systemic biokinetics of inorganic cobalt in adult humans. The model was developed as part of an effort to update the models of the International Commission on Radiological Protection (ICRP) for addressing intakes of radionuclides by workers but is also applicable to environmental or medical exposures to inorganic forms of radiocobalt. The model can be used in conjunction with any respiratory, gastrointestinal, or wound model that provides predictions of the time-dependent feed of cobalt to blood. In contrast to the ICRP's current systemic model for cobalt, which is a simple open catenary system, the proposed model is constructed within a physiologically realistic framework that depicts recycling of cobalt between blood and tissues and transfer from blood to excretion pathways. Compared with the ICRP's current model, the proposed model yields similar predictions of whole-body retention but substantially different predictions of the systemic distribution of cobalt as a function of time after uptake to blood.

  5. Coordination tuning of cobalt phosphates towards efficient water oxidation catalyst

    PubMed Central

    Kim, Hyunah; Park, Jimin; Park, Inchul; Jin, Kyoungsuk; Jerng, Sung Eun; Kim, Sun Hee; Nam, Ki Tae; Kang, Kisuk

    2015-01-01

    The development of efficient and stable water oxidation catalysts is necessary for the realization of practically viable water-splitting systems. Although extensive studies have focused on the metal-oxide catalysts, the effect of metal coordination on the catalytic ability remains still elusive. Here we select four cobalt-based phosphate catalysts with various cobalt- and phosphate-group coordination as a platform to better understand the catalytic activity of cobalt-based materials. Although they exhibit various catalytic activities and stabilities during water oxidation, Na2CoP2O7 with distorted cobalt tetrahedral geometry shows high activity comparable to that of amorphous cobalt phosphate under neutral conditions, along with high structural stability. First-principles calculations suggest that the surface reorganization by the pyrophosphate ligand induces a highly distorted tetrahedral geometry, where water molecules can favourably bind, resulting in a low overpotential (∼0.42 eV). Our findings emphasize the importance of local cobalt coordination in the catalysis and suggest the possible effect of polyanions on the water oxidation chemistry. PMID:26365091

  6. Cobalt silicon mixed oxide nanocomposites by modified sol gel method

    NASA Astrophysics Data System (ADS)

    Esposito, Serena; Turco, Maria; Ramis, Gianguido; Bagnasco, Giovanni; Pernice, Pasquale; Pagliuca, Concetta; Bevilacqua, Maria; Aronne, Antonio

    2007-12-01

    Cobalt-silicon mixed oxide materials (Co/Si=0.111, 0.250 and 0.428) were synthesised starting from Co(NO 3) 2·6H 2O and Si(OC 2H 5) 4 using a modified sol-gel method. Structural, textural and surface chemical properties were investigated by thermogravimetric/differential thermal analyses (TG/DTA), XRD, UV-vis, FT-IR spectroscopy and N 2 adsorption at -196 °C. The nature of cobalt species and their interactions with the siloxane matrix were strongly depending on both the cobalt loading and the heat treatment. All dried gels were amorphous and contained Co 2+ ions forming both tetrahedral and octahedral complexes with the siloxane matrix. After treatment at 400 °C, the sample with lowest Co content appeared amorphous and contained only Co 2+ tetrahedral complexes, while at higher cobalt loading Co 3O 4 was present as the only crystalline phase, besides Co 2+ ions strongly interacting with siloxane matrix. At 850 °C, in all samples crystalline Co 2SiO 4 was formed and was the only crystallising phase for the nanocomposite with the lowest cobalt content. All materials retained high surface areas also after treatments at 600 °C and exhibited surface Lewis acidity, due to cationic sites. The presence of cobalt affected the textural properties of the siloxane matrix decreasing microporosity and increasing mesoporosity.

  7. DNA Interactions with Ruthenium(ll) Polypyridine Complexes Containing Asymmetric Ligands

    PubMed Central

    Chao, Hui

    2005-01-01

    In an attempt to probe nucleic acid structures, numerous Ru(II) complexes with different ligands have been synthesized and investigated. In this contribution we focus on the DNA-binding properties of ruthenium(II) complexes containing asymmetric ligands that have attracted little attention in the past decades. The influences of the shape and size of the ligand on the binding modes, affinity, enantioselectivities and photocleavage of the complexes to DNA are described. PMID:18365086

  8. Interaction and reactivity of nitric oxide and carbon monoxide on ruthenium surfaces

    SciTech Connect

    Quick, E.E.

    1980-03-01

    A multifaceted investigation of the reduction of nitric oxide by carbon monoxide using a ruthenium (102) single crystal catalyst in the pressure range 10/sup -3/ to 10 Torr and temperature range of 300 to 475/sup 0/C has been undertaken. Kinetic and isotopic results indicate that the reaction products CO/sub 2/ and N/sub 2/ were produced via two reaction mechanisms. Using a reducing gas mixture (low P/sub NO//P/sub CO/ ratio) a two site mechanism was operative involving NO dissociation. The carbon monoxide kinetic order varied from +1 to -3 and the nitric oxide order varied from +1 to 0. The catalyst under these conditions was determined to be metallic ruthenium with oxygen bonded within the first surface layer. The oxygen was unreactive and formed a (1 x 3)-0 LEED pattern. Under oxidizing conditions (high P/sub NO//P/sub CO/ ratio) the catalyst was ruthenium dioxide and the functional mechanism under these reaction conditions yielded a nitric oxide order of +2 to -4. Inclusion of a site poisoning mechanism under reducing conditions and an RuO/sub 2/ growth mechanism involving ruthenium cation transfer under oxidizing conditions into the kinetic rate laws led to an overall rate law which could be fit to the carbon monoxide and nitric oxide order plots. Using isotopically oxygen labelled reactants, it was observed that the three possible isotopes of carbon dioxide were produced. A ..gamma..-CO surface species is postulated as an intermediate in the exchange process. The reaction was observed to be initially surface structure insensitive and the reaction kinetics were derived using a Langmuir-Hinshelwood formalism.

  9. Prototypes of molecular motors based on star-shaped organometallic ruthenium complexes.

    PubMed

    Vives, Guillaume; de Rouville, Henri-Pierre Jacquot; Carella, Alexandre; Launay, Jean-Pierre; Rapenne, Gwénaël

    2009-06-01

    This tutorial review presents our strategy to control the rotation in a molecular rotary motor, and the family of star-shaped ruthenium complexes designed to perform such a task. The molecules have a piano-stool structure with a "stator" meant to be grafted on a surface, and a "rotor" bearing redox-active groups, so that addressing the molecule with nano-electrodes would trigger rotation.

  10. Ruthenium(II)-catalyzed C-H activation with isocyanates: a versatile route to phthalimides.

    PubMed

    De Sarkar, Suman; Ackermann, Lutz

    2014-10-20

    A cationic ruthenium(II)-complex was utilized in the efficient synthesis of phthalimide derivatives by C-H activation with synthetically useful amides. The reaction proceeded through a mechanistically unique insertion of a cycloruthenated species into a C-Het multiple bond of isocyanate. The novel method also proved applicable for the synthesis of heteroaromatic unsymmetric diamides as well as a potent COX-2 enzyme inhibitor.

  11. Synthesis and ECL performance of highly efficient bimetallic ruthenium tris-bipyridyl complexes.

    PubMed

    Sun, Shiguo; Li, Fusheng; Liu, Fengyu; Yang, Xue; Fan, Jiangli; Song, Fengling; Sun, Licheng; Peng, Xiaojun

    2012-10-28

    In order to find the ideal carbon chain linkage number n for achieving the highest ECL in bimetallic ruthenium tris-bipyridyl complexes, a series of novel complexes [(bpy)(2)Ru(bpy')(CH(2))(n)(bpy')Ru(bpy)(2)](4+) (, where bpy is 2,2'-bipyridyl, n = 10, 12, 14) for a coreactant electrochemiluminescence (ECL) system have been synthesized. Their ECL properties at a Au electrode have been studied in 0.1 M phosphate buffer by using tripropylamine (TPrA), 2-(dibutylamino)ethanol (DBAE) and melamine as the coreactant, to compare with that of the previously reported bimetallic ruthenium analogous complex [(bpy)(2)Ru(bpy')(CH(2))(8)(bpy')Ru(bpy)(2)](4+). The results demonstrate that the ECL intensity depends largely on the length of the saturated carbon chain linkage number n. The highest ECL is reached when n = 10, suggesting that a synergistic effect on ECL enhancement co-exists between the two intramolecular linked ruthenium activating centers. Density functional theory (DFT) calculation demonstrated that the optimized bond distances between Ru and N(bpy') are the longest both in the ground and the excited triplet states in the case of n = 10, while those for Ru and N(bpy) are the shortest in the excited triplet states. All these factors may be responsible for the above mentioned results. This study provided a methodology to further improve and tune ECL efficiency by using bimetallic ruthenium complexes linked by a flexible saturated carbon chain.

  12. Synthesis, Structure and Antitumour Properties of a New 1,2-Propylenediaminetetraacetate-Ruthenium(III) Compound

    PubMed Central

    Vilaplana, R.; Romero, M. A.; Quirós, M.; Salas, J. M.

    1995-01-01

    A novel complex formed by ruthenium (III) and the sequestering ligand 1,2-propylenediaminetetraacetic acid (PDTA) has been synthetized and characterized. The structure of the monomeric compound, studied by X-ray diffraction , shows an almost symmetric octahedral geometry around the metal ion, with two chlorine atoms in a cis conformation. The antitumour activity against a variety of murine and human cancers is reported. PMID:18472768

  13. Molecular Engineering Combined with Cosensitization Leads to Record Photovoltaic Efficiency for Non-ruthenium Solar Cells.

    PubMed

    Hill, Jonathan P

    2016-02-24

    Here comes the sun: By using a combined strategy of molecular engineering and cosensitization, impressively high Jsc and Voc values were achieved for porphyrin dyes, resulting in high photovoltaic efficiencies up to 11.5 %, a record for non-ruthenium dye-sensitized solar cells (DSSCs) with the I(-) /I3 (-) electrolyte. The results provide insight into furthering the development of efficient DSSCs through synergistically enhanced photovoltage and photocurrent.

  14. Transferrin serves as a mediator to deliver organometallic ruthenium(II) anticancer complexes into cells.

    PubMed

    Guo, Wei; Zheng, Wei; Luo, Qun; Li, Xianchan; Zhao, Yao; Xiong, Shaoxiang; Wang, Fuyi

    2013-05-06

    We report herein a systematic study on interactions of organometallic ruthenium(II) anticancer complex [(η(6)-arene)Ru(en)Cl](+) (arene = p-cymene (1) or biphenyl (2), en = ethylenediamine) with human transferrin (hTf) and the effects of the hTf-ligation on the bioavailability of these complexes with cisplatin as a reference. Incubated with a 5-fold excess of complex 1, 2, or cisplatin, 1 mol of diferric hTf (holo-hTf) attached 0.62 mol of 1, 1.01 mol of 2, or 2.14 mol of cisplatin. Mass spectrometry revealed that both ruthenium complexes coordinated to N-donors His242, His273, His578, and His606, whereas cisplatin bound to O donors Tyr136 and Tyr317 and S-donor Met256 in addition to His273 and His578 on the surface of both apo- and holo-hTf. Moreover, cisplatin could bind to Thr457 within the C-lobe iron binding cleft of apo-hTf. Neither ruthenium nor platinum binding interfered with the recognition of holo-hTf by the transferrin receptor (TfR). The ruthenated/platinated holo-hTf complexes could be internalized via TfR-mediated endocytosis at a similar rate to that of holo-hTf itself. Moreover, the binding to holo-hTf well preserved the bioavailability of the ruthenium complexes, and the hTf-bound 1 and 2 showed a similar cytotoxicity toward the human breast cancer cell line MCF-7 to those of the complexes themselves. However, the conjugation with holo-hTf significantly reduced the cellular uptake of cisplatin and the amount of platinated DNA adducts formed intracellularly, leading to dramatic reduction of cisplatin cytotoxicity toward MCF-7. These findings suggest that hTf can serve as a mediator for the targeting delivery of Ru(arene) anticancer complexes while deactivating cisplatin.

