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Sample records for rhodium 99

  1. 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%

  2. 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

  3. 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...

  4. 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.

  5. 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.

  6. 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.

  7. 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

  8. 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

  9. 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

  10. 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

  11. 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.

  12. 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)

  13. 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)

  14. 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

  15. 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)

  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. 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.

  18. 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

  19. 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

  20. 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.

  1. 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.

  2. 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...

  3. 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

  4. 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

  5. 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

  6. 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...

  7. 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.

  8. 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)

  9. 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(+).

  10. 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

  11. 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...

  12. 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

  13. 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.

  14. 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.

  15. 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.

  16. 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

  17. 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.

  18. 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.)

  19. Catalytic wet oxidation of ammonia solution: Activity of the nanoscale platinum-palladium-rhodium composite oxide catalyst

    International Nuclear Information System (INIS)

    Hung, C.-M.

    2009-01-01

    Aqueous solutions of 400-1000 mg/L of ammonia were oxidized in a trickle-bed reactor (TBR) in this study of nanoscale platinum-palladium-rhodium composite oxide catalysts, which were prepared by the co-precipitation of H 2 PtCl 6 , Pd(NO 3 ) 3 and Rh(NO 3 ) 3 . Hardly any of the dissolved ammonia was removed by wet oxidation in the absence of any catalyst, whereas about 99% of the ammonia was reduced during wet oxidation over nanoscale platinum-palladium-rhodium composite oxide catalysts at 503 K in an oxygen partial pressure of 2.0 MPa. A synergistic effect exists in the nanoscale platinum-palladium-rhodium composite structure, which is the material with the highest ammonia reduction activity. The nanometer-sized particles were characterized by TEM, XRD and FTIR. The effect of the initial concentration and reaction temperature on the removal of ammonia from the effluent streams was also studied at a liquid hourly space velocity of under 9 h -1 in the wet catalytic processes

  20. Catalytic wet oxidation of ammonia solution: Activity of the nanoscale platinum-palladium-rhodium composite oxide catalyst

    Energy Technology Data Exchange (ETDEWEB)

    Hung, C.-M. [Department of Industry Engineering and Management, Yung-Ta Institute of Technology and Commerce, 316 Chung-shan Road, Linlo, Pingtung 909, Taiwan (China)], E-mail: hungcm1031@gmail.com

    2009-04-15

    Aqueous solutions of 400-1000 mg/L of ammonia were oxidized in a trickle-bed reactor (TBR) in this study of nanoscale platinum-palladium-rhodium composite oxide catalysts, which were prepared by the co-precipitation of H{sub 2}PtCl{sub 6}, Pd(NO{sub 3}){sub 3} and Rh(NO{sub 3}){sub 3}. Hardly any of the dissolved ammonia was removed by wet oxidation in the absence of any catalyst, whereas about 99% of the ammonia was reduced during wet oxidation over nanoscale platinum-palladium-rhodium composite oxide catalysts at 503 K in an oxygen partial pressure of 2.0 MPa. A synergistic effect exists in the nanoscale platinum-palladium-rhodium composite structure, which is the material with the highest ammonia reduction activity. The nanometer-sized particles were characterized by TEM, XRD and FTIR. The effect of the initial concentration and reaction temperature on the removal of ammonia from the effluent streams was also studied at a liquid hourly space velocity of under 9 h{sup -1} in the wet catalytic processes.

  1. Catalytic wet oxidation of ammonia solution: activity of the nanoscale platinum-palladium-rhodium composite oxide catalyst.

    Science.gov (United States)

    Hung, Chang-Mao

    2009-04-15

    Aqueous solutions of 400-1000 mg/L of ammonia were oxidized in a trickle-bed reactor (TBR) in this study of nanoscale platinum-palladium-rhodium composite oxide catalysts, which were prepared by the co-precipitation of H(2)PtCl(6), Pd(NO(3))(3) and Rh(NO(3))(3). Hardly any of the dissolved ammonia was removed by wet oxidation in the absence of any catalyst, whereas about 99% of the ammonia was reduced during wet oxidation over nanoscale platinum-palladium-rhodium composite oxide catalysts at 503 K in an oxygen partial pressure of 2.0 MPa. A synergistic effect exists in the nanoscale platinum-palladium-rhodium composite structure, which is the material with the highest ammonia reduction activity. The nanometer-sized particles were characterized by TEM, XRD and FTIR. The effect of the initial concentration and reaction temperature on the removal of ammonia from the effluent streams was also studied at a liquid hourly space velocity of under 9 h(-1) in the wet catalytic processes.

  2. 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...

  3. 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

  4. Rhodium-catalyzed Asymmetric Hydrogenation of α-Dehydroamino Ketones: A General Approach to Chiral α-amino Ketones.

    Science.gov (United States)

    Gao, Wenchao; Wang, Qingli; Xie, Yun; Lv, Hui; Zhang, Xumu

    2016-01-01

    Rhodium/DuanPhos-catalyzed asymmetric hydrogenation of aliphatic α-dehydroamino ketones has been achieved and afforded chiral α-amino ketones in high yields and excellent enantioselectives (up to 99 % ee), which could be reduced further to chiral β-amino alcohols by LiAlH(tBuO)3 with good yields. This protocol provides a readily accessible route for the synthesis of chiral α-amino ketones and chiral β-amino alcohols. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. 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)

  6. 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.

  7. 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

  8. 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.

  9. 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.

  10. 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

  11. 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

  12. 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

  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. 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.

  15. 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

  16. 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.

  17. 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

  18. 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)

  19. 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.

  20. 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.

  1. 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

  2. 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

  3. 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

  4. 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.

  5. 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.

  6. 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.

  7. 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

  8. 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

  9. 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

  10. 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.

  11. 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

  12. 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

  13. 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

  14. 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.

  15. 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.

  16. 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.

  17. 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

  18. 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.

  19. "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

  20. Rhodium/chiral diene-catalyzed asymmetric 1,4-addition of arylboronic acids to chromones: a highly enantioselective pathway for accessing chiral flavanones.

    Science.gov (United States)

    He, Qijie; So, Chau Ming; Bian, Zhaoxiang; Hayashi, Tamio; Wang, Jun

    2015-03-01

    Chromone has been noted to be one of the most challenging substrates in the asymmetric 1,4-addition of α,β-unsaturated carbonyl compounds. By employing the rhodium complex associated with a chiral diene ligand, (R,R)-Ph-bod*, the 1,4-addition of a variety of arylboronic acids was realized to give high yields of the corresponding flavanones with excellent enantioselectivities (≥97% ee, 99% ee for most substrates). Ring-opening side products, which would lead to erosion of product enantioselectivity, were not observed under the stated reaction conditions. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. 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

  2. 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

  3. 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)

  4. 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...

  5. 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.

  6. 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

  7. 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)

  8. 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

  9. 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.

  10. 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

  11. 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

  12. 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

  13. 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...

  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. 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

  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. 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

  20. 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.

  1. 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

  2. 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)

  3. 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.

  4. 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

  5. Radionuclide Basics: Technetium-99

    Science.gov (United States)

    Technetium-99 (chemical symbol Tc-99) is a silver-gray, radioactive metal. It occurs naturally in very small amounts in the earth's crust, but is primarily man-made. Technetium-99m is a short-lived form of Tc-99 that is used as a medical diagnostic tool.

  6. 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.

  7. 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.

  8. 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.

  9. Molybdenum-99/technetium-99M generators

    International Nuclear Information System (INIS)

    Morcos, N.A.; Bruno, G.A.; Haney, T.A.

    1981-01-01

    A 99 Mo/sup(99m)Tc generator is described which has an alumina support medium consisting of multiple beds of controlled pH and in which no bed has a pH value higher than the bed preceding it. It is claimed that by using this method low yield problems of such generators can be mitigated. (U.K.)

  10. 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.

  11. 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.

  12. 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.

  13. 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

  14. 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.

  15. 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)

  16. 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

  17. 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.

  18. 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

  19. Decay of 99Mo

    International Nuclear Information System (INIS)

    Dickens, J.K.; Love, T.A.

    1976-01-01

    Relative intensities for K x-rays and gamma rays emanating from 99 Mo in equilibrium with its 99 Tc* daughter have been measured using several Ge photon detectors. Combining these intensities with an evaluated set of electron-conversion coefficients has provided a set of absolute intensities for the observed gamma rays. The absolute intensity for the dominant 140.5-keV gamma ray in 99 Tc was determined to be 90.7 +- 0.6/100 99 Mo disintegrations for 99 Mo decay in equilibrium with decay of the 99 Tc* daughter

  20. 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)

  1. 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)

  2. Progress in chemical processing of LEU targets for 99Mo production - 1997

    International Nuclear Information System (INIS)

    Vandegrift, G.F.; Conner, C.; Sedlet, J.; Wygmans, D.G.; Wu, D.; Iskander, F.; Landsberger, S.

    1997-01-01

    Presented here are recent experimental results of our continuing development activities associated with converting current processes for producing fission-product 99 Mo from targets using high-enriched uranium (HEU) to low-enriched uranium (LEU). Studies were focused in four areas: (1) measuring the chemical behavior of iodine, rhodium, and silver in the LEU-modified Cintichem process, (2) performing experiments and calculations to assess the suitability of zinc fission barriers for LEU metal foil targets, (3) developing an actinide separations method for measuring alpha contamination of the purified 99 Mo product, and (4) developing a cooperation with Sandia National Laboratories and Los Alamos National Laboratory that will lead to approval by the U.S. Federal Drug Administration for production of 99 Mo from LEU targets. Experimental results continue to show the technical feasibility of converting current HEU processes to LEU. (author)

  3. 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...

  4. 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)

  5. 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.

  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. 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.

  8. 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.

  9. 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.

  10. 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

  11. 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%.

  12. 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

  13. 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

  14. 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

  15. 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

  16. 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

  17. 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

  18. 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...

  19. 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

  20. 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.

  1. 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.

  2. 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.

  3. 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

  4. 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.

  5. 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.

  6. 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.

  7. 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

  8. 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

  9. 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

  10. 40 CFR 86.1729-99-86.1733-99 - [Reserved

    Science.gov (United States)

    2010-07-01

    ... 40 Protection of Environment 19 2010-07-01 2010-07-01 false [Reserved] 86.1729-99-86.1733-99 Section 86.1729-99-86.1733-99 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) AIR... Light-Duty Trucks §§ 86.1729-99—86.1733-99 [Reserved] ...

  11. 14 CFR 99.19-99.31 - [Reserved

    Science.gov (United States)

    2010-01-01

    ... 14 Aeronautics and Space 2 2010-01-01 2010-01-01 false [Reserved] 99.19-99.31 Section 99.19-99.31 Aeronautics and Space FEDERAL AVIATION ADMINISTRATION, DEPARTMENT OF TRANSPORTATION (CONTINUED) AIR TRAFFIC AND GENERAL OPERATING RULES SECURITY CONTROL OF AIR TRAFFIC General §§ 99.19-99.31 [Reserved] ...

  12. 40 CFR 86.1736-99-86.1769-99 - [Reserved

    Science.gov (United States)

    2010-07-01

    ... 40 Protection of Environment 19 2010-07-01 2010-07-01 false [Reserved] 86.1736-99-86.1769-99 Section 86.1736-99-86.1769-99 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) AIR... Light-Duty Trucks §§ 86.1736-99—86.1769-99 [Reserved] ...

  13. 40 CFR 86.1718-99-86.1720-99 - [Reserved

    Science.gov (United States)

    2010-07-01

    ... 40 Protection of Environment 19 2010-07-01 2010-07-01 false [Reserved] 86.1718-99-86.1720-99 Section 86.1718-99-86.1720-99 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) AIR... Light-Duty Trucks §§ 86.1718-99—86.1720-99 [Reserved] ...

  14. 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.

  15. 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

  16. 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.

  17. 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)

  18. 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)

  19. 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...

  20. 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

  1. 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.

  2. 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

  3. 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.

  4. 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)

  5. 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.

  6. 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.

  7. 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.

  8. 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.

  9. 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.

  10. 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.

  11. 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

  12. 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

  13. 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.

  14. 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.

  15. 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

  16. 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.

  17. 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.

  18. 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)

  19. 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.)

  20. 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

  1. 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

  2. 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.

  3. 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

  4. 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

  5. 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.

  6. 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.

  7. 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.

  8. 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.

  9. 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

  10. 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.

  11. Microsoft Encarta 99 Encyclopedia

    African Journals Online (AJOL)

    Finally, a future is envisioned in which the Internet will be the logical culmination of the ultimate potential of compu- ters as accessible, user-friendly reference .... The microstructure. In this article the central focus is on the ways in which Encarta 99 guides the user to the required information and not on the information itself.

  12. Quality assurance of Mo-99/Tc-99m radionuclide generators

    Science.gov (United States)

    Uzunov, Nikolay; Yordanova, Galina; Salim, Seniha; Stancheva, Natalya; Mineva, Vanya; Meléndez-Alafort, Laura; Rosato, Antonio

    2018-03-01

    Gamma-ray spectrometry analyses of the radionuclide content of eluate from two Mo-99/Tc-99m radionuclide generators POLTECHNET have been performed. The relative activities of 99Mo 103Ru and 131I radioisotopes with respect to the activity of 99mTc at different time intervals after the primary pertechnetate elution of the generators have been analyzed. The relative activities of the isotopes were determined and compared to the radionuclidic purity requirements for 99mTc.

  13. 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

  14. 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.

  15. 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.

  16. 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.

  17. 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.

  18. Method of producing molybdenum-99

    Science.gov (United States)

    Pitcher, Eric John

    2013-05-28

    Method of producing molybdenum-99, comprising accelerating ions by means of an accelerator; directing the ions onto a metal target so as to generate neutrons having an energy of greater than 10 MeV; directing the neutrons through a converter material comprising techentium-99 to produce a mixture comprising molybdenum-99; and, chemically extracting the molybdenum-99 from the mixture.

  19. 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.

  20. 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

  1. 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.

  2. 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)

  3. 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

  4. 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.

  5. 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

  6. 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.

  7. 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.

  8. 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.

  9. 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)

  10. 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.

  11. 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.

  12. 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.

  13. 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....

  14. K2-99

    DEFF Research Database (Denmark)

    Smith, A. M. S.; Gandolfi, D.; Barragan, O.

