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Sample records for iron rhodium ruthenium

  1. Separation of carrier-free rhodium isotopes from ruthenium cyclotron targets by the extraction of nitrosylruthenium from hydrochloric acid solution

    International Nuclear Information System (INIS)

    Haasbroek, F.J.; Strelow, F.W.E.; Van der Walt, T.N.

    1981-01-01

    A method is presented for the separation of rhodium isotopes from ruthenium cyclotron targets. After bombardment with deuterons and dissolution of the target material, the ruthenium is converted into a nitrosyl complex by treatment with hydroxylammonium chloride. Aluminium and other elements which have been introduced in the dissolution step, are separated by cation exchange. Ruthenium is then separated by extraction with a mixture of tri-n-butyl phosphate and hexane (4:1), leaving the rhodium in the aqueous phase. No ruthenium is found in the rhodium fraction and the recovery of rhodium is better than 90 per cent [af

  2. Extraction of ruthenium thiocyanate and its separation from rhodium by polyurethane foam

    International Nuclear Information System (INIS)

    Al-Bazi, S.J.; Chow, A.

    1984-01-01

    Conditions for the formation and extraction of the thiocyanate complex of ruthenium are reported. Distribution coefficients of more than 10 4 and a capacity of about 0.24 mole per kg of foam were obtained. The effect of the chloride salts of various univalent cations on the extraction of Ru(SCN) 6 3- indicated that the efficiency of ruthenium extraction depends on how well the cation fits into the polyether segment of the polyurethane foam, which agrees with the 'cation-chelation' mechanism. The separation of ruthenium and rhodium indicated that more than 95% of the rhodium remained in the aqueous phase and about 95% of the ruthenium was retained by the polyurethane foam and could be easily recovered. (author)

  3. Identification of short-lived neutron-rich ruthenium and rhodium isotopes in fission

    International Nuclear Information System (INIS)

    Franz, G.; Herrmann, G.

    1975-01-01

    Short-lived ruthenium and rhodium isotopes ( 107 Ru, 108 Ru, 108 Rh, 109 Ru, 109 Rh, 110 Ru, 110 Rh, 111 Ru, 111 Rh, 112 Ru, 112 Rh, 113 Ru) have been separated from fission products by a rapid chemical procedure and identified by means of γ-ray spectroscopy. Nuclides with half-lives down to 3 sec were accessible. Ruthenium isotopes up to mass number 113 have been identified. (author)

  4. Spectrophotometric determination of ruthenium(III) and rhodium(III) after extraction of their cyclohexylthioglycolate complexes into chloroform

    International Nuclear Information System (INIS)

    Rao, A.L.J.; Gupta, Usha; Puri, B.K.

    1986-01-01

    Cyclohexylthioglycolate has been used as a reagent for the spectrophotometric determination of ruthenium(III) and rhodium(III) after the extraction of their complexes into chloroform. Various parameters involved in the extraction have been studied and the composition of the extracted complex has been established in each instance. Ruthenium and rhodium complexes are extracted into chloroform in the pH ranges 5.0-9.0 and 9.0-12.5, respectively. The ruthenium complex absorbs strongly at 365 nm, whereas the rhodium complex shows a maximum absorption at 345 nm. Beer's law is obeyed over the concentration range 6-96 μg for ruthenium and 2-41 μg for rhodium in 10 ml of the chloroform solution. The molar absorptivities are 5.02 x 10 3 l mol -1 cm -1 for ruthenium and 1.60 x 10 4 l mol -1 cm -1 for rhodium. Ten replicate determinations on a sample solution containing 60.3 μg of ruthenium or 20.6 μg of rhodium gave mean absorbances of 0.300 and 0.320 with standard deviations of 0.0021 and 0.0025 and relative standard deviations of 0.70% and 0.78%, respectively. The interference of various ions has been studied and the method has been applied to the determination of the metals in various synthetic samples. Conditions have also been developed for the simultaneous determination of ruthenium and rhodium. (author)

  5. Spectrophotometric determination of ruthenium (III) and rhodium (III) with 9,10-phenanthrenequinone monoxime after extraction into molten naphthalene

    International Nuclear Information System (INIS)

    Wasey, A.; Bansal, R.K.; Puri, B.K.; Satake, Masatada.

    1983-01-01

    9,10-Phenanthrenequinone monoxime has been used as a reagent for the spectrophotometric determination of ruthenium(III) and rhodium(III) after extraction into molten naphthalene. The extracted mixture of the metal complex and naphthalene was dissolved in chloroform and ruthenium and rhodium were determined spectrophotometrically. Beer's law holds in the concentration range of 0.2-4.1 μg/cm 3 for ruthenium and 0.3-5.3 μg/cm 3 for rhodium in 10 cm 3 of the final solution. The molar absorptivities and Sandell sensitivities are calculated to be 9.70 x 10 3 l mol -1 cm -1 and 0.01 μg/cmsup(2 ) (660 nm) for ruthenium and 1.13 x 10 4 l mol -1 cm -1 and 0.009 μg/cm 2 (410 nm) for rhodium respectively. Aliquots containing 2.0 μg of ruthenium and 4.1 μg of rhodium give mean absorbances of 0.192 and 0.451 with standard deviations of 0.0017 and 0.0039, respectively. Interference of various ions has been studied and the method has been applied to the determination of ruthenium and rhodium in various synthetic mixtures. This procedure is also applied to the simultaneous determination of ruthenium and rhodium present together in a solution. (author)

  6. Activity of iridium-ruthenium and iridium-rhodium adsorption catalysts in decomposition of hydrogen peroxide

    Energy Technology Data Exchange (ETDEWEB)

    Zubovich, I A; Mikhaylov, V A; Migulina, N N [Yaroslavskij Politekhnicheskij Inst. (USSR)

    1976-06-01

    Experimental data for the activities of iridium-ruthenium and iridium-rhodium adsorption catalysts in the decomposition of hydrogen peroxide are considered and the results of magnetic susceptibility measurements are presented. It is concluded that surface structures (complexes) may be formed and that micro-electronic feaures play a role in heterogeneous catalysis.

  7. Selective catalytic reduction system and process for treating NOx emissions using a palladium and rhodium or ruthenium catalyst

    Science.gov (United States)

    Sobolevskiy, Anatoly [Orlando, FL; Rossin, Joseph A [Columbus, OH; Knapke, Michael J [Columbus, OH

    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.

  8. Ammonia synthesis in the presence of rhodium-ruthenium-iridium carbonyl clusters

    International Nuclear Information System (INIS)

    Fedoseev, I.V.; Solov'ev, N.V.

    2007-01-01

    Researches in the field of platinum metal coordination compounds, where nitrogen enters as a ligand in coordination sphere of metal, are discussed. Results of experiments on the ammonia synthesis during the CO+N 2 mixture passing through alkali solution containing mixture of carbonyl clusters of rhodium, ruthenium and iridium at atmospheric pressure are given. Technique of the experiment and steps of assumed reactions of nitrogen fixation by Rh, Ir and Ru carbonyl clusters are demonstrated [ru

  9. Ruthenium, osmium and rhodium complexes of polypyridyl ligands ...

    Indian Academy of Sciences (India)

    Unknown

    Discipline of Silicates and Catalysis, Central Salt and Marine Chemicals ... However, synthetic methods have also been developed to prepare complexes with ... 3.2 Synthesis and characterisation of ruthenium(II) and osmium(II) complexes18, ...

  10. Thermodynamic assessment of the rhodium-ruthenium-oxygen (Rh-Ru-O) system

    Science.gov (United States)

    Gossé, S.; Bordier, S.; Guéneau, C.; Brackx, E.; Domenger, R.; Rogez, J.

    2018-03-01

    Ruthenium (Ru) and rhodium (Rh) are abundant platinum-group metals formed during burn-up of nuclear fuels. Under normal operating conditions, Rh and Ru accumulate and predominantly form metallic precipitates with other fission products like Mo, Pd and Tc. In the framework of vitrification of high-level nuclear waste, these fission products are poorly soluble in molten glasses. They precipitate as metallic particles and oxide phases. Moreover, these Ru and Rh rich phases strongly depend on temperature and the oxygen fugacity of the glass melt. In case of severe accidental conditions with air ingress, oxidation of the Ru and Rh is possible. At low temperatures (T 1422 K for rhodium sesquioxide and T > 1815 K for ruthenium dioxide), they may decompose into (Rh)-FCC or (Ru)-HCP metallic phases and radiotoxic volatile gaseous species. A thermodynamic assessment of the Rh-Ru-O system will enable the prediction of: (1) the metallic and oxide phases that form during the vitrification of high-level nuclear wastes and (2) the release of volatile gaseous species during a severe accident. The Calphad method developed herein employs a thermodynamic approach in the investigation of the thermochemistry of rhodium and ruthenium at high temperatures. Current literature on the thermodynamic properties and phase diagram data enables preliminary thermodynamic assessments of the Rh-O and Ru-O systems. Additionally, select compositions in the ternary Rh-Ru-O system underwent experimental tests to complement data found in literature and to establish the phase equilibria in the ternary system.

  11. Electrochemical behavior of ruthenium (III), rhodium (III) and palladium (II) in 1-butyl-3-methylimidazolium chloride ionic liquid

    Energy Technology Data Exchange (ETDEWEB)

    Jayakumar, M.; Venkatesan, K.A. [Fuel Chemistry Division, Indira Gandhi Centre for Atomic Research, Kalpakkam 603102 (India); Srinivasan, T.G. [Fuel Chemistry Division, Indira Gandhi Centre for Atomic Research, Kalpakkam 603102 (India)], E-mail: tgs@igcar.gov.in; Vasudeva Rao, P.R. [Fuel Chemistry Division, Indira Gandhi Centre for Atomic Research, Kalpakkam 603102 (India)

    2009-11-01

    Electrochemical behavior of ruthenium (III), rhodium (III) and palladium (II) in 1-butyl-3-methylimidazolium chloride (bmimCl) and their ternary and binary solutions in bmimCl was studied at various working electrodes at 373 K by cyclic voltammetry and chronoamperometry. Ruthenium (III) chloride forms a stable solution with bmimCl and the cyclic voltammogram of ruthenium (III) in bmimCl recorded at glassy carbon electrode consisted of several redox waves due to the complex nature of ruthenium to exist in several oxidation states. Electrolysis of ruthenium (III) chloride in bmimCl at the cathodic limit of bmimCl (-1.8 V (vs. Pd)) did not result in ruthenium metal deposition. However, it was deposited from bmimPF{sub 6} and bmimNTf{sub 2} room temperature ionic liquids at -0.8 V (vs. Pd). The electrochemical behavior of ruthenium (III) in bmimCl in the presence of palladium (II) and rhodium (III) was studied by cyclic voltammetry. The presence of palladium (II) in bmimCl favors underpotential deposition of ruthenium metal. The nuclear loop at -0.5 V (vs. Pd) was observed in all solutions when palladium (II) co-existed with other two metal ions. Nucleation and growth of the metal on glassy carbon working electrode was investigated by chronoamperometry. The growth and decay of chronocurrents has been found to follow the instantaneous nucleation model with three-dimensional growth of nuclei.

  12. Mono and dinuclear iridium, rhodium and ruthenium complexes containing chelating carboxylato pyrazine ligands: Synthesis, molecular structure and electrochemistry

    Czech Academy of Sciences Publication Activity Database

    Govindaswamy, P.; Therrien, B.; Süss-Fink, G.; Štěpnička, P.; Ludvík, Jiří

    2007-01-01

    Roč. 692, č. 8 (2007), s. 1661-1671 ISSN 0022-328X R&D Projects: GA MŠk LC510; GA MŠk(CZ) LC06070 Institutional research plan: CEZ:AV0Z40400503 Keywords : dinuclear complexes * iridium * rhodium * ruthenium * electrochemistry Subject RIV: CG - Electrochemistry Impact factor: 2.168, year: 2007

  13. Hydroformylation and kinetics of 1-hexene over ruthenium, cobalt and rhodium zerolite catalysts

    International Nuclear Information System (INIS)

    Wang, C.; Wei, W.

    1989-01-01

    In this paper, six kinds of catalysts were prepared by cation exchange with rhodium, ruthenium and cobalt chloropentaamino dichoride and zeolites. Effects such as support materials, PPH 3 to metal ratio, reaction temperature, total pressure, H 2 /CO ratio, reaction time and solvents have been investigated in an autoclave. The most favorable results of 1-hexene hydroformylation were obtained in the temperature range 100-150 degrees C at a pressure of 5.0MPa (H 2 /CO=1:1) and the addition of free PPh 3 . The bimetallic catalysts showed high catalytic activing for hydroformylation because of the synergistic effect of bimetallic systems. This paper reports the results of experiments and catalysts characterization by means of IR and XRD spectroscopy

  14. The liquid-liquid extraction of chloro-(trichlorostannato)-rhodium(I/III) and -ruthenium (II) complexes from dilute hydrochloric acid into 4-methylpentan-2-one

    International Nuclear Information System (INIS)

    Wyrley-Birch, J.M.

    1984-10-01

    The effect of stannous chloride on the liquid-liquid extraction of rhodium and ruthenium from hydrochloric acid solutions into 4-methyl-pentan-2-one (MIBK)/hexane mixtures was studied in detail. Stannous chloride concentrations were found to considerably increase the efficiency of the extraction of rhodium and ruthenium into the organic phase. Chloro-(trichlorostannato)-rhodium (I/III) complexes were formed at room temperature. The rate of chloro-(trichlorostannato)-ruthenium (II) complex formation was extremely slow at room temperature, but increased on heating of the aqueous solutions. The amount of rhodium and ruthenium extracted into the organic phase depend on the Sn(II):M molar ratio, the HCl, H sup(+) and Cl sup(-) concentrations, as well as the equilibration time. A 119 Sn NMR study of the MIBK extracts, showed that the stoichiometry of the chloro-(trichlorostannato)-rhodium (I/III) complexes extracted into the organic phase was dependent on the Sn(II):Rh(III) molar ratio as well as the HCl, H sup(+) and Cl sup(-) concentrations in the aqueous phase. The predominant species observed in the organic phase from HCl solutions containing Sn(II):Rh(III) ratios >= 5:1, was shown to be an hydrido complex having the form [RhH(SnCl 3 ) 4 Cl] 3 sup(-) or [RhH(SnCl 3 ) 4 ]2 sup(-). An essentially quantitative separation of rhodium and ruthenium was achieved utilising the variation in the rates of rhodium-tin and ruthenium-tin complex formation

  15. The determination, by atomic-absorption spectrophotometry using electrothermal atomization, of platinum, palladium, rhodium, ruthenium, and iridium

    International Nuclear Information System (INIS)

    Haines, J.; Robert, R.V.D.

    1982-01-01

    A method that involves measurement by atomic-absorption spectrophotometry using electrothermal atomization has been developed for the determination of trace quantities of platinum, palladium, rhodium, ruthenium, and iridium in mineralogical samples. The elements are separated and concentrated by fusion, nickel sulphide being used as the collector, and the analyte elements are measured in the resulting acid solution. An organic extraction procedure was found to offer no advantages over the proposed method. Mutual interferences between the five platinum-group metals examined, as well as interferences from gold, silver, and nickel were determined. The accuracy of the measurement was established by the analysis of a platinum-ore reference material. The lower limits of determination of each of the analyte elements in a sample material are as follows: platinum 1,6μg/l, palladium 0,2μg/1, rhodium 0,5μg/l, ruthenium 3μg/l, and iridium 2,5μg/l. The relative standard deviations range from 0,05 for rhodium to 0.08 for iridium. The method, which is described in detail in the Appendix, is applicable to the determination of these elements in ores, tailings, and geological materials in which the total concentration of the noble metals is less than 1g/t

  16. A method for recovering and separating palladium, technetium, rhodium and ruthenium contained in solutions resulting from nuclear fuel recycling

    International Nuclear Information System (INIS)

    Moore, R.H.

    1974-01-01

    The invention relates to a method for recovering and separating technetium and metals of the platinum group, i.e. palladium, rhodium and ruthenium existing as fission products. The method according to the invention is characterized by contacting a residuary acid aqueous solution provided by nuclear fuel recycling with successive carbon beds which have adsorbed different chelating agents specific for the metals to be recovered in order that said metals be selectively chelated and extracted from the solution. This method is suitable for recovering the above metals from solutions provided by reprocessing spent fuels [fr

  17. Electrodeposition of ruthenium, rhodium and palladium from nitric acid and ionic liquid media: Recovery and surface morphology of the deposits

    Energy Technology Data Exchange (ETDEWEB)

    Jayakumar, M.; Venkatesan, K.A.; Sudha, R. [Fuel Chemistry Division, Indira Gandhi Centre for Atomic Research, Kalpakkam, Tamil Nadu 603102 (India); Srinivasan, T.G., E-mail: tgs@igcar.gov.com [Fuel Chemistry Division, Indira Gandhi Centre for Atomic Research, Kalpakkam, Tamil Nadu 603102 (India); Vasudeva Rao, P.R. [Fuel Chemistry Division, Indira Gandhi Centre for Atomic Research, Kalpakkam, Tamil Nadu 603102 (India)

    2011-07-15

    Research highlights: {yields} Platinum group metals are man-made noble metals. {yields} Electrochemical recovery of fission platinoids. {yields} Recovery from nitric acid medium. {yields} Recovery from ionic liquid medium. {yields} Platinoids with exotic surface morphologies. - Abstract: Electrodeposition is a promising technique for the recovery of platinum group metals with unique surface morphologies. The electrodeposition of palladium, ruthenium and rhodium from aqueous nitric acid, and non-aqueous 1-butyl-3-methylimidazolium chloride ionic liquid medium was studied at stainless steel electrode. The surface morphology and elemental composition of the resultant deposit were probed by scanning electron microscopy (SEM) and energy dispersive X-ray (EDS) analysis. Deposits with diverse surface morphologies and metal compositions were obtained by varying the composition of the electrolytic medium and applied potential. The results demonstrate the possibility of tailoring the morphologies of PGMs by controlling the composition and potential needed for electrodeposition.

  18. Partitioning of rhodium and ruthenium between Pd–Rh–Ru and (Ru,Rh)O{sub 2} solid solutions in high-level radioactive waste glass

    Energy Technology Data Exchange (ETDEWEB)

    Sugawara, Toru, E-mail: toru@gipc.akita-u.ac.jp [Center for Engineering Science, Akita University, 1-1, Tegatagakuenmachi, Akita City, Akita 010-8502 (Japan); Ohira, Toshiaki [Center for Engineering Science, Akita University, 1-1, Tegatagakuenmachi, Akita City, Akita 010-8502 (Japan); Komamine, Satoshi; Ochi, Eiji [Research and Development Department, Reprocessing Business Division, Japan Nuclear Fuel Limited, 4-108, Okitsuke, Obuchi, Rokkasho-mura, Aomori 039-3212 (Japan)

    2015-10-15

    The partitioning of rhodium and ruthenium between Pd–Rh–Ru alloy with a face-centered cubic (FCC) structure and (Ru,Rh)O{sub 2} solid solution has been investigated between 1273 and 1573 K at atmospheric oxygen fugacity. The rhodium and ruthenium contents in FCC increase, while the RhO{sub 2} content in (Ru,Rh)O{sub 2} decreases with increasing temperature due to progressive reduction of the system. Based on the experimental results and previously reported thermodynamic data, the thermodynamic mixing properties of FCC phase and (Ru,Rh)O{sub 2} have been calibrated in an internally consistent manner. Phase equilibrium of platinum grope metals in an HLW glass was calculated by using the obtained thermodynamic parameters.

  19. Enantioselective rhodium/ruthenium photoredox catalysis en route to chiral 1,2-aminoalcohols.

    Science.gov (United States)

    Ma, Jiajia; Harms, Klaus; Meggers, Eric

    2016-08-09

    A rhodium-based chiral Lewis acid catalyst combined with [Ru(bpy)3](PF6)2 as a photoredox sensitizer allows for the visible-light-activated redox coupling of α-silylamines with 2-acyl imidazoles to afford, after desilylation, 1,2-amino-alcohols in yields of 69-88% and with high enantioselectivity (54-99% ee). The reaction is proposed to proceed via an electron exchange between the α-silylamine (electron donor) and the rhodium-chelated 2-acyl imidazole (electron acceptor), followed by a stereocontrolled radical-radical reaction. Substrate scope and control experiments reveal that the trimethylsilyl group plays a crucial role in this reductive umpolung of the carbonyl group.

  20. Adsorption of Ruthenium, Rhodium and Palladium from Simulated High-Level Liquid Waste by Highly Functional Xerogel - 13286

    Energy Technology Data Exchange (ETDEWEB)

    Onishi, Takashi [Fukushima Fuels and Materials Department O-arai Research and Development Center Japan Atomic Energy Agency, Narita-cho 4002, O-arai-machi, Ibaraki, 311-1393 (Japan); Koyama, Shin-ichi [Fukushima Fuels and Materials Department O-arai Research and Development Center Japan Atomic Energy Agency, Narita-cho 4002, O-arai-machi, Ibaraki, 311-1393 (Japan); Mimura, Hitoshi [Dept. of Quantum Science and Energy Engineering, Graduate School of Engineering, Tohoku University Aramaki-Aza-Aoba 6-6-01-2,Aoba-ku, Sendai-shi, Miyagi-ken, 980-8579 (Japan)

    2013-07-01

    Fission products are generated by fission reactions in nuclear fuel. Platinum group (Pt-G) elements, such as palladium (Pd), rhodium (Rh) and ruthenium (Ru), are also produced. Generally, Pt-G elements play important roles in chemical and electrical industries. Highly functional xerogels have been developed for recovery of these useful Pt-G elements from high - level radioactive liquid waste (HLLW). An adsorption experiment from simulated HLLW was done by the column method to study the selective adsorption of Pt-G elements, and it was found that not only Pd, Rh and Ru, but also nickel, zirconium and tellurium were adsorbed. All other elements were not adsorbed. Adsorbed Pd was recovered by washing the xerogel-packed column with thiourea solution and thiourea - nitric acid mixed solution in an elution experiment. Thiourea can be a poison for automotive exhaust emission system catalysts, so it is necessary to consider its removal. Thermal decomposition and an acid digestion treatment were conducted to remove sulfur in the recovered Pd fraction. The relative content of sulfur to Pd was decreased from 858 to 0.02 after the treatment. These results will contribute to design of the Pt-G element separation system. (authors)

  1. 16 CFR 23.7 - Misuse of the words “platinum,” “iridium,” “palladium,” “ruthenium,” “rhodium,” and “osmium.”

    Science.gov (United States)

    2010-01-01

    ... 16 Commercial Practices 1 2010-01-01 2010-01-01 false Misuse of the words âplatinum,â âiridium,â... § 23.7 Misuse of the words “platinum,” “iridium,” “palladium,” “ruthenium,” “rhodium,” and “osmium.” (a) It is unfair or deceptive to use the words “platinum,” “iridium,” “palladium,” “ruthenium,” “rhodium...

  2. Ruthenium determination in new composite materials by coulometric titration with generated iron(2)

    International Nuclear Information System (INIS)

    Butakova, N.A.; Oganesyan, L.B.

    1983-01-01

    A coulometric technique is developed for ruthenium (4) titration with generated iron (2) in a mixture of hydrochloric-, sulfuric- and phosphoric acids with potentiometric and biammetric indication of the final titration point. Bi (3), Pd (2), Nb (5), Pt (4) Pb (2), Rh (3) do not interfere with the titration. Together with Ru (4) titrated are Ir (4), V (5), Au (3). The method is applied to analyze commercial samples of ruthenium dioxides, lead- and bismuth ruthenites, ruthenium pentafluorides containing 30-80% of ruthenium. The Ssub(r) values do not exceed 0.002

  3. New data on some short-lived isotopes of ruthenium and rhodium

    International Nuclear Information System (INIS)

    Baumgartner, F.; Plata Bedmar, A.

    1961-01-01

    Ru and Rd isotopes with mass numbers 107 and 108 and 1 09Rh, has been obtained from fission products. 1 07 Ru has also been prepared by the nuclear process 1 10Pd (n,α) 1 07 Ru. Beta and gamma energies of these nuclides have been studied spectropolarimetry and the gamma lines found for 1 07 Ru and 1 08Ru ( and daughter) have been very useful for the precise determination of their half-lives. 1 09Rh has been identified through its daughter 1 09Pd in the mixture of rhodium isotopes from fission products. Irradiation of natural palladium with fast neutrons has lead to an activity that may only be attributed to 1 10rh. Neither its half life nor its decay energy have been possible to determine accurately. (Author) 1 refs

  4. Substrate-induced antiferromagnetism of ultrathin iron overlayers on the iridium and rhodium (001) surfaces

    Czech Academy of Sciences Publication Activity Database

    Máca, František; Kudrnovský, Josef; Drchal, Václav; Turek, Ilja; Bengone, O.; Redinger, J.

    2009-01-01

    Roč. 11, - (2009), s. 38-40 ISSN 1642-6037 R&D Projects: GA ČR GA202/07/0456; GA MŠk OC09028 Institutional research plan: CEZ:AV0Z10100520; CEZ:AV0Z20410507 Keywords : iridium * rhodium * iron * magnetismus in thin layers * density functional calculations Subject RIV: BM - Solid Matter Physics ; Magnetism

  5. Moessbauer study of iron-cobalt-rhodium spinels

    Energy Technology Data Exchange (ETDEWEB)

    Spencer, C D; Smith, P A; Karnes, C M; Shepard, W A [Ithaca Coll., NY (USA). Dept. of Physics

    1980-01-01

    Moessbauer source and absorber studies have been carried out on the spinel system CoFesub(x)Rhsub(2-x)O/sub 4/ for x 0.005, 0.3, 0.5, 1.0, 1.2 and 1.5. For 0.005 =< x =< 1.2, the cation distribution is normal with Co/sup 2 +/ on A sites. At x = 1.5, the distribution is nearly inverse. In the cases x = 0.005 and 0.3, iron on the B sites does not produce a quadrupole doublet indicating that the B sites are cubic which is contrary to the usual case in spinels.

  6. Extraction and atomic absorption spectrophotometric determination of iron and ruthenium by using potassium xanthates

    Energy Technology Data Exchange (ETDEWEB)

    Aihara, M; Kiboku, M [Kinki Univ., Higashi-Osaka, Osaka (Japan)

    1981-06-01

    Potassium xanthates (potassium o-alkyl dithiocarbonate; KRX) react with many metal ions, and so the complex formation with iron (II, III) ion and the extraction of their complexes has been studied to some extent, but those of ruthenium (III) have not been. Iron-xanthate and ruthenium-xanthate complexes can be extracted into methyl isobutyl ketone (MIBK) from weakly acidic solution to weakly alkaline solution. For quantitative extraction of iron (20 ..mu..g/40 ml), KRX concentration should be above 2.0 x 10/sup -2/ mol dm/sup -3/ of KEtX, 1.0 x 10/sup -2/ mol dm/sup -3/ of KPrX, and 5.0 x 10/sup -3/ mol dm/sup -3/ of KBtX and KPeX, and for that of ruthenium (202 ..mu..g/40 ml), it should be above 2.0 x 10/sup -1/ mol dm/sup -3/ of KEtX and KPrX. Formation constant of ruthenium-xanthate complexes is presumed to be small. A 100-fold excess of Ni(II), Co(II), Cu(II), WO/sub 4//sup 2 -/, PO/sub 4//sup 3 -/, CrO/sub 4//sup 2 -/, and Cr/sub 2/O/sub 7//sup 2 -/ interfered with the determination of iron, however, the interferences are eliminated by adding 5 ml of 0.1 mol dm/sup -3/ ascorbic acid solution. For the determination of ruthenium, a 50-fold excess of Ag(I), Hg(II), Pb(II), Zn(II), Mn(II), Cr(III), and Pt(II), or a 100-fold excess of NO/sub 2//sup -/, S/sub 2/O/sub 3//sup 2 -/, CrO/sub 4//sup 2 -/ and Cr/sub 2/O/sub 7//sup 2 -/, respectively, interfered. The coefficient of variation after each ten runs, ranges from 0.9% to 3.2% in the determination of 10 ..mu..g, 20 ..mu..g, and 30 ..mu..g of iron, and from 1.4% to 4.3% in the determination of 100 ..mu..g, 200 ..mu..g, and 300 ..mu..g of ruthenium. The determination limit in aqueous samples is 0.02 ppm for iron and 0.2 ppm for ruthenium, when the volume ratio of aqueous phase to organic phase (MIBK) is 10:1.

  7. 9,10-phenanthrenesemiquinone radical complexes of ruthenium(III), osmium(III) and rhodium(III) and redox series.

    Science.gov (United States)

    Biswas, Manas Kumar; Patra, Sarat Chandra; Maity, Amarendra Nath; Ke, Shyue-Chu; Weyhermüller, Thomas; Ghosh, Prasanta

    2013-05-14

    Reactions of 9,10-phenanthrenequinone (PQ) in toluene with [M(II)(PPh3)3X2] at 298 K afford green complexes, trans-[M(PQ)(PPh3)2X2] (M = Ru, X = Cl, 1; M = Os, X = Br, 2) in moderate yields. Reaction of anhydrous RhCl3 with PQ and PPh3 in boiling ethanol affords the dark brown paramagnetic complex, cis-[Rh(PQ)(PPh3)2Cl2] (3) in good yields. Diffusion of iodine solution in n-hexane to the trans-[Os(PQ) (PPh3)2(CO)(Br)] solution in CH2Cl2 generates the crystals of trans-[Os(PQ)(PPh3)2(CO)(Br)](+)I3(-), (4(+))I3(-)), in lower yields. Single crystal X-ray structure determinations of 1·2toluene, 2·CH2Cl2 and 4(+)I3(-), UV-vis/NIR absorption spectra, EPR spectra of 3, electrochemical activities and DFT calculations on 1, 2, trans-[Ru(PQ)(PMe3)2Cl2] (1Me), trans-[Os(PQ)(PMe3)2Br2] (2Me), cis-[Rh(PQ)(PMe3)2Cl2] (3Me) and their oxidized and reduced analogues including trans-[Os(PQ)(PMe3)2(CO)(Br)](+) (4Me(+)) substantiated that 1-3 are the 9,10-phenanthrenesemiquinone radical (PQ(˙-)) complexes of ruthenium(III), osmium(III) and rhodium(III) and are defined as trans/cis-[M(III)(PQ(˙-))(PPh3)2X2] with a minor contribution of the resonance form trans/cis-[M(II)(PQ)(PPh3)2X2]. Two comparatively longer C-O (1.286(4) Å) and the shorter C-C lengths (1.415(7) Å) of the OO-chelate of 1·2toluene and 2·CH2Cl2 and the isotropic fluid solution EPR signal at g = 1.999 of 3 are consistent with the existence of the reduced PQ(˙-) ligand in 1-3 complexes. Anisotropic EPR spectra of the frozen glasses (g11 = g22 = 2.0046 and g33 = 1.9874) and solids (g11 = g22 = 2.005 and g33 = 1.987) instigate the contribution of the resonance form, cis-[Rh(II)(PQ)(PPh3)2Cl2] in 3. DFT calculations established that the closed shell singlet (CSS) solutions of 1Me and 2Me are unstable due to open shell singlet (OSS) perturbation. However, the broken symmetry (BS) (1,1) Ms = 0 solutions of 1Me and 2Me are respectively 22.6 and 24.2 kJ mole(-1) lower in energy and reproduced the experimental bond

  8. Determination of molybdenum, ruthenium, rhodium, and palladium in radioinactive simulated waste of the nuclear fuel cycle by solid sampling graphite furnace atomic absorption spectrometry (GFAAS)

    International Nuclear Information System (INIS)

    Schmiedel, G.; Mainka, E.; Ache, H.J.

    1989-01-01

    In relation with insoluble particles in the nuclear fuel cycle waste, the solid sampling GFAAS was used to determine molybdenum, ruthenium, rhodium, and palladium in such waste. Two methods for the direct determination of these elements are described. The samples must be handled in glove boxes or moreover in hot cells with a robot. The determination of the elements by the cup-in-tube technique needs a very sensitive balance (microbalance) for weighing in μg-range and the handling of this method is not practical in glove boxes and hot cells. An alternative technique of solid sampling GFAAS, which can be used without great problems in glove boxes and hot cells is the slurry technique. In this case two methods have been used. One method uses graphite powder as a diluter, the other is the direct suspension of the sample in a matrix modifier solution. In the case of slurry technique with predilution of the sample with graphite powder, recoveries between 91 and 102% and RSD between 4 and 8% were obtained, whereas in the case of slurry technique with direct suspension of the waste sample recoveries between 91 and 103% and RSD between 14 and 20% for the above mentioned elements were obtained. (orig.)

  9. Rhodium complexes as therapeutic agents.

    Science.gov (United States)

    Ma, Dik-Lung; Wang, Modi; Mao, Zhifeng; Yang, Chao; Ng, Chan-Tat; Leung, Chung-Hang

    2016-02-21

    The landscape of inorganic medicinal chemistry has been dominated by the investigation of platinum, and to a lesser extent ruthenium, complexes over the past few decades. Recently, complexes based on other metal centers such as rhodium have attracted attention due to their tunable chemical and biological properties as well as distinct mechanisms of action. This perspective highlights recent examples of rhodium complexes that show diverse biological activities against various targets, including enzymes and protein-protein interactions.

  10. A rapid and practical strategy for the determination of platinum, palladium, ruthenium, rhodium, iridium and gold in large amounts of ultrabasic rock by inductively coupled plasma optical emission spectrometry combined with ultrasound extraction

    Science.gov (United States)

    Zhang, Gai; Tian, Min

    2015-04-01

    This proposed method regulated the determination of platinum, palladium, ruthenium, rhodium, iridium and gold in platinum-group ores by nickel sulfide fire assay—inductively coupled plasma optical emission spectrometry (ICP-OES) combined with ultrasound extraction for the first time. The quantitative limits were 0.013-0.023μg/g. The samples were fused to separate the platinum-group elements from matrix. The nickel sulfide button was then dissolved with hydrochloric acid and the insoluble platinum-group sulfide residue was dissolved with aqua regia by ultrasound bath and finally determined by ICP-OES. The proposed method has been applied into the determination of platinum-group element and gold in large amounts of ultrabasic rocks from the Great Dyke of Zimbabwe.

  11. Alkyl Chain Growth on a Transition Metal Center: How Does Iron Compare to Ruthenium and Osmium?

    Directory of Open Access Journals (Sweden)

    Mala A. Sainna

    2015-09-01

    Full Text Available Industrial Fischer-Tropsch processes involve the synthesis of hydrocarbons usually on metal surface catalysts. On the other hand, very few homogeneous catalysts are known to perform a Fischer-Tropsch style of reaction. In recent work, we established the catalytic properties of a diruthenium-platinum carbene complex, [(CpRu2(μ2-H (μ2-NHCH3(μ3-CPtCH3(P(CH332](COn+ with n = 0, 2 and Cp = η5-C5(CH35, and showed it to react efficiently by initial hydrogen atom transfer followed by methyl transfer to form an alkyl chain on the Ru-center. In particular, the catalytic efficiency was shown to increase after the addition of two CO molecules. As such, this system could be viewed as a potential homogeneous Fischer-Tropsch catalyst. Herein, we have engineered the catalytic center of the catalyst and investigated the reactivity of trimetal carbene complexes of the same type using iron, ruthenium and osmium at the central metal scaffold. The work shows that the reactivity should increase from diosmium to diruthenium to diiron; however, a non-linear trend is observed due to multiple factors contributing to the individual barrier heights. We identified all individual components of these reaction steps in detail and established the difference in reactivity of the various complexes.

  12. Alkyl Chain Growth on a Transition Metal Center: How Does Iron Compare to Ruthenium and Osmium?

    Science.gov (United States)

    Sainna, Mala A.; de Visser, Sam P.

    2015-01-01

    Industrial Fischer-Tropsch processes involve the synthesis of hydrocarbons usually on metal surface catalysts. On the other hand, very few homogeneous catalysts are known to perform a Fischer-Tropsch style of reaction. In recent work, we established the catalytic properties of a diruthenium-platinum carbene complex, [(CpRu)2(μ2-H)(μ2-NHCH3)(μ3-C)PtCH3(P(CH3)3)2](CO)n+ with n = 0, 2 and Cp = η5-C5(CH3)5, and showed it to react efficiently by initial hydrogen atom transfer followed by methyl transfer to form an alkyl chain on the Ru-center. In particular, the catalytic efficiency was shown to increase after the addition of two CO molecules. As such, this system could be viewed as a potential homogeneous Fischer-Tropsch catalyst. Herein, we have engineered the catalytic center of the catalyst and investigated the reactivity of trimetal carbene complexes of the same type using iron, ruthenium and osmium at the central metal scaffold. The work shows that the reactivity should increase from diosmium to diruthenium to diiron; however, a non-linear trend is observed due to multiple factors contributing to the individual barrier heights. We identified all individual components of these reaction steps in detail and established the difference in reactivity of the various complexes. PMID:26426009

  13. Exploring cellular uptake of iron oxide nanoparticles associated with rhodium citrate in breast cancer cells.

    Science.gov (United States)

    Chaves, Natalia L; Estrela-Lopis, Irina; Böttner, Julia; Lopes, Cláudio Ap; Guido, Bruna C; de Sousa, Aparecido R; Báo, Sônia N

    2017-01-01

    Nanocarriers have the potential to improve the therapeutic index of currently available drugs by improving their efficacy and achieving therapeutic steady-state levels over an extended period. The association of maghemite-rhodium citrate (MRC) nanoparticles (NPs) has the potential to increase specificity of the cytotoxic action. However, the interaction of these NPs with cells, their uptake mechanism, and subcellular localization need to be elucidated. This work evaluates the uptake mechanism of MRC NPs in metastatic and nonmetastatic breast cancer-cell models, comparing them to a nontumor cell line. MRC NPs uptake in breast cancer cells was more effective than in normal cells, with regard to both the amount of internalized material and the achievement of more strategic intracellular distribution. Moreover, this process occurred through a clathrin-dependent endocytosis pathway with different basal expression levels of this protein in the cell lines tested.

  14. New data on some short-lived isotopes of ruthenium and rhodium; Nuevos datos sobre algunos isotopos de rutenio y rodio de vida corta

    Energy Technology Data Exchange (ETDEWEB)

    Baumgartner, F.; Plata Bedmar, A.

    1961-07-01

    Ru and Rd isotopes with mass numbers 107 and 108 and {sup 1}09Rh, has been obtained from fission products. {sup 1}07 Ru has also been prepared by the nuclear process {sup 1}10Pd (n,{alpha}) {sup 1}07 Ru. Beta and gamma energies of these nuclides have been studied spectropolarimetry and the gamma lines found for {sup 1}07 Ru and {sup 1}08Ru ( and daughter) have been very useful for the precise determination of their half-lives. {sup 1}09Rh has been identified through its daughter {sup 1}09Pd in the mixture of rhodium isotopes from fission products. Irradiation of natural palladium with fast neutrons has lead to an activity that may only be attributed to {sup 1}10rh. Neither its half life nor its decay energy have been possible to determine accurately. (Author) 1 refs.

  15. Effect of rhodium traces on the reducibility of silica-supported iron particles

    KAUST Repository

    Bonnefille, Eric

    2012-06-19

    Fe/SiO 2 and Rh-Fe/SiO 2 catalysts with increasing Fe/Rh ratio have been prepared and characterized by TEM, XRD, oxygen adsorption and Mössbauer spectroscopy. It was confirmed that Fe/SiO 2 catalysts cannot be reduced under hydrogen flow, to more than 50 % whatever the temperature in the 200-500 °C range and shown that the presence of even a small amount of Rh (Fe/Rh ≤2,000) promoted the reduction of iron up to 85-95 %. This promoting effect also took place with a Fe/SiO 2 + Rh/SiO 2 physical mixture (Fe/Rh B2,000). Therefore, the occurrence of a hydrogen spillover effect may be involved in the observed process. © 2012 Springer Science+Business Media, LLC.

  16. Effect of rhodium traces on the reducibility of silica-supported iron particles

    KAUST Repository

    Bonnefille, Eric; Millet, Jean Marc M M; Candy, Jean Pierre; Thivolle-Cazat, Jean; Bellabarba, Roñ an M.; Tooze, Robert P.; Basset, Jean-Marie

    2012-01-01

    Fe/SiO 2 and Rh-Fe/SiO 2 catalysts with increasing Fe/Rh ratio have been prepared and characterized by TEM, XRD, oxygen adsorption and Mössbauer spectroscopy. It was confirmed that Fe/SiO 2 catalysts cannot be reduced under hydrogen flow, to more than 50 % whatever the temperature in the 200-500 °C range and shown that the presence of even a small amount of Rh (Fe/Rh ≤2,000) promoted the reduction of iron up to 85-95 %. This promoting effect also took place with a Fe/SiO 2 + Rh/SiO 2 physical mixture (Fe/Rh B2,000). Therefore, the occurrence of a hydrogen spillover effect may be involved in the observed process. © 2012 Springer Science+Business Media, LLC.

  17. Ruthenium and iron complexes with benzotriazole and benzimidazole derivatives as simple models for proton-coupled electron transfer systems

    Directory of Open Access Journals (Sweden)

    Rocha Reginaldo C.

    2001-01-01

    Full Text Available Iron and ruthenium complexes of the type [M-LH]n (where M = RuII,III(NH35(2+,3+, RuII,III(edta2-,- [edta = ethylenedinitrilotetraacetate], or FeII,III(CN5(3-,2- and LH = benzotriazole or benzimidazole were prepared and characterized in aqueous solutions by means of electrochemical and spectroelectrochemical methods. Special emphasis was given to the pH-dependent redox processes, exhibited by all the investigated complexes. From their related Pourbaix diagrams, which displayed a typically Nernstian behavior, the pKa and formal reduction potential values were extracted. In addition, these E1/2 versus pH curves were also used to illustrate the partitioning relationship concerning the redox and acid-base species, and their interconversion equilibria. The active area in which the dependence of the M III/M II couple on the pH takes place, as delimited by pKaIII and pKaII, was taken into account in order to evaluate the usefulness of such simple complexes as models for proton-coupled electron transfer (PCET. The results were interpreted in terms of the acceptor/donor electronic character of the ligands and sigma,pi-metal-ligand interactions in both redox states of the metal ion.

  18. The effect of diluting ruthenium by iron in RuxSey catalyst for oxygen reduction

    International Nuclear Information System (INIS)

    Delacote, Cyril; Lewera, Adam; Pisarek, Marcin; Kulesza, Pawel J.; Zelenay, Piotr; Alonso-Vante, Nicolas

    2010-01-01

    This study has focused on the synthesis of novel oxygen reduction reaction (ORR) chalcogenide catalysts, with Ru partially replaced by Fe in a cluster-type Ru x Se y . The catalysts were obtained by thermal decomposition of Ru 3 (CO) 12 and Fe(CO) 5 in the presence of Se. As indicated by the XPS data, the composition of catalyst nanoparticles depends on the solvent used (either p-xylene or dichlorobenzene). The presence of iron in synthesized catalysts has been confirmed by both EDAX and XPS. Voltammetric activation of the catalysts results in a partial removal of iron and unreacted selenium from the surface. The ORR performance of electrochemically pre-treated catalysts was evaluated using rotating disk and ring-disk electrodes in a sulfuric acid solution. No major change in the ORR mechanism relative to the Se/Ru catalyst has been observed with Fe-containing catalysts.

  19. Antagonizing STAT3 dimerization with a rhodium(III) complex.

    Science.gov (United States)

    Ma, Dik-Lung; Liu, Li-Juan; Leung, Ka-Ho; Chen, Yen-Ting; Zhong, Hai-Jing; Chan, Daniel Shiu-Hin; Wang, Hui-Min David; Leung, Chung-Hang

    2014-08-25

    Kinetically inert metal complexes have arisen as promising alternatives to existing platinum and ruthenium chemotherapeutics. Reported herein, to our knowledge, is the first example of a substitutionally inert, Group 9 organometallic compound as a direct inhibitor of signal transducer and activator of transcription 3 (STAT3) dimerization. From a series of cyclometalated rhodium(III) and iridium(III) complexes, a rhodium(III) complex emerged as a potent inhibitor of STAT3 that targeted the SH2 domain and inhibited STAT3 phosphorylation and dimerization. Significantly, the complex exhibited potent anti-tumor activities in an in vivo mouse xenograft model of melanoma. This study demonstrates that rhodium complexes may be developed as effective STAT3 inhibitors with potent anti-tumor activity. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Rhodium thioacetate complexes

    International Nuclear Information System (INIS)

    Baranovskij, I.B.; Golubnichaya, M.A.; Mazo, G.Ya.

    1976-01-01

    Thioacetato-complexes of rhodium(II) were prepared by the reaction of thioacetic acid with rhodium(II) carboxylates. Diamagnetic compounds of the type Rh 2 (CH 3 COS) 4 2A, where A=H 2 O, Py, N 2 H 4 .HCl, Thio, KNCS, DMSO, CH 3 CN, CsCl, or CH 3 COSH, were isolated. Their infrared spectra were recorded, and the principal vibrational wavenumbers assigned. The X-ray electron spectra confirm that rhodium is divalent. The thioacetato-complexes are dimeric, with a metal-metal bond. [Rh(NH 3 ) 5 (CH 3 COS)]I 2 was prepared, and its properties studied. The significant decrease in the strength of the bonds formed by the axial ligands with rhodium is due to the strong trans-influence of the covalent rhodium-rhodium sigma-bond

  1. Ruthenium perovskites of type Ba/sub 2/BRuO/sub 6/ and Ba/sub 3/BRu/sub 2/O/sub 9/ with B = indium, rhodium

    Energy Technology Data Exchange (ETDEWEB)

    Schaller, H U; Kemmler-Sack, S [Tuebingen Univ. (Germany, F.R.). Lehrstuhl fuer Anorganische Chemie 2

    1981-02-01

    The black perovskites Ba/sub 2/InRu/sup 5 +/O/sub 6/ and Ba/sub 3/InRu/sub 2/O/sub 9/ (mean oxydation state of ruthenium: +4.5) adopt the hexagonal BaTiO/sub 3/ structure and form a continuous series of mixed crystals. According to the intensity calculations and analysis of the vibrational spectroscopic data an ordered distribution between indium and ruthenium is present: 1:1 order in Ba/sub 2/RuO/sub 6/ (space group P-3m1 respective Dsub(3d)/sup 3/; R' = 5.3%); 1:2 order in Ba/sub 3/InRu/sub 2/O/sub 9/ (space group P6/sub 3//mmc respective Dsub(6h)/sup 4/; R' = 4.6%). The corresponding black Rh compounds, Ba/sub 2/RhRuO/sub 6/ and Ba/sub 3/RhRu/sub 2/O/sub 9/, crystallize in the rhombohedral 9 L type of BaRuO/sub 3/ (author).

  2. Radiochemistry of ruthenium

    Energy Technology Data Exchange (ETDEWEB)

    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.

  3. Radiochemistry of ruthenium

    International Nuclear Information System (INIS)

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

    1984-01-01

    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 4 , precipitation and coprecipitation, solvent extraction, chromatographic techniques, and analysis for radioruthenium. 445 refs., 7 figs., 23 tabs

  4. The effect of diluting ruthenium by iron in Ru{sub x}Se{sub y} catalyst for oxygen reduction

    Energy Technology Data Exchange (ETDEWEB)

    Delacote, Cyril [Laboratory of Electrocatalysis, CNRS, University of Poitiers, F-86022 Poitiers Cedex (France); CEISAM, CNRS, University of Nantes, F-44322 Nantes Cedex 3 (France); Lewera, Adam [University of Warsaw, Department of Chemistry, ul. Pasteura 1, 02-093 Warsaw (Poland); Pisarek, Marcin [Institute of Physical Chemistry, Polish Academy of Sciences, ul. Kasprzaka 44/52, 01-224 Warsaw (Poland); Kulesza, Pawel J. [University of Warsaw, Department of Chemistry, ul. Pasteura 1, 02-093 Warsaw (Poland); Zelenay, Piotr [Materials Physics and Applications, Los Alamos National Laboratory, Los Alamos, NM 87545 (United States); Alonso-Vante, Nicolas, E-mail: nicolas.alonso.vante@univ-poitiers.f [Laboratory of Electrocatalysis, CNRS, University of Poitiers, F-86022 Poitiers Cedex (France)

    2010-11-01

    This study has focused on the synthesis of novel oxygen reduction reaction (ORR) chalcogenide catalysts, with Ru partially replaced by Fe in a cluster-type Ru{sub x}Se{sub y}. The catalysts were obtained by thermal decomposition of Ru{sub 3}(CO){sub 12} and Fe(CO){sub 5} in the presence of Se. As indicated by the XPS data, the composition of catalyst nanoparticles depends on the solvent used (either p-xylene or dichlorobenzene). The presence of iron in synthesized catalysts has been confirmed by both EDAX and XPS. Voltammetric activation of the catalysts results in a partial removal of iron and unreacted selenium from the surface. The ORR performance of electrochemically pre-treated catalysts was evaluated using rotating disk and ring-disk electrodes in a sulfuric acid solution. No major change in the ORR mechanism relative to the Se/Ru catalyst has been observed with Fe-containing catalysts.

  5. A multi-target caffeine derived rhodium(i) N-heterocyclic carbene complex: evaluation of the mechanism of action.

    Science.gov (United States)

    Zhang, Jing-Jing; Muenzner, Julienne K; Abu El Maaty, Mohamed A; Karge, Bianka; Schobert, Rainer; Wölfl, Stefan; Ott, Ingo

    2016-08-16

    A rhodium(i) and a ruthenium(ii) complex with a caffeine derived N-heterocyclic carbene (NHC) ligand were biologically investigated as organometallic conjugates consisting of a metal center and a naturally occurring moiety. While the ruthenium(ii) complex was largely inactive, the rhodium(i) NHC complex displayed selective cytotoxicity and significant anti-metastatic and in vivo anti-vascular activities and acted as both a mammalian and an E. coli thioredoxin reductase inhibitor. In HCT-116 cells it increased the reactive oxygen species level, leading to DNA damage, and it induced cell cycle arrest, decreased the mitochondrial membrane potential, and triggered apoptosis. This rhodium(i) NHC derivative thus represents a multi-target compound with promising anti-cancer potential.

  6. Molecular recognition in protein modification with rhodium metallopeptides

    Science.gov (United States)

    Ball, Zachary T.

    2015-01-01

    Chemical manipulation of natural, unengineered proteins is a daunting challenge which tests the limits of reaction design. By combining transition-metal or other catalysts with molecular recognition ideas, it is possible to achieve site-selective protein reactivity without the need for engineered recognition sequences or reactive sites. Some recent examples in this area have used ruthenium photocatalysis, pyridine organocatalysis, and rhodium(II) metallocarbene catalysis, indicating that the fundamental ideas provide opportunities for using diverse reactivity on complex protein substrates and in complex cell-like environments. PMID:25588960

  7. Colloidal stability, surface characterisation and intracellular accumulation of Rhodium(II) citrate coated superparamagnetic iron oxide nanoparticles in breast tumour: a promising platform for cancer therapy

    Energy Technology Data Exchange (ETDEWEB)

    Silva Nunes, Eloiza da [Universidade Federal de Goias, Campus Samambaia, Instituto de Quimica (Brazil); Lemos Brettas Carneiro, Marcella; Guirelli Simoes de Oliveira, Ricardo; Nair Bao, Sonia [Universidade de Brasilia (UnB), Instituto de Ciencias Biologicas (Brazil); Ribeiro de Souza, Aparecido, E-mail: ardsouza@quimica.ufg.br [Universidade Federal de Goias, Campus Samambaia, Instituto de Quimica (Brazil)

    2013-06-15

    The colloidal stability of a rhodium(II) citrate, Rh{sub 2}(H{sub 2}cit){sub 4}, coating on the surface of maghemite ({gamma}-Fe{sub 2}O{sub 3}) nanoparticles was studied and compared in different dispersion media. The adsorption of Rh{sub 2}(H{sub 2}cit){sub 4} at the water-maghemite interface was evaluated as a function of pH and complex concentration. A slight pH-dependent adsorption of the complex was observed with a maximum at pH 3. The colloidal stability of the functionalised nanoparticles with different amounts of Rh{sub 2}(H{sub 2}cit){sub 4} as a function of pH was evaluated using dynamic light scattering measurements. The particles have a mean magnetic core size of 5.6 nm and the hydrodynamic diameters are approximately 60 nm, which remained unchanged in the pH range in which the samples were a stable sol. The tolerance to different dispersion media, which were deionised water, saline, phosphate-buffered saline (PBS), foetal bovine serum (FBS) and NaCl solutions with different concentrations, was investigated. At moderate ionic strength, the colloidal stability of the dispersions was similar in saline and in PBS compared to the stability of dispersions diluted in water. Moreover, the intracellular accumulation of nanoparticles in 4T1 breast tumour was examined by ultrastructural analysis performed by transmission electron microscopy. The rhodium(II) citrate-coated nanoparticles were found mostly in the cytoplasm and nucleus. Thus, we suggest that these SPIO nanoparticles functionalized with Rh{sub 2}(H{sub 2}Cit){sub 4} can be potential tools for anticancer therapy.

  8. Rhodium Catalyzed Decarbonylation

    DEFF Research Database (Denmark)

    Garcia Suárez, Eduardo José; Kahr, Klara; Riisager, Anders

    2017-01-01

    Rhodium catalyzed decarbonylation has developed significantly over the last 50 years and resulted in a wide range of reported catalyst systems and reaction protocols. Besides experimental data, literature also includes mechanistic studies incorporating Hammett methods, analysis of kinetic isotope...

  9. Rhodium platings – experimental study

    OpenAIRE

    Rudolf, R.; Budić, B.; Stamenković, D.; Čolić, M.; Ivanič, A.; Kosec, B.

    2013-01-01

    Modern rhodium plating solutions are based on either sulphate or phosphate. Although in theory there are four possible combinations, in practice only three different rhodium electrolytes are used. These are based on dilutions of rhodium sulphate or phosphate concentrates with added sulphuric or phosphoric acid. These processes are be discussed in this paper with a demonstration of Rh platings in the Slovenian firm Zlatarna Celje d.d.

  10. Rhodium platings – experimental study

    Directory of Open Access Journals (Sweden)

    R. Rudolf

    2013-07-01

    Full Text Available Modern rhodium plating solutions are based on either sulphate or phosphate. Although in theory there are four possible combinations, in practice only three different rhodium electrolytes are used. These are based on dilutions of rhodium sulphate or phosphate concentrates with added sulphuric or phosphoric acid. These processes are be discussed in this paper with a demonstration of Rh platings in the Slovenian firm Zlatarna Celje d.d.

  11. Antitumor effect and toxicity of free rhodium (II) citrate and rhodium (II) citrate-loaded maghemite nanoparticles in mice bearing breast cancer.

    Science.gov (United States)

    Carneiro, Marcella Lemos Brettas; Peixoto, Raphael C A; Joanitti, Graziela A; Oliveira, Ricardo G S; Telles, Luis A M; Miranda-Vilela, Ana L; Bocca, Anamélia L; Vianna, Leonora M S; da Silva, Izabel C R; de Souza, Aparecido R; Lacava, Zulmira G M; Báo, Sônia N

    2013-02-16

    Magnetic fluids containing superparamagnetic iron oxide nanoparticles represent an attractive platform as nanocarriers in chemotherapy. Recently, we developed a formulation of maghemite nanoparticles coated with rhodium (II) citrate, which resulted in in vitro cytotoxicity enhanced up to 4.6 times when compared to free rhodium (II) citrate formulation on breast carcinoma cells. In this work, we evaluate the antitumor activity and toxicity induced by these formulations in Balb/c mice bearing orthotopic 4T1 breast carcinoma. Mice were evaluated with regard to the treatments' toxicity through analyses of hemogram, serum levels of alanine aminotransferase, iron, and creatinine; DNA fragmentation and cell cycle of bone marrow cells; and liver, kidney and lung histology. In addition, the antitumor activity of rhodium (II) citrate and maghemite nanoparticles coated with rhodium (II) citrate was verified by tumor volume reduction, histology and immunohistochemistry. Regarding the treatments' toxicity, no experimental groups had alterations in levels of serum ALT or creatinine, and this suggestion was corroborated by the histopathologic examination of liver and kidney of mice. Moreover, DNA fragmentation frequency of bone marrow cells was lower than 15% in all experimental groups. On the other hand, the complexes rhodium (II) citrate-functionalized maghemite and free rhodium (II) citrate led to a marked growth inhibition of tumor and decrease in CD31 and Ki-67 staining. In summary, we demonstrated that both rhodium (II) citrate and maghemite nanoparticles coated with rhodium (II) citrate formulations exhibited antitumor effects against 4T1 metastatic breast cancer cell line following intratumoral administration. This antitumor effect was followed by inhibition of both cell proliferation and microvascularization and by tumor tissue injury characterized as necrosis and fibrosis. Remarkably, this is the first published report demonstrating the therapeutic efficacy of maghemite

  12. Half-sandwich ruthenium, rhodium and iridium complexes of ...

    Indian Academy of Sciences (India)

    p-cymene/benzene/Cp* and M = Ru/Rh/Ir) with ligand L in methanol. The reaction in 1:2 ... drazine with dipyridyl ketone using glacial acetic acid, we ended up with the .... dimethyl sulphoxide, soluble in hot water (up to 40. ◦. C) and they are ...

  13. Activity of ruthenium, rhodium, iridium-ruthenium and iridium-rhodium adsorbed catalysts in dehydrogenation of formic acid

    Energy Technology Data Exchange (ETDEWEB)

    Mikhailov, V A; Zubovich, I A [Yaroslavskij Politekhnicheskij Inst. (USSR)

    1977-04-01

    The activity of Ru-, Rh- (Ir+nRu)- and (Ir+nRn) catalysts on sugar carbon and silicon dioxide in decomposition of HCOOH was studied. The catalyst activity increases in the series Ir

  14. Committee's report on ruthenium fall-out incident

    International Nuclear Information System (INIS)

    Borkowski, C.J.; Crawford, J.H.; Livingston, R.; Ritchie, R.H.; Rupp, A.F.; Taylor, E.H.