  15. Tri- and tetra-nuclear polypyridyl ruthenium(II) complexes as antimicrobial agents.

    PubMed

    Gorle, Anil K; Feterl, Marshall; Warner, Jeffrey M; Wallace, Lynne; Keene, F Richard; Collins, J Grant

    2014-11-28

    A series of inert tri- and tetra-nuclear polypyridylruthenium(II) complexes that are linked by the bis[4(4'-methyl-2,2'-bipyridyl)]-1,n-alkane ligand ("bb(n)" for n = 10, 12 and 16) have been synthesised and their potential as antimicrobial agents examined. Due to the modular nature of the synthesis of the oligonuclear complexes, it was possible to make both linear and non-linear tetranuclear ruthenium species. The minimum inhibitory concentrations (MIC) of the ruthenium(II) complexes were determined against four strains of bacteria--Gram positive Staphylococcus aureus (S. aureus) and methicillin-resistant S. aureus (MRSA), and Gram negative Escherichia coli (E. coli) and Pseudomonas aeruginosa (P. aeruginosa). In order to gain an understanding of the relative antimicrobial activities, the cellular uptake and water-octanol partition coefficients (log P) were determined for a selection of the ruthenium complexes. Although the trinuclear complexes were the most lipophilic based upon log P values and showed the greatest cellular uptake, the linear tetranuclear complexes were generally more active, with MIC values <1 μM against the Gram positive bacteria. Similarly, although the non-linear tetranuclear complexes were slightly more lipophilic and were taken up to a greater extent by the bacteria, they were consistently less active than their linear counterparts. Of particular note, the cellular accumulation of the oligonuclear ruthenium complexes was greater in the Gram negative strains compared to that in the Gram positive S. aureus and MRSA. The results demonstrate that the lower antimicrobial activity of polypyridylruthenium(II) complexes towards Gram negative bacteria, particularly P. aeruginosa, is not strongly correlated to the cellular accumulation but rather to a lower intrinsic ability to kill the Gram negative cells.

  16. RNA and DNA binding of inert oligonuclear ruthenium(II) complexes in live eukaryotic cells.

    PubMed

    Li, Xin; Gorle, Anil K; Ainsworth, Tracy D; Heimann, Kirsten; Woodward, Clifford E; Collins, J Grant; Keene, F Richard

    2015-02-28

    Confocal microscopy was used to study the intracellular localisation of a series of inert polypyridylruthenium(II) complexes with three eukaryotic cells lines - baby hamster kidney (BHK), human embryonic kidney (HEK-293) and liver carcinoma (Hep-G2). Co-staining experiments with the DNA-selective dye DAPI demonstrated that the di-, tri- and tetra-nuclear polypyridylruthenium(II) complexes that are linked by the bis[4(4'-methyl-2,2'-bipyridyl)]-1,12-dodecane bridging ligand ("bb12") showed a high degree of selectivity for the nucleus of the eukaryotic cells. Additional co-localisation experiments with the general nucleic acid stain SYTO 9 indicated that the ruthenium complexes showed a considerable preference for the RNA-rich nucleolus, rather than chromosomal DNA. No significant differences were observed in the intracellular localisation between the ΔΔ and ΛΛ enantiomers of the dinuclear complex. Cytotoxicity assays carried out over 72 hours indicated that the ruthenium complexes, particularly the tri- and tetra-nuclear species, were significantly toxic to the eukaryotic cells. However, when the activity of the least cytotoxic compound (the ΔΔ enantiomer of the dinuclear species) was determined over a 24 hour period, the results indicated that the ruthenium complex was approximately a 100-fold less toxic to liver and kidney cells than to Gram positive bacteria. Circular dichroism (CD) spectroscopy was used to examine the effect of the ΔΔ and ΛΛ enantiomers of the dinuclear complex on the solution conformations of RNA and DNA. The CD experiments indicated that the RNA maintained the A-type conformation, and the DNA the B-type structure, upon binding by the ruthenium complexes.

  17. Antitumor and antiparasitic activity of novel ruthenium compounds with polycyclic aromatic ligands.

    PubMed

    Miserachs, Helena Guiset; Cipriani, Micaella; Grau, Jordi; Vilaseca, Marta; Lorenzo, Julia; Medeiros, Andrea; Comini, Marcelo A; Gambino, Dinorah; Otero, Lucía; Moreno, Virtudes

    2015-09-01

    Five novel ruthenium(II)-arene complexes with polycyclic aromatic ligands were synthesized, comprising three compounds of the formula [RuCl(η(6)-p-cym)(L)][PF6], where p-cym = 1-isopropyl-4-methylbenzene and L are the bidentate aromatic ligands 1,10-phenanthroline-5,6-dione, 1, 5-amine-1,10-phenanthroline, 4, or 5,6-epoxy-5,6-dihydro-phenanthroline, 5. In the other two complexes [RuCl2(η(6)-p-cym)(L')], the metal is coordinated to a monodentate ligand L', where L' is phenanthridine, 2, or 9-carbonylanthracene, 3. All compounds were fully characterized by mass spectrometry and elemental analysis, as well as NMR and IR spectroscopic techniques. Obtained ruthenium compounds as well as their respective ligands were tested for their antiparasitic and antitumoral activities. Even though all compounds showed lower Trypanosoma brucei activity than the free ligands, they also resulted less toxic on mammalian cells. Cytotoxicity assays on HL60 cells showed a moderate antitumoral activity for all ruthenium compounds. Compound 1 was the most potent antitumoral (IC50 = 1.26±0.78 μM) and antiparasitic (IC50 = 0.19 ± 0.05 μM) agent, showing high selectivity towards the parasites (selectivity index >100). As complex 1 was the most promising antitumoral compound, its interaction with ubiquitin as potential target was also studied. In addition, obtained ruthenium compounds were found to bind DNA, and they are thought to interact with this macromolecule mainly through intercalation of the aromatic ligand.

  18. Effect of mechanical activation on the characteristics of ruthenium and aluminum powder mixtures

    NASA Astrophysics Data System (ADS)

    Povarova, K. B.; Morozov, A. E.; Skachkov, O. A.; Drozdov, A. A.; Kazanskaya, N. K.; Korenovskii, N. L.; D'Yakonova, N. B.

    2008-06-01

    The effect of treatment in a high-energy mill-attritor on the structure of RuAl-based alloy powder mixtures and the exothermic effects in them is studied. The mechanical activation (MA) of aluminum and ruthenium powder mixtures is found to mill the conglomerates of hard disperse (0.5-2 μm) ruthenium particles in the initial mixtures and to produce composite granules. These granules consist of hard disperse ruthenium particles connected by plastic fcc aluminum particles. The structure of these granules differs from that of the layered granules that form during the MA of powder mixtures of two plastic fcc metals (nickel, aluminum). The cold working of the hard ruthenium particles, which have the hcp lattice and are deformed via twinning, occurs due to a decrease in the coherent domain size (to 120-80 nm) rather than to an increase in the dislocation density (as in the case of the MA of Ni-Al powders). Every granule contains all alloy (composite) components, including disperse or nanosize oxide particles, bound to the components that form an intermetallic matrix during reaction sintering. In granules of both types, MA increases the contact area between both metals entering into the reaction of RuAl (NiAl) formation and sharply decreases the diffusion path length of Al in Ru (Ni). This results in a decrease in the temperature of the onset of reaction alloy formation, which begins now in a solid phase, and in a decrease in the exothermic effect of the monoaluminide formation with the participation of a liquid phase (Al). MA for 15-16 h of powder mixtures provides a microuniform distribution of base and alloying elements and phases in the deformable alloys with an intermetallic matrix that are produced by reaction sintering.

  19. Ruthenium-catalyzed direct C3 alkylation of indoles with α,β-unsaturated ketones.

    PubMed

    Li, Shuai-Shuai; Lin, Hui; Zhang, Xiao-Mei; Dong, Lin

    2015-01-28

    In this paper, a simple and highly efficient ruthenium-catalyzed direct C3 alkylation of indoles with various α,β-unsaturated ketones without chelation assistance has been developed. This novel C-H activation methodology exhibits a broad substrate scope such as different substituted indoles, pyrroles, and other azoles. Further synthetic applications of the alkylation products can lead to more attractive 3,4-fused tricyclic indoles.

  20. Enantioselective synthesis of 5-epi-citreoviral using ruthenium-catalyzed asymmetric ring-closing metathesis.

    PubMed

    Funk, Timothy W

    2009-11-05

    Chiral ruthenium olefin metathesis catalysts can perform asymmetric ring-closing reactions in > or = 90% ee with low catalyst loadings. To illustrate the practicality of these reactions and the products they form, an enantioselective total synthesis of 5-epi-citreoviral was completed by using an asymmetric ring-closing olefin metathesis reaction as a key step early in the synthesis. All of the stereocenters in the final compound were set by using the chiral center generated by asymmetric olefin metathesis.

  1. Bifunctional ruthenium(II) hydride complexes with pendant strong Lewis acid moieties: structure, dynamics, and cooperativity.

    PubMed

    Ostapowicz, Thomas G; Merkens, Carina; Hölscher, Markus; Klankermayer, Jürgen; Leitner, Walter

    2013-02-13

    The synthesis of a novel class of bifunctional ruthenium hydride complexes incorporating Lewis acidic BR(2) moieties is reported. Determination of the molecular structures in the solid state and in solution provided evidence for tunable interaction between the two functionalities. Cooperative effects on the reactivity of the complexes were demonstrated including the activation of small Lewis basic molecules by reversible anchoring at the boron center.

  2. Synthesis and resolution of planar-chiral ruthenium-palladium complexes with ECE' pincer ligands.

    PubMed

    Bonnet, Sylvestre; Li, Jie; Siegler, Maxime A; von Chrzanowski, Lars S; Spek, Anthony L; van Koten, Gerard; Klein Gebbink, Robertus J M

    2009-01-01

    Feel the pinch! Planar-chiral, cationic, ruthenium-palladium complexes based on eta(6),eta(1)-coordinated ECE' pincer ligands are synthesized as racemic mixtures by reacting ECE'-palladium complexes and [Ru(C(5)R(5))(MeCN)(3)](+) arenophiles (R=H or Me). Chiral resolution of the cationic complexes was achieved by using the chiral counterion [Delta-TRISPHAT](-), and solving the X-ray crystal structure of one diastereoisomer (shown here).

  3. A Robust, Air-Stable, Reusable Ruthenium Catalyst for Dehydrogenation of Ammonia Borane

    PubMed Central

    Conley, Brian L.; Guess, Denver; Williams, Travis J.

    2011-01-01

    We describe an efficient homogeneous ruthenium catalyst for the dehydrogenation of ammonia borane (AB). This catalyst liberates greater than 2 equivalents of H2 and up to 4.6 system wt% H2 from concentrated AB suspensions under air. Importantly, this catalyst is robust, delivering several cycles of dehydrogenation at high [AB] without loss of catalytic activity, even with exposure to air and water. PMID:21827173

  4. Cobalt mineral exploration and supply from 1995 through 2013

    USGS Publications Warehouse

    Wilburn, David R.

    2011-01-01

    The global mining industry has invested a large amount of capital in mineral exploration and development over the past 15 years in an effort to ensure that sufficient resources are available to meet future increases in demand for minerals. Exploration data have been used to identify specific sites where this investment has led to a significant contribution in global mineral supply of cobalt or where a significant increase in cobalt production capacity is anticipated in the next 5 years. This report provides an overview of the cobalt industry, factors affecting mineral supply, and circumstances surrounding the development, or lack thereof, of key mineral properties with the potential to affect mineral supply. Of the 48 sites with an effective production capacity of at least 1,000 metric tons per year of cobalt considered for this study, 3 producing sites underwent significant expansion during the study period, 10 exploration sites commenced production from 1995 through 2008, and 16 sites were expected to begin production by 2013 if planned development schedules are met. Cobalt supply is influenced by economic, environmental, political, and technological factors affecting exploration for and production of copper, nickel, and other metals as well as factors affecting the cobalt industry. Cobalt-rich nickel laterite deposits were discovered and developed in Australia and the South Pacific and improvements in laterite processing technology took place during the 1990s and early in the first decade of the 21st century when mining of copper-cobalt deposits in Congo (Kinshasa) was restricted because of regional conflict and lack of investment in that country's mining sector. There was also increased exploration for and greater importance placed on cobalt as a byproduct of nickel mining in Australia and Canada. The emergence of China as a major refined cobalt producer and consumer since 2007 has changed the pattern of demand for cobalt, particularly from Africa and

  5. Cobalt ferrite based magnetostrictive materials for magnetic stress sensor and actuator applications

    NASA Technical Reports Server (NTRS)

    Jiles, David C. (Inventor); Paulsen, Jason A. (Inventor); Snyder, John E. (Inventor); Lo, Chester C. H. (Inventor); Ring, Andrew P. (Inventor); Bormann, Keith A. (Inventor)

    2008-01-01

    Magnetostrictive material based on cobalt ferrite is described. The cobalt ferrite is substituted with transition metals (such manganese (Mn), chromium (Cr), zinc (Zn) and copper (Cu) or mixtures thereof) by substituting the transition metals for iron or cobalt to form substituted cobalt ferrite that provides mechanical properties that make the substituted cobalt ferrite material effective for use as sensors and actuators. The substitution of transition metals lowers the Curie temperature of the material (as compared to cobalt ferrite) while maintaining a suitable magnetostriction for stress sensing applications.