    2017-01-01

    We report the discovery from K2 of a transiting planet in an 18.25-d, eccentric (0.19 +/- 0.04) orbit around K2-99, an 11th magnitude subgiant in Virgo. We confirm the planetary nature of the companion with radial velocities, and determine that the star is a metal-rich ([ Fe/H] = 0.20 +/- 0...

  15. 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.

  16. 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

  17. 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

  18. 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

  19. 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

  20. 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

  1. 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%

  2. 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

  3. 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

  4. 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

  5. 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.

  6. 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.

  7. 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.

  8. 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.

  9. 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.

  10. 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.

  11. Production technologies for molybdenum-99 and technetium-99m

    International Nuclear Information System (INIS)

    1999-02-01

    Technetium-99m (6.02 h) is the most widely used radioisotope in nuclear medicine, accounting for more than 80% of all diagnostic nuclear medicine procedures. It is almost exclusively produced from the decay of its parent 99 Mo. The present sources of 99 Mo are research reactors by using the (n,γ) nuclear reaction with natural Mo ( 98 Mo, ∼24%), resulting in inexpensive but low-specific activity 99 Mo, or by neutron-induced fission of 235 U, which results in expensive but high specific activity 99 Mo. This publication covers several aspects related to the production of 99 Mo and 99m Tc. The contributed papers reflect the current status of the technology and discuss potential alternative methodologies for the production of 99 Mo and 99m Tc for medical use. The first four papers address the technologies using nuclear reactors, including the description of a new method using an aqueous homogenous reactor core for production of fission 99 Mo and the latest development efforts to fabricate 235 U low enriched targets (LEU, 235 U). The next five papers discuss the potential of utilizing particle accelerators and assess the current status of the available nuclear data for the production of both, 99 Mo and 99m Tc with proton and deuteron beams. The last paper discusses a new technology based on gel system for the preparation of 99 Mo/ 99m Tc generators using low specific activity 99 Mo produced in research reactors by the neutron activation of natural and inexpensive molybdenum oxide targets. Each individual paper was indexed and abstracted

  12. Spent 99Mo/99mTc generator as an economical source of 99Mo

    International Nuclear Information System (INIS)

    El-Kolaly, M.T.

    1990-01-01

    An improved method for utilization and purification of 99 Mo from spent 90 Mo/ 99m Tc generators has been described. After washing the generator with saline to remove the generated 99m Tc, followed by 2 mL 5 M NaOH containing a few drops of H 2 O 2 , the 99 Mo was quantitatively eluted from the generator with 5 mL 5 M NaOH. The alkaline eluate containing 99 Mo was contaminated with partially dissolved alumina. In the present method, an anion-exchange resin Dowex 1 x 8 column was used for purification of 99 Mo from the contaminating alumina. The resultant 99 Mo was of high purity and contained 3+ /mL 99 Mo solution, as estimated by atomic absorption. (author)

  13. Minimizing Molybdenum 99 contamination in Technetium 99m Pertechnetate from the elution of 99Mo/ 99m Tc Generator

    International Nuclear Information System (INIS)

    Zakaria Ibrahim; Zulkifli Hashim; Bohari Yaacob

    2011-01-01

    Radioisotope Tc-99m is widely used for variety of nuclear medicine diagnostic procedures. For many commercial applications, it is prepared in a portable type generator. Nuclear Malaysia has been producing a dry type alumina chromatographic column generator utilizing fission Mo-99. This injectable Tc-99m must meet the British Pharmacopeia [1] product specification prior to be apply on patient. This paper provides a method to minimize the up to acceptable level Mo-99 in the final product. Purposely made pertechnetate contaminated with Mo-99 and re-eluate by using old generator. Excellent removal of Mo-99 impurity was achieved and more than 80 % of Tc-99m total activity was recovered. (author)

  14. 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

  15. 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

  16. 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.

  17. 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)

  18. 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

  19. 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.

  20. 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.

  1. 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

  2. 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.

  3. 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.

  4. 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

  5. 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.

  6. 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

  7. 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.

  8. 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.

  9. 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.

  10. 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.

  11. Determination of 99Mo contamination in 99mTc elute obtained from 99Mo/99mTc- generator

    International Nuclear Information System (INIS)

    Momennezhad, M.; Zakavi, S. R.; Sadeghi, R.

    2010-01-01

    99m Tc is a widely used radioisotope in nuclear medicine centers which is obtained by elution from Mo-99/Tc-99m generators. Usually the generators are either supplied by the Iran Atomic Energy Agency or by private companies from foreign countries. In this study we have measured 99 Mo contamination in 99m Tc elute from different generators in a period of one year. Materials and Methods: The radionuclide impurity of the 99m Tc elute were studied in two types of radionuclide generators (A: produced in Iran and B: Imported from other country). In-vitro measurements were performed using dose calibrator. Direct measurements were made, using a standard canister at the time of milking of the generators and also in Subsequent hours after milking. Results: The results showed a mean of 99 Mo impurity in generators A and B to be 0.00932±0.0043 and 0.0170±0.0127 respectively. Although the results showed that the 99 Mo contamination in 99 mTc elute was lesser than the maximum accepted activity limit of 0.015%, the difference in these two types may reflect different methods of productions of generator, as well as the quality control procedures. Conclusion: The mean of 99 Mo contamination in generators produced in Iran Atomic Energy Organization was lesser than generators imported from foreign origin.

  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. BEAUTY'99 Conference Summary

    International Nuclear Information System (INIS)

    Eerola, Paula

    2000-01-01

    Investigations of B hadrons are expected to break new ground in measuring CP-violation effects. This series of BEAUTY conferences, originating from the 1993 conference in Liblice, has contributed significantly in developing ideas of CP-violation measurements using B hadrons and formulating and comparing critically the B-physics experiments. In the '99 conference in Bled we saw the ripening of the field and the first fruit emerging - Tevatron have produced beautiful B-physics results and more are expected to come with the next run, while the B-physics experiments at DESY, SLAC and KEK are starting their operation. The longer-term projects at LHC and Tevatron have taken their shape and detailed prototyping work is going on. Meanwhile, on the phenomenological side, there has been impressive theoretical progress in understanding deeper the 'standard' measurements and proposing new signatures. In this summary, I will highlight the status of the field as presented in the conference, concentrating on signatures, experiments and R and D programmes

  14. Initial Stages in the Rhodium(III)-Catalyzed C-H Bond Activation of Primary Alcohols in Aqueous Solution

    DEFF Research Database (Denmark)

    Eriksen, J.; Monsted, L.; Monsted, O.

    2010-01-01

    The mechanism of the catalytic HID exchange in primary alcohol substrates derived from aldopentoses, promoted by a macrocyclic rhodium(III) complex, has been shown to occur by a reversible redox reaction that gives aldehyde and a rhodium hydride complex. Hydride exchange in the latter complex...... promotes the introduction of solvent hydrogen in the primary alcohol formed by the reverse reaction. The hydride complex has been crystallographically characterized as a trifluoromethanesulfonate salt that contains the trans-[Rh(cycb)(H)(OH2)](2+) (cycb = rac-5,5,7,12,12,14-hexamethyl-1......,4,8,11-tetraazacyclotetradecane) cation. The hydride complex is stable for extended periods of time in acidic solution in the absence of oxidants. In basic solutions a series of base-catalyzed reactions take place to yield ultimately the same mixture of [Rh(cycb)(OH)(2)](+) isomers as produced by base hydrolysis of the trans...

  15. A Mixed-Ligand Chiral Rhodium(II) Catalyst Enables the Enantioselective Total Synthesis of Piperarborenine B.

    Science.gov (United States)

    Panish, Robert A; Chintala, Srinivasa R; Fox, Joseph M

    2016-04-11

    A novel, mixed-ligand chiral rhodium(II) catalyst, Rh2(S-NTTL)3(dCPA), has enabled the first enantioselective total synthesis of the natural product piperarborenine B. A crystal structure of Rh2(S-NTTL)3(dCPA) reveals a "chiral crown" conformation with a bulky dicyclohexylphenyl acetate ligand and three N-naphthalimido groups oriented on the same face of the catalyst. The natural product was prepared on large scale using rhodium-catalyzed bicyclobutanation/ copper-catalyzed homoconjugate addition chemistry in the key step. The route proceeds in ten steps with an 8% overall yield and 92% ee. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Enantioselective synthesis of chiral 3-aryl-1-indanones through rhodium-catalyzed asymmetric intramolecular 1,4-addition.

    Science.gov (United States)

    Yu, Yue-Na; Xu, Ming-Hua

    2013-03-15

    Enantioselective synthesis of potentially useful chiral 3-aryl-1-indanones was achieved through a rhodium-catalyzed asymmetric intramolecular 1,4-addition of pinacolborane chalcone derivatives using extraordinary simple MonoPhos as chiral ligand under relatively mild conditions. This novel protocol offers an easy access to a wide variety of enantioenriched 3-aryl-1-indanone derivatives in high yields (up to 95%) with excellent enantioselectivities (up to 95% ee).

  17. Enantioselective Construction of 3-Hydroxypiperidine Scaffolds by Sequential Action of Light and Rhodium upon N-Allylglyoxylamides.

    Science.gov (United States)

    Ishida, Naoki; Nečas, David; Masuda, Yusuke; Murakami, Masahiro

    2015-06-15

    3-Hydroxypiperidine scaffolds were enantioselectively constructed in an atom-economical way by sequential action of light and rhodium upon N-allylglyoxylamides. In a formal sense, the allylic C-H bond was selectively cleaved and enantioselectively added across the ketonic carbonyl group with migration of the double bond (carbonyl-ene-type reaction). © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Sequential rhodium/palladium catalysis: enantioselective formation of dihydroquinolinones in the presence of achiral and chiral ligands.

    Science.gov (United States)

    Zhang, Lei; Qureshi, Zafar; Sonaglia, Lorenzo; Lautens, Mark

    2014-12-08

    Compatible combinations of achiral and chiral ligands can be used in rhodium/palladium catalysis to achieve highly enantioselective domino reactions. The difference in rates of catalysis and minimal effects of ligand interference confer control in the domino sequence. The "all-in-one" 1,4-conjugate arylation and C-N cross-coupling through sequential Rh/Pd catalysis provides access to enantioenriched dihydroquinolinone building blocks. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Applying Adjacent Hyperbolas to Calculation of the Upper Limit of the Periodic Table of Elements, with Use of Rhodium

    Directory of Open Access Journals (Sweden)

    Khazan A.

    2011-01-01

    Full Text Available In the earlier study (Khazan A. Upper Limit in Mendeleev’s Periodic Table — Ele- ment No. 155. 2nd ed., Svenska fysikarkivet, Stockholm, 2010 the author showed how Rhodium can be applied to the hyperbolic law of the Periodic Table of Elements in or- der to calculate, with high precision, all other elements conceivable in the Table. Here we obtain the same result, with use of fraction linear functions (adjacent hyperbolas.

  20. Construction of axial chirality by rhodium-catalyzed asymmetric dehydrogenative Heck coupling of biaryl compounds with alkenes.

    Science.gov (United States)

    Zheng, Jun; You, Shu-Li

    2014-11-24

    Enantioselective construction of axially chiral biaryls by direct C-H bond functionalization reactions has been realized. Novel axially chiral biaryls were synthesized by the direct C-H bond olefination of biaryl compounds, using a chiral [Cp*Rh(III)] catalyst, in good to excellent yields and enantioselectivities. The obtained axially chiral biaryls were found as suitable ligands for rhodium-catalyzed asymmetric conjugate additions. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Rhodium(III)-catalyzed three-component reaction of imines, alkynes, and aldehydes through C-H activation.

    Science.gov (United States)

    Huang, Ji-Rong; Song, Qiang; Zhu, Yu-Qin; Qin, Liu; Qian, Zhi-Yong; Dong, Lin

    2014-12-15

    An efficient rhodium(III)-catalyzed tandem three-component reaction of imines, alkynes and aldehydes through CH activation has been developed. High stereo- and regioselectivity, as well as good yields were obtained in most cases. The simple and atom-economical approach offers a broad scope of substrates, providing polycyclic skeletons with potential biological properties. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Applying Adjacent Hyperbolas to Calculation of the Upper Limit of the Periodic Table of Elements, with Use of Rhodium

    Directory of Open Access Journals (Sweden)

    Khazan A.

    2011-01-01

    Full Text Available In the earlier study (Khazan A. Upper Limit in Mendeleev's Periodic Table - Element No.155. 2nd ed., Svenska fysikarkivet, Stockholm, 2010 the author showed how Rhodium can be applied to the hyperbolic law of the Periodic Table of Elements in order to calculate, with high precision, all other elements conceivable in the Table. Here we obtain the same result, with use of fraction linear functions (adjacent hyperbolas.

  3. Generators of 99Mo-99mTc

    International Nuclear Information System (INIS)

    Robles, A.M.

    1994-01-01

    Between the radioisotopes family pairs we find the 99 Molibdenum - 99m technetium pairs. Such as isotope production,decay and chemical toxic, humid and dry generators,radiation protection handling practice and blinding had been sudied in this work.Tabs

  4. Effect of milking efficiency on Tc-99 content of Tc-99m derived from Tc-99m generators

    International Nuclear Information System (INIS)

    Bonnyman, J.

    1983-01-01

    Tc-99m obtained by separation from its parent Mo-99 always contains Tc-99 produced by decay of Tc-99m and Mo-99. Factors effecting the Tc-99/Tc-99m ratios are discussed. An HPLC method has been developed to measure the 99 TcO 4- content of sodium pertechnetate from generators with a detection limit of 0.9 ng Tc-99 for a 500 μl/ aliquot of TcO 4- -99m. First eluates of 10 chromatograph-ic generators gave Tc-99/Tc-99m ratios ranging from 3.5-46 ng Tc/mCi Tc-99m measured at the time of milking. The measurements indicate that Tc-99/Tc-99m ratios high enough to cause adverse labelling effects could be found in 'instant pertechnetate' and in the first eluate from Tc-99m generators for the activities normally used in radiopharmaceutical production

  5. 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

  6. 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.

  7. 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

  8. In Situ Structure-Function Studies of Oxide Supported Rhodium Catalysts by Combined Energy Dispersive XAFS and DRIFTS Spectroscopies

    International Nuclear Information System (INIS)

    Evans, John; Dent, Andrew J.; Diaz-Moreno, Sofia; Fiddy, Steven G.; Jyoti, Bhrat; Tromp, Moniek; Newton, Mark A.