    1983-07-01

    Investigations of the fall-out incident of November 11 and 12, 1959, by responsible parties (Health Physics Division and Operations Division personnel) established beyond reasonable doubt that the incident had its origin in the expulsion of particles, heavily contaminated with ruthenium, which had been detached from the walls of the electric fan housing and ducts in the off-gas system associated with the brick stack. All available evidence indicates that the particles were loosened during maintenance work on the exhaust damper and the bearings of the electric fan and were carried up the stack in two bursts as particulate fall-out when this fan was put back into service. Radiographic and chemical analysis showed the activity to be almost entirely ruthenium (Ru 106 ) and its daughter rhodium (Rh 106 ) with very little, if any, strontium being present. This report summarizes the findings and sets forth the conclusions and recommendations of the Committee asked to investigate the incident

  15. Polarographic determination of ruthenium

    International Nuclear Information System (INIS)

    Li Jifu; Duan Shirong; Wu Xi

    1989-01-01

    It is suggested to use 0.5 mol/l HClO 4 -0.5 mol/l NaNO 3 -0.1 mol/l NaClO 4 as supporting electrolyte for determining ruthenium. In the supporting electrolyte there is a clear polarographic wave of ruthenium (IV) at -0.8 V vs. SCE. The wave height of ruthenium(IV) is linear in the range from 0.1 to 0.4 μg. ml -1 . The effect of the component of supporting electroylte and the other ion in the samples on the measurement of ruthenium are studied. The analysis methods for measuring ruthenium in both acidic or basic imitative radioactive waste solutions which is used in study of glass solidification are worked out. Imitative samples are analysised

  16. Synthesis of ruthenium phosphides

    International Nuclear Information System (INIS)

    Chernogorenko, V.B.; Lynchak, K.A.; Kulik, L.Ya.; Shkaravskij, Yu.F.; Klochkov, L.A.

    1977-01-01

    A method of ampoule synthesis of ruthenium phosphides, Ru 2 P, RuP, and RuP 2 , with stepwise heating of stoichimetric charges in a single-zone furnace is developed. A method for synthesizing ruthenium diphosphide by phosphidization of a ruthenium powder with phosphine at 1150 deg C is worked out. The optimum conditions of its manufacture are found by planning an extremal experiment. Interaction of PH 3 with ruthenium proceeds by the diffusion mechanism and obeys the parabolic law. An extraction-photometric method for determining phosphorus in phosphides is elaborated. Ruthenium phosphides are extremely corrosion-resistant in acids and alkalis. Ru 2 P and RuP exhibit metallic conductivity

  17. Rhodium-103m generator

    International Nuclear Information System (INIS)

    Mamadaliev, N.; Levin, V.I.; Malinin, A.B.

    1978-01-01

    103 Pd separated from metal rhodium irradiated with deuterons has been used without a carrier for sup( 03m)Rh generator The generator of sup(103m)Rh is a column 6mm in diameter filled with an anionite in Cl - form (Dowex-2,8,200-400 mesh) with an adsorbed parent isotope of 103 Pd. As a result of its decay, a 103 Rh daughter isotope is accumulated, which can be washed out from the generator from time to time with a corresponding solution. To prepare the generator, 0.5g of the resin with an adsorbed 103 Pd is charged into the column containing 1g of the same resin. Washing out with 2N HCl yields more than 90% of sup(103m)Rh with a radionuclide purity of more than 99.99%

  18. Ruthenium removing device

    International Nuclear Information System (INIS)

    Kitamura, Masafumi; Shirado, Katsuyuki.

    1990-01-01

    A processing gas supply system and a NO x supply system for supplying NO x to be mixed with processed gases are connected to the gas plenum in the lower portion of reaction vessel. Further, a cleaning station is disposed above the gas plenum for introducing a mixed gas stream from the gas plenum into a liquid detergent thereby trapping NO x and ruthenium reduction products into the liquid detergent. Volatile ruthenium contained in the processed gases is reduced into ruthenium reduction products and formed as mists. They are trapped in the cleaning liquid and the remaining gases are discharged out of the liquid detergent to the outside of the reaction vessel. Accordingly, solid radioactive wastes are not formed and the decontaminating efficiency for volatile ruthenium can be improved. (T.M.)

  19. Rhodium segregation in dilute silver-rhodium alloys

    International Nuclear Information System (INIS)

    Krolas, K.; Sternik, M.

    1995-01-01

    Segregation of Rh in Ag-based alloys has been studied using the perturbed angular correlation of γ-rays emitted in the nuclear decay of radioactive 111 In. The formation of impurity complexes, consisting of an 111 In probe atom and one or more Rh atoms, was observed as a function of annealing time and temperature. Rhodium atom aggregation starts at about 600 K. From the fraction of 111 In bound to isolated Rh atoms the solute rhodium atom concentration was determined. It increases with the nominal alloy concentration up to about 0.04 at.% and then it is essentially constant for the nominal Rh concentration varying between 0.1 and 0.5 at.%. The solute rhodium atom concentration is 3 times larger at the melting point than at 750 K

  20. Measurement of the hyperfine magnetic field on rhodium in chromium

    International Nuclear Information System (INIS)

    Peretto, P.; Teisseron, G.; Berthier, J.

    1978-01-01

    Hyperfine magnetic field of rhodium in a chromium matrix is studied. Anisotropy of rhodium 100 is + 0.17. Time dependence of angular correlation is given with a sample containing 145 ppm of rhodium despite the short life [fr

  1. Analysis of radioactive ruthenium

    International Nuclear Information System (INIS)

    1977-01-01

    This manual explains the procedures of analysis of radioactive ruthenium in the drain water from atomic energy plants. The most important radioactive ruthenium is 106 Ru, and the method of measurement described in this manual is to measure the beta ray of the daughter nuclide 106 Rh. The samples to be measured are collected from seawater, marine living things, and sediment of sea bottom near atomic energy plants. In case of sea water, the ruthenium is separated by the co-precipitation with magnesium hydroxide and distillation or the extraction with carbon tetrachloride, reduction and precipitation. The beta ray of the obtained sample is measured by a gas-flow type low background β counting system. Alkali dissolution-distillation or nitric acid extraction-distillation, reduction and precipitation are applied for marine living things. The sediment of sea bottom is treated with nitric acid or strong phosphoric acid, and distilled then the ruthenium is reduced and precipitated, and the beta-counting of the precipitation is made. The method to fix radioactive ruthenium on polyethylene films after the co-precipitation is also described for reference. The detectable levels by the present methods are 0.05 pCi/l for sea water, 0.1 pCi/g for marine living things, and 20 pCi/kg for the sediment of sea bottom. (Kato, T.)

  2. Iron

    Science.gov (United States)

    Iron is a mineral that our bodies need for many functions. For example, iron is part of hemoglobin, a protein which carries ... It helps our muscles store and use oxygen. Iron is also part of many other proteins and ...

  3. Synthesis and characterization of the Rhodium (II) citrate complex

    International Nuclear Information System (INIS)

    Najjar, R.; Santos, F.S. dos; Seidel, W.

    1987-01-01

    The preparation and characterization of the rhodium (II) citrate is described. Rhodium citrate was prepared by reacting citric acid trihydrated (3,4 g, 16 mmols) with anhydrous rhodium acetate (0,44 g, 1 mmol). Th electronic instruments, thermogravimetric curve and spectrum of rhodium (II) citrate are analysed. (M.J.C.) [pt

  4. Recent advances in the ruthenium-catalyzed hydroarylation of alkynes with aromatics: synthesis of trisubstituted alkenes.

    Science.gov (United States)

    Manikandan, Rajendran; Jeganmohan, Masilamani

    2015-11-14

    The hydroarylation of alkynes with substituted aromatics in the presence of a metal catalyst via chelation-assisted C-H bond activation is a powerful method to synthesize trisubstituted alkenes. Chelation-assisted C-H bond activation can be done by two ways: (a) an oxidative addition pathway and (b) a deprotonation pathway. Generally, a mixture of cis and trans stereoisomeric as well as regioisomeric trisubstituted alkenes was observed in an oxidative addition pathway. In the deprotonation pathway, the hydroarylation reaction can be done in a highly regio- and stereoselective manner, and enables preparation of the expected trisubstituted alkenes in a highly selective manner. Generally, ruthenium, rhodium and cobalt complexes are used as catalysts in the reaction. In this review, a ruthenium-catalyzed hydroarylation of alkynes with substituted aromatics is covered completely. The hydroarylation reaction of alkynes with amide, azole, carbamate, phosphine oxide, amine, acetyl, sulfoxide and sulphur directed aromatics is discussed.

  5. Titrimetric determination of ruthenium

    International Nuclear Information System (INIS)

    Velichko, V.V.; Belyaeva, T.I.; Kudinova, V.K.; Usatenko, Yu.I.

    1978-01-01

    Titration of ruthenium(4) hydrochloric-acid solutions with Mohr's salt, hydroquinone, and thiourea has been studied with the use of biampero- and potentiometric indication of the titration end point (t.e.p.) Potentiometric and amperometric indication of the t.e.p. is applicable when Ru(4) concentration is from 20 to 6000 mkg in 20 ml of the titrated solution; biamperometric indication can be used at a concentration of 5-1000 mkg in the same volume. It has been established that titration of Ru(4) (in the form of the Na 2 RuCl 6 solution) with Mohr's salt is not hindered by the presence of 1000-fold excess of alkaline and alkali-earth metals, Al, Ti(4), Mn(2), Cr(3), Fe(3), Co, Ni, Cu, Zn, Ga, Ge(4), As, Se, Mo(6), Cd, In, and Te; 100-fold excess of Rh, Pd, W, Bi, and Sn; 10-fold excess of Ag, Au, Pt, Hg, Os. Along with Ru(4) titrated are Ir(4), Te(3), V(5), and Ce(4). Selectivity of hydroquinone and thiourea is lower. Titrimetric procedure of determining ruthenium has been tested for ruthenium alloy containing cobalt tungsten. It cannot be recommended for analysis of the samples which dissolve in aqua regia

  6. Free Rhodium (II) citrate and rhodium (II) citrate magnetic carriers as potential strategies for breast cancer therapy

    Science.gov (United States)

    2011-01-01

    Background Rhodium (II) citrate (Rh2(H2cit)4) has significant antitumor, cytotoxic, and cytostatic activity on Ehrlich ascite tumor. Although toxic to normal cells, its lower toxicity when compared to carboxylate analogues of rhodium (II) indicates Rh2(H2cit)4 as a promising agent for chemotherapy. Nevertheless, few studies have been performed to explore this potential. Superparamagnetic particles of iron oxide (SPIOs) represent an attractive platform as carriers in drug delivery systems (DDS) because they can present greater specificity to tumor cells than normal cells. Thus, the association between Rh2(H2cit)4 and SPIOs can represent a strategy to enhance the former's therapeutic action. In this work, we report the cytotoxicity of free rhodium (II) citrate (Rh2(H2cit)4) and rhodium (II) citrate-loaded maghemite nanoparticles or magnetoliposomes, used as drug delivery systems, on both normal and carcinoma breast cell cultures. Results Treatment with free Rh2(H2cit)4 induced cytotoxicity that was dependent on dose, time, and cell line. The IC50 values showed that this effect was more intense on breast normal cells (MCF-10A) than on breast carcinoma cells (MCF-7 and 4T1). However, the treatment with 50 μM Rh2(H2cit)4-loaded maghemite nanoparticles (Magh-Rh2(H2cit)4) and Rh2(H2cit)4-loaded magnetoliposomes (Lip-Magh-Rh2(H2cit)4) induced a higher cytotoxicity on MCF-7 and 4T1 than on MCF-10A (p rhodium (II) citrate-loaded maghemite nanoparticles and magnetoliposomes induced more specific cytotoxicity on breast carcinoma cells than on breast normal cells, which is the opposite of the results observed with free Rh2(H2cit)4 treatment. Thus, magnetic nanoparticles represent an attractive platform as carriers in Rh2(H2cit)4 delivery systems, since they can act preferentially in tumor cells. Therefore, these nanopaticulate systems may be explored as a potential tool for chemotherapy drug development. PMID:21443799

  7. Reactivity of rhodium during co-deposition of rhodium and carbon

    International Nuclear Information System (INIS)

    Marot, Laurent; Steiner, Roland; De Temmerman, Gregory; Oelhafen, Peter

    2009-01-01

    The detailed characterizations of rhodium/carbon films prepared by co-deposition using a dual magnetron sputtering have been carried out on silicon substrates at room temperature. Effects of the carbon incorporated in the film on the chemical bonding state, optical reflectivity and crystallinity were investigated using XPS, reflectivity measurements, XRD and SEM. The incorporation of carbon changes the films' crystallinity and thus producing amorphous films. The reflectivity of the films decreases linearly as the rhodium concentration decreases. It is important to note that no chemical bonding was observed between rhodium and carbon whatever the deposition conditions, even at high deposition temperature. Concerning the reactivity of rhodium films with oxygen, after long term storage in air the rhodium surface is covered with a thin rhodium oxide (few nanometers). However, for these films no variation of the optical reflectivity was observed after long air storage.

  8. Rhodium. Suppl. Vol. B1

    International Nuclear Information System (INIS)

    Griffith, W.P.; Jehn, H.; McCleverty, J.A.; Raub, C.J.; Robinson, S.D.

    1982-01-01

    The present rhodium vol. B1 is concerned largely with linary compounds and coordination complexes of this important metal, which is used either alone or in alloy form for fabrication of other materials or for heterogeneous catalysis. In first two chapters are devoted for hydrides, oxides, ternary and quaternary oxorhodates. Third chapter is on different type of complexes with nitrogen. From chapter four to seven is on halogen complexes with this metal. Next chapters are on sulphides, sulphoxide and sulphito complexes, sulphates and sulphato complexes, selenides and tellurides, borides, borane complexes, carbides, carbonato, cyno, fulminato and thiocyanato complexes. Finally, silicide, phosphides, phosphito and arsenides are treated over here. (AB)

  9. Ruthenium separation device from radioactive waste

    International Nuclear Information System (INIS)

    Ayabe, Osao.

    1988-01-01

    Purpose: To efficiently oxidize ruthenium in radioactive wastes and evaporize ruthenium tetraoxide after oxidization thereof, thereby improve the separation and recovery rate. Constitution: The device comprises an oxidization vessel for supplying an oxidizing agent into radioactive wastes to oxidize ruthenium in the wastes into ruthenium tetraoxide, and a distillation vessel for introducing radioactive wastes after oxidization, distillating under heating ruthenium tetraoxide leached into the wastes and evaporizing ruthenium tetraoxide. By dividing the device into the oxidizing vessel and the distillation vessel, the oxidizing treatment and the distilling treatment can individually be operated optimally to improve the separation and recovery rate of ruthenium. (Takahashi, M.)

  10. Iron

    DEFF Research Database (Denmark)

    Hansen, Jakob Bondo; Moen, I W; Mandrup-Poulsen, T

    2014-01-01

    and discuss recent evidence, suggesting that iron is a key pathogenic factor in both type 1 and type 2 diabetes with a focus on inflammatory pathways. Pro-inflammatory cytokine-induced β-cell death is not fully understood, but may include iron-induced ROS formation resulting in dedifferentiation by activation...... of transcription factors, activation of the mitochondrial apoptotic machinery or of other cell death mechanisms. The pro-inflammatory cytokine IL-1β facilitates divalent metal transporter 1 (DMT1)-induced β-cell iron uptake and consequently ROS formation and apoptosis, and we propose that this mechanism provides...

  11. Iron

    Science.gov (United States)

    ... Share: Search the ODS website Submit Search NIH Office of Dietary Supplements Consumer Datos en español Health ... eating a variety of foods, including the following: Lean meat, seafood, and poultry. Iron-fortified breakfast cereals ...

  12. The fission products palladium and rhodium: Their state in solutions, their behavior in the regeneration of fuel of atomic power stations, and the search for selective extraction techniques

    International Nuclear Information System (INIS)

    Arseenkov, L.V.; Zakharkin, B.S.; Lunichkina, K.P.; Renard, E.V.; Rogozhkin, V.Yu.; Shorokhov, N.A.

    1992-01-01

    At the present time many research centers are working on the extraction of noble metals in the form of fission fragments. Consistent data has been obtained on the mass accumulation of noble metals in various forms of processed nuclear fuel. Requirements are noted that must be met for obtaining industrial and economic efficiency in the extraction of noble metals by the Purex process. Presently there is a lack of information on the extraction of noble metals from spent fuel, particularly as far as the nitric acid media of the Purex process are concerned. The authors will discuss individual test observations on simulating systems and real systems with noble metals. The investigations focused on the noble metals of lowest radioactivity, namely palladium and rhodium. The complexity of the chemistry of ruthenium, on the one hand, and the possible selective, clearing distillation of ruthenium tetroxide from nitric acid solutions, on the other hand, make it necessary to focus the attention on the unresolved problems of the extraction of palladium and rhodium. The article further includes discussion on the following topics: noble metals in solutions of purex process, electrochemical operations involving noble metals, extraction systems for rhodium and palladium, separation of palladium from real solutions

  13. Method of dissolving metal ruthenium

    International Nuclear Information System (INIS)

    Tsuno, Masao; Soda, Yasuhiko; Kuroda, Sadaomi; Koga, Tadaaki.

    1988-01-01

    Purpose: To dissolve and clean metal ruthenium deposited to the inner surface of a dissolving vessel for spent fuel rods. Method: Metal ruthenium is dissolved in a solution of an alkali metal hydroxide to which potassium permanganate is added. As the alkali metal hydroxide used herein there can be mentioned potassium hydroxide, sodium hydroxide and lithium hydroxide can be mentioned, which is used as an aqueous solution from 5 to 20 % concentration in view of the solubility of metal ruthenium and economical merit. Further, potassium permanganate is used by adding to the solution of alkali metal hydroxide at a concentration of 1 to 5 %. (Yoshihara, H.)

  14. Rhodium(I) catalysis in olefin photoreactions

    International Nuclear Information System (INIS)

    Salomon, R.G.; El Sanadi, N.

    1975-01-01

    The photorearrangement (254 nm) of 1,5-cyclooctadiene (1) in the presence of rhodium(I) chloride to give 1,4-cyclooctadiene (4) was found by deuterium labeling to involve an intramolecular [1,3] shift of hydrogen. A rate-determining cleavage of an allylic C--H bond is indicated by a deuterium isotope effect, k/sub H//k/sub D/ = 1.55 +- 0.03 for the 1 → 4 rearrangement. The acyclic 1,5-diene, 3,3-dimethyl-1,5-hexadiene (8), rearranges in the presence of rhodium(I) chloride upon uv irradiation (254 nm) to give cis-3,3-dimethyl-1,4-hexadiene (10) and the trans isomer 11 in a 1:4 ratio, respectively. This observation supports a mechanism for the photorearrangement of olefins catalyzed by rhodium(I) involving an initial photodissociation of one of two rhodium(I) coordinated carbon-carbon double bonds. This results in an increase in the coordinative unsaturation of rhodium(I) and enhances the proclivity of this d/sub s/ metal atom toward oxidative addition of an allylic C--H bond. A eta 3 -allylrhodium hydride intermediate then gives rearranged olefin by reductive elimination. Lastly, a novel photochemical, rhodium(I) catalyzed hydrogen transfer is reported which gives cyclooctene (7) from cyclooctadienes under unprecedentedly mild conditions. (auth)

  15. Recent advances in the ruthenium(ii)-catalyzed chelation-assisted C-H olefination of substituted aromatics, alkenes and heteroaromatics with alkenes via the deprotonation pathway.

    Science.gov (United States)

    Manikandan, Rajendran; Jeganmohan, Masilamani

    2017-08-08

    The transition-metal-catalyzed chelation-assisted alkenylation at the inert C-H bond of aromatics with alkenes is one of the efficient methods to synthesize substituted vinylarenes in a highly regio- and stereoselective manner. Palladium, rhodium and ruthenium complexes are frequently used as catalysts for this type of transformation. The present review describes the recent advances in the ruthenium-catalyzed chelation-assisted alkenylation at the C-H bond of aromatics, alkenes and heteroaromatics with alkenes via the deprotonation pathway. Several directing groups including 2-pyridyl, carbonyl, amidine, amide, amine, imidate, sulphonic acid, triazole, cyano, oxazolidinone and hydontoin are widely used in the reaction. The scope, limitation and mechanistic investigation of the alkenylation reactions are discussed elaborately. This feature article includes all the reported ruthenium-catalyzed alkenylation reactions via the deprotonation pathway until the end of March 2017.

  16. Quantification of Rhodium in a Series of Inorganic and ...

    African Journals Online (AJOL)

    NICO

    ... such as rhodium hydridocarbonyl tristriphenylphosphine, [HRh(CO)(PPh3)3], .... The selection of the most suitable wavelengths for rhodium, yttrium and cobalt ... chloride ions were removed from the CRM samples as chlorine gas with the ...

  17. The barium iron ruthenium oxide system

    Science.gov (United States)

    Kemmler-Sack, S.; Ehmann, A.

    1986-01-01

    In the system BaFe(1-x)Ru(x)O(3-y), three phases, separated by immiscibility gaps, are present: an Fe-rich phase (x = 0 to 0.75) with hexagonal BaTiO3 structure (6H; sequence (hcc)2), a Ru-rich phase (x = 0.9) of hexagonal 4H-type (sequence (hc)2), and the pure Ru compounds BaRuO3 with rhombohedral 9R structure (sequence (hhc)3). By vibrational spectroscopic investigations in the 6H phase a transition from n-type semiconduction (Fe-rich compounds with complete O lattice) can be detected. The 4H and 9R stacking polytypes are good, metal-like conductors. The lattice parameters are given.

  18. Impurities determination in precious metals like rhodium, palladium and platinum by neutron activation without separation

    International Nuclear Information System (INIS)

    May, S.; Piccot, D.; Pinte, G.

    1978-01-01

    The possibilities of the method explored using an installation of gamma or X ray spectrometry of good performance. The irradiations were realized in the reactors EL.3 (flux approximately 6.10 12 n.cm -2 .s -1 ) and Osiris (flux > 10 14 n.cm -2 .s -1 ) of the CEN Saclay. In rhodium the presence of iridium limits the analysis possibilities. However gold, silver and platinum are easily determined, just as the other elements (As, Br, Cl, Co, Mn, Na, Sb). In platinum it is possible to determine the elements of long period, especially antimony, silver, cobalt, iridium, tantalum and zinc. As for palladium the principal impurities are gold, silver and ruthenium for what is of precious metals and particularly zinc among the other metals. For the three matrices considered the detection limits of a certain number of elements are indicated [fr

  19. Enhancement of ethanol oxidation at Pt and PtRu nanoparticles dispersed over hybrid zirconia-rhodium supports

    Science.gov (United States)

    Rutkowska, Iwona A.; Koster, Margaretta D.; Blanchard, Gary J.; Kulesza, Pawel J.

    2014-12-01

    A catalytic material for electrooxidation of ethanol that utilizes PtRu nanoparticles dispersed over thin films of rhodium-free and rhodium-containing zirconia (ZrO2) supports is described here. The enhancement of electrocatalytic activity (particularly in the potential range as low as 0.25-0.5 V vs. RHE), that has been achieved by dispersing PtRu nanoparticles (loading, 100 μg cm-2) over the hybrid Rh-ZrO2 support composed of nanostructured zirconia and metallic rhodium particles, is clearly evident from comparison of the respective voltammetric and chronoamperometric current densities recorded at room temperature (22 °C) in 0.5 mol dm-3 H2SO4 containing 0.5 mol dm-3 ethanol. Porous ZrO2 nanostructures, that provide a large population of hydroxyl groups in acidic medium in the vicinity of PtRu sites, are expected to facilitate the ruthenium-induced removal of passivating CO adsorbates from platinum, as is apparent from the diagnostic experiments with a small organic molecule such as methanol. Although Rh itself does not show directly any activity toward ethanol oxidation, the metal is expected to facilitate C-C bond splitting in C2H5OH. It has also been found during parallel voltammetric and chronoamperometric measurements that the hybrid Rh-ZrO2 support increases activity of the platinum component itself toward ethanol oxidation in the low potential range.

  20. Preparation of rhodium target for cyclone-30 accelerator

    International Nuclear Information System (INIS)

    Deng Xuesong; Li Dakang; Xie Xiangqian; Li Chao

    2002-01-01

    The rhodium target for Cyclone-30 accelerator is prepared by pulse electroplating method. The effects of pulse parameters, rhodium concentration, acidity and temperature on the properties of the target layer are studied, and the optimal process is determined. The rhodium target, mass thickness is more than 150 mg/cm 2 , adapts to producing 103 Pd on Cyclone-30 accelerator

  1. Synthesis and structural study of the transition metal doped rhodium perovskites

    International Nuclear Information System (INIS)

    Ting, J.; Kennedy, B.; Zhang, Z.

    2009-01-01

    Full text: One of the most common structures encountered in solid state chemistry is the perovskite structure. With a general formula of AB0 3, the A-type cations are 12-coordinate within a cubo-octahedral environment, while the B-type cations are 6-coordinate, forming an interconnecting three-dimensional octahedral network with neighbouring oxygen anions. While the ideal perovskite structure is cubic in Pm 3 m, many perovskites exhibit symmetry lowering tilting of the corner-sharing B0 6o ctahedral units as a result of A- and B-type cation size disparity. This is also evident in substituted perovskites, where two cations occupy the smaller octahedral site, AB 1- xB' x0 3' Electronic effects can also lower the symmetry. The two most commonly observed effects are the polarisation of the B-cation with a d 0 electronic configuration and Jahn-Teller distortion where the B-cation has a d 4 or d 9 electronic configuration, such as Mn 3+ or Cu 2+ respectively. Manganese containing perovskites have been shown in some compounds to exhibit long-range orbital ordering, giving rise to interesting properties. Heavier transition metals such as ruthenium and iridium have been previously incorporated into these perovskites as an avenue to regulate the properties of these materials. Two orthorhombic rhodium perovskite structures are presented, LaMn 0 . 5 Rh 0 . 5 O 3 and LaCu 05 Rh 0 . 5 O 3 ' A combination of synchrotron x-ray and neutron powder diffraction has been used to elucidate their structures, and have shown both B- and B'-type cations to be disordered across the same crystallographic site for both compounds. x-ray absorption spectroscopy measurements have been used to provide an insight into the valence states of the cations, which show a valency of +3.5 for rhodium due to an extensive charge delocalisation between copper and rhodium.

  2. Thermodynamic behaviour of ruthenium at high temperatures

    International Nuclear Information System (INIS)

    Garisto, F.

    1988-01-01

    Thermodynamic equilibrium calculations are used to determine the chemical speciation of ruthenium under postulated reactor accident conditions. The speciation of ruthenium is determined for various values of temperature, pressure, oxygen partial pressure and ruthenium concentration. The importance of these variables, in particular the oxygen partial pressure, in determining the volatility of ruthenium is clearly demonstrated in this report. Reliable thermodynamic data are required to determine the behaviour of ruthenium using equilibrium calculations. Therefore, it was necessary to compile a thermodynamic database for the ruthenium species that can be formed under reactor accident conditions. The origin of the thermodynamic data for the ruthenium species included in our calculations is discussed in detail in Appendix A. 23 refs

  3. Line profile analyses of rhodium metal obtained by decomposition of rhodium carbonyl

    International Nuclear Information System (INIS)

    Chandra, D.; Mandalia, H.; Garner, M.L.; Blakely, M.K.; Lau, K.H.

    1995-01-01

    Metal carbonyls are important for chemical vapor deposition (CVD) of metals and alloys and formation of high surface area metallic particles which have potential applications as catalysts. Rhodium carbonyl [Rh 6 (CO) 16 ] produces high surface area metallic particles whose structure has been reported as monoclinic (I2/a) with lattice dimensions, a=17.00(±0.03)Angstrom, b=9.78(±0.02)Angstrom, c=17.53(±0.03)Angstrom and Β=121 degrees 45' ± 30' at room temperature. Generally, metal carbonyl crystals dissociate under vacuum as carbonyl gas and decompose to metallic crystals and carbon monoxide at higher temperatures. However, the behavior of rhodium carbonyl crystals is different; they decompose directly to metallic rhodium without the formation of rhodium carbonyl gas in vacuum. Several residual fine grains of rhodium metal are found after the decomposition in vacuum at relatively low temperatures. The metallic samples of rhodium were obtained from vapor pressure experiments using torsion Knudsen-effusion apparatus. X-ray diffraction analyses performed on these gains showed severely broadened Bragg reflections indicative of small particle size and/or lattice microgram. In this study, a comparison of lattice strains and domain sizes obtained by integral breadth and Fourier methods has been made. In addition a comparison of the lattice strains and domain sizes has been made between the Cauchy, Gaussian, Cauchy-Gaussian and Aqua integral breadth methods

  4. Superconductivity in zirconium-rhodium alloys

    Science.gov (United States)

    Zegler, S. T.

    1969-01-01

    Metallographic studies and transition temperature measurements were made with isothermally annealed and water-quenched zirconium-rhodium alloys. The results clarify both the solid-state phase relations at the Zr-rich end of the Zr-Rh alloy system and the influence upon the superconducting transition temperature of structure and composition.

  5. Rhodium-Catalyzed Decarbonylation of Aldoses

    DEFF Research Database (Denmark)

    Monrad, Rune; Madsen, Robert

    2007-01-01

    A catalytic procedure is described for decarbonylation of unprotected aldoses to afford alditols with one less carbon atom. The reaction is performed with the rhodium complex Rh(dppp)2Cl in a refluxing diglyme - DMA solution. A slightly improved catalyst turnover is observed when a catalytic amount...

  6. Correction of rhodium detector signals for comparison to design calculations

    International Nuclear Information System (INIS)

    Judd, J.L.; Chang, R.Y.; Gabel, C.W.

    1989-01-01

    Rhodium detectors are used in many commercial pressurized water reactors PWRs [pressurized water reactor] as in-core neutron detectors. The signals from the detectors are the result of neutron absorption in 103 Rh and the subsequent beta decay of 104 Rh to 104 Pd. The rhodium depletes ∼1% per full-power month, so corrections are necessary to the detector signal to account for the effects of the rhodium depletion. These corrections result from the change in detector self-shielding with rhodium burnup and the change in rhodium concentration itself. Correction for the change in rhodium concentration is done by multiplication of the factor N(t)/N 0 , where N(t) is the rhodium concentration at time t and N 0 is the initial rhodium concentration. The calculation of the self-shielding factor is more complicated and is presented. A self-shielding factor based on the fraction of rhodium remaining was calculated with the CASMO-3 code. The results obtained from our comparisons of predicted and measured in-core detector signals show that the CASMO-3/SIMULATE-3 code package is an effective tool for estimating pin peaking and power distributions

  7. Reaction pathways for reduction of nitrate ions on platinum, rhodium, and platinum-rhodium alloy electrodes

    International Nuclear Information System (INIS)

    Cunha, M.C.P.M. da; De Souza, J.P.I.; Nart, F.C.

    2000-01-01

    The reduction of nitrate ions on platinum, rhodium, and platinum-rhodium alloy electrodes has been investigated using differential electrochemical mass spectrometry and in situ FTIR measurements. For 3 M HNO 3 concentration it has been found that nitrate starts the reduction with partial N-O bond dissociation and N-N bond formation generating NO and N 2 O. At potentials lower than 0.2 V the reaction proceeds forming dissolved NH 4 + . For potentials lower than 0 V the reduction continues via a multiple pathway reaction leading to the nonselective production of N 2 , NH 2 OH, and N 2 H 2 . On the alloyed electrodes, the production of NO and N 2 O has been observed in both cathodic and anodic scans, while on pure platinum and rhodium electrodes the reaction has been observed only during the cathodic scan. Contrasting with the pure platinum and rhodium alloys, where the N-O bond break starts forming NO and N 2 O, on the alloys HNO 2 has been observed as the first reaction step. For alloys with higher rhodium composition, like Pt 75 Rh 25 , no N 2 has been detected for potentials lower than 0 V

  8. Investigation into cathode polarization during deposition of rhodium-nickel and rhodium-indium alloys

    International Nuclear Information System (INIS)

    Evdokimova, N.V.; Byacheslavov, P.M.; Lokshtanova, O.G.

    1979-01-01

    The results of kinetic regularities experimental investigations during electrodeposition of rhodium-nickel and rhonium-indium alloys are presented. Methods of general and partial polarization curves have been used to show the nature of polarization during the rhonium-nickel and rhodium-indium alloys deposition. It is shown that indium into the rhodium-indium alloy and nickel into the rhodium-nickel alloy deposit with great depolarization ( PHIsub(In)sup(0)=-0.33B, PHIsub(Ni)sup(0)=-0.23B). Indium and nickel in pure form do not deposit from the electrolytes of the given composition (H 2 SO 4 - 50 g/l, HNH 2 SO 3 -10 g/l). The recalculation of partial polarization curve of indium precipitation into the rhodium-indium alloy in the mixed kinetics coordinates gives a straight line with 40 mV inclination angle. This corresponds to the delayed stage of the second electron addition with the imposition of diffusion limitations

  9. Distribution of Rhodium in Mice Submitted to Treatment With the Adduct of Rhodium Propionate and Sodium Isonicotinate

    OpenAIRE

    de Souza, Aparecido Ribeiro; Najjar, Renato; de Oliveira, Elizabeth; Zyngier, Szulim Ber

    1997-01-01

    The distribution of rhodium in Balb/c mice following intraperitoneal (ip) administration of a solution of adduct of rhodium propionate and sodium isonicotinate has been investigated. The metal concentration was determined in blood and in the following organ tissues: brain, heart, lung, liver, spleen, kidney, testes, and uterus/ovary, and the rhodium concentration was obtained by Inductively Coupled Argon Atomic Emission Spectroscopy (ICP-AES). The metal was detected in all organ tissues exami...

  10. Solvent extraction separation and spectrographic determination of palladium, rhodium and ruthenium in uranium

    International Nuclear Information System (INIS)

    Capdevilla, C.; Alduan, F. A.

    1980-01-01

    The determination of Pd, Rh and Ru in uranium at low ppm level, using solvent extraction has been studied. BPHA, TNOA, TOPO and TBP have been tried as complexing agents; TBP In hexane and 5 M nitric acid medium provides a virtually quantitative extraction. The layer containing the impurities is collected Into graphite powder, and this powder is analysed spectro graphically using carrier destination method with % CuF 2 as a carrier. (Author) 11 refs

  11. Spectrographic determination of zirconium, niobium, rhodium, ruthenium, tantalum, and tungsten in uranium and its compounds

    International Nuclear Information System (INIS)

    Alduan, F.A.; Capdevila, C.

    1976-01-01

    The determination of Nb, Rh, Ru, Ta, W and Zr in uranium and its compounds has been studied, using the carrier distillation method with either AgCl or AgCl-SrF 2 (4:3) as carrier. In order to get the best sensitivity, the influence of the carrier concentration, the dc arc intensity and several controlled atmospheres on the variation of the line to background ratio of intensities has been considered. With the most suitable conditions, the sensitivities achieved for the considered elements are in the range 1-10 ppm. (author)

  12. Separation of rhodium-103m from ruthenium-103 by solvent extraction

    International Nuclear Information System (INIS)

    Chiu, J.H.; Landolt, R.R.; Kessler, W.V.

    1978-01-01

    The results for eight replications of the solvent extraction and purification procedures were /sup 103m/Rh yield, 100.9 +- 2.1% and 103 Ru contamination, 0.0%. The use of sodium hypochlorite as the oxidizing agent eliminated the need for fuming with 1:1 H 2 SO 4 to eliminate chlorides as was required when ceric sulfate was used as the oxidizing agent. The optimum pH for extraction of RuO 4 into CCl 4 was determined to be in the range 6.5 to 7.5. A boiling procedure was used to purify the extracted aqueous solution of /sup 103m/Rh

  13. Charge-delocalized κ2 C, N-NHC-amine complexes of rhodium, iridium, and ruthenium

    NARCIS (Netherlands)

    Jansen, Eveline; Lutz, Martin; Bruin, Bas De; Elsevier, Cornelis J.

    2014-01-01

    The development of a novel set of complexes bearing an NHC-amine ligand (CNHC-NH2) is described. M(cod) complexes (M = Ir, Rh) and a Ru complex have been synthesized in which three different coordination modes of the ligand were established: monodentate, neutral bidentate, and anionic bidentate. The

  14. Palladium, platinum, rhodium, iridium and ruthenium in chromite- rich rocks from the Samail ophiolite, Oman.

    Science.gov (United States)

    Page, N.J.; Pallister, J.S.; Brown, M.A.; Smewing, J.D.; Haffty, J.

    1982-01-01

    30 samples of chromitite and chromite-rich rocks from two stratigraphic sections, 250 km apart, through the basal ultramafic member of the Samail ophiolite were spectrographically analysed for platinum-group elements (PGE) and for Co, Cu, Ni and V. These data are reported as are Cr/(Cr + Al), Mg/(Mg + Fe) and wt.% TiO2 for most samples. The chromitite occurs as pods or lenses in rocks of mantle origin or as discontinuous layers at the base of the overlying cumulus sequence. PGE abundances in both sections are similar, with average contents in chromite-rich rocks: Pd 8 ppb, Pt 14 ppb, Rh 6 ppb, Ir 48 ppb and Ru 135 ppb. The PGE data, combined with major-element and petrographic data on the chromitite, suggest: 1) relatively larger Ir and Ru contents and highest total PGE in the middle part of each section; 2) PGE concentrations and ratios do not correlate with coexisting silicate and chromite abundances or chromite compositions; 3) Pd/PGE, on average, increases upward in each section; 4) Samail PGE concentrations, particularly Rh, Pt and Pd, are lower than the average values for chromite-rich rocks in stratiform intrusions. 2) suggests that PGEs occur in discrete alloy or sulphide phases rather than in the major oxides or silicates, and 4) suggests that chromite-rich rocks from the oceanic upper mantle are depleted in PGE with respect to chondrites. L.C.C.

  15. PALLADIUM, PLATINUM, RHODIUM, RUTHENIUM AND IRIDIUM IN PERIDOTITES AND CHROMITITES FROM OPHIOLITE COMPLEXES IN NEWFOUNDLAND.

    Science.gov (United States)

    Page, Norman J; Talkington, Raymond W.

    1984-01-01

    Samples of spinel lherzolite, harzburgite, dunite, and chromitite from the Bay of Islands, Lewis Hills, Table Mountain, Advocate, North Arm Mountain, White Hills Periodite Point Rousse, Great Bend and Betts Cove ophiolite complexes in Newfoundland were analyzed for the platinum-group elements (PGE) Pd, Pt, Rh, Ru and Ir. The ranges of concentration (in ppb) observed for all rocks are: less than 0. 5 to 77 (Pd), less than 1 to 120 (Pt), less than 0. 5 to 20 (Rh), less than 100 to 250 (Ru) and less than 20 to 83 (Ir). Chondrite-normalized PGE ratios suggest differences between rock types and between complexes. Samples of chromitite and dunite show relative enrichment in Ru and Ir and relative depletion in Pt and Pd.

  16. Electrochemical studies of ruthenium compounds

    International Nuclear Information System (INIS)

    Kumar Ghosh, B.; Chakravorty, A.

    1989-01-01

    In many ways the chemistry of transition metals is the chemistry of multiple oxidation states and the associated redox phenomena. If a particular element were to be singeld out to illustrate this viewpoint, a model choice would be ruthenium - an element that is directly or indirectly the active centre of a plethora of redox phenomena encompassing ten different oxidation states and a breathtaking diversity of structure and bonding. In the present review the authors are primarily concerned with the oxidation states of certain ligands coordinated to ruthenium. This choice is deliberate since this is one area where the unique power of electrochemical methods is splendidly revealed. Without these methods, development in this area would have been greatly hampered. A brief summary of metal oxidation states is also included as a prelude to the main subject of this review. The authors have generally emphasize the information derived which is of chemical interest leaving the details of formal electrochemical arguments in the background. The authors have reviewed the pattern and systematics of ligand redox in ruthenium complexes. The synergistic combination of electrochemical and spectroscopic methods have vastly increased our understanding of ligand phenomena during the last 15 years or so. This in turn has led to better understanding and new developments in other fields. Photophysics and photochemistry could be cited as examples. (author). 176 refs.; 10 figs.; 10 tabs

  17. Solventless synthesis of ruthenium nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    García-Peña, Nidia G. [Departmento de Tecnociencias, Universidad Nacional Autónoma de México, Centro de Ciencias Aplicadas y Desarrollo Tecnológico, Universidad Nacional Autónoma de México, Cd. Universitaria A.P. 70-186, C.P. 04510 Coyoacán, México D.F. (Mexico); Redón, Rocío, E-mail: rredon@unam.mx [Departmento de Tecnociencias, Universidad Nacional Autónoma de México, Centro de Ciencias Aplicadas y Desarrollo Tecnológico, Universidad Nacional Autónoma de México, Cd. Universitaria A.P. 70-186, C.P. 04510 Coyoacán, México D.F. (Mexico); Herrera-Gomez, Alberto [Estudios Avanzados del Instituto Politécnico Nacional, Campus Juriquilla, Querétaro (Mexico); Fernández-Osorio, Ana Leticia [FES-Cuautitlán, Universidad Nacional Autónoma de México, Edo. de Mexico (Mexico); Bravo-Sanchez, Mariela; Gomez-Sosa, Gustavo [Estudios Avanzados del Instituto Politécnico Nacional, Campus Juriquilla, Querétaro (Mexico)

    2015-06-15

    Graphical abstract: - Highlights: • Successful synthesis of Ru nanoparticles by a cheap, fast and solventless approach was achieved. • The zero-valent state as well as the by-product/impurity free of the mechanochemical obtained Ru nanoparticles was proven by XPS, TEM and XRD. • Compared to two other synthesis strategies, the above-mentioned synthesis was more suitable to obtain smaller particles with fewer impurities in shorter time. - Abstract: This paper presents a novel solventless method for the synthesis of zero-valent ruthenium nanoparticles Ru(0). The proposed method, although not entirely new in the nanomaterials world, was used for the first time to synthesize zero-valent ruthenium nanoparticles. This new approach has proved to be an environmentally friendly, clean, cheap, fast, and reproducible technique which employs low amounts of solvent. It was optimized through varying amounts of reducing salt on a determined quantity of precursor and measuring the effect of this variation on the average particle size obtained. The resulting products were fully characterized by powder XRD, TEM, HR-TEM, and XPS studies, all of which corroborated the purity of the nanoparticles achieved. In order to verify the advantages of our method over other techniques, we compared our nanoparticles with two common colloidal-synthesized ruthenium nanoparticles.

  18. Hydroformylation of methyl oleate catalyzed by rhodium complexes

    International Nuclear Information System (INIS)

    Mendes, Ana Nery Furlan; Rosa, Ricardo Gomes da; Gregorio, Jose Ribeiro

    2012-01-01

    In this work, we describe the hydroformylation of methyl oleate catalyzed by several rhodium complexes. Parameters including total pressure, phosphorous/rhodium and CO/H 2 ratio, temperature and phosphorous ligands were scanned. Total conversion of the starting double bonds was achieved while maintaining excellent selectivity in aldehydes. (author)

  19. Cyclopentadiene-mediated hydride transfer from rhodium complexes.

    Science.gov (United States)

    Pitman, C L; Finster, O N L; Miller, A J M

    2016-07-12

    Attempts to generate a proposed rhodium hydride catalytic intermediate instead resulted in isolation of (Cp*H)Rh(bpy)Cl (1), a pentamethylcyclopentadiene complex, formed by C-H bond-forming reductive elimination from the fleeting rhodium hydride. The hydride transfer ability of diene 1 was explored through thermochemistry and hydride transfer reactions, including the reduction of NAD(+).

  20. Dinuclear ditertiary phosphite derivatives of rhodium

    International Nuclear Information System (INIS)

    Meintjies, E.

    1981-08-01

    The overall objective of the research described in this thesis was the design, synthesis, characterization and chemistry of dinuclear complexes of rhodium in which the metal atoms are held in close proximity to each other. Complexes of this nature are of considerable interest owing, in part, to their potential as models for multicentred metal catalysts, as well as to the highly novel and unusual chemistry already discovered for a number of them. A survey of dinuclear complexes of rhodium containing carbonyl and group V donor ligands has been presented as a background introduction to the research reported in this thesis. The coordination behaviour of the diphosphazane ligands, (RO) 2 PN(R')P(OR) 2 (R=Ph or Me, R' = Et; R = Et or Pr/i, R' = Me), and the ditertiary phosphite ligand, (EtO) 2 POP(OEt) 2 , towards certain rhodium precursors has been investigated. A number of highly unusual neutral dinuclear complexes of rhodium, in which these ligands bridge-bond the two rhodium atoms, have been synthesized. Two types of monocarbonyl decarbonylation products are observed for compounds of the type, [Rh 2 Cl 2 (CO) 2 (μ-diphosphazane) 2 ]. 1 H and 31 P[ 1 H] n.m.r. spectral studies have been carried out with the object of establishing the nature of the bridging halogen ligands in the tricarbonyl species. Asymetric zerovalent dinuclear species of the type, [Rh 2 (CO) 3 -[μ-(RO) 2 PN(R')P(OR) 2 ] 2 ] (R = Ph or Me, R' = Et; R = Pr/i, R' = Me), are obtained. A single crystal X-ray analysis has been carried out. Homoleptic cationic species are obtained by reaction of the alkoxydiphosphazane ligands with [Rh(C 8 H 12 )(solvent)(n)] + under the appropriate reaction conditions. The solution and solid-state infrared spectra and the 31 P[ 1 H] n.m.r. spectra of all new compounds synthesized in this study are discussed in terms of possible structures for these compounds. Where appropriate, the n.m.r. spectral data are also discussed in terms of fluxional behaviour

  1. Antitumor effect of free rhodium (II) citrate and rhodium (II) citrate-loaded maghemite nanoparticles on mice bearing breast cancer: a systemic toxicity assay.

    Science.gov (United States)

    Peixoto, Raphael Cândido Apolinário; Miranda-Vilela, Ana Luisa; de Souza Filho, José; Carneiro, Marcella Lemos' Brettas; Oliveira, Ricardo G S; da Silva, Matheus Oliveira; de Souza, Aparecido R; Báo, Sônia Nair

    2015-05-01

    Breast cancer is one of the most prevalent cancer types among women. The use of magnetic fluids for specific delivery of drugs represents an attractive platform for chemotherapy. In our previous studies, it was demonstrated that maghemite nanoparticles coated with rhodium (II) citrate (Magh-Rh2Cit) induced in vitro cytotoxicity and in vivo antitumor activity, followed by intratumoral administration in breast carcinoma cells. In this study, our aim was to follow intravenous treatment to evaluate the systemic antitumor activity and toxicity induced by these formulations in Balb/c mice bearing orthotopic 4T1 breast carcinoma. Female Balb/c mice were evaluated with regard to toxicity of intravenous treatments through analyses of hemogram, serum levels of alanine aminotransferase, iron, and creatinine and liver, kidney, and lung histology. The antitumor activity of rhodium (II) citrate (Rh2Cit), Magh-Rh2Cit, and maghemite nanoparticles coated with citrate (Magh-Cit), used as control, was evaluated by tumor volume reduction, histology, and morphometric analysis. Magh-Rh2Cit and Magh-Cit promoted a significant decrease in tumor area, and no experimental groups presented hematotoxic effects or increased levels of serum ALT and creatinine. This observation was corroborated by the histopathological examination of the liver and kidney of mice. Furthermore, the presence of nanoparticles was verified in lung tissue with no morphological changes, supporting the idea that our nanoformulations did not induce toxicity effects. No studies about the systemic action of rhodium (II) citrate-loaded maghemite nanoparticles have been carried out, making this report a suitable starting point for exploring the therapeutic potential of these compounds in treating breast cancer.

  2. IR-doped ruthenium oxide catalyst for oxygen evolution

    Science.gov (United States)

    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.

  3. Utilization of ruthenium volatilization at heating of residue containing phosphates and nitrates for ruthenium separation and for its qualitative proof

    International Nuclear Information System (INIS)

    Holgye, Z.

    1979-01-01

    The volatility of ruthenium during the heating of a residue after evaporation of a solution containing ruthenium, phosphates and nitrates may be utilized for the separation of ruthenium from various substances. Sup(103,106) Ru may be rapidly, selectively, and quantitatively separated from fission products mixture. Ruthenium may be also separated in this way from various inorganic salts or from biological material. The volatility of ruthenium may be used also for its qualitative proof. (author)

  4. Relaxation of polarized nuclei in superconducting rhodium

    DEFF Research Database (Denmark)

    Knuuttila, T.A.; Tuoriniemi, J.T.; Lefmann, K.

    2000-01-01

    Nuclear spin lattice relaxation rates were measured in normal and superconducting (sc) rhodium with nuclear polarizations up to p = 0.55. This was sufficient to influence the sc state of Rh, whose T, and B-c, are exceptionally low. Because B-c ... is unchanged, the nuclear spin entropy was fully sustained across the sc transition. The relaxation in the sc state was slower at all temperatures without the coherence enhancement close to T-c. Nonzero nuclear polarization strongly reduced the difference between the relaxation rates in the sc and normal...

  5. Adhesion of rhodium films on metallic substrates

    International Nuclear Information System (INIS)

    Marot, L.; Covarel, G.; Tuilier, M.-H.; Steiner, R.; Oelhafen, P.

    2008-01-01

    Rhodium coated metallic films were prepared by magnetron sputtering on metallic substrates. All films were elaborated in same conditions on copper, molybdenum and stainless steel. Adhesion strength tests were carried out by scratch test. The results reveal that the adhesion strength between the film and the substrate is influenced by the hardness of the substrate. Increase of deposition temperature improves the adhesion of the coating. In addition, pre-treatment of substrates by a filtered cathodic vacuum arc and the layer thickness have has some effects on the final adhesion strength

  6. Adhesion of rhodium films on metallic substrates

    Energy Technology Data Exchange (ETDEWEB)

    Marot, L. [Department of Physics, University of Basel, Klingelbergstrasse 82, CH-4056 Basel (Switzerland)], E-mail: laurent.marot@unibas.ch; Covarel, G.; Tuilier, M.-H. [Laboratoire Mecanique, Materiaux et Procedes de Fabrication, Pole STIC-SPI-Math 61 rue Albert Camus, Universite de Haute-Alsace, F-68093 - Mulhouse Cedex (France); Steiner, R.; Oelhafen, P. [Department of Physics, University of Basel, Klingelbergstrasse 82, CH-4056 Basel (Switzerland)

    2008-09-01

    Rhodium coated metallic films were prepared by magnetron sputtering on metallic substrates. All films were elaborated in same conditions on copper, molybdenum and stainless steel. Adhesion strength tests were carried out by scratch test. The results reveal that the adhesion strength between the film and the substrate is influenced by the hardness of the substrate. Increase of deposition temperature improves the adhesion of the coating. In addition, pre-treatment of substrates by a filtered cathodic vacuum arc and the layer thickness have has some effects on the final adhesion strength.

  7. Electronic and magnetic properties of ultrathin rhodium nanowires

    CERN Document Server

    Wang Bao Lin; Ren-Yun; Sun Hou Qian; Chen Xiao Shuang; Zhao Ji Jun

    2003-01-01

    The structures of ultrathin rhodium nanowires are studied using empirical molecular dynamics simulations with a genetic algorithm. Helical multishell cylindrical and pentagonal packing structures are found. The electronic and magnetic properties of the rhodium nanowires are calculated using an spd tight-binding Hamiltonian in the unrestricted Hartree-Fock approximation. The average magnetic moment and electronic density of states are obtained. Our results indicate that the electronic and magnetic properties of the rhodium nanowires depend not only on the size of the wire but also on the atomic structure. In particular, centred pentagonal and hexagonal structures can be unusually ferromagnetic.

  8. Structural properties of small rhodium clusters

    Energy Technology Data Exchange (ETDEWEB)

    Soon, Yee Yeen; Yoon, Tiem Leong [School of Physics, Universiti Sains Malaysia, 11800 USM, Penang (Malaysia); Lim, Thong Leng [Faculty of Engineering and Technology, Multimedia University, Melaka Campus, 75450 Melaka (Malaysia)

    2015-04-24

    We report a systematic study of the structural properties of rhodium clusters at the atomistic level. A novel global-minimum search algorithm, known as parallel tempering multicanonical basin hopping plus genetic algorithm (PTMBHGA), is used to obtain the geometrical structures with lowest minima at the semi-empirical level where Gupta potential is used to describe the atomic interaction among the rhodium atoms. These structures are then re-optimized at the density functional theory (DFT) level with exchange-correlation energy approximated by Perdew-Burke-Ernzerhof (PBE) generalized gradient approximation (GGA). The structures are optimized for different spin multiplicities. The ones with lowest energies will be taken as ground-state structures. In most cases, we observe only minor changes in the geometry and bond length of the clusters as a result of DFT-level re-optimization. Only in some limited cases, the initial geometries obtained from the PTMBHGA are modified by the re-optimization. The variation of structural properties, such as ground-state geometry, symmetry and binding energy, with respect to the cluster size is studied and agreed well with other results available in the literature.

  9. Interface behaviour and electrical performance of ruthenium ...

    Indian Academy of Sciences (India)

    Rutherford backscattering spectrometry; Raman spectroscopy; oxidation; silicide; Schottky barrier diodes; ruthenium ... water and then dried with nitrogen gas before being loaded into the vacuum ... laser of wavelength 514.6 nm. Full I–V and ...

  10. Rhodium-Catalyzed Dehydrogenative Borylation of Cyclic Alkenes

    Science.gov (United States)

    Kondoh, Azusa; Jamison, Timothy F.

    2010-01-01

    A rhodium-catalyzed dehydrogenative borylation of cyclic alkenes is described. This reaction provides direct access to cyclic 1-alkenylboronic acid pinacol esters, useful intermediates in organic synthesis. Suzuki-Miyaura cross-coupling applications are also presented. PMID:20107646

  11. Low gravity containerless processing of immiscible gold rhodium alloys

    Science.gov (United States)

    Andrews, J. Barry

    1986-01-01

    Under normal one-g conditions immiscible alloys segregate extensively during solidification due to sedementation of the more dense of the immiscible liquid phases. However, under low-g conditions it should be possible to form a dispersion of the two immiscible liquids and maintain this dispersed structure during solidification. Immiscible (hypermonotectic) gold-rhodium alloys were processed in the Marshall Space Flight Center 105 meter drop tube in order to investigate the influence of low gravity, containerless solidification on their microstructure. Hypermonotectic alloys composed of 65 atomic % rhodium exhibited a tendency for the gold rich liquid to wet the outer surface of the containerless processed samples. This tendency led to extensive segregation in several cases. However, well dispersed microstructures consisting of 2 to 3 micron diameter rhodium-rich spheres in a gold-rich matrix were produced in 23.4 atomic % rhodium alloys. This is one of the best dispersions obtained in research on immiscible alloy-systems to data.

  12. The influence of rhodium burn-up on the sensitivity of rhodium self-powered neutron detectors

    International Nuclear Information System (INIS)

    Erben, O.

    1980-01-01

    Depression and self-shielding coefficients are presented for thermal and epithermal neutron flux densities. Functions are shown describing the distribution of beta particle sources on the emitter cross section for 0 to 50% rhodium burnup. The values are calculated of detector sensitivity to thermal and epithermal neutron flux densities for the said burnup for main types of rhodium SPN detectors made by SODERN. (J.B.)

  13. Ruthenium (4) and ruthenium (3) state in hydrochloric acid solutions under microwave irradiation

    International Nuclear Information System (INIS)

    Bashilov, A.V.; Kuz'min, N.M.; Nesterov, A.A.; Runov, V.K.

    2000-01-01

    Reactions of hydration, poly- and depolymerization, oxidation-reduction processes with ruthenium (4) and ruthenium (3) participation are investigated in hydrochloric acid solutions under microwave irradiation by the methods of molecular absorption spectroscopy in UV visible region taking K 4 [Ru 2 OCl 10 ] as an example. Content of state forms of ruthenium (4) and ruthenium (3), absorption characteristics of forming complexes are calculated. Variation of microwave irradiation parameters and HCl concentration permits to prepare solutions containing [RuCl 6 ] 2+ (95 %) and [(RuOH) 2 (H 2 O) 6 (OH) 2 ] 4+ (98 %) preeminently predominant forms. The role of microwave effect directly is established taking as an example the process of ruthenium (4) hydration [ru

  14. Rhodium and Hafnium Influence on the Microstructure, Phase Composition, and Oxidation Resistance of Aluminide Coatings

    OpenAIRE

    Maryana Zagula-Yavorska; Małgorzata Wierzbińska; Jan Sieniawski

    2017-01-01

    A 0.5 μm thick layer of rhodium was deposited on the CMSX 4 superalloy by the electroplating method. The rhodium-coated superalloy was hafnized and aluminized or only aluminized using the Chemical vapour deposition method. A comparison was made of the microstructure, phase composition, and oxidation resistance of three aluminide coatings: nonmodified (a), rhodium-modified (b), and rhodium- and hafnium-modified (c). All three coatings consisted of two layers: the additive layer and the interdi...

  15. Cyclotron production of ruthenium-97 for radiopharmaceutical applications

    International Nuclear Information System (INIS)

    Music, S.; Gessner, M.

    1980-01-01

    Ruthenium-97 is of interest for clinical practice in nuclear medicine. The combination of the excellent physical and chemical properties of Ruthenium-97 make this isotope worth evaluating. Ruthenium-97 has been prepared by irradiation of a sheet of molybdenum with the internal alpha-beam of the Ruthenium-97 as a function of the alpha particle energy has been measured. The radiochemical separation and its possible clinical applications have been discussed. (author)

  16. Analysis of uranium and its compounds. Ruthenium spectrographic determination

    International Nuclear Information System (INIS)

    Anon.

    Ruthenium determination in uranium and its compounds, suitable for content greater than 0.1 ppm with respect to uranium, by dissolution in sulfuric acid and addition of palladium as an internal standard, separation of the precipitated ruthenium, in the presence of gold, by reduction with zinc, the precipitate is calcined and ruthenium is determined by spectrography [fr

  17. 10 CFR Appendix C to Part 20 - Quantities 1 of Licensed Material Requiring Labeling

    Science.gov (United States)

    2010-01-01

    ... Ruthenium-105 1,000 Ruthenium-106 1 Rhodium-99m 1,000 Rhodium-99 100 Rhodium-100 100 Rhodium-101m 1,000 Rhodium-101 10 Rhodium-102m 10 Rhodium-102 10 Rhodium-103m 1,000 Rhodium-105 100 Rhodium-106m 1,000 Rhodium-107 1,000 Palladium-100 100 Palladium-101 1,000 Palladium-103 100 Palladium-107 10 Palladium-109...