  6. Chemical amplification methods for the sequential determination of trace amounts of ruthenium by titrimetric and spectrophotometric procedures.

    PubMed

    El-Shahawi, M S; Barakat, S A

    1995-11-01

    Two simple, inexpensive and rapid iodometric and spectrophotometric procedures were developed for trace amount determination of ruthenium. The proposed methods were based on the oxidation of ruthenium(II or III) with sodium periodate at pH 2.4-3.6, masking the excess periodate with sodium molybdate. The released iodate was then allowed to react with KI at pH 3, with subsequent determination of the released iodine spectrophotometry as triiodide at 350 nm or iodometry with 0.005 M sodium thiosulphate. This procedure offers an 18- and 15-fold amplification per Ru(II) or Ru(III) ion, respectively. Alternatively, the produced iodine was extracted with CHCl(3), shaken with an aqueous solution of sodium sulphite and the produced iodide ion was then allowed to react with bromine (or sodium periodate). The released iodate was subsequently determined by iodometry or spectrophotometry after addition of KI. The bromine and sodium periodate oxidation procedures offered 90- and 360-fold amplification per ruthenium(III) ion, and 108- and 432-fold amplification per ruthenium(II) ion. Ruthenium(IV) content was determined by these procedures after prior reduction to Ru(III) with sulphurous acid. The binary mixtures Ru(II)-Ru(III); Ru(III)-Ru(IV) and Ru(II)-Ru(IV) in aqueous solution at concentration 0.05 mug ml(-1) were successfully analyzed by the developed procedures. The utility of the proposed methods for the analysis of ruthenium in its complexes was demonstrated. Natural seawater and seawater spiked with ruthenium were analyzed satisfactorily.

  7. C-H Bond Activation/Arylation Catalyzed by Arene-Ruthenium-Aniline Complexes in Water.

    PubMed

    Binnani, Chinky; Tyagi, Deepika; Rai, Rohit K; Mobin, Shaikh M; Singh, Sanjay K

    2016-11-07

    Water-soluble arene-ruthenium complexes coordinated with readily available aniline-based ligands were successfully employed as highly active catalysts in the C-H bond activation and arylation of 2-phenylpyridine with aryl halides in water. A variety of (hetero)aryl halides were also used for the ortho-C-H bond arylation of 2-phenylpyridine to afford the corresponding ortho- monoarylated products as major products in moderate to good yields. Our investigations, including time-scaled NMR spectroscopy and mass spectrometry studies, evidenced that the coordinating aniline-based ligands, having varying electronic and steric properties, had a significant influence on the catalytic activity of the resulting arene-ruthenium-aniline-based complexes. Moreover, mass spectrometry identification of the cycloruthenated species, {(η(6) -arene)Ru(κ(2) -C,N-phenylpyridine)}(+) , and several ligand-coordinated cycloruthenated species, such as [(η(6) -arene)Ru(4-methylaniline)(κ(2) -C,N-phenylpyridine)](+) , found during the reaction of 2-phenylpyridine with the arene-ruthenium-aniline complexes further authenticated the crucial roles of these species in the observed highly active and tuned catalyst. At last, the structures of a few of the active catalysts were also confirmed by single-crystal X-ray diffraction studies.

  8. Pharmacological Activities of Ruthenium Complexes Related to Their NO Scavenging Properties

    PubMed Central

    Castellarin, Anna; Zorzet, Sonia; Bergamo, Alberta; Sava, Gianni

    2016-01-01

    Angiogenesis is considered responsible for the growth of primary tumours and of their metastases. With the present study, the effects of three ruthenium compounds, potassiumchlorido (ethylendiamminotetraacetate)rutenate(III) (RuEDTA), sodium (bis-indazole)tetrachloro-ruthenate(III), Na[trans-RuCl4Ind2] (KP1339) and trans-imidazoledimethylsulphoxidetetrachloro-ruthenate (NAMI-A), are studied in vitro in models mimicking the angiogenic process. The ruthenium compounds reduced the production and the release of nitrosyls from either healthy macrophages and immortalized EA.hy926 endothelial cells. The effects of NAMI-A are qualitatively similar and sometimes quantitatively superior to those of RuEDTA and KP1339. NAMI-A reduces the production and release of nitric oxide (NO) by the EA.hy926 endothelial cells and correspondingly inhibits their invasive ability; it also strongly inhibits the angiogenesis in matrigel sponges implanted subcutaneously in healthy mice. Taken together, these data support the anti-angiogenic activity of the tested ruthenium compounds and they contribute to explain the selective activity of NAMI-A against solid tumour metastases, the tumour compartment on which angiogenesis is strongly involved. This anti-angiogenic effect may also contribute to the inhibition of the release of metastatic cells from the primary tumour. Investigations on the anti-angiogenic effects of NAMI-A at this level will increase knowledge of its pharmacological properties and it will give a further impulse to the development of this class of innovative metal-based drugs. PMID:27490542

  9. Voltammetric determination of ruthenium in the form of complexes with biologically active ligands

    SciTech Connect

    Medyantseva, E.P.; Budnikov, G.K.; Balakaeva, T.A.

    1992-02-10

    The interest in the analytical chemistry of ruthenium and its compounds has recently been increasing. Ruthenium compounds can be used an antitumor agents and in the treatment of tuberculosis and fungal infections. It has been suggested that there is a specific relationship between the reduction potentials of the compounds and their biological activity. Of greatest interest among the biologically active compounds are the compounds with nitrogen-containing heterocycles. In order to obtain information on the degree of oxidation of the central atom in the complexes and to select the optimum conditions for the determination of the mono- and bi-nuclear complexes of ruthenium compounds with biologically active ligands such as imidazole (Im), histidine (His), benzimidazole (BIm) and its methyl derivative [1,2(CH{sub 3}){sub 2} - BIm], benzohyroxamic acid (Bha), and 1-phenyl-2-methylamino-1-propanol or ephedrine (Eph) in the present work, the authors studied their electrochemical behavior at dropping mercury (dme) and a platinum electrodes. 6 refs., 1 fig., 2 tabs.

  10. Negative lattice expansion from the superconductivity--antiferromagnetism crossover in ruthenium copper oxides.

    PubMed

    McLaughlin, A C; Sher, F; Attfield, J P

    2005-08-11

    The mechanism of high-transition-temperature (high-T(c)) superconductivity in doped copper oxides is an enduring problem. Antiferromagnetism is established as the competing order, but the relationship between the two states in the intervening 'pseudogap' regime has become a central puzzle. The role of the crystal lattice, which is important in conventional superconductors, also remains unclear. Here we report an anomalous increase of the distance between copper oxide planes on cooling, which results in negative thermal volume expansion, for layered ruthenium copper oxides that have been doped to the boundary of antiferromagnetism and superconductivity. We propose that a crossover between these states is driven by spin ordering in the ruthenium oxide layers, revealing a novel mechanism for negative lattice expansion in solids. The differences in volume and lattice strain between the distinct superconducting and antiferromagnetic states can account for the phase segregation phenomena found extensively in low-doped copper oxides, and show that Cooper pair formation is coupled to the lattice. Unusually large variations of resistivity with magnetic field are found in these ruthenium copper oxides at low temperatures through coupling between the ordered Ru and Cu spins.

  11. Long-Range Ruthenium-Amine Electronic Communication through the para-Oligophenylene Wire

    PubMed Central

    Shen, Jun-Jian; Zhong, Yu-Wu

    2015-01-01

    The studies of long-range electronic communication are hampered by solubility and potential-splitting issues. A “hybridized redox-asymmetry” method using a combination of organic and inorganic redox species is proposed and exemplified to overcome these two issues. Complexes 1(PF6)–6(PF6) (from short to long in length) with the organic redox-active amine and inorganic cyclometalated ruthenium termini bridged by the para-oligophenylene wire have been prepared. Complex 6 has the longest Ru-amine geometrical distance of 27.85 Å. Complexes 3(PF6) and 4(PF6) show lamellar crystal packing on the basis of a head-to-tail anti-parallelly aligned dimeric structure. Two redox waves are observed for all complexes in the potential region between +0.2 and +0.9 V vs Ag/AgCl. The electrochemical potential splitting is 410, 220, 143, 112, 107, and 105 mV for 1(PF6) through 6(PF6), respectively. Ruthenium (+2) to aminium (N•+) charge transfer transitions have been identified for the odd-electron compounds 12+–62+ by spectroelectrochemical measurements. The electronic communication between amine and ruthenium decreases exponentially with a decay slope of −0.137 Å−1. DFT calculations have been performed to complement these experimental results. PMID:26344929

  12. Ruthenium(II)-PNN pincer complex catalyzed dehydrogenation of benzyl alcohol to ester: A DFT study

    NASA Astrophysics Data System (ADS)

    Tao, Jingcong; Wen, Li; Lv, Xiaobo; Qi, Yong; Yin, Hailiang

    2016-04-01

    The molecular mechanism of the dehydrogenation of primary alcohol to ester catalyzed by the ruthenium(II)-PNN pincer complex Ru(H)(η2-BH4)(PNN), [PNN: (2-(di-tert-butylphosphinomethyl)-6-(diethlaminomethyl)-pyridine)] has been investigated using density functional theory calculations. The catalytic cycle includes three stages: (stage I) alcohol dehydrogenation to form aldehyde, (stage II) coupling of aldehyde with alcohol to give hemiacetal or ester, and (stage III) hemiacetal dehydrogenation to form ester. Two dehydrogenation reactions occur via the β-H elimination mechanism rather than the bifunctional double hydrogen transfer mechanism, which could be rationalized as the fluxional behavior of the BH4- ligand. At the second stage, the coupling reaction requires alcohol or the ruthenium catalyst as mediator. The formation of hemiacetal through the alcohol-mediated pathway is kinetically favorable than the ruthenium catalyst-mediated one, which may be attributed to the smaller steric hindrance when the aldehyde approaches the alcohol moiety in the reaction system. Our results would be helpful for experimental chemists to design more effective transition metal catalysts for dehydrogenation of alcohols.

  13. Half-sandwich ruthenium(II) biotin conjugates as biological vectors to cancer cells.

    PubMed

    Babak, Maria V; Plażuk, Damian; Meier, Samuel M; Arabshahi, Homayon John; Reynisson, Jóhannes; Rychlik, Błażej; Błauż, Andrzej; Szulc, Katarzyna; Hanif, Muhammad; Strobl, Sebastian; Roller, Alexander; Keppler, Bernhard K; Hartinger, Christian G

    2015-03-23

    Ruthenium(II)-arene complexes with biotin-containing ligands were prepared so that a novel drug delivery system based on tumor-specific vitamin-receptor mediated endocytosis could be developed. The complexes were characterized by spectroscopic methods and their in vitro anticancer activity in cancer cell lines with various levels of major biotin receptor (COLO205, HCT116 and SW620 cells) was tested in comparison with the ligands. In all cases, coordination of ruthenium resulted in significantly enhanced cytotoxicity. The affinity of Ru(II) -biotin complexes to avidin was investigated and was lower than that of unmodified biotin. Hill coefficients in the range 2.012-2.851 suggest strong positive cooperation between the complexes and avidin. To estimate the likelihood of binding to the biotin receptor/transporter, docking studies with avidin and streptavidin were conducted. These explain, to some extent, the in vitro anticancer activity results and support the conclusion that these novel half-sandwich ruthenium(II)-biotin conjugates may act as biological vectors to cancer cells, although no clear relationship between the cellular Ru content, the cytotoxicity, and the presence of the biotin moiety was observed.