    2007-01-01

    The techniques of energy dispersive EXAFS (EDE), diffuse reflectance Fourier transform infrared spectroscopy (DRIFTS) and mass spectrometry (MS) have been combined to study the structure and function of an oxide supported metal catalyst, namely 5 wt% Rh/Al2O3. Using a FreLoN camera as the EDE detector and a rapid-scanning IR spectrometer, experiments could be performed with a repetition rate of 50 ms. The results show that the nature of the rhodium centers is a function of the partial pressures of the reacting gases (CO and NO) and also temperature. This combination of gases oxidizes metallic rhodium particles to Rh(CO)2 at room temperature. The proportion of the rhodium adopting this site increases as the temperature is raised (up to 450 K). Above that temperature the dicarbonyl decomposes and the metal reclusters. Once this condition is met, catalysis ensues. Gas switching techniques show that at 573 K with NO in excess, the clusters can be oxidized rapidly to afford a linear nitrosyl complex; re-exposure to CO also promotes reclustering and the CO adopts terminal (atop) and bridging (2-fold) sites

  9. Photocatalytic carbon dioxide reduction with rhodium-based catalysts in solution and heterogenized within metal-organic frameworks.

    Science.gov (United States)

    Chambers, Matthew B; Wang, Xia; Elgrishi, Noémie; Hendon, Christopher H; Walsh, Aron; Bonnefoy, Jonathan; Canivet, Jérôme; Quadrelli, Elsje Alessandra; Farrusseng, David; Mellot-Draznieks, Caroline; Fontecave, Marc

    2015-02-01

    The first photosensitization of a rhodium-based catalytic system for CO2 reduction is reported, with formate as the sole carbon-containing product. Formate has wide industrial applications and is seen as valuable within fuel cell technologies as well as an interesting H2 -storage compound. Heterogenization of molecular rhodium catalysts is accomplished via the synthesis, post-synthetic linker exchange, and characterization of a new metal-organic framework (MOF) Cp*Rh@UiO-67. While the catalytic activities of the homogeneous and heterogeneous systems are found to be comparable, the MOF-based system is more stable and selective. Furthermore it can be recycled without loss of activity. For formate production, an optimal catalyst loading of ∼10 % molar Rh incorporation is determined. Increased incorporation of rhodium catalyst favors thermal decomposition of formate into H2 . There is no precedent for a MOF catalyzing the latter reaction so far. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Status of Tc-99m and 99Mo/99mTc generator production in Bangladesh

    International Nuclear Information System (INIS)

    Abedin, Md. Zainul; Haque, Md. Azizul; Ali, Md. Ramjan; Hossain, Md. Anwar; Razzaque, Md. Abdur; Yasmin, Lyzu; Waheed, M. Fatima; Akhter, Rabeya; Mondal, Rafiuddin

    2007-01-01

    Radioisotope Production Division (RIPD) produced instant technetium-99m by solvent extraction method for several years. On R and D basis, the division produced portable sterile Tc-99m sublimation generator by irradiating titanium molybdate in the reactor. The division produced (4/batch) from imported fission Mo-99 till June 2005. Since August 2005, as per demand of the government hospitals, the division have been producing 12-14 pieces of 15 GBq chromatographic 99m Tc-generators weekly by using the new generator production plant installed last year having online Mo-99 loading system with the of producing 50 generator per batch. Development of PZC and (n,γ) 99 Mo based generator holds potential in Bangladesh. (author)

  11. Measurement of Mo-99 column activity in the evaluation of Mo-99/Tc-99m generator

    International Nuclear Information System (INIS)

    Kuster, Z.

    1994-01-01

    In order to calculate the real elution efficiency of Mo-99/Tc-99m generator the Mo-99 content on the column has to be previously determined. As found in this work, the external measurement of Mo-99-column activity by means of Geiger-Mueller counter is a simple, fast and reliable method. Generally, Mo-99-column is placed slightly out of the center of the generator; therefore the externally measured flux of photons (φ) is an angular-dependent function. If the thickness of the lead container is radially uniform, the flux measured at some distance from the generator (which is rotated in 2π/3 steps) is given by the equation φ = A (1 + Bcos (α-2π(i - 2)/3)) -1 , i=1,2 or 3 (Eq.1) where A is a numerical constant depending on the Mo-99-column activity, B is a numerical constant depending on the Mo-99- column position within the lead container, the angle α depends on the initial orientation of the generator. A total of 20 generator were studied. The measured Mo-99-column activities (Capintec dose calibrator) were in the range 13.1- 35.11 GBq. Contrary to the findings of Vinberg and Kristensen (Eur J Nucl Med 1/1976(219), values of A (Eq. 1) are in good correlation (r 2 =0.9794) with the measured Mo-99-column activities. (author)

  12. Environmental behavior of technetium-99

    International Nuclear Information System (INIS)

    Turcotte, M.D.S.

    1982-12-01

    This report presents a review of the literature on technetium-99. The chemical and physical properties of some technetium compounds are considered, and a discussion of possible source terms is included. Literature on the environmental behavior of technetium is presented, including its behavior in the bodies of animals and humans. The primary sources of Tc-99 in the environment are fallout from atomic detonations and releases from nuclear fuel reprocessing plants. The environmental behavior of technetium-99 has been studied predominantly with respect to movement in soil and accumulation in plants. There is a surprising scarcity of data on behavior of Tc-99 in the atmosphere and in aquatic systems. Additional work needs to be conducted in these two areas to determine behavior and to acquire baseline concentration data. Much of the soil work has produced contradictory results. In-depth studies of holdup mechanisms for Tc-99 in both geological repositories and soil need to be conducted. Since plants represent a potential bioaccumulation of Tc-99, plant uptake studies of Tc-99 under field conditions also need to be done

  13. Synthesis and structures of a pincer-type rhodium(iii) complex: reactivity toward biomolecules.

    Science.gov (United States)

    Milutinović, Milan M; Bogojeski, Jovana V; Klisurić, Olivera; Scheurer, Andreas; Elmroth, Sofi K C; Bugarčić, Živadin D

    2016-10-04

    A novel rhodium(iii) complex [Rh III (H 2 L tBu )Cl 3 ] (1) (H 2 L tBu = 2,6-bis(5-tert-butyl-1H-pyrazol-3-yl)pyridine) containing a pincer type, tridentate nitrogen-donor chelate system was synthesized. Single crystal X-ray structure analysis revealed that 1 crystallizes in the orthorhombic space group Pbcn with a = 20.7982(6), b = 10.8952(4), c = 10.9832(4) Å, V = 2488.80(15) Å 3 , and eight molecules in the unit cell. The rhodium center in the complex [Rh III (H 2 L tBu )Cl 3 ] (1) is coordinated in a slightly distorted octahedral geometry by the tridentate N,N,N-donor and three chloro ligands, adopting a mer arrangement with an essentially planar ligand skeleton. Due to the tridentate coordination of the N,N,N-donor, the central nitrogen atom N1 is located closer to the Rh III center. The reactivity of the synthesized complex toward small biomolecules (l-methionine (l-Met), guanosine-5'-monophosphate (5'-GMP), l-histidine (l-His) and glutathione (GSH)) and to a series of duplex DNAs and RNA was investigated. The order of reactivity of the studied small biomolecules is: 5'-GMP > GSH > l-Met > l-His. Duplex RNA reacts faster with the [Rh III (H 2 L tBu )Cl 3 ] complex than duplex DNA, while shorter duplex DNA (15mer GG) reacts faster compared with 22mer GG duplex DNA. In addition, a higher reactivity is achieved with a DNA duplex with a centrally located GG-sequence than with a 22GTG duplex DNA, in which the GG-sequence is separated by a T base. Furthermore, the interaction of this metal complex 1 with calf thymus DNA (CT-DNA) and bovine serum albumin (BSA) was examined by absorption (UV-Vis) and emission spectral studies (EthBr displacement studies). Overall, the studied complex exhibited good DNA and BSA interaction ability.

  14. Fission 99Mo production technology

    International Nuclear Information System (INIS)

    Miao Zengxing; Luo Zhifu; Ma Huimin; Liang Yufu; Yu Ningwen

    2003-01-01

    This paper describes a production technology of fission 99 Mo in the Department Isotope, CIAE. The irradiation target is tubular U-Al alloy containing highly enriched uranium. The target is irradiated in the swimming pool reactor core. The neutron flux is about 4x10 13 /cm 2 .sec. The production scale is 3.7-7.4 TBq (100-200Ci) of fission 99 Mo per batch. Total recovery of 99 Mo is more than 70%. The production practice proves that the process and equipment are safe and reliable. (author)

  15. Elucidation of structural isomers from the homogeneous rhodium-catalyzed isomerization of vegetable oils.

    Science.gov (United States)

    Andjelkovic, Dejan D; Min, Byungrok; Ahn, Dong; Larock, Richard C

    2006-12-13

    The structural isomers formed by the homogeneous rhodium-catalyzed isomerization of several vegetable oils have been elucidated. A detailed study of the isomerization of the model compound methyl linoleate has been performed to correlate the distribution of conjugated isomers, the reaction kinetics, and the mechanism of the reaction. It has been shown that [RhCl(C8H8)2]2 is a highly efficient and selective isomerization catalyst for the production of highly conjugated vegetable oils with a high conjugated linoleic acid (CLA) content, which is highly desirable in the food industry. The combined fraction of the two major CLA isomers [(9Z,11E)-CLA and (10E,12Z)-CLA] in the overall CLA mixture is in the range from 76.2% to 93.4%. The high efficiency and selectivity of this isomerization method along with the straightforward purification process render this approach highly promising for the preparation of conjugated oils and CLA. Proposed improvements in catalyst recovery and reusability will only make this method more appealing to the food, paint, coating, and polymer industries in the future.

  16. Separation of Hydridocarbonyltris(triphenylphosphine) Rhodium (I) Catalyst Using Solvent Resistant Nano filtration Membrane

    International Nuclear Information System (INIS)

    Razak, N.S.A.; Hilmi Mukhtar; Maizatul, S. Shaharun; Mohd, F. Taha

    2013-01-01

    An investigation was conducted into the nano filtration of rhodium tris(triphenyl-phosphine) [HRh(CO)(PPh3)3] catalyst used in the hydroformylation of olefins. The large size of the catalyst (>400 Da) - relative to other components of the reaction provides the opportunity for a membrane separation based on retention of the catalyst species while permeating the solvent. The compatibility of the solvent-polyimide membrane (STARMEMTM 122 and STARMEMTM 240) combinations was assessed in terms of the membrane stability in solvent plus non-zero solvent flux at 2.0 MPa. The morphology of the membrane was studied by field emission scanning electron microscopy (FESEM). The solvent flux and membrane rejection of HRh(CO)(PPh3)3 was then determined for the catalyst-solvent-membrane combination in a dead-end pressure cell. Good HRh(CO)(PPh3)3 rejection (>0.93) coupled with good solvent fluxes (>72 L/ m 2 h 1 at 2.0 MPa) were obtained in one of the systems tested. The effect of pressure and catalyst concentration on the solvent flux and catalyst rejection was conducted. Increasing pressure substantially improved both solvent flux and catalyst rejection, while increasing catalyst concentration was found to be beneficial in terms of substantial increases in catalyst rejection without significantly affecting the solvent flux. (author)

  17. Enhanced electrocatalytic oxidation of isoniazid at electrochemically modified rhodium electrode for biological and pharmaceutical analysis.

    Science.gov (United States)

    Cheemalapati, Srikanth; Chen, Shen-Ming; Ali, M Ajmal; Al-Hemaid, Fahad M A

    2014-09-01

    A simple and sensitive electrochemical method has been proposed for the determination of isoniazid (INZ). For the first time, rhodium (Rh) modified glassy carbon electrode (GCE) has been employed for the determination of INZ by linear sweep voltammetry technique (LSV). Compared with the unmodified electrode, the proposed Rh modified electrode provides strong electrocatalytic activity toward INZ with significant enhancement in the anodic peak current. Scanning electron microscopy (SEM) and field emission scanning electron microscopy (FESEM) results reveal the morphology of Rh particles. With the advantages of wide linearity (70-1300μM), good sensitivity (0.139μAμM(-1)cm(-2)) and low detection limit (13μM), this proposed sensor holds great potential for the determination of INZ in real samples. The practicality of the proposed electrode for the detection of INZ in human urine and blood plasma samples has been successfully demonstrated using LSV technique. Through the determination of INZ in commercially available pharmaceutical tablets, the practical applicability of the proposed method has been validated. The recovery results are found to be in good agreement with the labeled amounts of INZ in tablets, thus showing its great potential for use in clinical and pharmaceutical analysis. Copyright © 2014 Elsevier B.V. All rights reserved.

  18. Laser cleaning of pulsed laser deposited rhodium films for fusion diagnostic mirrors

    International Nuclear Information System (INIS)

    Uccello, A.; Maffini, A.; Dellasega, D.; Passoni, M.