  18. About the extraction recovery of fission rhodium from radioactive wastes

    International Nuclear Information System (INIS)

    Khaperskaya, A.V.; Renard, E.V.; Koltunov, V.S.

    2000-01-01

    The report will cover a radically new approach to the problem of rhodium recovery from HLLW after the transformation of kinetically inert poly-aqua cation of trivalent rhodium (which is not recoverable by the majority known extractants) to Rh (IV) form by chemical methods. Presented are the research results of Rh (IV) extraction from nitric acid solutions by several extractants that are of considerable current use in noble metals and radiochemical industries (tri-n-butyl phosphate, di-octyl-sulphide, tri-n-octylamine, quaternary ammonium bases). High level of rhodium extraction has been found for the above extractants: for several systems, for example, tri-n-octylamine - diethyl-benzene, rhodium distribution coefficient achieves high values (10-plus), as well as the sufficient extraction kinetics. Rhodium extraction increases with a decrease of the acidity, a rise in phase mixing time and in the following series: tri-n-butyl phosphate → di-octyl-sulphide → quaternary ammonium bases → tri-n-octylamine. Rh (IV) can be easily reduced to non-extractable Rh (III) by such reductants as Fe (II), HCOOH, C 6 H 8 O 6 , NH 2 OH, N 2 H 4 et al, that may be applied for the re-extraction process. (authors)

  19. Block copolymer lithography of rhodium nanoparticles for high temperature electrocatalysis.

    Science.gov (United States)

    Boyd, David A; Hao, Yong; Li, Changyi; Goodwin, David G; Haile, Sossina M

    2013-06-25

    We present a method for forming ordered rhodium nanostructures on a solid support. The approach makes use of a block copolymer to create and assemble rhodium chloride nanoparticles from solution onto a surface; subsequent plasma and thermal processing are employed to remove the polymer and fully convert the nanostructures to metallic rhodium. Films cast from a solution of the triblock copolymer poly(styrene-b-2-vinyl pyridine-b-ethylene oxide) dissolved in toluene with rhodium(III) chloride hydrate were capable of producing a monolayer of rhodium nanoparticles of uniform size and interparticle spacing. The nanostructures were characterized by scanning electron microscopy, X-ray photoelectron spectroscopy, and atomic force microscopy. The electrocatalytic performance of the nanoparticles was investigated with AC impedance spectroscopy. We observed that the addition of the particles to a model solid oxide fuel cell anode provided up to a 14-fold improvement in the anode activity as evidenced by a decrease in the AC impedance resistance. Examination of the anode after electrochemical measurement revealed that the basic morphology and distribution of the particles were preserved.

  20. Method of suppressing evaporation loss of ruthenium

    International Nuclear Information System (INIS)

    Muromura, Tadazumi; Sato, Tadashi.

    1987-01-01

    Purpose: To prevent evaporation loss of ruthenium from liquid wastes by adding an aluminum compound upon applying evaporating and drying to solid treatment to reprocessing liquid wastes for spent fuels. Method: An aluminum compound such as aluminum nitrate or aluminum hydroxide to reprocessing liquid wastes of spent fuels such that aluminum/ruthenium mixing ratio corresponds to 1.3 - 70.0 by g/atom ratio (0.34 - 187 by weight ratio), and the liquid mixture is heated to a temperature of about 130 deg C to be evaporated and dried to solidness. This enables to recover ruthenium without settling and depositing insoluble matters in the liquid wastes and without decomposing nitric acid. (Yoshino, Y.)

  1. Adsorption of aliphatic alcohols on ruthenium

    International Nuclear Information System (INIS)

    Shapovalova, L.B.; Zakumbaeva, G.D.

    1977-01-01

    The adsorption is studied of allyl-, propyl- and propargyl alcohols on a ruthenium catalyst-electrode at 20, 30 and 40 deg C in H 2 SO 4 in helium. Above adsorption has been found to grow with increased concentration of the alcohols in the solution. In solutions with the same concentration, propargyl alcohol has been noted to show highest sorptive capacity, followed by that of allyl- and propyl alcohols. With variations in the ruthenium electrode potential, alcohol adsorption occurs via maximum at potential = 0.18

  2. Processing of radioactive ruthenium with aluminosilicate gels

    International Nuclear Information System (INIS)

    Kanno, Takuji; Ichinose, Yasuhiro; Ito, Katsuo

    1979-01-01

    Coprecipitation of radioactive Ru with hydroxides has been studied for the purpose of the management of the high level waste from the nuclear fuel reprocessing. Aluminosilicate gel used as coprecipitant was prepared by addition of aqueous sodium hydroxide to sodium aluminate-sodium silicate solution containing ruthenium nitrate. Ruthenium quantitatively precipitates under the conditions, aluminate > 4 x 10 -2 M, Al/Si 0 C. However, volatilization rate of Ru is suppressed by coating with mullite phase into which aluminosilicate gel transformes above 900 0 C. The amount of Ru volatilized in Ar-flow was reduced to about 10% of that in air-flow. (author)

  3. Kalman filtering for rhodium self-powered neutron detectors

    International Nuclear Information System (INIS)

    Kantrowitz, M.L.

    1988-01-01

    Rhodium self-powered neutron detectors are utilized in many pressurized water reactors to determine the neutronic behavior within the core. In order to compensate for the inherent time delay associated with the response of these detectors, a dynamic compensation algorithm is currently used in Combustion Engineering plants to reconstruct the dynamic flux signal which is being sensed by the rhodium detectors. This paper describes a new dynamic compensation algorithm, based on Kalman filtering, which improves on the noise gain and response time characteristics of the algorithm currently used, and offers the possibility of utilizing the proven rhodium detector based fixed in-core detector system as an integral part of advanced core control and/or protection systems

  4. Chemical Posttranslational Modification with Designed Rhodium(II) Catalysts.

    Science.gov (United States)

    Martin, S C; Minus, M B; Ball, Z T

    2016-01-01

    Natural enzymes use molecular recognition to perform exquisitely selective transformations on nucleic acids, proteins, and natural products. Rhodium(II) catalysts mimic this selectivity, using molecular recognition to allow selective modification of proteins with a variety of functionalized diazo reagents. The rhodium catalysts and the diazo reactivity have been successfully applied to a variety of protein folds, the chemistry succeeds in complex environments such as cell lysate, and a simple protein blot method accurately assesses modification efficiency. The studies with rhodium catalysts provide a new tool to study and probe protein-binding events, as well as a new synthetic approach to protein conjugates for medical, biochemical, or materials applications. © 2016 Elsevier Inc. All rights reserved.

  5. Ruthenium nanocatalysis on redox reactions.

    Science.gov (United States)

    Veerakumar, Pitchaimani; Ramdass, Arumugam; Rajagopal, Seenivasan

    2013-07-01

    Nanoparticles have generated intense interest over the past 20 years due to their high potential applications in different areas such as catalysis, sensors, nanoscale electronics, fuel and solar cells and optoelectronics. As the large fractions of metal atoms are exposed to the surface, the use of metal nanoparticles as nanocatalysts allows mild reaction conditions and high catalytic efficiency in a large number of chemical transformations. They have emerged as sustainable heterogeneous catalysts and catalyst supports alternative to conventional materials. This review focuses on the synthesis, characterization and catalytic role of ruthenium nanoparticles (RuNPs) on the redox reactions of heteroatom containing organic compounds with the green reagent H2O2, a field that has attracted immense interest among the chemical, materials and industrial communities. We intend to present a broad overview of Ru nanocatalysts for redox reactions with an emphasis on their performance, stability and reusability. The growth in the chemistry of organic sulfoxides and N-oxides during last decade was due to their importance as synthetic intermediates for the production of a wide range of chemically and biologically active molecules. Thus design of efficient methods for the synthesis of sulfoxides and N-oxides becomes important. This review concentrates on the catalysis of RuNPs on the H2O2 oxidation of organic sulfides to sulfoxides and amines to N-oxides. The deoxygenation reactions of sulfoxides to sulfides and reduction of nitro compounds to amines are fundamental reactions in both chemistry and biology. Here, we also highlight the catalysis of metal nanoparticles on the deoxygenation of sulfoxides and sulfones and reduction of nitro compounds with particular emphasis on the mechanistic aspects.

  6. Snapshot analysis for rhodium fixed incore detector using BEACON methodology

    International Nuclear Information System (INIS)

    Cha, Kyoon Ho; Choi, Yu Sun; Lee, Eun Ki; Park, Moon Ghu; Morita, Toshio; Heibel, Michael D.

    2004-01-01

    The purpose of this report is to process the rhodium detector data of the Yonggwang nuclear unit 4 cycle 5 core for the measured power distribution by using the BEACON methodology. Rhodium snapshots of the YGN 4 cycle 5 have been analyzed by both BEACON/SPINOVA and CECOR to compare the results of both codes. By analyzing a large number of snapshots obtained during normal plant operation. Reviewing the results of this analysis, the BEACON/SPNOVA can be used for the snapshot analysis of Korean Standard Nuclear Power (KSNP) plants

  7. Rhodium-catalyzed regioselective olefination directed by a carboxylic group.

    Science.gov (United States)

    Mochida, Satoshi; Hirano, Koji; Satoh, Tetsuya; Miura, Masahiro

    2011-05-06

    The ortho-olefination of benzoic acids can be achieved effectively through rhodium-catalyzed oxidative coupling with alkenes. The carboxylic group is readily removable to allow ortho-olefination/decarboxylation in one pot. α,β-Unsaturated carboxylic acids such as methacrylic acid also undergo the olefination at the β-position. Under the rhodium catalysis, the cine-olefination of heteroarene carboxylic acids such as thiophene-2-carboxylic acid proceeds smoothly accompanied by decarboxylation to selectively produce the corresponding vinylheteroarene derivatives. © 2011 American Chemical Society

  8. Structure and reactivity of Ruthenium nanoparticles

    DEFF Research Database (Denmark)

    Gavnholt, Jeppe; Schiøtz, Jakob

    2008-01-01

    We present a method for obtaining detailed structural information of ruthenium nanoparticles in at least the diameter range from 1.5 to 5 nm. The method is based on an ensemble approach where a large number of low-energy structures are collected in an ensemble, from which average properties can...

  9. Thermodynamic properties of gaseous ruthenium species.

    Science.gov (United States)

    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.

  10. Enyne Metathesis Catalyzed by Ruthenium Carbene Complexes

    DEFF Research Database (Denmark)

    Poulsen, Carina Storm; Madsen, Robert

    2003-01-01

    Enyne metathesis combines an alkene and an alkyne into a 1,3-diene. The first enyne metathesis reaction catalyzed by a ruthenium carbene complex was reported in 1994. This review covers the advances in this transformation during the last eight years with particular emphasis on methodology...

  11. Support Effect in Hydrodesulfurization over Ruthenium Sulfide

    Czech Academy of Sciences Publication Activity Database

    Gulková, Daniela; Kaluža, Luděk; Vít, Zdeněk; Zdražil, Miroslav

    2009-01-01

    Roč. 51, č. 2 (2009), s. 146-149 ISSN 1337-7027 R&D Projects: GA ČR GA104/06/0705 Institutional research plan: CEZ:AV0Z40720504 Keywords : ruthenium sulfide * hydrodesulfurization * support effect Subject RIV: CC - Organic Chemistry

  12. Ruthenium transport experiments in air ingress accident conditions

    Energy Technology Data Exchange (ETDEWEB)

    Teemu, Karkele; Ulrika, Backman; Ari, Auvinen; Unto, Tapper; Jorma, Jokiniemi [VTT Technical Research Centre of Finland, Fine Particles (Finland); Riitta, Zilliacus; Maija, Lipponen; Tommi, Kekki [VTT Technical Research Centre of Finland, Accident Management (Finland); Jorma, Jokiniemi [Kuopio Univ., Dept. of Environmental Sciences, Fine Particle and Aerosol Technology Lab. (Finland)

    2007-07-01

    In this study the release, transport and speciation of ruthenium in conditions simulating an air ingress accident was studied. Ruthenium dioxide was exposed to oxidising environment at high temperature (1100-1700 K) in a tubular flow furnace. At these conditions volatile ruthenium species were formed. A large fraction of the released ruthenium was deposited in the tube as RuO{sub 2}. Depending on the experimental conditions 1-26 wt% of the released ruthenium was trapped in the outlet filter as RuO{sub 2} particles. In stainless steel tube 0-8.8 wt% of the released ruthenium reached the trapping bottle as gaseous RuO{sub 4}. A few experiments were carried out, in which revaporization of ruthenium deposited on the tube walls was studied. In these experiments, oxidation of RuO{sub 2} took place at a lower temperature. During revaporization experiments 35-65 % of ruthenium was transported as gaseous RuO{sub 4}. In order to close mass balance and achieve better time resolution 4 experiments were carried out using a radioactive tracer. In these experiments ruthenium profiles were measured. These experiments showed that the most important retention mechanism was decomposition of gaseous RuO{sub 3} into RuO{sub 2} as the temperature of the furnace was decreasing. In these experiments the transport rate of gaseous ruthenium was decreasing while the release rate was constant.

  13. Rhodium enalcarbenoids: direct synthesis of indoles by rhodium(II)-catalyzed [4+2] benzannulation of pyrroles.

    Science.gov (United States)

    Dawande, Sudam Ganpat; Kanchupalli, Vinaykumar; Kalepu, Jagadeesh; Chennamsetti, Haribabu; Lad, Bapurao Sudam; Katukojvala, Sreenivas

    2014-04-14

    Disclosed herein is the design of an unprecedented electrophilic rhodium enalcarbenoid which results from rhodium(II)-catalyzed decomposition of a new class of enaldiazo compounds. The synthetic utility of these enalcarbenoids has been successfully demonstrated in the first transition-metal-catalyzed [4+2] benzannulation of pyrroles, thus leading to substituted indoles. The new benzannulation has been applied to the efficient synthesis of the natural product leiocarpone as well as a potent adipocyte fatty-acid binding protein inhibitor. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Organometallic rhodium(III) and iridium(III) cyclopentadienyl complexes with curcumin and bisdemethoxycurcumin co-ligands.

    Science.gov (United States)

    Pettinari, Riccardo; Marchetti, Fabio; Pettinari, Claudio; Condello, Francesca; Petrini, Agnese; Scopelliti, Rosario; Riedel, Tina; Dyson, Paul J

    2015-12-21

    A series of half-sandwich cyclopentadienyl rhodium(III) and iridium(III) complexes of the type [Cp*M(curc/bdcurc)Cl] and [Cp*M(curc/bdcurc)(PTA)][SO3CF3], in which Cp* = pentamethylcyclopentadienyl, curcH = curcumin and bdcurcH = bisdemethoxycurcumin as O^O-chelating ligands, and PTA = 1,3,5-triaza-7-phosphaadamantane, is described. The X-ray crystal structures of three of the complexes, i.e. [Cp*Rh(curc)(PTA)][SO3CF3] (5), [Cp*Rh(bdcurc)(PTA)][SO3CF3] (6) and [Cp*Ir(bdcurc)(PTA)][SO3CF3] (8), confirm the expected "piano-stool" geometry. With the exception of 5, the complexes are stable under pseudo-physiological conditions and are moderately cytotoxic to human ovarian carcinoma (A2780 and A2780cisR) cells and also to non-tumorigenic human embryonic kidney (HEK293) cells, but lack the cancer cell selectivity observed for related arene ruthenium(II) complexes.

  15. Increased electrochemical properties of ruthenium oxide and graphene/ruthenium oxide hybrid dispersed by polyvinylpyrrolidone

    International Nuclear Information System (INIS)

    Chen, Yao; Zhang, Xiong; Zhang, Dacheng; Ma, Yanwei

    2012-01-01

    Highlights: ► A good dispersion of RuO 2 and graphene/RuO 2 is obtained by polyvinylpyrrolidone. ► PVP as a dispersant also can prevent the formation of metal Ru in graphene/RuO 2 . ► The max capacitances of the hybrid and RuO 2 reach 435 and 597 F g −1 at 0.2 A g −1 . ► The hybrid shows the best rate capability of 39% at 50 A g −1 . - Abstract: Ruthenium oxide has been prepared by a sol–gel method. Polyvinylpyrrolidone (PVP) as an excellent polymeric dispersant is adopted to prevent aggregation of ruthenium oxide. In order to enhance the rate capability of ruthenium oxide, graphene with residual oxygen functional groups as a 2D support has been merged into ruthenium oxide. These oxygen functional groups not only favor to form stable few layers of graphene colloids, but also offer the sites to anchor ruthenium oxide nanoparticles. X-ray diffraction infers that PVP can also hinder the partial formation of Ru by blocking the direct contact between the Ru 3+ and the graphene in the sol–gel synthesis of the hybrids. The ruthenium oxide and the graphene/ruthenium oxide hybrids dispersed by PVP have superior electrochemical properties due to good dispersing and protecting ability of PVP. Especially, the hybrids using PVP exhibit the best rate capability, indicating that the composites possess an advanced structure of combining sheets and particles in nano-scale.

  16. Electronic and magnetic properties of small rhodium clusters

    Energy Technology Data Exchange (ETDEWEB)

    Soon, Yee Yeen; Yoon, Tiem Leong [School of Physics, Universiti Sains Malaysia, 11800 USM, Penang (Malaysia); Lim, Thong Leng [Faculty of Engineering and Technology, Multimedia University, Melaka Campus, 75450 Melaka (Malaysia)

    2015-04-24

    We report a theoretical study of the electronic and magnetic properties of rhodium-atomic clusters. The lowest energy structures at the semi-empirical level of rhodium clusters are first obtained from a novel global-minimum search algorithm, known as PTMBHGA, where Gupta potential is used to describe the atomic interaction among the rhodium atoms. The structures are then re-optimized at the density functional theory (DFT) level with exchange-correlation energy approximated by Perdew-Burke-Ernzerhof generalized gradient approximation. For the purpose of calculating the magnetic moment of a given cluster, we calculate the optimized structure as a function of the spin multiplicity within the DFT framework. The resultant magnetic moments with the lowest energies so obtained allow us to work out the magnetic moment as a function of cluster size. Rhodium atomic clusters are found to display a unique variation in the magnetic moment as the cluster size varies. However, Rh{sub 4} and Rh{sub 6} are found to be nonmagnetic. Electronic structures of the magnetic ground-state structures are also investigated within the DFT framework. The results are compared against those based on different theoretical approaches available in the literature.

  17. Ring Expansion and Rearrangements of Rhodium(II) Azavinyl Carbenes

    Science.gov (United States)

    Selander, Nicklas; Worrell, Brady T.

    2013-01-01

    An efficient, regioselective and convergent method for the ring expansion and rearrangement of 1-sulfonyl-1,2,3-triazoles under rhodium(II)-catalyzed conditions is described. These denitrogenative reactions form substituted enaminone and olefin-based products, which in the former case can be further functionalized to unique products rendering the sulfonyl triazole traceless. PMID:23161725

  18. In vitro permeation of platinum and rhodium through Caucasian skin.

    Science.gov (United States)

    Franken, A; Eloff, F C; Du Plessis, J; Badenhorst, C J; Jordaan, A; Du Plessis, J L

    2014-12-01

    During platinum group metals (PGMs) refining the possibility exists for dermal exposure to PGM salts. The dermal route has been questioned as an alternative route of exposure that could contribute to employee sensitisation, even though literature has been focused on respiratory exposure. This study aimed to investigate the in vitro permeation of platinum and rhodium through intact Caucasian skin. A donor solution of 0.3mg/ml of metal, K2PtCl4 and RhCl3 respectively, was applied to the vertical Franz diffusion cells with full thickness abdominal skin. The receptor solution was removed at various intervals during the 24h experiment, and analysed with high resolution ICP-MS. Skin was digested and analysed by ICP-OES. Results indicated cumulative permeation with prolonged exposure, with a significantly higher mass of platinum permeating after 24h when compared to rhodium. The mass of platinum retained inside the skin and the flux of platinum across the skin was significantly higher than that of rhodium. Permeated and skin retained platinum and rhodium may therefore contribute to sensitisation and indicates a health risk associated with dermal exposure in the workplace. Copyright © 2014 Elsevier Ltd. All rights reserved.

  19. Kinetic method of determination of rhodium trace amounts

    International Nuclear Information System (INIS)

    Kalinina, V.E.; Lyakushina, V.M.; Rybina, A.E.

    1978-01-01

    A catalytic action of rhodium compounds has been detected and studied in the reaction of copper (2) tellurate oxidation with hypobromite to ditelluratocuprate (3) in an alkaline medium. The relationships between the reaction rate and concentrations of copper, tellurate, and hypobromite have been established. The optimum concentrations of the used compounds have been found: Csub(Cu(2))=4x10 -5 g-ion/l; Csub(OHsup(-))=3.0 g-ion/l; Csub(Te)=1.4x10 -2 g-ion/l; Csub(NaBrO)=2.17x10 -3 M. It has been established for chloride, sulphate, and perchlorate solutions of rhodium (3) and (4) that the reaction sensitivity increases by 2-3-fold with a temperature rise from 25-60 deg C. The technique of determining rhodium traces has been developed based on its catalytic action. The low limit of determined rhodium amounts is about 10 -3 mkg/ml

  20. Extraction of fission product rhodium from nitric acid solutions. 1

    International Nuclear Information System (INIS)

    Gorski, B.; Beer, M.; Russ, L.

    1988-01-01

    The extraction of noble metals from nitric acid solutions represents one problem of separating valueable substances from nuclear wastes in nuclear fuel reprocessing. Results of distribution experiments demonstrate the possibility of solvent extraction of rhodium using tertiary amines in presence of nitrite. Even short mixing times realize high distribution coefficients allowing quantitative separation from aqueous solutions. (author)

  1. Rhodium(iii)-catalyzed ortho-olefination of aryl phosphonates.

    Science.gov (United States)

    Chary, Bathoju Chandra; Kim, Sunggak

    2013-09-25

    Rhodium(iii)-catalyzed C-H olefination of aryl phosphonic esters is reported for the first time. In this mild and efficient process, the phosphonic ester group is utilized successfully as a new directing group. In addition, mono-olefination for aryl phosphonates is observed using a phosphonic diamide directing group.

  2. Relativistic effects in iron-, ruthenium-, and osmium porphyrins

    International Nuclear Information System (INIS)

    Liao Mengsheng; Scheiner, Steve

    2002-01-01

    Nonrelativistic and relativistic DFT calculations are performed on four-coordinate metal porphyrins MP and their six-coordinate adducts MP(py) 2 and MP(py)(CO) (py=pyridine) with M=Fe, Ru, and Os. The electronic structures of the MPs are investigated by considering all possible low-lying states with different configurations of nd-electrons. FeP and OsP have a 3 A 2g ground state, while this state is nearly degenerate with 3 E g for RuP. Without relativistic corrections, the ground states of both RuP and OsP would be 3 E g . For the six-coordinate adducts with py and CO, the strong-field axial ligands raise the energy of the M d z 2 -orbital, thereby making the M II ion diamagnetic. The calculated redox properties of MP(py) 2 and MP(py)(CO) are in agreement with experiment. The difference between RuP(py)(CO) and OsP(py)(CO), in terms of site of oxidation, is due to relativistic effects

  3. Rhodium trichloride as a homogeneous catalyst for isotopic hydrogen exchange. Comparison with heterogeneous rhodium in the deuteriation of aromatic compounds and alkanes

    Energy Technology Data Exchange (ETDEWEB)

    Blake, M R; Garnett, J L; Gregor, I K; Hannan, W; Hoa, K; Long, M A [New South Wales Univ., Kensington (Australia)

    1975-12-03

    The use of rhodium trichloride as a homogeneous catalyst for the exchange of aromatic compounds and alkanes is described; comparison of the results with corresponding data from heterogeneous rhodium metal and other homogeneous systems, e.g., platinum and iridium, supports the proposal that specific type of ..pi..-complex mechanisms are common to all such exchange systems.

  4. Contribution to the study of ruthenium fluorides, oxyfluorides and oxides

    International Nuclear Information System (INIS)

    Corbin, Odile.

    1982-08-01

    Studies on the dry processing of spent fuels reveal a poor ruthenium decontamination of plutonium. For a better understanding of this result a study of ruthenium fluorides, oxyfluorides and oxides is carried out here as follows: - bibliographical review; - thermochromatographic identification of the number and nature of compounds formed by fluorination of microquantities of ruthenium; - confirmation of the thermochromatographic results by two other analytical methods: thermogravimetry and infrared spectroscopy [fr

  5. Structure of Rhodium in an Ultradispersed Rhodium/Alumina Catalyst as Studied by EXAFS and Other Technique

    NARCIS (Netherlands)

    Koningsberger, D.C.; Blik, H.F.J. van 't; Zon, J.B.A.D. van; Huizinga, T.; Vis, J.C.; Prins, R.

    1985-01-01

    The structure of rhodium in an ultradispersed 0.57 wt % Rh/y-Al,O, catalyst before and after CO adsorption was studied with extended X-ray absorption fine structure (EXAFS), X-ray photoelectron spectroscopy (XPS), electron spin resonance (ESR), temperature programmed reduction (TPR), CO infrared

  6. Local Electric Field Effects on Rhodium-Porphyrin and NHC-Gold Catalysts

    Science.gov (United States)

    2015-01-05

    AFRL-OSR-VA-TR-2015-0023 (NII) - Local Electric Field Effects on Rhodium -Porphyrin and NHC-Gold Catalysts MATTHEW KANAN LELAND STANFORD JUNIOR UNIV...Effects on Rhodium -Porphyrin and NHC-Gold Catalysts Principal Investigator: Matthew W. Kanan Project Publications: 1. “An Electric Field–Induced Change...Stanford University Grant/Contract Title The full title of the funded effort. (NII)-Local Electric Field Effects on Rhodium -Porphyrin and NHC-Gold

  7. Rhodium self-powered neutron detector's lifetime for korean standard nuclear power plants

    International Nuclear Information System (INIS)

    Yoo, Choon Sung; Kim, Byoung Chul; Park, Jong Ho; Fero, Arnold H.; Anderson, S. L.

    2005-01-01

    A method to estimate the relative sensitivity of a self-powered rhodium detector for an upcoming cycle is developed by combining the rhodium depletion data from a nuclear design with the site measurement data. This method can be used both by nuclear power plant designers and by site staffs of Korean standard nuclear power plants for determining which rhodium detectors should be replaced during overhauls

  8. Ruthenium-Catalyzed Aerobic Oxidation of Amines.

    Science.gov (United States)

    Ray, Ritwika; Hazari, Arijit Singha; Lahiri, Goutam Kumar; Maiti, Debabrata

    2018-01-18

    Amine oxidation is one of the fundamental reactions in organic synthesis as it leads to a variety of value-added products such as oximes, nitriles, imines, and amides among many others. These products comprise the key N-containing building blocks in the modern chemical industry, and such transformations, when achieved in the presence of molecular oxygen without using stoichiometric oxidants, are much preferred as they circumvent the production of unwanted wastes. In parallel, the versatility of ruthenium catalysts in various oxidative transformations is well-documented. Herein, this review focuses on aerobic oxidation of amines specifically by using ruthenium catalysts and highlights the major achievements in this direction and challenges that still need to be addressed. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Determination of total iron in iron ore by x-ray fluorescence analysis using the Compton effect: comparison with others analytical techniques

    International Nuclear Information System (INIS)

    Castilho, M.V. de; Oliveira, R.C.

    1991-01-01

    Total iron in iron ores is determines by X-ray fluorescence analysis method using the compton effect. The Bragg angle is determined for compton no-coherent scattering related to K alpha of Rhodium. This measurement procedure can be used for best fitting of analytical results in X-ray fluorescence, when compared with others methods used for results corrections. (M.V.M.)

  10. Solvent--solvent extraction of rhodium-103m from ruthenium-103 employing a sulfate-carbon tetrachloride medium

    International Nuclear Information System (INIS)

    Epperson, C.E.; Landolt, R.R.; Kessler, W.V.

    1976-01-01

    /sup 103m/Rh in equilibrium with parent 103 Ru was separated in yields of 94 percent of those theoretically possible. 103 Ru chloride was first converted to the tetroxide which was then extracted from an aqueous solution of the equilibrium mixture with carbon tetrachloride

  11. Charge-Delocalized κC-2,N-NHC-Amine Complexes of Rhodium, Iridium, and Ruthenium

    NARCIS (Netherlands)

    Jansen, E.; Lutz, M.; de Bruin, B.; Elsevier, C.J.

    2014-01-01

    The development of a novel set of complexes bearing an NHC-amine ligand (C-NHC-NH2) is described. M(cod) complexes (M = 1r, Rh) and a Ru complex have been synthesized in which three different coordination modes of the ligand were established: monodentate, neutral bidentate, and anionic bidentate.

  12. Palladium, platinum, rhodium, ruthenium, and iridium in chromitites from the Massif du Sud and Tiebaghi massif, New Caledonia.

    Science.gov (United States)

    Page, N.J.; Cassard, D.; Haffty, J.

    1982-01-01

    The massive and disseminated podiform chromitites from 43 mines and other occurrences in the area contain up to (in ppb) Pd 9, Pt 45, Rh 31, Ir 410 and Ru 1300. The possble origins of the chromitites are discussed. -K.A.R.

  13. Interfacial bonding stabilizes rhodium and rhodium oxide nanoparticles on layered Nb oxide and Ta oxide supports.

    Science.gov (United States)

    Strayer, Megan E; Binz, Jason M; Tanase, Mihaela; Shahri, Seyed Mehdi Kamali; Sharma, Renu; Rioux, Robert M; Mallouk, Thomas E

    2014-04-16

    Metal nanoparticles are commonly supported on metal oxides, but their utility as catalysts is limited by coarsening at high temperatures. Rhodium oxide and rhodium metal nanoparticles on niobate and tantalate supports are anomalously stable. To understand this, the nanoparticle-support interaction was studied by isothermal titration calorimetry (ITC), environmental transmission electron microscopy (ETEM), and synchrotron X-ray absorption and scattering techniques. Nanosheets derived from the layered oxides KCa2Nb3O10, K4Nb6O17, and RbTaO3 were compared as supports to nanosheets of Na-TSM, a synthetic fluoromica (Na0.66Mg2.68(Si3.98Al0.02)O10.02F1.96), and α-Zr(HPO4)2·H2O. High surface area SiO2 and γ-Al2O3 supports were also used for comparison in the ITC experiments. A Born-Haber cycle analysis of ITC data revealed an exothermic interaction between Rh(OH)3 nanoparticles and the layered niobate and tantalate supports, with ΔH values in the range -32 kJ·mol(-1) Rh to -37 kJ·mol(-1) Rh. In contrast, the interaction enthalpy was positive with SiO2 and γ-Al2O3 supports. The strong interfacial bonding in the former case led to "reverse" ripening of micrometer-size Rh(OH)3, which dispersed as 0.5 to 2 nm particles on the niobate and tantalate supports. In contrast, particles grown on Na-TSM and α-Zr(HPO4)2·H2O nanosheets were larger and had a broad size distribution. ETEM, X-ray absorption spectroscopy, and pair distribution function analyses were used to study the growth of supported nanoparticles under oxidizing and reducing conditions, as well as the transformation from Rh(OH)3 to Rh nanoparticles. Interfacial covalent bonding, possibly strengthened by d-electron acid/base interactions, appear to stabilize Rh(OH)3, Rh2O3, and Rh nanoparticles on niobate and tantalate supports.

  14. Characterization of self-assembled monolayers on a ruthenium surface

    NARCIS (Netherlands)

    Shaheen, Amrozia; Sturm, Jacobus Marinus; Ricciardi, R.; Huskens, Jurriaan; Lee, Christopher James; Bijkerk, Frederik

    2017-01-01

    We have modified and stabilized the ruthenium surface by depositing a self-assembled monolayer (SAM) of 1-hexadecanethiol on a polycrystalline ruthenium thin film. The growth mechanism, dynamics, and stability of these monolayers were studied. SAMs, deposited under ambient conditions, on

  15. Application of the chemical properties of ruthenium to decontamination processes

    International Nuclear Information System (INIS)

    Fontaine, A.; Berger, D.

    1965-01-01

    The chemical properties of ruthenium in the form of an aqueous solution of the nitrate and of organic tributylphosphate solution are reviewed. From this data, some known examples are given: they demonstrate the processes of separation or of elimination of ruthenium from radioactive waste. (authors) [fr

  16. Volatilization and trapping of ruthenium in high temperature processes

    International Nuclear Information System (INIS)

    Klein, M.; Weyers, C.; Goossens, W.R.A.

    1983-01-01

    This experimental study has indicated the importance of moisture and NO/sub x/ vapors on the volatility and trapping conditions of ruthenium in high temperature processes. Also the process operating conditions have a great influence on the ruthenium behavior in the off-gas purification units. Of particular interest is the observation that the ruthenium release during direct vitrification of simulated high-level liquid waste is a factor of about 5 smaller than the ruthenium release during calcination of this type of waste. Moreover, in the direct vitrification case the ruthenium escapes mostly in the form of an aerosol whereas in the calcination case a volatile ruthenium compound is dominating. Consequently, a specific ruthenium filter is not needed in the off-gas line of a direct vitrifier simplifying in this way the number of units in this off-gas line and avoiding the handling and controlling problems of such a ruthenium filter. In the future, a similar program will be started on the volatility of cesium and antimony in a liquid fed melter and on the technical reliability of the liquid fed melter and its associated gas purification units on a semi-pilote scale under simulated conditions

  17. The biokinetics of ruthenium in the human body

    International Nuclear Information System (INIS)

    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.

  18. Activation of heterogenised rhodium carbonylation catalyst infrared spectroscopic study

    Energy Technology Data Exchange (ETDEWEB)

    Scurrell, M S

    1977-01-01

    In a study related to heterogeneous versions of homogeneous catalysts active in carbonylation of methanol to acetic acid, the catalyst consisted of 1Vertical Bar3< rhodium as rhodium trichloride supported on 13X zeolite and evacuated at 437/sup 0/K. Contacting the catalyst with carbon monoxide caused two bands, at 2025 and 2095 cm/sup -1/, to appear. Contact with a mixture of carbon monoxide and methyl iodide (the usual promoter) caused bands at 2085, 1710, 1440, and 1370 cm/sup -1/ to appear; the first two correspond to the bands at 2062 and 1711 cm/sup -1/ in homogeneous catalysts attributed to the formation of Rh(CH/sup 3/CO)(CO)X/sup 2/I/sup -/. Spectra.

  19. Bioenvironmental aspects of europium and rhodium: a selected bibliography

    International Nuclear Information System (INIS)

    Fore, C.S.; Carrier, R.F.; Talmage, S.S.; Fielden, J.M.; Daniel, E.W.

    1983-09-01

    This bibliography of 428 abstracted references represents a summary of the domestic and foreign literature relevant to the biological and environmental aspects of europium and rhodium. The collected data are organized by current NAEG interests - research highlighting inventory and distribution of the radionulcides, ecological studies covering terrestrial and aquatic systems, and biological studies in both man and animals. Studies that focus directly on research conducted at specific sites (e.g., the Nevada Test Site) are emphasized throughout the bibliography

  20. Diphosphinoazine Rhodium(I) and Iridium(I) Complexes

    Czech Academy of Sciences Publication Activity Database

    Pošta, Martin; Čermák, Jan; Vojtíšek, P.; Císařová, I.

    2006-01-01

    Roč. 71, č. 2 (2006), s. 197-206 ISSN 0010-0765 R&D Projects: GA ČR(CZ) GA203/01/0554; GA ČR(CZ) GA203/99/M037 Institutional research plan: CEZ:AV0Z40720504 Keywords : diphosphinoazines * rhodium complexes * iridium complexes Subject RIV: CC - Organic Chemistry Impact factor: 0.881, year: 2006

  1. Arylation of Rhodium(II) Azavinyl Carbenes with Boronic Acids

    Science.gov (United States)

    Selander, Nicklas; Worrell, Brady T.; Chuprakov, Stepan; Velaparthi, Subash; Fokin, Valery V.

    2013-01-01

    A highly efficient and stereoselective arylation of in situ generated azavinyl carbenes affording 2,2-diaryl enamines at ambient temperatures has been developed. These transition metal carbenes are directly produced from readily available and stable 1-sulfonyl-1,2,3-triazoles in the presence of a rhodium carboxylate catalyst. In several cases, the enamines generated in this reaction can be cyclized into substituted indoles employing copper catalysts. PMID:22913576

  2. Rhodium(II)-catalyzed enantioselective synthesis of troponoids.

    Science.gov (United States)

    Murarka, Sandip; Jia, Zhi-Jun; Merten, Christian; Daniliuc, Constantin-G; Antonchick, Andrey P; Waldmann, Herbert

    2015-06-22

    We report a rhodium(II)-catalyzed highly enantioselective 1,3-dipolar cycloaddition reaction between the carbonyl moiety of tropone and carbonyl ylides to afford troponoids in good to high yields with excellent enantioselectivity. We demonstrate that α-diazoketone-derived carbonyl ylides, in contrast to carbonyl ylides derived from diazodiketoesters, undergo [6+3] cycloaddition reactions with tropone to yield the corresponding bridged heterocycles with excellent stereoselectivity. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Inter-diffusion study of rhodium and tantalum by RBS

    International Nuclear Information System (INIS)

    Nuttens, V.E.; Hubert, R.L.; Bodart, F.; Lucas, S.

    2005-01-01

    The inter-diffusion of rhodium and tantalum has been studied with the goal of synthesizing an alloy acting as a diffusion barrier for high temperature applications. Rh/Ta sandwiched samples were annealed in vacuum at temperature ranging from 800 to 900 deg. C and from 1000 to 1075 deg. C. The diffusion profiles were obtained by RBS. They suggest the formation of two clearly different phases in each temperature range considered

  4. Rhodium coated mirrors deposited by magnetron sputtering for fusion applications

    International Nuclear Information System (INIS)

    Marot, L.; De Temmerman, G.; Oelhafen, P.; Covarel, G.; Litnovsky, A.

    2007-01-01

    Metallic mirrors will be essential components of all optical spectroscopy and imaging systems for ITER plasma diagnostics. Any change in the mirror performance, in particular, its reflectivity, due to erosion of the surface by charge exchange neutrals or deposition of impurities will influence the quality and reliability of the detected signals. Due to its high reflectivity in the visible wavelength range and its low sputtering yield, rhodium appears as an attractive material for first mirrors in ITER. However, the very high price of the raw material calls for using it in the form of a film deposited onto metallic substrates. The development of a reliable technique for the preparation of high reflectivity rhodium films is therefore of the highest importance. Rhodium layers with thicknesses of up to 2 μm were produced on different substrates of interest (Mo, stainless steel, Cu) by magnetron sputtering. Produced films exhibit a low roughness and crystallite size of about 10 nm with a dense columnar structure. No impurities were detected on the surface after deposition. Scratch tests demonstrate that adhesion properties increase with substrate hardness. Detailed optical characterizations of Rh-coated mirrors as well as results of erosion tests performed both under laboratory conditions and in the TEXTOR tokamak are presented in this paper

  5. DNA Mismatch Binding and Antiproliferative Activity of Rhodium Metalloinsertors

    Science.gov (United States)

    Ernst, Russell J.; Song, Hang; Barton, Jacqueline K.

    2009-01-01

    Deficiencies in mismatch repair (MMR) are associated with carcinogenesis. Rhodium metalloinsertors bind to DNA base mismatches with high specificity and inhibit cellular proliferation preferentially in MMR-deficient cells versus MMR-proficient cells. A family of chrysenequinone diimine complexes of rhodium with varying ancillary ligands that serve as DNA metalloinsertors has been synthesized, and both DNA mismatch binding affinities and antiproliferative activities against the human colorectal carcinoma cell lines HCT116N and HCT116O, an isogenic model system for MMR deficiency, have been determined. DNA photocleavage experiments reveal that all complexes bind to the mismatch sites with high specificities; DNA binding affinities to oligonucleotides containing single base CA and CC mismatches, obtained through photocleavage titration or competition, vary from 104 to 108 M−1 for the series of complexes. Significantly, binding affinities are found to be inversely related to ancillary ligand size and directly related to differential inhibition of the HCT116 cell lines. The observed trend in binding affinity is consistent with the metalloinsertion mode where the complex binds from the minor groove with ejection of mismatched base pairs. The correlation between binding affinity and targeting of the MMR-deficient cell line suggests that rhodium metalloinsertors exert their selective biological effects on MMR-deficient cells through mismatch binding in vivo. PMID:19175313

  6. Scalar Relativistic Study of the Structure of Rhodium Acetate

    Directory of Open Access Journals (Sweden)

    Emily E. Edwards

    2004-01-01

    Full Text Available Abstract: Rhodium acetate, related rhodium carboxylates, and rhodium amide complexes are powerful catalysts for carbene chemistry. They readily promote the decomposition of diazo compounds and transfer the resulting carbene to a variety of substrates. There have been several quantum chemistry studies of these compounds, particularly of the acetate. These have all used non-relativistic methods, and all have shown optimized Rh-Rh bond lengths significantly longer than the experimental value. In this study we have surveyed several scalar relativistic DFT methods using Gaussian, Slater, and numerical basis functions (in DGAUSS, ADF, and DMOL3. Several combinations of exchange-correlation functionals with relativistic and non-relativistic effective core potentials (ECP were investigated, as were non-relativistic and all electron scalar relativistic methods. The combination of the PW91 exchange and PW91 correlation functional with the Christiansen-Ermler ECP gave the best results: 2.3918 Å compared to the experimental value of 2.3855±0.0005 Å.

  7. Electrochemical behavior of rhodium(III) in 1-butyl-3-methylimidazolium chloride ionic liquid

    Energy Technology Data Exchange (ETDEWEB)

    Jayakumar, M.; Venkatesan, K.A. [Fuel Chemistry Division, Indira Gandhi Centre for Atomic Research, Kalpakkam 603102 (India); Srinivasan, T.G. [Fuel Chemistry Division, Indira Gandhi Centre for Atomic Research, Kalpakkam 603102 (India)], E-mail: tgs@igcar.gov.in

    2008-02-15

    Electrochemical behavior of rhodium(III) chloride in 1-butyl-3-methylimidazolium chloride was investigated by various electrochemical transient techniques at glassy carbon working electrode at different temperatures (343-373 K). Cyclic voltammogram of rhodium(III) in bmimCl consisted of a surge in reduction current occurring at a potential of -0.48 V (vs. Pd) is due to the reduction of Rh(III) to metallic rhodium and a very small oxidation wave occurring at -0.1 V. Increase of scan rate increases the peak current and remarkably shifts the cathodic peak potential (E{sub p}{sup c1}) in negative direction indicating the irreversibility of electroreduction of rhodium(III). The diffusion coefficient of rhodium(III) in bmimCl ({approx}10{sup -9} cm{sup 2}/s) was determined and the energy of activation ({approx}25 kJ/mol) was deduced from cyclic voltammograms at various temperatures. The cathodic ({tau}{sub r}) and anodic ({tau}{sub o}) transition times were measured from chronopotential transients and the ratio {tau}{sub o}/{tau}{sub r} was found to be 1:7. Electrowinning of rhodium from bmimCl medium results in a deposition of metallic rhodium with lower (20-25%) Faradaic efficiency. A separation factor of rhodium from co-existing noble metal fission product palladium in bmimCl was determined during electrodeposition.

  8. Inhibiting prolyl isomerase activity by hybrid organic-inorganic molecules containing rhodium(II) fragments.

    Science.gov (United States)

    Coughlin, Jane M; Kundu, Rituparna; Cooper, Julian C; Ball, Zachary T

    2014-11-15

    A small molecule containing a rhodium(II) tetracarboxylate fragment is shown to be a potent inhibitor of the prolyl isomerase FKBP12. The use of small molecules conjugates of rhodium(II) is presented as a general strategy for developing new protein inhibitors based on distinct structural and sequence features of the enzyme active site. Copyright © 2014 Elsevier Ltd. All rights reserved.

  9. Energetic driving force of H spillover between rhodium and titania surfaces : a DFT view

    NARCIS (Netherlands)

    Conradie, J.; Gracia, J.; Niemantsverdriet, J.W.

    2012-01-01

    Hydrogen spillover from a rhodium particle, over the most stable (111) surface, to a TiO2 rutile support occurs at low hydrogen coverage because the adsorption energy of H atoms at low hydrogen coverage on rutile is larger than that on rhodium. H diffuses over the support with an activation barrier

  10. The isomerization of allylrhodium intermediates in the rhodium-catalyzed nucleophilic allylation of cyclic imines.

    Science.gov (United States)

    Hepburn, Hamish B; Lam, Hon Wai

    2014-10-20

    Allylrhodium species generated from potassium allyltrifluoroborates can undergo isomerization by 1,4-rhodium(I) migration to give more complex isomers, which then react with cyclic imines to provide products with up to three new stereochemical elements. High enantioselectivities are obtained using chiral diene-rhodium complexes. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. "On-water" rhodium-catalysed hydroformylation for the production of linear alcohols

    NARCIS (Netherlands)

    Diebolt, O.H.; Müller, Christian; Vogt, D.

    2012-01-01

    Optimisation of the reaction conditions for the rhodium-catalysed aldehyde hydrogenation under hydroformylation conditions showed that water used as co-solvent enhances both rate and selectivity towards primary alcohols. One-pot hydroformylation–hydrogenation using rhodium as the only transition

  12. An Extended X-ray Absorption Fine Structure Study of Rhodium-Oxygen Bonds in a Highly Dispersed Rhodium/Aluminum Oxide Catalyst

    NARCIS (Netherlands)

    Koningsberger, D.C.; Zon, J.B.A.D. van; Blik, H.F.J. van 't; Visser, G.J.; Prins, R.; Mansour, A.N.; Sayers, D.E.; Short, D.R.

    1985-01-01

    Analysis of in situ EXAFS measurements on a 2.4 wt % Rh/A120, catalyst, reduced at 473 K after calcination at 623 K, shows the presence of two different rhodium-oxygen bonds (viz. 2.05 and 2.68 A). The oxygen neighbors of rhodium at a distance of 2.05 A disappear after reduction at 673 K. The

  13. Experiments on the behaviour of ruthenium in air ingress accidents

    International Nuclear Information System (INIS)

    Kaerkelae, T.; Backman, Ul; Auvinen, A.; Zilliacus, R.; Lipponen, M.; Kekki, T.; Tapper, U.; Jokiniemi, J.

    2007-03-01

    During routine nuclear reactor operation, ruthenium will accumulate in the fuel in relatively high concentrations. In a severe accident in a nuclear power plant it is possible that air gets into contact with the reactor core. In this case ruthenium may oxidise and form volatile ruthenium species, RuO3 and RuO4, which can be transported into the containment. In order to estimate the amount of gaseous ruthenium species, it is of interest to know, how they are formed and how they behave. In our experiments the formation and transport of volatile ruthenium oxides was studied by exposing RuO2 powder to diverse oxidising atmospheres at a relatively high temperature. Transport of gaseous RuO4 was further investigated by injecting it into the facility in similar conditions. Upon cooling of the gas flow RuO2 aerosol particles were formed in the system. They were removed from the gas stream with plane filters. Gaseous ruthenium species were trapped in 1M NaOH-water solution, which is capable of trapping RuO4 totally. Ruthenium in the solution was filtered for analysis. The determination of ruthenium both in aerosol and in liquid filters was made using instrumental neutron activation analysis (INAA). In order to close the mass balance and to achieve better time resolution seven experiment were carried out using radioactive tracer. In this report, the facility for the ruthenium behaviour study and results from experiments are presented. Preliminary conclusions from the experiments are reported as well. Final conclusions will be made after modelling of the facility is completed in a continuation work of this study. (au)

  14. Experiments on the behaviour of ruthenium in air ingress accidents

    Energy Technology Data Exchange (ETDEWEB)

    Kaerkelae, T.; Backman, Ul; Auvinen, A.; Zilliacus, R.; Lipponen, M.; Kekki, T.; Tapper, U.; Jokiniemi, J. [Technical Research Centre of Finland VTT (Finland)

    2007-03-15

    During routine nuclear reactor operation, ruthenium will accumulate in the fuel in relatively high concentrations. In a severe accident in a nuclear power plant it is possible that air gets into contact with the reactor core. In this case ruthenium may oxidise and form volatile ruthenium species, RuO3 and RuO4, which can be transported into the containment. In order to estimate the amount of gaseous ruthenium species, it is of interest to know, how they are formed and how they behave. In our experiments the formation and transport of volatile ruthenium oxides was studied by exposing RuO2 powder to diverse oxidising atmospheres at a relatively high temperature. Transport of gaseous RuO4 was further investigated by injecting it into the facility in similar conditions. Upon cooling of the gas flow RuO2 aerosol particles were formed in the system. They were removed from the gas stream with plane filters. Gaseous ruthenium species were trapped in 1M NaOH-water solution, which is capable of trapping RuO4 totally. Ruthenium in the solution was filtered for analysis. The determination of ruthenium both in aerosol and in liquid filters was made using instrumental neutron activation analysis (INAA). In order to close the mass balance and to achieve better time resolution seven experiment were carried out using radioactive tracer. In this report, the facility for the ruthenium behaviour study and results from experiments are presented. Preliminary conclusions from the experiments are reported as well. Final conclusions will be made after modelling of the facility is completed in a continuation work of this study. (au)

  15. Characterization of ultrasonic spray pyrolysed ruthenium oxide thin films

    Energy Technology Data Exchange (ETDEWEB)

    Patil, P.S.; Ennaoui, E.A.; Lokhande, C.D.; Mueller, M.; Giersig, M.; Diesner, K.; Tributsch, H. [Hahn-Meitner-Institut Berlin GmbH (Germany). Bereich Physikalische Chemie

    1997-11-21

    The ultrasonic spray pyrolysis (USP) technique was employed to deposit ruthenium oxide thin films. The films were prepared at 190 C substrate temperature and further annealed at 350 C for 30 min in air. The films were 0.22 {mu} thick and black grey in color. The structural, compositional and optical properties of ruthenium oxide thin films are reported. Contactless transient photoconductivity measurement was carried out to calculate the decay time of excess charge carriers in ruthenium oxide thin films. (orig.) 28 refs.

  16. Hazards and control of ruthenium in the nuclear fuel cycle

    International Nuclear Information System (INIS)

    Eichholz, G.G.

    1978-01-01

    A review is presented of present information on the possible hazards of radioruthenium in the nuclear fuel cycle and its behaviour in nuclear operations and in the environment. The subject is dealt with under the following headings: basic chemical and nuclear properties of ruthenium; chemistry (including the ruthenium-nitric acid system, electrochemistry, extraction processes); ruthenium toxicity; generation of radioruthenium (fallout sources, reactor sources, fuel reprocessing operations); waste treatment (cementation and bitumenization, calcining processes, vitrification); movement in the environment (movement of airborne effluents, liquid effluents and the freshwater environment, marine environment, bottom sediments, marine organisms, terrestrial environments, uptake in vegetation and animals); conclusion. (U.K.)

  17. Scaling-resistance of ruthenium- and ruthenium phosphides powders in argon and air

    International Nuclear Information System (INIS)

    Chernogorebko, V.B.; Semenov-Kobzar', A.A.; Kulik, L.Ya.

    1976-01-01

    The thermal stability of ruthenium phosphides in air diminishes as the content of phosphorus in the compound increases. The temperatures at which active oxidation of the powders starts are as follows: Ru-600, Ru 2 P-590, RuP-390, and RuP 2 -270 0 C. The oxidation of phosphorus in the phosphides proceeds in steps. The atoms of phosphorus which are most accessible to oxygen are first oxidated. Phosphorus atoms in the octahedral spaces are oxidated less easily, simultaneously with the oxidation of the ruthenium atoms. When heated in argon, Ru 2 P and RuP fuse congruently at 1,500 and 1,555 0 C respectively, while RuP 2 dissociates at 950 0 C. (author)

  18. Industrial tests of rhodium self-powered detectors: the Golfech 2 experimentation

    International Nuclear Information System (INIS)

    Mourlevat, J.L.; Janvier, D.; Warren, H.D.

    2000-01-01

    In co-operation with Electricite de France (EDF), FRAMATOME has been testing two in-core strings which are equipped with rhodium self-powered detectors (SPDs) in the Golfech Unit 2 reactor (1300 MW, 4L plant) since August 1997. The rhodium SPDs and the strings which support them were designed and built by the US FRAMATOME subsidiary FRAMATOME-COGEMA-FUEL (FCF). The rhodium signals and some other plant parameters are acquired through the use of a specific device designed by the CEA (Commissariat a l'Energie Atomique) and are processed off-line by FRAMATOME. This demonstration test is planned to last until mid-2000. The following presentation is focused on the results obtained during the first demonstration cycle (from 08/97 to 12/98). The tests that have been conducted consist of checking the rhodium depletion and of comparing the rhodium signals to the movable probes. In order to compensate for the delay in the rhodium signals, a deconvolution algorithm has also been tested. Up to now, the results are very satisfactory and a future large scale industrial application is being discussed with the EDF. The main objective of the next experimentation phase is to test - under industrial conditions - a prototype of an on-line monitoring unit known as the Partial In-Core Monitoring System (PIMS). This system will include 16 rhodium in-core strings and will use an on-line 3-D core model. (authors)

  19. Synthesis and electrochemistry of tri- and tetranuclear polypyridine derivations of ruthenium

    International Nuclear Information System (INIS)

    Francis, A.M.A.

    1990-01-01

    The synthesis of clusters of ruthenium is the focus of this work. The electrochemistry of metal cluster derivatives of ruthenium, iron and osmium are reviewed. The ability of these compounds to undergo more than one electron transfer reaction and to act as electron reservoirs is evident. The synthesis and characterisation of a range of polypyridine derivatives of [Ru 3 (CO) 12 ]; [Ru 3 (CO) 10 (napy)]; [Ru 3 (CO) 10 (bipy)]; [Ru 4 H 4 (CO) 12 ]; [Ru 4 H 4 (CO) 8 (bipy) 2 ] and [Ru 4 H 4 (CO) 10 (bipy)] were dealt with. The crystal structures of [Ru 3 (CO) 10 (napy)] and [Ru 4 H 4 (CO) 10 (bipy)] were also determined. The six compounds were fully investigated and a mechanism for their electrochemical reduction was postulated based on their observed experimental data, and that of the relevant compounds. The techniques used are also described and a brief introduction to the actual theory and practise of these techniques is discussed. 132 refs., 33 figs., 22 tabs

  20. Unsaturated carbone and allenylidene ruthenium complexes from alkynes

    International Nuclear Information System (INIS)

    Bozek, Yu.L.; Diznev, P.A.

    1995-01-01

    The author's studies aimed at activation of terminal alkynes by metal complexes, reactivity patterns and selective preparations of unsaturated carbene, allenylidene and cumulenylidene derivatives of (arene)ruthenium complexes are reviewed. 48 refs

  1. Synthesis of ruthenium (III) complexes with benzimidazole derivatives

    International Nuclear Information System (INIS)

    Vyas, P.C.; Chahar, Yogesh K.; Garg, Yajula; Seth, Gita

    2003-01-01

    Complexes of ruthenium with biologically important benzimidazole derivatives, viz. 2-(2'-hydroxyphenyl) benzimidazole (HOPBI), 2-2'- mercaptophenyl) benzimidazole (HSPBI), 2- (2'-hydroxynaphthyl) benzimidazole (HONBI) have been synthesized and characterized. (author)

  2. Supercapacitive performance of hydrous ruthenium oxide (RuO2 ...

    Indian Academy of Sciences (India)

    gel method have been employed to prepare ruthenium oxide thin films. Recently ... the potentiostat (263A EG&G, Princeton Applied Research. Potentiostat). .... is a mixed conductor that conducts protons and electrons in acidic solution (as ...

  3. Methane Steam Reforming Kinetics for a Rhodium-Based Catalyst

    DEFF Research Database (Denmark)

    Jakobsen, Jon Geest; Jakobsen, M.; Chorkendorff, Ib

    2010-01-01

    Methane steam reforming is the key reaction to produce synthesis gas and hydrogen at the industrial scale. Here the kinetics of methane steam reforming over a rhodium-based catalyst is investigated in the temperature range 500-800 A degrees C and as a function of CH4, H2O and H-2 partial pressures....... The methane steam reforming reaction cannot be modeled without taking CO and H coverages into account. This is especially important at low temperatures and higher partial pressures of CO and H-2. For methane CO2 reforming experiments, it is also necessary to consider the repulsive interaction of CO...

  4. A Recyclable Nanoparticle-Supported Rhodium Catalyst for Hydrogenation Reactions

    Directory of Open Access Journals (Sweden)

    Maria Michela Dell’Anna

    2010-05-01

    Full Text Available Catalytic hydrogenation under mild conditions of olefins, unsaturated aldeydes and ketones, nitriles and nitroarenes was investigated, using a supported rhodium complex obtained by copolymerization of Rh(cod(aaema [cod: 1,5-cyclooctadiene, aaema–: deprotonated form of 2-(acetoacetoxyethyl methacrylate] with acrylamides. In particular, the hydrogenation reaction of halonitroarenes was carried out under 20 bar hydrogen pressure with ethanol as solvent at room temperature, in order to minimize hydro-dehalogenation. The yields in haloanilines ranged from 85% (bromoaniline to 98% (chloroaniline.

  5. Hydrogen adsorption on skeletal rhodium-tantalum electrodes-catalysts

    International Nuclear Information System (INIS)

    Tsinstevich, V.M.; Krejnina, N.M.

    1975-01-01

    Skeleton rhodium-tantalic catalyst electrodes with a tantalum mass percentage of 0 to 100 have been obtained by the methodology of Crupp and others. The hydrogen adsorption is studied through the method of removing the galvano-static and potentiodynamic curves of charging in sulfuric acid and potassium hydroxide. It has been discovered that the maximum adsorption ability relatively to the hydrogen can be observed in an alloy with a 5% tantalum contents. The energetic characteristics of the alloys are higher in alkali than in acid

  6. Rhodium in car exhaust tips by total automatic activation analysis

    International Nuclear Information System (INIS)

    Grass, F.; Westphal, G.P.; Lemmel, H.; Sterba, J.