  14. Synthesis, characterization and antibacterial studies of ruthenium(III) complexes derived from chitosan schiff base.

    PubMed

    Vadivel, T; Dhamodaran, M

    2016-09-01

    Chitosan can be modified chemically by condensation reaction of deacetylated chitosan with aldehyde in homogeneous phase. This condensation is carried by primary amine (NH2) with aldehyde (CHO) to form corresponding schiff base. The chitosan biopolymer schiff base derivatives are synthesized with substituted aldehydes namely 4-hydroxy-3-methoxy benzaldehyde, 2-hydroxy benzaldehyde, and 2-hydroxy-3-methoxy benzaldehyde, becomes a complexing agent or ligand. The Ruthenium(III) complexes were obtained by complexation of Ruthenium with schiff base ligands and this product exhibits as an excellent solubility and more biocompatibility. The novel series of schiff base Ruthenium(III) complexes are characterized by Elemental analysis, FT-IR spectroscopy, and Thermo-gravimetric analysis (TGA). The synthesized complexes have been subjected to antibacterial study. The antibacterial results indicated that the antibacterial activity of the complexes were more effective against Gram positive and Gram negative pathogenic bacteria. These findings are giving suitable support for developing new antibacterial agent and expand our scope for applications.

  15. Enhancing vascular relaxing effects of nitric oxide-donor ruthenium complexes.

    PubMed

    Paulo, Michele; Banin, Tamy M; de Andrade, Fernanda A; Bendhack, Lusiane M

    2014-05-01

    Ruthenium-derived complexes have emerged as new nitric oxide (NO) donors that may help circumvent the NO deficiency that impairs vasodilation. NO in vessels can be produced by the endothelial cells and/or released by NO donors. NO interacts with soluble guanylyl-cyclase to produce cGMP to activate the kinase-G pathway. As a result, conductance arteries, veins and resistance arteries dilate, whereas the cytosolic Ca(2+) levels in the smooth muscle cells decrease. NO also reacts with oxygen or the superoxide anion, to generate reactive oxygen species that modulate NO-induced vasodilation. In this article, we focus on NO production by NO synthase and discuss the vascular changes taking place during hypertension originating from endothelial dysfunction. We will describe how the NO released from ruthenium-derived complexes enhances the vascular effects arising from failed NO generation or lack of NO bioavailability. In addition, how ruthenium-derived NO donors induce the hypotensive effect by vasodilation is also discussed.

  16. Ruthenium (II) complexes interact with human serum albumin and induce apoptosis of tumor cells.

    PubMed

    Sun, Jing; Huang, Yongchao; Zheng, Chuping; Zhou, Yanhui; Liu, Ying; Liu, Jie

    2015-02-01

    The interaction of ruthenium (II) complex [Ru(bpy)2(mal)](2+) (RBM) and [Ru(phen)2(mal)](2+) (RPM) (bpy = 2, 2-bipyridine, phen = 1,10-phenanthroline, mal = malonyl carboxylate) with human serum albumin (HSA) has been investigated by using fluorescence, UV absorption and circular dichroism (CD) spectroscopy approaches. A strong fluorescence quenching reaction of complexes to HSA was observed and the quenching mechanism was suggested as static quenching according to the Stern-Volmer (S-V) equation. The number of binding sites n and observed binding constant Kb was measured by fluorescence quenching method. The thermodynamic parameters ΔH, ΔS, and ΔG at different temperatures were calculated and the results indicate the binding reaction is mainly entropy-driven and Vander Waals force played a major role in the reaction. The result of CD showed that the secondary structure of HSA molecules was changed in the presence of the ruthenium (II) complexes. Furthermore, the cell viability of ruthenium (II) complexes was evaluated by MTT and complex RPM has shown significant higher anticancer potency than RBM against all the cell lines screened. RPM showed a significant antitumor activity through induction of apoptosis in A549 cells.

  17. Radiosensitisation of human colorectal cancer cells by ruthenium(II) arene anticancer complexes.

    PubMed

    Carter, R; Westhorpe, A; Romero, M J; Habtemariam, A; Gallevo, C R; Bark, Y; Menezes, N; Sadler, P J; Sharma, R A

    2016-02-12

    Some of the largest improvements in clinical outcomes for patients with solid cancers observed over the past 3 decades have been from concurrent treatment with chemotherapy and radiotherapy (RT). The lethal effects of RT on cancer cells arise primarily from damage to DNA. Ruthenium (Ru) is a transition metal of the platinum group, with potentially less toxicity than platinum drugs. We postulated that ruthenium-arene complexes are radiosensitisers when used in combination with RT. We screened 14 ruthenium-arene complexes and identified AH54 and AH63 as supra-additive radiosensitisers by clonogenic survival assays and isobologram analyses. Both complexes displayed facial chirality. At clinically relevant doses of RT, radiosensitisation of cancer cells by AH54 and AH63 was p53-dependent. Radiation enhancement ratios for 5-10 micromolar drug concentrations ranged from 1.19 to 1.82. In p53-wildtype cells, both drugs induced significant G2 cell cycle arrest and apoptosis. Colorectal cancer cells deficient in DNA damage repair proteins, EME1 and MUS81, were significantly more sensitive to both agents. Both drugs were active in cancer cell lines displaying acquired resistance to oxaliplatin or cisplatin. Our findings broaden the potential scope for these drugs for use in cancer therapy, including combination with radiotherapy to treat colorectal cancer.

  18. Interactions of ruthenium complexes containing indoloquinoline moiety with human telomeric G-quadruplex DNA.

    PubMed

    Yu, Hui-juan; Yu, Lin; Hao, Zhi-feng; Zhao, Ying

    2014-04-24

    G-quadruplex structures are attractive targets for the development of anticancer drugs, as their formation in human telomere could impair telomerase activity, thus inducing apoptosis in cancer cells. Vast majority of G-quadruplex binding molecules have been designed and synthesized. Ruthenium complexes have also been reported to induction or stabilization of G-quadruplex structure of human telomeric sequence, whereas most of them generally promote the formation of antiparallel or hybrid-type G-quadruplex structure. Ruthenium complex that selectively promotes the formation of parallel G-quadruplex structure has rarely been reported. We reported here the interaction of two ruthenium complexes [Ru(bpy)2(mitatp)](2+)1 and [Ru(phen)2(mitatp)](2+)2 (bpy=2,2' bipyridine, phen=1,10-phenanthroline, mitatp=5-methoxy-isatino[1,2-b]-1,4,8,9-tetraazatriphenylene) containing indoloquinoline moiety with human telomeric G-quadruplex DNA (Telo22). Complex 1 binds to Telo22 tightly via a stable π-π stacking interaction and efficiently stabilizes the G-quadruplex structure. Circular dichroism (CD) spectra titration results suggest that complex 1 could induce Telo22 to fold into antiparallel G-quadruplex conformation. Complex 2 exhibits moderate G-quadruplex binding and stabilizing ability, while CD titration data reveals that complex 2 could promote the formation of parallel G-quadruplex structure.

  19. Influence of PPh₃ moiety in the anticancer activity of new organometallic ruthenium complexes.

    PubMed

    Sáez, Rubén; Lorenzo, Julia; Prieto, Ma Jose; Font-Bardia, Mercè; Calvet, Teresa; Omeñaca, Nuria; Vilaseca, Marta; Moreno, Virtudes

    2014-07-01

    The effect of the PPh3 group in the antitumor activity of some new organometallic ruthenium(II) complexes has been investigated. Several complexes of the type [Ru((II))(Cl)(PPh3)(Lig-N)], [Ru((II))(Cl)2(Lig-N)] (where Lig-N=pyridine derivate) and [Ru((II))(Cl)(PPh3)2], have been synthesized and characterized. A noticeable increment of the antitumor activity and cytotoxicity of the complexes due to the presence of PPh3 moiety has also been demonstrated, affording IC50 values of 5.2 μM in HL-60 tumor cell lines. Atomic force microscopy, circular dichroism and electrophoresis experiments have proved that these complexes can bind DNA resulting in a distortion of both secondary and tertiary structures. Ethidium bromide displacement fluorescence spectroscopy studies and viscosity measurements support that the presence of PPh3 group induces intercalation interactions with DNA. Indeed, crystallographic analysis, suggest that intra-molecular π-π interactions could be involved in the intercalation within DNA base pairs. Furthermore, high performance liquid chromatography mass spectrometry (HPLC-MS) studies have confirmed a strong interaction between ruthenium complexes and proteins (ubiquitin and potato carboxypeptidase inhibitor - PCI) including slower kinetics due to the presence of PPh3 moiety, which could have an important role in detoxification mechanism and others. Finally, ion mobility mass spectrometry (IMMS) experiments have proved that there is no significant change in the gas phase structural conformation of the proteins owing to their bonding to ruthenium complexes.

  20. Pharmacological Activities of Ruthenium Complexes Related to Their NO Scavenging Properties.

    PubMed

    Castellarin, Anna; Zorzet, Sonia; Bergamo, Alberta; Sava, Gianni

    2016-08-02

    Angiogenesis is considered responsible for the growth of primary tumours and of their metastases. With the present study, the effects of three ruthenium compounds, potassiumchlorido (ethylendiamminotetraacetate)rutenate(III) (RuEDTA), sodium (bis-indazole)tetrachloro-ruthenate(III), Na[trans-RuCl₄Ind₂] (KP1339) and trans-imidazoledimethylsulphoxidetetrachloro-ruthenate (NAMI-A), are studied in vitro in models mimicking the angiogenic process. The ruthenium compounds reduced the production and the release of nitrosyls from either healthy macrophages and immortalized EA.hy926 endothelial cells. The effects of NAMI-A are qualitatively similar and sometimes quantitatively superior to those of RuEDTA and KP1339. NAMI-A reduces the production and release of nitric oxide (NO) by the EA.hy926 endothelial cells and correspondingly inhibits their invasive ability; it also strongly inhibits the angiogenesis in matrigel sponges implanted subcutaneously in healthy mice. Taken together, these data support the anti-angiogenic activity of the tested ruthenium compounds and they contribute to explain the selective activity of NAMI-A against solid tumour metastases, the tumour compartment on which angiogenesis is strongly involved. This anti-angiogenic effect may also contribute to the inhibition of the release of metastatic cells from the primary tumour. Investigations on the anti-angiogenic effects of NAMI-A at this level will increase knowledge of its pharmacological properties and it will give a further impulse to the development of this class of innovative metal-based drugs.

  1. Nitrile-functionalized ruthenium nanoparticles: charge delocalization through Ru - N ≡ C interface

    NASA Astrophysics Data System (ADS)

    Zhang, Fengqi; Huang, Lin; Zou, Jiasui; Yan, Jinwu; Zhu, Jiaying; Kang, Xiongwu; Chen, Shaowei

    2017-03-01

    Ruthenium nanoparticles (2.06 ± 0.46 nm in diameter) were stabilized by the self-assembly of nitrile molecules onto the ruthenium colloid surface by virtue of the formation of Ru-N≡C interfacial bonding linkages. Thermogravimetric analysis showed that there were about 63 nitrile ligands per nanoparticle, corresponding to an average molecular footprint of 22.4 Å2. Proton nuclear magnetic resonance (NMR) studies suggested an end-on configuration of the nitrile moiety on the metal core surface. Meanwhile, infrared measurements showed that the C≡N stretch red-shifted from 2246 to 1944 cm-1 upon adsorption on the nanoparticle surfaces, as confirmed by 15N isotopic labeling. This apparent red-shift suggests extensive intraparticle charge delocalization, which was further manifested by photoluminescence measurements of 1-cyanopyrene-functionalized ruthenium nanoparticles that exhibited a red shift of 40 nm of the emission maximum, in comparison to that of free monomers. The results further highlight the significance of metal-organic contacts in the manipulation of the dynamics of intraparticle charge transfer and the nanoparticle optical and electronic properties.