    2013-01-01

    Highlights: ► Pulsed laser deposition is exploited to produce Rh films for first mirrors. ► Pulsed laser deposition is exploited to produce tokamak-like C contaminants. ► Rh laser damage threshold has been evaluated for infrared pulses. ► Laser cleaning of C contaminated Rh films gives promising results. -- Abstract: In this paper an experimental investigation on the laser cleaning process of rhodium films, potentially candidates to be used as tokamak first mirrors (FMs), from redeposited carbon contaminants is presented. A relevant issue that lowers mirror's performance during tokamak operations is the redeposition of sputtered material from the first wall on their surface. Among all the possible techniques, laser cleaning, in which a train of laser pulses is launched to the surface that has to be treated, is a method to potentially mitigate this problem. The same laser system (Q-switched Nd:YAG laser with a fundamental wavelength of 1064-nm and 7-ns pulses) has been employed with three aims: (i) production by pulsed laser deposition (PLD) of Rh film mirrors, (ii) production by PLD of C deposits with controlled morphology, and (iii) investigation of the laser cleaning method onto C contaminated Rh samples. The evaluation of Rh films laser damage threshold, as a function of fluence and number of pulses, is discussed. Then, the C/Rh films have been cleaned by the laser beam. The exposed zones have been characterized by visual inspection and scanning electron microscopy (SEM), showing promising results

  19. Comparative analysis for the measured and the predicted relative sensitivity of rhodium In core detector

    International Nuclear Information System (INIS)

    Moon, Sang Rae; Cha, Kyoon Ho; Bae, Seong Man

    2012-01-01

    Self-powered neutron detector (SPND) is widely used as in-core flux monitoring in nuclear power plants. OPR1000 has applied a rhodium (Rh) as the emitter of the SPND. The SPND contains a neutron-sensitive metallic emitter surrounded by a ceramic insulator. When capturing a neutron, the Rh will be decayed by emitting some electrons which is crossing the sheath and produce current. This current can be measured externally using pico-ammeter. The sensitivity of detectors is closely related with the geometry and material of the detectors. The lifetime of in-core detector is determined by calculating the relative sensitivity of Rh detector. It is required that the Rh detector should be replaced before the burn-up of Rh detector has reached 66% of its original compositions. To predict Rh detector's relative sensitivity ANC code, advanced nodal code capable of two-dimensional and three-dimensional calculations, is used. It is determined that the Rh detectors should be replaced on the basis of the predicted sensitivity value calculated by ANC code. When evaluating the life of Rh detectors using ANC code, it is assumed that the uncertainty of the sensitivity calculation include the measurement error of 5%. As a result of the analysis of measured and predicted data for the Rh detector's relative sensitivity, it is possible to reduce the assumed uncertainty

  20. Size effects on rhodium nanoparticles related to hydrogen-storage capability.

    Science.gov (United States)

    Song, Chulho; Yang, Anli; Sakata, Osami; Kumara, L S R; Hiroi, Satoshi; Cui, Yi-Tao; Kusada, Kohei; Kobayashi, Hirokazu; Kitagawa, Hiroshi

    2018-06-06

    To unveil the origin of the hydrogen-storage properties of rhodium nanoparticles (Rh NPs), we investigated the electronic and crystal structures of the Rh NPs using various synchrotron based X-ray techniques. Electronic structure studies revealed that the hydrogen-storage capability of Rh NPs could be attributed to their more unoccupied d-DOSs than that of the bulk near the Fermi level. Crystal structure studies indicated that lattice distortion and mean-square displacement increase while coordination number decreases with decreasing particle size and the hydrogen-absorption capability of Rh NPs improves to a greater extent with increased structural disorder in the local structure than with that in the mean structure. The smallest Rh NPs, having the largest structural disorder/increased vacancy spaces and the smallest coordination number, exhibited excellent hydrogen-storage capacity. Finally, from the bond-orientational order analysis, we confirmed that the localized disordering is distributed more over the surface part than the core part and hydrogen can be trapped on the surface part of Rh NPs which increases with a decrease in NP diameter.

  1. Manifestation of external size reduction effects on the yield point of nanocrystalline rhodium using nanopillars approach

    International Nuclear Information System (INIS)

    Alshehri, Omar; Yavuz, Mustafa; Tsui Ting

    2013-01-01

    In this study, pure rhodium was fabricated and mechanically investigated at the nanoscale for the first time. The nanopillars approach was employed to study the effects of size on the yield point. Nanopillars with different diameters were fabricated using electroplating followed by uniaxial compression tests. Scanning electron microscopy (SEM) was used as a quality control technique by imaging the pillars before and after compression to ensure the absence of cracks, buckling, barrelling or any other problems. Transmission electron microscopy and SEM were used as microstructural characterization techniques. Due to substrate-induced effects, only the plastic region of the stress–strain curves were investigated, and it was revealed that the yield point increases with size reduction up to certain limit, then decreases with further reduction of the nanopillar size (diameter). The later weakening effect is consistent with the literature, which demonstrates the reversed size effect (the failure of the plasticity theory) in nanocrystalline metals, i.e. smaller is weaker. In this study, however, the effect of size reduction is not only weakening, but is strengthening-then-weakening, which the authors believe is the true behavior of nanocrystalline materials.

  2. Reactivity Control of Rhodium Cluster Ions by Alloying with Tantalum Atoms.

    Science.gov (United States)

    Mafuné, Fumitaka; Tawaraya, Yuki; Kudoh, Satoshi

    2016-02-18

    Gas phase, bielement rhodium and tantalum clusters, RhnTam(+) (n + m = 6), were prepared by the double laser ablation of Rh and Ta rods in He carrier gas. The clusters were introduced into a reaction gas cell filled with nitric oxide (NO) diluted with He and were subjected to collisions with NO and He at room temperature. The product species were observed by mass spectrometry, demonstrating that the NO molecules were sequentially adsorbed on the RhnTam(+) clusters to form RhnTam(+)NxOx (x = 1, 2, 3, ...) species. In addition, oxide clusters, RhnTam(+)O2, were also observed, suggesting that the NO molecules were dissociatively adsorbed on the cluster, the N atoms migrated on the surface to form N2, and the N2 molecules were released from RhnTam(+)N2O2. The reactivity, leading to oxide formation, was composition dependent: oxide clusters were dominantly formed for the bielement clusters containing both Rh and Ta atoms, whereas such clusters were hardly formed for the single-element Rhn(+) and Tam(+) clusters. DFT calculations indicated that the Ta atoms induce dissociation of NO on the clusters by lowering the dissociation energy, whereas the Rh atoms enable release of N2 by lowering the binding energy of the N atoms on the clusters.

  3. Comparative analysis for the measured and the predicted relative sensitivity of rhodium In core detector

    Energy Technology Data Exchange (ETDEWEB)

    Moon, Sang Rae; Cha, Kyoon Ho; Bae, Seong Man [Nuclear Reactor Safety Lab., KHNP Central Research Institute, Daejeon (Korea, Republic of)

    2012-10-15

    Self-powered neutron detector (SPND) is widely used as in-core flux monitoring in nuclear power plants. OPR1000 has applied a rhodium (Rh) as the emitter of the SPND. The SPND contains a neutron-sensitive metallic emitter surrounded by a ceramic insulator. When capturing a neutron, the Rh will be decayed by emitting some electrons which is crossing the sheath and produce current. This current can be measured externally using pico-ammeter. The sensitivity of detectors is closely related with the geometry and material of the detectors. The lifetime of in-core detector is determined by calculating the relative sensitivity of Rh detector. It is required that the Rh detector should be replaced before the burn-up of Rh detector has reached 66% of its original compositions. To predict Rh detector's relative sensitivity ANC code, advanced nodal code capable of two-dimensional and three-dimensional calculations, is used. It is determined that the Rh detectors should be replaced on the basis of the predicted sensitivity value calculated by ANC code. When evaluating the life of Rh detectors using ANC code, it is assumed that the uncertainty of the sensitivity calculation include the measurement error of 5%. As a result of the analysis of measured and predicted data for the Rh detector's relative sensitivity, it is possible to reduce the assumed uncertainty.

  4. Electrochemical behavior of rhodium acetamidate immobilized on a carbon paste electrode: a hydrazine sensor

    Directory of Open Access Journals (Sweden)

    Gil Eric de S.

    2000-01-01

    Full Text Available The electrochemical behavior of rhodium acetamidate immobilized in carbon paste electrode and the consequences for sensor construction were evaluated. The electrode showed good stability and redox properties. Two reversible redox couples with midpoint potentials between 0.15 and 0.55 V vs SCE were observed. However, peak resolution in voltammetric studies was very dependent on the supporting electrolyte. The correlation between coordinating power of the electrolyte and peak potential suggests that the electrolyte can coordinate through the axial position of the complexes. Furthermore, the axial position may be also the catalytic site, as a catalytical response was observed for hydrazine oxidation. A good linear response range for hydrazine was fit by the equation i = 23.13 (± 0.34 c , where i = current in mA and c = concentration in mol dm-3 in the range of 10-5 up to 10-2 mol dm-3. The low applied potential (<300 mV indicates a good device for hydrazine sensor, minimizing interference problems. The short response time (~1 s may be useful in flow injection analysis. Furthermore, this system was very stable presenting good repeatability even after 30 measurements with a variance of 0.5 %.

  5. Rhodium metalloinsertor binding generates a lesion with selective cytotoxicity for mismatch repair-deficient cells.

    Science.gov (United States)

    Bailis, Julie M; Weidmann, Alyson G; Mariano, Natalie F; Barton, Jacqueline K

    2017-07-03

    The DNA mismatch repair (MMR) pathway recognizes and repairs errors in base pairing and acts to maintain genome stability. Cancers that have lost MMR function are common and comprise an important clinical subtype that is resistant to many standard of care chemotherapeutics such as cisplatin. We have identified a family of rhodium metalloinsertors that bind DNA mismatches with high specificity and are preferentially cytotoxic to MMR-deficient cells. Here, we characterize the cellular mechanism of action of the most potent and selective complex in this family, [Rh(chrysi)(phen)(PPO)] 2+ (Rh-PPO). We find that Rh-PPO binding induces a lesion that triggers the DNA damage response (DDR). DDR activation results in cell-cycle blockade and inhibition of DNA replication and transcription. Significantly, the lesion induced by Rh-PPO is not repaired in MMR-deficient cells, resulting in selective cytotoxicity. The Rh-PPO mechanism is reminiscent of DNA repair enzymes that displace mismatched bases, and is differentiated from other DNA-targeted chemotherapeutics such as cisplatin by its potency, cellular mechanism, and selectivity for MMR-deficient cells.

  6. Versatile deprotonated NHC: C,N-bridged dinuclear iridium and rhodium complexes

    Directory of Open Access Journals (Sweden)

    Albert Poater

    2016-01-01

    Full Text Available Bearing the versatility of N-heterocyclic carbene (NHC ligands, here density functional theory (DFT calculations unravel the capacity of coordination of a deprotonated NHC ligand (pNHC to generate a doubly C2,N3-bridged dinuclear complex. Here, in particular the discussion is based on the combination of the deprotonated 1-arylimidazol (aryl = mesityl (Mes with [M(cod(μ-Cl] (M = Ir, Rh generated two geometrical isomers of complex [M(cod{µ-C3H2N2(Mes-κC2,κN3}]2. The latter two isomers display conformations head-to-head (H-H and head-to-tail (H-T of CS and C2 symmetry, respectively. The isomerization from the H-H to the H-T conformation is feasible, whereas next substitutions of the cod ligand by CO first, and PMe3 later confirm the H-T coordination as the thermodynamically preferred. It is envisaged the exchange of the metal, from iridium to rhodium, confirming here the innocence of the nature of the metal for such arrangements of the bridging ligands.

  7. The effects of rhodium on the renal function of female Wistar rats.

    Science.gov (United States)

    Iavicoli, Ivo; Leso, Veruscka; Fontana, Luca; Marinaccio, Alessandro; Bergamaschi, Antonio; Calabrese, Edward J

    2014-06-01

    In recent years, the increased use of rhodium (Rh) as an active catalyst material in modern three-way automobile catalytic converters has led to a parallel rise in environmental levels of this metal. In spite of this, the literature contains few studies of the effects of Rh on human health. The aim of this study is to assess the effects of Rh on the renal function of female Wistar rats. Our findings show that sub-acute exposure to six increasing concentrations, ranging from 0.001 to 1 mg L(-1), of Rh (III) chloride hydrate in drinking water does not induce alterations in urinary albumin levels, while, at concentrations from 0.1 to 1 mg L(-1), a significant rise in urinary levels of Retinol Binding Protein is evident and an increasing trend in urinary β2-microglobulin, which becomes significant at 1 mg L(-1), is observed. These results therefore demonstrate a nephrotoxic action of Rh at tubular level in a wide range of doses. Interestingly, because of the recent increase in environmental Rh levels, these findings may have relevant implications both for occupationally exposed subjects and for the general population, especially children. Copyright © 2013 Elsevier Ltd. All rights reserved.

  8. trans-Carbonylchloridobis[dicyclohexyl(4-isopropylphenylphosphane]rhodium(I acetone monosolvate

    Directory of Open Access Journals (Sweden)

    Sizwe Makhoba

    2011-09-01

    Full Text Available The title rhodium Vaska-type complex, trans-[RhCl{P(C6H112(C6H4-4-C3H72}2(CO], crystallizes with an accompanying acetone solvent molecule. The metal atom shows a distorted square-planar coordination environment with selected important geometrical parameters of Rh—P = 2.3237 (6 and 2.3253 (6 Å, Rh—Cl = 2.3724 (6 Å, Rh—C = 1.802 (2 Å, P—Rh—P = 173.42 (2° and Cl—Rh—C = 179.13 (7°. Effective cone angles for the two P atoms are 165 and 161°, respectively. Both isopropyl groups and the acetone molecule are disordered with occupancy values of 0.523 (5:0.477 (5, 0.554 (8:0.446 (8 and 0.735 (4:0.265 (4, respectively. The crystal packing is stabilized by weak C—H...O and C—H...Cl contacts.

  9. Technetium-99 in ''instant'' sup(99m)Tc-pertechnetate

    International Nuclear Information System (INIS)

    Mattsson, S.

    1978-01-01

    The 99 Tc-content in sup(99m)Tc-pertechnetate separated from 99 Mo by distillation or extraction has been studied with a plastic scintillation detector. The identification of the measured activity was achieved by beta-spectrometry, chemical separation and half-life studies. The frequency distribution of the sup(99)Tc/sup(99m)Tc-ratios in the different samples was observed to be log-normal. The most likely activity ratio was 0.4x10 -6 , the maximum value being 5x10 -6 . The specific activity of ''instant'' pertechnetate is approximately a factor of 60 lower than that normally recorded in pertechnetate derived from daily eluted column generators. The low specific activity of ''instant'' pertechnetate is primarily explained by the long time between separation and usage and secondly by the low yield of Tc in the distillation and extraction processes. In several of the ''instant'' pertechnetate solutions the carrier concentration exceeded the reductive capacity of the stannous ions in ''kits'' with small amounts of Sn(II) in usable form. (T.G.)

  10. Rhodium(I)-catalyzed cyclization of allenynes with a carbonyl group through unusual insertion of a C-O bond into a rhodacycle intermediate.

    Science.gov (United States)

    Oonishi, Yoshihiro; Yokoe, Takayuki; Hosotani, Akihito; Sato, Yoshihiro

    2014-01-20

    Rhodium(I)-catalyzed cyclization of allenynes with a tethered carbonyl group was investigated. An unusual insertion of a CO bond into the C(sp(2) )-rhodium bond of a rhodacycle intermediate occurs via a highly strained transition state. Direct reductive elimination from the obtained rhodacyle intermediate proceeds to give a tricyclic product containing an 8-oxabicyclo[3.2.1]octane skeleton, while β-hydride elimination from the same intermediate gives products that contain fused five- and seven-membered rings in high yields. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. The divergent synthesis of nitrogen heterocycles by rhodium(II)-catalyzed cycloadditions of 1-sulfonyl 1,2,3-triazoles with 1,3-dienes.