    2007-01-01

    Exhaust systems of modern cars contain catalysts for the reduction of CO, NO x and hydrocarbons. These catalysts are made of ceramic materials with a large surface on which platinum metals catalyse the oxidation. The catalysts contain approximately 2 g of platinum and 0.4 g of rhodium. Recently platinum is being replaced by palladium. During driving the platinum-group elements (PGEs) are expelled from the tip in fine particles and are deposited in the environment. For a projected study of emissions from cars driven on streets and highways it is important to know which elements can be measured by short time activation analysis without any chemical procedure. (author)

  7. Rare earth-ruthenium-magnesium intermetallics

    Energy Technology Data Exchange (ETDEWEB)

    Stein, Sebastian; Kersting, Marcel; Heletta, Lukas; Poettgen, Rainer [Muenster Univ. (Germany). Inst. fuer Anorganische und Analytische Chemie

    2017-07-01

    Eight new intermetallic rare earth-ruthenium-magnesium compounds have been synthesized from the elements in sealed niobium ampoules using different annealing sequences in muffle furnaces. The compounds have been characterized by powder and single crystal X-ray diffraction. Sm{sub 9.2}Ru{sub 6}Mg{sub 17.8} (a=939.6(2), c=1779(1) pm), Gd{sub 11}Ru{sub 6}Mg{sub 16} (a=951.9(2), c=1756.8(8) pm), and Tb{sub 10.5}Ru{sub 6}Mg{sub 16.5} (a=942.5(1), c=1758.3(4) pm) crystallize with the tetragonal Nd{sub 9.34}Ru{sub 6}Mg{sub 17.66} type structure, space group I4/mmm. This structure exhibits a complex condensation pattern of square-prisms and square-antiprisms around the magnesium and ruthenium atoms, respectively. Y{sub 2}RuMg{sub 2} (a=344.0(1), c=2019(1) pm) and Tb{sub 2}RuMg{sub 2} (a=341.43(6), c=2054.2(7) pm) adopt the Er{sub 2}RuMg{sub 2} structure and Tm{sub 3}Ru{sub 2}Mg (a=337.72(9), c=1129.8(4) pm) is isotypic with Sc{sub 3}Ru{sub 2}Mg. Tm{sub 3}Ru{sub 2}Mg{sub 2} (a=337.35(9), c=2671(1) pm) and Lu{sub 3}Ru{sub 2}Mg{sub 2} (a=335.83(5), c=2652.2(5) pm) are the first ternary ordered variants of the Ti{sub 3}Cu{sub 4} type, space group I4/mmm. These five compounds belong to a large family of intermetallics which are completely ordered superstructures of the bcc subcell. The group-subgroup scheme for Lu{sub 3}Ru{sub 2}Mg{sub 2} is presented. The common structural motif of all three structure types are ruthenium-centered rare earth cubes reminicent of the CsCl type. Magnetic susceptibility measurements of Y{sub 2}RuMg{sub 2} and Lu{sub 3}Ru{sub 2}Mg{sub 2} samples revealed Pauli paramagnetism of the conduction electrons.

  8. Atmosphere-Controlled Chemoselectivity: Rhodium-Catalyzed Alkylation and Olefination of Alkylnitriles with Alcohols.

    Science.gov (United States)

    Li, Junjun; Liu, Yuxuan; Tang, Weijun; Xue, Dong; Li, Chaoqun; Xiao, Jianliang; Wang, Chao

    2017-10-17

    The chemoselective alkylation and olefination of alkylnitriles with alcohols have been developed by simply controlling the reaction atmosphere. A binuclear rhodium complex catalyzes the alkylation reaction under argon through a hydrogen-borrowing pathway and the olefination reaction under oxygen through aerobic dehydrogenation. Broad substrate scope is demonstrated, permitting the synthesis of some important organic building blocks. Mechanistic studies suggest that the alkylation product may be formed through conjugate reduction of an alkene intermediate by a rhodium hydride, whereas the formation of olefin product may be due to the oxidation of the rhodium hydride complex with molecular oxygen. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Rhodium-Catalyzed Enantioselective Cyclopropanation of Olefins with N-Sulfonyl 1,2,3-Triazoles

    Science.gov (United States)

    Chuprakov, Stepan; Kwok, Sen Wai; Zhang, Li; Lercher, Lukas; Fokin, Valery V.

    2009-01-01

    N-Sulfonyl 1,2,3-triazoles readily form rhodium(II) azavinyl carbenes, which react with olefins to produce cyclopropanes with excellent diastereo- and enantioselectivity and in high yield. PMID:19928917

  10. First-principles study of hydrogen diffusion in transition metal Rhodium

    International Nuclear Information System (INIS)

    Bao, Wulijibilige; Cui, Xin; Wang, Zhi-Ping

    2015-01-01

    In this study, the diffuse pattern and path of hydrogen in transition metal rhodium are investigated by the first-principles calculations. Density functional theory is used to calculate the system energies of hydrogen atom occupying different positions in rhodium crystal lattice. The results indicate that the most stable position of hydrogen atom in rhodium crystal lattice locates at the octahedral interstice, and the tetrahedral interstice is the second stable site. The activation barrier energy for the diffusion of atomic hydrogen in transition metal rhodium is quantified by determining the most favorable path, i.e., the minimum-energy pathway for diffusion, that is the indirect octahedral-tetrahedral-octahedral (O-T-O) pathway, and the activation energy is 0.8345eV

  11. Rhodium-catalyzed Chemo- and Regioselective Cross-dimerization of Two Terminal Alkynes

    Science.gov (United States)

    Xu, Hua-Dong; Zhang, Ren-Wei; Li, Xiaoxun; Huang, Suyu; Tang, Weiping; Hu, Wen-Hao

    2013-01-01

    Cross-dimerization of terminal arylacetylenes and terminal propargylic alcohols/amides has been achieved in the effect of a rhodium catalyst. This method features high chemo- and regioselectivities rendering convenient and atom economical access to functionalized enynes. PMID:23356993

  12. Crystal structures of fac-tri?chlorido?tris?(tri?methyl?phosphane-?P)rhodium(III) monohydrate and fac-tri?chlorido?tris?(tri?methyl?phosphane-?P)rhodium(III) methanol hemisolvate: rhodium structures that are isotypic with their iridium analogs

    OpenAIRE

    Merola, Joseph S.; Franks, Marion A.

    2015-01-01

    The crystal structures of two solvates of fac-tri-chlorido-tris-(tri-methyl-phosphane-κP)rhodium(III) are reported, i.e. one with water in the crystal lattice, fac-[RhCl3(Me3P)3]·H2O, and one with methanol in the crystal lattice, fac-[RhCl3(Me3P)3]·0.5CH3OH. These rhodium compounds exhibit distorted octahedral coordination spheres at the metal and are isotypic with the analogous iridium compounds previously reported by us [Merola et al. (2013 ▶). Polyhedron, 54, 67-73]. Comparison is made bet...

  13. Ruthenium Sensitizers and Their Applications in Dye-Sensitized Solar Cells

    Directory of Open Access Journals (Sweden)

    Yuancheng Qin

    2012-01-01

    Full Text Available Dye-sensitized solar cells (DSSCs have attracted considerable attention in recent years due to the possibility of low-cost conversion of photovoltaic energy. The DSSCs-based ruthenium complexes as sensitizers show high efficiency and excellent stability, implying potential practical applications. This review focuses on recent advances in design and preparation of efficient ruthenium sensitizers and their applications in DSSCs, including thiocyanate ruthenium sensitizers and thiocyanate-free ruthenium sensitizers.

  14. Modifiers in rhodium catalysts for carbon monoxide hydrogenation: Structure-activity relationships

    Energy Technology Data Exchange (ETDEWEB)

    Bhore, N. A.

    1989-05-01

    This report is aimed at identifying interesting modified rhodium systems and elucidating structure-activity relationships in these systems with the overall goal of understanding the scientific issues in the catalytic conversion of syngas to oxygenates. Specific additives (sodium and molybdenum) are selected based on the scoping experiments. The effect of the additives on supported rhodium catalysts is then investigated. Throughout the investigation, experiments and analysis were performed on real systems instead of ideal systems. 374 refs., 82 figs., 57 tabs.

  15. Rhodium-Catalyzed Linear Codimerization and Cycloaddition of Ketenes with Alkynes

    Directory of Open Access Journals (Sweden)

    Teruyuki Kondo

    2010-06-01

    Full Text Available A novel rhodium-catalyzed linear codimerization of alkyl phenyl ketenes with internal alkynes to dienones and a novel synthesis of furans by an unusual cycloaddition of diaryl ketenes with internal alkynes have been developed. These reactions proceed smoothly with the same rhodium catalyst, RhCl(PPh33, and are highly dependent on the structure and reactivity of the starting ketenes.

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

    Science.gov (United States)

    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…

  17. The effects of primary beam filters on the analysis of rhodium and cadmium using a rhodium target x-ray tube

    International Nuclear Information System (INIS)

    Anzelmo, J.A.; Boyer, B.W.

    1986-01-01

    Since its introduction in 1964, the thin end-window rhodium target x-ray tube has been considered to be an excellent general purpose source of excitation. Heavy elements are efficiently excited by high Bremsstrahlung and the K lines of rhodium while the light elements are excited by the L lines of rhodium. The ability to efficiently excite both heavy and light elements is essential to special applications such as auto catalysts, which are composed of precious metals in a clay-like matrix. Close control of the light elements, including sodium, phosphorous, aluminum and silicon, and the heavy element precious metals, such as rhodium, are necessary to keep operating characteristics and manufacturing expense at desired levels. A quick survey of typical x-ray tube targets shows that some targets are more efficient for light elements while others are more efficient for heavy elements. The few general purpose x-ray tubes that are available have characteristic lines which overlap on elements to be determined. The rhodium target, which is a good excitation source for most of the elements mentioned, contains line overlaps on cadmium (RHKB) and rhodium (RHKA). When using a sequential wavelength dispersive XRF spectrometer, the characteristic lines of the tube scattered from the sample can be removed by a programmable primary beam filter having an absorption edge just higher in wavelength than the wavelengths to be removed. The thickness and composition of the filter, as well as the choice of KV and MA, will determine the operating parameter necessary to achieve the optimum precision and lowest limits of detection. For this study, synthetic samples are made up using Kaolin as the matrix

  18. Synthesis and characterization of rhodium sulfide nanoparticles and thin films

    International Nuclear Information System (INIS)

    Sosibo, Ndabenhle M.; Revaprasadu, Neerish

    2008-01-01

    The synthesis and characterization of a rhodium complex, [Rh(S 2 CNEt 2 ) 2 ] is described. The complex was thermolysed at a high temperature (280 deg. C) in the presence of capping agent, hexadecylamine (HDA) to form Rh 2 S 3 nanoparticles. Rod-shaped Rh 2 S 3 nanoparticles with an average length of 26.7 nm and an average breadth of 7.8 nm were synthesized. The complex was also used as a single molecule precursor for the deposition of Rh 2 S 3 thin films on a glass substrate at 350 deg. C and 450 deg. C using the Aerosol Assisted Chemical Vapour Deposition (AACVD) technique. The resultant thin films showed temperature dependent morphologies and showed (0 2 2), (4 1 1) and (6 1 1) lattice planes characteristic of to the orthorhombic Rh 2 S 3 phase. X-ray diffraction and scanning electron microscopy techniques were used to characterize the films

  19. Towards PSII analogs driven by ruthenium photophysics

    International Nuclear Information System (INIS)

    Olsson, Jerry

    2002-01-01

    A number of model complexes have been prepared in an attempt to develop models for photosystem II (PSII) in green plants. As replacement for the chlorophyll photosensitizer, we have used Ru(ll) tris-2,2-bipyridyl or Ru(ll) bis-2,2';6',2 - terpyridyl complexes linked to a pendant 2,2'-bipyridyl or 2,2';6',2''-terpyridyl moieties via spacers of varying lengths. Manganese (ll) has been covalently linked to the pendant 2,2'-bipyridyl /2,2';6',2''-terpyridyl moieties. The use of different ruthenium centres and spacers has made it possible to make assumptions about the way and how easily manganese is coordinated through self-assembly to the pendant 2,2'-bipyridyl or 2,2';6',2''-terpyridyl groups. Several polynuclear complexes containing a photoactive centre (Ru(ll) tris-2,2'-bipyridine or Ru(ll) bis-2,2';6',2''-terpyridine) or other metal ions (Co 2+ , Fe 2+ , Mn 2= ) have been prepared and characterised. The main work has been focused on organic synthesis and characterisation of polypyridine ligands and coordinated to different metal centres. The complexes have been investigated electrochemically and photophysically. Several new phenol-based ligands have been prepared by organic synthetic methods and characterised by various different methods. (author)

  20. Reactions of dihydridotetrakis(triphenylphosphine)ruthenium(II) with olefins and isolation of new ruthenium-olefin complexes

    International Nuclear Information System (INIS)

    Komiya, Sanshiro; Yamamoto, Akio

    1976-01-01

    Dihydridotetrakis(triphenylphosphine)ruthenium (II), RuH 2 (PPh 3 ) 4 , reacts with olefins (ethylene, propylene, stylene and butadiene) to give olefin-coordinated complexes of the type, Ru(olefin)(PPh 3 ) 3 and equimolar amounts of their hydrogenation products per mol of the dihydride complex. The olefin coordinated with ruthenium can be exchanged with other olefins. Olefin-coordinated complexes easily react with molecular hydrogen to afford tetrahydridotris(triphenylphosphine)ruthenium, RuH 4 (PPh 3 ) 3 , releasing alkane at room temperature, Under hydrogen atmosphere catalytic hydrogenation of the olefins smoothly takes place with RuH 2 (PPh 3 ) 4 . (Ethylene)tris(triphenylphosphine)ruthenium(0) reacts with methyl iodide to give propylene and a trace of butadiene along with methane, ethylene, and small amounts of ethane and butenes. The formation of propylene suggests that oxidative addition involving cleavage of the C-H bond of ethylene to ruthenium giving a hydridovinyl complex may be taking place. Reactions of Ru(C 2 H 4 )(PPh 3 ) 3 with methyl-d 3 iodide and ethyl iodide, and of Ru(C 3 H 6 )(PPh 3 ) 3 with methyl iodide were examined to test the generality of this type of reaction. The reaction of Ru(C 2 H 4 )(PPh 3 ) 3 with CD 3 I released CD 4 and CD 2 H 2 together with CD 3 H suggesting the involvement of α-hydrogen abstraction. (auth.)

  1. Ruthenium Dioxide Catalysts for the Selective Oxidation of Benzylamine to Benzonitrile: Investigating the Effect of Ruthenium Loading on Physical and Catalytic Properties

    DEFF Research Database (Denmark)

    Nordvang, Emily Catherine; Schill, Leonhard; Riisager, Anders

    2017-01-01

    The oxidative dehydrogenation of benzylamine to benzonitrile was studied in batch and continuous flow processes using ruthenium dioxide catalysts with varying ruthenium loadings. Increased conversions were observed in the continuous flow process compared with the batch process (up to 100% in the ......The oxidative dehydrogenation of benzylamine to benzonitrile was studied in batch and continuous flow processes using ruthenium dioxide catalysts with varying ruthenium loadings. Increased conversions were observed in the continuous flow process compared with the batch process (up to 100......% in the flow process compared with up to 92% in the batch process), with increased selectivity to benzonitrile (82 and 65%, respectively) and benzonitrile yields (84 and 58%, respectively). The major by-product was N-benzylidenebenzylamine. The ruthenium loading in the catalyst was successfully optimised...... and the most active catalyst had a ruthenium loading of 2.5-3.5 wt%....

  2. Hydrothermal synthesis and physicochemical properties of ruthenium(0) nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    Dikhtiarenko, A., E-mail: dikhtiarenkoalla@uniovi.es [Departamento de Quimica Organica e Inorganica, Universidad de Oviedo - CINN, 33006 Oviedo (Spain); Khainakov, S.A.; Garcia, J.R.; Gimeno, J. [Departamento de Quimica Organica e Inorganica, Universidad de Oviedo - CINN, 33006 Oviedo (Spain); Pedro, I. de; Fernandez, J. Rodriguez [CITIMAC, Facultad de Ciencias, Universidad de Cantabria, 39005 Santander (Spain); Blanco, J.A. [Departamento de Fisica, Universidad de Oviedo, 33007 Oviedo (Spain)

    2012-09-25

    Highlights: Black-Right-Pointing-Pointer Ruthenium nanoparticles were synthesized by hydrothermal technique. Black-Right-Pointing-Pointer The average size of the nanoparticles are depend on the reducing agent used. Black-Right-Pointing-Pointer The magnetic response seems to be dominated by a paramagnetic contribution characteristic of the band electronic magnetism of the ruthenium(0) nanoparticles. - Abstract: The synthesis of ruthenium nanoparticles in hydrothermal conditions using mild reducing agents (succinic acid, ascorbic acid and sodium citrate) is reported. The shape of the nanoparticles depends on the type of the reducing agent, while the size is more influenced by the pH of the medium. The magnetic response seems to be dominated by a paramagnetic contribution characteristic of the band electronic magnetism of the nanoparticles.

  3. Confinement of ruthenium oxides volatilized during nuclear fuels reprocessing

    International Nuclear Information System (INIS)

    Maas, E.T. Jr.; Longo, J.M.

    1980-01-01

    While many materials have been suggested and employed as trapping agents for gaseous oxides of fission product ruthenium volatilized during nuclear fuels reprocessing, none that is known to form thermodynamically stable compounds with rutheniunm has been utilized. We have employed alkaline earth metal compounds for this purpose because of their ability to form stable mixed metal oxide phases with ruthenium. Results of experiments in which RuO 4 was volatilized from either a solid source (RuO 2 .xH 2 O) or from solution [Ru(NO)(NO 3 ) 3 ] in HNO 3 and passed through beds of alkaline earth metal carbonates and calcium oxide held at 600 to 750 0 C have demonstrated that compounds of formulation MRuO 3 (M = calcium, strontium, barium) are formed. Under oxidizing conditions, these materials exist as stable ceramic phases, whereas under reducing conditions, they are transformed into intimate mixtures of the alkaline earth metal oxide and nonvolatile ruthenium metal

  4. Device for separating ruthenium ion from spent fuel material

    International Nuclear Information System (INIS)

    Izumida, Tatsuo; Sasahira, Akira; Ozawa, Yoshihiro; Kawamura, Fumio.

    1988-01-01

    Purpose: To separate plutonium ions efficiently and selectively from organic solvent containing tributyl phosphate used in the main step of reprocessing process. Constitution: The device comprises, as the main constituent factor, a liquid-liquid contact device for bringing not water soluble organic solvent into contact with a nitric acid solution of spent fuel substances and a liquid-liquid contact-separation device for bringing an organic solvent solution containing spent fuel substances separated with nitric acid into contact again with nitric acid. Then, a device is disposed between two liquid-liquid contact devices for staying ruthenium ions and organic solvent for a sufficient time. In this way, ruthenium ions in the organic solvent containing butyl phosphate are gradually converted into complex compounds combined with tributyl phosphate thereby enabling to separate ruthenium ions efficiently and remarkably reduce the corrosion of equipments. (Horiuchi, T.)

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

    International Nuclear Information System (INIS)

    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 2 , RuO 4 , and possibly RuO 3 (thin film), and known hydroxides/hydrated oxides (all amorphous) are Ru(OH) 3 . H 2 O, RuO 2 . 2H 2 O, RuO 2 . H 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 2 (cr) formation. Characterized aqueous species of ruthenium include RuO 4 (which slowly oxidizes water and which dissociates as a weak acid), RuO 4 - and RuO 4 2- (which probably contain lesser amounts of RuO 3 (OH) 2 - and RuO 3 (OH) 2 2- , respectively, and other species), Ru(OH) 2 2+ , Ru 4 (OH) 12 4+ , Ru(OH) 4 , Ru 3+ , Ru(OH) 2+ , Ru(OH) 2 + , Ru 2+ , and some hydroxytetramers with formal ruthenium valences of 3.75 ≥ Z ≥ 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

  6. Method of removing clogging materials due to ruthenium precipitates and sealing them in device

    International Nuclear Information System (INIS)

    Hoshikawa, Tadahiro; Sasahira, Akira.

    1994-01-01

    In a facility, such as a reprocessing facility, for processing a solution containing a great amount of ruthenium, precipitates due to evaporated ruthenium and cooled NO x are brought into contact with each other to decompose the precipitates due to the evaporated ruthenium. Precipitates due to ruthenium evaporated from the solution are reacted with cooled NO x , and the precipitates of ruthenium are decomposed and returned to the solution in the form of extremely fine particles together with recycling flow from the inner wall of the device. Since the precipitates of ruthenium returned to the solution are stable, they are no more evaporated and precipitated on the inner wall of the device. In the solution processing device having a possibility of clogging, clogging can be prevented and the precipitates of ruthenium can be sealed by decomposing them. (T.M.)

  7. A study on the sensitivity depletion laws for rhodium self-powered neutron detectors

    International Nuclear Information System (INIS)

    Kim, Gil Gon

    1999-02-01

    The rhodium self-powered neutron detectors (SPND) in a reactor core provide the operator with the on-line 3-dimensional nuclear power distribution. The signal produced by rhodium SPND is interpreted into the local neutron flux by using a sensitivity depletion law and the local neutron flux is interpreted into the local power by using a power conversion factor. This work on the sensitivity depletion laws for rhodium self-powered neutron detectors (SPND) is performed to improve the uncertainty of the sensitivity depletion law used in ABB-CE reactors employing a rhodium SPND and to develop a calculational tool for providing the sensitivity depletion laws to interpret the signal of the newly designed rhodium SPND into the local neutron flux. The calculational tools for a time dependent neutron flux distribution in the rhodium emitter during depletion and for a time dependent beta escape probability that a beta generated in the emitter is escaped into the collector were developed. Due to the cost, the exposure to the radiation, and the longer fuel cycle, there is a strong incentive that the loading density of an in-core instrumentation is reduced and the lifetime of the detector is lengthened. These objectives can be achieved by reducing the uncertainty which is amplified as it depletes. The calculational tools above provide the sensitivity depletion law and show the reduction of the uncertainty to about 1 % in interpreting the signal into the local neutron flux compared to the method employed by ABB-CE. The reduction in the uncertainty of 1 % in interpreting the signal into the local neutron flux is equivalent to the reduction in the uncertainty of 1 % or more in interpreting the signal into the local power and to the extension of the lifetime of rhodium SPND to about 10 % as reported by ABB-CE

  8. Ruthenium oxide resistors as sensitive elements of composite bolometers

    International Nuclear Information System (INIS)

    Benassai, M.; Gallinaro, G.; Gatti, F.; Siri, S.; Vitale, S.

    1988-01-01

    Bolometers for particle detection made with Ruthenium oxide thermistors could be produced by means of a simple technique on a variety of different materials as substrata. Preliminary results on alpha particle detection with devices realized using commercial RuO 2 thick film resistor (Tfr) are considered positive for devices operating between. 3 and .1 k and determined us to pursue further the idea. Ruthenium oxide resistors on sapphire at the moment are being prepared. The behaviour of these devices st temperatures lower than .1 k has to be investigated in more detail

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

    Energy Technology Data Exchange (ETDEWEB)

    Coloma Ribera, R., E-mail: r.colomaribera@utwente.nl; Kruijs, R. W. E. van de; Yakshin, A. E.; Bijkerk, F. [MESA+ Institute for Nanotechnology, University of Twente, P.O. Box 217, 7500 AE Enschede (Netherlands)

    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.

  10. Development of a method for analyzing traces of ruthenium in plant materials and determination of the transfer factors soil/plant for ruthenium compounds from reprocessing plants

    International Nuclear Information System (INIS)

    Blasius, E.; Huth, R.; Neumann, W.

    1988-01-01

    In an artificial humous and sandy soil spiked with 106 Ru as RuO 2 and RuCl 3 , pasture grass was grown under artificial illumination in our laboratory. The amounts of ruthenium taken up by the plants were determined by γ-spectrometry. For open-air investigations with pasture grass, wheat and potatoes inactive ruthenium(III) chloride and ruthenium nitrosylchloride were used. Ruthenium was determined by electrothermal atomic absorption spectrometry (ETAAS) after destroying the organic material and concentrating the solution. The concentration and chemical form of the ruthenium exert an unimportant influence on the transfer factor. For the pasture-grass, the stems of wheat and the weed of potatoes it amounts to 0.00005 to 0.0015, for the ear of wheat to about 0.00005. In peeled potatoes there was no ruthenium detectable, therefore the limit of detection leads to a transfer factor ≤ 0.00001. So it is evident that ruthenium is little available for the roots of the plants. In the event of an accident in a nuclear plant the uptake of radioactive ruthenium by roots has only negligible radioecological consequences. This applies even if 50 years of ruthenium enrichment in the soil are assumed. (orig./RB)

  11. Application of the chemical properties of ruthenium to decontamination processes; L'application des proprietes chimiques du ruthenium a des procedes de decontamination

    Energy Technology Data Exchange (ETDEWEB)

    Fontaine, A.; Berger, D. [Commissariat a l' Energie Atomique, Centre de Production de Plutonium, Marcoule (France). Centre d' Etudes Nucleaires

    1965-07-01

    The chemical properties of ruthenium in the form of an aqueous solution of the nitrate and of organic tributylphosphate solution are reviewed. From this data, some known examples are given: they demonstrate the processes of separation or of elimination of ruthenium from radioactive waste. (authors) [French] Les proprietes chimiques du ruthenium en solutions aqueuses nitriques et en solutions organiques de tributylphosphate, sont passees en revue. A partir de ces donnees, quelques exemples connus sont cites: ils exposent des procedes de separation ou d'elimination du ruthenium de dechets radioactifs. (auteurs)

  12. Application of the chemical properties of ruthenium to decontamination processes; L'application des proprietes chimiques du ruthenium a des procedes de decontamination

    Energy Technology Data Exchange (ETDEWEB)

    Fontaine, A; Berger, D [Commissariat a l' Energie Atomique, Centre de Production de Plutonium, Marcoule (France). Centre d' Etudes Nucleaires

    1965-07-01

    The chemical properties of ruthenium in the form of an aqueous solution of the nitrate and of organic tributylphosphate solution are reviewed. From this data, some known examples are given: they demonstrate the processes of separation or of elimination of ruthenium from radioactive waste. (authors) [French] Les proprietes chimiques du ruthenium en solutions aqueuses nitriques et en solutions organiques de tributylphosphate, sont passees en revue. A partir de ces donnees, quelques exemples connus sont cites: ils exposent des procedes de separation ou d'elimination du ruthenium de dechets radioactifs. (auteurs)

  13. Ruthenium catalysts bearing a benzimidazolylidene ligand for the metathetical ring-closure of tetrasubstituted cycloolefins

    KAUST Repository

    Borguet, Yannick

    2015-01-01

    © The Royal Society of Chemistry. Deprotonation of 1,3-di(2-tolyl)benzimidazolium tetrafluoroborate with a strong base afforded 1,3-di(2-tolyl)benzimidazol-2-ylidene (BTol), which dimerized progressively into the corresponding dibenzotetraazafulvalene. The complexes [RhCl(COD)(BTol)] (COD is 1,5-cyclooctadiene) and cis-[RhCl(CO)2(BTol)] were synthesized to probe the steric and electronic parameters of BTol. Comparison of the percentage of buried volume (%VBur) and of the Tolman electronic parameter (TEP) of BTol with those determined previously for 1,3-dimesitylbenzimidazol-2-ylidene (BMes) revealed that the two N-heterocyclic carbenes displayed similar electron donicities, yet the 2-tolyl substituents took a slightly greater share of the rhodium coordination sphere than the mesityl groups, due to a more pronounced tilt. The anti,anti conformation adopted by BTol in the molecular structure of [RhCl(COD)(BTol)] ensured nonetheless a remarkably unhindered access to the metal center, as evidenced by steric maps. Second-generation ruthenium-benzylidene and isopropoxybenzylidene complexes featuring the BTol ligand were obtained via phosphine exchange from the first generation Grubbs and Hoveyda-Grubbs catalysts, respectively. The atropisomerism of the 2-tolyl substituents within [RuCl2(=CHPh)(PCy3)(BTol)] was investigated by using variable temperature NMR spectroscopy, and the molecular structures of all four possible rotamers of [RuCl2(=CH-o-OiPrC6H4)(BTol)] were determined by X-ray crystallography. Both complexes were highly active at promoting the ring-closing metathesis (RCM) of model α,ω-dienes. The replacement of BMes with BTol was particularly beneficial to achieve the ring-closure of tetrasubstituted cycloalkenes. More specifically, the stable isopropoxybenzylidene chelate enabled an almost quantitative RCM of two challenging substrates, viz., diethyl 2,2-bis(2-methylallyl)malonate and N,N-bis(2-methylallyl)tosylamide, within a few hours at 60°C.

  14. Electro-volatilization of ruthenium in nitric medium: influences of ruthenium species nature and models solutions composition

    International Nuclear Information System (INIS)

    Mousset, F.

    2004-12-01

    Ruthenium is one of the fission products in the reprocessing of irradiated fuels that requires a specific processing management. Its elimination, upstream by the PUREX process, has been considered. A process, called electro-volatilization, which take advantage of the RuO 4 volatility, has been optimised in the present study. It consists in a continuous electrolysis of ruthenium solutions in order to generate RuO 4 species that is volatilized and easily trapped. This process goes to satisfying ruthenium elimination yields with RuNO(NO 3 ) 3 (H 2 O) 2 synthetic solutions but not with fuel dissolution solutions. Consequently, this work consisted in the speciation studies of dissolved ruthenium species were carried out by simulating fuel solutions produced by hot acid attack of several ruthenium compounds (Ru(0), RuO 2 ,xH 2 O, polymetallic alloy). In parallel with dissolution kinetic studies, the determination of dissolved species was performed using voltammetry, spectrometry and spectro-electrochemistry. The results showed the co-existence of Ru(IV) and RuNO(NO 2 ) 2 (H 2 O) 3 . Although these species are different from synthetic RuNO(NO 3 ) 3 (H 2 O) 2 , their electro-oxidation behaviour are similar. The electro-volatilization tests of these dissolution solutions yielded to comparable results as the synthetic RuNO(NO 3 ) 3 (H 2 O) 2 solutions. Then, complexity increase of models solutions was performed by in-situ generation of nitrous acid during ruthenium dissolution. Nitrous acid showed a catalytic effect on ruthenium dissolution. Its presence goes to quasi exclusively RuNO(NO 2 ) 2 (H 2 O) 3 species. It is also responsible of the strong n-bond formation between Ru 2+ and NO + . In addition, it has been shown that its reducing action on RuO 4 hinders the electro-volatilization process. Mn 2+ and Ce 3+ cations also reveal, but to a lesser extent, an electro-eater behaviour as well as Pu 4+ and Cr 3+ according to the thermodynamics data. These results allow one to

  15. Electrodeposition of carrier-free 57Co on rhodium as an approach to the preparation of Moessbauer sources

    International Nuclear Information System (INIS)

    Cieszykowska, Izabela; ZoLtowska, MaLgorzata; Mielcarski, MieczysLaw

    2011-01-01

    Electrodeposition of carrier-free 57 Co on a rhodium matrix as the first step of preparing Moessbauer sources was studied. To optimize the plating parameters, the influences of current density, volume and pH of the electrolyte solution, shape, thickness, and surface area of the rhodium cathode, mode of cathode pretreatment, concentration of 57 Co and duration of electrolysis were investigated.

  16. Transient-response study of CO insertion into CHx surface intermediates on a vanadium-promoted rhodium catalyst

    NARCIS (Netherlands)

    Koerts, T.; Santen, van R.A.

    1992-01-01

    The rate of CO insertion into surface CHx species was investigated on silica-supported rhodium and rhodium-vanadium catalysts. Isotopically labelled 13CO was used in a transient kinetic experiment under steady-state conditions. A main conclusion is that vanadium promotion does not affect the rate of

  17. Hydroformylation of methyl oleate catalyzed by rhodium complexes; Hidroformilacao do oleato de metila catalisada por complexos de rodio

    Energy Technology Data Exchange (ETDEWEB)

    Mendes, Ana Nery Furlan [Universidade Federal do Espirito Santo (UFES), Sao Mateus, ES (Brazil). Centro Universitario Norte do Espirito Santo. Dept. de Ciencias Naturais; Rosa, Ricardo Gomes da; Gregorio, Jose Ribeiro, E-mail: jrg@iq.ufrgs.br [Universidade Federal do Rio Grande do Sul (UFRGS), Porto Alegre, RS (Brazil). Inst. de Quimica

    2012-07-01

    In this work, we describe the hydroformylation of methyl oleate catalyzed by several rhodium complexes. Parameters including total pressure, phosphorous/rhodium and CO/H{sub 2} ratio, temperature and phosphorous ligands were scanned. Total conversion of the starting double bonds was achieved while maintaining excellent selectivity in aldehydes. (author)

  18. Interaction between water-soluble rhodium complex RhCl(CO)(TPPTS)₂ and surfactants probed by spectroscopic methods.

    Science.gov (United States)

    Zhou, Li-Mei; Guo, Cai-Hong; Fu, Hai-Yan; Jiang, Xiao-Hui; Chen, Hua; Li, Rui-Xiang; Li, Xian-Jun

    2012-07-01

    The interactions of rhodium complex RhCl(CO)(TPPTS)(2) [TPPTS=P(m-C(6)H(4)SO(3)Na)(3)] with cationic, nonionic, and anionic surfactants have been investigated by UV-vis, fluorescence and (1)H NMR measurements. The presence of four different species of RhCl(CO)(TPPTS)(2) in cationic cetyltrimethylammonium (CTAB) solution has been demonstrated: free rhodium complex, rhodium complex bound to CTAB monomer, rhodium complex bound to CTAB premicelles, rhodium complex bound to CTAB micelles. The spectroscopy data show that RhCl(CO)(TPPTS)(2) can adsorb on the interface of cationic CTAB micelles by strong electrostatic attraction, weakly bind to the nonionic polyoxyethylene (20) sorbitan monolaurate (Tween 20) micelles by hydrophobic interaction, and does not interact with anion sodium dodecyl sulfate (SDS) micelles due to the strong electrostatic repulsion. Copyright © 2012 Elsevier B.V. All rights reserved.

  19. Rhodium mediated bond activation: from synthesis to catalysis

    Energy Technology Data Exchange (ETDEWEB)

    Ho, Hung-An [Iowa State Univ., Ames, IA (United States)

    2012-01-01

    Recently, our lab has developed monoanionic tridentate ligand, ToR, showing the corresponding coordination chemistry and catalyst reactivity of magnesium, zirconium, zinc and iridium complexes. This thesis details synthetic chemistry, structural study and catalytic reactivity of the ToR-supported rhodium compounds. Tl[ToR] has been proved to be a superior ligand transfer agent for synthesizing rhodium complexes. The salt metathesis route of Tl[ToM] with [Rh(μ-Cl)(CO)]2 and [Rh(μ- Cl)(COE)]2 gives ToMRh(CO)2 (2.2) and ToMRhH(β3-C8H13) (3.1) respectively while Tl[ToM] with [Rh(μ-Cl)(CO)]2 affords ToPRh(CO)2 (2.3). 2.2 reacts with both strong and weak electrophiles, resulting in the oxazoline N-attacked and the metal center-attacked compounds correspondingly. Using one of the metal center-attacked electrophiles, 2.3 was demonstrated to give high diastereoselectivity. Parallel to COE allylic C-H activation complex 3.1, the propene and allylbenzene allylic C-H activation products have also been synthesized. The subsequent functionalization attempts have been examined by treating with Brønsted acids, Lewis acids, electrophiles, nucleophiles, 1,3-dipolar reagents and reagents containing multiple bonds able to be inserted. Various related complexes have been obtained under these conditions, in which one of the azide insertion compounds reductively eliminates to give an allylic functionalization product stoichiometrically. 3.1 reacts with various primary alcohols to give the decarbonylation dihydride complex ToMRh(H)2CO (4.1). 4.1 shows catalytic reactivity for primary alcohol decarbonylation under a photolytic condition. Meanwhile, 2.2 has been found to be more reactive than 4.1 for catalytic alcohol decarbonylation under the same condition. Various complexes and primary

  20. The trans influence in mer-trichloronitridobis(triphenylarsine)ruthenium(VI)

    DEFF Research Database (Denmark)

    Magnussen, Magnus; Bendix, Jesper

    2003-01-01

    The title compound, mer-[RuCl(3)N(C(18)H(15)As)(2)], is the first structurally characterized example of a nitride complex in which ruthenium is six-coordinated to monodentate ligands only. The Ru[triple-bond]N bond length [1.6161 (15) A] is relatively long, and the trans influence of the nitride...

  1. Polystyrene with pendant mixed functional ruthenium(II)-terpyridine complexes

    NARCIS (Netherlands)

    Heller, M.; Schubert, U.S.

    2002-01-01

    A vinyl substituted 2,2:6,2-terpyridine and a mixed, bifunctional ruthenium(II)-terpyridine complex bearing a vinyl and a hydroxymethyl group are utilized as comonomers for radical copolymerization with styrene. The resulting polymers are characterized by means of UV-vis spectroscopy and gel

  2. Electroerosion method for preparation of saturated solutions of ruthenium hydroxochloride

    International Nuclear Information System (INIS)

    Mikhalev, V.A.; Andrianov, G.A.; Zhadanov, B.V.; Ryazanov, A.I.

    1987-01-01

    A pilot plant for carrying out electroerosion processes using pulse current of high unit power is developed. The solution process of metallic Ru in concentrated HCl is investigated. The possibility of preparation of ruthenium hydroxochloride solutions of 300 g/l concentration is established; it gives the possibility of Ru solution under conditions similar to the process of salting out

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

    International Nuclear Information System (INIS)

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

    2016-01-01

    Highlights: • We bring out a new method to synthesize noble metal phosphides at low temperature. • Both RuP and Ru_2P were synthesized using triphenylphosphine as phosphorus sources. • Ru_2P was the better active phase for HDS than RuP and metal Ru. • RuP/SiO_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_2-thermal treatment method using triphenylphosphine (TPP) as phosphorus sources at low temperatures. Two phosphides RuP and Ru_2P 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_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_2P 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.

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

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Qingfang [Tianjin Key Laboratory of Water Environment and Resources, Tianjin Normal University, Tianjin 300387 (China); Key Laboratory of Advanced Energy Materials Chemistry (MOE), Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), College of Chemistry, Nankai University, Tianjin 300071 (China); Wang, Zhiqiang [Tianjin Key Laboratory of Water Environment and Resources, Tianjin Normal University, Tianjin 300387 (China); Yin, Xiaoqian; Zhou, Linxi [Key Laboratory of Advanced Energy Materials Chemistry (MOE), Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), College of Chemistry, Nankai University, Tianjin 300071 (China); Zhang, Minghui, E-mail: zhangmh@nankai.edu.cn [Key Laboratory of Advanced Energy Materials Chemistry (MOE), Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), College of Chemistry, Nankai University, Tianjin 300071 (China); College of Chemistry and Environmental Science, Kashgar University, Kashgar 844006 (China)

    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.

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

    NARCIS (Netherlands)

    Coloma Ribera, R.; van de Kruijs, Robbert Wilhelmus Elisabeth; Yakshin, Andrey; Bijkerk, Frederik

    2015-01-01

    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

  6. An XPS study on ruthenium compounds and catalysts

    International Nuclear Information System (INIS)

    Bianchi, C.L.; Ragaini, V.; Cattania, M.G.

    1991-01-01

    The binding energy (BE) of the relevant peaks of several ruthenium compounds have been measured with a monochromatic small spot XPS. The BE of the 3d 5/2 level of ruthenium is in the range 279.91-282.88 eV. The variation of BE is due either to the variation of the oxidation state or to the different counter-ion. A series of catalysts with varying amounts of ruthenium supported on alumina and prepared using different precursors was also analyzed. The presence of more ruthenium species other than the metal was observed. On the basis of the values previously obtained on unsupported compounds, the species with higher BE were assigned to oxides. On all the samples prepared from RuCl 3 , an additional peak at a very high BE (283.79 eV) has been observed. This peak is related to the presence of chlorine on the surface: it is suggested that it is related to a charge transfer interaction. The influence of this species on the CO reactivity in the Fischer-Tropsch reaction is discussed. (orig.)

  7. Oxidation of ruthenium thin films using atomic oxygen

    Energy Technology Data Exchange (ETDEWEB)

    McCoy, A.P.; Bogan, J.; Brady, A.; Hughes, G.

    2015-12-31

    In this study, the use of atomic oxygen to oxidise ruthenium thin films is assessed. Atomic layer deposited (ALD) ruthenium thin films (~ 3 nm) were exposed to varying amounts of atomic oxygen and the results were compared to the impact of exposures to molecular oxygen. X-ray photoelectron spectroscopy studies reveal substantial oxidation of metallic ruthenium films to RuO{sub 2} at exposures as low as ~ 10{sup 2} L at 575 K when atomic oxygen was used. Higher exposures of molecular oxygen resulted in no metal oxidation highlighting the benefits of using atomic oxygen to form RuO{sub 2}. Additionally, the partial oxidation of these ruthenium films occurred at temperatures as low as 293 K (room temperature) in an atomic oxygen environment. - Highlights: • X-ray photoelectron spectroscopy study of the oxidation of Ru thin films • Oxidation of Ru thin films using atomic oxygen • Comparison between atomic oxygen and molecular oxygen treatments on Ru thin films • Fully oxidised RuO{sub 2} thin films formed with low exposures to atomic oxygen.

  8. The use of ruthenium in various fields of industry

    International Nuclear Information System (INIS)

    Sinitsin, N.M.

    1990-03-01

    Metallic ruthenium, its alloys, and compounds with other metals have a number of valuable and specific properties which allow the usage of ruthenium in various fields of modern technology, which is described here. In the atomic technology, Ru can be used in the building of reactors as a material of construction since its isotopes don't possess a high neutron capture cross section. Ruthenium is used for the preparation of γ- and β-ray emission sources. Isotopes Ru-103 and Ru-106 are widely used as tracers. They are successfully used for the monitoring of production, for the development of new technological and analytical methods of the extraction of Ru, for the cleansing of other valuable metals from Ru, for the monitoring of the thickness of Ru microfilm on the substrate, and for the monitoring of Ru losses in various processes. In the nuclear reactor, during the process of uranium and plutonium decay, large amounts of stable Ru isotopes are formed together with radioactive isotopes. In such a manner, a nuclear reactor can supply Ru. Special attention must be paid to the usage of direct coordination Ru compounds. Ru and its compounds possess a large number of very valuable properties, many of the secrets of Ru must still be discovered. It can be presumed that the demand for ruthenium will grow in the forthcoming years and the range and volume of its applications will increase

  9. Volatility of ruthenium during vitrification operations on fission products. part 1. nitric solutions distillation concentrates calcination. part 2. fixation on a steel tube. decomposition of the peroxide; Volatilite du ruthenium au cours des operations de vitrification des produits de fission. 1. partie distillation des solutions nitriques calcination des concentrats 2. partie fixation sur un tube d'acier decomposition du peroxyde

    Energy Technology Data Exchange (ETDEWEB)

    Ortins de Bettencourt, A; Jouan, A [Commissariat a l' Energie Atomique, Fontenay-aux-Roses (France). Centre d' Etudes Nucleaires

    1969-07-01

    During vitrification of fission product solutions, a high percentage of the ruthenium initially present in these solutions in the form of nitrosyl-ruthenium nitrates is volatilized with the production of the peroxide which itself is decomposed to ruthenium dioxide. The aim of this work has been to study the volatility of the ruthenium during the vitrification processes. During the distillation of the nitric solutions, we have studied in particular the influence on the volatility of the temperature , of the chemical form in which the ruthenium is introduced, of the bubbling of a gas through the solution, of the nitric concentration and of the nitrate concentration. During the calcination, we have observed the influence of the temperature, of the time, of the flow rate and of the nature of the carrier gas, as well as of the action of the ruthenium bi-oxide and the iron oxide on the volatility of the ruthenium. Part 2. This report deals with the study of the thermal decomposition of ruthenium peroxide, RuO{sub 4}, and its deposition on steel tubing. After a brief bibliographic review of the various properties of this substance, a study is made, in the first part, of its deposition on a steel tube. In order to do this, we pass a gas current containing RuO{sub 4} marked with {sup 106}Ru through a stainless steel tube subjected to a temperature gradient which decreases in the direction of the gas flow. The temperature at which RuO{sub 4} is deposited or is fixed on the tube is determined and the influence of the flow rate on this deposit is studied. In the second part, an attempt has been made to study by a static method the kinetics of the decomposition reaction of ruthenium peroxide to give the dioxide: RuO{sub 4} {yields} RuO{sub 2} + O{sub 2}. To do this, we have tried to introduce gaseous RuO{sub 4} into a container placed in an electric oven, and to follow the reaction by {gamma} counting. (author) [French] Au cours de la vitrification des solutions de produits de

  10. Volatility of ruthenium during vitrification operations on fission products. part 1. nitric solutions distillation concentrates calcination. part 2. fixation on a steel tube. decomposition of the peroxide; Volatilite du ruthenium au cours des operations de vitrification des produits de fission. 1. partie distillation des solutions nitriques calcination des concentrats 2. partie fixation sur un tube d'acier decomposition du peroxyde

    Energy Technology Data Exchange (ETDEWEB)

    Ortins de Bettencourt, A.; Jouan, A. [Commissariat a l' Energie Atomique, Fontenay-aux-Roses (France). Centre d' Etudes Nucleaires

    1969-07-01

    During vitrification of fission product solutions, a high percentage of the ruthenium initially present in these solutions in the form of nitrosyl-ruthenium nitrates is volatilized with the production of the peroxide which itself is decomposed to ruthenium dioxide. The aim of this work has been to study the volatility of the ruthenium during the vitrification processes. During the distillation of the nitric solutions, we have studied in particular the influence on the volatility of the temperature , of the chemical form in which the ruthenium is introduced, of the bubbling of a gas through the solution, of the nitric concentration and of the nitrate concentration. During the calcination, we have observed the influence of the temperature, of the time, of the flow rate and of the nature of the carrier gas, as well as of the action of the ruthenium bi-oxide and the iron oxide on the volatility of the ruthenium. Part 2. This report deals with the study of the thermal decomposition of ruthenium peroxide, RuO{sub 4}, and its deposition on steel tubing. After a brief bibliographic review of the various properties of this substance, a study is made, in the first part, of its deposition on a steel tube. In order to do this, we pass a gas current containing RuO{sub 4} marked with {sup 106}Ru through a stainless steel tube subjected to a temperature gradient which decreases in the direction of the gas flow. The temperature at which RuO{sub 4} is deposited or is fixed on the tube is determined and the influence of the flow rate on this deposit is studied. In the second part, an attempt has been made to study by a static method the kinetics of the decomposition reaction of ruthenium peroxide to give the dioxide: RuO{sub 4} {yields} RuO{sub 2} + O{sub 2}. To do this, we have tried to introduce gaseous RuO{sub 4} into a container placed in an electric oven, and to follow the reaction by {gamma} counting. (author) [French] Au cours de la vitrification des solutions de produits de

  11. Ruthenium based redox flow battery for solar energy storage

    International Nuclear Information System (INIS)

    Chakrabarti, Mohammed Harun; Roberts, Edward Pelham Lindfield; Bae, Chulheung; Saleem, Muhammad

    2011-01-01

    Research highlights: → Undivided redox flow battery employing porous graphite felt electrodes was used. → Ruthenium acetylacetonate dissolved in acetonitrile was the electrolyte. → Charge/discharge conditions were determined for both 0.02 M and 0.1 M electrolytes. → Optimum power output of 0.180 W was also determined for 0.1 M electrolyte. → 55% voltage efficiency was obtained when battery was full of electrolytes. -- Abstract: The technical performance for the operation of a stand alone redox flow battery system for solar energy storage is presented. An undivided reactor configuration has been employed along with porous graphite felt electrodes and ruthenium acetylacetonate as electrolyte in acetonitrile solvent. Limiting current densities are determined for concentrations of 0.02 M and 0.1 M ruthenium acetylacetonate. Based on these, operating conditions for 0.02 M ruthenium acetylacetonate are determined as charging current density of 7 mA/cm 2 , charge electrolyte superficial velocity of 0.0072 cm/s (through the porous electrodes), discharge current density of 2 mA/cm 2 and discharge electrolyte superficial velocity of 0.0045 cm/s. An optimum power output of 35 mW is also obtained upon discharge at 2.1 mA/cm 2 . With an increase in the concentration of ruthenium species from 0.02 M to 0.1 M, the current densities and power output are higher by a factor of five approximately (at same superficial velocities) due to higher mass transport phenomenon. Moreover at 0.02 M concentration the voltage efficiency is better for battery full of electrolytes prior to charging (52.1%) in comparison to an empty battery (40.5%) due to better mass transport phenomenon. Voltage efficiencies are higher as expected at concentrations of 0.1 M ruthenium acetylacetonate (55% when battery is full of electrolytes and 48% when empty) showing that the all-ruthenium redox flow battery has some promise for future applications in solar energy storage. Some improvements for the

  12. Recommendation of ruthenium source for sludge batch flowsheet studies

    Energy Technology Data Exchange (ETDEWEB)

    Woodham, W. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL)

    2017-09-13

    Included herein is a preliminary analysis of previously-generated data from sludge batches 7a, 7b, 8, and 9 sludge simulant and real-waste testing, performed to recommend a form of ruthenium for future sludge batch simulant testing under the nitric-formic flowsheet. Focus is given to reactions present in the Sludge Receipt and Adjustment Tank cycle, given that this cycle historically produces the most changes in chemical composition during Chemical Process Cell processing. Data is presented and analyzed for several runs performed under the nitric-formic flowsheet, with consideration given to effects on the production of hydrogen gas, nitrous oxide gas, consumption of formate, conversion of nitrite to nitrate, and the removal and recovery of mercury during processing. Additionally, a brief discussion is given to the effect of ruthenium source selection under the nitric-glycolic flowsheet. An analysis of data generated from scaled demonstration testing, sludge batch 9 qualification testing, and antifoam degradation testing under the nitric-glycolic flowsheet is presented. Experimental parameters of interest under the nitric-glycolic flowsheet include N2O production, glycolate destruction, conversion of glycolate to formate and oxalate, and the conversion of nitrite to nitrate. To date, the number of real-waste experiments that have been performed under the nitric-glycolic flowsheet is insufficient to provide a complete understanding of the effects of ruthenium source selection in simulant experiments with regard to fidelity to real-waste testing. Therefore, a determination of comparability between the two ruthenium sources as employed under the nitric-glycolic flowsheet is made based on available data in order to inform ruthenium source selection for future testing under the nitric-glycolic flowsheet.

  13. Exposure of the German general population to platinum and rhodium - Urinary levels and determining factors.

    Science.gov (United States)

    Munker, Sven; Kilo, Sonja; Röß, Christoph; Jeitner, Peter; Schierl, Rudolf; Göen, Thomas; Drexler, Hans

    2016-11-01

    In this study the exposure of the general population in Germany to platinum and rhodium and its determinants was investigated in 259 participants (subdivided in three groups) by urine analyses and assessment of the dental status. Complementary, an interview including questions characterising possible exposure to traffic exhaust was conducted. The median excretion was 2.42ng platinum/g creatinine and 7.27ng rhodium/g creatinine. The detailed analysis of the collected data showed significant higher platinum excretion values with increasing number of surfaces covered with restorations containing precious metals (R=0.389; prhodium excretion values (median=7.27ng/g; 95th percentile=13.5 ng/g). In summary, the study showed that exhaust emissions have an influence on platinum and rhodium excretion, but for platinum this influence is rather low compared to the influence of precious metals containing restorations. Copyright © 2016 Elsevier GmbH. All rights reserved.

  14. Co-deposition of rhodium and tungsten films for the first-mirror on ITER

    International Nuclear Information System (INIS)

    Marot, Laurent; Steiner, Roland; Gantenbein, Markus; Mathys, Daniel; Meyer, Ernst

    2011-01-01

    The detailed characterizations of rhodium/tungsten films prepared by co-deposition using a dual magnetron sputtering have been carried out on silicon substrates at room temperature. Effects of the tungsten incorporated in the film on the chemical bonding state, optical reflectivity and crystallinity were investigated using X-ray photoelectron spectroscopy (XPS), reflectivity measurements, X-rays diffraction (XRD) and scanning electron microscopy (SEM). The incorporation of tungsten changes the films crystalline structure i.e. leading to Rh 3 W formation. The reflectivity of the films decreases linearly with the decrease of rhodium concentration. XPS and ultraviolet photoemission spectroscopy (UPS) measurements show a positive shift of the core level binding energy of rhodium which is coupled to a shift of the Rh d-band ΔE d away from the Fermi level. Opposite shifts are observed for tungsten.

  15. Rhodium(III)-Catalyzed Amidation of Unactivated C(sp(3) )-H Bonds.

    Science.gov (United States)

    Wang, He; Tang, Guodong; Li, Xingwei

    2015-10-26

    Nitrogenation by direct functionalization of C-H bonds represents an important strategy for constructing C-N bonds. Rhodium(III)-catalyzed direct amidation of unactivated C(sp(3) )-H bonds is rare, especially under mild reaction conditions. Herein, a broad scope of C(sp(3) )-H bonds are amidated under rhodium catalysis in high efficiency using 3-substituted 1,4,2-dioxazol-5-ones as the amide source. The protocol broadens the scope of rhodium(III)-catalyzed C(sp(3) )-H activation chemistry, and is applicable to the late-stage functionalization of natural products. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Disposition of nonflammable low-level radioactive wastes using supercritical water with ruthenium(IV) oxide catalyst

    International Nuclear Information System (INIS)

    Sugiyama, Wataru

    2013-01-01

    This paper presents the distribution behavior of iron, cobalt, cesium, iodine and strontium attached to nonflammable organic materials, in solid, liquid and gas phases during the decomposition of these materials using supercritical water with ruthenium(IV) oxide (RuO 2 ) catalyst. The distributions of these elements under various conditions (initial amounts, with/without precipitation reagent) were determined by using their radioisotopes as simulated low-level radioactive wastes (LLW) in order to ease the detection of trace amounts of elements even in solid and gas phases. Iron and cobalt were found only in the solid phase when iron hydroxide was added as a precipitation reagent before the supercritical water reaction. Cesium, iodine and strontium were found in the liquid phase after the reaction. Therefore, by adding precipitation reagents such as sodium tetraphenylborate, and sodium carbonate (Na 2 CO 3 ) (or sodium hydrogen carbonate (NaHCO 3 )) and silver nitrate (AgNO 3 ) aqueous solutions to each resultant liquid phase containing cesium, strontium and iodine, respectively, these elements can be successfully recovered only in the solid phase. The gases produced during the decomposition of the organic material contain no radioactivity under all conditions in this study. These results indicate that all of the elements investigated in this study (iron, cobalt, cesium, iodine and strontium) can be recovered successfully by this supercritical water process using RuO 2 Consequently, this process is suggested as a predominant candidate for the treatment of nonflammable organic materials in LLW. (author)

  17. Monodisperse Platinum and Rhodium Nanoparticles as Model Heterogeneous Catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Grass, Michael Edward [Univ. of California, Berkeley, CA (United States)

    2008-09-01

    Model heterogeneous catalysts have been synthesized and studied to better understand how the surface structure of noble metal nanoparticles affects catalytic performance. In this project, monodisperse rhodium and platinum nanoparticles of controlled size and shape have been synthesized by solution phase polyol reduction, stabilized by polyvinylpyrrolidone (PVP). Model catalysts have been developed using these nanoparticles by two methods: synthesis of mesoporous silica (SBA-15) in the presence of nanoparticles (nanoparticle encapsulation, NE) to form a composite of metal nanoparticles supported on SBA-15 and by deposition of the particles onto a silicon wafer using Langmuir-Blodgett (LB) monolayer deposition. The particle shapes were analyzed by transmission electron microscopy (TEM) and high resolution TEM (HRTEM) and the sizes were determined by TEM, X-ray diffraction (XRD), and in the case of NE samples, room temperature H2 and CO adsorption isotherms. Catalytic studies were carried out in homebuilt gas-phase reactors. For the nanoparticles supported on SBA-15, the catalysts are in powder form and were studied using the homebuilt systems as plug-flow reactors. In the case of nanoparticles deposited on silicon wafers, the same systems were operated as batch reactors. This dissertation has focused on the synthesis, characterization, and reaction studies of model noble metal heterogeneous catalysts. Careful control of particle size and shape has been accomplished though solution phase synthesis of Pt and Rh nanoparticles in order to elucidate further structure-reactivity relationships in noble metal catalysis.

  18. Synthesis and characterization of rhodium sulfide nanoparticles and thin films

    Energy Technology Data Exchange (ETDEWEB)

    Sosibo, Ndabenhle M. [Department of Chemistry, University of Zululand, Private Bag X1001, KwaDlangezwa 3886 (South Africa); Revaprasadu, Neerish [Department of Chemistry, University of Zululand, Private Bag X1001, KwaDlangezwa 3886 (South Africa)], E-mail: nrevapra@pan.uzulula.za

    2008-05-15

    The synthesis and characterization of a rhodium complex, [Rh(S{sub 2}CNEt{sub 2}){sub 2}] is described. The complex was thermolysed at a high temperature (280 deg. C) in the presence of capping agent, hexadecylamine (HDA) to form Rh{sub 2}S{sub 3} nanoparticles. Rod-shaped Rh{sub 2}S{sub 3} nanoparticles with an average length of 26.7 nm and an average breadth of 7.8 nm were synthesized. The complex was also used as a single molecule precursor for the deposition of Rh{sub 2}S{sub 3} thin films on a glass substrate at 350 deg. C and 450 deg. C using the Aerosol Assisted Chemical Vapour Deposition (AACVD) technique. The resultant thin films showed temperature dependent morphologies and showed (0 2 2), (4 1 1) and (6 1 1) lattice planes characteristic of to the orthorhombic Rh{sub 2}S{sub 3} phase. X-ray diffraction and scanning electron microscopy techniques were used to characterize the films.

  19. The UV Plasmonic Behavior of Distorted Rhodium Nanocubes

    Directory of Open Access Journals (Sweden)

    Yael Gutiérrez

    2017-12-01

    Full Text Available For applications of surface-enhanced spectroscopy and photocatalysis, the ultraviolet (UV plasmonic behavior and charge distribution within rhodium nanocubes is explored by a detailed numerical analysis. The strongest plasmonic hot-spots and charge concentrations are located at the corners and edges of the nanocubes, exactly where they are the most spectroscopically and catalytically active. Because intense catalytic activity at corners and edges will reshape these nanoparticles, distortions of the cubical shape, including surface concavity, surface convexity, and rounded corners and edges, are also explored to quantify how significantly these distortions deteriorate their plasmonic and photocatalytic properties. The fact that the highest fields and highest carrier concentrations occur in the corners and edges of Rh nanocubes (NCs confirms their tremendous potential for plasmon-enhanced spectroscopy and catalysis. It is shown that this opportunity is fortuitously enhanced by the fact that even higher field and charge concentrations reside at the interface between the metal nanoparticle and a dielectric or semiconductor support, precisely where the most chemically active sites are located.