  2. Chromium and Ruthenium-Doped Zinc Oxide Thin Films for Propane Sensing Applications

    PubMed Central

    Gómez-Pozos, Heberto; González-Vidal, José Luis; Torres, Gonzalo Alberto; Rodríguez-Baez, Jorge; Maldonado, Arturo; de la Luz Olvera, María; Acosta, Dwight Roberto; Avendaño-Alejo, Maximino; Castañeda, Luis

    2013-01-01

    Chromium and ruthenium-doped zinc oxide (ZnO:Cr) and (ZnO:Ru) thin solid films were deposited on soda-lime glass substrates by the sol-gel dip-coating method. A 0.6 M solution of zinc acetate dihydrate dissolved in 2-methoxyethanol and monoethanolamine was used as basic solution. Chromium (III) acetylacetonate and Ruthenium (III) trichloride were used as doping sources. The Ru incorporation and its distribution profile into the films were proved by the SIMS technique. The morphology and structure of the films were studied by SEM microscopy and X-ray diffraction measurements, respectively. The SEM images show porous surfaces covered by small grains with different grain size, depending on the doping element, and the immersions number into the doping solutions. The sensing properties of ZnO:Cr and ZnO:Ru films in a propane (C3H8) atmosphere, as a function of the immersions number in the doping solution, have been studied in the present work. The highest sensitivity values were obtained for films doped from five immersions, 5.8 and 900, for ZnO:Cr and ZnO:Ru films, respectively. In order to evidence the catalytic effect of the chromium (Cr) and ruthenium (Ru), the sensing characteristics of undoped ZnO films are reported as well. PMID:23482091

  3. Nanoformulation improves activity of the (pre)clinical anticancer ruthenium complex KP1019.

    PubMed

    Heffeter, P; Riabtseva, A; Senkiv, Y; Kowol, C R; Körner, W; Jungwith, U; Mitina, N; Keppler, B K; Konstantinova, T; Yanchuk, I; Stoika, R; Zaichenko, A; Berger, W

    2014-05-01

    Ruthenium anticancer drugs belong to the most promising non-platinum anticancer metal compounds in clinical evaluation. However, although the clinical results are promising regarding both activity and very low adverse effects, the clinical application is currently hampered by the limited solubility and stability of the drug in aqueous solution. Here, we present a new nanoparticle formulation based on polymer-based micelles loaded with the anticancer lead ruthenium compound KP1019. Nanoprepared KP1019 was characterised by enhanced stability in aqueous solutions. Moreover, the nanoparticle formulation facilitated cellular accumulation of KP1019 (determined by ICP-MS measurements) resulting in significantly lowered IC50 values. With regard to the mode of action, increased cell cycle arrest in G2/M phase (PI-staining), DNA damage (Comet assay) as well as enhanced levels of apoptotic cell death (caspase 7 and PARP cleavage) were found in HCT116 cells treated with the new nanoformulation of KP1019. Summarizing, we present for the first time evidence that nanoformulation is a feasible strategy for improving the stability as well as activity of experimental anticancer ruthenium compounds.

  4. Radiosensitisation of human colorectal cancer cells by ruthenium(II) arene anticancer complexes

    PubMed Central

    Carter, R; Westhorpe, A; Romero, MJ; Habtemariam, A; Gallevo, CR; Bark, Y; Menezes, N; Sadler, PJ; Sharma, RA

    2016-01-01

    Some of the largest improvements in clinical outcomes for patients with solid cancers observed over the past 3 decades have been from concurrent treatment with chemotherapy and radiotherapy (RT). The lethal effects of RT on cancer cells arise primarily from damage to DNA. Ruthenium (Ru) is a transition metal of the platinum group, with potentially less toxicity than platinum drugs. We postulated that ruthenium-arene complexes are radiosensitisers when used in combination with RT. We screened 14 ruthenium-arene complexes and identified AH54 and AH63 as supra-additive radiosensitisers by clonogenic survival assays and isobologram analyses. Both complexes displayed facial chirality. At clinically relevant doses of RT, radiosensitisation of cancer cells by AH54 and AH63 was p53-dependent. Radiation enhancement ratios for 5–10 micromolar drug concentrations ranged from 1.19 to 1.82. In p53-wildtype cells, both drugs induced significant G2 cell cycle arrest and apoptosis. Colorectal cancer cells deficient in DNA damage repair proteins, EME1 and MUS81, were significantly more sensitive to both agents. Both drugs were active in cancer cell lines displaying acquired resistance to oxaliplatin or cisplatin. Our findings broaden the potential scope for these drugs for use in cancer therapy, including combination with radiotherapy to treat colorectal cancer. PMID:26867983

  5. Ruthenium complexes of substituted hydrazine: new solution- and solid-state binding modes.

    PubMed

    Dabb, Serin L; Messerle, Barbara A; Otting, Gottfried; Wagler, Jörg; Willis, Anthony

    2008-01-01

    The methylhydrazine complex [Ru(NH(2)NHMe)(PyP)(2)]Cl(BPh(4)) (PyP=1-[2-(diphenylphosphino)ethyl]pyrazole) was synthesised by addition of methylhydrazine to the bimetallic complex [Ru(mu-Cl)(PyP)(2)](2)(BPh(4))(2). The methylhydrazine ligand of the ruthenium complex has two different binding modes: side-on (eta(2)-) when the complex is in the solid state and end-on (eta(1)-) when the complex is in solution. The solid-state structure of [Ru(PyP)(2)(NH(2)NHMe)]Cl(BPh(4)) was determined by X-ray crystallography. 2D NMR spectroscopic experiments with (15)N at natural abundance confirmed that in solution the methylhydrazine is bound to the metal centre by only the -NH(2) group and the ruthenium complex retains an octahedral conformation. Hydrazine complexes [RuCl(PyP)(2)(eta(1)-NH(2)NRR')]OSO(2)CF(3) (in which R=H, R'=Ph, R=R'=Me and NRR'=NC(5)H(10)) were formed in situ by the addition of phenylhydrazine, 1,1-dimethylhydrazine and N-aminopiperidine, respectively, to a solution of the bimetallic complex [Ru(mu-Cl)(PyP)(2)](2)(OSO(2)CF(3))(2) in dichloromethane. These substituted hydrazine complexes of ruthenium were shown to exist in an equilibrium mixture with the bimetallic starting material.

  6. Nickel-cobalt alloy nanosheets obtained from reductive hydrothermal-treatment of nickel-cobalt hydroxide carbonate

    SciTech Connect

    Ghotbi, Mohammad Yeganeh; Jolagah, Ali; Afrasiabi, Hasan-ali

    2012-03-15

    Highlights: Black-Right-Pointing-Pointer An anionic layered material, nickel-cobalt hydroxide carbonate was synthesized. Black-Right-Pointing-Pointer Reductive hydrothermal-treatment of the layered precursor produced an alloy. Black-Right-Pointing-Pointer The alloy is a bimetallic nanostructured nickel-cobalt and a soft magnet material. -- Abstract: Nickel-cobalt hydroxide carbonate, a layered material was synthesized by the co-precipitation method using urea as precipitant agent. This anionic layered material with hexagonal structure is constructed from nickel and cobalt ions within the layers and carbonate anions between the layers. Nickel-cobalt alloy with pure cubic phase was obtained by a reductive hydrothermal-treatment of the layered precursor. Powder X-ray diffraction pattern and Fourier transform infrared spectroscopy confirmed the formation of the initial layered material and its metallic alloy product. That is, the nickel-cobalt alloy has really produced via a wet chemical route for the first time. Magnetic measurement revealed that the alloy sample is a soft magnet material.

  7. Tailoring ruthenium exposure to enhance the performance of fcc platinum@ruthenium core-shell electrocatalysts in the oxygen evolution reaction.

    PubMed

    AlYami, Noktan M; LaGrow, Alec P; Joya, Khurram S; Hwang, Jinyeon; Katsiev, Khabiboulakh; Anjum, Dalaver H; Losovyj, Yaroslav; Sinatra, Lutfan; Kim, Jin Young; Bakr, Osman M

    2016-06-28

    The catalytic properties of noble metal nanocrystals are a function of their size, structure, and surface composition. In particular, achieving high activity without sacrificing stability is essential for designing commercially viable catalysts. A major challenge in designing state-of-the-art Ru-based catalysts for the oxygen evolution reaction (OER), which is a key step in water splitting, is the poor stability and surface tailorability of these catalysts. In this study, we designed rapidly synthesizable size-controlled, morphology-selective, and surface-tailored platinum-ruthenium core-shell (Pt@Ru) and alloy (PtRu) nanocatalysts in a scalable continuous-flow reactor. These core-shell nanoparticles with atomically precise shells were produced in a single synthetic step with carbon monoxide as the reducing agent. By varying the metal precursor concentration, a dendritic or layer-by-layer ruthenium shell can be grown. The synthesized Pt@Ru and PtRu nanoparticles exhibit noticeably higher electrocatalytic activity in the OER compared to that of pure Pt and Ru nanoparticles. Promisingly, Pt@Ru nanocrystals with a ∼2-3 atomic layer Ru cuboctahedral shell surpass conventional Ru nanoparticles in terms of both durability and activity.

  8. Tuning of magnetic parameters in cobalt-polystyrene nanocomposites by reduction cycling

    SciTech Connect

    Nair, Swapna S.; Sunny, Vijutha; Anantharaman, M.R.

    2011-10-15

    Graphical abstract: Cobalt nanoparticles were prepared by a reduction process inside polymer pores. A porous polymer network (polystyrene) was chosen as the template for the synthesis of elementary cobalt as high surface area cobalt nanoparticles are prone to oxidation. The preliminary studies reveal that the cobalt is first formed with an oxide protective layer outside and upon repeating the reduction cycles, inner pores of the polymers are opened which enhanced the yield of metallic cobalt. These high surface area cobalt nanoparticles embedded in a polymer are ideal for the synthesis of carbon nanotubes as cobalt can act as a catalyst for the nanotube synthesis. The concentration of cobalt can be tuned in this technique by repeating the cycling process. Highlights: {yields} Elementary cobalt nanoparticles were synthesized inside polystyrene by a novel process. {yields} The self protection is achieved by the auto-shelling with the metal oxide. {yields} The magnetisation and coercivity could be tuned by repeating the cycles. {yields} Tuning of magnetic properties (both coercivity and magnetisation) could be achieved by the repetition of reduction cycles. {yields} Synthesized nanocomposite can act as a catalyst for carbon nanotube synthesis. -- Abstract: Cobalt nanoparticles were prepared by a reduction process inside polymer pores using CoSO{sub 4}.7H{sub 2}O and NaBH{sub 4}. A porous polymer network (sulphonated polystyrene) was chosen, as the template for the synthesis of elementary cobalt as high surface area cobalt nanoparticles are prone to oxidation. The preliminary studies reveal that the cobalt is first formed with an oxide protective layer outside and upon repeating the reduction cycles, inner pores of the polymers are opened which enhanced the yield of metallic cobalt. These high surface area cobalt nanoparticles embedded in a polymer are ideal for the synthesis of carbon nanotubes as cobalt can act as a catalyst for the nanotube synthesis. The

  9. A dissolved cobalt plume in the oxygen minimum zone of the eastern tropical South Pacific

    NASA Astrophysics Data System (ADS)

    Hawco, Nicholas J.; Ohnemus, Daniel C.; Resing, Joseph A.; Twining, Benjamin S.; Saito, Mak A.

    2016-10-01

    Cobalt is a nutrient to phytoplankton, but knowledge about its biogeochemical cycling is limited, especially in the Pacific Ocean. Here, we report sections of dissolved cobalt and labile dissolved cobalt from the US GEOTRACES GP16 transect in the South Pacific. The cobalt distribution is closely tied to the extent and intensity of the oxygen minimum zone in the eastern South Pacific with highest concentrations measured at the oxycline near the Peru margin. Below 200 m, remineralization and circulation produce an inverse relationship between cobalt and dissolved oxygen that extends throughout the basin. Within the oxygen minimum zone, elevated concentrations of labile cobalt are generated by input from coastal sources and reduced scavenging at low O2. As these high cobalt waters are upwelled and advected offshore, phytoplankton export returns cobalt to low-oxygen water masses underneath. West of the Peru upwelling region, dissolved cobalt is less than 10 pM in the euphotic zone and strongly bound by organic ligands. Because the cobalt nutricline within the South Pacific gyre is deeper than in oligotrophic regions in the North and South Atlantic, cobalt involved in sustaining phytoplankton productivity in the gyre is heavily recycled and ultimately arrives from lateral transport of upwelled waters from the eastern margin. In contrast to large coastal inputs, atmospheric deposition and hydrothermal vents along the East Pacific Rise appear to be minor sources of cobalt. Overall, these results demonstrate that oxygen biogeochemistry exerts a strong influence on cobalt cycling.