    Science.gov (United States)

    Shang, Hai; Wang, Yuanhao; Tian, Yu; Feng, Juan; Tang, Yefeng

    2014-05-26

    The first rhodium(II)-catalyzed aza-[4+3] cycloadditions of 1-sulfonyl 1,2,3-triazoles with 1,3-dienes have been developed, and enable the efficient synthesis of highly functionalized 2,5-dihydroazepines from readily available precursors. In some cases, the reaction pathway could divert to formal aza-[3+2] cycloadditions, thus leading to 2,3-dihydropyrroles. In this context, the titled reaction represents a capable tool for the divergent synthesis of two types of synthetically valuable aza-heterocycles from common rhodium(II) iminocarbene intermediates. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. One-pot synthesis of 2,5-dihydropyrroles from terminal alkynes, azides, and propargylic alcohols by relay actions of copper, rhodium, and gold.

    Science.gov (United States)

    Miura, Tomoya; Tanaka, Takamasa; Matsumoto, Kohei; Murakami, Masahiro

    2014-12-01

    Relay actions of copper, rhodium, and gold formulate a one-pot multistep pathway, which directly gives 2,5-dihydropyrroles starting from terminal alkynes, sulfonyl azides, and propargylic alcohols. Initially, copper-catalyzed 1,3-dipolar cycloaddition of terminal alkynes with sulfonyl azides affords 1-sulfonyl-1,2,3-triazoles, which then react with propargylic alcohols under the catalysis of rhodium. The resulting alkenyl propargyl ethers subsequently undergo the thermal Claisen rearrangement to give α-allenyl-α-amino ketones. Finally, a gold catalyst prompts 5-endo cyclization to produce 2,5-dihydropyrroles. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Oxidative Olefination of Anilides with Unactivated Alkenes Catalyzed by an (Electron-Deficient η(5) -Cyclopentadienyl)Rhodium(III) Complex Under Ambient Conditions.

    Science.gov (United States)

    Takahama, Yuji; Shibata, Yu; Tanaka, Ken

    2015-06-15

    The oxidative olefination of sp(2) C-H bonds of anilides with both activated and unactivated alkenes using an (electron-deficient η(5) -cyclopentadienyl)rhodium(III) complex is reported. In contrast to reactions using this electron-deficient rhodium(III) catalyst, [Cp*RhCl2 ]2 showed no activity against olefination with unactivated alkenes. In addition, the deuterium kinetic isotope effect (DKIE) study revealed that the C-H bond cleavage step is thought to be the turnover-limiting step. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. 32 CFR 99.3 - General definitions.

    Science.gov (United States)

    2010-07-01

    ... 32 National Defense 1 2010-07-01 2010-07-01 false General definitions. 99.3 Section 99.3 National... PROCEDURES FOR STATES AND LOCALITIES TO REQUEST INDEMNIFICATION § 99.3 General definitions. For the purposes of §§ 99.1 through 99.9 of this part: Criminal history record information: information collected by...

  15. Electrochemical Sensor Based on Rh(III) Ion-Imprinted Polymer as a New Modifying Agent for Rhodium Determination.

    Science.gov (United States)

    Bai, Huiping; Xiong, Caiyun; Wang, Chunqiong; Liu, Peng; Dong, Su; Cao, Qiue

    2018-05-01

    A rhodium (III) ion carbon paste electrode (CPE) based on an ion imprinted polymer (IIP) as a new modifying agent has been prepared and studied. Rh(III) ion imprinted polymer was synthesized by copolymerization of acrylamide-Rh(III) complex and ethylene glycol dimethacrylate according to the precipitation polymerization. Acrylamide acted as both functional monomer and complexing agent to create selective coordination sites in a cross-linked polymer. The ion imprinted carbon paste electrode (IIP-CPE) was prepared by mixing rhodium IIP-nanoparticles and graphite powder in n-eicosane as an adhesive and then embedding them in a Teflon tube. Amperometric i-t curve method was applied as the determination technique. Several parameters, including the functional monomer, molar ratio of template, monomer and cross-linking agent, the amounts of IIP, the applied potential, the buffer solution and pH have been studied. According to the results, IIP-CPE showed a considerably higher response in comparison with the electrode embedded with non-imprinted polymer (NIP), indicating the formation of suitable recognition sites in the IIP structure during the polymerization stage. The introduced electrode showed a linear range of 1.00×10-8~3.0×10-5 mol·L-1 and detection limit of 6.0 nmol L-1 (S/N = 3). The IIP-CPE was successfully applied for the trace rhodium determination in catalyst and plant samples with RSD of less than 3.3% (n = 5) and recoveries in the range of 95.5~102.5%.

  16. Rhodium-Catalyzed Insertion Reaction of PhP Group of Pentaphenylcyclopentaphosphine with Acyclic and Cyclic Disulfides.

    Science.gov (United States)

    Arisawa, Mieko; Sawahata, Kyosuke; Yamada, Tomoki; Sarkar, Debayan; Yamaguchi, Masahiko

    2018-02-16

    Organophosphorus compounds with a phosphorus atom attached to a phenyl group and two organothio/organoseleno groups were synthesized using the rhodium-catalyzed insertion reaction of the PhP group of pentaphenylcyclopentaphosphine (PhP) 5 with acyclic disulfides and diselenides. The method was applied to the synthesis of heterocyclic compounds containing the S-P-S group by the reaction of (PhP) 5 and cyclic disulfides such as 1,2-dithietes, 1,2-dithiocane, 1,4,5-dithiopane, and 1,2-dithiolanes.

  17. Rhodium catalyzed regioselective arene homologation of aryl urea via double C-H bond activation and migratory insertion of alkyne

    Institute of Scientific and Technical Information of China (English)

    Yan Wang; Hao Zhou; Ke Xu; Mei-Hua Shen; Hua-Dong Xu

    2017-01-01

    A convenient rhodium catalyzed oxidative arene homologation of aniline derivatives with symmetrical or unsymmetrical alkynes using Cu(OAc)2 as oxidant is described.Urea group is shown to be effective as a directing group for initial ortho C-H activation.Two migratory insertion events of alkyne into Rh-C bond occur successively,both with complete regioselectivity.This method is particularly useful for synthesis of polyarenes with different substituents,which has not been reported with conventional protocol.A mechanism has been proposed to explain the observed data.

  18. Rhodium-catalyzed annulation of arenes with alkynes through weak chelation-assisted C-H activation.

    Science.gov (United States)

    Yang, Yudong; Li, Kaizhi; Cheng, Yangyang; Wan, Danyang; Li, Mingliang; You, Jingsong

    2016-02-18

    The purpose of this article is to give a brief review of weak chelation-assistance as a powerful means for the rhodium-catalyzed annulation of arenes with alkynes. The use of commonly occurring functional groups (e.g., ketones, aldehydes, carboxylic acids and alcohols) as the directing groups enriches the versatility of auxiliary ligands and extends the scope of products. This short article offers an overview on emerging procedures, highlights their advantages and limitations, and covers the latest progress in the rapid synthesis of organic functional materials and natural products.

  19. Rhodium-catalyzed enantioselective intramolecular C-H silylation for the syntheses of planar-chiral metallocene siloles.

    Science.gov (United States)

    Zhang, Qing-Wei; An, Kun; Liu, Li-Chuan; Yue, Yuan; He, Wei

    2015-06-01

    Reported herein is the rhodium-catalyzed enantioselective C-H bond silylation of the cyclopentadiene rings in Fe and Ru metallocenes. Thus, in the presence of (S)-TMS-Segphos, the reactions took place under very mild conditions to afford metallocene-fused siloles in good to excellent yields and with ee values of up to 97%. During this study it was observed that the steric hindrance of chiral ligands had a profound influence on the reactivity and enantioselectivity of the reaction, and might hold the key to accomplishing conventionally challenging asymmetric C-H silylations. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Regio- and enantioselective synthesis of N-substituted pyrazoles by rhodium-catalyzed asymmetric addition to allenes.

    Science.gov (United States)

    Haydl, Alexander M; Xu, Kun; Breit, Bernhard

    2015-06-08

    The rhodium-catalyzed asymmetric N-selective coupling of pyrazole derivatives with terminal allenes gives access to enantioenriched secondary and tertiary allylic pyrazoles, which can be employed for the synthesis of medicinally important targets. The reaction tolerates a large variety of functional groups and labelling experiments gave insights into the reaction mechanism. This new methodology was further applied in a highly efficient synthesis of JAK 1/2 inhibitor (R)-ruxolitinib. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Synthesis and structural studies of Cp{sup *} rhodium and Cp{sup *} iridium complexes of picolinic hydrazine ligand

    Energy Technology Data Exchange (ETDEWEB)

    Palepu, Narasinga Rao; Kollipara, Mohan Rao [Centre for Advanced Studies in Chemistry, North-Eastern Hill University, Shillong (India); Kaminsky Werner [Dept. of Chemistry, University of Washington, Seattle (United States)

    2017-01-15

    A series of Cp{sup *}Rh and Cp{sup *}Ir complexes of picolinic hydrazine ligand are synthesized and characterized. Picolinic hydrazine has yielded only dinuclear complexes in the case of rhodium metal whereas both mono and dinuclear complexes with iridium metal. Iridium complexes are formed as quaternary salts by the migration of the N–H proton onto the adjacent amine group of the hydrazine after binding to the metal. Picolinic hydrazine acts as nitrogen and oxygen donor ligand in the form of bi and tetradentate bonding modes.

  2. 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

    2015-06-15

    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. © 2015 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA. This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited.

  3. 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

  4. ECNS '99 - Young scientists forum

    DEFF Research Database (Denmark)

    Ceretti, M.; Janssen, S.; McMorrow, D.F.

    2000-01-01

    The Young Scientists Forum is a new venture for ECNS and follows the established tradition of an active participation by young scientists in these conferences. At ECNS '99 the Young Scientists Forum brought together 30 young scientists from 13 European countries. In four working groups, they disc......The Young Scientists Forum is a new venture for ECNS and follows the established tradition of an active participation by young scientists in these conferences. At ECNS '99 the Young Scientists Forum brought together 30 young scientists from 13 European countries. In four working groups......, they discussed emerging scientific trends in their areas of expertise and the instrumentation required to meet the scientific challenges. The outcome was presented in the Young Scientists Panel on the final day of ECNS '99. This paper is a summary of the four working group reports prepared by the Group Conveners...

  5. 14 CFR 99.1 - Applicability.

    Science.gov (United States)

    2010-01-01

    ... 14 Aeronautics and Space 2 2010-01-01 2010-01-01 false Applicability. 99.1 Section 99.1... AND GENERAL OPERATING RULES SECURITY CONTROL OF AIR TRAFFIC General § 99.1 Applicability. (a) This... Identification Zone (ADIZ) designated in subpart B. (b) Except for §§ 99.7, 99.13, and 99.15 this subpart does...

  6. Materials for Molybdenum 99 purification

    International Nuclear Information System (INIS)

    Wilkinson, M. Victoria; Mondino, Angel V.; Manzini, Alberto C.

    2003-01-01

    The National Atomic Energy Commission (CNEA) produces fission Mo 99, an isotope of wide use in nuclear medicine. In order to simplify the current Mo 99 production process, to shorten its duration and reduce impurities in the final product, alternative methods for purification steps were looked for. In this work a variety of new materials for the purification columns were designed, all of them with carbon. These materials were studied and a material which contribute with the best results for molybdenum retention, was selected. The preparation procedure and the working conditions were determined. (author)

  7. Mild oxidation of methane to methanol or acetic acid on supported isolated rhodium catalysts

    Science.gov (United States)

    Shan, Junjun; Li, Mengwei; Allard, Lawrence F.; Lee, Sungsik; Flytzani-Stephanopoulos, Maria

    2017-11-01

    An efficient and direct method of catalytic conversion of methane to liquid methanol and other oxygenates would be of considerable practical value. However, it remains an unsolved problem in catalysis, as typically it involves expensive or corrosive oxidants or reaction media that are not amenable to commercialization. Although methane can be directly converted to methanol using molecular oxygen under mild conditions in the gas phase, the process is either stoichiometric (and therefore requires a water extraction step) or is too slow and low-yielding to be practical. Methane could, in principle, also be transformed through direct oxidative carbonylation to acetic acid, which is commercially obtained through methane steam reforming, methanol synthesis, and subsequent methanol carbonylation on homogeneous catalysts. However, an effective catalyst for the direct carbonylation of methane to acetic acid, which might enable the economical small-scale utilization of natural gas that is currently flared or stranded, has not yet been reported. Here we show that mononuclear rhodium species, anchored on a zeolite or titanium dioxide support suspended in aqueous solution, catalyse the direct conversion of methane to methanol and acetic acid, using oxygen and carbon monoxide under mild conditions. We find that the two products form through independent pathways, which allows us to tune the conversion: three-hour-long batch-reactor tests conducted at 150 degrees Celsius, using either the zeolite-supported or the titanium-dioxide-supported catalyst, yield around 22,000 micromoles of acetic acid per gram of catalyst, or around 230 micromoles of methanol per gram of catalyst, respectively, with selectivities of 60-100 per cent. We anticipate that these unusually high activities, despite still being too low for commercial application, may guide the development of optimized catalysts and practical processes for the direct conversion of methane to methanol, acetic acid and other useful

  8. A rhodium(III) complex for high-affinity DNA base-pair mismatch recognition

    Science.gov (United States)

    Junicke, Henrik; Hart, Jonathan R.; Kisko, Jennifer; Glebov, Oleg; Kirsch, Ilan R.; Barton, Jacqueline K.