  20. Biological effects of simple changes in functionality on rhodium metalloinsertors

    Science.gov (United States)

    Weidmann, Alyson G.; Komor, Alexis C.; Barton, Jacqueline K.

    2013-01-01

    DNA mismatch repair (MMR) is crucial to ensuring the fidelity of the genome. The inability to correct single base mismatches leads to elevated mutation rates and carcinogenesis. Using metalloinsertors–bulky metal complexes that bind with high specificity to mismatched sites in the DNA duplex–our laboratory has adopted a new chemotherapeutic strategy through the selective targeting of MMR-deficient cells, that is, those that have a propensity for cancerous transformation. Rhodium metalloinsertors display inhibitory effects selectively in cells that are deficient in the MMR machinery, consistent with this strategy. However, a highly sensitive structure–function relationship is emerging with the development of new complexes that highlights the importance of subcellular localization. We have found that small structural modifications, for example a hydroxyl versus a methyl functional group, can yield profound differences in biological function. Despite similar binding affinities and selectivities for DNA mismatches, only one metalloinsertor shows selective inhibition of cellular proliferation in MMR-deficient versus -proficient cells. Studies of whole-cell, nuclear and mitochondrial uptake reveal that this selectivity depends upon targeting DNA mismatches in the cell nucleus. PMID:23776288

  1. Tandem rhodium catalysis: exploiting sulfoxides for asymmetric transition-metal catalysis.

    Science.gov (United States)

    Kou, K G M; Dong, V M

    2015-06-07

    Sulfoxides are uncommon substrates for transition-metal catalysis due to their propensity to inhibit catalyst turnover. In a collaborative effort with Ken Houk, we developed the first dynamic kinetic resolution (DKR) of allylic sulfoxides using asymmetric rhodium-catalyzed hydrogenation. A detailed mechanistic analysis of this transformation using both experimental and theoretical methods revealed rhodium to be a tandem catalyst that promoted both hydrogenation of the alkene and racemization of the allylic sulfoxide. Using a combination of deuterium labelling and DFT studies, a novel mode of allylic sulfoxide racemization via a Rh(III)-π-allyl intermediate was identified.

  2. The extraction of rhodium from aqueous nitric acid by dinonylnaphthalene sulphonic acid

    International Nuclear Information System (INIS)

    Patel, N.M.; Miles, J.H.; Thornback, J.R.

    1987-01-01

    The extraction of rhodium from aqueous nitric acid using dinonylnaphthalene sulphonic acid has been investigated. The extraction occurs readily from 0.1 M to 1.0 M nitric acid and, since the rhodium is extracted as {Rh(H 2 O) 6 } 3+ into the inverted micelles of the organic solution, equilibration times are less than 5 minutes. Extraction is enhanced by addition of nitrite ion to form {Rh(H 2 O) 5 NO 2 } 2+ as the extracted species. (author)

  3. Sorption properties study of nitron fibre S-3 relative to rhodium (III)

    International Nuclear Information System (INIS)

    Rustamov, S.; Khusainov, A.D.; Shadieva, S.F.

    2001-01-01

    The purpose of present work is studying of sorption properties of nitron fibre S-3 relative to rhodium (III) from chloride solutions. Nitron sorbent S-3 was synthesised by reprocessing of wastes of production of nitron fibre by sulfited compound Na 2 Sn:NH 4 SCN=50:50 during 3 hours at temperature 90 d ig C . The sulfur containing in the sorbent was about 9%. During investigation by authors was determined that fibre nitron-S has good kinetic characteristics relative to rhodium (III), limitative stage of sorption process is diffusion and kinetics of sorption has mixed-diffusion character

  4. Rhodium-catalyzed C-H alkynylation of arenes at room temperature.

    Science.gov (United States)

    Feng, Chao; Loh, Teck-Peng

    2014-03-03

    The rhodium(III)-catalyzed ortho C-H alkynylation of non-electronically activated arenes is disclosed. This process features a straightforward and highly effective protocol for the synthesis of functionalized alkynes and represents the first example of merging a hypervalent iodine reagent with rhodium(III) catalysis. Notably, this reaction proceeds at room temperature, tolerates a variety of functional groups, and more importantly, exhibits high selectivity for monoalkynylation. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. A Concise Synthesis of the Erythrina Alkaloid 3–Demethoxyerythratidinone via Combined Rhodium Catalysis

    Science.gov (United States)

    Joo, Jung Min; David, Ramoncito A.; Yuan, Yu; Lee, Chulbom

    2010-01-01

    The total synthesis of the erythrina alkaloid 3–demethoxyerythratidinone has been achieved via a strategy based on combined rhodium catalysis. The catalytic tandem cyclization effected by the interplay of alkynyl and vinylidene rhodium species allows for efficient access to the A and B rings of the tetracyclic erythrinane skeleton in a single step. The synthesis also features rapid preparation of the requisite precursor for the double ring closure and thus has been completed in only 7 total steps in 41% overall yield. PMID:21090648

  6. N-doping of organic semiconductors by bis-metallosandwich compounds

    Science.gov (United States)

    Barlow, Stephen; Qi, Yabing; Kahn, Antoine; Marder, Seth; Kim, Sang Bok; Mohapatra, Swagat K.; Guo, Song

    2016-01-05

    The various inventions disclosed, described, and/or claimed herein relate to the field of methods for n-doping organic semiconductors with certain bis-metallosandwich compounds, the doped compositions produced, and the uses of the doped compositions in organic electronic devices. Metals can be manganese, rhenium, iron, ruthenium, osmium, rhodium, or iridium. Stable and efficient doping can be achieved.

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

    Energy Technology Data Exchange (ETDEWEB)

    Kato, Tetsuya, E-mail: tkato@criepi.denken.or.jp [Nuclear Technology Research Laboratory, Central Research Institute of Electric Power Industry, 2-11-1 Iwado-kita, Komae-shi, Tokyo 201-8511 (Japan); Usami, Tsuyoshi; Tsukada, Takeshi [Nuclear Technology Research Laboratory, Central Research Institute of Electric Power Industry, 2-11-1 Iwado-kita, Komae-shi, Tokyo 201-8511 (Japan); Shibata, Yuki; Kodama, Takashi [Safety Technology Division, Japan Nuclear Fuel Ltd., Obuchi, Rokkasho-mura, Aomori 039-3212 (Japan)

    2016-10-15

    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)(NO{sub 3}){sub 3}) dissolved in nitric acid (HNO{sub 3}), 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 (RuO{sub 4}) was detected in a temperature range between 390 K and 500 K with the peak top around 440 K. Various gases such as HNO{sub 3}, nitrogen dioxide (NO{sub 2}), nitrogen monoxide (NO) also evolved due to evaporation of the nitric acid and decomposition of the nitrate ions. The ion current of RuO{sub 4} seems to increase with the increasing decomposition of nitrate, while the evaporation of HNO{sub 3} decreases. More volatilization of RuO{sub 4} was observed from the HNO{sub 3} solution containing not only Ru(NO)(NO{sub 3}){sub 3} but also cerium nitrate (Ce(NO{sub 3}){sub 3}·6H{sub 2}O) which was added for extra supply of nitrate ion, compared with that from the HNO{sub 3} solution containing only Ru(NO)(NO{sub 3}){sub 3}. These experimental results suggest that Ru could be oxidized to form RuO{sub 4} by the nitrate ion as well as HNO{sub 3}. - Graphical abstract: Ion current intensities of the mass numbers corresponding to O, NO, O{sub 2}, NO{sub 2}, HNO{sub 3}, and RuO{sub 4} obtained in mass spectrometry for dried nitric acid solution containing Ru(NO)(NO{sub 3}){sub 3}. Heating rate: 5 K min{sup −1}, sample solution weight: 6.61 mg, contained Ru weight: 0.56 mg. The ion current of RuO{sub 4} increases with the increasing decomposition of nitrate, while the evaporation of HNO{sub 3} decreases. - Highlights: • Nitrosyl Ru nitrate (Ru(NO)(NO{sub 3}){sub 3}) dissolved in

  8. C-N bond cleavage of anilines by a (salen)ruthenium(VI) nitrido complex.

    Science.gov (United States)

    Man, Wai-Lun; Xie, Jianhui; Pan, Yi; Lam, William W Y; Kwong, Hoi-Ki; Ip, Kwok-Wa; Yiu, Shek-Man; Lau, Kai-Chung; Lau, Tai-Chu

    2013-04-17

    We report experimental and computational studies of the facile oxidative C-N bond cleavage of anilines by a (salen)ruthenium(VI) nitrido complex. We provide evidence that the initial step involves nucleophilic attack of aniline at the nitrido ligand of the ruthenium complex, which is followed by proton and electron transfer to afford a (salen)ruthenium(II) diazonium intermediate. This intermediate then undergoes unimolecular decomposition to generate benzene and N2.

  9. Ruthenium(III Chloride Catalyzed Acylation of Alcohols, Phenols, and Thiols in Room Temperature Ionic Liquids

    Directory of Open Access Journals (Sweden)

    Mingzhong Cai

    2009-09-01

    Full Text Available Ruthenium(III chloride-catalyzed acylation of a variety of alcohols, phenols, and thiols was achieved in high yields under mild conditions (room temperature in the ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate ([bmim][PF6]. The ionic liquid and ruthenium catalyst can be recycled at least 10 times. Our system not only solves the basic problem of ruthenium catalyst reuse, but also avoids the use of volatile acetonitrile as solvent.

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

    Science.gov (United States)

    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.

  11. Experiments on the behaviour of ruthenium in air ingress accidents - Progress report

    International Nuclear Information System (INIS)

    Kaerkelae, T.; Backman, U.; Auvinen, A.; Ziliacus, R.; Lipponen, M.; Kekki, T.; Tapper, U.; Jokiniemi, J.

    2006-02-01

    During routine nuclear reactor operation, ruthenium will accumulate in the fuel in relatively high concentrations. In an accident in a nuclear power plant it is possible that air gets into contact with the reactor core. In this case ruthenium can oxidise and form volatile ruthenium species, RuO3 and RuO4, which can be transported into the containment. In order to estimate the amount of gaseous ruthenium species it is of interest to know, how it is formed and how it behaves. In our experiments RuO2 is exposed to diverse oxidising atmospheres at a relatively high temperature. In this report, the experimental system for the ruthenium behaviour study is presented. Also preliminary results from experiments carried out during year 2005 are reported. In the experiments gaseous ruthenium oxides were produced in a furnace. Upon cooling RuO2 aerosol particles were formed in the system. They were removed with plane filters from the gas stream. Gaseous ruthenium species were trapped in 1M NaOH-water solution, which is capable of trapping RuO4 totally. Ruthenium in the solution was filtered for analysis. The determination of ruthenium both in aerosol and in liquid filters was made using instrumental neutron activation analysis (INAA). In order to close mass balance and achieve better time resolution three experiment using radioactive tracer were carried out. (au)

  12. Optimization of screen-printed ruthenium dioxide electrodes for pH measurements

    International Nuclear Information System (INIS)

    Wyzkiewicz, I.

    2002-01-01

    Optimization of disposable, screen-printed pH-sensors based on ruthenium dioxide is described in this paper. The electrodes were prepared with the use of thick-film technology. The pH-sensitive layers were deposited onto polyester foil. Polymer graphite paste containing ruthenium dioxide from 0% to 90% has been investigated. The dependence of the pH-sensitive layers related to ruthenium dioxide content is presented. The investigation proved that the electrodes containing 40-60% ruthenium dioxide exhibit linear high sensitivity (∼ 50 mV/pH) in the wide range of pH (2 - 11) as well as very good reproducibility. (author)

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

    Energy Technology Data Exchange (ETDEWEB)

    Coloma Ribera, R.; Kruijs, R. W. E. van de; Yakshin, A. E.; Bijkerk, F. [MESA+ Institute for Nanotechnology, University of Twente, P.O. Box 217, 7500 AE Enschede (Netherlands); Kokke, S.; Zoethout, E. [FOM Dutch Institute for Fundamental Energy Research (DIFFER), P.O. Box 1207, 3430 BE Nieuwegein (Netherlands)

    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.

  14. Experiments on the behaviour of ruthenium in air ingress accidents - Progress report

    Energy Technology Data Exchange (ETDEWEB)

    Kaerkelae, T.; Backman, U.; Auvinen, A.; Ziliacus, R.; Lipponen, M.; Kekki, T.; Tapper, U.; Jokiniemi, J. [VTT Technical Research Centre of Finland (Finland)

    2006-02-15

    During routine nuclear reactor operation, ruthenium will accumulate in the fuel in relatively high concentrations. In an accident in a nuclear power plant it is possible that air gets into contact with the reactor core. In this case ruthenium can oxidise and form volatile ruthenium species, RuO3 and RuO4, which can be transported into the containment. In order to estimate the amount of gaseous ruthenium species it is of interest to know, how it is formed and how it behaves. In our experiments RuO2 is exposed to diverse oxidising atmospheres at a relatively high temperature. In this report, the experimental system for the ruthenium behaviour study is presented. Also preliminary results from experiments carried out during year 2005 are reported. In the experiments gaseous ruthenium oxides were produced in a furnace. Upon cooling RuO2 aerosol particles were formed in the system. They were removed with plane filters from the gas stream. Gaseous ruthenium species were trapped in 1M NaOH-water solution, which is capable of trapping RuO4 totally. Ruthenium in the solution was filtered for analysis. The determination of ruthenium both in aerosol and in liquid filters was made using instrumental neutron activation analysis (INAA). In order to close mass balance and achieve better time resolution three experiment using radioactive tracer were carried out. (au)

  15. Evaluation of radiolabeled ruthenium compounds as tumor-localizing agents

    International Nuclear Information System (INIS)

    Srivastava, S.C.; Richards, P.; Meinken, G.E.; Som, P.; Atkins, H.L.; Larson, S.M.; Grunbaum, Z.; Rasey, J.S.; Clarke, M.H.; Dowling, M.

    1979-01-01

    This work introduces a new class of radiopharmaceuticals based on ruthenium-97. The excellent physical properties of Ru-97, the high chemical reactivity of Ru, the potential antitumor activity of several Ru coordination compounds, and BLIP production of Ru-97, provide a unique combination for the application of this isotope in nuclear oncology. A systematic study was undertaken on the synthesis, characterization, and evaluation of a number of ruthenium-labeled compounds. In a variety of animal tumor models, several compounds show considerable promise as tumor-localizing agents when compared to gallium-67 citrate. The compounds studied (with Ru in different oxidation states) include ionic Ru, a number of hydrophilic and lipophilic chelates, and various ammine derivatives

  16. Chemical vapor deposition of amorphous ruthenium-phosphorus alloy films

    International Nuclear Information System (INIS)

    Shin Jinhong; Waheed, Abdul; Winkenwerder, Wyatt A.; Kim, Hyun-Woo; Agapiou, Kyriacos; Jones, Richard A.; Hwang, Gyeong S.; Ekerdt, John G.

    2007-01-01

    Chemical vapor deposition growth of amorphous ruthenium-phosphorus films on SiO 2 containing ∼ 15% phosphorus is reported. cis-Ruthenium(II)dihydridotetrakis-(trimethylphosphine), cis-RuH 2 (PMe 3 ) 4 (Me = CH 3 ) was used at growth temperatures ranging from 525 to 575 K. Both Ru and P are zero-valent. The films are metastable, becoming increasingly more polycrystalline upon annealing to 775 and 975 K. Surface studies illustrate that demethylation is quite efficient near 560 K. Precursor adsorption at 135 K or 210 K and heating reveal the precursor undergoes a complex decomposition process in which the hydride and trimethylphosphine ligands are lost at temperatures as low at 280 K. Phosphorus and its manner of incorporation appear responsible for the amorphous-like character. Molecular dynamics simulations are presented to suggest the local structure in the films and the causes for phosphorus stabilizing the amorphous phase

  17. Ruthenium Complexes as NO Donors for Vascular Relaxation Induction

    Directory of Open Access Journals (Sweden)

    Renata Galvão de Lima

    2014-07-01

    Full Text Available Nitric oxide (NO donors are substances that can release NO. Vascular relaxation induction is among the several functions of NO, and the administration of NO donors is a pharmacological alternative to treat hypertension. This review will focus on the physicochemical description of ruthenium-derived NO donor complexes that release NO via reduction and light stimulation. In particular, we will discuss the complexes synthesized by our research group over the last ten years, and we will focus on the vasodilation and arterial pressure control elicited by these complexes. Soluble guanylyl cyclase (sGC and potassium channels are the main targets of the NO species released from the inorganic compounds. We will consider the importance of the chemical structure of the ruthenium complexes and their vascular effects.

  18. Olefins hydro-formylation catalysed by rhodium complexes using ionic liquids; Hydroformylation des olefines par les complexes du rhodium dans les liquides ioniques

    Energy Technology Data Exchange (ETDEWEB)

    Favre, F.

    2000-10-26

    Biphasic long chain olefins hydro-formylation catalysed by rhodium complexes using ionic liquids allows a selective reaction and an easy separation of the products from the catalyst. This study reports the synthesis of ionic liquids that were used as the catalyst's solvent. Their physical and chemical properties (melting point, solubility of organic substrates) can be varied with the structure of the organic cation (imidazolium, pyridinium, pyrrolydinium) and with its substituents (nature, length, number). It depends also on the nature of the inorganic anion (hexa-fluoro-phosphate, tetrafluoroborate, tri-fluoro-acetate, triflate, bistriflylamidure...). The use of phosphorus ligands bearing ionic functions proved to be efficient to maintain the onerous rhodium catalyst in the ionic liquid phase. Phosphines, phosphites and phosphinites including anionic (sulfonate, carboxylate) or cationic (imidazolium, pyridinium, guanidinium, phosphonium) groups have been synthesised. Finally, the influences of the ligand and of the ionic liquid on the catalytic system performances are described. Selectivities in aldehydes and reaction rates proved to be highly dependent on the nature of the ligand and of the ionic liquid. The different possibilities of recycling the ionic phase containing the rhodium catalyst have been also studied. (author)

  19. Direct C-H alkylation and indole formation of anilines with diazo compounds under rhodium catalysis.

    Science.gov (United States)

    Mishra, Neeraj Kumar; Choi, Miji; Jo, Hyeim; Oh, Yongguk; Sharma, Satyasheel; Han, Sang Hoon; Jeong, Taejoo; Han, Sangil; Lee, Seok-Yong; Kim, In Su

    2015-12-18

    The rhodium(III)-catalyzed direct functionalization of aniline C-H bonds with α-diazo compounds is described. These transformations provide a facile construction of ortho-alkylated anilines with diazo malonates or highly substituted indoles with diazo acetoacetates.

  20. Rhodium(II)-Catalyzed Asymmetric Sulfur(VI) Reduction of Diazo Sulfonylamidines

    OpenAIRE

    Selander, Nicklas; Fokin, Valery V.

    2012-01-01

    Diazo sulfonylamidines readily undergo enantioselective oxygen transfer from sulfur to carbon atom in the presence of chiral rhodium(II) carboxylates resulting in chiral sulfinylamidines. This unusual asymmetric atom transfer “reduction” occurs rapidly under mild conditions, and sulfinylamidines are obtained in excellent yield.

  1. Enantioselective rhodium enolate protonations. A new methodology for the synthesis of beta2-amino acids.

    Science.gov (United States)

    Sibi, Mukund P; Tatamidani, Hiroto; Patil, Kalyani

    2005-06-23

    [reaction: see text] Rhodium-catalyzed conjugate addition of an aryl boronic acid to alpha-methylamino acrylates followed by enantioselective protonation of the oxa-pi-allylrhodium intermediate provides access to aryl-substituted beta(2)-amino acids. The impact of the different variables of the reaction on the levels of enantioselectivity has been assessed.

  2. Rhodium-catalyzed chemo- and regioselective decarboxylative addition of β-ketoacids to alkynes.

    Science.gov (United States)

    Li, Changkun; Grugel, Christian P; Breit, Bernhard

    2016-04-30

    A highly efficient rhodium-catalyzed chemo- and regioselective addition of β-ketoacids to alkynes is reported. Applying a Rh(i)/(S,S)-DIOP catalyst system, γ,δ-unsaturated ketones were prepared with exclusively branched selectivity under mild conditions. This demonstrates that readily available alkynes can be an alternative entry to allyl electrophiles in transition-metal catalyzed allylic alkylation reactions.

  3. Immobilization of rhodium complexes at thiolate monolayers on gold surfaces : Catalytic and structural studies

    NARCIS (Netherlands)

    Belser, T; Stöhr, Meike; Pfaltz, A

    2005-01-01

    Chiral rhodium-diphosphine complexes have been incorporated into self-assembled thiolate monolayers (SAMS) on gold colloids. Catalysts of this type are of interest because they combine properties of homogeneous and heterogeneous systems. In addition, it should be possible to influence the catalytic

  4. The Role of the Element Rhodium in the Hyperbolic Law of the Periodic Table of Elements

    Directory of Open Access Journals (Sweden)

    Albert Khazan

    2008-07-01

    Full Text Available The role of the element rhodium as an independent affirmation of calculations by the Hyperbolic Law and validity of all its relations is shown herein. The deviation in calculation by this method of the atomic mass of heaviest element is 0.0024%, and its coefficient of scaling 0.001-0.005%.

  5. STABLE SILICA-GRAFTED POLYMER-BOUND BULKY-PHOSPHITE MODIFIED RHODIUM HYDROFORMYLATION CATALYSTS

    NARCIS (Netherlands)

    JONGSMA, T; VANAERT, H; FOSSEN, M; CHALLA, G; VANLEEUWEN, PWNM

    1993-01-01

    The present study demonstrates that silica-grafted polymer-bound phosphite modified rhodium complexes can be used in continuous flow reactors. The hydroformylation of styrene was carried out at moderate pressure (p(CO/H-2) = 30 bar) and temperature (T = 100-degrees-C), yielding constant conversions

  6. A NEW TYPE OF HIGHLY-ACTIVE POLYMER-BOUND RHODIUM HYDROFORMYLATION CATALYST

    NARCIS (Netherlands)

    JONGSMA, T; KIMKES, P; CHALLA, G; VANLEEUWEN, PWNM

    1992-01-01

    A new route of attaching phosphites to a (co)polymer chain is described. These copolymers are used for the preparation of a rhodium phosphite hydroformylation catalyst. The catalytic activity of this polymer-bound system is identical to that of the low molecular weight analogue. The catalysts show a

  7. Komplexe zouten van trans-1-2-diaminocyclohexaan met driewaardig rhodium en kobalt

    NARCIS (Netherlands)

    Bijkerk, Lucas

    1937-01-01

    Some complex salts of trans-I-2-díominocyclohexane with trivalent cobaltum and rhodium were prepared and their properties described in detail. Diaminocyclohexanwe as obtained by the following series of reactions: cyclohexanone --> cyclohexanone-I-oxalylicester --> cyclohexonone-I-carboxylicester-2

  8. Rhodium Phosphine-π-Arene Intermediates in the Hydroamination of Alkenes

    Science.gov (United States)

    Liu, Zhijian; Yamamichi, Hideaki; Madrahimov, Sherzod T.; Hartwig, John F.

    2011-01-01

    A detailed mechanistic study of the intramolecular hydroamination of alkenes with amines catalyzed by rhodium complexes of a biaryldialkylphosphine are reported. The active catalyst is shown to contain the phosphine ligand bound in a κ1, η6 form in which the arene is π-bound to rhodium. Addition of deuterated amine to an internal olefin showed that the reaction occurs by trans addition of the N-H bond across the C=C bond, and this stereochemistry implies that the reaction occurs by nucleophilic attack of the amine on a coordinated alkene. Indeed, the cationic rhodium fragment binds the alkene over the secondary amine, and the olefin complex was shown to be the catalyst resting state. The reaction was zero-order in substrate, when the concentration of olefin was high, and a primary isotope effect was observed. The primary isotope effect, in combination with the observation of the alkene complex as the resting state, implies that nucleophilic attack of the amine on the alkene is reversible and is followed by turnover-limiting protonation. This mechanism constitutes an unusual pathway for rhodium-catalyzed additions to alkenes and is more closely related to the mechanism for palladium-catalyzed addition of amide N-H bonds to alkenes. PMID:21309512

  9. A MECHANISTIC STUDY OF RHODIUM TRI(ORTHO-TERT-BUTYLPHENYL)PHOSPHITE COMPLEXES AS HYDROFORMYLATION CATALYSTS

    NARCIS (Netherlands)

    JONGSMA, T; CHALLA, G; VANLEEUWEN, PWNM

    1991-01-01

    A mechanistic study of the hydroformylation cycle with a rhodium tri(o-t-butylphenyl)phosphite complex as catalyst is presented. Spectroscopic experiments prove that under hydroformylation conditions this complex is coordinated by only one phosphite. The complex has a high activity in the

  10. Enantioselective Rhodium Enolate Protonations. A New Methodology for the Synthesis of β2-Amino Acids

    Science.gov (United States)

    Sibi, Mukund P.; Tatamidani, Hiroto; Patil, Kalyani

    2008-01-01

    Rhodium catalyzed conjugate addition of an aryl boronic acid to α-methylamino acrylates followed by enantioselective protonation of the oxa-π-allylrhodium intermediate provides access to aryl substituted β2-amino acids. The impact of the different variables of the reaction on the levels of enantioselectivity has been assessed. PMID:15957893

  11. Double-spin-flip resonance of rhodium nuclei at positive and negative spin temperatures

    DEFF Research Database (Denmark)

    Tuoriniemi, J.T.; Knuuttila, T.A.; Lefmann, K.

    2000-01-01

    Sensitive SQUID-NMR measurements were used to study the mutual interactions in the highly polarized nuclear-spin system of rhodium metal. The dipolar coupling gives rise to a weak double-spin-flip resonance. The observed frequency shifts allow deducing separately the dipolarlike contribution...

  12. Rhodium Catalyzed Annulation of N-Benzoylsulfonamide with Isocyanide via C-H Activation

    Science.gov (United States)

    Zhu, Chen; Xie, Weiqing; Falck, John R.

    2012-01-01

    Isocyanide insertion: the first rhodium-catalyzed annulation of N-benzoylsulfonamide incorporating with isocyanide via C-H activation is described. The transformation is broadly compatible with N-benzoylsulfonamides bearing various electron-properties as well as isocyanides. From practical point of view, this methodology provides the most straightforward approach to a series of 3-(imino)isoindolinones. PMID:21972033

  13. Rhodium-Catalyzed Regioselective C7-Olefination of Indazoles Using an N-Amide Directing Group.

    Science.gov (United States)

    Guo, Lei; Chen, Yanyu; Zhang, Rong; Peng, Qiujun; Xu, Lanting; Pan, Xianhua

    2017-02-01

    A rhodium-catalyzed regioselective C-H olefination of indazole is described. This protocol relies on the use of an efficient and removable N,N-diisopropylcarbamoyl directing group, which offers facile access to C7-olefinated indazoles with high regioselectivity, ample substrate scope and broad functional group tolerance. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. The Biological Side of Water-Soluble Arene Ruthenium Assemblies

    OpenAIRE

    Therrien, Bruno; Furrer, Julien

    2014-01-01

    This review article covers the synthetic strategies, structural aspects, and host-guest properties of ruthenium metalla-assemblies, with a special focus on their use as drug delivery vectors. The two-dimensional metalla-rectangles show interesting host-guest possibilities but seem less appropriate for being used as drug carriers. On the other hand, metalla-prisms allow encapsulation and possible targeted release of bioactive molecules and consequently show some potential as drug delivery vect...

  15. THE SYNTHESIS AND THE REACTIVITY OF ARENE RUTHENIUM ...

    African Journals Online (AJOL)

    a

    [RuCl(η6-p-cymene)(η2-dppm)][PF6] ruthenium complexes with C2O4(Me4N)2 in the ... the Service de Microanalyse du CNRS (Vernaison/France). .... Once bonded to the Ru(II), the characterization of the oxalato ligand by infrared .... The 1H NMR spectrum shows signals of the aromatic proton resonances at 5.45 and 5.15,.

  16. Allenylidene Complexes of Ruthenium: Synthesis, Spectroscopy and Electron Transfer Properties

    Czech Academy of Sciences Publication Activity Database

    Winter, R. F.; Záliš, Stanislav

    2004-01-01

    Roč. 248, 15/16 (2004), s. 1565-1583 ISSN 0010-8545 R&D Projects: GA ČR GA203/03/0821; GA MŠk OC D14.20 Institutional research plan: CEZ:AV0Z4040901 Keywords : spectroscopy * allenylidine complexes of ruthenium * electron transfer Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 6.446, year: 2004

  17. Behaviour of ruthenium (3) bromocomplexes in nonaqueous solvents

    International Nuclear Information System (INIS)

    Rudnitskaya, O.V.; Miroshnichenko, I.V.; Pichkov, V.N.

    1989-01-01

    Behaviour of K 3 [RuBr 6 ] · H 2 O and K 3 [Ru 2 Br 9 ] in solutions of dimethylsulfoxide and dimethylformamide is investigated by absorption and ESR spectroscopy. Complexes are shown to be labile in solutions, interact easily with solvents. Formation of ruthenium (3) and (2) bromide-dimethylsulfoxide complexes occurs gradually in DMSO, final product is trans-[Ru(DMSO) 4 Br 2

  18. Role of ligands in controlling the regioselectivity in ruthenium ...

    Indian Academy of Sciences (India)

    of Hay and Wadt (LANL2DZ)11 for ruthenium atom and 6-31G(d)12 for other .... C2 atom in 3x/3′ x. To understand the wider role of lig- ands in modulating the regio-selectivity of product for- mation, we have studied the benzoic acid addition to the selected .... at C1 and the localization of electron density in the. M=C double ...

  19. Mechanism of ruthenium dioxide crystallization during high level waste vitrification

    International Nuclear Information System (INIS)

    Boucetta, H.

    2012-01-01

    Ruthenium, arising from the reprocessing of spent uranium oxide fuel, has a low solubility in glass melt. It crystallizes in the form of particles of RuO 2 of acicular or polyhedral morphology dispersed in fission product and actinides waste containment glass. Since the morphology of these particles strongly influences the physico-chemical properties, the knowledge and the control of their mechanism of formation are of major importance. The goal of this work is to determine the chemical reactions responsible for the formation of RuO 2 particles of acicular or polyhedral shape during glass synthesis. Using a simplification approach, the reactions between RuO 2 -NaNO 3 , and more complex calcine RuO 2 -Al 2 O 3 -Na 2 O and a sodium borosilicate glass are studied. In situ scanning electron microscopy and XANES at increasing temperatures are used to follow changes in composition, speciation and morphology of the ruthenium intermediate species. Those compounds are thoroughly characterised by SEM, XRD, HRTEM, and ruthenium K-edge X-ray absorption spectroscopy. This combined approach allows us to show that the ruthenium speciation modification during vitrification is the key of control of the morphology of RuO 2 particles in the glass. In particular, the formation of a specific intermediate compound (Na 3 RuO 4 ) is one of the main steps that lead to the precipitation of needle-shaped RuO 2 particles in the melt. The formation of polyhedral particles, on the contrary, results from the direct incorporation of RuO 2 crystals in the melt followed by an Ostwald ripening mechanism. (author) [fr

  20. The influence of pH on the in vitro permeation of rhodium through human skin.

    Science.gov (United States)

    Jansen Van Rensburg, Sané; Franken, Anja; Du Plessis, Jeanetta; Du Plessis, Johannes Lodewykus

    2017-06-01

    Workers in precious metals refineries are at risk of exposure to salt compounds of the platinum group metals through inhalation, as well as through the skin. Rhodium salt permeation through the skin has previously been proven using rhodium trichloride (RhCl 3 ) dissolved in synthetic sweat at a pH of 6.5. However, the skin surface pH of refinery workers may be lower than 6.5. The aim of this study was to investigate the influence of pH 6.5 and 4.5 on the in vitro permeation of rhodium through intact Caucasian skin using Franz diffusion cells. A concentration of 0.3 mg mL -1 rhodium was used and analyses were performed using inductively coupled plasma mass spectrometry and inductively coupled plasma optical emission spectrometry. Results indicated a cumulative increase in permeation over 24 h. Rhodium permeation after 12 h was significantly greater at pH 4.5 (1.56 ± 0.24 ng cm -2 ) than at 6.5 (0.85 ± 0.13 ng cm -2 ; p = 0.02). At both pH levels, there was a highly significant difference ( p rhodium remaining in the skin (1428.68 ± 224.67 ng cm -2 at pH 4.5 and 1029.90 ± 115.96 ng cm -2 at pH 6.5) and the mass that diffused through (0.88 ± 0.17 ng cm -2 at pH 4.5 and 0.62 ± 0.10 ng cm -2 at pH 6.5). From these findings, it is evident that an acidic working environment or low skin surface pH may enhance permeation of rhodium salts, contributing to sensitization and adverse health effects.

  1. Behaviour of ruthenium dioxide particles in borosilicate glasses and melts

    Energy Technology Data Exchange (ETDEWEB)

    Pflieger, Rachel [DEN/DTCD-SCDV/CEA Valrho, Centre de Marcoule, BP17171, 30207 Bagnols-sur-Ceze (France); Institut de Chimie Separative de Marcoule, UMR5257, Centre de Marcoule, BP17171, 30207 Bagnols-sur-Ceze Cedex (France)], E-mail: rachel_pflieger@yahoo.fr; Lefebvre, Leila [DEN/DTCD-SCDV/CEA Valrho, Centre de Marcoule, BP17171, 30207 Bagnols-sur-Ceze (France); Malki, Mohammed [CNRS/CEMHTI-1D Av. de la Recherche Scientifique, 45701 Orleans cedex 2 (France); Polytech Orleans, Universite d' Orleans, 8 rue Leonard de Vinci, 45072 Orleans cedex 2 (France); Allix, Mathieu [CNRS/CEMHTI-1D Av. de la Recherche Scientifique, 45701 Orleans cedex 2 (France); Grandjean, Agnes [DEN/DTCD-SCDV/CEA Valrho, Centre de Marcoule, BP17171, 30207 Bagnols-sur-Ceze (France); Institut de Chimie Separative de Marcoule, UMR5257, Centre de Marcoule, BP17171, 30207 Bagnols-sur-Ceze Cedex (France)

    2009-06-01

    Ruthenium-glass systems are formed during the vitrification of nuclear waste. They are also widely used in micro-electronics because of their unique electrical properties. However, the interaction of this element with the glass matrix remains poorly understood. This work focuses on a RuO{sub 2} particles-nuclear alumino-borosilicate glass system in which the electrical conductivity is known to vary considerably with the RuO{sub 2} content and to become electronic above about 0.5-0.7 vol.% RuO{sub 2} [R. Pflieger, M. Malki, Y. Guari, J. Larionova, A. Grandjean, J. Am. Ceram. Soc., accepted for publication]. Some RuO{sub 2} segregation was observed in SEM/TEM investigations but no continuous chain of RuO{sub 2} particles could be seen. Electron relays between the particles are then necessary for a low-rate percolation, such as the nanoclusters suggested by Adachi et al. [K. Adachi, S. Iida, K. Hayashi, J. Mater. Res. 9 (7) (1994) 1866; K. Adachi, H. Kuno, J. Am. Ceram. Soc. 83 (10) (2000) 2441], which could consist in dissolved ruthenium. Indeed, several observations made here clearly indicate the presence of dissolved ruthenium in the glass matrix, like the modification of the glass density in presence of RuO{sub 2} particles or the diffusion-limited growth of RuO{sub 2} particles in the melt.

  2. Molecular mass spectrometry in metallodrug development: A case of mapping transferrin-mediated transformations for a ruthenium(III) anticancer drug

    Energy Technology Data Exchange (ETDEWEB)

    Jarosz, Maciej [Chair of Analytical Chemistry, Faculty of Chemistry, Warsaw University of Technology, Noakowskiego St. 3, 00-664 Warsaw (Poland); Matczuk, Magdalena, E-mail: mmatczuk@ch.pw.edu.pl [Chair of Analytical Chemistry, Faculty of Chemistry, Warsaw University of Technology, Noakowskiego St. 3, 00-664 Warsaw (Poland); Pawlak, Katarzyna [Chair of Analytical Chemistry, Faculty of Chemistry, Warsaw University of Technology, Noakowskiego St. 3, 00-664 Warsaw (Poland); Timerbaev, Andrei R. [Vernadsky Institute of Geochemistry and Analytical Chemistry, Russian Academy of Sciences, Kosygin St. 19, 119991 Moscow (Russian Federation)

    2014-12-03

    Highlights: • Extra- and intra-cellular interactions of Ru(III) anticancer drug candidate. • ESI-TOF-MS mapping of the ruthenium species bound to transferring. • ESI-QqQ-MS identification of released Ru species under cytosol simulated conditions. - Abstract: Electrospray ionization mass spectrometry (ESI-MS) techniques have been used to characterize the speciation of a Ru(III) anticancer drug, indazolium trans-[tetrachloridobis(1H-indazole) ruthenate(III)], upon its binding to transferrin and the impact of cellular reducing components on drug–transferrin adducts. Using time-of-flight ESI-MS, the polymorphism of apo- (iron-free) and holo-form (iron-saturated) of the protein was confirmed. While the ruthenium moieties bound to each of five isoforms under simulated extracellular conditions are essentially identical in numbers for apo- and holo-transferrin, distinct differences were found in the composition of Ru(III) species attached to either of the protein forms, which are dominated by differently coordinated aquated complexes. On the other hand, at least one of the Ru-N bonds in metal-organic framework remains intact even after prolonged interaction with the protein. Triple quadrupole tandem ESI-MS measurements demonstrated that the ruthenium species released from drug adducts with holo-transferrin in simulated cancer cytosol are underwent strong ligand exchange (as compared to the protein-bound forms) but most strikingly, they contain the metal center in the reduced Ru(II) state. In vitro probing the extra- and intracellular interactions of promising Ru(III) drug candidate performed by ESI-MS is thought to shed light on the transportation to tumor cells by transferrin and on the activation to more reactive species by the reducing environment of solid tumors.

  3. Chemo- and regioselective homogeneous rhodium-catalyzed hydroamidomethylation of terminal alkenes to N-alkylamides.

    Science.gov (United States)

    Raoufmoghaddam, Saeed; Drent, Eite; Bouwman, Elisabeth

    2013-09-01

    A rhodium/xantphos homogeneous catalyst system has been developed for direct chemo- and regioselective mono-N-alkylation of primary amides with 1-alkenes and syngas through catalytic hydroamidomethylation with 1-pentene and acetamide as model substrates. For appropriate catalyst performance, it appears to be essential that catalytic amounts of a strong acid promoter, such as p-toluenesulfonic acid (HOTs), as well as larger amounts of a weakly acidic protic promoter, particularly hexafluoroisopropyl alcohol (HOR(F) ) are applied. Apart from the product N-1-hexylacetamide, the isomeric unsaturated intermediates, hexanol and higher mass byproducts, as well as the corresponding isomeric branched products, can be formed. Under optimized conditions, almost full alkene conversion can be achieved with more than 80% selectivity to the product N-1-hexylamide. Interestingly, in the presence of a relatively high concentration of HOR(F) , the same catalyst system shows a remarkably high selectivity for the formation of hexanol from 1-pentene with syngas, thus presenting a unique example of a selective rhodium-catalyzed hydroformylation-hydrogenation tandem reaction under mild conditions. Time-dependent product formation during hydroamidomethylation batch experiments provides evidence for aldehyde and unsaturated intermediates; this clearly indicates the three-step hydroformylation/condensation/hydrogenation reaction sequence that takes place in hydroamidomethylation. One likely role of the weakly acidic protic promoter, HOR(F) , in combination with the strong acid HOTs, is to establish a dual-functionality rhodium catalyst system comprised of a neutral rhodium(I) hydroformylation catalyst species and a cationic rhodium(III) complex capable of selectively reducing the imide and/or ene-amide intermediates that are in a dynamic, acid-catalyzed condensation equilibrium with the aldehyde and amide in a syngas environment. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Atomic Layer Deposition of Ruthenium with TiN Interface for Sub-10 nm Advanced Interconnects beyond Copper

    DEFF Research Database (Denmark)

    Wen, Liang Gong; Roussel, Philippe; Pedreira, Olalla Varela

    2016-01-01

    . These extremely scaled ruthenium lines show excellent electromigration behavior. Time-dependent dielectric breakdown measurements reveal negligible ruthenium ion drift into low-kappa dielectrics up to 200 degrees C, demonstrating that ruthenium can be used as a barrierless metallization in interconnects...

  5. Efficient Synthesis of Spirobarbiturates and Spirothiobarbiturates Bearing Cyclopropane Rings by Rhodium(II)-Catalyzed Reactions of Cyclic Diazo Compounds

    International Nuclear Information System (INIS)

    Wang, Xue; Lee, Yong Rok

    2013-01-01

    Rhodium(II)-catalyzed reactions of cyclic diazo compounds derived from barbituric acid and thiobarbituric acid with a variety of styrene moieties were examined. These reactions provide rapid synthetic routes to the preparations of spirobarbiturates and spirothiobarbiturates bearing cyclopropane rings

  6. Efficient Synthesis of Spirobarbiturates and Spirothiobarbiturates Bearing Cyclopropane Rings by Rhodium(II)-Catalyzed Reactions of Cyclic Diazo Compounds

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Xue; Lee, Yong Rok [Yeungnam Univ., Gyeongsan (Korea, Republic of)

    2013-06-15

    Rhodium(II)-catalyzed reactions of cyclic diazo compounds derived from barbituric acid and thiobarbituric acid with a variety of styrene moieties were examined. These reactions provide rapid synthetic routes to the preparations of spirobarbiturates and spirothiobarbiturates bearing cyclopropane rings.

  7. Burnup Estimation of Rhodium Self-Powered Neutron Detector Emitter in VVER Reactor Core Using Monte Carlo Simulations

    OpenAIRE

    Khrutchinsky, А. А.; Kuten, S. A.; Babichev, L. F.

    2011-01-01

    Estimation of burn-up in a rhodium-103 emitter of self-powered neutron detector in VVER-1000 reactor core has been performed using Monte Carlo simulations within approximation of a constant neutron flux.

  8. Recent developments in the nanostructured materials functionalized with ruthenium complexes for targeted drug delivery to tumors

    Directory of Open Access Journals (Sweden)

    Thangavel P

    2017-04-01

    Full Text Available Prakash Thangavel,1 Buddolla Viswanath,1 Sanghyo Kim1,2 1Department of Bionanotechnology, Gachon University, Bokjeong-Dong, Sujeong-Gu, Seongnam-Si, Gyeonggi-Do, 2Graduate Gachon Medical Research Institute, Gil Medical Center, Incheon, Republic of Korea Abstract: In recent years, the field of metal-based drugs has been dominated by other existing precious metal drugs, and many researchers have focused their attention on the synthesis of various ruthenium (Ru complexes due to their potential medical and pharmaceutical applications. The beneficial properties of Ru, which make it a highly promising therapeutic agent, include its variable oxidation states, low toxicity, high selectivity for diseased cells, ligand exchange properties, and the ability to mimic iron binding to biomolecules. In addition, Ru complexes have favorable adsorption properties, along with excellent photochemical and photophysical properties, which make them promising tools for photodynamic therapy. At present, nanostructured materials functionalized with Ru complexes have become an efficient way to administer Ru-based anticancer drugs for cancer treatment. In this review, the recent developments in the nanostructured materials functionalized with Ru complexes for targeted drug delivery to tumors are discussed. In addition, information on “traditional” (ie, non-nanostructured Ru-based cancer therapies is included in a precise manner. Keywords: metallodrugs, nanotechnology, cancer treatment, cell apoptosis, DNA damage, toxicity

  9. Ruthenium release from thermally overheated nitric acid solution containing ruthenium nitrosyl nitrate and sodium nitrate to solidify

    Energy Technology Data Exchange (ETDEWEB)

    Sawada, Kayo; Ueda, Yasuyuki; Enokida, Youichi [Nuclear Chemical Engineering Laboratory, Nagoya University, Nagoya 4648603 (Japan)

    2016-07-01

    Radioactive ruthenium (Ru) is one of the dominant elemental species released into the environment from a fuel reprocessing plant in a hypothetical design accident due to its relatively higher fission yield and longer half-life. After the hypothetical accident assuming the loss of all electric power and cooling functions, high-level liquid waste (HLLW) may be overheated by the energetic decays of many fission products in it, and Ru may be oxidized to the volatile tetroxide, RuO{sub 4}, which is released through the off-gas pathway. At a reprocessing plant in Japan, alkaline solution from the solvent scrubbing stream is sometimes mixed with the HLLW followed by vitrification, which can be influenced by the addition of sodium nitrate to a simulated HLLW containing ruthenium nitrosyl nitrate that was experimentally evaluated on a small scale using the overheated nitric acid solution of 2 mol/dm{sup 3}, which was kept at 180 Celsius degrees in a glass evaporator placed in a thermostatic bath. The release fraction of Ru increased by approximately 30% by the addition of sodium nitrate. This may be partially explained by the existence of relatively highly concentrated nitrate ions in the liquid phase that oxidize the ruthenium species to RuO{sub 4} during the drying process. (authors)

  10. Catalytic Ammonia Decomposition Over Ruthenium Nanoparticles Supported on Nano-Titanates

    DEFF Research Database (Denmark)

    Klerke, Asbjørn; Klitgaard, Søren Kegnæs; Fehrmann, Rasmus

    2009-01-01

    Nanosized Na2Ti3O7, K2Ti6O13 and Cs2Ti6O13 materials were prepared and used as supports of ruthenium nanoparticles for catalytic ammonia decomposition. It is shown that these catalysts exhibit higher catalytic activity than ruthenium supported on TiO2 nanoparticles promoted with cesium. The diffe...

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

    NARCIS (Netherlands)

    Coloma Ribera, R.; van de Kruijs, Robbert Wilhelmus Elisabeth; Kokke, S.; Zoethout, E.; Yakshin, Andrey; Bijkerk, Frederik

    2014-01-01

    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

  12. Synthesis and characterization of novel heteroleptic ruthenium sensitizer for nanocrystalline dye-sensitized solar cells

    NARCIS (Netherlands)

    Sivakumar, R.; Marcelis, A.T.M.; Anandan, S.

    2009-01-01

    A novel heteroleptic ruthenium complex of the type [Ru(bpin)(dcbpyH2)Cl]Cl (where bpin is 2,6-bis(pyrazol-1-yl)isonicotinic acid and dcbpyH2 is 4,4'-dicarboxy-2,2'-bipyridine) was synthesized and characterized for tuning the LUMO level of the ruthenium sensitizer to achieve greater stabilization in

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

    Science.gov (United States)

    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...

  14. Dihydropyranone Formation by Ipso C–H Activation in a Glucal 3-Carbamate-Derived Rhodium Acyl Nitrenoid

    Science.gov (United States)

    Hurlocker, Brisa; Abascal, Nadia C.; Repka, Lindsay M.; Santizo-Deleon, Elsy; Smenton, Abigail L.; Baranov, Victoria; Gupta, Ritu; Bernard, Sarah E.; Chowdhury, Shenjuti; Rojas, Christian M.

    2011-01-01

    By using (N-tosyloxy)-3-O-carbamoyl-D-glucal 10, which removes the need for a hypervalent iodine(III) oxidant, we provide evidence for rhodium nitrenoid-mediated ipso C–H activation as the origin of a C3-oxidized dihydropyranone product 3. This system may be especially susceptible to such a pathway due to the ease of forming a cation upon hydride transfer to the rhodium-complexed acyl nitrene. PMID:21381715

  15. Environmentally safe separation and pre-concentration of rhodium and ruthenium from spent nuclear fuel using mixed-micelle cloud point extraction and determination by ICP-MS

    International Nuclear Information System (INIS)

    Ranjit, M.; Meeravali, N.N.; Kumar, S.J.

    2010-01-01

    Full text: Recently, spend nuclear fuel waste of thermal and fast reactors are emerging as an alternative valuable resource for Rh, Ru and Pd. In addition, its presence causes the difficulty in the vitrification process. Hence, its safe extraction from these wastes has to be carried out by using the environmental friendly extraction procedure. In this study, we have reported the simple mixed-micelle cloud point extraction (MM-CPE) procedure for separation as well as pre-concentration of Rh, Ru and Pd. This MM-CPE is carried out preliminarily from aqueous chloride medium with Aliquat-336/Triton X-114 mixed-micelles in the absence and presence of tin(II) chloride. In presence of chloride medium alone, only Pd get extracted quantitatively, while extraction of Rh and Ru are negligible. In presence of tin chloride, the extraction of Rh and Ru increases and becomes quantitative, without affecting the extraction of Pd. The MM-CPE conditions are optimized under influence of variables such as HCI, Aliquat-336, Triton X-114 and tin chloride concentrations and incubation time and temperature. Under the optimized conditions, the accuracy of the procedure is verified by using recovery study carried out from real water samples. This work is under progress to apply real nuclear fuel waste samples

  16. Mono and dinuclear rhodium, iridium and ruthenium complexes containing chelating 2,2´-bipyrimidine ligands: Synthesis, molecular structure, electrochemistry and catalytic properties

    Czech Academy of Sciences Publication Activity Database

    Govindaswamy, P.; Canivet, J.; Therrien, B.; Süss-Fink, G.; Štěpnička, P.; Ludvík, Jiří

    2007-01-01

    Roč. 692, č. 17 (2007), s. 3664-3675 ISSN 0022-328X R&D Projects: GA MŠk(CZ) LC06070 Institutional research plan: CEZ:AV0Z40400503 Keywords : arene ligands * electrochemistry * dinuclear complexes * transfer hydrogenation Subject RIV: CG - Electrochemistry Impact factor: 2.168, year: 2007

  17. Homoleptic mono- and dinuclear cationic alkoxydiphosphazane derivatives of rhodium

    International Nuclear Information System (INIS)

    Edwards, K.J.; Haines, R.J.; Meintjies, E.; Sigwarth, B.

    1990-01-01

    Treatment of the solvento species [Rh(C 8 H 12 )(solvent) 2 ][SbF 6 ] (solvent = methanol, ethanol, or tetrahydrofuran) with a twice-molar amount of the diphosphazane ligands (RO) 2 PN(R') P(OR) 2 (R' = Me or Et; R = Me, Et, or Pr i ) in the appropriate solvent leads to the ready formation of monocationic [Rh{(RO) 2 PN(R')P(OR) 2 } 2 ] + and/or dicationic [Rh 2 {μ-(RO) 2 PN(R')P(OR) 2 } 2 {(RO) 2 PN(R')P(OR) 2 } 2 ] 2+ hexafluoroantimonate salts, with the tendency to afford dinuclear derivatives decreasing along the series Me>Et>Pr i . Carbon monoxide readily forms addition products with these ionic species, giving rise to five-coordinate derivatives of the type [Rh(CO){(RO) 2 PN(R')P (OR) 2 } 2 ][SbF 6 ] in the case of the mononuclear derivatives, and inserting across the two rhodium atoms to afford [Rh 2 (μ-CO){μ-(MeO) 2 PN(Et)P(OMe) 2 } 2 {(MeO) 2 PN(Et)P(OMe) 2 } 2 ][SbF 6 ] 2 in the case of [Rh 2 {μ-(MeO) 2 PN (Et)P(OMe) 2 } 2 {(MeO) 2 PN(Et)P(OMe) 2 } 2 ][SbF 6 ] 2 . These mono- and dicationic derivatives also react readily with iodine affording [RhI 2 {(RO) 2 PN(R')P(OR) 2 } 2 ][SbF 6 ] and [Rh 2 (μ-I){μ-(MeO) 2 PN(Et)P(OMe) 2 } 2 {(MeO) 2 PN(Et)P(OMe) 2 } 2 ][SbF 6 ] n (n = 2 or 3) respectively. The coordination behaviour of the diphosphorus ligands (MeO) 2 PCH 2 P(OMe) 2 and Me 2 PCH 2 PMe 2 towards [Rh(C 8 H 12 )(solvent) 2 ][SbF 6 ] has also been investigated. 1 fig., 1 tab., 19 refs

  18. Relationship between electronic structure and electric conductivity of double rhodium oxides from X-ray spectral data

    International Nuclear Information System (INIS)

    Firsov, M.N.; Nefedov, V.I.; Shaplygin, I.S.

    1983-01-01

    Quantum yield spectra of X-ray photoemission of O K - and Rh M 3 -bands of double rhodium oxides with Be, Mg, Ca, Sr, Ba, Cd, V, Nb, Ta, Mo, W are obtained. Quantum yield spectra are analogous to absorption spectra and reflect vacant states in a crystal, in particular, the quantum yield spectrum of O K-band is associated with oxygen vacant states of p-symmetry while Rh M 3 -band spectrum with rhomium vacant states of d-symmetry. In all rhodium compounds investigated the first vacant band is formed by the rhodium 4d-states. The forbidden zone between the last occupied and first free states of rhodiUm has a small width (eV fractions), which explains the semiconductor character of electric conductivity of the investigated compounds. Electric resistance variation in investigated series of rhodium compounds is in agreement with peculiarities of their electronic structure and entirely depends on variation in the electron density on rhodium atoms

  19. Method of improving the decontaminating efficiency of ruthenium in evaporating treatment of nitric acid

    International Nuclear Information System (INIS)

    Kubota, Kanya; Yamana, Hajime; Takeda, Seiichiro.

    1984-01-01

    Purpose: To significantly improve the ruthenium removing efficiency in a nitric acid solution in an acid recovery system for the recovery of nitric acid from nitric acid liquid wastes through evaporating condensation. Method: Upon evaporating treatment of nitric acid solution containing ruthenium by supplying and heating the solution to a nitric acid evaporating device, hydrazine is previously added to the nitric acid solution. Hydrazine and intermediate reaction product of hydrazine such as azide causes a reduction reaction with intermediate reaction product of ruthenium tetraoxide to suppress the oxidation of ruthenium and thereby improve the decontaminating efficiency of ruthenium. The amount of hydrazine to be added is preferably between 20 - 500 mg/l and most suitably between 200 - 2000 mg/l per one liter of the liquid in the evaporating device. (Seki, T.)

  20. Late side effects of Ruthenium 106 therapy for uveal melanomas

    International Nuclear Information System (INIS)

    Langmann, G.; Faulborn, J.; Poier, E.

    1994-01-01

    When effectiveness is evaluated in brachytherapy with Ruthenium 106 special emphasis has to be put on tumor destruction and late side effects responsible for the definite functional results. We evaluated the late side effects of 22 uveal melanomas, which had been treated with 106 Ruthenium plaques. The tumor prominences ranged from 3 to 10 mm, the diameter from 4 to 9 disc diameters. In 4 patients the tumor involved the posterior pole, 14 melanomas were located in the midperiphery of the fundus, 4 tumors were ciliary body melanomas. The total radiation dose of the apex ranged from 100 to 240 Gy with a corresponding dose to the sclera between 540 to 1000 Gy. Because of the short half life of the plaque we have been using different dose rates (1.6-11 Gy/h). In 17/22 eyes adequate regression could be achieved by Ruthenium therapy alone. In one case additional laser treatment of the macular part of the melanoma had to be performed, Gamma Knife therapy was necessary in another melanoma with 10 mm tumor prominence. 3 recurrences led to enucleation. The mean follow up was 4.8 years ranging from 1 to 7 years. In 2/22 patients opticopathy caused severe visual impairment, in another 2 patients radiation maculopathy and opticopathy was observed. 7/22 developed vasculopathy with neovascularization treated by photocoagulation. In one case of focal radiation maculopathy laser treatment could prevent further visual impairment. The following factors are responsible for a higher incidence of late side effects: 1. High dose rate of the plaques in combination with a high radiation dose to the sclera 2. Location of the tumor within a minimum distance of 2 disc diameters to the optic nerve or macula 3. Tumor location at the ciliary body Laser treatment in case of neovascularization and focal radiation maculopathy is the only effective treatment with regard to late side effects. Ischemic maculopathy and radiation opticopathy are responsible for late visual impairment. (authors)

  1. Radiation related complications after ruthenium plaque radiotherapy of uveal melanoma

    Energy Technology Data Exchange (ETDEWEB)

    Summanen, P.; Immonen, I.; Kivela, T.; Tommila, P.; Tarkkanen, A. [Helsinki Univ. Central Hospital (Finland). Meilahti Clinic; Heikkonen, J. [Helsinki Univ. (Finland). Dept of Radiotherapy and Oncology

    1996-08-01

    The aims were to analyse radiation related complications and secondary enucleation after irradiation of malignant uveal melanoma with ruthenium-106 plaques. A series of 100 consecutive eyes irradiated in 1981-91 was analysed using the life table method and the Cox proportional hazards model. The 3 and 5 year probabilities of being without radiation cataract were 73% and 63%, without neovascular glaucoma 91% and 81%, without vitreous haemorrhage 83% and 74%, without radiation maculopathy 85% and 70%, and without radiation optic neuropathy 90% and 88%, respectively. (Author).

  2. Radiation related complications after ruthenium plaque radiotherapy of uveal melanoma

    International Nuclear Information System (INIS)

    Summanen, P.; Immonen, I.; Kivela, T.; Tommila, P.; Tarkkanen, A.; Heikkonen, J.

    1996-01-01

    The aims were to analyse radiation related complications and secondary enucleation after irradiation of malignant uveal melanoma with ruthenium-106 plaques. A series of 100 consecutive eyes irradiated in 1981-91 was analysed using the life table method and the Cox proportional hazards model. The 3 and 5 year probabilities of being without radiation cataract were 73% and 63%, without neovascular glaucoma 91% and 81%, without vitreous haemorrhage 83% and 74%, without radiation maculopathy 85% and 70%, and without radiation optic neuropathy 90% and 88%, respectively. (Author)

  3. Progress in doping of ruthenium silicide (Ru2Si3)

    International Nuclear Information System (INIS)

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

    1992-01-01

    This paper reports that ruthenium silicide (Ru 2 Si 3 ) 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

  4. Ruthenium-Catalyzed Dehydrogenative Decarbonylation of Primary Alcohols

    DEFF Research Database (Denmark)

    Mazziotta, Andrea; Madsen, Robert

    2017-01-01

    Dehydrogenative decarbonylation of a primary alcohol involves the release of both dihydrogen and carbon monoxide to afford the one-carbon shorter product. The transformation has now been achieved with a ruthenium-catalyzed protocol by using the complex Ru(COD)Cl2 and the hindered monodentate ligand...... P(o-tolyl)3 in refluxing p-cymene. The reaction can be applied to both benzylic and long chain linear aliphatic alcohols. The intermediate aldehyde can be observed during the transformation, which is therefore believed to proceed through two separate catalytic cycles involving first dehydrogenation...... of the alcohol and then decarbonylation of the resulting aldehyde....