  10. Carboxylate-assisted ruthenium-catalyzed alkyne annulations by C-H/Het-H bond functionalizations.

    PubMed

    Ackermann, Lutz

    2014-02-18

    To improve the atom- and step-economy of organic syntheses, researchers would like to capitalize upon the chemistry of otherwise inert carbon-hydrogen (C-H) bonds. During the past decade, remarkable progress in organometallic chemistry has set the stage for the development of increasingly viable metal catalysts for C-H bond activation reactions. Among these methods, oxidative C-H bond functionalizations are particularly attractive because they avoid the use of prefunctionalized starting materials. For example, oxidative annulations that involve sequential C-H and heteroatom-H bond cleavages allow for the modular assembly of regioselectively decorated heterocycles. These structures serve as key scaffolds for natural products, functional materials, crop protecting agents, and drugs. While other researchers have devised rhodium or palladium complexes for oxidative alkyne annulations, my laboratory has focused on the application of significantly less expensive, yet highly selective ruthenium complexes. This Account summarizes the evolution of versatile ruthenium(II) complexes for annulations of alkynes via C-H/N-H, C-H/O-H, or C-H/N-O bond cleavages. To achieve selective C-H bond functionalizations, we needed to understand the detailed mechanism of the crucial C-H bond metalation with ruthenium(II) complexes and particularly the importance of carboxylate assistance in this process. As a consequence, our recent efforts have resulted in widely applicable methods for the versatile preparation of differently decorated arenes and heteroarenes, providing access to among others isoquinolones, 2-pyridones, isoquinolines, indoles, pyrroles, or α-pyrones. Most of these reactions used Cu(OAc)2·H2O, which not only acted as the oxidant but also served as the essential source of acetate for the carboxylate-assisted ruthenation manifold. Notably, the ruthenium(II)-catalyzed oxidative annulations also occurred under an ambient atmosphere of air with cocatalytic amounts of Cu(OAc)2

  11. Electromagnetic containerless reaction of samarium with cobalt for the formation of samarium-cobalt alloys

    NASA Technical Reports Server (NTRS)

    Chang, C. W.; Das, D. K.; Kumar, K.; Frost, R. T.

    1982-01-01

    The electromagnetic levitation technique has been used to obtain nearly stoichiometric SmCo5, with the reaction temperature controlled by a gas jet. The results of several experiments carried out at a 450 kHz, 25 kw RF power levitation facility using different reaction times and cooling rates are presented. It is shown that reaction rates achieved with the levitation technique are larger than the expected diffusion rate in the system liquid samarium-solid cobalt. It is also shown that substantial mixing occurs in the RF-levitated melt.

  12. A sensitive quantum dots-based "OFF-ON" fluorescent sensor for ruthenium anticancer drugs and ctDNA.

    PubMed

    Huang, Shan; Zhu, Fawei; Qiu, Hangna; Xiao, Qi; Zhou, Quan; Su, Wei; Hu, Baoqing

    2014-05-01

    In this contribution, a simple and sensitive fluorescent sensor for the determination of both the three ruthenium anticancer drugs (1 to 3) and calf thymus DNA (ctDNA) was established based on the CdTe quantum dots (QDs) fluorescence "OFF-ON" mode. Under the experimental conditions, the fluorescence of CdTe QDs can be effectively quenched by ruthenium anticancer drugs because of the surface binding of these drugs on CdTe QDs and the subsequent photoinduced electron transfer (PET) process from CdTe QDs to ruthenium anticancer drugs, which render the system into fluorescence "OFF" status. The system can then be "ON" after the addition of ctDNA which brought the restoration of CdTe QDs fluorescence intensity, since ruthenium anticancer drugs broke away from the surface of CdTe QDs and inserted into double helix structure of ctDNA. The fluorescence quenching effect of the CdTe QDs-ruthenium anticancer drugs systems was mainly concentration dependent, which could be used to detect three ruthenium anticancer drugs. The limits of detection were 5.5 × 10(-8) M for ruthenium anticancer drug 1, 7.0 × 10(-8) M for ruthenium anticancer drug 2, and 7.9× 10(-8) M for ruthenium anticancer drug 3, respectively. The relative restored fluorescence intensity was directly proportional to the concentration of ctDNA in the range of 1.0 × 10(-8) M ∼ 3.0 × 10(-7) M, with a correlation coefficient (R) of 0.9983 and a limit of detection of 1.1 × 10(-9) M. The relative standard deviation (RSD) for 1.5 × 10(-7) M ctDNA was 1.5% (n = 5). There was almost no interference to some common chemical compounds, nucleotides, amino acids, and proteins. The proposed method was applied to the determination of ctDNA in three synthetic samples with satisfactory results. The possible reaction mechanism of CdTe QDs fluorescence "OFF-ON" was further investigated. This simple and sensitive approach possessed some potential applications in the investigation of interaction between drug molecules and DNA.

  13. Cobalt monolayer islands on Ag(111) for ORR catalysis.

    PubMed

    Loglio, Francesca; Lastraioli, Elisa; Bianchini, Claudio; Fontanesi, Claudio; Innocenti, Massimo; Lavacchi, Alessandro; Vizza, Francesco; Foresti, Maria Luisa

    2011-08-22

    The design of a catalyst for one of the most important electrocatalytic reactions, the oxygen reduction reaction (ORR), was done following the most recent guidelines of theoretical studies on this topic. Aim of this work was to achieve a synergic effect of two different metals acting on different steps of the ORR. The catalytic activity of Ag, already known and characterized, was enhanced by the presence of a monolayer of cobalt subdivided into nanosized islands. To obtain such a controlled nanostructure, a novel method utilizing self-assembled monolayers (SAMs) as templates was employed. In a recent study, we were able to perform a confined electrodeposition of cobalt onto Ag(111) in a template formed by selectively desorbing a short-chain thiol (3-mercaptopropionic acid, MPA) from binary SAMs using 1-dodecanthiols (DDT). This method allows for an excellent control of the morphology of the deposit by varying the molar ratio of the two thiols. Because cobalt does not deposit on silver at an underpotential, the alternative approach of surface limited redox replacement (SLRR) was used. This method, recently developed by Adžić et al., consists of the use of a monolayer of a third metal, which can be deposited at an underpotential, as a template for the spontaneous deposition of a more noble metal. Herein, we choose zinc as template for the deposition of cobalt. Ag(111) crystals were covered by monolayer islands consisting of cobalt, with the surface atomic ratios ranging from 12 to 39% for cobalt. The catalytic activity of such samples towards ORR was evaluated and the best improvement in activity was found to be that of the sample with a cobalt percentage of approximately 30% with respect to the bare silver, which is in good agreement with theoretical hypotheses.

  14. Chronic cobalt treatment decreases hyperglycemia in streptozotocin-diabetic rats.

    PubMed

    Vasudevan, Harish; McNeill, John H

    2007-04-01

    Diabetes is a metabolic disorder characterized by elevated blood glucose levels. Although conventional treatments such as insulin and other drugs reduce blood glucose, there is still a therapeutic need for effective orally administered drugs. Trace elements like vanadium and tungstate have been successfully demonstrated to reduce blood glucose in experimental diabetes with minimal chronic complications. We investigated the anti-hyperglycemic effects of cobalt in streptozotocin-diabetic rats. Normal and diabetic rats were provided with drinking water containing 3.5 mM cobalt chloride for three weeks followed by 4 mM for four weeks. Body weights and fluid consumption were monitored on a daily basis, while food intake was recorded twice every week. Prior to termination, an oral glucose tolerance test was performed on the animals. Diabetic rats lost significant body weight (357 +/- 2 gm) compared to controls (482 +/- 3 gm). Body weight was further reduced by cobalt treatment (290 +/- 2 gm). Although it was difficult to establish a dosing regimen without weight loss, food and fluid consumption in cobalt-treated diabetic rats improved significantly compared to untreated diabetics. Plasma glucose levels were significantly reduced with reference to diabetic controls (29.3 +/- 0.9 mM) by the fourth week to a lower but still hyperglycemic level (13.6 +/- 3.4 mM). Cobalt-treated diabetic rats demonstrated an enhanced ability to clear a glucose load compared to untreated diabetics. Cobalt treatment neither affected the feeding and drinking patterns nor plasma glucose in normoglycemic animals although body weights decreased compared to untreated controls. We conclude that chronic cobalt treatment decreases plasma glucose levels in STZ-diabetic rats and improves tolerance to glucose.

  15. Organometallic ruthenium complexes with thiosemicarbazone ligands: Synthesis, structure and cytotoxicity of [(η6-p-cymene)Ru(NS)Cl]+ (NS = 9-anthraldehyde thiosemicarbazones)

    PubMed Central

    Beckford, Floyd A.; Leblanc, Gabriel; Thessing, Jeffrey; Shaloski, Michael; Frost, Brian J.; Li, Liya; Seeram, Navindra P.

    2009-01-01

    A series of half-sandwich arene-ruthenium complexes of the type [(η6-p-cymene) Ru(thiosemicarbazone)Cl]+ have been synthesized and their biological activity investigated. The first structurally characterized arene-ruthenium half-sandwich complex with a thiosemicarbazone ligand is reported. PMID:20160909

  16. Ruthenium(II)-catalyzed C-H activation/alkyne annulation by weak coordination with O2 as the sole oxidant.

    PubMed

    Warratz, Svenja; Kornhaaß, Christoph; Cajaraville, Ana; Niepötter, Benedikt; Stalke, Dietmar; Ackermann, Lutz

    2015-04-27

    Aerobic oxidative CH functionalizations of weakly coordinating benzoic acids have been accomplished with versatile ruthenium(II) biscarboxylates under ambient oxygen or air. Mechanistic studies identified the key factors controlling the elementary step of the oxidation of the ruthenium(0) complex.

  17. Synthesis and Catalytic Activity of Ruthenium-Indenylidene Complexes for Olefin Metathesis: Microscale Experiments for the Undergraduate Inorganic or Organometallic Laboratories

    ERIC Educational Resources Information Center

    Pappenfus, Ted M.; Hermanson, David L.; Ekerholm, Daniel P.; Lilliquist, Stacie L.; Mekoli, Megan L.

    2007-01-01

    A series of experiments for undergraduate laboratory courses (e.g., inorganic, organometallic or advanced organic) have been developed. These experiments focus on understanding the design and catalytic activity of ruthenium-indenylidene complexes for olefin metathesis. Included in the experiments are the syntheses of two ruthenium-indenylidene…

  18. Photoinduced interactions of supramolecular ruthenium(II) complexes with plasmid DNA: synthesis and spectroscopic, electrochemical, and DNA photocleavage studies.

    PubMed

    Swavey, Shawn; DeBeer, Madeleine; Li, Kaiyu

    2015-04-06

    Two new bridging ligands have been synthesized by combining substituted benzaldehydes with phenanthrolinopyrrole (php), resulting in new polyazine bridging ligands. The ligands have been characterized by (1)H NMR, mass spectroscopy, and elemental analysis. These new ligands display π-π* transitions above 500 nm with modest molar absorptivities. Upon excitation at the ligand-centered charge-transfer transition, weak emission with a maximum wavelength of 612 nm is observed. When coordinated to two ruthenium(II) bis(bipyridyl) groups, the new bimetallic complexes generated give an overall 4+ charge. The electronic transitions of the bimetallic ruthenium(II) complexes display traditional π-π* transitions at 287 nm and metal-to-ligand charge-transfer transitions at 452 nm with molar absorptivities greater than 30000 M(-1) cm(-1). Oxidation of the ruthenium(II) metal centers to ruthenium(III) occurs at potentials above 1.4 V versus the Ag/AgCl reference electrode. Spectroscopic and electrochemical measurements indicate that the ruthenium(II) moieties behave independently. Both complexes are water-soluble and show the ability to photonick plasmid DNA when irradiated with low-energy light above 550 nm. In addition, one of the complexes, [Ru(bpy)2php]2Van(4+), shows the ability to linearize plasmid DNA and gives evidence, by gel electrophoresis, of photoinduced binding to plasmid DNA.

  19. Dialkylmethyl-2-(N,N-diisobutyl)acetamidoammonium iodide as a ruthenium selective ligand from nitric acid medium.

    PubMed

    Sharma, Shikha; Ghosh, Sunil K; Sharma, Joti N

    2015-09-15

    A new class of quaternary ammonium iodide based ligands with 2-(N,N-diisobutyl)acetamide as an alkyl appendage have been designed, synthesized and tested for their ability to extract ruthenium selectively from nitric acid medium. The 2-(N,N-diisobutyl)acetamido ammonium iodide with two propyl and a methyl substituents showed best results for the recovery of ruthenium. The optimized concentration of the solvent was found to be 0.2M in 30% isodecyl alcohol/n-dodecane. The stoichiometry of the complex was ascertained by slope analysis method and was found to be 1:1 with respect to ligand L(+)I(-) and Ru(NO)(NO3)3. Ruthenium formed an adduct of structure LRu(NO)(NO3)3 I in the extraction medium. Iodide ion played an important role in the formation of the stable and extractable complex of ruthenium. No extraction was observed when iodide was replaced by nitrate anion in the ligand. The ligand also showed good selectivity for ruthenium in the presence of other metal ions commonly found in nitric acid solutions of nuclear waste.

  20. Cobalt-60 gamma irradiation of shrimp

    SciTech Connect

    Sullivan, N.L.B.