    2003-01-01

    A rhodium(III) complex, rac-[Rh(bpy)2phzi]3+ (bpy, 2,2′-bipyridine; phzi, benzo[a]phenazine-5,6-quinone diimine) has been designed as a sterically demanding intercalator targeted to destabilized mismatched sites in double-helical DNA. The complex is readily synthesized by condensation of the phenazine quinone with the corresponding diammine complex. Upon photoactivation, the complex promotes direct strand scission at single-base mismatch sites within the DNA duplex. As with the parent mismatch-specific reagent, [Rh(bpy)2(chrysi)]3+ [chrysene-5,6-quinone diimine (chrysi)], mismatch selectivity depends on the helix destabilization associated with mispairing. Unlike the parent chrysi complex, the phzi analogue binds and cleaves with high affinity and efficiency. The specific binding constants for CA, CC, and CT mismatches within a 31-mer oligonucleotide duplex are 0.3, 1, and 6 × 107 M−1, respectively; site-specific photocleavage is evident at nanomolar concentrations. Moreover, the specificity, defined as the ratio in binding affinities for mispaired vs. well paired sites, is maintained. The increase in affinity is attributed to greater stability in the mismatched site associated with stacking by the heterocyclic aromatic ligand. The high-affinity complex is also applied in the differential cleavage of DNA obtained from cell lines deficient in mismatch repair vs. those proficient in mismatch repair. Agreement is found between photocleavage by the mismatch-specific probes and deficiency in mismatch repair. This mismatch-specific targeting, therefore, offers a potential strategy for new chemotherapeutic design. PMID:12610209

  9. Toxicity of platinum, palladium and rhodium to Daphnia magna in single and binary metal exposure experiments.

    Science.gov (United States)

    Zimmermann, Sonja; Wolff, Carolina; Sures, Bernd

    2017-05-01

    Mainly due to automobile traffic, but also due to other sources, the platinum group elements (PGE) platinum (Pt), palladium (Pd) and rhodium (Rh) are introduced into aquatic biotopes where they accumulate in sediments of lakes and rivers. However, the toxicity of these noble metals to aquatic organisms is not well understood and especially toxicity studies under standardized condition are lacking. Thus, the toxicity of Pt, Pd and Rh to Daphnia magna was tested in single metal exposure experiments according to OECD guideline 202. Immobility and lethality was recorded after 24 h and 48 h of exposure and EC 50 and LC 50 , respectively, were determined. As the nominal exposure concentration of Pd differed significantly from the quantified concentration, the control of the real exposure concentration by chemical analysis is mandatory, especially for Pd. The toxicity decreased in the order Pd > Pt ≫ Rh with e.g. LC 50 (48 h) values of 14 μg/L for Pd, 157 μg/L for Pt and 56,800 μg/L for Rh. The exposure period had a clear effect on the toxicity of Pt, Pd and Rh. For Pt and Rh the endpoint immobility was more sensitive than the endpoint lethality whereas Pd toxicity was similar for both endpoints. The Hill slopes, which are a measure for the steepness of the concentration-response curves, showed no significant discrepancies between the different metals. The binary metal exposure to Pt and Pd revealed a more-than-additive, i.e. a synergistic toxicity using the toxic unit approach. The present study is a start to understand the toxicity of interacting PGE. The modes of action behind the synergistic effect are unclear. Copyright © 2017 Elsevier Ltd. All rights reserved.

  10. Alternativa nomer 99 / Boris Tuch

    Index Scriptorium Estoniae

    Tuch, Boris, 1946-

    2008-01-01

    Teatri NO99 ajaloost ja lavastustest - Tiit Ojasoo "Nafta", "Kuningas Ubu", "GEP", "Seitse samuraid","Perikles"ja Sebastian Hartmani lavastus "Stalker" Andrei Tarkovski filmi põhjal ning Hendrik Toompere "Kommunisti surm". Ka Tiit Ojasoo lavastusest "Julia" Shakespeare'i ainetel Eesti Draamateatris

  11. Tc-99m imaging agents

    International Nuclear Information System (INIS)

    Weininger, J.; Trumper, J.

    1984-01-01

    A wide range of pharmaceuticals for labeling with Tc-99m, developed by the Soreq Radiopharmaceuticals Department, is described. Details of the production and quality control of 13 kits are given, as well as the range of results required for consistently high quality imaging agents

  12. Treatment of ammonia by catalytic wet oxidation process over platinum-rhodium bimetallic catalyst in a trickle-bed reactor: effect of pH.

    Science.gov (United States)

    Hung, Chang-Mao; Lin, Wei-Bang; Ho, Ching-Lin; Shen, Yun-Hwei; Hsia, Shao-Yi

    2010-08-01

    This work adopted aqueous solutions of ammonia for use in catalytic liquid-phase reduction in a trickle-bed reactor with a platinum-rhodium bimetallic catalyst, prepared by the co-precipitation of chloroplatinic acid (H2PtCl6) and rhodium nitrate [Rh(NO3)3]. The experimental results demonstrated that a minimal amount of ammonia was removed from the solution by wet oxidation in the absence of any catalyst, while approximately 97.0% of the ammonia was removed by wet oxidation over the platinum-rhodium bimetallic catalyst at 230 degrees C with an oxygen partial pressure of 2.0 MPa. The oxidation of ammonia has been studied as a function of pH, and the main reaction products were determined. A synergistic effect is manifest in the platinum-rhodium bimetallic structure, in which the material has the greatest capacity to reduce ammonia. The reaction pathway linked the oxidizing ammonia to nitric oxide, nitrogen, and water.

  13. Liquid-liquid extraction/separation of platinum(IV) and rhodium(III) from acidic chloride solutions using tri-iso-octylamine

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Jin-Young, E-mail: jinlee@kigam.re.kr [Metals Recovery Department, Minerals Resources Research Division, Korea Institute of Geoscience and Mineral Resources (KIGAM), 92 Gahangno, Yuesong-gu, Daejeon 305-350 (Korea, Republic of); Rajesh Kumar, J., E-mail: rajeshkumarphd@rediffmail.com [Metals Recovery Department, Minerals Resources Research Division, Korea Institute of Geoscience and Mineral Resources (KIGAM), 92 Gahangno, Yuesong-gu, Daejeon 305-350 (Korea, Republic of); Kim, Joon-Soo; Park, Hyung-Kyu; Yoon, Ho-Sung [Metals Recovery Department, Minerals Resources Research Division, Korea Institute of Geoscience and Mineral Resources (KIGAM), 92 Gahangno, Yuesong-gu, Daejeon 305-350 (Korea, Republic of)

    2009-08-30

    Liquid-liquid extraction/separation of platinum(IV) and rhodium(III) from acidic chloride solutions was carried out using tri-iso-octylamine (Alamine 308) as an extractant diluted in kerosene. The percentage extraction of platinum(IV) and rhodium(III) increased with increase in acid concentration up to 8 mol L{sup -1}. However, at 10 mol L{sup -1} HCl concentration, the extraction behavior was reversed, indicating the solvation type mechanism during extraction. The quantitative extraction of {approx}98% platinum(IV) and 36% rhodium(III) was achieved with 0.01 mol L{sup -1} Alamine 308. The highest separation factor (S.F. = 184.7) of platinum(IV) and rhodium(III) was achieved with 0.01 mol L{sup -1} Alamine 308 at 1.0 mol L{sup -1} of hydrochloric acid concentration. Alkaline metal salts like sodium chloride, sodium nitrate, sodium thiocyanate, lithium chloride, lithium nitrate, potassium chloride and potassium thiocyanate used for the salting-out effect. LiCl proved as best salt for the extraction of platinum(IV). Temperature effect demonstrates that the extraction process is exothermic. Hydrochloric acid and thiourea mixture proved to be better stripping reagents when compared with other mineral acids and bases.

  14. Development of accurate mass spectrometric routine and reference methods for the determination of trace amounts of iridium and rhodium in photographic emulsionsf

    NARCIS (Netherlands)

    Krystek, Petra; Heumann, Klaus G.

    1999-01-01

    For the determination of trace amounts of iridium and rhodium in photographic emulsions different sample treatment procedures were coupled with inductively coupled plasma mass spectrometry (ICP-MS) and, for iridium, also with negative thermal ionisation isotope dilution mass spectrometry (NTI-IDMS)

  15. Coupling of Electron Transfer and Bond Dissociation Processes in Dinuclear Complexes with Rhodium and Iridium Reaction Centers Bridged by 2,2'-Bipyrimidine

    Czech Academy of Sciences Publication Activity Database

    Kaim, W.; Reinhardt, R.; Greulich, S.; Sieger, M.; Klein, A.; Fiedler, Jan

    2001-01-01

    Roč. 66, č. 2 (2001), s. 291-306 ISSN 0010-0765 R&D Projects: GA MŠk OC D15.10 Institutional research plan: CEZ:AV0Z4040901 Keywords : EPR spectroscopy * iridium complexes * rhodium complexes Subject RIV: CG - Electrochemistry Impact factor: 0.778, year: 2001

  16. Simultaneous determination of palladium, platinum and rhodium by on-line column enrichment and HPLC with 2,4-dihydroxybenzylidenethiorhodanine as pre-column derivatization reagent

    Directory of Open Access Journals (Sweden)

    Dong Xuechang

    2006-01-01

    Full Text Available A new method for the simultaneous determination of palladium, platinum and rhodium ions as metal-DHBTR chelates was developed. The palladium, platinum and rhodium ions were pre-column derivatized with 2,4-dihydroxybenzylidenethiorhodanine (DHBTR to form colored chelates. The Pd-DHBTR, Pt-DHBTR and Rh-DHBTR chelates can be absorbed onto the front of the enrichment column when they were injected into the injector and sent to the enrichment column with a 0.05 mol L-1 sodium acetate-acetic acid buffer solution (pH 3.5 as mobile phase. After the enrichment had finished, by switching the six ports switching valve, the retained chelates were back-flushed by mobile phase and traveling towards the analytical column. These chelates separation on the analytical column was satisfactory with 62% (v/v acetonitrile (containing 0.05 mol L-1 of pH 3.5 sodium acetate-acetic acid buffer salt and 0.1% (m/v of tritonX-100 as mobile phase. The Limits of detection of palladium, platinum and rhodium are 3.6 ng L-1, 3.2 ng L-1 and 4.5 ng L-1, respectively. This method was applied to the determination of palladium, platinum and rhodium in water, urine and soil samples with good results.

  17. CTAB micelles and the hydroformylation of octene with rhodium/TPPTS catalysts - Evidence for the interaction of TPPTS with micelle surfaces

    DEFF Research Database (Denmark)

    Riisager, Anders; Hanson, Brian E.

    2002-01-01

    The addition of cetyltrimethylammonium bromide (CTAB) to TPPTS/rhodium hydroformylation catalysts has a complicated effect on reaction activity and selectivity. In water alone as the solvent, high CTAB concentration leads to the formation of emulsions and reaction selectivity drops. In aqueous...

  18. Identification of a rhodium(iii) complex as a Wee1 inhibitor against TP53-mutated triple-negative breast cancer cells.

    Science.gov (United States)

    Yang, Guan-Jun; Zhong, Hai-Jing; Ko, Chung-Nga; Wong, Suk-Yu; Vellaisamy, Kasipandi; Ye, Min; Ma, Dik-Lung; Leung, Chung-Hang

    2018-03-06

    The rhodium(iii) complex 1 was identified as a potent Wee1 inhibitor in vitro and in cellulo. It decreased Wee1 activity and unscheduled mitotic entry, and induced cell damage and death in TP53-mutated triple-negative breast cancer cells. 1 represents a promising scaffold for further development of more potent metal-based Wee1 antagonists.

  19. REGIOSELECTIVE OXIDATIONS OF EQUILENIN DERIVATIVES CATALYZED BY A RHODIUM (III) PORPHYRIN COMPLEX-CONTRAST WITH THE MANGANESE (III) PORPHYRIN. (R826653)

    Science.gov (United States)

    AbstractEquilenin acetate and dihydroequilenin acetate were oxidized with iodosobenzene and a rhodium(III) porphyrin catalyst. The selectivity of the reactions differs from that with the corresponding Mn(III) catalyst, or from that of free radical chain oxidation.

  20. Successful labeling of 99mTc-MDP using 99mTc separated from 99Mo produced by 100Mo(n,2n)99Mo

    International Nuclear Information System (INIS)

    Nagai, Yasuki; Hatsukawa, Yuichi; Kin, Tadahiro; Hashimoto, Kazuyuki; Motoishi, Shoji; Konno, Chikara; Ochiai, Kentaro; Takakura, Kosuke; Sato, Yuichi; Sato, Norihito; Ohta, Akio; Yamabayashi, Hisamichi; Tanase, Masakazu; Fujisaki, Saburo; Kawauchi, Yukimasa; Teranaka, Tomoyuki; Takeuchi, Nobuhiro; Igarashi, Takashi

    2011-01-01

    We have for the first time succeeded in separating 99m Tc from a MoO 3 sample irradiated with accelerator neutrons free from any radioactive impurities and in formulating 99m Tc-methylene diphosphonate ( 99 mTc-MDP). 99 Mo, the mother nuclide of 99m Tc, was produced by the 100 Mo(n,2n) 99 Mo reaction using about 14 MeV neutrons provided by the 3 H(d,n) 4 He reaction at the Fusion Neutronics Source of Japan Atomic Energy Agency. The 99m Tc was separated from 99 Mo by sublimation and its radionuclide purity was confirmed to be higher than 99.99% by γ-spectroscopy. The labeling efficiency of 99m Tc-MDP was shown to be higher than 99% by thin-layer chromatography. These values exceed the United States Pharmacopeia requirements for a fission product, 99 Mo. Consequently, a 99m Tc radiopharmaceutical preparation formed by using the mentioned 99 Mo can be a promising substitute for the fission product 99 Mo, which is currently produced using a highly enriched uranium target in aging research reactors. A longstanding problem to ensure a reliable and constant supply of 99 Mo in Japan can be partially mitigated. (author)

  1. Current status of production and supply of molybdenum-99 and 99Mo/99mTc generators in Indonesia

    International Nuclear Information System (INIS)

    Mutalib, A.

    2003-01-01

    Production of high-specific activity molybdenum-99 and 99 Mo/ 99m Tc Generators in Indonesia commenced when a new production facility supported by the presence of a 30 MW multipurpose reactor (RSG-GAS) was established in Serpong in 1990. This report describes the current production and supply of molybdenum-99m devoted mainly to fulfill the domestic demands in supplying 99 Mo/ 99m Tc Generators. Recent development on the use of LEU (Low Enriched Uranium) targets for replacing current HEU (High Enriched Uranium) targets in the production of 99 Mo will be reviewed briefly. (author)

  2. 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.