  5. Selective Cytotoxicity of Rhodium Metalloinsertors in Mismatch Repair-Deficient Cells†

    Science.gov (United States)

    Ernst, Russell J.; Komor, Alexis C.; Barton, Jacqueline K.

    2011-01-01

    Mismatches in DNA occur naturally during replication and as a result of endogenous DNA damaging agents, but the mismatch repair (MMR) pathway acts to correct mismatches before subsequent rounds of replication. Rhodium metalloinsertors bind to DNA mismatches with high affinity and specificity and represent a promising strategy to target mismatches in cells. Here we examine the biological fate of rhodium metalloinsertors bearing dipyridylamine ancillary ligands in cells deficient in MMR versus those that are MMR-proficient. These complexes are shown to exhibit accelerated cellular uptake which permits the observation of various cellular responses, including disruption of the cell cycle, monitored by flow cytometry assays, and induction of necrosis, monitored by dye exclusion and caspase inhibition assays, that occur preferentially in the MMR-deficient cell line. These cellular responses provide insight into the mechanisms underlying the selective activity of this novel class of targeted anti-cancer agents. PMID:22103240

  6. Asymmetric Synthesis of Hydrocarbazoles Catalyzed by an Octahedral Chiral-at-Rhodium Lewis Acid.

    Science.gov (United States)

    Huang, Yong; Song, Liangliang; Gong, Lei; Meggers, Eric

    2015-12-01

    A bis-cyclometalated chiral-at-metal rhodium complex catalyzes the Diels-Alder reaction between N-Boc-protected 3-vinylindoles (Boc = tert-butyloxycarbonyl) and β-carboxylic ester-substituted α,β-unsaturated 2-acyl imidazoles with good-to-excellent regioselectivity (up to 99:1) and excellent diastereoselectivity (>50:1 d.r.) as well as enantioselectivity (92-99% ee) under optimized conditions. The rhodium catalyst serves as a chiral Lewis acid to activate the 2-acyl imidazole dienophile by two-point binding and overrules the preferred regioselectivity of the uncatalyzed reaction. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Effects of human serun albumin in some biological properties of rhodium(II complexes

    Directory of Open Access Journals (Sweden)

    Espósito Breno P.

    2000-01-01

    Full Text Available The affinities for human albumin (HSA of five rhodium(II complexes of general formula [Rh2(bridge4] (bridge = acetate, propionate, butyrate, trifluoroacetate and trifluoroacetamidate were determined by spectrophotometry. In the case of the alkylcarboxylates, an inverse correlation of affinity with their liposolubilities was observed. Diffusion of the free or protein-bound complexes into Ehrlich cells in vitro seems to be primarily governed by the hydrophobic character of the complex. The complex [Rh2(tfc4] exhibited affinity towards the protein (K = 214.1 as well as cell partition both in the absence (32.1% and presence (48.6% of HSA. The compound HSA: [Rh2(tfc4] has had its antitumoral action in tumor-bearing Balb-c mice investigated, showing that HSA can be a drug reservoir for the rhodium complex.

  8. Removal of fission product ruthenium from purex process solutions: thiourea as complexing agent

    International Nuclear Information System (INIS)

    Floh, B.; Abrao, A.

    1980-01-01

    A new method for the treatment of spent uranium fuel is presented. It is based on the Purex Process using thiourea to increase the ruthenium decontamination factor. Thiourea exhibits a strong tendency for the formation of coordination compounds in acidic media. This tendency serves as a basis to transform nitrosyl-ruthenium species into Ru /SC(NH)(NH 2 )/ 2+ and Ru /SC(NH)(NH 2 )/ 3 complexes which are unextractable by TBP-varsol. The best conditions for the ruthenium-thiourea complex formation were found to be: thiourea-ruthenium ratio (mass/mass) close to 42, at 75 0 C, 30 minutes reaction time and aging period of 60 minutes. The ruthenium decontamination factor for a single uranium extraction are ca. 80-100, not interfering with extraction of actinides. These values are rather high in comparison to those obtained using the conventional Purex Process (e.g. F.D. sub(Ru)=10). By this reason the method developed here is suitable for the treatment of spent uranium fuels. Thiourea (100g/l) scrubbing experiments of ruthenium, partially co-extracted with actinides, confirmed the possibility of its removal from the extract. A decontamination greater than 83,5% for ruthenium as fission product is obtained in two stages with this procedure. (Author) [pt

  9. A thermodynamic/mass-transport model for the release of ruthenium from irradiated fuel

    International Nuclear Information System (INIS)

    Garisto, F.; Iglesias, F.C.; Hunt, C.E.L.

    1990-01-01

    Some postulated nuclear reactor accidents lead to fuel failures and hence release of fission products into the primary heat transport system (PHTS). To determine the consequences of such accidents, it is important to understand the behavior of fission products both in the PHTS and in the reactor containment building. Ruthenium metal has a high boiling point and is nonvolatile under reducing conditions. However, under oxidizing conditions ruthenium can form volatile oxides at relatively low temperatures and, hence, could escape from failed fuel and enter the containment building. The ruthenium radioisotope Ru-106 presents a potentially significant health risk if it is released outside the reactor containment building. Consequently, it is important to understand the behavior of ruthenium during a nuclear reactor accident. The authors review the thermodynamic behavior of ruthenium at high temperatures. The qualitative behavior of ruthenium, predicted using thermodynamic calculations, is then compared with experimental results from the Chalk River Nuclear Laboratories (CRNL). Finally, a simple thermodynamic/mass-transport model is proposed to explain the release behavior of ruthenium in a steam atmosphere

  10. Complexes of technetium, rhenium, and rhodium with sexidentate Schiff-base ligands

    International Nuclear Information System (INIS)

    Hunter, G.; Kilcullen, N.

    1989-01-01

    The monocationic technetium (IV) and rhenium (IV) complexes with the sexidentate Schiff-base ligands tris[2-(2'-hydroxybenzylideneethyl)]amine and its substituted derivatives have been prepared and their electrochemical properties studied. The variable-temperature 90.6 MHz 13 C-{ 1 H} n.m.r. spectrum of the rhodium (III) complex of tris[2-(2-hydroxy-5'-isopropylbenzylideneethyl)-amine] has been observed, indicating fluxionality at temperatures above 218 K. (author)

  11. Bifunctional Rhodium Intercalator Conjugates as Mismatch-Directing DNA Alkylating Agents

    OpenAIRE

    Schatzschneider, Ulrich; Barton, Jacqueline K.

    2004-01-01

    A conjugate of a DNA mismatch-specific rhodium intercalator, containing the bulky chrysenediimine ligand, and an aniline mustard has been prepared, and targeting of mismatches in DNA by this conjugate has been examined. The preferential alkylation of mismatched over fully matched DNA is found by a mobility shift assay at concentrations where untethered organic mustards show little reaction. The binding site of the Rh intercalator was determined by DNA photocleavage, and the position of covale...

  12. Dynamical model of computation of the rhodium self-powered neutron detector current

    International Nuclear Information System (INIS)

    Erben, O.; Slovacek, M.; Zerola, L.

    1992-01-01

    A model is presented for the calculation of the rhodium self-powered neutron detector current in dependence on the neutron flux density during reactor core transients. The total signal consists of a beta emission, prompt, and gamma component and a background signal. The model has been verified by means of experimental data obtained during measurements on the LVR-15 research reactor and at the Dukovany nuclear power plant. (author) 9 figs., 21 refs

  13. Rhodium-catalyzed asymmetric hydroboration of γ,δ-unsaturated amide derivatives: δ-borylated amides.

    Science.gov (United States)

    Hoang, G L; Zhang, S; Takacs, J M

    2018-05-08

    γ,δ-Unsaturated amides in which the alkene moiety bears an aryl or heteroaryl substituent undergo regioselective rhodium-catalyzed δ-borylation by pinacolborane to afford chiral secondary benzylic boronic esters. The results contrast the γ-borylation of γ,δ-unsaturated amides in which the disubstituted alkene moiety bears only alkyl substituents; the reversal in regiochemistry is coupled with a reversal in the sense of π-facial selectivity.

  14. Examining Rhodium Catalyst complexes for Use with Conducting Polymers Designed for Fuel Cells in Preparing Biosensors

    Energy Technology Data Exchange (ETDEWEB)

    Carpio, M.M.; Kerr, J.B.

    2005-01-01

    Biosensing devices are important because they can detect, record, and transmit information regarding the presence of, or physiological changes in, different chemical or biological materials in the environment. The goal of this research is to prepare a biosensing device that is effective, quick, and low cost. This is done by examining which chemicals will work best when placed in a biosensor. The first study involved experimenting on a rhodium catalyst complexed with ligands such as bipyridine and imidazole. The rhodium catalyst is important because it is reduced from RhIII to RhI, forms a hydride by reaction with water and releases the hydride to react with nicotinamide adenine dinucleotide (NAD+) to selectively produce 1,4-NADH, the reduced form of NAD+. The second study looked at different types of ketones and enzymes for the enzyme-substrate reaction converting a ketone into an alcohol. Preliminary results showed that the rhodium complexed with bipyridine was able to carry out all the reactions, while the rhodium complexed with imidazole was not able to produce and release hydrides. In addition, the most effective ketone to use is benzylacetone with the enzyme alcohol dehydrogenase from baker’s yeast. Future work includes experimenting with bis-imidazole, which mimics the structure of bipyridine to see if it has the capability to reduce and if the reduction rate is comparable to the bipyridine complex. Once all testing is completed, the fastest catalysts will be combined with polymer membranes designed for fuel cells to prepare biosensing devices that can be used in a variety of applications including ones in the medical and environmental fields.

  15. Rhodium-catalyzed C-H functionalization with N-acylsaccharins.

    Science.gov (United States)

    Wu, Hongxiang; Liu, Tingting; Cui, Ming; Li, Yue; Jian, Junsheng; Wang, Hui; Zeng, Zhuo

    2017-01-18

    A rhodium-catalyzed C-H functionalization with activated amides by decarbonylation has been developed. Notably, this is the first C-H arylation employing N-acylsaccharins as coupling partners to give biaryls in good to excellent yields. The highlight of the work is the high tolerance of functional groups such as formyl, ester, and vinyl and the use of a removable directing group.

  16. Rhodium-catalyzed asymmetric hydrogenation of unprotected NH imines assisted by a thiourea.

    Science.gov (United States)

    Zhao, Qingyang; Wen, Jialin; Tan, Renchang; Huang, Kexuan; Metola, Pedro; Wang, Rui; Anslyn, Eric V; Zhang, Xumu

    2014-08-04

    Asymmetric hydrogenation of unprotected NH imines catalyzed by rhodium/bis(phosphine)-thiourea provided chiral amines with up to 97% yield and 95% ee. (1)H NMR studies, coupled with control experiments, implied that catalytic chloride-bound intermediates were involved in the mechanism through a dual hydrogen-bonding interaction. Deuteration experiments proved that the hydrogenation proceeded through a pathway consistent with an imine. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Regioselective syntheses of 1,2-benzothiazines by rhodium-catalyzed annulation reactions.

    Science.gov (United States)

    Cheng, Ying; Bolm, Carsten

    2015-10-12

    Rhodium-catalyzed directed carbene insertions into aromatic CH bonds of S-aryl sulfoximines lead to intermediates, which upon dehydration provide 1,2-benzothiazines in excellent yields. The domino-type process is regioselective and shows a high functional-group tolerance. It is scalable, and the only by-products are dinitrogen and water. Three illustrative transformations underscore the synthetic value of the products. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Rhodium-catalyzed chemo-, regio-, and enantioselective addition of 2-pyridones to terminal allenes.

    Science.gov (United States)

    Li, Changkun; Kähny, Matthias; Breit, Bernhard

    2014-12-08

    A rhodium-catalyzed chemo-, regio-, and enantioselective addition of 2-pyridones to terminal allenes to give branched N-allyl 2-pyridones is reported. Preliminary mechanistic studies support the hypothesis that the reaction was initiated from the more acidic 2-hydroxypyridine form, and the initial kinetic O-allylation product was finally converted into the thermodynamically more stable N-allyl 2-pyridones. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Rhodium-catalyzed triarylphosphine synthesis via cross-coupling of aryl iodides and acylphosphines

    Directory of Open Access Journals (Sweden)

    Jiefang Yang

    2018-01-01

    Full Text Available Rhodium(I-catalyzed C–P cross-coupling reaction with aryl iodides and acylphosphines was disclosed for a straight forward synthesis of triarylphosphines. The acylphosphines were successfully employed as both the phosphorus source and the ligand to the Rh(I catalyst. The triarylphosphines could be afforded in a yield up to 98% with good toleration of wide functional groups.

  20. Divergent Reactivity of Rhodium(I) Carbenes Derived from Indole Annulations.

    Science.gov (United States)

    Li, Xiaoxun; Li, Hui; Song, Wangze; Tseng, Po-Sen; Liu, Lingyan; Guzei, Ilia A; Tang, Weiping

    2015-10-26

    Rhodium(I) carbenes were generated from propargylic alcohol derivatives as the result of a dehydrative indole annulation. Depending on the choice of the electron-withdrawing group on the aniline nitrogen nucleophile, either a cyclopropanation product or dimerization product was obtained chemoselectively. Intramolecular hydroamidation occurred for the same type of propargylic alcohol derivatives when other transition-metal catalysts were employed. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Rhodium SPND's Error Reduction using Extended Kalman Filter combined with Time Dependent Neutron Diffusion Equation

    International Nuclear Information System (INIS)

    Lee, Jeong Hun; Park, Tong Kyu; Jeon, Seong Su

    2014-01-01

    The Rhodium SPND is accurate in steady-state conditions but responds slowly to changes in neutron flux. The slow response time of Rhodium SPND precludes its direct use for control and protection purposes specially when nuclear power plant is used for load following. To shorten the response time of Rhodium SPND, there were some acceleration methods but they could not reflect neutron flux distribution in reactor core. On the other hands, some methods for core power distribution monitoring could not consider the slow response time of Rhodium SPND and noise effect. In this paper, time dependent neutron diffusion equation is directly used to estimate reactor power distribution and extended Kalman filter method is used to correct neutron flux with Rhodium SPND's and to shorten the response time of them. Extended Kalman filter is effective tool to reduce measurement error of Rhodium SPND's and even simple FDM to solve time dependent neutron diffusion equation can be an effective measure. This method reduces random errors of detectors and can follow reactor power level without cross-section change. It means monitoring system may not calculate cross-section at every time steps and computing time will be shorten. To minimize delay of Rhodium SPND's conversion function h should be evaluated in next study. Neutron and Rh-103 reaction has several decay chains and half-lives over 40 seconds causing delay of detection. Time dependent neutron diffusion equation will be combined with decay chains. Power level and distribution change corresponding movement of control rod will be tested with more complicated reference code as well as xenon effect. With these efforts, final result is expected to be used as a powerful monitoring tool of nuclear reactor core

  2. Rhodium SPND's Error Reduction using Extended Kalman Filter combined with Time Dependent Neutron Diffusion Equation

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Jeong Hun; Park, Tong Kyu; Jeon, Seong Su [FNC Technology Co., Ltd., Yongin (Korea, Republic of)

    2014-05-15

    The Rhodium SPND is accurate in steady-state conditions but responds slowly to changes in neutron flux. The slow response time of Rhodium SPND precludes its direct use for control and protection purposes specially when nuclear power plant is used for load following. To shorten the response time of Rhodium SPND, there were some acceleration methods but they could not reflect neutron flux distribution in reactor core. On the other hands, some methods for core power distribution monitoring could not consider the slow response time of Rhodium SPND and noise effect. In this paper, time dependent neutron diffusion equation is directly used to estimate reactor power distribution and extended Kalman filter method is used to correct neutron flux with Rhodium SPND's and to shorten the response time of them. Extended Kalman filter is effective tool to reduce measurement error of Rhodium SPND's and even simple FDM to solve time dependent neutron diffusion equation can be an effective measure. This method reduces random errors of detectors and can follow reactor power level without cross-section change. It means monitoring system may not calculate cross-section at every time steps and computing time will be shorten. To minimize delay of Rhodium SPND's conversion function h should be evaluated in next study. Neutron and Rh-103 reaction has several decay chains and half-lives over 40 seconds causing delay of detection. Time dependent neutron diffusion equation will be combined with decay chains. Power level and distribution change corresponding movement of control rod will be tested with more complicated reference code as well as xenon effect. With these efforts, final result is expected to be used as a powerful monitoring tool of nuclear reactor core.

  3. Dynamics of the contact between a ruthenium surface with a single nanoasperity and a flat ruthenium surface: Molecular dynamics simulations

    International Nuclear Information System (INIS)

    Barros de Oliveira, Alan; Fortini, Andrea; Buldyrev, Sergey V.; Srolovitz, David

    2011-01-01

    We study the dynamics of the contact between a pair of surfaces (with properties designed to mimic ruthenium) via molecular dynamics simulations. In particular, we study the contact between a ruthenium surface with a single nanoasperity and a flat ruthenium surface. The results of such simulations suggest that contact behavior is highly variable. The goal of this study is to investigate the source and degree of this variability. We find that during compression, the behavior of the contact force displacement curves is reproducible, while during contact separation, the behavior is highly variable. Examination of the contact surfaces suggests that two separation mechanisms are in operation and give rise to this variability. One mechanism corresponds to the formation of a bridge between the two surfaces that plastically stretches as the surfaces are drawn apart and eventually separate in shear. This leads to a morphology after separation in which there are opposing asperities on the two surfaces. This plastic separation/bridge formation mechanism leads to a large work of separation. The other mechanism is a more brittle-like mode in which a crack propagates across the base of the asperity (slightly below the asperity/substrate junction) leading to most of the asperity on one surface or the other after separation and a slight depression facing this asperity on the opposing surface. This failure mode corresponds to a smaller work of separation. This failure mode corresponds to a smaller work of separation. Furthermore, contacts made from materials that exhibit predominantly brittle-like behavior will tend to require lower work of separation than those made from ductile-like contact materials.

  4. Selectivity of a heterogeneous rhodium catalyst for the carbonylation of monohydric alcohols

    Energy Technology Data Exchange (ETDEWEB)

    Christensen, B; Scurrell, M S

    1977-01-01

    Selectivity of a heterogeneous rhodium catalyst for the carbonylation of monohydric alcohols with carbon monoxide in the presence of the corresponding alkyl iodides as promotors was studied in a glass reactor at approx. 0.05:1 alcohol/carbon monoxide ratio. The 1% by wt rhodium-zeolite catalyst was prepared by immersing a Linde molecular sieve zeolite Type 13X in rhodium trichloride at 80/sup 0/C for 15 hr. Methanol was converted to methyl acetate at 433/sup 0/-513/sup 0/K with selectivites > 90% even at the highest temperatures, and dimethyl ether was by-produced. In the absence of methyl iodide, the carbonylation rate decreased drastically but the dehydration was virtually unaffected. The selectivity for ethanol carbonylation decreased from 99% at 383/sup 0/K to 6% at 523/sup 0/K due to the formation of ethylene (predominant at > 470/sup 0/K) and diethyl ether. The only product of the reaction with propan-2-ol studied at 433/sup 0/ or 473/sup 0/K was propene with 100% conversion at 473/sup 0/K. These results are consistent with the relative ease of reactant dehydration on polar catalysts. Table and 13 references.

  5. Spatial and temporal distribution of platinum, palladium and rhodium in Zagreb air.

    Science.gov (United States)

    Rinkovec, Jasmina; Pehnec, Gordana; Godec, Ranka; Davila, Silvije; Bešlić, Ivan

    2018-09-15

    Platinum (Pt), palladium (Pd) and rhodium (Rh) are most widely used in the production of automotive catalytic converters that serve to reduce toxic emissions from motor vehicles. The aim of this study was to quantitatively determine the levels of platinum, palladium and rhodium in the PM 10 and PM 2.5 fraction of airborne particle matter and find their spatial and temporal distribution at different polluted areas of the city of Zagreb, Croatia. The method used in this paper included weekly sampling of airborne particle matter on quartz filters, microwave digestion in acid under high pressure and temperature, and analysis by inductively coupled plasma mass spectrometry (ICP MS). The results have shown that the highest mean values at all three sampling stations (North, Center, South) were obtained for palladium (3.856 pg m -3 , 5.396 pg m -3 , 5.600 pg m -3 ) and the lowest for rhodium (0.444 pg m -3 , 0.643 pg m -3 , 0.750 pg m -3 ). The average mass concentrations of platinum group elements (PGE) in PM 10 increased for all three elements in the direction North Zagreb are the first results of their kind for this area and will provide insights into the contribution of catalytic converters to the presence of these elements in the environment. Copyright © 2018 Elsevier B.V. All rights reserved.

  6. Rhodium self-powered detector for monitoring neutron fluence, energy production, and isotopic composition of fuel

    International Nuclear Information System (INIS)

    Sokolov, A.P.; Pochivalin, G.P.; Shipovskikh, Yu.M.; Garusov, Yu.V.; Chernikov, O.G.; Shevchenko, V.G.

    1993-01-01

    The use of self-powered detectors (SPDs) with a rhodium emitter customarily involves monitoring of neutron fields in the core of a nuclear reactor. Since current in an SPD is generated primarily because of the neutron flux, which is responsible for the dynamics of particular nuclear transformations, including fission reactions of heavy isotopes, the detector signal can be attributed unambiguously to energy release at the location of the detector. Computation modeling performed with the KOMDPS package of programs of the current formation in a rhodium SPD along with the neutron-physical processes that occur in the reactor core makes it possible to take account of the effect of the principal factors characterizing the operating conditions and the design features of the fuel channel and the detector, reveal quantitative relations between the generated signal and individual physical parameters, and determine the metrological parameters of the detector. The formation and transport of changed particles in the sensitive part of the SPC is calculated by the Monte Carlo method. The emitter activation, neutron transport, and dynamics of the isotopic composition in the fuel channel containing the SPD are determined by solving the kinetic equation in the multigroup representation of the neutron spectrum, using the discrete ordinate method. In this work the authors consider the operation of a rhodium SPD in a bundle of 49 fuel channels of the RBMK-1000 reactor with a fuel enrichment of 2.4% from the time it is inserted into a fresh channel

  7. Stereoselective hydrogenation of olefins using rhodium-substituted carbonic anhydrase--a new reductase.

    Science.gov (United States)

    Jing, Qing; Okrasa, Krzysztof; Kazlauskas, Romas J

    2009-01-01

    One useful synthetic reaction missing from nature's toolbox is the direct hydrogenation of substrates using hydrogen. Instead nature uses cofactors like NADH to reduce organic substrates, which adds complexity and cost to these reductions. To create an enzyme that can directly reduce organic substrates with hydrogen, researchers have combined metal hydrogenation catalysts with proteins. One approach is an indirect link where a ligand is linked to a protein and the metal binds to the ligand. Another approach is direct linking of the metal to protein, but nonspecific binding of the metal limits this approach. Herein, we report a direct hydrogenation of olefins catalyzed by rhodium(I) bound to carbonic anhydrase (CA-[Rh]). We minimized nonspecific binding of rhodium by replacing histidine residues on the protein surface using site-directed mutagenesis or by chemically modifying the histidine residues. Hydrogenation catalyzed by CA-[Rh] is slightly slower than for uncomplexed rhodium(I), but the protein environment induces stereoselectivity favoring cis- over trans-stilbene by about 20:1. This enzyme is the first cofactor-independent reductase that reduces organic molecules using hydrogen. This catalyst is a good starting point to create variants with tailored reactivity and selectivity. This strategy to insert transition metals in the active site of metalloenzymes opens opportunities to a wider range of enzyme-catalyzed reactions.

  8. Functionalized cyclopentadienyl rhodium(III) bipyridine complexes: synthesis, characterization, and catalytic application in hydrogenation of ketones.

    Science.gov (United States)

    Wang, Wan-Hui; Suna, Yuki; Himeda, Yuichiro; Muckerman, James T; Fujita, Etsuko

    2013-07-14

    A series of highly functionalized cyclopentadienyl rhodium(III) complexes, [Cp'Rh(bpy)Br](ClO4) (Cp' = substituted cyclopentadienyl), was synthesized from various multi-substituted cyclopentadienes (Cp'H). [Rh(cod)Cl]2 and Cp'H were firstly converted to [Cp'Rh(cod)] complexes, which were then treated with Br2 to give the rhodium(III) dibromides [Cp'RhBr2]2. The novel complexes [Cp'Rh(bpy)Br](ClO4) were obtained readily by the reaction of 2,2'-bipyridine with [Cp'RhBr2]2. These rhodium complexes [Cp'Rh(bpy)Br](ClO4) were fully characterized and utilized in the hydrogenation of cyclohexanone and acetophenone with generally high yields, but they did not exhibit the same reactivity trends for the two substrate ketones. The different activity of these complexes for the different substrates may be due to the influence of the substituents on the Cp' rings.

  9. Rhodium (II) cycle alkanecarboxylate: synthesis, spectroscopic and thermo analytic studies and evaluation of the antitumor potential

    International Nuclear Information System (INIS)

    Souza, Aparecido Ribeiro de

    1995-01-01

    Four new rhodium(II) carboxylates (cyclopropane, cyclobutane, cyclopentane, and cyclohexanecarboxylate), and other already known rhodium (II) carboxylates (acetate, propionate, butyrate, metoxyacetate, dichloroacetate, and trifluoroacetate), have been prepared for study in this work. The compounds were characterized by elementary and thermogravimetric analysis, magnetic susceptibility, and electronic, Raman, and infrared spectroscopy. The reaction of Rh CL 3 .aq with the sodium carboxylates was studied aiming to improve the understanding of the redox process involved. Spectroscopy studies (Raman and electronic) were made to examine the transition involved in the Rh-Rh and Rh-O bonds. The results have shown a direct relation between the force of the carboxylic acid and the Rh-O force, but show a inverse relation with the Rh-Rh bond force. Thermal analysis studies were undertaken and the obtained date show a resemblance of the TG/DTG curves with that found in literature. In the other hand, the DSC curves show a different results: in open crucible, the peaks associated with the cage breakdown are exothermic and, in closed crucible this peaks are endothermic. The thermodecomposition products were analyzed. The evolved gases were identified by GC?MS and 1 H and 13 C NMR spectra. The residues were analyzed by X-ray diffraction. Antitumor activity of rhodium cyclopropanecarboxylate was evaluated in vitro (cell cultures K562 and Ehrlich) and in vivo (Balb-c mice with ascite Ehrlich tumor), indicating an increased life span (87.5%) of the treated animals. (author)

  10. Rhodium-coated mirrors deposited by magnetron sputtering for fusion applications

    International Nuclear Information System (INIS)

    Marot, L.; Temmermann, G. de; Oelhafen, P.; Mathys, D.; Covarel, G.; Litnovsky, A.

    2007-01-01

    Metallic mirrors will be essential components of all optical spectroscopy and imaging systems for plasma diagnostics that will be used in ITER. Any change in the mirror performance, in particular its reflectivity, will influence the quality and reliability of detected signals. Due to its high reflectivity in the visible wavelength range and its low sputtering yield, rhodium may be a good candidate material for first mirrors in ITER. However, the very high price of the raw material calls for using it in the form of a film deposited onto metallic substrates. The development of a reliable technique for the preparation of high reflectivity rhodium films is therefore of the highest importance. Rhodium layers with thicknesses of up to 2 μm were produced on different relevant substrates (Mo, Stainless Steel, Cu) by magnetron sputtering. Produced films exhibit a low roughness, crystallite size of about 10 nm with a dense columnar structure. No impurities were detected on the surface after deposition. Scratch test results demonstrate that adhesion properties increase with the substrate hardness. The detailed optical characterizations of Rh coated mirrors as well as the results of erosion tests performed both under laboratory conditions and in TEXTOR will be presented in this paper. (orig.)

  11. Cell-Selective Biological Activity of Rhodium Metalloinsertors Correlates with Subcellular Localization

    Science.gov (United States)

    Komor, Alexis C.; Schneider, Curtis J.; Weidmann, Alyson G.; Barton, Jacqueline K.

    2013-01-01

    Deficiencies in the mismatch repair (MMR) pathway are associated with several types of cancers, as well as resistance to commonly used chemotherapeutics. Rhodium metalloinsertors have been found to bind DNA mismatches with high affinity and specificity in vitro, and also exhibit cell-selective cytotoxicity, targeting MMR-deficient cells over MMR-proficient cells. Ten distinct metalloinsertors with varying lipophilicities have been synthesized and their mismatch binding affinities and biological activities determined. Although DNA photocleavage experiments demonstrate that their binding affinities are quite similar, their cell-selective antiproliferative and cytotoxic activities vary significantly. Inductively coupled plasma mass spectrometry (ICP-MS) experiments have uncovered a relationship between the subcellular distribution of these metalloinsertors and their biological activities. Specifically, we find that all of our metalloinsertors localize in the nucleus at sufficient concentrations for binding to DNA mismatches. However, the metalloinsertors with high rhodium localization in the mitochondria show toxicity that is not selective for MMR-deficient cells, whereas metalloinsertors with less mitochondrial rhodium show activity that is highly selective for MMR-deficient versus proficient cells. This work supports the notion that specific targeting of the metalloinsertors to nuclear DNA gives rise to their cell-selective cytotoxic and antiproliferative activities. The selectivity in cellular targeting depends upon binding to mismatches in genomic DNA. PMID:23137296

  12. Intramolecular Hydroamination of Unbiased and Functionalized Primary Aminoalkenes Catalyzed by a Rhodium Aminophosphine Complex

    Science.gov (United States)

    Julian, Lisa D.; Hartwig, John F.

    2010-01-01

    We report a rhodium catalyst that exhibits high reactivity for the hydroamination of primary aminoalkenes that are unbiased toward cyclization and that possess functional groups that would not be tolerated in hydroaminations catalyzed by more electrophilic systems. This catalyst contains an unusual diaminophosphine ligand that binds to rhodium in a κ3-P,O,P mode. The reactions catalyzed by this complex typically proceed at mild temperatures (room temperature to 70 °C), occur with primary aminoalkenes lacking substituents on the alkyl chain that bias the system toward cyclization, occur with primary aminoalkenes containing chloride, ester, ether, enolizable ketone, nitrile, and unprotected alcohol functionality, and occur with primary aminoalkenes containing internal olefins. Mechanistic data imply that these reactions occur with a turnover-limiting step that is different from that of reactions catalyzed by late transition metal complexes of Pd, Pt, and Ir. This change in the turnover-limiting step and resulting high activity of the catalyst stem from favorable relative rates for protonolysis of the M-C bond to release the hydroamination product vs reversion of the aminoalkyl intermediate to regenerate the acyclic precursor. Probes for the origin of the reactivity of the rhodium complex of L1 imply that the aminophosphine groups lead to these favorable rates by effects beyond steric demands and simple electron donation to the metal center. PMID:20839807

  13. Column preconcentration and electrothermal atomic absorption spectrometric determination of rhodium in some food and standard samples.

    Science.gov (United States)

    Taher, Mohammad Ali; Pourmohammad, Fatemeh; Fazelirad, Hamid

    2015-12-01

    In the present work, an electrothermal atomic absorption spectrometric method has been developed for the determination of ultra-trace amounts of rhodium after adsorption of its 2-(5-bromo-2-pyridylazo)-5-diethylaminophenol/tetraphenylborate ion associated complex at the surface of alumina. Several factors affecting the extraction efficiency such as the pH, type of eluent, sample and eluent flow rates, sorption capacity of alumina and sample volume were investigated and optimized. The relative standard deviation for eight measurements of 0.1 ng/mL of rhodium was ±6.3%. In this method, the detection limit was 0.003 ng/mL in the original solution. The sorption capacity of alumina and the linear range for Rh(III) were evaluated as 0.8 mg/g and 0.015-0.45 ng/mL in the original solution, respectively. The proposed method was successfully applied for the extraction and determination of rhodium content in some food and standard samples with high recovery values. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Cast irons

    CERN Document Server

    1996-01-01

    Cast iron offers the design engineer a low-cost, high-strength material that can be easily melted and poured into a wide variety of useful, and sometimes complex, shapes. This latest handbook from ASM covers the entire spectrum of one of the most widely used and versatile of all engineered materials. The reader will find the basic, but vital, information on metallurgy, solidification characteristics, and properties. Extensive reviews are presented on the low-alloy gray, ductile, compacted graphite, and malleable irons. New and expanded material has been added covering high-alloy white irons used for abrasion resistance and high-alloy graphitic irons for heat and corrosion resistance. Also discussed are melting furnaces and foundry practices such as melting, inoculation, alloying, pouring, gating and rising, and molding. Heat treating practices including stress relieving, annealing, normalizing, hardening and tempering, autempering (of ductile irons), and surface-hardening treatments are covered, too. ASM Spec...

  15. Quantum chemical studies on electronic structure and photodynamics of ruthenium complexes

    International Nuclear Information System (INIS)

    Freitag, L.

    2015-01-01

    Ruthenium complexes have found their way into many applications in the last decades. Among those, ruthenium polypyridyl compounds have been employed as light harvesting devices and photosensitisers in artificial photosynthesis and molecular photocatalysis. Ruthenium nitrosyl complexes are rapidly emerging as NO delivery agents to biological tissues with promising applications in anticancer photodynamic therapy, thanks to their ability to photorelease nitric oxide (NO). This thesis encompasses computational studies on reactivity, electronic structure, excited states and photodynamics of several ruthenium nitrosyl and polypyridyl complexes. The first part of the thesis deals with ruthenium nitrosyls. The cis-trans isomerisation mechanism of RuHIndNO, a ruthenium nitrosyl derivate of the prominent anti-cancer drug candidate KP1019, is investigated with density functional theory calculations. Next, the electronic structure of the ground and the first excited triplet state of RuHIndNO is studied with multiconfigurational methods including the density-matrix renormalisation group (DMRG). The obtained multiconfigurational wavefunctions and DMRG-based orbital entanglement analysis provides theoretical insight into the non-innocence of the NO ligand in nitrosyl complexes by describing the electron correlation in the Ru--NO bond and assigning oxidation states to the metal and the NO ligand. Another study is performed on excited states of ruthenium nitrosyl complexes with quantum chemical calculations and surface-hopping dynamics to obtain insights into the photodissociation mechanism of NO. The second part of this thesis is devoted to the excited states and photophysics of ruthenium polypyridyl complexes. Accurate excitation energies of tris(2,2-bipyridine)ruthenium (II), the prototype ruthenium polypyridyl are obtained with multiconfigurational calculations assisted by an orbital entanglement analysis. Subsequently, the effect of the ligand substitution on the photophysics

  16. Ruthenium determination by the method of inversion voltammetry on graphite electrode

    Energy Technology Data Exchange (ETDEWEB)

    Dominova, I G; Kolpakova, N A; Stromberg, A G [Tomskij Politekhnicheskij Inst. (USSR)

    1978-12-01

    Optimal conditions for determining ruthenium by inversion voltammetry on a graphite electrode are 0.1 M KCl or KNO/sub 3/, pH 2-3, electrolysis potential - 1.0 V. A linear dependence of ruthenium electrodissolution current on its concentration in the solution makes it possible to use inversion voltammetry for determining 5x10/sup -7/ - 1x10/sup -4/ g-ion Ru/l. Ruthenium can be determined in the presence of a large excess of nickel and copper but commensurable amounts of mercury adn platinum metals interfere.

  17. Ruthenium behaviour in severe nuclear accident conditions - Progress report

    International Nuclear Information System (INIS)

    Backman, U.; Lipponen, M.; Zilliacus, R.; Auvinen, A.; Jokiniemi, J.

    2004-03-01

    In order to prevent the radioactive ruthenium from spreading in gaseous form in case of an accident in a nuclear power plant it is of interest to know how it is formed and how it behaves. In the experiments the behaviour of ruthenium in oxidising atmosphere at high temperatures is studied. The methods for trapping and analysing RuO4 has been studied. It was found that 1M NaOH is capable of trapping RuO4 totally. The determination of Ru from the solution can be made using ICP-MS (inductively coupled plasma mass spectrometry) and from the reduced precipitates on filters by INAA (instrumental neutron activation analysis). The results of the experiments carried out so far is reported. A significant difference in the decomposition rate of gaseous RuO4 depending on the tube material was found. In all experiments only a minor fraction of Ru remained in gaseous form until the bubbler. In order to achieve a better mass balance an experiment using radioactive tracer was carried out. In the decomposition of gaseous Ru needle-shaped RuO2 crystallites were formed. (au)

  18. The reaction mechanism of the partial oxidation of methane to synthesis gas: a transient kinetic study over rhodium and a comparison with platinum

    NARCIS (Netherlands)

    Mallens, E.P.J.; Hoebink, J.H.B.J.; Marin, G.B.M.M.

    1997-01-01

    The partial oxidation of methane to synthesis gas over rhodium sponge has been investigated by admitting pulses of pure methane and pure oxygen as well as mixtures of methane and oxygen to rhodium sponge at temperatures from 873 to 1023 K. Moreover, pulses of oxygen followed by methane and vice

  19. Controlled Oxygen Chemisorption on an Alumina Supported Rhodium Catalyst. The Formation of a New Metal-Metal Oxide Interface Determined with EXAFS.

    NARCIS (Netherlands)

    Koningsberger, D.C.; Martens, J.H.A.; Prins, R.

    1989-01-01

    An alumina-supported rhodium catalyst has been studied with EXAFS. After reduction and evacuation, oxygen was admitted at 100 and 300 K. EXAFS spectra of the catalyst after oxygen admission at 100 K indicated the beginning of oxidation. At 300 K only a small part of the rhodium particles remained

  20. Iron-Deficiency Anemia

    Medline Plus

    Full Text Available ... risk for iron-deficiency anemia, including: Vegetarian or vegan eating patterns. Not eating enough iron-rich foods, ... iron-fortified foods that have iron added. Vegetarian diets can provide enough iron if you choose nonmeat ...

  1. Determination of rhodium in metallic alloy and water samples using cloud point extraction coupled with spectrophotometric technique

    Science.gov (United States)

    Kassem, Mohammed A.; Amin, Alaa S.

    2015-02-01

    A new method to estimate rhodium in different samples at trace levels had been developed. Rhodium was complexed with 5-(4‧-nitro-2‧,6‧-dichlorophenylazo)-6-hydroxypyrimidine-2,4-dione (NDPHPD) as a complexing agent in an aqueous medium and concentrated by using Triton X-114 as a surfactant. The investigated rhodium complex was preconcentrated with cloud point extraction process using the nonionic surfactant Triton X-114 to extract rhodium complex from aqueous solutions at pH 4.75. After the phase separation at 50 °C, the surfactant-rich phase was heated again at 100 °C to remove water after decantation and the remaining phase was dissolved using 0.5 mL of acetonitrile. Under optimum conditions, the calibration curve was linear for the concentration range of 0.5-75 ng mL-1 and the detection limit was 0.15 ng mL-1 of the original solution. The enhancement factor of 500 was achieved for 250 mL samples containing the analyte and relative standard deviations were ⩽1.50%. The method was found to be highly selective, fairly sensitive, simple, rapid and economical and safely applied for rhodium determination in different complex materials such as synthetic mixture of alloys and environmental water samples.

  2. Adducts of nitrogenous ligands with rhodium(II) tetracarboxylates and tetraformamidinate: NMR spectroscopy and density functional theory calculations.

    Science.gov (United States)

    Cmoch, Piotr; Głaszczka, Rafał; Jaźwiński, Jarosław; Kamieński, Bohdan; Senkara, Elżbieta

    2014-03-01

    Complexation of tetrakis(μ2-N,N'-diphenylformamidinato-N,N')-di-rhodium(II) with ligands containing nitrile, isonitrile, amine, hydroxyl, sulfhydryl, isocyanate, and isothiocyanate functional groups has been studied in liquid and solid phases using (1)H, (13)C and (15)N NMR, (13)C and (15)N cross polarisation-magic angle spinning NMR, and absorption spectroscopy in the visible range. The complexation was monitored using various NMR physicochemical parameters, such as chemical shifts, longitudinal relaxation times T1 , and NOE enhancements. Rhodium(II) tetraformamidinate selectively bonded only unbranched amine (propan-1-amine), pentanenitrile, and (1-isocyanoethyl)benzene. No complexation occurred in the case of ligands having hydroxyl, sulfhydryl, isocyanate, and isothiocyanate functional groups, and more expanded amine molecules such as butan-2-amine and 1-azabicyclo[2.2.2]octane. Such features were opposite to those observed in rhodium(II) tetracarboxylates, forming adducts with all kind of ligands. Special attention was focused on the analysis of Δδ parameters, defined as a chemical shift difference between signal in adduct and corresponding signal in free ligand. In the case of (1)H NMR, Δδ values were either negative in adducts of rhodium(II) tetraformamidinate or positive in adducts of rhodium(II) tetracarboxylates. Experimental findings were supported by density functional theory molecular modelling and gauge independent atomic orbitals chemical shift calculations. The calculation of chemical shifts combined with scaling procedure allowed to reproduce qualitatively Δδ parameters. Copyright © 2013 John Wiley & Sons, Ltd.

  3. Ruthenium nitrosyl complexes in radioactive waste solutions in reprocessing plants. Pt. 3

    International Nuclear Information System (INIS)

    Blasius, E.; Mueller, K.

    1984-01-01

    With capillary isotachophoresis and free-flow isotachophoresis it is possible to separate and isolate preparatively the mononuclear cationic ruthenium nitrosyl nitrato complexes. The behaviour of these complexes during storage, concentration and calcination is studied: The conversion of six ruthenium nitrosyl nitrato complexes as a function of time is studied at -36 0 C, 0 0 C, +3 0 C and 100 0 C. The percentage of ruthenium nitrosyl complexes with NO 3 - as ligand increased markedly during concentration experiments. Above 250 0 C NOsub(x) is liberated and the colour of the residue changes from brown to brownish-grey. At 400 0 C ruthenium complexes are no longer detected and the inner walls of the apparatus are covered with RuO 2 . (orig.)

  4. Synthesis and catalytic activity of ruthenium complexes modified with chiral racemic per- and polyfluorooxaalkanoates

    Czech Academy of Sciences Publication Activity Database

    Lipovská, P.; Rathouská, L.; Šimůnek, O.; Hošek, J.; Kolaříková, V.; Rybáčková, M.; Cvačka, Josef; Svoboda, Martin; Kvíčala, J.

    2016-01-01

    Roč. 191, Nov (2016), s. 14-22 ISSN 0022-1139 Institutional support: RVO:61388963 Keywords : racemic * chiral * ruthenium complex * perfluorooxaalkanoate * polyfluorooxaalkanoate Subject RIV: CC - Organic Chemistry Impact factor: 2.101, year: 2016

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

    Energy Technology Data Exchange (ETDEWEB)

    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.

  6. Some thermophysical properties of ruthenium in the neighbourhood of the melting point

    International Nuclear Information System (INIS)

    Sheindlin, A.E.; Kats, S.A.; Berezin, B.Ya.; Chekhovskoy, V.Ya.; Kenisarin, M.M.

    1975-01-01

    The technique of levitation calorimetry has been used to study for the first time thermophysical properties of ruthenium in the neighbourhood of the melting point. To measure enthalpy a copper block calorimeter with an istohermal jacket has been used. Basing on the values measured the equations for enthalpy of solid and liquid ruthenium within the temperature ranges of 2,270-2,607 K and 2,607-2,760 K respectively have been obtained by the least squares method. In addition the melting temperature of ruthenium and its brightness temperature at the melting point, the wavelength being 0.65 micron, have been measured. The results of the measurements have been used to calculate the heat and entropy of fusion, the specific heat of solid and that of liquid ruthenium and its normal spectral emissivity at the melting point

  7. IRON DOME

    African Journals Online (AJOL)

    6 Israeli Navy 'First Arm of the Sea: The Successful Interception of the Iron Dome Rocket .... sky to destroy them whilst in flight to minimise civilian casualties. ..... Including The Moon and Celestial Bodies.53 Demeyere further emphasises the.

  8. Iron overdose

    Science.gov (United States)

    ... tracing) X-ray to detect and track iron tablets through the stomach and intestines Treatment may include: ... BF, St. Geme JW, Schor NF, eds. Nelson Textbook of Pediatrics . 20th ed. Philadelphia, PA: Elsevier; 2016: ...

  9. Flameless atomic absorption determination of ruthenium using a ''Saturn-1'' spectrophotometer

    International Nuclear Information System (INIS)

    Pichkov, V.N.; Sinitsyn, N.M.; Sadikova, F.G.; Govorova, M.I.; Yakshinskij, A.I.

    1980-01-01

    A flameless atomic absorption method is suggested for determining ruthenium in samples of complicated composition using a ''Saturn-1'' spectrophotometer with a L'vov graphite cuvette. The method was used for determining ruthenium in a copper-based sample (10 -3 % Ru) and in electrolyte slurries (10 -3 -10 -2 %). The limit of detection Csub(min, 0.95) = 3.0x10 -3 μg Ru/ml. Other platinum metals do not interfere [ru

  10. Role of the Bridging Arylethynyl Ligand in Bi- and Trinuclear Ruthenium and Iron Complexes

    Czech Academy of Sciences Publication Activity Database

    Klein, A.; Lavastre, O.; Fiedler, Jan

    2006-01-01

    Roč. 25, č. 3 (2006), s. 635-643 ISSN 0276-7333 R&D Projects: GA MŠk 1P05OC068; GA MŠk LC510 Institutional research plan: CEZ:AV0Z40400503 Keywords : X-ray crystal * nonlinear optical properties * sigma-acetylide complexes Subject RIV: CG - Electrochemistry Impact factor: 3.632, year: 2006

  11. Hydrocarbon synthesis using Iron and Ruthenium/SiO2 with FISCHER-TROPSCH catalysis.

    Directory of Open Access Journals (Sweden)

    Y.J. Fonseca

    2007-12-01

    Full Text Available Fe2(CO9, Fe3(CO12 and Ru3(CO12 clusters were used as precursors for silica supported metals. The impregnated silica solids were obtained in organic solvents under inert atmosphere and the adsorbed complexes and reduced metals characterized by FT-IR, SEM EDX and HRTEM. The catalysts showed good Fischer–Tropsch (FT activity; the main products were alkanes, alkenes and medium and higher alcohols as analyzed by GCMS. The Ru catalysts showed higher alcohols selectivity. HRTEM showed Ru nanoparticle size.

  12. A New Homogeneous Catalyst for the Dehydrogenation of Dimethylamine Borane Starting with Ruthenium(III Acetylacetonate

    Directory of Open Access Journals (Sweden)

    Ebru Ünel Barın

    2015-06-01

    Full Text Available The catalytic activity of ruthenium(III acetylacetonate was investigated for the first time in the dehydrogenation of dimethylamine borane. During catalytic reaction, a new ruthenium(II species is formed in situ from the reduction of ruthenium(III and characterized using UV-Visible, Fourier transform infrared (FTIR, 1H NMR, and mass spectroscopy. The most likely structure suggested for the ruthenium(II species is mer-[Ru(N2Me43(acacH]. Mercury poisoning experiment indicates that the catalytic dehydrogenation of dimethylamine-borane is homogeneous catalysis. The kinetics of the catalytic dehydrogenation of dimethylamine borane starting with Ru(acac3 were studied depending on the catalyst concentration, substrate concentration and temperature. The hydrogen generation was found to be first-order with respect to catalyst concentration and zero-order regarding the substrate concentration. Evaluation of the kinetic data provides the activation parameters for the dehydrogenation reaction: the activation energy Ea = 85 ± 2 kJ·mol−1, the enthalpy of activation ∆H# = 82 ± 2 kJ·mol−1 and the entropy of activation; ∆S# = −85 ± 5 J·mol−1·K−1. The ruthenium(II catalyst formed from the reduction of ruthenium(III acetylacetonate provides 1700 turnovers over 100 hours in hydrogen generation from the dehydrogenation of dimethylamine borane before deactivation at 60 °C.

  13. Mechanism of intermolecular hydroacylation of vinylsilanes catalyzed by a rhodium(I) olefin complex: a DFT study.

    Science.gov (United States)

    Meng, Qingxi; Shen, Wei; Li, Ming

    2012-03-01

    Density functional theory (DFT) was used to investigate the Rh(I)-catalyzed intermolecular hydroacylation of vinylsilane with benzaldehyde. All intermediates and transition states were optimized completely at the B3LYP/6-31G(d,p) level (LANL2DZ(f) for Rh). Calculations indicated that Rh(I)-catalyzed intermolecular hydroacylation is exergonic, and the total free energy released is -110 kJ mol(-1). Rh(I)-catalyzed intermolecular hydroacylation mainly involves the active catalyst CA2, rhodium-alkene-benzaldehyde complex M1, rhodium-alkene-hydrogen-acyl complex M2, rhodium-alkyl-acyl complex M3, rhodium-alkyl-carbonyl-phenyl complex M4, rhodium-acyl-phenyl complex M5, and rhodium-ketone complex M6. The reaction pathway CA2 + R2 → M1b → T1b → M2b → T2b1 → M3b1 → T4b → M4b → T5b → M5b → T6b → M6b → P2 is the most favorable among all reaction channels of Rh(I)-catalyzed intermolecular hydroacylation. The reductive elimination reaction is the rate-determining step for this pathway, and the dominant product predicted theoretically is the linear ketone, which is consistent with Brookhart's experiments. Solvation has a significant effect, and it greatly decreases the free energies of all species. The use of the ligand Cp' (Cp' = C(5)Me(4)CF(3)) decreased the free energies in general, and in this case the rate-determining step was again the reductive elimination reaction.

  14. The Biological Side of Water-Soluble Arene Ruthenium Assemblies

    Directory of Open Access Journals (Sweden)

    Bruno Therrien

    2014-01-01

    Full Text Available This review article covers the synthetic strategies, structural aspects, and host-guest properties of ruthenium metalla-assemblies, with a special focus on their use as drug delivery vectors. The two-dimensional metalla-rectangles show interesting host-guest possibilities but seem less appropriate for being used as drug carriers. On the other hand, metalla-prisms allow encapsulation and possible targeted release of bioactive molecules and consequently show some potential as drug delivery vectors. The reactivity of these metalla-prisms can be fine-tuned to allow a fine control of the guest’s release. The larger metalla-cubes can be used to stabilize the formation of G-quadruplex DNA and can be used to encapsulate and release photoactive molecules such as porphins. These metalla-assemblies demonstrate great prospective in photodynamic therapy.

  15. Raman spectra of ruthenium and tantalum trimers in argon matrices

    Science.gov (United States)

    Fang, Li; Shen, Xiaole; Chen, Xiaoyu; Lombardi, John R.

    2000-12-01

    The resonance Raman spectra of ruthenium trimers (Ru 3) in argon matrices have been obtained. Three resonance Raman transitions were observed between 570 and 590 nm. Two of them (303.4 and 603.7 cm -1) are assigned to the totally symmetric vibrational progression, giving k e=1.86 mdyne/ Å. The line at 581.5 cm-1 is assigned as the origin of a low-lying electronic state. We also report on the observation of a resonance Raman spectrum of tantalum trimers (Ta 3). Observed lines include 251.2 and 501.9 cm-1 which we assign to the fundamental and the first overtone of the symmetric stretch in Ta 3. This gives k e=2.25 mdyne/ Å.

  16. Cathodic processes during ruthenium electrodeposition from a chloride melt

    International Nuclear Information System (INIS)

    Sokol'skij, D.V.

    1985-01-01

    Cathodic processes occurring during the electrolysis of chloride melts in the presence of oxygen-containing impurities were studied. The experiments were carried out at 500, 550 600 and 680 deg C, ruthenium ions concentration in KCl-NaCl-CsCl eutectic melt being 0.4-1.5 mol% and BaO additions 4.8x10 -2 mol%. Temperature dependence of Ru(3) ion diffusion coefficient in the chloride melt (lg D=3.25-1508/T+-0.02) and activation energy of the diffusion process (6.9 k cal/mol) were determined. It is shown that changes of the shape of E, t-curve and the deviation of values determined in the cause of chronopotentiometric investigations from the corresponding values of reversable processes are related in many respects to the participation of oxygen-containing compounds in the cathodic process. Irreversibility of the cathodic process is also connected with metal crystallization during electrodeposition

  17. Evidence for Dynamic Chemical Kinetics at Individual Molecular Ruthenium Catalysts.

    Science.gov (United States)

    Easter, Quinn T; Blum, Suzanne A

    2018-02-05

    Catalytic cycles are typically depicted as possessing time-invariant steps with fixed rates. Yet the true behavior of individual catalysts with respect to time is unknown, hidden by the ensemble averaging inherent to bulk measurements. Evidence is presented for variable chemical kinetics at individual catalysts, with a focus on ring-opening metathesis polymerization catalyzed by the second-generation Grubbs' ruthenium catalyst. Fluorescence microscopy is used to probe the chemical kinetics of the reaction because the technique possesses sufficient sensitivity for the detection of single chemical reactions. Insertion reactions in submicron regions likely occur at groups of many (not single) catalysts, yet not so many that their unique kinetic behavior is ensemble averaged. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Moessbauer spectroscopic characterisation of catalysts obtained by interaction between tetra-n-butyl-tin and silica or silica supported rhodium

    International Nuclear Information System (INIS)

    Millet, J.M.M.; Toyir, J.; Didillon, B.; Candy, J.P.; Nedez, C.; Basset, J.M.

    1997-01-01

    Moessbauer spectroscopy at 78 K was used to study the interaction between tetra-n-butyl-tin and the surfaces of silica or silica supported rhodium. At room temperature, the tetra-n-butyl-tin was physically adsorbed on the surfaces. After reaction under hydrogen at 373 K, the formation of grafted organometallic fragments on the Rh surface was confirmed whereas with pure silica, ≡SiO-Sn(n-C 4 H 9 ) 3 moieties were observed. After treatment at 523 K, the rhodium grafted organometallic species was completely decomposed and there was formation of a defined bimetallic RhSn compound

  19. Electrooxidative Rhodium-Catalyzed C-H/C-H Activation: Electricity as Oxidant for Cross-Dehydrogenative Alkenylation.

    Science.gov (United States)

    Qiu, Youai; Kong, Wei-Jun; Struwe, Julia; Sauermann, Nicolas; Rogge, Torben; Scheremetjew, Alexej; Ackermann, Lutz

    2018-04-06

    Rhodium(III) catalysis has enabled a plethora of oxidative C-H functionalizations, which predominantly employ stoichiometric amounts of toxic and/or expensive metal oxidants. In contrast, we describe the first electrochemical C-H activation by rhodium catalysis that avoids hazardous chemical oxidants. Thus, environmentally-benign twofold C-H/C-H functionalizations were accomplished with weakly-coordinating benzoic acids and benzamides, employing electricity as the terminal oxidant with H2 as the sole byproduct. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Permeation of platinum and rhodium nanoparticles through intact and damaged human skin

    International Nuclear Information System (INIS)

    Mauro, Marcella; Crosera, Matteo; Bianco, Carlotta; Adami, Gianpiero; Montini, Tiziano; Fornasiero, Paolo; Jaganjac, Morana; Bovenzi, Massimo; Filon, Francesca Larese

    2015-01-01

    The aim of the study was to evaluate percutaneous penetration of platinum and rhodium nanoparticles (PtNPs: 5.8 ± 0.9 nm, RhNPs: 5.3 ± 1.9 nm) through human skin. Salts compounds of these metals are sensitizers and some also carcinogenic agents. In vitro permeation experiments were performed using Franz diffusion cells with intact and damaged skin. PtNPs and RhNPs, stabilized with polyvinylpyrrolidone, were synthesized by reduction of Na 2 PtC l6 and RhCl 3 ·3H 2 O respectively. Suspensions with a concentration of 2.0 g/L of PtNPs and RhNPs were dispersed separately in synthetic sweat at pH 4.5 and applied as donor phases to the outer surface of the skin for 24 h. Measurements of the content of the metals in the receiving solution and in the skin were performed subsequently. Rhodium skin permeation was demonstrated through damaged skin, with a permeation flux of 0.04 ± 0.04 μg cm −2  h −1 and a lag time of 7.9 ± 1.1 h, while no traces of platinum were found in receiving solutions. Platinum and rhodium skin-analysis showed significantly higher concentrations of the metals in damaged skin. Rh and Pt applied as NPs can penetrate the skin barrier and Rh can be found in receiving solutions. These experiments pointed out the need for skin contamination prevention, since even a minor injury to the skin barrier can significantly increase penetration

  1. A rhodium(III)-based inhibitor of autotaxin with antiproliferative activity.

    Science.gov (United States)

    Kang, Tian-Shu; Wang, Wanhe; Zhong, Hai-Jing; Liang, Jia-Xin; Ko, Chung-Nga; Lu, Jin-Jian; Chen, Xiu-Ping; Ma, Dik-Lung; Leung, Chung-Hang

    2017-02-01

    Cancer of the skin is by far the most common of all cancers. Melanoma accounts for only about 1% of skin cancers but causes a large majority of skin cancer deaths. Autotaxin (ATX), also known as ectonucleotide pyrophosphatase/phosphodiesterase 2 (ENPP2), regulates physiological and pathological functions of lysophosphatidic acid (LPA), and is thus an important therapeutic target. We synthesized ten metal-based complexes and a novel cyclometalated rhodium(III) complex 1 was identified as an ATX enzymatic inhibitor using multiple methods, including ATX enzymatic assay, thermal shift assay, western immunoblotting and so on. Protein thermal shift assays showed that 1 increased the melting temperature (T m ) of ATX by 3.5°C. 1 also reduced ATX-LPA mediated downstream survival signal pathway proteins such as ERK and AKT, and inhibited the activation of the transcription factor nuclear factor κB (NF-κB) and signal transducer and activator of transcription 3 (STAT3). 1 also exhibited strong anti-proliferative activity against A2058 melanoma cells (IC 50 =0.58μM). Structure-activity relationship indicated that both the rhodium(III) center and the auxiliary ligands of complex 1 are important for bioactivity. 1 represents a promising scaffold for the development of small-molecule ATX inhibitors for anti-tumor applications. To our knowledge, complex 1 is the first metal-based ATX inhibitor reported to date. Rhodium complexes will have the increased attention in therapeutic and bioanalytical applications. Copyright © 2016 Elsevier B.V. All rights reserved.