    1993-01-01

    Meta- and ortho-tyrosine were measured using high performance liquid chromatography (HPLC) in conjunction with electrochemical detection in shrimp irradiated using cobalt-60 gamma radiation in the absorbed dose range 0.8 to 6.0 kGy, in nonirradiated shrimp, and in bovine serum albumin (BSA) irradiated in dilute aqueous solution at 25.0 kGy. Ortho-tyrosine was measured in nonirradiated BSA. Para-, meta-, and ortho-tyrosine was measured using HPLC in conjunction with uv-absorption detection in dilute aqueous solutions of phenylalanine irradiated in the absorbed dose range 16.0 to 195.0 kGy. The measured yields of tyrosine isomers were approximately linear as a function of absorbed dose in shrimp, and in irradiated solutions of phenylalanine up to 37.0 kGy. The occurrence of meta- and ortho-tyrosine, which had formerly been considered unique radiolytic products, has not previously been reported in nonirradiated shrimp or BSA. The conventional hydrolyzation and analytical techniques used in the present study to measure meta- and ortho-tyrosine may provide the basis for a method to detect and determine the dose used in food irradiation.

  1. Cobalt chloride attenuates hypobaric hypoxia induced vascular leakage in rat brain: molecular mechanisms of action of cobalt chloride.

    PubMed

    Kalpana, S; Dhananjay, S; Anju, B; Lilly, G; Sai Ram, M

    2008-09-15

    This study reports the efficacy of cobalt preconditioning in preventing hypobaric hypoxia induced vascular leakage (an indicator of cerebral edema) using male Sprague-Dawley rats as model system. Exposure of animals to hypobaric hypoxia led to a significant increase in vascular leakage, reactive oxygen species (ROS), nitric oxide (NO), and vascular endothelial growth factor (VEGF) levels. There was a marked increase in Nuclear Factor kappaB (NFkappaB) DNA binding activity and levels of pro-inflammatory cytokines such as Monocyte chemoattractant protein (MCP-1), Interferon-gamma (IFN-gamma), Interleukin-1 (IL-1), and Tumor Necrosis Factor-alpha (TNF-alpha) and cell adhesion molecules such as Vascular Cell Adhesion Molecule-1 (VCAM-1), and P-selectin. Chemical preconditioning by cobalt for 7 days (12.5 mg Co/kg b.w., oral) significantly attenuated cerebral vascular leakage and the expression of inflammatory mediators induced by hypoxia. Administration of NFkappaB inhibitor, curcumin (50 mg/kg b.w.; i.p.) appreciably inhibited hypoxia induced vascular leakage indicating the involvement of NFkappaB in causing vascular leakage. Interestingly, cobalt when administered at 12.5 mg Co/kg b.w. (i.p.), 1 h before hypoxia could not prevent the vascular leakage indicating that cobalt per se did not have an effect on NFkappaB. The lower levels of NFkappaB observed in the brains of cobalt administered animals might be due to higher levels of antioxidant and anti-inflammatory proteins (hemeoxygenase-1 and metallothionein). To conclude cobalt preconditioning inhibited hypobaric hypoxia induced cerebral vascular leakage by lowering NFkappaB DNA binding activity and its regulated pro-inflammatory mediators. This is contemplated to be mediated by cobalt induced reduction in ROS/NO and increase in HO-1 and MT.

  2. Cobalt chloride attenuates hypobaric hypoxia induced vascular leakage in rat brain: Molecular mechanisms of action of cobalt chloride

    SciTech Connect

    Kalpana, S.; Dhananjay, S.; Anju, B. Lilly, G.; Sai Ram, M.

    2008-09-15

    This study reports the efficacy of cobalt preconditioning in preventing hypobaric hypoxia induced vascular leakage (an indicator of cerebral edema) using male Sprague-Dawley rats as model system. Exposure of animals to hypobaric hypoxia led to a significant increase in vascular leakage, reactive oxygen species (ROS), nitric oxide (NO), and vascular endothelial growth factor (VEGF) levels. There was a marked increase in Nuclear Factor {kappa}B (NF{kappa}B) DNA binding activity and levels of pro-inflammatory cytokines such as Monocyte chemoattractant protein (MCP-1), Interferon-{gamma} (IFN-{gamma}), Interleukin-1 (IL-1), and Tumor Necrosis Factor-{alpha} (TNF-{alpha}) and cell adhesion molecules such as Vascular Cell Adhesion Molecule-1 (VCAM-1), and P-selectin. Chemical preconditioning by cobalt for 7 days (12.5 mg Co/kg b.w., oral) significantly attenuated cerebral vascular leakage and the expression of inflammatory mediators induced by hypoxia. Administration of NF{kappa}B inhibitor, curcumin (50 mg/kg b.w.; i.p.) appreciably inhibited hypoxia induced vascular leakage indicating the involvement of NF{kappa}B in causing vascular leakage. Interestingly, cobalt when administered at 12.5 mg Co/kg b.w. (i.p.), 1 h before hypoxia could not prevent the vascular leakage indicating that cobalt per se did not have an effect on NF{kappa}B. The lower levels of NF{kappa}B observed in the brains of cobalt administered animals might be due to higher levels of antioxidant and anti-inflammatory proteins (hemeoxygenase-1 and metallothionein). To conclude cobalt preconditioning inhibited hypobaric hypoxia induced cerebral vascular leakage by lowering NF{kappa}B DNA binding activity and its regulated pro-inflammatory mediators. This is contemplated to be mediated by cobalt induced reduction in ROS/NO and increase in HO-1 and MT.

  3. Electrosynthesis of highly transparent cobalt oxide water oxidation catalyst films from cobalt aminopolycarboxylate complexes.

    PubMed

    Bonke, Shannon A; Wiechen, Mathias; Hocking, Rosalie K; Fang, Xi-Ya; Lupton, David W; MacFarlane, Douglas R; Spiccia, Leone

    2015-04-24

    Efficient catalysis of water oxidation represents one of the major challenges en route to efficient sunlight-driven water splitting. Cobalt oxides (CoOx ) have been widely investigated as water oxidation catalysts, although the incorporation of these materials into photoelectrochemical devices has been hindered by a lack of transparency. Herein, the electrosynthesis of transparent CoOx catalyst films is described by utilizing cobalt(II) aminopolycarboxylate complexes as precursors to the oxide. These complexes allow control over the deposition rate and morphology to enable the production of thin, catalytic CoOx films on a conductive substrate, which can be exploited in integrated photoelectrochemical devices. Notably, under a bias of 1.0 V (vs. Ag/AgCl), the film deposited from [Co(NTA)(OH2 )2 ](-) (NTA=nitrilotriacetate) decreased the transmission by only 10 % at λ=500 nm, but still generated >80 % of the water oxidation current produced by a [Co(OH2 )6 ](2+) -derived oxide film whose transmission was only 40 % at λ=500 nm.

  4. Analysis of cobalt(II) in 2-(5-cyanotetrazolato)pentaammine cobalt(III) perchlorate

    SciTech Connect

    Schumacher, R.J.; Brown, N.E.; Deutsch, E.A.

    1985-10-30

    A new method of analysis is described for cobalt(II) complexes in 2-(5-cyanotetrazolato)pentaammine cobalt(III) perchlorate. The color reagent is 2,2'-dipyridyl-2-pyridyl hydrazone (DPPH), which complexes with the Co(II) and is oxidized to a substitution inert Co(III) (DPPH)/sub 2/ complex. Interferences from other ions is not a problem because the complex is stable at pH 2 - where complexes formed between DPPH and other ions are not stable. The usual air oxidant in this type of analysis has been replaced with ammonium peroxydisulfate improving both the precision and accuracy. The Sandell sensitivity is 0.0015 ..mu..g Co(II)/cm/sup 2/. The system obeys Beer's Law up to 4 ..mu..g in Co(II)mL of solution and has a molar absorptivity of 3.9 x 10/sup 4/ L/mole cm at 514 nm. The procedure was used to determine the degree of decomposition in samples that had undergone partial thermal decomposition. 11 refs., 4 figs., 6 tabs.

  5. Evidence from bond lengths and bond angles for enneacovalence of cobalt, rhodium, iridium, iron, ruthenium, and osmium is compounds with elements of medium electronegativity

    SciTech Connect

    Pauling, L.

    1984-03-01

    Enneacovalence of neutral atoms can be achieved for Co, Rh, and Ir by promoting some electrons from the nd orbital to the (n + 1)s and (n + 1)p orbitals and for Fe, Ru, and Os by a similar promotion together with the addition of an electron, which may be provided by an electron pair from a singly bonded carbonyl group or other group. The bond lengths and bond angles are predicted by the theory of enneacovalence to be significantly different for the different transition metals. Recently reported experimental values are shown to be in good agreement with the predicted values, providing support for the theory of enneacovalence and the theory of hybrid spTdV bond orbitals. 48 references, 4 tables.

  6. Graphene/cobalt nanocarrier for hyperthermia therapy and MRI diagnosis.

    PubMed

    Hatamie, Shadie; Ahadian, Mohammad Mahdi; Ghiass, Mohammad Adel; Iraji Zad, Azam; Saber, Reza; Parseh, Benyamin; Oghabian, Mohammad Ali; Shanehsazzadeh, Saeed

    2016-10-01

    Graphene/cobalt nanocomposites are promising materials for theranostic nanomedicine applications, which are defined as the ability to diagnose, provide targeted therapy and monitor the response to the therapy. In this study, the composites were synthesized via chemical method, using graphene oxide as the source material and assembling cobalt nanoparticles of 15nm over the surface of graphene sheets. Various characterization techniques were then employed to reveal the morphology, size and structure of the nanocomposites, such as X-ray diffraction analysis, X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy, high resolution transmission electron microscopy and ultraviolet visible spectroscopy. Using ion-coupled plasma optical emission spectroscopy, cobalt concentration in the nanocomposites was found to be 80%. In addition, cytotoxicity of graphene/cobalt nanocomposites were evaluated using 3-[4,5-dimethylthiazol-2yl]-2,5-diphenyltetrazolium bromide or MTT assay. MTT viability assay exhibited biocompatibility to L929 mouse fibroblasts cells, under a high dose of 100μg/mL over 24h. Hyperthermia results showed the superior conversion of electromagnetic energy into heat at 350kHz frequency for 0.01 and 0.005g/L of the nanocomposites solution. The measured heat generation and energy transfer results were anticipated by the finite element analysis, conducted for the 3D structure. Magnetic resonance imaging characteristics also showed that negatively charge graphene/cobalt nanocomposites are suitable for T1-weighted imaging.

  7. Physiological Remediation of Cobalt Ferrite Nanoparticles by Ferritin

    PubMed Central

    Volatron, Jeanne; Kolosnjaj-Tabi, Jelena; Javed, Yasir; Vuong, Quoc Lam; Gossuin, Yves; Neveu, Sophie; Luciani, Nathalie; Hémadi, Miryana; Carn, Florent; Alloyeau, Damien; Gazeau, Florence

    2017-01-01

    Metallic nanoparticles have been increasingly suggested as prospective therapeutic nanoplatforms, yet their long-term fate and cellular processing in the body is poorly understood. Here we examined the role of an endogenous iron storage protein – namely the ferritin – in the remediation of biodegradable cobalt ferrite magnetic nanoparticles. Structural and elemental analysis of ferritins close to exogenous nanoparticles within spleens and livers of mice injected in vivo with cobalt ferrite nanoparticles, suggests the intracellular transfer of degradation-derived cobalt and iron, entrapped within endogenous protein cages. In addition, the capacity of ferritin cages to accommodate and store the degradation products of cobalt ferrite nanoparticles was investigated in vitro in the acidic environment mimicking the physiological conditions that are present within the lysosomes. The magnetic, colloidal and structural follow-up of nanoparticles and proteins in the lysosome-like medium confirmed the efficient remediation of nanoparticle-released cobalt and iron ions by ferritins in solution. Metal transfer into ferritins could represent a quintessential process in which biomolecules and homeostasis regulate the local degradation of nanoparticles and recycle their by-products. PMID:28067263

  8. Physiological Remediation of Cobalt Ferrite Nanoparticles by Ferritin

    NASA Astrophysics Data System (ADS)

    Volatron, Jeanne; Kolosnjaj-Tabi, Jelena; Javed, Yasir; Vuong, Quoc Lam; Gossuin, Yves; Neveu, Sophie; Luciani, Nathalie; Hémadi, Miryana; Carn, Florent; Alloyeau, Damien; Gazeau, Florence

    2017-01-01

    Metallic nanoparticles have been increasingly suggested as prospective therapeutic nanoplatforms, yet their long-term fate and cellular processing in the body is poorly understood. Here we examined the role of an endogenous iron storage protein – namely the ferritin – in the remediation of biodegradable cobalt ferrite magnetic nanoparticles. Structural and elemental analysis of ferritins close to exogenous nanoparticles within spleens and livers of mice injected in vivo with cobalt ferrite nanoparticles, suggests the intracellular transfer of degradation-derived cobalt and iron, entrapped within endogenous protein cages. In addition, the capacity of ferritin cages to accommodate and store the degradation products of cobalt ferrite nanoparticles was investigated in vitro in the acidic environment mimicking the physiological conditions that are present within the lysosomes. The magnetic, colloidal and structural follow-up of nanoparticles and proteins in the lysosome-like medium confirmed the efficient remediation of nanoparticle-released cobalt and iron ions by ferritins in solution. Metal transfer into ferritins could represent a quintessential process in which biomolecules and homeostasis regulate the local degradation of nanoparticles and recycle their by-products.