  3. Determination of Rhodium(III Ions by Flame Atomic Absorption Spectrometry after Preconcentration with Modified Magnetic Activated Carbon

    Directory of Open Access Journals (Sweden)

    Maryam Fayazi

    2016-06-01

    Full Text Available A new method for analysis of trace amount of Rh(III ions by magnetic activated carbon modified with 2,3,5,6-tetra(2-pyridylpyrazine (MAC/TPPZ as the magnetic sorbent has been proposed. The proposed adsorbent was found to be advantageous over conventional solid phase extraction (SPE in terms of operational simplicity and low time-consuming. The experimental parameters affecting the extraction/preconcentration and determination of the analyte were systematically examined. In order to investigate the selectivity of this magnetic sorbent, the effect of a variety of ions on preconcentration and recovery of Rh(III ions were also investigated. Under optimum conditions, the calibration graph was linear for the concentration range of 0.8-650 µg l-1. The limit of detection (LOD, 3Sb/m and the relative standard deviation (RSD, n = 8, c = 50 µg l-1 were 0.1 µg l-1 and 3.6%, respectively. The maximum sorption capacity of the adsorbent for rhodium was found to be 21.6 mg g-1. The presented procedure was applied to monitoring rhodium in water and synthetic samples.

  4. An operando FTIR spectroscopic and kinetic study of carbon monoxide pressure influence on rhodium-catalyzed olefin hydroformylation.

    Science.gov (United States)

    Kubis, Christoph; Sawall, Mathias; Block, Axel; Neymeyr, Klaus; Ludwig, Ralf; Börner, Armin; Selent, Detlef

    2014-09-08

    The influence of carbon monoxide concentration on the kinetics of the hydroformylation of 3,3-dimethyl-1-butene with a phosphite-modified rhodium catalyst has been studied for the pressure range p(CO)=0.20-3.83 MPa. Highly resolved time-dependent concentration profiles of the organometallic intermediates were derived from IR spectroscopic data collected in situ for the entire olefin-conversion range. The dynamics of the catalyst and organic components are described by enzyme-type kinetics with competitive and uncompetitive inhibition reactions involving carbon monoxide taken into account. Saturation of the alkyl-rhodium intermediates with carbon monoxide as a cosubstrate occurs between 1.5 and 2 MPa of carbon monoxide pressure, which brings about a convergence of aldehyde regioselectivity. Hydrogenolysis of the acyl intermediate is fast at 30 °C and low pressure of p(CO)=0.2 MPa, but is of minus first order with respect to the solution concentration of carbon monoxide. Resting 18-electron hydrido and acyl complexes that correspond to early and late rate-determining states, respectively, coexist as long as the conversion of the substrate is not complete. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Study of activation cross-sections of deuteron induced reactions on rhodium up to 40 MeV

    International Nuclear Information System (INIS)

    Ditroi, F.; Tarkanyi, F.; Takacs, S.; Hermanne, A.; Yamazaki, H.; Baba, M.; Mohammadi, A.; Ignatyuk, A.V.

    2011-01-01

    Highlights: → Excitation function measurement of deuteron induced reactions on rhodium up to 40 MeV. → Model code calculations with EMPIRE, ALICE and TALYS. → Integral production yield calculation. → Thin layer activation (TLA) with the produced isotopes. - Abstract: In the frame of a systematic study of the activation cross-sections of deuteron induced nuclear reactions, excitation functions of the 103 Rh(d,x) 100,101,103 Pd, 100g,101m,101g,102m,102g Rh and 103g Ru reactions were determined up to 40 MeV. Cross-sections were measured with the activation method using a stacked foil irradiation technique. Excitation functions of the contributing reactions were calculated using the ALICE-IPPE, EMPIRE-II and TALYS codes. From the measured cross-section data integral production yields were calculated and compared with experimental integral yield data reported in the literature. From the measured cross-sections and previous data, activation curves were deduced to support thin layer activation (TLA) on rhodium and Rh containing alloys.

  6. A chemical-biological evaluation of rhodium(I) N-heterocyclic carbene complexes as prospective anticancer drugs.

    Science.gov (United States)

    Oehninger, Luciano; Küster, Laura Nadine; Schmidt, Claudia; Muñoz-Castro, Alvaro; Prokop, Aram; Ott, Ingo

    2013-12-23

    Rhodium(I) complexes bearing N-heterocyclic carbene (NHC) ligands have been widely used in catalytic chemistry, but there are very few reports of biological properties of these organometallics. A series of Rh(I)-NHC derivatives with 1,5-cyclooctadiene and CO as secondary ligands were synthesized, characterized, and biologically investigated as prospective antitumor drug candidates. Pronounced antiproliferative effects were noted for all complexes, along with moderate inhibitory activity of thioredoxin reductase (TrxR) and efficient binding to biomolecules (DNA, albumin). Biodistribution studies showed that the presence of albumin lowered the cellular uptake and confirmed the transport of rhodium into the nuclei. Changes in the mitochondrial membrane potential (MMP) were observed as well as DNA fragmentation in wild-type and daunorubicin- or vincristine-resistant Nalm-6 leukemia cells. Overall, these studies indicated that Rh(I)-NHC fragments could be used as partial structures of new antitumor agents, in particular in those drugs designed to address resistant malignant tissues. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. A rhodium(III) complex inhibits LPS-induced nitric oxide production and angiogenic activity in cellulo.

    Science.gov (United States)

    Liu, Li-Juan; Lin, Sheng; Chan, Daniel Shiu-Hin; Vong, Chi Teng; Hoi, Pui Man; Wong, Chun-Yuen; Ma, Dik-Lung; Leung, Chung-Hang

    2014-11-01

    Metal-containing complexes have arisen as viable alternatives to organic molecules as therapeutic agents. Metal complexes possess a number of advantages compared to conventional carbon-based compounds, such as distinct geometries, interesting electronic properties, variable oxidation states and the ability to arrange different ligands around the metal centre in a precise fashion. Meanwhile, nitric oxide (NO) plays key roles in the regulation of angiogenesis, vascular permeability and inflammation. We herein report a novel cyclometalated rhodium(III) complex as an inhibitor of lipopolysaccharides (LPS)-induced NO production in RAW264.7 macrophages. Experiments suggested that the inhibition of NO production in cells by complex 1 was mediated through the down-regulation of nuclear factor-κB (NF-κB) activity. Furthermore, complex 1 inhibited angiogenesis in human umbilical vein endothelial cells (HUVECs) as revealed by an endothelial tube formation assay. This study demonstrates that kinetically inert rhodium(III) complexes may be potentially developed as effective anti-angiogenic agents. Copyright © 2014 Elsevier Inc. All rights reserved.

  8. JENDL dosimetry file 99 (JENDL/D-99)

    International Nuclear Information System (INIS)

    Kobayashi, Katsuhei; Iwasaki, Shin

    2002-01-01

    The JENDL Dosimetry File 99 (JENDL/D-99), which is a revised version of the JENDL Dosimetry File 91 (JENDL/D-91), has been compiled and released for the determination of neutron flux and energy spectra. This work was undertaken to remove the inconsistency between the cross sections and their covariances in JENDL/D-91 since the covariances were mainly taken from IRDF-85 although the cross sections were based on JENDL-3. Dosimetry cross sections have been evaluated for 67 reactions on 47 nuclides together with covariances. The cross sections for 34 major reactions and their covariances were simultaneously generated, and the remaining 33 reaction data were mainly taken from JENDL/D-91. Latest measurements were taken into account in the evaluation. The resultant evaluated data are given in the neutron energy region below 20 MeV in both of point-wise and group-wise files in the ENDF-6 format. In order to confirm the reliability of the evaluated data, several integral tests have been carried out: comparisons with average cross sections measured in fission neutron fields, fast/thermal reactor spectra, DT neutron fields and Li(d,n) neutron fields. It was found from the comparisons that the cross sections calculated from JENDL/D-99 are generally in good agreement with the measured data. The contents of JENDL/D-99 and the results of the integral tests are described in this report. All of the dosimetry cross sections are shown in a graphical form in the Appendix. (author)

  9. 29 CFR 99.505 - Audit reporting.

    Science.gov (United States)

    2010-07-01

    ... 29 Labor 1 2010-07-01 2010-07-01 true Audit reporting. 99.505 Section 99.505 Labor Office of the Secretary of Labor AUDITS OF STATES, LOCAL GOVERNMENTS, AND NON-PROFIT ORGANIZATIONS Auditors § 99.505 Audit... is required to report under § 99.510(a); (vii) An identification of major programs; (viii) The dollar...

  10. 29 CFR 99.310 - Financial statements.

    Science.gov (United States)

    2010-07-01

    ... 29 Labor 1 2010-07-01 2010-07-01 true Financial statements. 99.310 Section 99.310 Labor Office of the Secretary of Labor AUDITS OF STATES, LOCAL GOVERNMENTS, AND NON-PROFIT ORGANIZATIONS Auditees § 99... have separate audits in accordance with § 99.500(a) and prepare separate financial statements. (b...

  11. 29 CFR 99.300 - Auditee responsibilities.

    Science.gov (United States)

    2010-07-01

    ... 29 Labor 1 2010-07-01 2010-07-01 true Auditee responsibilities. 99.300 Section 99.300 Labor Office... § 99.300 Auditee responsibilities. The auditee shall: (a) Identify, in its accounts, all Federal awards... the schedule of expenditures of Federal awards in accordance with § 99.310. (e) Ensure that the audits...

  12. 29 CFR 99.405 - Management decision.

    Science.gov (United States)

    2010-07-01

    ... 29 Labor 1 2010-07-01 2010-07-01 true Management decision. 99.405 Section 99.405 Labor Office of... Agencies and Pass-through Entities § 99.405 Management decision. (a) General. The management decision shall... process available to the auditee. (b) Federal agency. As provided in § 99.400(a)(7), the cognizant agency...

  13. 29 CFR 99.230 - Audit costs.

    Science.gov (United States)

    2010-07-01

    ... 29 Labor 1 2010-07-01 2010-07-01 true Audit costs. 99.230 Section 99.230 Labor Office of the Secretary of Labor AUDITS OF STATES, LOCAL GOVERNMENTS, AND NON-PROFIT ORGANIZATIONS Audits § 99.230 Audit... years ending after December 31, 2003) and is thereby exempted under § 99.200(d) from having an audit...

  14. 29 CFR 99.105 - Definitions.

    Science.gov (United States)

    2010-07-01

    ... 29 Labor 1 2010-07-01 2010-07-01 true Definitions. 99.105 Section 99.105 Labor Office of the Secretary of Labor AUDITS OF STATES, LOCAL GOVERNMENTS, AND NON-PROFIT ORGANIZATIONS General § 99.105 Definitions. Audit finding means deficiencies which the auditor is required by § 99.510(a) to report in the...

  15. 29 CFR 99.200 - Audit requirements.

    Science.gov (United States)

    2010-07-01

    ... 29 Labor 1 2010-07-01 2010-07-01 true Audit requirements. 99.200 Section 99.200 Labor Office of the Secretary of Labor AUDITS OF STATES, LOCAL GOVERNMENTS, AND NON-PROFIT ORGANIZATIONS Audits § 99.... Guidance on determining Federal awards expended is provided in § 99.205. (b) Single audit. Non-Federal...

  16. 29 CFR 99.510 - Audit findings.

    Science.gov (United States)

    2010-07-01

    ... 29 Labor 1 2010-07-01 2010-07-01 true Audit findings. 99.510 Section 99.510 Labor Office of the Secretary of Labor AUDITS OF STATES, LOCAL GOVERNMENTS, AND NON-PROFIT ORGANIZATIONS Auditors § 99.510 Audit... schedule of prior audit findings prepared by the auditee in accordance with § 99.315(b) materially...

  17. 29 CFR 99.400 - Responsibilities.

    Science.gov (United States)

    2010-07-01

    ... 29 Labor 1 2010-07-01 2010-07-01 true Responsibilities. 99.400 Section 99.400 Labor Office of the... Pass-through Entities § 99.400 Responsibilities. (a) Cognizant agency for audit responsibilities... the report submission due date required by § 99.320(a). The cognizant agency for audit may grant...

  18. Turbine-99 unsteady simulations - Validation

    International Nuclear Information System (INIS)

    Cervantes, M J; Andersson, U; Loevgren, H M

    2010-01-01

    The Turbine-99 test case, a Kaplan draft tube model, aimed to determine the state of the art within draft tube simulation. Three workshops were organized on the matter in 1999, 2001 and 2005 where the geometry and experimental data were provided as boundary conditions to the participants. Since the last workshop, computational power and flow modelling have been developed and the available data completed with unsteady pressure measurements and phase resolved velocity measurements in the cone. Such new set of data together with the corresponding phase resolved velocity boundary conditions offer new possibilities to validate unsteady numerical simulations in Kaplan draft tube. The present work presents simulation of the Turbine-99 test case with time dependent angular resolved inlet velocity boundary conditions. Different grids and time steps are investigated. The results are compared to experimental time dependent pressure and velocity measurements.

  19. Turbine-99 unsteady simulations - Validation

    Science.gov (United States)

    Cervantes, M. J.; Andersson, U.; Lövgren, H. M.

    2010-08-01

    The Turbine-99 test case, a Kaplan draft tube model, aimed to determine the state of the art within draft tube simulation. Three workshops were organized on the matter in 1999, 2001 and 2005 where the geometry and experimental data were provided as boundary conditions to the participants. Since the last workshop, computational power and flow modelling have been developed and the available data completed with unsteady pressure measurements and phase resolved velocity measurements in the cone. Such new set of data together with the corresponding phase resolved velocity boundary conditions offer new possibilities to validate unsteady numerical simulations in Kaplan draft tube. The present work presents simulation of the Turbine-99 test case with time dependent angular resolved inlet velocity boundary conditions. Different grids and time steps are investigated. The results are compared to experimental time dependent pressure and velocity measurements.

  20. Forskning i aeroelasticitet EFP-99

    DEFF Research Database (Denmark)

    2000-01-01

    - variabelt omløbstal. Aeroakustisk modellering af støjudbredelse fra vingeprofil. Som en fortsættelse af aktiviteterne underEFP-97 og EFP-98 med afklaring af årsagerne til dobbelt-stall og udarbejdelse af løsningsforslag til afhjælpning af dette fænomen er der under EFP-99 delen af forskningsprogrammet...

  1. Rhodium(III)-Catalyzed [3+2]/[5+2] Annulation of 4-Aryl 1,2,3-Triazoles with Internal Alkynes through Dual C(sp2)-H Functionalization.