  2. Permeation of platinum and rhodium nanoparticles through intact and damaged human skin

    Energy Technology Data Exchange (ETDEWEB)

    Mauro, Marcella [University of Trieste, Clinical Unit of Occupational Medicine, Department of Medical Sciences (Italy); Crosera, Matteo; Bianco, Carlotta; Adami, Gianpiero; Montini, Tiziano; Fornasiero, Paolo [University of Trieste, Department of Chemical and Pharmaceutical Sciences (Italy); Jaganjac, Morana [Rudjer Boskovic Institute, Laboratory for Oxidative Stress, Department of Molecular Medicine (Croatia); Bovenzi, Massimo; Filon, Francesca Larese, E-mail: larese@units.it [University of Trieste, Clinical Unit of Occupational Medicine, Department of Medical Sciences (Italy)

    2015-06-15

    The aim of the study was to evaluate percutaneous penetration of platinum and rhodium nanoparticles (PtNPs: 5.8 ± 0.9 nm, RhNPs: 5.3 ± 1.9 nm) through human skin. Salts compounds of these metals are sensitizers and some also carcinogenic agents. In vitro permeation experiments were performed using Franz diffusion cells with intact and damaged skin. PtNPs and RhNPs, stabilized with polyvinylpyrrolidone, were synthesized by reduction of Na{sub 2}PtC{sub l6} and RhCl{sub 3}·3H{sub 2}O respectively. Suspensions with a concentration of 2.0 g/L of PtNPs and RhNPs were dispersed separately in synthetic sweat at pH 4.5 and applied as donor phases to the outer surface of the skin for 24 h. Measurements of the content of the metals in the receiving solution and in the skin were performed subsequently. Rhodium skin permeation was demonstrated through damaged skin, with a permeation flux of 0.04 ± 0.04 μg cm{sup −2} h{sup −1} and a lag time of 7.9 ± 1.1 h, while no traces of platinum were found in receiving solutions. Platinum and rhodium skin-analysis showed significantly higher concentrations of the metals in damaged skin. Rh and Pt applied as NPs can penetrate the skin barrier and Rh can be found in receiving solutions. These experiments pointed out the need for skin contamination prevention, since even a minor injury to the skin barrier can significantly increase penetration.

  3. Trans-Selective Rhodium Catalysed Conjugate Addition of Organoboron Reagents to Dihydropyranones

    Directory of Open Access Journals (Sweden)

    Hannah J. Edwards

    2015-04-01

    Full Text Available The selective synthesis of 2,6-trans-tetrahydropyran derivatives employing the rhodium catalysed addition of organoboron reagents to dihydropyranone templates, derived from a zinc-catalysed hetero-Diels-Alder reaction, is reported. The addition of both arylboronic acids and potassium alkenyltrifluoroborates have been accomplished in high yields using commercially-available [Rh(cod(OH]2 catalyst. The selective formation of the 2,6-trans-tetrahydropyran stereoisomer is consistent with a mechanism involving alkene association and carbometalation on the less hindered face of the dihydropyranone.

  4. Experimental demonstration of H∞ filter performance for dynamic compensation of rhodium neutron detectors

    International Nuclear Information System (INIS)

    Park, Moon-Ghu; Choi, Yu-Sun; Lee, Kwang-Dae

    2008-01-01

    This paper describes the experimental demonstration of the theoretical result of the previous work on LMI (linear matrix inequality) based H ∞ filter for time-delay compensation of self-powered neutron detectors. The filter gains are optimized in the sense of noise attenuation level of H ∞ setting. By introducing bounded real lemma, the conventional algebraic Riccati inequalities are converted into linear matrix inequalities (LMIs). Finally, the filter design problem is solved via the convex optimization framework using LMIs. The experimental measurements of rhodium detector signal from a research reactor show that the predicted theoretical filter performance is verified by showing successful reconstruction of the reference power signal

  5. Rhodium deposition onto a 4-mercaptopyridine SAM on Au(1 1 1)

    Energy Technology Data Exchange (ETDEWEB)

    Manolova, M. [Institute of Electrochemistry, University of Ulm, 89069 Ulm (Germany); Kayser, M. [Institute of Electrochemistry, University of Ulm, 89069 Ulm (Germany); Kolb, D.M. [Institute of Electrochemistry, University of Ulm, 89069 Ulm (Germany)]. E-mail: dieter.kolb@uni-ulm.de; Boyen, H.-G. [Institute of Solid State Physics, University of Ulm, 89069 Ulm (Germany); Ziemann, P. [Institute of Solid State Physics, University of Ulm, 89069 Ulm (Germany); Mayer, D. [BASF Electronic Materials GmbH, 67056 Ludwigshafen (Germany); Wirth, A. [BASF Electronic Materials GmbH, 67056 Ludwigshafen (Germany)

    2007-02-10

    The application of a recently developed method for the deposition of Pd and Pt on top of a SAM, has been successfully extended to Rh, thus proving the versatility of the new concept. Experimental evidence from cyclic voltammetry, in situ STM and ex situ X-ray photoemission spectroscopy is presented for the deposition of monoatomic high rhodium islands onto a 4-mercaptopyridine self-assembled monolayer on a Au(1 1 1) electrode. By repetitive complexation of the Rh ions to the ring-nitrogen and reduction in a Rh-ion free solution, an almost completely covered SAM is obtained. The consequences of making contacts for molecular electronics are briefly discussed.

  6. Study of heat transfer parameters on rhodium target for 103Pd production

    International Nuclear Information System (INIS)

    Sadeghi, M.; Tenreiro, C.; Van den Winkel, P.

    2009-01-01

    The efficiency of cooling and the particle beam characteristics are important when high beam current irradiations are intended for production of radionuclides. The efficiency of cooling is determined by both the target carrier geometry and the flow rate of coolant, while the beam characteristics deal with the current density distribution on the irradiated surface area. Heat transfer on rhodium target to produce 103 Pd via the 103 Rh(p,n) 103 Pd reaction was investigated and the beam current was obtained more than 500 μA. (authors)

  7. Predictable and Regioselective Insertion of Internal Unsymmetrical Alkynes in Rhodium-Catalyzed Cycloadditions with Alkenyl Isocyanates

    Science.gov (United States)

    Friedman, Rebecca Keller; Rovis, Tomislav

    2009-01-01

    A regioselective, rhodium-catalyzed cycloaddition between a variety of internal, unsymmetrical alkynes is described. We document the impact of both steric and electronic properties of the alkyne on reaction course, efficiency and enantioselectivity. The substituent that better stabilizes a positive charge or the larger group, all else being equal, inserts distal to the carbonyl moiety in a predictable and controllable fashion. The reaction scope is broad and the enantioselectivities are high, providing an ‘instruction manual’ for substrate choice when utilizing this reaction as a synthetic tool. PMID:19569692

  8. Rhodium(III) as a potentiator of the effects of X-rays on cells

    Energy Technology Data Exchange (ETDEWEB)

    Richmond, R C; Centilli, M A; Cross, M H; Powers, E L

    1986-08-01

    A rhodium compound, Rh(NH/sub 3/)/sub 3/Cl/sub 3/, does not sensitize the spores of Bacillus megaterium to X-rays. However, it is a very effective sensitizer of vegetative cells of Staphylococcus aureus, raising the sensitivity four times in O/sub 2/ and over 100 times in anoxia. The inhibition by oxygen of the sensitizing action of Rh(III), which operates over a wide range of (O/sub 2/), is noteworthy. These experiments were performed in saline-phosphate buffer using 50 kVp X-rays. The results are discussed in terms of the known radiation chemistry of this compound.

  9. Stereoselective 1,3-Insertions of Rhodium(II) Azavinyl Carbenes

    Science.gov (United States)

    Chuprakov, Stepan; Worrell, Brady T.; Selander, Nicklas; Sit, Rakesh K.; Fokin, Valery V.

    2014-01-01

    Rhodium(II) azavinyl carbenes, conveniently generated from 1-sulfonyl-1,2,3-triazoles, undergo a facile, mild and convergent formal 1,3-insertion into N–H and O–H bonds of primary and secondary amides, various alcohols, and carboxylic acids to afford a wide range of vicinally bis-functionalized Z-olefins with perfect regio- and stereoselectively. Utilizing the distinctive functionality installed through these reactions, a number of subsequent rearrangements and cyclizations expand the repertoire of valuable organic building blocks constructed by reactions of transition metal carbene complexes, including α-allenyl ketones and amino-substituted heterocycles. PMID:24295389

  10. Platinum, palladium, and rhodium in volcanic and plutonic rocks from the Gravina-Nutzotin belt, Alaska

    Science.gov (United States)

    Page, Norman J; Berg, Henry C.; Haffty, Joseph

    1977-01-01

    The Gravina-Nutzotin belt of Middle (?) Jurassic to middle Cretaceous sedimentary and volcanic rocks in south and southeastern Alaska includes concentrically zoned ultramafic complexes known to contain platinum-group metals. Previous isotopic, petrologic, and geologic studies suggested a close relation in time and space between the volcanic rocks and the ultramafic complexes. Interpretation of 40 analyses for platinum, palladium, and rhodium in volcanic and plutonic rocks of the belt indicates a strong geochemical correlation between the two groups of rocks and is in support of their being cogenetic either from directly connected magma chambers and flows or indirectly by selective concentration processes from similar mantle material.

  11. Hydrolysis of Letrozole catalyzed by macrocyclic Rhodium (I) Schiff-base complexes.

    Science.gov (United States)

    Reddy, P Muralidhar; Shanker, K; Srinivas, V; Krishna, E Ravi; Rohini, R; Srikanth, G; Hu, Anren; Ravinder, V

    2015-03-15

    Ten mononuclear Rhodium (I) complexes were synthesized by macrocyclic ligands having N4 and N2O2 donor sites. Square planar geometry is assigned based on the analytical and spectral properties for all complexes. Rh(I) complexes were investigated as catalysts in hydrolysis of Nitrile group containing pharmaceutical drug Letrozole. A comparative study showed that all the complexes are efficient in the catalysis. The percent yields of all the catalytic reaction products viz. drug impurities were determined by spectrophotometric procedures and characterized by spectral studies. Copyright © 2014 Elsevier B.V. All rights reserved.

  12. Enantioselective Access to Spirocyclic Sultams by Chiral Cp(x) -Rhodium(III)-Catalyzed Annulations.

    Science.gov (United States)

    Pham, Manh V; Cramer, Nicolai

    2016-02-12

    Chiral spirocyclic sultams are a valuable compound class in organic and medicinal chemistry. A rapid entry to this structural motif involves a [3+2] annulation of an N-sulfonyl ketimine and an alkyne. Although the directing-group properties of the imino group for C-H activation have been exploited, the developments of related asymmetric variants have remained very challenging. The use of rhodium(III) complexes equipped with a suitable atropchiral cyclopentadienyl ligand, in conjunction with a carboxylic acid additive, enables an enantioselective and high yielding access to such spirocyclic sultams. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Sensitivity change of rhodium self -powered detectors with burn-up

    International Nuclear Information System (INIS)

    Girgis, R.; Akimov, I.S.; Hamouda, I.

    1976-01-01

    The scope of the present paper is to obtain the calculation formulae to evaluate the rate of sensitivity change of the neutron self-powered detectors with burn-up. A code written in FORTRAN 4 was developed to be operational on the IBM-1130 computer. It has been established in the case of rhodium detectors that neglecting the β-particle absorption in the calculations leads to the underestimation of the detector sensitivity decrease up to 40%. The derived formulae can be used for other self-powered detectors. (author)

  14. Redox-Neutral Rhodium-Catalyzed [4+1] Annulation through Formal Dehydrogenative Vinylidene Insertion.

    Science.gov (United States)

    Liu, Huan; Song, Shengjin; Wang, Cheng-Qiang; Feng, Chao; Loh, Teck-Peng

    2017-01-10

    A synthetic protocol for the expedient construction of 5-methylene-1H-pyrrol-2(5H)-one derivatives through rhodium-catalyzed [4+1] annulation with gem-difluoroacrylate as the C 1 component was reported. By taking advantage of the twofold C-F bond cleavage occurring during the annulation, this reaction not only allows the synthesis of these heterocyclic compounds under overall oxidant-free conditions but also renders the transformation stereospecific. The very mild reaction conditions employed ensure compatibility with a wide variety of synthetically useful functional groups. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Rhodium-catalyzed redox-neutral coupling of phenidones with alkynes.

    Science.gov (United States)

    Fan, Zhoulong; Lu, Heng; Li, Wei; Geng, Kaijun; Zhang, Ao

    2017-07-21

    A switchable synthesis of N-substituted indole derivatives from phenidones via rhodium-catalyzed redox-neutral C-H activation has been achieved. In this protocol, we firstly disclosed that the reactivity of Rh(iii) catalysis could be enhanced through employing palladium acetate as an additive. Some representative features include external oxidant-free, applicable to terminal alkynes, short reaction time and operational simplicity. The utility of this method is further showcased by the economical synthesis of potent anticancer PARP-1 inhibitors.

  16. Platinum, palladium, and rhodium analyses of ultramafic and mafic rocks from the Stillwater Complex, Montana

    Science.gov (United States)

    Page, Norman J; Riley, Leonard Benjamin; Haffty, Joseph

    1969-01-01

    Analyses by a combination fire- assay-solution-optical-emission spectrographic method of 137 rocks from the Stillwater Complex, Mont., indicate that platinum, palladium, and rhodium are preferentially concentrated in chromitite zones. The A chromitite zone (21 samples) has an average of 988.9 ppb (pans per billion, 10-9) Pt, 2290.2 ppb Pd, and 245.9 ppb Rh and reaches a maximum (to date) of 8,000 ppb Pt, 11,000 ppb Pd, and 1,700 ppb Rh.

  17. Complexation of diphenyl(phenylacetenyl)phosphine to rhodium(III) tetraphenyl porphyrins

    DEFF Research Database (Denmark)

    Stulz, Eugen; Scott, Sonya M; Bond, Andrew D

    2003-01-01

    ). The methylide on rhodium in 3 is not displaced, leading selectively to the mono-phosphine complex (DPAP)(Me)Rh(TPP) (5). The first and second association constants, as determined by isothermal titration calorimetry and UV-vis titrations, are in the range 10(4)-10(7) M(-1) (in CH(2)Cl(2)). Using LDI-TOF mass....... The largest values of DeltaG degrees are found for 6. The thermodynamic and UV-vis data reveal that the methylide and the phosphine ligand have an almost identical electronic trans-influence on the sixth ligand....

  18. Iron-Deficiency Anemia

    Medline Plus

    Full Text Available ... iron-rich foods, especially during certain stages of life when more iron is needed, such as childhood and pregnancy. Good sources of iron are meat, poultry, fish, and iron- ...

  19. Iron-Deficiency Anemia

    Medline Plus

    Full Text Available ... that are good sources of iron include dried beans, dried fruits, eggs, lean red meat, salmon, iron- ... of iron, including iron-fortified breads and cereals, beans, tofu, dried fruits, and spinach and other dark ...

  20. Iron in diet

    Science.gov (United States)

    ... Reasonable amounts of iron are also found in lamb, pork, and shellfish. Iron from vegetables, fruits, grains, ... strawberries, tomatoes, and potatoes) also increase iron absorption. Cooking foods in a cast-iron skillet can also ...

  1. Iron-Deficiency Anemia

    Medline Plus

    Full Text Available ... from developing iron-deficiency anemia. Foods that are good sources of iron include dried beans, dried fruits, ... iron is needed, such as childhood and pregnancy. Good sources of iron are meat, poultry, fish, and ...

  2. Iron-Deficiency Anemia

    Medline Plus

    Full Text Available ... you are diagnosed with iron-deficiency anemia. Risk Factors You may have an increased risk for iron- ... iron-deficiency anemia if you have certain risk factors , including pregnancy. To prevent iron-deficiency anemia, your ...

  3. Iron-Deficiency Anemia

    Medline Plus

    Full Text Available ... for your body to absorb iron from the gastrointestinal tract (GI tract). Blood loss When you lose blood, ... iron deficiency. Endurance athletes lose iron through their gastrointestinal tracts. They also lose iron through the breakdown of ...

  4. Iron-Deficiency Anemia

    Medline Plus

    Full Text Available ... iron in your body is low. For this reason, other iron tests are also done. Ferritin measure ... iron is needed, such as childhood and pregnancy. Good sources of iron are meat, poultry, fish, and ...

  5. Iron-Deficiency Anemia

    Medline Plus

    Full Text Available ... develop new therapies for conditions that affect the balance of iron in the body and lead to ... Disease Control and Prevention) Iron - Health Professional Fact Sheet (NIH) Iron Dietary Supplement Fact Sheet (NIH) Iron- ...

  6. Iron-Deficiency Anemia

    Medline Plus

    Full Text Available ... to moderate iron-deficiency anemia, or red blood cell transfusion for severe iron-deficiency anemia. You may ... body needs iron to make healthy red blood cells. Iron-deficiency anemia usually develops over time because ...

  7. Iron-Deficiency Anemia

    Medline Plus

    Full Text Available ... enough iron-rich foods, such as meat and fish, may result in you getting less than the ... pregnancy. Good sources of iron are meat, poultry, fish, and iron-fortified foods that have iron added. ...

  8. Iron Dextran Injection

    Science.gov (United States)

    Iron dextran injection is used to treat iron-deficiency anemia (a lower than normal number of red blood cells ... treated with iron supplements taken by mouth. Iron dextran injection is in a class of medications called ...

  9. Iron-Deficiency Anemia

    Medline Plus

    Full Text Available ... and severity. Treatments may include iron supplements, procedures, surgery, and dietary ... iron supplements, also called iron pills or oral iron, by mouth once or several times a ...

  10. Iron-Deficiency Anemia

    Medline Plus

    Full Text Available ... developing iron-deficiency anemia. Foods that are good sources of iron include dried beans, dried fruits, eggs, ... is needed, such as childhood and pregnancy. Good sources of iron are meat, poultry, fish, and iron- ...

  11. Iron deficiency

    DEFF Research Database (Denmark)

    Schou, Morten; Bosselmann, Helle; Gaborit, Freja

    2015-01-01

    BACKGROUND: Both iron deficiency (ID) and cardiovascular biomarkers are associated with a poor outcome in heart failure (HF). The relationship between different cardiovascular biomarkers and ID is unknown, and the true prevalence of ID in an outpatient HF clinic is probably overlooked. OBJECTIVES.......043). CONCLUSION: ID is frequent in an outpatient HF clinic. ID is not associated with cardiovascular biomarkers after adjustment for traditional confounders. Inflammation, but not neurohormonal activation is associated with ID in systolic HF. Further studies are needed to understand iron metabolism in elderly HF...

  12. Light-induced reduction of rhodium(III) and palladium(II) on titanium dioxide dispersions and the selective photochemical separation and recovery of gold(III), platinum(IV), and rhodium(III) in chloride media

    Energy Technology Data Exchange (ETDEWEB)

    Borgarello, E.; Serpone, N.; Emo, G.; Harris, R.; Pelizzetti, E.; Minero, C.

    1986-12-03

    Irradiation of aqueous TiO/sub 2/ dispersions containing palladium(II) or rhodium(III) chloride salts with AM1 simulated sunlight leads to the photoreduction of these metals, which are deposited on the semiconductor particle surface. Oxygen is detrimental to the photoreduction of rhodium(III) but not the photoreduction of palladium(II). However, in both cases the reduction process is most efficient if the solution contains CH/sub 3/OH, which acts to scavenge valence band holes of the illuminated TiO/sub 2/ semiconductor. The selective photoreduction and recovery of precious metals from a dilute solution (as might be found in industrial wastes) have been investigated for a mixture of gold(III), platinum(IV), and rhodium(III) chloride salts as a function of various parameters (pH, presence or absence of O/sub 2/, presence or absence of a hole scavenger, and the concentration of the semiconductor). At pH 0, gold is easily separated from platinum and rhodium. The rate of photoreduction of gold(III) on TiO/sub 2/ is nearly independent of the concentration of the semiconductor, under the experimental conditions employed; the limiting rate is 2.7 x 10/sup -7/ M s/sup -1/. The potential utility of this selective photochemical technique is discussed.

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

    Science.gov (United States)

    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 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.

  14. Behavior of ruthenium in the case of shutdown of the cooling system of HLLW storage tanks

    International Nuclear Information System (INIS)

    Philippe, M.; Mercier, J.P.; Gue, J.P.

    1990-01-01

    The consequences of the failure of the cooling system of fission product storage tanks over a variable period were investigated as part of the safety analysis of the La Hague spent fuel reprocessing plant. Due to the considerable heat release, induced by the fission products, a prolonged shutdown of the tank cooling system could cause the progressive evaporation of the solutions to dryness, and culminate in the formation of volatile species of ruthenium and their release in the tank venting circuit. To determine the fraction of ruthenium likely to be transferred from the storage tanks in volatile or aerosol form during the failure, evaporation tests were conducted by evaporating samples of actual nitric acid solutions of fission products, obtained on the laboratory scale after the reprocessing of several kilograms of MOX fuels irradiated to 30,000 MWday.t -1 . A distillation apparatus was designed to operate with small volume solution samples, reproducing the heating conditions existing in the reprocessing plant within a storage tank for fission products. The main conclusions drawn from these experiments are as follows: - ruthenium is only volatilized in the final phase of evaporation, just before desiccation, - for a final temperature limited to 160 0 C, the total fraction of volatilized ruthenium reaches 12%, in the presence of H 2 0, HN0 3 , N0 x and 0 2 , the volatilized ruthenium recombines mainly in the form of ruthenium nitrosyl nitrates, or decomposes into ruthenium oxide on the walls of the apparatus. Assuming a heating power density of 10 W/liter of concentrate, and a perfectly adiabatic storage system, the minimum time required to reach dryness can be estimated at 90 h, allowing substantial time to take action to restore a cooling source

  15. Behavior of ruthenium in the case of shutdown of the cooling system of HLLW storage tanks

    International Nuclear Information System (INIS)

    Philippe, M.; Mercier, J.P.; Gue, J.P.

    1991-01-01

    The consequences of the failure of the cooling system of fission product storage tanks over a variable period were investigated as part of the safety analysis of the La Hague spent fuel reprocessing plant. Due to the considerable heat release, induced by the fission products, a prolonged shutdown of the tank cooling system could cause the progressive evaporation of the solutions to dryness, and culminate in the formation of volatile species of ruthenium and their release in the tank venting circuit. To determine the fraction of ruthenium likely to be transferred from the storage tanks in volatile or aerosol form during the failure, evaporation tests were conducted by evaporating samples of actual nitric acid solutions of fission products, obtained on the laboratory scale after the reprocessing of several kilograms of MOX fuels irradiated to 30,000 MW day·t -1 . A distillation apparatus was designed to operate with small-volume solution samples, reproducing the heating conditions existing in the reprocessing plant within a storage tank for fission products. The main conclusions drawn from these experiments are as follows: ruthenium is only volatilized in the final phase of evaporation, just before desiccation; for a final temperature limited to 160 degree C, the total fraction of volatilized ruthenium reaches 12%; in the presence of H 2 O, HNO 3 , NO x and O 2 , the volatilized ruthenium recombines mainly in the form of ruthenium nitrosyl nitrates, or decomposes into ruthenium oxide (probably RuO 2 ) on the walls of the apparatus. Assuming a heating power density of 10 W/liter of concentrate, and a perfectly adiabatic storage system, the minimum time required to reach dryness can be estimated at 90 h, allowing substantial time to take action to restore a cooling source

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

    Science.gov (United States)

    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 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. Excess Substrate is a Spectator Ligand in a Rhodium-Catalyzed Asymmetric [2+2+2] Cycloaddition of Alkenyl Isocyanates with Tolanes

    Science.gov (United States)

    Oinen, Mark Emil; Yu, Robert T.; Rovis, Tomislav

    2009-01-01

    Excess substrate has been identified as an unintended spectator ligand affecting enantioselectivity in the [2+2+2] cycloaddition of alkenyl isocyanates with tolanes. Replacement of excess substrate with an exogenous additive affords products with consistent and higher ee’s. The increase in enantioselectivity is the result of a change in composition of a proposed rhodium(III) intermediate on the catalytic cycle. The net result is a rational probe of a short-lived rhodium(III) intermediate, and gives insight that may have applications in many rhodium catalyzed reactions. PMID:19803471

  18. Iron-Deficiency Anemia

    Medline Plus

    Full Text Available ... Research Home / < Back To Health Topics / Iron-Deficiency Anemia Iron-Deficiency Anemia Also known as Leer en español Iron-deficiency ... iron-deficiency anemia. Blood tests to screen for iron-deficiency anemia To screen for iron-deficiency anemia, your doctor ...

  19. Carbonyl complexes of rhodium with N-donor ligands: factors determining the formation of terminal versus bridging carbonyls

    NARCIS (Netherlands)

    Dzik, W.I.; Creusen, C.; de Gelder, R.; Peters, T.P.J.; Smits, J.M.M.; de Bruin, B.

    2010-01-01

    Cationic rhodium carbonyl complexes supported by a series of different N-3- and N-4-donor ligands were prepared, and their ability to form carbonyl-bridged species was evaluated. Complex [Rh(K3-bpa)(cod)r (1(+)) (bpa = bis(2-picolyBamine, cod = cis,cis-1,5-cyclooctadiene) reacts with I bar of CO to

  20. Extraction of carrier-free 103Pd from thin rhodium wire irradiated with a proton beam in U-150 cyclotron

    International Nuclear Information System (INIS)

    Yuldashev, B.S.; Khudajbergenov, U.; Gulamov, I.R.; Mirzarva, M.A.; Rylov, A.A.

    2003-01-01

    A procedure for preparation of 103 Pd isotope of 99.9 % purity from a thin rhodium wire irradiated by 21 MeV proton beam in a cyclotron was developed. The desired product was prepared by electrolytic dissolution of the irradiated target in 6 M HCl with subsequent extraction of 103 Pd isotope without carrier by dimethylglyoxime in chloroform [ru

  1. Solvent extraction of no-carrier-added 103Pd from irradiated rhodium target with α-furyldioxime

    International Nuclear Information System (INIS)

    Mahdi Sadeghi; Behrouz Shirazi; Nami Shadanpour

    2006-01-01

    Solvent extraction of no-carrier-added 103 Pd was investigated from irradiated rhodium target with a-furyldioxime in chloroform from diluted hydrochloric acid. Extraction yield was 85.3% for a single extraction from 0.37M HCl and 103 Pd purity was better than 99%. (author)

  2. Dispersive oxidation of rhodium clusters in Na-Y by the combined action of zeolite protons and carbon monoxide

    International Nuclear Information System (INIS)

    Wong, T.T.T.; Sachtler, W.M.H.; Stakheev, A.Yu.

    1992-01-01

    This paper uses x-ray photoelectron spectroscopy, fourier transform infrared spectroscopy and temperature programmed mass-spectrometric analysis to study the interaction of Na-Y supported rhodium with hydrogen, carbon monoxide, and zeolite protons. This report attempts to clarify the mechanism of dispersive oxidation of reduced Rh particles in the presence of CO, leading to the formation of Rh + (CO) 2 cations

  3. PipPhos and MorfPhos : Privileged monodentate phosphoramidite ligands for rhodium-catalyzed asymmetric hydrogenation

    NARCIS (Netherlands)

    Bernsmann, Heiko; van den Berg, M; Hoen, Robert; Minnaard, AJ; Mehler, G; Reetz, MT; De Vries, JG; Feringa, BL

    2005-01-01

    A library of 20 monodentate phosphoramidite ligands has been prepared and applied in rhodium-catalyzed asymmetric hydrogenation. This resulted in the identification of two ligands, PipPhos and MorfPhos, that afford excellent and in several cases unprecedented enantioselectivities in the

  4. Reversible switching of the sol- gel transition with ultrasound in rhodium(I) and iridium(I) coordination networks

    NARCIS (Netherlands)

    Paulusse, J.M.J.; Beek, van D.J.M.; Sijbesma, R.P.

    2007-01-01

    Reversible coordination networks were prepared by combining diphenylphosphinite telechelic polytetrahydrofuran (2) with [RhCl(COD)]2 or [IrCl(COD)]2 in chloroform. Both systems resulted in stable gels at concentrations above 50 and 30 g/L for the rhodium(I) and iridium(I) networks, respectively. The

  5. The Rôle of the Element Rhodium in the Hyperbolic Law of the Periodic Table of Elements

    Directory of Open Access Journals (Sweden)

    Khazan A.

    2008-07-01

    Full Text Available The role of the element rhodium as an independent affirmation of calculations by the Hyperbolic Law and validity of all its relations is shown herein. The deviation in cal- culation by this method of the atomic mass of heaviest element is 0.0024%, and its coefficient of scaling 0.001–0.005%

  6. Intermolecular rhodium-catalyzed [2 + 2 + 2] carbocyclization reactions of 1,6-enynes with symmetrical and unsymmetrical alkynes†

    Science.gov (United States)

    Andrew Evans, P.; Sawyer, James R.; Lai, Kwong Wah; Huffman, John C.

    2006-01-01

    The crossed intermolecular rhodium-catalyzed [2 + 2 + 2] carbocyclization of carbon and heteroatom tethered 1,6-enynes can be accomplished with symmetrical and unsymmetrical alkynes, to afford the corresponding bicyclohexadienes in an efficient and highly selective manner. PMID:16075089

  7. Direct Synthesis of 5-Aryl Barbituric Acids by Rhodium(II)-Catalyzed Reactions of Arenes with Diazo Compounds**

    Science.gov (United States)

    Best, Daniel; Burns, David J; Lam, Hon Wai

    2015-01-01

    A commercially available rhodium(II) complex catalyzes the direct arylation of 5-diazobarbituric acids with arenes, allowing straightforward access to 5-aryl barbituric acids. Free N—H groups are tolerated on the barbituric acid, with no complications arising from N—H insertion processes. This method was applied to the concise synthesis of a potent matrix metalloproteinase (MMP) inhibitor. PMID:25959544

  8. Complexation of rhodium(II) tetracarboxylates with aliphatic diamines in solution: 1H and 13C NMR and DFT investigations.

    Science.gov (United States)

    Jaźwiński, Jarosław; Sadlej, Agnieszka

    2013-10-01

    The complexation of rhodium(II) tetraacetate, tetrakistrifluoroaceate and tetrakisoctanoate with a set of diamines (ethane-1,diamine, propane-1,3-diamine and nonane-1,9-diamine) and their N,N'-dimethyl and N,N,N',N'-tetramethyl derivatives in chloroform solution has been investigated by (1) H and (13) C NMR spectroscopy and density functional theory (DFT) modelling. A combination of two bifunctional reagents, diamines and rhodium(II) tetracarboxylates, yielded insoluble coordination polymers as main products of complexation and various adducts in the solution, being in equilibrium with insoluble material. All diamines initially formed the 2 : 1 (blue), (1 : 1)n oligomeric (red) and 1 : 2 (red) axial adducts in solution, depending on the reagents' molar ratio. Adducts of primary and secondary diamines decomposed in the presence of ligand excess, the former via unstable equatorial complexes. The complexation of secondary diamines slowed down the inversion at nitrogen atoms in NH(CH3 ) functional groups and resulted in the formation of nitrogenous stereogenic centres, detectable by NMR. Axial adducts of tertiary diamines appeared to be relatively stable. The presence of long aliphatic chains in molecules (adducts of nonane-1,9-diamines or rhodium(II) tetrakisoctanoate) increased adduct solubility. Hypothetical structures of the equatorial adduct of rhodium(II) tetraacetate with ethane-1,2-diamine and their NMR parameters were explored by means of DFT calculations. Copyright © 2013 John Wiley & Sons, Ltd.

  9. Iron and iron derived radicals

    International Nuclear Information System (INIS)

    Borg, D.C.; Schaich, K.M.

    1987-04-01

    We have discussed some reactions of iron and iron-derived oxygen radicals that may be important in the production or treatment of tissue injury. Our conclusions challenge, to some extent, the usual lines of thought in this field of research. Insofar as they are born out by subsequent developments, the lessons they teach are two: Think fast! Think small! In other words, think of the many fast reactions that can rapidly alter the production and fate of highly reactive intermediates, and when considering the impact of competitive reactions on such species, think how they affect the microenvironment (on the molecular scale) ''seen'' by each reactive molecule. 21 refs., 3 figs., 1 tab

  10. Gravimetric preparation and characterization of primary reference solutions of molybdenum and rhodium.

    Science.gov (United States)

    Kaltenbach, Angela; Noordmann, Janine; Görlitz, Volker; Pape, Carola; Richter, Silke; Kipphardt, Heinrich; Kopp, Gernot; Jährling, Reinhard; Rienitz, Olaf; Güttler, Bernd

    2015-04-01

    Gravimetrically prepared mono-elemental reference solutions having a well-known mass fraction of approximately 1 g/kg (or a mass concentration of 1 g/L) define the very basis of virtually all measurements in inorganic analysis. Serving as the starting materials of all standard/calibration solutions, they link virtually all measurements of inorganic analytes (regardless of the method applied) to the purity of the solid materials (high-purity metals or salts) they were prepared from. In case these solid materials are characterized comprehensively with respect to their purity, this link also establishes direct metrological traceability to The International System of Units (SI). This, in turn, ensures the comparability of all results on the highest level achievable. Several national metrology institutes (NMIs) and designated institutes (DIs) have been working for nearly two decades in close cooperation with commercial producers on making an increasing number of traceable reference solutions available. Besides the comprehensive characterization of the solid starting materials, dissolving them both loss-free and completely under strict gravimetric control is a challenging problem in the case of several elements like molybdenum and rhodium. Within the framework of the European Metrology Research Programme (EMRP), in the Joint Research Project (JRP) called SIB09 Primary standards for challenging elements, reference solutions of molybdenum and rhodium were prepared directly from the respective metals with a relative expanded uncertainty associated with the mass fraction of U rel(w) methods required to assist with the preparation and as dissemination tools.

  11. Ion flotation of rhodium(III) and palladium(II) with anionic surfactants.

    Science.gov (United States)

    He, X C

    1991-03-01

    The ion flotation of rhodium(III) and palladium(II) with some anionic surfactants has been investigated. Two flotation procedures are proposed for the separation of some platinum metals, based on differences in the kinetic properties of the chloro-complexes of rhodium(III), palladium(II) and platinum(IV). The first involves the selective flotation of Rh(H(2)O)(3+)(6) from PdCl(2-)(4) and PtCl(2-)(6) in dilute hydrochloric acid with sodium dodecylbenzenesulfonate (SDBS). After precipitation of the hydroxide and redissolution in dilute acid, the Rh(III) is converted into Rh(H(2)O)(3+)(6), Pd(II) and Pt(IV) remaining as PdCl(2-)(4) and PtCl(2-)(6) respectively, and separation is achieved by floating the Rh(H(2)O)(3+)(6) with SDBS. The second is for separation of Pd(II). Prior to flotation, the solution of PdCl(2-)(4) and PtCl(2-)(6) is heated with ammonium acetate to convert PdCl(2-)(4) into Pd(NH(3))(2+)(4). The chloro-complex of Pt(IV) is unaffected. The complex cation, Pd(NH(3))(2+)(4), is then selectively floated with SDBS. The procedures are fast, simple and do not require expensive reagents and apparatus.

  12. Bimetallic poly- and oligo-nuclear complexes based on a rhodium(III) metalloligand

    Science.gov (United States)

    Vasilchenko, Danila B.; Venediktov, Anatoliy B.; Korenev, Sergey V.; Filatov, Evgeniy Yu.; Baidina, Iraida A.; Nadolinnyi, Vladimir A.

    2012-10-01

    Interaction of trans-[Rh(i-Nic)4Cl2]3- anions (i-Nic- - isonicotinate anion) with Cuaq2+ and Coaq2+ cations in water has afforded complex salts Co3[Rh(i-Nic)4Cl2]2·17H2O (1) and Cu3[Rh(i-Nic)4Cl2]2·14H2O (2). Oligonuclear character of 1 and 2 has been established. A coordination polymer Cu5[Rh(i-Nic)4Cl2]2(i-Nic)2(OH)2·2H2O (3) has been crystallized by hydrothermal treatment of 2 at 160 °C, and its structure was determined by X-ray structural analysis. EPR data for the complexes has been collected and interpreted. Thermal decomposition of the salts was studied by c-DTA. Bimetallic alloys rhodium-copper and rhodium-cobalt have been obtained as final products of thermal decomposition.

  13. Rhodium-catalysed syn-carboamination of alkenes via a transient directing group.

    Science.gov (United States)

    Piou, Tiffany; Rovis, Tomislav

    2015-11-05

    Alkenes are the most ubiquitous prochiral functional groups--those that can be converted from achiral to chiral in a single step--that are accessible to synthetic chemists. For this reason, difunctionalization reactions of alkenes (whereby two functional groups are added to the same double bond) are particularly important, as they can be used to produce highly complex molecular architectures. Stereoselective oxidation reactions, including dihydroxylation, aminohydroxylation and halogenation, are well established methods for functionalizing alkenes. However, the intermolecular incorporation of both carbon- and nitrogen-based functionalities stereoselectively across an alkene has not been reported. Here we describe the rhodium-catalysed carboamination of alkenes at the same (syn) face of a double bond, initiated by a carbon-hydrogen activation event that uses enoxyphthalimides as the source of both the carbon and the nitrogen functionalities. The reaction methodology allows for the intermolecular, stereospecific formation of one carbon-carbon and one carbon-nitrogen bond across an alkene, which is, to our knowledge, unprecedented. The reaction design involves the in situ generation of a bidentate directing group and the use of a new cyclopentadienyl ligand to control the reactivity of rhodium. The results provide a new way of synthesizing functionalized alkenes, and should lead to the convergent and stereoselective assembly of amine-containing acyclic molecules.

  14. Correlation between the Stereochemistry and Bioactivity in Octahedral Rhodium Prolinato Complexes.

    Science.gov (United States)

    Rajaratnam, Rajathees; Martin, Elisabeth K; Dörr, Markus; Harms, Klaus; Casini, Angela; Meggers, Eric

    2015-08-17

    Controlling the relative and absolute configuration of octahedral metal complexes constitutes a key challenge that needs to be overcome in order to fully exploit the structural properties of octahedral metal complexes for applications in the fields of catalysis, materials sciences, and life sciences. Herein, we describe the application of a proline-based chiral tridentate ligand to decisively control the coordination mode of an octahedral rhodium(III) complex. We demonstrate the mirror-like relationship of synthesized enantiomers and differences between diastereomers. Further, we demonstrate, using the established pyridocarbazole pharmacophore ligand as part of the organometallic complexes, the importance of the relative and absolute stereochemistry at the metal toward chiral environments like protein kinases. Protein kinase profiling and inhibition data confirm that the proline-based enantiopure rhodium(III) complexes, despite having all of the same constitution, differ strongly in their selectivity properties despite their unmistakably mutual origin. Moreover, two exemplary compounds have been shown to induce different toxic effects in an ex vivo rat liver model.

  15. Ground vs. excited state interaction in ruthenium-thienyl dyads : implications for through bond interactions in multicomponent systems

    NARCIS (Netherlands)

    Henry, William; Browne, Wesley R.; Ronayne, Kate L.; O’Boyle, Noel M.; Vos, Johannes G.; McGarvey, John J.

    2005-01-01

    The vibrational and photophysical properties of mononuclear ruthenium(II) and ruthenium(III) polypyridyl complexes based on the, ligands 2-(5-(pyridin-2"-yl)-1'H-1',2',4'-triaz-3'-yl)-thiophene, 2-(5-(pyrazin-2"-yl)-1'H-1',2,4-triaz-3'-yl)-thiophene, are reported. The effect of the introduction of

  16. Dehydrogenative Coupling of Primary Alcohols To Form Esters Catalyzed by a Ruthenium N-Heterocyclic Carbene Complex

    DEFF Research Database (Denmark)

    Sølvhøj, Amanda Birgitte; Madsen, Robert

    2011-01-01

    The ruthenium complex [RuCl2(IiPr)(p-cymene)] catalyzes the direct condensation of primary alcohols into esters and lactones with the release of hydrogen gas. The reaction is most effective with linear aliphatic alcohols and 1,4-diols and is believed to proceed with a ruthenium dihydride...

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

    Science.gov (United States)

    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...

  18. One-pot hydrothermal synthesis of ruthenium oxide nanodots on reduced graphene oxide sheets for supercapacitors

    Energy Technology Data Exchange (ETDEWEB)

    Chen Yao [Institute of Electrical Engineering, Chinese Academy of Sciences, Beijing 100190 (China); Graduate University of Chinese Academy Sciences, Beijing 100049 (China); Zhang Xiong [Institute of Electrical Engineering, Chinese Academy of Sciences, Beijing 100190 (China); Zhang Dacheng [Institute of Electrical Engineering, Chinese Academy of Sciences, Beijing 100190 (China); Graduate University of Chinese Academy Sciences, Beijing 100049 (China); Ma Yanwei, E-mail: ywma@mail.iee.ac.cn [Institute of Electrical Engineering, Chinese Academy of Sciences, Beijing 100190 (China)

    2012-01-15

    Highlights: > Graphite oxide instead of graphene as precursor has been used to synthesize reduced graphene oxide/ruthenium oxide composites by a hydrothermal treatment. > Using NaOH solution to adjust pH of GO colloids leads to homogeneous ruthenium oxide deposited on reduced graphene oxide sheets. > A maximum capacitance of 471 F g{sup -1} is obtained at 0.5 A g{sup -1} for the composites when loading 40% of RuO{sub 2} and its life retention reaches 92% after 3000 cycles. - Abstract: Ruthenium oxide nanodots have been deposited on reduced graphene oxide (RGO) sheets homogeneously by hydrothermal and annealing methods. Adding NaOH solution in GO colloids prevents the restack and agglomeration of GO sheets when mixed with ruthenium chloride solution. Local crystallization of RuO{sub 2} in the composites is revealed by X-ray diffraction and transmission electron microscopy. The element mapping image demonstrates the uniform distribution of Ru on RGO sheets. Unlike the pure crystalline RuO{sub 2} exhibiting poor electrochemical performance, the composites present superior capacitive properties. The hydrothermal time is optimized and a maximum of 471 F g{sup -1} is measured in the composites at 0.5 A g{sup -1} when loaded with 45 wt% of RuO{sub 2}. After 3000 cycles, its specific capacitance remains 92% of the maximum capacitance. Our results suggest potential application of the reduced graphene oxide/ruthenium oxide composites to supercapacitors.

  19. Activity and selectivity regulation of synthesis gas reaction over supported ruthenium catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Fujimoto, K; Nobusawa, T; Fukushima, T; Tominaga, H

    1985-01-01

    The catalytic activities of supported ruthenium for synthesis-gas conversion to hydrocarbons was found to be in the following order: TiOS > Nb2O3 > ZrO2 > SiO2 > Ta2O5 > Al2O3 > V2O5 > MoO3 > WO3 > MnO2 > ZnO. Turnover frequencies of the supported ruthenium increased with decrease in dispersion of the metal particles for every carrier material. Even the activities per unit weight of metals were higher for low-dispersion ruthenium of Al2O3, TiO2, and ZrO2. The chain-growth probability of a hydrocarbon product, which is characterized by the Schulz-Flory distribution, increased markedly with decrease in the metal dispersion irrespective of the carrier material. The catalytic activity of ruthenium particles with a dispersed ruthenium increased almost linearly with an increase in reaction pressure (up to at least 2.0 MPa). 23 references, 10 figures, 3 tables.

  20. One-pot hydrothermal synthesis of ruthenium oxide nanodots on reduced graphene oxide sheets for supercapacitors

    International Nuclear Information System (INIS)

    Chen Yao; Zhang Xiong; Zhang Dacheng; Ma Yanwei

    2012-01-01

    Highlights: → Graphite oxide instead of graphene as precursor has been used to synthesize reduced graphene oxide/ruthenium oxide composites by a hydrothermal treatment. → Using NaOH solution to adjust pH of GO colloids leads to homogeneous ruthenium oxide deposited on reduced graphene oxide sheets. → A maximum capacitance of 471 F g -1 is obtained at 0.5 A g -1 for the composites when loading 40% of RuO 2 and its life retention reaches 92% after 3000 cycles. - Abstract: Ruthenium oxide nanodots have been deposited on reduced graphene oxide (RGO) sheets homogeneously by hydrothermal and annealing methods. Adding NaOH solution in GO colloids prevents the restack and agglomeration of GO sheets when mixed with ruthenium chloride solution. Local crystallization of RuO 2 in the composites is revealed by X-ray diffraction and transmission electron microscopy. The element mapping image demonstrates the uniform distribution of Ru on RGO sheets. Unlike the pure crystalline RuO 2 exhibiting poor electrochemical performance, the composites present superior capacitive properties. The hydrothermal time is optimized and a maximum of 471 F g -1 is measured in the composites at 0.5 A g -1 when loaded with 45 wt% of RuO 2 . After 3000 cycles, its specific capacitance remains 92% of the maximum capacitance. Our results suggest potential application of the reduced graphene oxide/ruthenium oxide composites to supercapacitors.

  1. Mitigation of strontium and ruthenium release in the CANDU primary heat transport system

    Energy Technology Data Exchange (ETDEWEB)

    McFarlane, J

    1998-03-01

    In certain severe accident scenarios, low-volatility fission products can appear to contribute significantly to dose, if treated with undue conservatism. Hence a survey was performed, to see if factors that may mitigate release of strontium and ruthenium could be incorporated into safety analyses, to cover parameters such as location in the fuel matrix under normal operating conditions, release from fuel, transport and deposition in the primary heat transport system and chemistry. In addition chemical equilibrium calculations were performed to investigate the volatility of strontium and ruthenium in the presence of uranium and important fission products. Strontium is very soluble in the U0{sub 2} fuel, up to 12 atom %, and hence release is improbable, particularly under oxidizing conditions until volatilization of the fuel matrix itself occurs. Ruthenium, however, can be released at low temperatures, but only under oxidizing conditions. These may occur during a fuel-handling accident or as a result of an end-fitting failure. Under these conditions, the primary heat transport system cannot be credited for retention. The volatile form of ruthenium, RuO{sub 4}(g), is thermally unstable above 381 K and decomposes to RuO{sub 2}(s) and O{sub 2}(g) upon contact with surfaces, a factor that is likely to minimize the release of ruthenium into the environment. (author)

  2. Mitigation of strontium and ruthenium release in the CANDU primary heat transport system

    International Nuclear Information System (INIS)

    McFarlane, J.

    1998-03-01

    In certain severe accident scenarios, low-volatility fission products can appear to contribute significantly to dose, if treated with undue conservatism. Hence a survey was performed, to see if factors that may mitigate release of strontium and ruthenium could be incorporated into safety analyses, to cover parameters such as location in the fuel matrix under normal operating conditions, release from fuel, transport and deposition in the primary heat transport system and chemistry. In addition chemical equilibrium calculations were performed to investigate the volatility of strontium and ruthenium in the presence of uranium and important fission products. Strontium is very soluble in the U0 2 fuel, up to 12 atom %, and hence release is improbable, particularly under oxidizing conditions until volatilization of the fuel matrix itself occurs. Ruthenium, however, can be released at low temperatures, but only under oxidizing conditions. These may occur during a fuel-handling accident or as a result of an end-fitting failure. Under these conditions, the primary heat transport system cannot be credited for retention. The volatile form of ruthenium, RuO 4 (g), is thermally unstable above 381 K and decomposes to RuO 2 (s) and O 2 (g) upon contact with surfaces, a factor that is likely to minimize the release of ruthenium into the environment. (author)

  3. Interaction of ruthenium (4) and osmium (4) with 2-mercaptobenzimidazole, 2-mercaptobenzoxazole and 2-mercaptobenzothiazole in the presence of edta

    International Nuclear Information System (INIS)

    Busev, A.I.; Ignat'eva, T.I.; Lomakina, L.N.

    1975-01-01

    Interaction of ruthenium (4) and osmium (4) with 2-mercaptobenzimidazole (2MBI), 2-mercaptobenzoxazole (2MBO) and 2-mercaptobenzothiazole (2MBT) in the presence of EDTA was studied. The interaction of ruthenium (4) and osmium (4) with EDTA was constidered. Ruthenium complex is formed with constant output at 2-4.5 pH after 30 min.heating. In the lowacid solution (pH 2-4) osmium reacts with EDTA forming soluble compound. Characteristics of ruthenium (4) compound with 2MBI, 2MBO and 2MBT produced in the presence of EDTA are presented. Osmium (4) in the presence of EDTA and above mentioned organic reagents and when heating forms lowsoluble compounds. Possibility of joint determination of ruthenium and osmium with help of 2MBI in the presence of EDTA under conditions of minimum complexing osmium with EDTA was investigated

  4. Interaction of ruthenium (4) and osmium (4) with 2-mercaptobenzimidazole, 2-mercaptobenzoxazole and 2-mercaptobenzothiazole in the presence of EDTA

    Energy Technology Data Exchange (ETDEWEB)

    Busev, A I; Ignat' eva, T I; Lomakina, L N [Moskovskij Gosudarstvennyj Univ. (USSR). Kafedra Analiticheskoj Khimii

    1975-05-01

    Interaction of ruthenium (4) and osmium (4) with 2-mercaptobenzimidazole (2MBI), 2-mercaptobenzoxazole (2MBO) and 2-mercaptobenzothiazole (2MBT) in the presence of EDTA was studied. The interaction of ruthenium (4) and osmium (4) with EDTA was considered. Ruthenium complex is formed with constant output at 2-4.5 pH after 30 min. heating. In the low acid solution (pH 2-4) osmium reacts with EDTA forming soluble compound. Characteristics of ruthenium (4) compound with 2MBI, 2MBO and 2MBT produced in the presence of EDTA are presented. Osmium (4) in the presence of EDTA and above mentioned organic reagents and when heating forms low soluble compounds. Possibility of joint determination of ruthenium and osmium with help of 2MBI in the presence of EDTA under conditions of minimum complexing osmium with EDTA was investigated.

  5. Ruthenium sulfoxides structure and reactivity with nitrogen heterocyclic bases

    International Nuclear Information System (INIS)

    Oliveira, Denise de.

    1990-01-01

    Ruthenium (II) sulfoxides are compounds of great interest in oxidative catalysis and in chemotherapy. In order to contribute for the understanding of the chemistry and electronic structure of this class of compounds, it has been studied a series of [Ru Cl 2 (S-DMSO) 2 L x ] complexes, where x = 1 (polymeric compounds) or 2 (monomers) and L N-heterocyclic ligands (pyridine, pyrazine and imidazole derivatives). The nature of N-heterocyclic ligand and their coordination are of great relevance to the stability, spectroscopic and electrochemical characteristics of the complexes. The trans-interactions are extremely important in this series, influencing the strength of the Ru(II)-> S-DMSO and Ru(II)-> L π-back donation. The DMSO and L ligands are π-acceptors. The metal-> ligand π-back donation is strengthened when the ligand is trans to chloride, which is π-donor, due to trans-cooperative interactions of the type: π-donor -> Ru(II) π-acceptor. Another interesting aspect in the series of [Ru Cl 2 (S-DMSO) 2 L 2 ] complexes is the occurrence of dissociative equilibria in the solution, due to the existence of three types of ligands. It was observed that the trans-N isomer of 2,6-dimethyl pyrazine derivative undergoes thermal substitution, with preferential liabilization of the N-heterocyclic ligand. Chloride ion is the most inert ligand in this complex. (author). 145 refs., 76 figs., 21 tabs

  6. Coordinatively unsaturated ruthenium complexes as efficient alkyneazide cycloaddition catalysts

    KAUST Repository

    Lamberti, Marina; Fortman, George C.; Poater, Albert; Broggi, Julie; Slawin, Alexandra M. Z.; Cavallo, Luigi; Nolan, Steven P.

    2012-01-01

    The performance of 16-electron ruthenium complexes with the general formula Cp*Ru(L)X (in which L = phosphine or N-heterocyclic carbene ligand; X = Cl or OCH2CF3) was explored in azidealkyne cycloaddition reactions that afford the 1,2,3- triazole products. The scope of the Cp*Ru(PiPr 3)Cl precatalyst was investigated for terminal alkynes leading to new 1,5-disubstituted 1,2,3-triazoles in high yields. Mechanistic studies were conducted and revealed a number of proposed intermediates. Cp*Ru- (PiPr3)(2-HCCPh)Cl was observed and characterized by 1H, 13C, and 31P NMR at temperatures between 273 and 213 K. A rare example of N,N-κ2-phosphazide complex, Cp*Ru(κ2- iPr3PN3Bn)Cl, was fully characterized, and a single-crystal X-ray diffraction structure was obtained. DFT calculations describe a complete map of the catalytic reactivity with phenylacetylene and/or benzylazide. © 2012 American Chemical Society.

  7. Graphene Oxide/ Ruthenium Oxide Composites for Supercapacitors Electrodes

    Science.gov (United States)

    Amir, Fatima

    Supercapacitors are electrical energy storage devices with high power density, high rate capability, low maintenance cost, and long life cycle. They complement or replace batteries in harvesting applications when high power delivery is needed. An important improvement in performance of supercapacitors has been achieved through recent advances in the development of new nanostructured materials. Here we will discuss the fabrication of graphene oxide/ ruthenium oxide supercacitors electrodes including electrophoretic deposition. The morphology and structure of the fabricated electrodes were investigated and will be discussed. The electrochemical properties were determined using cyclic voltammetry and galvanostatic charge/discharge techniques and the experiments that demonstrate the excellent capacitive properties of the obtained supercapacitors will also be discussed. The fabrication and characterization of the samples were performed at the Center of Functional Nanomaterials at Brookhaven National Lab. The developed approaches in our study represent an exciting direction for designing the next generation of energy storage devices. This work was supported in part by the U.S. Department of Energy through the Visiting Faculty Program and the research used resources of the Center for Functional Nanomaterials at Brookhaven National Laboratory.

  8. Visual acuity after Ruthenium106 brachytherapy of choroidal melanomas

    International Nuclear Information System (INIS)

    Damato, Bertil; Patel, Imran M.; Campbell, Ian R.; Mayles, Helen M.; Errington, R. Douglas

    2005-01-01

    Purpose: To report on conservation of visual acuity after Ruthenium 106 (Ru-106) brachytherapy of choroidal melanoma. Methods and materials: This study was a noncomparative interventional case series of 458 patients with choroidal melanoma treated at a single center between January 1993 and December 2001. The intervention consisted of Ru-106 brachytherapy delivering minimum scleral and apex doses of 300 Gy and 80 Gy, respectively, using a 15-mm or 20-mm plaque. For discrete, posterior tumors, the plaque was positioned eccentrically with its posterior edge aligned with the posterior tumor margin. To ensure correct plaque positioning, any overlying extraocular muscles were dis-inserted, and the locations of both tumor and plaque edges were confirmed by transillumination and indentation. The main outcome measures were conservation of vision of 20/40 or better, 20/200 or better, and Counting Fingers or better, according to baseline variables. Results: The actuarial rate of conservation of 20/40 or better was 55% at 9 years, loss of such vision correlating with posterior tumor extension (p 106 brachytherapy of posterior choroidal melanoma achieves good conservation of vision if the tumor does not extend close to the optic nerve or fovea

  9. Coordinatively unsaturated ruthenium complexes as efficient alkyneazide cycloaddition catalysts

    KAUST Repository

    Lamberti, Marina

    2012-01-23

    The performance of 16-electron ruthenium complexes with the general formula Cp*Ru(L)X (in which L = phosphine or N-heterocyclic carbene ligand; X = Cl or OCH2CF3) was explored in azidealkyne cycloaddition reactions that afford the 1,2,3- triazole products. The scope of the Cp*Ru(PiPr 3)Cl precatalyst was investigated for terminal alkynes leading to new 1,5-disubstituted 1,2,3-triazoles in high yields. Mechanistic studies were conducted and revealed a number of proposed intermediates. Cp*Ru- (PiPr3)(2-HCCPh)Cl was observed and characterized by 1H, 13C, and 31P NMR at temperatures between 273 and 213 K. A rare example of N,N-κ2-phosphazide complex, Cp*Ru(κ2- iPr3PN3Bn)Cl, was fully characterized, and a single-crystal X-ray diffraction structure was obtained. DFT calculations describe a complete map of the catalytic reactivity with phenylacetylene and/or benzylazide. © 2012 American Chemical Society.

  10. Rapid visual and spectrophotometric nitrite detection by cyclometalated ruthenium complex.

    Science.gov (United States)

    Lo, Hoi-Shing; Lo, Ka-Wai; Yeung, Chi-Fung; Wong, Chun-Yuen

    2017-10-16

    Quantitative determination of nitrite ion (NO 2 - ) is of great importance in environmental and clinical investigations. A rapid visual and spectrophotometric assay for NO 2 - detection was developed based on a newly designed ruthenium complex, [Ru(npy)([9]aneS3)(CO)](ClO 4 ) (denoted as RuNPY; npy = 2-(1-naphthyl)pyridine, [9]aneS3 = 1,4,7-trithiacyclononane). This complex traps NO + produced in acidified NO 2 - solution, and yields observable color change within 1 min at room temperature. The assay features excellent dynamic range (1-840 μmol L -1 ) and high selectivity, and its limit of detection (0.39 μmol L -1 ) is also well below the guideline values for drinking water recommended by WHO and U.S. EPA. Practical use of this assay in tap water and human urine was successfully demonstrated. Overall, the rapidity and selectivity of this assay overcome the problems suffered by the commonly used modified Griess assays for nitrite determination. Copyright © 2017 Elsevier B.V. All rights reserved.