  9. Microstructure and Magnetic Properties of Electrodeposited Cobalt Film

    SciTech Connect

    Bhuiyan, Md S; Taylor, B. J.; Paranthaman, Mariappan Parans; Thompson, James R; Sinclair, J.

    2008-01-01

    Cobalt films were electrodeposited onto both iron and copper substrates from an aqueous solution containing a mixture of cobalt sulfate, boric acid, sodium citrate, and vanadyl sulfate. The structural, intermetallic diffusion and magnetic properties of the electrodeposited films were studied. Cobalt electrodeposition was carried out in a passively divided cell aided by addition of vanadyl sulfate to keep the counter electrode clean. The divided electrolytic cell with very negative current densities cause the electrodeposited Co to adopt a face-centered cubic (fcc) structure, which is more magnetically reversible than the hexagonally close-packed (hcp) structured Co. The coercive field is also significantly less in the fcc-electrodeposited cobalt than in the hcp. SEM images show dense, uniform Co films without any cracks or porosity. Beside the deposition current, thickness of the film was also found to affect the crystal orientation particularly on iron substrates. Diffusion of cobalt film into the iron substrate was studied under reduced environment and a fast process was observed.

  10. Enhancement of trichothecene production in Fusarium graminearum by cobalt chloride.

    PubMed

    Tsuyuki, Rie; Yoshinari, Tomoya; Sakamoto, Naoko; Nagasawa, Hiromichi; Sakuda, Shohei

    2011-03-09

    The effects of cobalt chloride on the production of trichothecene and ergosterol in Fusarium graminearum were examined. Incorporation experiments with (13)C-labeled acetate and leucine confirmed that both 3-acetyldeoxynivalenol and ergosterol were biosynthesized via a mevalonate pathway by the fungus, although hydroxymethyl-glutaryl CoA (HMG-CoA) from intact leucine was able to be partially used for ergosterol production. Addition of cobalt chloride at concentrations of 3-30 μM into liquid culture strongly enhanced 3-acetyldeoxynivalenol production by the fungus, whereas the amount of ergosterol and the mycelial weight of the fungus did not change. The mRNA levels of genes encoding trichothecene biosynthetic proteins (TRI4 and TRI6), ergosterol biosynthetic enzymes (ERG3 and ERG25), and enzymes involved in the mevalonate pathway (HMG-CoA synthase (HMGS) and HMG-CoA reductase (HMGR)) were all strongly up-regulated in the presence of cobalt chloride. Precocene II, a specific trichothecene production inhibitor, suppressed the effects of cobalt chloride on Tri4, Tri6, HMGS, and HMGR, but did not affect erg3 and erg25. These results indicate that cobalt chloride is useful for investigating regulatory mechanisms of trichothecene and ergosterol production in F. graminearum.

  11. Cobalt(II) complexes with hydroxypyridines and halogenides

    NASA Astrophysics Data System (ADS)

    Dojer, Brina; Pevec, Andrej; Jagličić, Zvonko; Kristl, Matjaž

    2017-01-01

    We have synthesized and characterized two new cobalt(II) complexes: difluoridotetrakis(3-hydroxypyridine-κN)cobalt(II), [CoF2(C5H5NO)4] (1) and hexa(2-pyridone-κO)cobalt(II) tetrachloridocobaltate(II), [Co(C5H5NO)6][CoCl4] (2). The complexes were prepared by solvothermal synthesis. A methanol solution of hydroxypyridine was added to water solution of cobalt(II) acetate dihydrate followed by a few drops of concentrated hydrofluoric or hydrochloric acid into the mixture. The crystals of the compounds 1 and 2 are stable on air. The compounds were characterized structurally by single-crystal X-ray diffraction analysis, spectrally by FT-IR spectroscopy and thermally. Thermal analysis showed that the final product of both complexes after heating to 900 °C is elemental cobalt. The interactions between building units in the crystal structures include intra- and intermolecular hydrogen bonds in both compounds and π-π interactions in compound 2.

  12. Synthesis and Magnetic Properties of Cobalt Ferrite with Different Morphologies

    NASA Astrophysics Data System (ADS)

    Nayak, Bibhuti B.; Nayak, Nadiya Bihary; Mallik, Rahul Kumar; Mondal, Aparna

    Different morphologies (spherical, flake and rod) of cobalt ferrite were synthesized using cobalt salt, iron salts, hydrazine hydrate (as a precipitating agent) and CTAB (surfactant) in water as well as ethylene glycol solvents. Four different synthesis ways (HIS, SIH, HISCO and HISG) were adopted to synthesize cobalt ferrite nanopowders using precipitation method. The as-prepared powders obtained after different synthesis ways were calcined at 800°C and structure, microstructure as well as magnetic properties are studied. X-ray diffraction (XRD), scanning electron microscope (SEM) and magnetization studies using pulsed field loop tracer were employed to characterize these cobalt ferrite powders, prepared using different precipitation ways. All the samples are identified with single phase cobalt ferrite and the crystallite size was found to be around 40 nm. Nearly spherical (multifaceted), rod with flake-like, nearly spherical and rod-like morphologies are obtained while synthesizing using HIS, SIH, HISCO and HISG ways, respectively. Rod with flake-like (SIH sample) and rod-like morphologies (HISG sample) show higher coercivity, than the spherical-like (SIH and HISCO smaples) morphology. The highest coericivty was found to be around 925 Oe for HISG sample and highest magnetization is 67 emu/g for HISCO sample.

  13. Physiological Remediation of Cobalt Ferrite Nanoparticles by Ferritin.

    PubMed

    Volatron, Jeanne; Kolosnjaj-Tabi, Jelena; Javed, Yasir; Vuong, Quoc Lam; Gossuin, Yves; Neveu, Sophie; Luciani, Nathalie; Hémadi, Miryana; Carn, Florent; Alloyeau, Damien; Gazeau, Florence

    2017-01-09

    Metallic nanoparticles have been increasingly suggested as prospective therapeutic nanoplatforms, yet their long-term fate and cellular processing in the body is poorly understood. Here we examined the role of an endogenous iron storage protein - namely the ferritin - in the remediation of biodegradable cobalt ferrite magnetic nanoparticles. Structural and elemental analysis of ferritins close to exogenous nanoparticles within spleens and livers of mice injected in vivo with cobalt ferrite nanoparticles, suggests the intracellular transfer of degradation-derived cobalt and iron, entrapped within endogenous protein cages. In addition, the capacity of ferritin cages to accommodate and store the degradation products of cobalt ferrite nanoparticles was investigated in vitro in the acidic environment mimicking the physiological conditions that are present within the lysosomes. The magnetic, colloidal and structural follow-up of nanoparticles and proteins in the lysosome-like medium confirmed the efficient remediation of nanoparticle-released cobalt and iron ions by ferritins in solution. Metal transfer into ferritins could represent a quintessential process in which biomolecules and homeostasis regulate the local degradation of nanoparticles and recycle their by-products.

  14. Preparation of Magnesium, Cobalt and Nickel Ferrite Nanoparticles from Metal Oxides using Deep Eutectic Solvents.

    PubMed

    Söldner, Anika; Zach, Julia; Iwanow, Melanie; Gärtner, Tobias; Schlosser, Marc; Pfitzner, Arno; König, Burkhard

    2016-09-05

    Natural deep eutectic solvents (DESs) dissolve simple metal oxides and are used as a reaction medium to synthesize spinel-type ferrite nanoparticles MFe2 O4 (M=Mg, Zn, Co, Ni). The best results for phase-pure spinel ferrites are obtained with the DES consisting of choline chloride (ChCl) and maleic acid. By employing DESs, the reactions proceed at much lower temperatures than usual for the respective solid-phase reactions of the metal oxides and at the same temperatures as synthesis with comparable calcination processes using metal salts. The method therefore reduces the overall required energy for the nanoparticle synthesis. Thermogravimetric analysis shows that the thermolysis process of the eutectic melts in air occurs in one major step. The phase-pure spinel-type ferrite particles are thoroughly characterized by X-ray diffraction, diffuse-reflectance UV/Vis spectroscopy, and scanning electron microscopy. The properties of the obtained nanoparticles are shown to be comparable to those obtained by other methods, illustrating the potential of natural DESs for processing metal oxides.

  15. Cobalt chloride induces apoptosis and zinc chloride suppresses cobalt-induced apoptosis by Bcl-2 expression in human submandibular gland HSG cells.

    PubMed

    Akita, Kazumi; Okamura, Hirohiko; Yoshida, Kaya; Morimoto, Hiroyuki; Ogawa-Iyehara, Hiroaki; Haneji, Tatsuji

    2007-10-01

    To determine the effects of cobalt chloride on human submandibular gland cells, HSG cells were exposed to various concentrations of cobalt chloride. Cobalt chloride induced cytotoxicity and cell death in HSG cells as determined by phase-contrast microscopy and WST-1 cell viability assay. By using the Hoechst 33342 staining, marked nuclear condensation and fragmentation of chromatin were observed in cobalt chloride-treated cells. Cobalt chloride induced DNA ladder formation in HSG cells in both dose- and time-dependent manner with maximal effect at a concentration of 0.5 mM and 48 h, respectively. Cobalt chloride inhibited the expression of both Bcl-2 protein and mRNA in dose- and time-dependent manner. Zinc chloride recovered the cobalt-suppressed Bcl-2 expression and protected against cobalt-induced apoptosis in HSG cells. Our results show that the pathway of the apoptosis in HSG cells is regulated by cobalt chloride and zinc chloride. Our results also indicate that cobalt-induced apoptotic steps in HSG cells are related to the production of Bcl-2 protein.

  16. 40 CFR 471.30 - Applicability; description of the nickel-cobalt forming subcategory.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... nickel-cobalt forming subcategory. 471.30 Section 471.30 Protection of Environment ENVIRONMENTAL... METAL POWDERS POINT SOURCE CATEGORY Nickel-Cobalt Forming Subcategory § 471.30 Applicability; description of the nickel-cobalt forming subcategory. This subpart applies to discharges of pollutants...

  17. 40 CFR 721.10529 - Cobalt iron manganese oxide, carboxylic acid-modified (generic).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Cobalt iron manganese oxide... Significant New Uses for Specific Chemical Substances § 721.10529 Cobalt iron manganese oxide, carboxylic acid... substance identified generically as cobalt iron manganese oxide, carboxylic acid-modified (PMN P-12-35)...

  18. The effect of cobalt content in U-700 type alloys on degradation of aluminide coatings

    NASA Technical Reports Server (NTRS)

    Zaplatynsky, I.

    1985-01-01

    The influence of cobalt content in U-700 type alloys on the behavior of aluminide coatings is studied in burner rig cyclic oxidation tests at 1100C. It is determined that aluminide coatings on alloys with higher cobalt offer better oxidation protection than the same coatings on alloys containing less cobalt.

  19. 40 CFR 421.230 - Applicability: Description of the primary nickel and cobalt subcategory.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... primary nickel and cobalt subcategory. 421.230 Section 421.230 Protection of Environment ENVIRONMENTAL... CATEGORY Primary Nickel and Cobalt Subcategory § 421.230 Applicability: Description of the primary nickel and cobalt subcategory. The provisions of this subpart are applicable to discharges resulting from...

  20. 40 CFR 721.10529 - Cobalt iron manganese oxide, carboxylic acid-modified (generic).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Cobalt iron manganese oxide... Significant New Uses for Specific Chemical Substances § 721.10529 Cobalt iron manganese oxide, carboxylic acid... substance identified generically as cobalt iron manganese oxide, carboxylic acid-modified (PMN P-12-35)...