  11. Ruthenium(V) oxides from low-temperature hydrothermal synthesis

    Energy Technology Data Exchange (ETDEWEB)

    Hiley, Craig I.; Walton, Richard I. [Department of Chemistry, University of Warwick, Coventry (United Kingdom); Lees, Martin R. [Department of Physics, University of Warwick, Coventry (United Kingdom); Fisher, Janet M.; Thompsett, David [Johnson Matthey Technology Centre, Reading (United Kingdom); Agrestini, Stefano [Max-Planck Institut, CPfS, Dresden (Germany); Smith, Ronald I. [ISIS Neutron and Muon Source, Rutherford Appleton Laboratory, Harwell Oxford, Didcot (United Kingdom)

    2014-04-22

    Low-temperature (200 C) hydrothermal synthesis of the ruthenium oxides Ca{sub 1.5}Ru{sub 2}O{sub 7}, SrRu{sub 2}O{sub 6}, and Ba{sub 2}Ru{sub 3}O{sub 9}(OH) is reported. Ca{sub 1.5}Ru{sub 2}O{sub 7} is a defective pyrochlore containing Ru{sup V/VI}; SrRu{sub 2}O{sub 6} is a layered Ru{sup V} oxide with a PbSb{sub 2}O{sub 6} structure, whilst Ba{sub 2}Ru{sub 3}O{sub 9}(OH) has a previously unreported structure type with orthorhombic symmetry solved from synchrotron X-ray and neutron powder diffraction. SrRu{sub 2}O{sub 6} exhibits unusually high-temperature magnetic order, with antiferromagnetism persisting to at least 500 K, and refinement using room temperature neutron powder diffraction data provides the magnetic structure. All three ruthenates are metastable and readily collapse to mixtures of other oxides upon heating in air at temperatures around 300-500 C, suggesting they would be difficult, if not impossible, to isolate under conventional high-temperature solid-state synthesis conditions. (copyright 2014 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  12. Placental transfer of ruthenium in rat and guinea-pig

    International Nuclear Information System (INIS)

    Levack, V.M.; Pottinger, H.; Harrison, J.D.

    1994-01-01

    Ruthenium-106 in citrate solution was administered intravenously to rat at different stages of pregnancy and to guinea-pig either before conception or in late pregnancy. The results for rat showed that retention in the embryo/foetus measured at 3-5 days after administration increased from about 0.0002% of injected activity per embryo/foetus on day 12 of gestation to about 0.05% at birth. The relative concentrations of 106 Ru in embryo/foetus and mother (C f /C m ratio) were about 0.1 in each case. Concentrations in the yolk sac on day 12 were about 1% g -1 compared with 0.01% g -1 kin the foetus/ Retention in the guinea-pig foetus in late gestation at 7 days after administration (days 50-57) was about 0.2% injected activity per foetus, corresponding to a C f /C m = 0.2. Retention in each foetoplacental unit was 2% of injected 106 Ru with 50% in the yolk sac, 35% in the placenta and 10% in the foetus. For administration 4 weeks prior to conception, the level of 106 Ru retained in the foetus on day 57 of gestation was two orders of magnitude lower than after short-term administration, with a C f /C m about 0.004. (author)

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

    Science.gov (United States)

    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.

  14. Iron and stony-iron meteorites

    DEFF Research Database (Denmark)

    Ruzicka, Alex M.; Haack, Henning; Chabot, Nancy L.

    2017-01-01

    By far most of the melted and differentiated planetesimals that have been sampled as meteorites are metal-rich iron meteorites or stony iron meteorites. The parent asteroids of these meteorites accreted early and differentiated shortly after the solar system formed, producing some of the oldest...... and interpretations for iron and stony iron meteorites (Plate 13.1). Such meteorites provide important constraints on the nature of metal-silicate separation and mixing in planetesimals undergoing partial to complete differentiation. They include iron meteorites that formed by the solidification of cores...... (fractionally crystallized irons), irons in which partly molten metal and silicates of diverse types were mixed together (silicate-bearing irons), stony irons in which partly molten metal and olivine from cores and mantles were mixed together (pallasites), and stony irons in which partly molten metal...

  15. Electron transfer reactions of ruthenium(II) complexes with polyphenolic acids in micelles

    Energy Technology Data Exchange (ETDEWEB)

    Rajeswari, Angusamy [School of Chemistry, Madurai Kamaraj University, Madurai 625 021 (India); Department of Chemistry, Fatima College, Madurai 625 018 (India); Ramdass, Arumugam [School of Chemistry, Madurai Kamaraj University, Madurai 625 021 (India); Research Department of Chemistry, Aditanar College of Arts and Science, Tiruchendur 628 216 (India); Muthu Mareeswaran, Paulpandian [School of Chemistry, Madurai Kamaraj University, Madurai 625 021 (India); Department of Industrial Chemistry, Alagappa University, Karaikudi 630 003 (India); Rajagopal, Seenivasan, E-mail: rajagopalseenivasan@yahoo.com [School of Chemistry, Madurai Kamaraj University, Madurai 625 021 (India)

    2016-02-15

    The electron transfer in a microhetrogeneous system is a perfect mimic of biological electron transfer. The electron transfer between biologically important phenolic acids and ruthenium (II) complexes is systematically studied in the presence of anionic and cationic micelles. The photophysical properties of these ruthenium (II) complexes with anionic and cationic micelles and their binding abilities with these two type of micelles are also studies using absorption, emission and excited state lifetime spectral techniques. Pseudophase Ion Exchange (PIE) Model is applied to derive mechanism of electron transfer in two types of micelles. - Highlights: • Effect of microhetrogeneous system is studied using ruthenium (II) complexes and gallic acid is studied. • Pseudophase Ion exchange model is applied to derive the mechanism. • Binding constants are in the range of 10{sup 2}–10{sup 4} M{sup −1}.

  16. Stable tracer investigations in humans for assessing the biokinetics of ruthenium and zirconium radionuclides

    International Nuclear Information System (INIS)

    Veronese, I.; Cantone, M.C.; Giussani, A.; Maggioni, T.; Birattari, C.; Bondardi, M.; Groppi, F.; Garlaschelli, I.; Werner, E.; Roth, P.; Hoellriegl, V.; Louvat, P.; Felgenhauer, N.; Zilker, Th.

    2003-01-01

    The interest in the biokinetics of ruthenium and zirconium in humans is justified by the potential radiological risk represented by their radionuclides. Only a few data related to the biokinetics of ruthenium and zirconium in humans are available and, accordingly, the biokinetic models currently recommended by the ICRP for these elements are mainly based on data from animal experiments. The use of stable isotopes as tracers, coupled with a proper analytical technique (nuclear activation analysis with protons) for their determination in biological samples, represents an ethically acceptable methodology for biokinetic investigations, being free from any radiation risk for the volunteer subjects. In this work, the results obtained in eight biokinetic investigations for ruthenium, conducted on a total of three healthy volunteers, and six for zirconium, performed on a total of three subjects, are presented and compared to the predictions of the ICRP models. (author)

  17. Amorphous carbon nanofibres inducing high specific capacitance of deposited hydrous ruthenium oxide

    International Nuclear Information System (INIS)

    Barranco, V.; Pico, F.; Ibanez, J.; Lillo-Rodenas, M.A.; Linares-Solano, A.; Kimura, M.; Oya, A.; Rojas, R.M.; Amarilla, J.M.; Rojo, J.M.

    2009-01-01

    Composites consisting of ruthenium oxide particles deposited on amorphous carbon nanofibres are prepared by a repetitive impregnation procedure. The choice of amorphous carbon nanofibres as support of amorphous ruthenium oxide leads to composites in which the deposited oxide consists of aggregates of extremely small primary particles (1-1.5 nm-size) and showing high porosity (specific surface area of 450 m 2 g -1 ). This special deposition of the oxide seems to favour: (i) high oxide capacitance (1000 Fg -1 ) at high oxide loadings (up to 20 wt%) and (ii) high capacitance retention (ca. 80% from the initial oxide capacitance) at high current densities (200 mA cm -2 ). Amorphous carbon nanofibres are suitable supports for amorphous ruthenium oxide and perhaps for other amorphous oxides acting as active electrode materials.

  18. Estimation of very low concentrations of Ruthenium by spectrophotometric method using barbituric acid as complexing agent

    International Nuclear Information System (INIS)

    Ramakrishna Reddy, S.; Srinivasan, R.; Mallika, C.; Kamachi Mudali, U.; Natarajan, R.

    2012-01-01

    Spectrophotometric method employing numerous chromogenic reagents like thiourea, 1,10-phenanthroline, thiocyanate and tropolone is reported in the literature for the estimation of very low concentrations of Ru. A sensitive spectrophotometric method has been developed for the determination of ruthenium in the concentration range 1.5 to 6.5 ppm in the present work. This method is based on the reaction of ruthenium with barbituric acid to produce ruthenium(ll)tris-violurate, (Ru(H 2 Va) 3 ) -1 complex which gives a stable deep-red coloured solution. The maximum absorption of the complex is at 491 nm due to the inverted t 2g → Π(L-L ligand) electron - transfer transition. The molar absorptivity of the coloured species is 9,851 dm 3 mol -1 cm -1

  19. Dye sensitized photovoltaic cells: Attaching conjugated polymers to zwitterionic ruthenium dyes

    DEFF Research Database (Denmark)

    Krebs, Frederik C; Biancardo, M.

    2006-01-01

    The synthesis of a zwitterionic ruthenium dye that binds to anatase surfaces and has a built-in functionality that allows for the attachment of a conjugated polymer chain is presented. The system was found to adsorb on the surface of anatase anchored by the ruthenium dye. Two types of devices were...... prepared: standard photoelectrochemical (PEC) solar cells and polymer solar cells. The PEC solar cells employed a sandwich geometry between TiO2 nanoporous photoanodes and Pt counter electrodes using LiI/I-2 in CH3CN as an electrolyte. The polymer solar cells employed planar anatase electrodes...

  20. Ruthenium phosphine complexes as catalysts for alternating co-polymerization of ethylene and CO

    International Nuclear Information System (INIS)

    Gusev, O.V.; Kal'sin, A.M.; Peganov, T.A.; Petrovskij, P.V.; Belov, G.P.; Novikova, E.V.

    2000-01-01

    Ruthenium (2) complexes, [Ru(dppe) 2 (OTs) 2 ] and [Ru(PhP(CH 2 CH 2 CH 2 PPh 2 ) 2 )(OTs) 2 ], where dppe (diphenylphosphino)ethane; OTs = tosylate, were synthesized with the yield of 67 and 76%, respectively, and characterized by 31 P NMR. The properties of the above complexes as catalysts of alternating co-polymerization of ethylene and carbon monoxide were studied. A considerable increase in catalytic activity of the complexes was established in the presence of trifluoroacetic acid and 1,4-benzoquinone. These compounds are the first example of ruthenium complexes that catalyse co-polymerization of ethylene and CO [ru

  1. Behaviour of ruthenium in the case of shutdown of the cooling system of HLLW storage tanks

    International Nuclear Information System (INIS)

    Philippe, M.; Gue, J.P.; Mercier, J.P.

    1990-12-01

    The consequences of the failure of the cooling system of fission product storage tanks over a variable period were investigated as part of the safety analysis of the La Hague spent fuel reprocessing plant. Due to the considerable heat release, induced by the fission products, a prolonged shutdown of the tank cooling system could cause the progressive evaporation of the solutions to dryness, and culminate in the formation of volatile species of ruthenium and their release in the tank venting circuit. To determine the fraction of ruthenium likely to be transferred from the storage tanks in volatile or aerosol form during the failure, evaporation tests were conducted by evaporating samples of actual nitric acid solutions of fission products, obtained on the laboratory scale after the reprocessing of several kilograms of MOX fuels irradiated to 30.000 MW day ·t -1 . A distillation apparatus was designed to operate with small-volume solution samples, reproducing the heating conditions existing in the reprocessing plant within a storage tank for fission products. The main conclusions drawn from these experiments are as follows: - ruthenium is only volatilized in the final phase of evaporation, just before desiccation, - for a final temperature limited to 160 deg. C, the total fraction of volatilized ruthenium reaches 12%, - in the presence of H 2 O, HNO 3 , NO x and O 2 , the volatilized ruthenium recombines mainly in the form of ruthenium nitrosyl nitrates, or decomposes into ruthenium oxide (probably RuO 2 ) on the walls of the apparatus. Assuming a heating power density of 10 W/liter of concentrate, and a perfectly adiabatic storage system, the minimum time required to reach dryness can be estimated at 90 h, allowing substantial time to take action to restore a cooling source. It is probable that, in an industrial storage tank, the heat losses from the tank and the offgas discharge ducts will cause recondensation and internal reflux, which will commensurately delay

  2. General synthesis of (salen)ruthenium(III) complexes via N...N coupling of (salen)ruthenium(VI) nitrides.

    Science.gov (United States)

    Man, Wai-Lun; Kwong, Hoi-Ki; Lam, William W Y; Xiang, Jing; Wong, Tsz-Wing; Lam, Wing-Hong; Wong, Wing-Tak; Peng, Shie-Ming; Lau, Tai-Chu

    2008-07-07

    Reaction of [Ru (VI)(N)(L (1))(MeOH)] (+) (L (1) = N, N'-bis(salicylidene)- o-cyclohexylenediamine dianion) with excess pyridine in CH 3CN produces [Ru (III)(L (1))(py) 2] (+) and N 2. The proposed mechanism involves initial equilibrium formation of [Ru (VI)(N)(L (1))(py)] (+), which undergoes rapid N...N coupling to produce [(py)(L (1))Ru (III) N N-Ru (III)(L (1))(py)] (2+); this is followed by pyridine substituion to give the final product. This ligand-induced N...N coupling of Ru (VI)N is utilized in the preparation of a series of new ruthenium(III) salen complexes, [Ru (III)(L)(X) 2] (+/-) (L = salen ligand; X = H 2O, 1-MeIm, py, Me 2SO, PhNH 2, ( t )BuNH 2, Cl (-) or CN (-)). The structures of [Ru (III)(L (1))(NH 2Ph) 2](PF 6) ( 6), K[Ru (III)(L (1))(CN) 2] ( 9), [Ru (III)(L (2))(NCCH 3) 2][Au (I)(CN) 2] ( 11) (L (2) = N, N'-bis(salicylidene)- o-phenylenediamine dianion) and [N ( n )Bu 4][Ru (III)(L (3))Cl 2] ( 12) (L (3) = N, N'-bis(salicylidene)ethylenediamine dianion) have been determined by X-ray crystallography.

  3. Recovery of nonradioactive palladium and rhodium from high-level radioactive wastes

    International Nuclear Information System (INIS)

    McDuffie, H.F.

    1979-01-01

    A possible method for recovering significant quantities of nonradioactive palladium from fission-product wastes requires essentially complete separation of the fission-product (radioactive) palladium from fission-product ruthenium. After the decay of 106 Ru via 106 Rh to 106 Pd, this nonradioactive palladium is recovered for normal commercial use. The U.S. production of palladium has never been above 1000 kg per year vs consumption of about 46,000 kg per year. Most of the supply comes from Russia and South Africa. It has been estimated that a 400-GW(e) nuclear reactor economy will make available 2000 kg per year of 106 Ru at reactor fuel discharge. A substantial increase might be achieved if plutonium were recycled as fissionable material because of the higher yields of the 106 chain from plutonium. A literature search has uncovered support for three promising approaches to the required separation of palladium from ruthenium: (1) recrystallization from solution in bismuth or in zinc; (2) selective precipitation of a titanium--ruthenium intermetallic compound from bismuth, followed by precipitation of a zinc--palladium intermetallic compound; and (3) dissolution in molten magnesium followed by partitioning between molten magnesium and a molten uranium-5 wt % chromium eutectic at a temperature above 870 0 C. Liquid-liquid extraction appears to be the most promising method from a technological point of view, although intermetallic compound formation is much more interesting chemically. Recovery of some nonradioactive 103 Rh may be possible by liquid-liquid extraction of the fuel before the decay of the 39.8-d 103 Ru has gone substantially to completion. Demonstration of the practicality of these separations will contribute a positive factor to the evaluation of resumption in the United States of nuclear fuel reprocessing and plutonium recycle in light-water-moderated reactors

  4. Evaluated phase diagrams of binary metal-tellurium systems of the D-block transition elements

    International Nuclear Information System (INIS)

    Chattopadhyay, G.; Bharadwaj, S.R.

    1989-01-01

    The binary phase diagrams of metal-tellurium systems for twenty seven d-block transition elements have been critically evaluated. Complete phase diagrams are presented for the elements, chromium, manganese, iron, cobalt, nickel, copper, molybdenum, palladium, silver, lanthanum, platinum and gold, whereas, for scandium, titanium, vanadium, yttrium, zirconium, niobium, technitium, ruthenium, rhodium, hafnium, tantalum, tungsten , rhenium, osmium and iridium, the phase diagrams are incomplete and tentative. (author). 20 refs., 27 tabs., 27 figs

  5. Annual reports in inorganic and general syntheses 1972

    CERN Document Server

    Niedenzu, Kurt

    1973-01-01

    Annual Reports in Inorganic and General Syntheses-1972 presents an organized annual summary of synthetic developments in inorganic chemistry and its related areas. The book discusses alkali and alkaline earth elements, alloys, silver, gold, zinc, cadmium, mercury, boron, aluminum, gallium, indium, thallium, yttrium, scandium, lanthanides, actinides, titanium, zirconium, hafnium, Group V and VI transition elements, manganese, technetium, rhenium, iron, cobalt, nickel, ruthenium, osmium, rhodium, and iridium. The text also describes the chemistry of palladium, platinum, silicon, germanium, tin,

  6. Iron-Deficiency Anemia

    Medline Plus

    Full Text Available ... Iron-Deficiency Anemia Iron-Deficiency Anemia Also known as Leer en español Iron-deficiency anemia is a ... address the cause of your iron deficiency, such as any underlying bleeding. If undiagnosed or untreated, iron- ...

  7. Iron-Deficiency Anemia

    Medline Plus

    Full Text Available ... To Health Topics / Iron-Deficiency Anemia Iron-Deficiency Anemia Also known as Leer en español Iron-deficiency ... anemia. Blood tests to screen for iron-deficiency anemia To screen for iron-deficiency anemia, your doctor ...

  8. Iron-Deficiency Anemia

    Science.gov (United States)

    ... To Health Topics / Iron-Deficiency Anemia Iron-Deficiency Anemia Also known as Leer en español Iron-deficiency ... anemia. Blood tests to screen for iron-deficiency anemia To screen for iron-deficiency anemia, your doctor ...

  9. Electrochemical and mass variation behaviour of rhodium oxide electrodes prepared by the polymeric precursor method

    International Nuclear Information System (INIS)

    Santos, M.C.; Oliveira, R.T.S.; Pereira, E.C.; Bulhoes, L.O.S.

    2005-01-01

    This paper describes an investigation of the charging processes of Rh 2 O 3 electrodes in acidic medium using Electrochemical Quartz Crystal Microbalance. The Rh 2 O 3 was prepared by the Pechini method. The microstructural characterization of the rhodium oxide was performed using Scanning Electron Microscopy and the structure was determined by X-ray diffraction. The Rh 2 O 3 oxidizes at potentials higher than 0.8 V. A mass loss of 60 ng was observed during the anodic sweep. The same amount is gained during the cathodic sweep indicating that the process is reversible. From the mass versus charge plots a slope of 8.5 g mol -1 is calculated. Considering a process that involves a two-electron transfer, the oxidation of Rh 2 O 3 to RhO 2 with the loss of a water molecule (18 g mol -1 ) is proposed

  10. Scanning tunneling microscopy studies of organic monolayers adsorbed on the rhodium(111) crystal surface

    Energy Technology Data Exchange (ETDEWEB)

    Cernota, Paul Davis [Univ. of California, Berkeley, CA (United States)

    1999-08-01

    Scanning Tunneling Microscopy studies were carried out on ordered overlayers on the (111) surface of rhodium. These adsorbates include carbon monoxide (CO), cyclohexane, cyclohexene, 1,4-cyclohexadiene, para-xylene, and meta-xylene. Coadsorbate systems included: CO with ethylidyne, CO with para- and meta-xylene, and para-xylene with meta-xylene. In the case of CO, the structure of the low coverage (2x2) overlayer has been observed. The symmetry of the unit cell in this layer suggests that the CO is adsorbed in the 3-fold hollow sites. There were also two higher coverage surface structures with (√7x√7) unit cells. One of these is composed of trimers of CO and has three CO molecules in each unit cell. The other structure has an additional CO molecule, making a total of four. This extra CO sits on a top site.

  11. Mapping of the radiation field of a mammography equipment using molybdenum and rhodium filters

    International Nuclear Information System (INIS)

    Barreira, Jacqueline S.; Campos, Daniela; Vivolo, Vitor

    2014-01-01

    The use of X rays for diagnostic radiology is very common and important to Medicine, including mammographic diagnosis focusing decreasing of the doses applied to the patients and preserving high quality of the diagnostic image. A quality control program of the irradiation systems it is very necessary. The Instruments Calibration Laboratory (LCI) of IPEN perform calibration in dosemeters used in radiation dosimetry (in diagnostic radiology) for many years. The objective of that paper is determining the point of greatest intensity of the beam issued by the mammography equipment. Exposures were made with filters Rhodium and Molybdenum. That mapping is important before applied a routine quality control program of the mammography equipment and the calibration of instruments in the diagnosis. (author)

  12. Bifunctional rhodium intercalator conjugates as mismatch-directing DNA alkylating agents.

    Science.gov (United States)

    Schatzschneider, Ulrich; Barton, Jacqueline K

    2004-07-21

    A conjugate of a DNA mismatch-specific rhodium intercalator, containing the bulky chrysenediimine ligand, and an aniline mustard has been prepared, and targeting of mismatches in DNA by this conjugate has been examined. The preferential alkylation of mismatched over fully matched DNA is found by a mobility shift assay at concentrations where untethered organic mustards show little reaction. The binding site of the Rh intercalator was determined by DNA photocleavage, and the position of covalent modification was established on the basis of the enhanced depurination associated with N-alkylation. The site-selective alkylation at mismatched DNA renders these conjugates useful tools for the covalent tagging of DNA base pair mismatches and new chemotherapeutic design.

  13. An investigation of models of rhodium emitter used in self-powered neutron detector

    International Nuclear Information System (INIS)

    Borisenko, V.I.; Piontkovskij, Yu.F.; Goranchuk, V.V.

    2017-01-01

    he paper presents the results of MCNP simulation of the self-powered neutron detector (SPND) signal formation as a result of emitter nuclei activation under the irradiation with neutrons generated in the fuel assemblies. To account for the non-uniformity of emitter burnup along the radius, its model was divided radially into 10 layers of equal thickness. It has been shown that the main contribution of about 88 % of SPND signal is provided by the four peripheral emitter layers. The contribution of different parts of emitter to the SPND signal formation throughout the lifetime of the SPND in the In-Core Monitoring System was found. Simulation results allow us to determine the SPND signal when the spectral characteristics of the neutron flux at the detector location change during the fuel campaign. The study has investigated and proposed a SPND model with the higher neutron sensitivity even though a smaller amount of expensive rhodium is used.

  14. Mathematical model of rhodium self-powered detectors and algorithms for correction of their time delay

    International Nuclear Information System (INIS)

    Bur'yan, V.I.; Kozlova, L.V.; Kuzhil', A.S.; Shikalov, V.F.

    2005-01-01

    The development of algorithms for correction of self-powered neutron detector (SPND) inertial is caused by necessity to increase the fast response of the in-core instrumentation systems (ICIS). The increase of ICIS fast response will permit to monitor in real time fast transient processes in the core, and in perspective - to use the signals of rhodium SPND for functions of emergency protection by local parameters. In this paper it is proposed to use mathematical model of neutron flux measurements by means of SPND in integral form for creation of correction algorithms. This approach, in the case, is the most convenient for creation of recurrent algorithms for flux estimation. The results of comparison for estimation of neutron flux and reactivity by readings of ionization chambers and SPND signals, corrected by proposed algorithms, are presented [ru

  15. Dimerisation, rhodium complex formation and rearrangements of N-heterocyclic carbenes of indazoles

    Directory of Open Access Journals (Sweden)

    Zong Guan

    2014-04-01

    Full Text Available Deprotonation of indazolium salts at low temperatures gives N-heterocyclic carbenes of indazoles (indazol-3-ylidenes which can be trapped as rhodium complexes (X-ray analysis. In the absence of Rh, the indazol-3-ylidenes spontaneously dimerize under ring cleavage of one of the N,N-bonds and ring closure to an indazole–indole spiro compound which possesses an exocyclic imine group. The E/Z isomers of the imines can be separated by column chromatography when methanol is used as eluent. We present results of a single crystal X-ray analysis of one of the E-isomers, which equilibrate in solution as well as in the solid state. Heating of the indazole–indole spiro compounds results in the formation of quinazolines by a ring-cleavage/ring-closure sequence (X-ray analysis. Results of DFT calculations are presented.

  16. Optimization of Rhodium-Based Catalysts for Mixed Alcohol Synthesis – 2012 Progress Report

    Energy Technology Data Exchange (ETDEWEB)

    Gerber, Mark A.; Gray, Michel J.; Albrecht, Karl O.; Thompson, Becky L.

    2012-11-01

    Pacific Northwest National Laboratory has been conducting research to investigate the feasibility of producing mixed alcohols from biomass-derived synthesis gas (syngas). In recent years, this research has primarily involved the further development of catalysts containing rhodium and manganese based on the results of earlier catalyst screening tests. Testing continued in FY 2012 to further improve the Ir-promoted RhMn catalysts on both silica and carbon supports for producing mixed oxygenates from synthesis gas. This testing re-examined selected alternative silica and carbon supports to follow up on some uncertainties in the results with previous test results. Additional tests were conducted to further optimize the total and relative concentrations of Rh, Mn, and Ir, and to examine selected promoters and promoter combinations based on earlier results. To establish optimum operating conditions, the effects of the process pressure and the feed gas composition also were evaluated.

  17. Rhodium Nanoparticle-mesoporous Silicon Nanowire Nanohybrids for Hydrogen Peroxide Detection with High Selectivity

    Science.gov (United States)

    Song, Zhiqian; Chang, Hucheng; Zhu, Weiqin; Xu, Chenlong; Feng, Xinjian

    2015-01-01

    Developing nanostructured electrocatalysts, with low overpotential, high selectivity and activity has fundamental and technical importance in many fields. We report here rhodium nanoparticle and mesoporous silicon nanowire (RhNP@mSiNW) hybrids for hydrogen peroxide (H2O2) detection with high electrocatalytic activity and selectivity. By employing electrodes that loaded with RhNP@mSiNW nanohybrids, interference caused from both many electroactive substances and dissolved oxygen were eliminated by electrochemical assaying at an optimal potential of +75 mV. Furthermore, the electrodes exhibited a high detection sensitivity of 0.53 μA/mM and fast response (< 5 s). This high-performance nanohybrid electrocatalyst has great potential for future practical application in various oxidase-base biosensors. PMID:25588953

  18. Highly Stereoselective Synthesis of Cyclopentanes bearing Four Stereocenters by a Rhodium Carbene–Initiated Domino Sequence

    Science.gov (United States)

    Parr, Brendan T.; Davies, Huw M. L.

    2014-01-01

    Stereoselective synthesis of a cyclopentane nucleus by convergent annulations constitutes a significant challenge for synthetic chemists. Though a number of biologically relevant cyclopentane natural products are known, more often than not, the cyclopentane core is assembled in a stepwise fashion due to lack of efficient annulation strategies. Herein, we report the rhodium-catalyzed reactions of vinyldiazoacetates with (E)-1,3-disubstituted 2-butenols generate cyclopentanes, containing four new stereogenic centers with very high levels of stereoselectivity (99% ee, >97 : 3 dr). The reaction proceeds by a carbene–initiated domino sequence consisting of five distinct steps: rhodium–bound oxonium ylide formation, [2,3]-sigmatropic rearrangement, oxy-Cope rearrangement, enol–keto tautomerization, and finally an intramolecular carbonyl ene reaction. A systematic study is presented detailing how to control chirality transfer in each of the four stereo-defining steps of the cascade, consummating in the development of a highly stereoselective process. PMID:25082301

  19. Ionic Liquids as Solvents for Rhodium and Platinum Catalysts Used in Hydrosilylation Reaction

    Directory of Open Access Journals (Sweden)

    Witold Zielinski

    2016-08-01

    Full Text Available A group of imidazolium and pyridinium based ionic liquids has been synthetized, and their ability to dissolve and activate the catalysts used in hydrosilylation reaction of 1-octane and 1,1,1,3,5,5,5-heptamethyltrisiloxane was investigated. An organometallic catalyst as well as inorganic complexes of platinum and rhodium dissolved in ionic liquids were used, forming liquid solutions not miscible with the substrates or with the products of the reaction. The results show that application of such a simple biphasic catalytic system enables reuse of ionic liquid phase with catalysts in multiple reaction cycles reducing the costs and decreasing the amount of catalyst needed per mole of product.

  20. Water resistant rhodium plated reflectors for use in the DIRC BaBar Cherenkov detector

    CERN Document Server

    Benkebil, M; Plaszczynski, S; Schune, M H; Wormser, G

    2000-01-01

    Early simulation studies showed that reflectors mounted on the photomultipliers would be useful for the DIRC BaBar Cherenkov detector, showing a gain between 20% and 30% in the number of Cherenkov photons. The proof of principle for these reflectors has been obtained during the beam test of a large-scale prototype of the DIRC detector. An extensive R and D has been conducted in order to test different metallization procedures. Indeed, the challenge was to find a metallization technique which can resist the pure de-ionized water (>15 M OMEGA) up to 10 yr. The chosen technology was rhodium plated reflectors. During the first BaBar cosmic run, the measured performance confirmed the results of the simulation, the prototype-II and the R and D.

  1. Highly enantioselective rhodium(I)-catalyzed carbonyl carboacylations initiated by C-C bond activation.

    Science.gov (United States)

    Souillart, Laetitia; Cramer, Nicolai

    2014-09-01

    The lactone motif is ubiquitous in natural products and pharmaceuticals. The Tishchenko disproportionation of two aldehydes, a carbonyl hydroacylation, is an efficient and atom-economic access to lactones. However, these reaction types are limited to the transfer of a hydride to the accepting carbonyl group. The transfer of alkyl groups enabling the formation of CC bonds during the ester formation would be of significant interest. Reported herein is such asymmetric carbonyl carboacylation of aldehydes and ketones, thus affording complex bicyclic lactones in excellent enantioselectivities. The rhodium(I)-catalyzed transformation is induced by an enantiotopic CC bond activation of a cyclobutanone and the formed rhodacyclic intermediate reacts with aldehyde or ketone groups to give highly functionalized lactones. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Selective rhodium-catalyzed reduction of tertiary amides in amino acid esters and peptides.

    Science.gov (United States)

    Das, Shoubhik; Li, Yuehui; Bornschein, Christoph; Pisiewicz, Sabine; Kiersch, Konstanze; Michalik, Dirk; Gallou, Fabrice; Junge, Kathrin; Beller, Matthias

    2015-10-12

    Efficient reduction of the tertiary amide bond in amino acid derivatives and peptides is described. Functional group selectivity has been achieved by applying a commercially available rhodium precursor and bis(diphenylphosphino)propane (dppp) ligand together with phenyl silane as a reductant. This methodology allows for specific reductive derivatization of biologically interesting peptides and offers straightforward access to a variety of novel peptide derivatives for chemical biology studies and potential pharmaceutical applications. The catalytic system tolerates a variety of functional groups including secondary amides, ester, nitrile, thiomethyl, and hydroxy groups. This convenient hydrosilylation reaction proceeds at ambient conditions and is operationally safe because no air-sensitive reagents or highly reactive metal hydrides are needed. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. A ruthenium anticancer compound interacts with histones and impacts differently on epigenetic and death pathways compared to cisplatin.

    Science.gov (United States)

    Licona, Cynthia; Spaety, Marie-Elodie; Capuozzo, Antonelle; Ali, Moussa; Santamaria, Rita; Armant, Olivier; Delalande, Francois; Van Dorsselaer, Alain; Cianferani, Sarah; Spencer, John; Pfeffer, Michel; Mellitzer, Georg; Gaiddon, Christian

    2017-01-10

    Ruthenium complexes are considered as potential replacements for platinum compounds in oncotherapy. Their clinical development is handicapped by a lack of consensus on their mode of action. In this study, we identify three histones (H3.1, H2A, H2B) as possible targets for an anticancer redox organoruthenium compound (RDC11). Using purified histones, we confirmed an interaction between the ruthenium complex and histones that impacted on histone complex formation. A comparative study of the ruthenium complex versus cisplatin showed differential epigenetic modifications on histone H3 that correlated with differential expression of histone deacetylase (HDAC) genes. We then characterized the impact of these epigenetic modifications on signaling pathways employing a transcriptomic approach. Clustering analyses showed gene expression signatures specific for cisplatin (42%) and for the ruthenium complex (30%). Signaling pathway analyses pointed to specificities distinguishing the ruthenium complex from cisplatin. For instance, cisplatin triggered preferentially p53 and folate biosynthesis while the ruthenium complex induced endoplasmic reticulum stress and trans-sulfuration pathways. To further understand the role of HDACs in these regulations, we used suberanilohydroxamic acid (SAHA) and showed that it synergized with cisplatin cytotoxicity while antagonizing the ruthenium complex activity. This study provides critical information for the characterization of signaling pathways differentiating both compounds, in particular, by the identification of a non-DNA direct target for an organoruthenium complex.

  4. In vitro evaluation of ruthenium complexes for photodynamic therapy.

    Science.gov (United States)

    Li, Wenna; Xie, Qiang; Lai, Linglin; Mo, Zhentao; Peng, Xiaofang; Leng, Ennian; Zhang, Dandan; Sun, Hongxia; Li, Yiqi; Mei, Wenjie; Gao, Shuying

    2017-06-01

    Photodynamic therapy (PDT) is a promising anti-tumor treatment strategy. Photosensitizer is one of the most important components of PDT. In this work, the anticancer activities of PDT mediated by six new ruthenium porphyrin complexes were screened. The mechanisms of the most efficacious candidate were investigated. Photocytotoxicity of the six porphyrins was tested. The most promising complex, Rup-03, was further investigated using Geimsa staining, which indirectly detects reactive oxygen species (ROS) and subcellular localization. Mitochondrial membrane potential (MMP), cell apoptosis, DNA fragmentation, c-Myc gene expression, and telomerase activities were also assayed. Rup-03 and Rup-04 had the lowest IC 50 values. Rup-03 had an IC 50 value of 29.5±2.3μM in HepG2 cells and 59.0±6.1μM in RAW264.7 cells, while Rup-04 had an IC 50 value of 40.0±3.8μM in SGC-7901 cells. The complexes also induced cellular morphological changes and impaired cellular ability to scavenge ROS, and accumulated preferentially in mitochondria and endoplasmic reticulum. Rup-03 reduced MMP levels, induced apoptosis, and repressed both c-Myc mRNA expression and telomerase activity in HepG2 cells. Among six candidates, Rup-03-mediated PDT is most effective against HepG2 and RAW264.7, with a similar efficacy as that of Rup-04-mediated PDT against SGC-7901 cells. Repression of ROS scavenging activities and c-Myc expression, which mediated DNA damage-induced cell apoptosis and repression of telomerase activity, respectively, were found to be involved in the anticancer mechanisms of Rup-03. Copyright © 2017 Elsevier B.V. All rights reserved.

  5. Dealloyed Ruthenium Film Catalysts for Hydrogen Generation from Chemical Hydrides

    Directory of Open Access Journals (Sweden)

    Ramis B. Serin

    2017-07-01

    Full Text Available Thin-film ruthenium (Ru and copper (Cu binary alloys have been prepared on a Teflon™ backing layer by cosputtering of the precious and nonprecious metals, respectively. Alloys were then selectively dealloyed by sulfuric acid as an etchant, and their hydrogen generation catalysts performances were evaluated. Sputtering time and power of Cu atoms have been varied in order to tailor the hydrogen generation performances. Similarly, dealloying time and the sulfuric acid concentration have also been altered to tune the morphologies of the resulted films. A maximum hydrogen generation rate of 35 mL min−1 was achieved when Cu sputtering power and time were 200 W and 60 min and while acid concentration and dealloying time were 18 M and 90 min, respectively. It has also been demonstrated that the Ru content in the alloy after dealloying gradually increased with the increasing the sputtering power of Cu. After 90 min dealloying, the Ru to Cu ratio increased to about 190 times that of bare alloy. This is the key issue for observing higher catalytic activity. Interestingly, we have also presented template-free nanoforest-like structure formation within the context of one-step alloying and dealloying used in this study. Last but not least, the long-time hydrogen generation performances of the catalysts system have also been evaluated along 3600 min. During the first 600 min, the catalytic activity was quite stable, while about 24% of the catalytic activity decayed after 3000 min, which still makes these systems available for the development of robust catalyst systems in the area of hydrogen generation.

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

    Energy Technology Data Exchange (ETDEWEB)

    Murakami, Naoya, E-mail: namuraka@ncc.go.jp [Department of Radiation Oncology, National Cancer Center Hospital, Tokyo (Japan); Suzuki, Shigenobu [Department of Ophthalmic Oncology, National Cancer Center Hospital, Tokyo (Japan); Ito, Yoshinori [Department of Radiation Oncology, National Cancer Center Hospital, Tokyo (Japan); Yoshimura, Ryoichi [Department of Diagnostic Radiology and Oncology, Head and Neck Reconstruction Division, Graduate School, Tokyo Medical and Dental University, Tokyo (Japan); Inaba, Koji; Kuroda, Yuki; Morota, Madoka; Mayahara, Hiroshi; Sakudo, Mototake; Wakita, Akihisa; Okamoto, Hiroyuki; Sumi, Minako; Kagami, Yoshikazu [Department of Radiation Oncology, National Cancer Center Hospital, Tokyo (Japan); Nakagawa, Keiichi; Ohtomo, Kuni [Department of Radiology, University of Tokyo Hospital, Tokyo (Japan); Itami, Jun [Department of Radiation Oncology, National Cancer Center Hospital, Tokyo (Japan)

    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.

  7. Behavior of ruthenium, cesium and antimony during simulated HLLW vitrification

    International Nuclear Information System (INIS)

    Klein, M.; Weyers, C.; Goossens, W.R.A.

    1985-01-01

    The behavior of ruthenium, cesium, and antimony during the vitrification of simulated high-level radioactive liquid wastes (HLLW) in a liquid fed melter was studied on a laboratory scale and on a semi-pilot scale. In the laboratory melter of a 2.5 kg capacity, a series of tests with the simulate traced with 103 Ru, 134 Cs and 124 Sb, has shown that the Ru and Cs losses to the melter effluent are generally higher than 10% whereas the antimony losses remain lower than 0.4%. A wet purification system comprising in series, a dust scrubber, a condenser, an ejector venturi and an NOx washing column retains most of the activity present in the off-gas so that the release fractions for Ru at the absolute filter inlet ranges between 5.10 -3 to 5.10 -5 % of the Ru fed, for Cs the corresponding release fraction ranges between 3.10 -3 to 10 -4 % and for Sb the release fraction ranges between 1.7 10 -4 to 1.7 10 -5 %. The same experiments were performed at a throughput of 1 to 2 1 h -1 of simulated solution in the semi-pilot scale unit RUFUS. The RUFUS unit comprises a glass melter with a 50 kg molten glass capacity and the wet purification train comprises in series a dust scrubber, a condenser, an ejector venturi and an NOx washing column. The tracer tests were restricted to 103 Ru and 134 Cs since the laboratory tests had shown that the antimony losses were very low. The results of the tests are presented

  8. Reaction mechanisms of ruthenium tetroxide mediated oxidations of organic compounds

    Energy Technology Data Exchange (ETDEWEB)

    Froehaug, Astrid Elisabeth

    1995-12-31

    This thesis reports a study of the mechanism of ruthenium tetroxide mediated oxidations of saturated hydrocarbons, ethers, alkenes and alcohols. Several methods were used. The RuO{sub 4}-mediated oxidations of adamantane and cis-decalin were studied in CCl{sub 4}-CH{sub 3}CN-H{sub 2}O and in acetone-water. The rate of reaction was found to be moderately influenced by the polarity of the solvent. Solvent properties other than the polarity were also found to influence the reaction rates. From the oxidations of adamantane and adamantane-1,3,5,7-d{sub 4} two primary kinetic deuterium isotope effects were found. These were comparable with the deuterium isotope effects found for the analogous oxidations of cis-decalin and cis-decalin-d{sub 18}. The results seem to exclude both a one step hydride abstraction reaction mechanism and a one step concerted mechanism, as well as a scheme where two such mechanisms compete. The observations may be explained by a two step reaction mechanism consisting of a pre-equilibrium with formation of a substrate-RuO{sub 4} complex followed by a concerted rate determining reaction. The RuO{sub 4}-mediated oxidation of ethers was of kinetic second order with a small enthalpy of activation and a large negative entropy of activation. Oxidation of cyclopropylmethyl methyl ether gave methyl cyclopropanecarboxylate, no rearranged products were observed. On RuO{sub 4} oxidations in CCl{sub 4} with NaIO{sub 4} as stoichiometric oxidant, no chlorinated products were observed. Several observations not in agreement with a hydride or a hydrogen abstraction mechanism may be explained by assuming that the reaction proceeds by either a concerted reaction or by a reversible oxidative addition of the ether to RuO{sub 4} followed by a slow concerted step. 228 refs., 9 figs., 27 tabs.

  9. Ruthenium porphyrin-induced photodamage in bladder cancer cells.

    Science.gov (United States)

    Bogoeva, Vanya; Siksjø, Monica; Sæterbø, Kristin G; Melø, Thor Bernt; Bjørkøy, Astrid; Lindgren, Mikael; Gederaas, Odrun A

    2016-06-01

    Photodynamic therapy (PDT) is a noninvasive treatment for solid malignant and flat tumors. Light activated sensitizers catalyze photochemical reactions that produce reactive oxygen species which can cause cancer cell death. In this work we investigated the photophysical properties of the photosensitizer ruthenium(II) porphyrin (RuP), along with its PDT efficiency onto rat bladder cancer cells (AY27). Optical spectroscopy verified that RuP is capable to activate singlet oxygen via blue and red absorption bands and inter system crossing (ISC) to the triplet state. In vitro experiments on AY27 indicated increased photo-toxicity of RuP (20μM, 18h incubation) after cell illumination (at 435nm), as a function of blue light exposure. Cell survival fraction was significantly reduced to 14% after illumination of 20μM RuP with 15.6J/cm(2), whereas the "dark toxicity" of 20μM RuP was 17%. Structural and morphological changes of cells were observed, due to RuP accumulation, as well as light-dependent cell death was recorded by confocal microscopy. Flow cytometry verified that PDT-RuP (50μM) triggered significant photo-induced cellular destruction with a photoxicity of (93%±0.9%). Interestingly, the present investigation of RuP-PDT showed that the dominating mode of cell death is necrosis. RuP "dark toxicity" compared to the conventional chemotherapeutic drug cisplatin was higher, both evaluated by the MTT assay (24h). In conclusion, the present investigation shows that RuP with or without photoactivation induces cell death of bladder cancer cells. Copyright © 2016 Elsevier B.V. All rights reserved.

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

    Science.gov (United States)

    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. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Conclusive evidence on the mechanism of the rhodium-mediated decyanative borylation.

    Science.gov (United States)

    Esteruelas, Miguel A; Oliván, Montserrat; Vélez, Andrea

    2015-09-30

    The stoichiometric reactions proposed in the mechanism of the rhodium-mediated decyanative borylation have been performed and all relevant intermediates isolated and characterized including their X-ray structures. Complex RhCl{xant(P(i)Pr2)2} (1, xant(P(i)Pr2)2 = 9,9-dimethyl-4,5-bis(diisopropylphosphino)xanthene) reacts with bis(pinacolato)diboron (B2pin2), in benzene, to give the rhodium(III) derivative RhHCl(Bpin){xant(P(i)Pr2)2} (4) and PhBpin. The reaction involves the oxidative addition of B2pin2 to 1 to give RhCl(Bpin)2{xant(P(i)Pr2)2}, which eliminates ClBpin generating Rh(Bpin){xant(P(i)Pr2)2} (2). The reaction of the latter with the solvent yields PhBpin and the monohydride RhH{xant(P(i)Pr2)2} (6), which adds the eliminated ClBpin. Complex 4 and its catecholboryl counterpart RhHCl(Bcat){xant(P(i)Pr2)2} (7) have also been obtained by oxidative addition of HBR2 to 1. Complex 2 is the promoter of the decyanative borylation. Thus, benzonitrile and 4-(trifluoromethyl)benzonitrile insert into the Rh-B bond of 2 to form Rh{C(R-C6H4)═NBpin}{xant(P(i)Pr2)2} (R = H (8), p-CF3 (9)), which evolve into the aryl derivatives RhPh{xant(P(i)Pr2)2} (3) and Rh(p-CF3-C6H4){xant(P(i)Pr2)2} (10), as a result of the extrusion of CNBpin. The reactions of 3 and 10 with B2pin2 yield the arylBpin products and regenerate 2.

  12. Bibliographies on radiation chemistry. 9. Metal ions and complexes. Part A: Cobalt, rhodium, iridium

    Energy Technology Data Exchange (ETDEWEB)

    Hoffman, M Z; Ross, A B

    1986-01-01

    The one-electron oxidation and reduction of metal ions and complexes can yield species in unusual oxidation states, and ligand-radicals coordinated to the central metal. These often unstable species can be mechanistically important intermediates in thermal, photochemical, and electrochemical reactions involving metal-containing substances. Their generation via radiolysis provides an alternate means of characterizing them using kinetic and spectroscopic techniques. We hope these bibliographies on the radiation chemistry of metal ions and complexes, presented according to periodic groups, will prove useful to researchers in metallo-redox chemistry. These bibliographies contain only primary literature sources; reviews are not included. However, a list of general review articles on the radiation chemistry of metal ions and complexes is presented here in the first section which covers cobalt, rhodium and iridium, Group 9 in the new IUPAC notation. Additional parts of the bibliography are planned, covering other periodic groups. Part A of the bibliography was prepared by a search of the Radiation Chemistry Data Center Bibliographic Data Base (RCDCbib) through January 1986 for papers on rhodium, iridium and cobalt compounds, and radiolysis (both continuous and pulsed). Papers in which the use of metal compounds was incidental to the primary objective of the study were excluded. Excluded also were publications in unrefereed and obscure sources such as meeting proceedings, internal reports, dissertations, and patents. The majority of the studies in the resultant compilation deal with experiments performed on solutions, mainly aqueous, although a substantial fraction is devoted to solid-state esr measurements. The references are listed in separate sections for each of the metals, and are presented in approximate chronological order.

  13. Rhodium target preparation from homemade chloride plating baths used for the industrial cyclotron production of palladium-L03

    International Nuclear Information System (INIS)

    Sadeghi, M.; Van den Winkel, P.; Afarideh, H.; Haji-Saeid, M.; Syrafi Nafis, H.

    2004-01-01

    Purpose: To avoid acquisition problems of commercially available western rhodium plating solutions in developing countries, a new plating/recovery cycle for Rh-103 electroplated target material (1 g Rh per target) used for the industrial cyclotron production of Pd-103 was developed. Rhodium chloride plating solutions can be prepared by dissolution of the analytical grade compound or from rhodium recovery solutions obtained after electrosolubilisation of irradiated targets and extraction of palladium. Methods: The technology involves the selective removal of the copper target backing of an irradiated target in concentrated nitric acid using a homemade flow-through stripper. The resulting rhodium fragments are dissolved in a constant-volume (40 ml), homemade graphite centrifugal ac-electrodissolution mini-reactor operating at 90 degree C, 2 A.cm-2 and 1000-rpm rotation speed. The system allows time-controlled 99 % solubilisation of up to 3g rhodium (as fragments, powder or small pieces of wire) in less than 3 hours when 12 N hydrochloric acid is applied. Upon solvent-solvent extraction of the non-carrier added Pd-103 from the resulting HCI solution; the following procedure can be used for the simultaneous preparation of 4 targets showing a surface area of 11.69 cm 2 and a physical thickness of 48 Um. Dissolve an amount of hydrated RhC13 containing 2.8 g of rhodium in 400 ml of water. Alternatively, the filtered (0.45 μm filter) combined recovery solutions containing the same weight of rhodium can be evaporated to near dryness (350 degree C at the start, 150 degree C near the end) and residue taken up (gentle stirring, 50 degree C) in 400 ml of distilled water, After filtration, a stress reducing agent (sulfamic acid) is added and the pH sodium hydroxide. Upon make up to volume (450 ml) adjusted to the optimum value (pH = 2) with and preheating to 40 degree C, the resulting solution is introduced in a cylindrical home-made constant-volume, 4- target plating vessel

  14. Iron-Deficiency Anemia

    Medline Plus

    Full Text Available ... making new blood cells. Visit our Aplastic Anemia Health Topic to learn more. ... recommend that you take iron supplements, also called iron pills or oral iron, by mouth once or several times a ...

  15. Iron-Deficiency Anemia

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    Full Text Available ... red meat, salmon, iron-fortified breads and cereals, peas, tofu, dried fruits, and dark green leafy vegetables. ... stored iron has been used. Ferritin is a protein that helps store iron in your body. Reticulocyte ...

  16. Iron-Deficiency Anemia

    Medline Plus

    Full Text Available ... drinking black tea, which reduces iron absorption. Other treatments If you have chronic kidney disease and iron- ... and lifestyle changes to avoid complications. Follow your treatment plan Do not stop taking your prescribed iron ...

  17. Iron-Deficiency Anemia

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    Full Text Available ... diagnoses you with iron-deficiency anemia, your treatment will depend on the cause and severity of the ... of iron. The recommended daily amounts of iron will depend on your age, sex, and whether you ...

  18. Iron-Deficiency Anemia

    Medline Plus

    Full Text Available ... heart failure . Increased risk of infections Motor or cognitive development delays in children Pregnancy complications, such as ... iron-deficiency anemia may require intravenous (IV) iron therapy or a blood transfusion . Iron supplements Your doctor ...

  19. Iron-Deficiency Anemia

    Medline Plus

    Full Text Available ... for iron-deficiency anemia. Lifestyle habits Certain lifestyle habits may increase your risk for iron-deficiency anemia, including: Vegetarian or vegan eating patterns. Not eating enough iron-rich foods, such ...

  20. Iron-Deficiency Anemia

    Medline Plus

    Full Text Available ... because your body’s intake of iron is too low. Low intake of iron can happen because of blood ... delivery or giving birth to a baby with low birth weight In people with chronic conditions, iron- ...

  1. Iron-Deficiency Anemia

    Medline Plus

    Full Text Available ... breastfeeding. Recommended daily iron intake for children and adults. The table lists the recommended amounts of iron, ... increased need for iron during growth spurts. Older adults, especially those over age 65. Unhealthy environments Children ...

  2. Iron-Deficiency Anemia

    Medline Plus

    Full Text Available ... girls. From birth to 6 months, babies need 0.27 mg of iron. This number goes up ... screen blood donors for low iron stores. Reliable point-of-care testing may help identify iron deficiency ...

  3. Iron metabolism and toxicity

    International Nuclear Information System (INIS)

    Papanikolaou, G.; Pantopoulos, K.

    2005-01-01

    Iron is an essential nutrient with limited bioavailability. When present in excess, iron poses a threat to cells and tissues, and therefore iron homeostasis has to be tightly controlled. Iron's toxicity is largely based on its ability to catalyze the generation of radicals, which attack and damage cellular macromolecules and promote cell death and tissue injury. This is lucidly illustrated in diseases of iron overload, such as hereditary hemochromatosis or transfusional siderosis, where excessive iron accumulation results in tissue damage and organ failure. Pathological iron accumulation in the liver has also been linked to the development of hepatocellular cancer. Here we provide a background on the biology and toxicity of iron and the basic concepts of iron homeostasis at the cellular and systemic level. In addition, we provide an overview of the various disorders of iron overload, which are directly linked to iron's toxicity. Finally, we discuss the potential role of iron in malignant transformation and cancer

  4. Iron-Deficiency Anemia

    Medline Plus

    Full Text Available ... amount of iron, and medical conditions that make it hard for your body to absorb iron from ... hepcidin. Hepcidin prevents iron from leaving cells where it is stored or from being absorbed in the ...

  5. Iron-Deficiency Anemia

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    Full Text Available ... bleeding. If undiagnosed or untreated, iron-deficiency anemia can cause serious complications, including heart failure and development ... iron is too low. Low intake of iron can happen because of blood loss, consuming less than ...

  6. Iron-Deficiency Anemia

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    Full Text Available ... iron-fortified foods that have iron added. Vegetarian diets can provide enough iron if you choose nonmeat ... Anemia in Chronic Kidney Disease (National Institute of Diabetes and Digestive and Kidney Diseases) Avoiding Anemia (National ...

  7. Iron-Deficiency Anemia

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    Full Text Available ... lean red meat, salmon, iron-fortified breads and cereals, peas, tofu, dried fruits, and dark green leafy ... sources of iron, including iron-fortified breads and cereals, beans, tofu, dried fruits, and spinach and other ...

  8. Iron-Deficiency Anemia

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    Full Text Available ... starch. Restless legs syndrome Shortness of breath Weakness Complications Undiagnosed or untreated iron-deficiency anemia may cause ... as complete blood count and iron studies. Prevent complications over your lifetime To prevent complications from iron- ...

  9. Iron-Deficiency Anemia

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    Full Text Available ... you do not have enough iron in your body. People with mild or moderate iron-deficiency anemia ... and where to find more information. Causes Your body needs iron to make healthy red blood cells. ...

  10. Iron-Deficiency Anemia

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    Full Text Available ... from developing iron-deficiency anemia. Foods that are good sources of iron include dried beans, dried fruits, eggs, lean red meat, ... signs of iron-deficiency anemia include: Brittle nails ...

  11. Taking iron supplements

    Science.gov (United States)

    ... medlineplus.gov/ency/article/007478.htm Taking iron supplements To use the sharing features on this page, ... levels. You may also need to take iron supplements as well to rebuild iron stores in your ...

  12. Iron-Deficiency Anemia

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    Full Text Available ... fruits, eggs, lean red meat, salmon, iron-fortified breads and cereals, peas, tofu, dried fruits, and dark ... choose nonmeat sources of iron, including iron-fortified breads and cereals, beans, tofu, dried fruits, and spinach ...

  13. Iron-Deficiency Anemia

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    Full Text Available ... ESAs are usually used with iron therapy or IV iron, or when iron therapy alone is not enough. Look for Living With will discuss what your doctor may recommend, including lifelong lifestyle changes ...

  14. Iron-Deficiency Anemia

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    Full Text Available ... and pregnancy. Good sources of iron are meat, poultry, fish, and iron-fortified foods that have iron ... Anemia Restless Legs Syndrome Von Willebrand Disease Other Resources NHLBI resources Your Guide to Anemia [PDF, 1. ...

  15. Genetics Home Reference: iron-refractory iron deficiency anemia

    Science.gov (United States)

    ... refractory iron deficiency anemia Iron-refractory iron deficiency anemia Printable PDF Open All Close All Enable Javascript ... expand/collapse boxes. Description Iron-refractory iron deficiency anemia is one of many types of anemia , which ...

  16. Biological properties of novel ruthenium- and osmium-nitrosyl complexes with azole heterocycles

    KAUST Repository

    Novak, Maria S.; Bü chel, Gabriel E.; Keppler, Bernhard K.; Jakupec, Michael A.

    2016-01-01

    Since the discovery that nitric oxide (NO) is a physiologically relevant molecule, there has been great interest in the use of metal nitrosyl compounds as antitumor pharmaceuticals. Particularly interesting are those complexes which can deliver NO to biological targets. Ruthenium- and osmium-based compounds offer lower toxicity compared to other metals and show different mechanisms of action as well as different spectra of activity compared to platinum-based drugs. Novel ruthenium- and osmium-nitrosyl complexes with azole heterocycles were studied to elucidate their cytotoxicity and possible interactions with DNA. Apoptosis induction, changes of mitochondrial transmembrane potential and possible formation of reactive oxygen species were investigated as indicators of NO-mediated damage by flow cytometry. Results suggest that ruthenium- and osmium-nitrosyl complexes with the general formula (indazolium)[cis/trans-MCl4(NO)(1H-indazole)] have pronounced cytotoxic potency in cancer cell lines. Especially the more potent ruthenium complexes strongly induce apoptosis associated with depolarization of mitochondrial membranes, and elevated reactive oxygen species levels. Furthermore, a slight yet not unequivocal trend to accumulation of intracellular cyclic guanosine monophosphate attributable to NO-mediated effects was observed.

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

    NARCIS (Netherlands)

    Coloma Ribera, R.; van de Kruijs, Robbert Wilhelmus Elisabeth; Zoethout, E.; Yakshin, Andrey; Bijkerk, Frederik

    2014-01-01

    For next generation Extreme UV photolithography, multilayer coatings may require protective capping layers against surface contamination. Ruthenium, as a low-oxidation metal, is often used as a reference material. The oxidation behaviour of Ru thin films has been studied using X-ray reflectometry

  18. Fabrication of ruthenium metal nanosheets via topotactic metallization of exfoliated ruthenate nanosheets.

    Science.gov (United States)

    Fukuda, Katsutoshi; Sato, Jun; Saida, Takahiro; Sugimoto, Wataru; Ebina, Yasuo; Shibata, Tatsuo; Osada, Minoru; Sasaki, Takayoshi

    2013-03-04

    The metallization behavior of molecularly thin RuO2 nanosheets obtained from complete delamination of layered ruthenates was studied. Interestingly, the RuO2 nanosheets in a monolayer state topotactically transformed into a single layer of Ru atoms, i.e., ruthenium metal nanosheets, which can be regarded as a new family of nanosized metals.

  19. Acetic Acid Formation by Selective Aerobic Oxidation of Aqueous Ethanol over Heterogeneous Ruthenium Catalysts

    DEFF Research Database (Denmark)

    Gorbanev, Yury; Kegnæs, Søren; Hanning, Christopher William

    2012-01-01

    Heterogeneous catalyst systems comprising ruthenium hydroxide supported on different carrier materials, titania, alumina, ceria, and spinel (MgAl2O4), were applied in selective aerobic oxidation ethanol to form acetic acid, an important bulk chemical and food ingredient. The catalysts were...

  20. Elimination of ionic interference effects in the atomic absorption spectrometric determination of ruthenium

    International Nuclear Information System (INIS)

    El-Defrawy, M.M.M.; Posta, J.; Beck, M.T.

    1978-01-01

    In connection with work on the catalytic effect of ruthenium complexes, new compounds were prepared. Atomic absorption spectrometry (a.a.s.) was to be used for their analysis. The standard methods could not be applied to the complexes studied, therefore the effect of cyanide ions for elimination of interfering effects has been studied, because of the great stability of cyanide complexes. (Auth.)