    Science.gov (United States)

    Yang, Yuan; Zhou, Ming-Bo; Ouyang, Xuan-Hui; Pi, Rui; Song, Ren-Jie; Li, Jin-Heng

    2015-05-26

    A rhodium(III)-catalyzed [3+2]/[5+2] annulation of 4-aryl 1-tosyl-1,2,3-triazoles with internal alkynes is presented. This transformation provides straightforward access to indeno[1,7-cd]azepine architectures through a sequence involving the formation of a rhodium(III) azavinyl carbene, dual C(sp(2))-H functionalization, and [3+2]/[5+2] annulation. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Anthrobiogeochemical platinum, palladium and rhodium cycles of earth: Emerging environmental contamination

    Science.gov (United States)

    Mitra, Arijeet; Sen, Indra Sekhar

    2017-11-01

    Anthrobiogeochemical cycles have been a subject of scientific research for many decades as they are important for identifying possible sources, sinks, and pathways of an element in the environment. In this study, we quantified global cycles for the platinum group elements (PGE; platinum (Pt), palladium (Pd) and rhodium (Rh)). We quantified the stocks of Pt, Pd, and Rh in Earth's various reservoirs, such as the core, mantle, consolidated crust, biomass, seawater, unconsolidated sediments, and atmosphere, as well as coal and petroleum deposits. We further quantified their fluxes, both natural and anthropogenic, between each reservoir, by identifying the flows across the hydrosphere, geosphere, biosphere, atmosphere and anthroposphere, including from mining activities, fossil fuel and biomass burning, construction activities, soil erosion, human contributions to net primary productivity, riverine transport, aeolian dust movement, primary production, volcanic eruption, sea-salt spray, crustal subduction, crust formation at mid ocean ridges, PGE recovery from recycling processes, and cosmic dust inputs at the Earth's surface. Stocks of PGEs were quantified by multiplying the mass of the reservoir by the average Pt, Pd and Rh concentration in the reservoir, whereas Pt, Pd and Rh fluxes were calculated by multiplying the rate of mass movement across the reservoirs with the Pt, Pd and Rh concentrations of the material. Uncertainties were explicitly incorporated in stock and flow estimations through Monte Carlo simulations. Our calculations reveal that the total surficial anthropogenic Pt, Pd, and Rh mobilizations were greater than their corresponding natural surficial mobilizations. We show that crustal subduction and crustal formation is the most important natural flow and contributes 21-42% of total PGE mobilization. When Earth's surficial processes are considered, soil erosion is the dominant flow for Rh and Pt mobilization, comprising 33% and 13%, respectively, of the

  3. Kinetics and thermodynamics of small molecule binding to pincer-PCP rhodium(I) complexes

    KAUST Repository

    Doherty, Mark D.

    2013-04-15

    The kinetics and thermodynamics of the binding of several small molecules, L (L = N2, H2, D2, and C2H 4), to the coordinatively unsaturated pincer-PCP rhodium(I) complexes Rh[tBu2PCH2(C6H3)CH 2PtBu2] (1) and Rh[tBu 2P(CH2)2(CH)(CH2)2P tBu2] (2) in organic solvents (n-heptane, toluene, THF, and cyclohexane-d12) have been investigated by a combination of kinetic flash photolysis methods, NMR equilibrium studies, and density functional theory (DFT) calculations. Using various gas mixtures and monitoring by NMR until equilibrium was established, the relative free energies of binding of N2, H2, and C2H4 in cyclohexane-d12 were found to increase in the order C 2H4 < N2 < H2. Time-resolved infrared (TRIR) and UV-vis transient absorption spectroscopy revealed that 355 nm excitation of 1-L and 2-L results in the photoejection of ligand L. The subsequent mechanism of binding of L to 1 and 2 to regenerate 1-L and 2-L is determined by the structure of the PCP ligand framework and the nature of the solvent. In both cases, the primary transient is a long-lived, unsolvated species (τ = 50-800 ns, depending on L and its concentration in solution). For 2, this so-called less-reactive form (LRF) is in equilibrium with a more-reactive form (MRF), which reacts with L at diffusion-controlled rates to regenerate 2-L. These two intermediates are proposed to be different conformers of the three-coordinate (PCP)Rh fragment. For 1, a similar mechanism is proposed to occur, but the LRF to MRF step is irreversible. In addition, a parallel reaction pathway was observed that involves the direct reaction of the LRF of 1 with L, with second-order rate constants that vary by almost 3 orders of magnitude, depending on the nature of L (in n-heptane, k = 6.7 × 10 5 M-1 s-1 for L = C2H4; 4.0 × 106 M-1 s-1 for L = N2; 5.5 × 108 M-1 s-1 for L = H2). Experiments in the more coordinating solvent, THF, revealed the binding of THF to 1 to generate 1-THF, and its subsequent reaction with L, as a

  4. Kinetics and thermodynamics of small molecule binding to pincer-PCP rhodium(I) complexes

    KAUST Repository

    Doherty, Mark D.; Grills, David C.; Huang, Kuo-Wei; Muckerman, James T.; Polyansky, Dmitry E.; Van Eldik, Rudi V.; Fujita, Etsuko

    2013-01-01

    The kinetics and thermodynamics of the binding of several small molecules, L (L = N2, H2, D2, and C2H 4), to the coordinatively unsaturated pincer-PCP rhodium(I) complexes Rh[tBu2PCH2(C6H3)CH 2PtBu2] (1) and Rh[tBu 2P(CH2)2(CH)(CH2)2P tBu2] (2) in organic solvents (n-heptane, toluene, THF, and cyclohexane-d12) have been investigated by a combination of kinetic flash photolysis methods, NMR equilibrium studies, and density functional theory (DFT) calculations. Using various gas mixtures and monitoring by NMR until equilibrium was established, the relative free energies of binding of N2, H2, and C2H4 in cyclohexane-d12 were found to increase in the order C 2H4 < N2 < H2. Time-resolved infrared (TRIR) and UV-vis transient absorption spectroscopy revealed that 355 nm excitation of 1-L and 2-L results in the photoejection of ligand L. The subsequent mechanism of binding of L to 1 and 2 to regenerate 1-L and 2-L is determined by the structure of the PCP ligand framework and the nature of the solvent. In both cases, the primary transient is a long-lived, unsolvated species (τ = 50-800 ns, depending on L and its concentration in solution). For 2, this so-called less-reactive form (LRF) is in equilibrium with a more-reactive form (MRF), which reacts with L at diffusion-controlled rates to regenerate 2-L. These two intermediates are proposed to be different conformers of the three-coordinate (PCP)Rh fragment. For 1, a similar mechanism is proposed to occur, but the LRF to MRF step is irreversible. In addition, a parallel reaction pathway was observed that involves the direct reaction of the LRF of 1 with L, with second-order rate constants that vary by almost 3 orders of magnitude, depending on the nature of L (in n-heptane, k = 6.7 × 10 5 M-1 s-1 for L = C2H4; 4.0 × 106 M-1 s-1 for L = N2; 5.5 × 108 M-1 s-1 for L = H2). Experiments in the more coordinating solvent, THF, revealed the binding of THF to 1 to generate 1-THF, and its subsequent reaction with L, as a

  5. Rhodium on tungsten carbide - a new catalyst for reforming CH{sub 4} with CO{sub 2}; Rhodium auf Wolframcarbid - ein neuer Katalysator zum Reformieren von CH{sub 4} mit CO{sub 2}

    Energy Technology Data Exchange (ETDEWEB)

    Voelter, J. [Inst. fuer Angewandte Chemie e.V., Berlin (Germany); Berndt, H. [Inst. fuer Angewandte Chemie e.V., Berlin (Germany); Lietz, G. [Inst. fuer Angewandte Chemie e.V., Berlin (Germany); Preiss, H. [TU Bergakademie Freiberg (Germany). Inst. fuer Energieverfahrenstechnik; Tamme, R. [Deutsche Forschungsanstalt fuer Luft- und Raumfahrt e.V., Stuttgart (Germany). Inst. fuer Technische Thermodynamik

    1997-02-01

    bei 600 bis 700 C wieder als Waerme gewonnen werden. Die vorliegende Arbeit betrifft Katalysatoren zum Reformieren im Solarreceiverreaktor. Bisher wurde eine mit dispersem Rhodium geschwaerzte, makroporoese Schaumkeramik sowohl zur Absorption von Solarenergie wie auch zur Aktivierung der Reformierreaktion benutzt. Dabei ist die Menge Rhodium, die fuer eine effektive Absorption der Strahlung eingesetzt werden muss, viel groesser als die Rh-Menge, die fuer die katalytische Reaktion erforderlich ist. Um hochdisperses Rhodium zu erzeugen, wird die Schaumkeramik aus {alpha}-Al{sub 2}O{sub 3} mit einem Washcoat ({gamma}-Al{sub 2}O{sub 3}) beschichtet. Ziel unserer Untersuchungen war es, Rh nur noch als Katalysator einzusetzen und fuer die Strahlungsabsorption ein anderes geeignetes Material zu verwenden. Es sollte untersucht werden, ob das die Strahlung reflektierende {gamma}-Al{sub 2}O{sub 3} durch einen schwarzen poroesen Katalysatortraeger ersetzt werden kann. Als Material, das auch der thermischen Belastung standhalten kann, kam Wolframcarbid (WC) in Frage. WC ist bisher in der Literatur noch nicht als Traeger fuer einen Metallkatalysator beschrieben worden. Fuer die spezielle Anwendung im Receiverreaktor musste untersucht werden, ob es als ein Traeger zur Dispergierung von Rhodium geeignet ist und wie es sich als Washcoat zur Beschichtung der Schaumkeramik verhaelt. (orig./SR)

  6. Pharmaceutical grade sodium (99mTc) pertechnetate from 99Mo/99mTc-TCM-Autosolex generator

    International Nuclear Information System (INIS)

    Chattopadhyay, Sankha; Barua, Luna; Das, Sujata Saha

    2014-01-01

    Technetium-99m (T 1/2 = 6.02h; 140.51 keV (89%)) is the most useful radioisotope in diagnostic nuclear medicine. More than 80% of all diagnostic procedures done worldwide in nuclear medicine centre are performed with 99m Tc. Worldwide crisis of fission 99 Mo based generator in recent past had put the nuclear medicine fraternity in very harsh situation. In order to have an indigenous solution of this problem, we tried to develop a computer controlled semi automated 99 Mo/ 99m Tc generator using MEK solvent extraction technique, which utilizes abundantly available 99 Mo produced by (n,γ) reaction in BARC reactors. The aim of this work is to provide a more reliable, computer controlled module (TCM- AUTOSOLEX) for the recovery of pharmaceutical grade 99m Tc from low specific activity 99 Mo based on solvent extraction methodology

  7. Concentration of sup(99m)Tc from the eluate of 99Mo-sup(99m)Tc generators

    International Nuclear Information System (INIS)

    Saucedo, T.; Mora, M.; Fraga de Suarez, A.H.; Mitta, A.E.A.

    1976-04-01

    A method is described to concentrate sup(99m)Tc solutions, originated in 99 Mo-sup(99m)Tc generators, independent of its age. The techniques of preparation of the different radiopharmaceuticals used in nuclear medicine are also described. (author) [es

  8. 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.

  9. Lignin and related compounds. VIII. Lignin monomers and dimers from hydrogenolysis of aspen wood using rhodium-on-charcoal catalyst

    Energy Technology Data Exchange (ETDEWEB)

    Sudo, K; Mullord, D J; Pepper, J M

    1981-04-01

    Aspen poplar wood meal has been subjected to catalytic hydrogenolysis in dioxane-water (9:1) at 500 psig initial pressure of hydrogen over a 5% rhodium-on-charcoal catalyst for five hours at 195 plus or minus 5 degrees C. The resulting chloroform-soluble lignin degradation products were separated by cellulose and silica gel column chromatography. The following compounds were isolated and identified: 4-hydroxybenzoic acid, 1-(4-hydroxy-3,4-dimethoxyphenyl)-1-propanone (propiosyringone), 2,2'-dihydroxy-3,3'-dimethoxy- 5,5'-dipropylbiphenyl, 2,3-bis(4-hydroxy-3,5- dimethoxyphenyl)-1-propanol, and a mixture of 3-(4-hydroxy-3,5-dimethoxyphenyl)-2(4-hydroxy- 3-methoxyphenyl)-1-propan and 3-(4-hydroxy-3- methoxyphenyl)-2-(4-hydroxy-3,5-dimethoxyphenyl)-1- propanol. 9 references.

  10. Rhodium(I)-Complexes Catalyzed 1,4-Conjugate Addition of Arylzinc Chlorides to N-Boc-4-pyridone.

    Science.gov (United States)

    Guo, Fenghai; McGilvary, Matthew A; Jeffries, Malcolm C; Graves, Briana N; Graham, Shekinah A; Wu, Yuelin

    2017-05-01

    Rhodium(I)-complexes catalyzed the 1,4-conjugate addition of arylzinc chlorides to N -Boc-4-pyridone in the presence of chlorotrimethylsilane (TMSCl). A combination of [RhCl(C₂H₄)₂]₂ and BINAP was determined to be the most effective catalyst to promote the 1,4-conjugate addition reactions of arylzinc chlorides to N -Boc-4-pyridone. A broad scope of arylzinc reagents with both electron-withdrawing and electron-donating substituents on the aromatic ring successfully underwent 1,4-conjugate addition to N -Boc-4-pyridone to afford versatile 1,4-adducts 2-substituted-2,3-dihydropyridones in good to excellent yields (up to 91%) and excellent ee (up to 96%) when ( S )-BINAP was used as chiral ligand.

  11. A monofunctional platinum complex coordinated to a rhodium metalloinsertor selectively binds mismatched DNA in the minor groove.

    Science.gov (United States)

    Weidmann, Alyson G; Barton, Jacqueline K

    2015-10-05

    We report the synthesis and characterization of a bimetallic complex derived from a new family of potent and selective metalloinsertors containing an unusual Rh-O axial coordination. This complex incorporates a monofunctional platinum center containing only one labile site for coordination to DNA, rather than two, and coordinates DNA nonclassically through adduct formation in the minor groove. This conjugate displays bifunctional, interdependent binding of mismatched DNA via metalloinsertion at a mismatch as well as covalent platinum binding. DNA sequencing experiments revealed that the preferred site of platinum coordination is not the traditional N7-guanine site in the major groove, but rather N3-adenine in the minor groove. The complex also displays enhanced cytotoxicity in mismatch repair-deficient and mismatch repair-proficient human colorectal carcinoma cell lines compared to the chemotherapeutic cisplatin, and it triggers cell death via an apoptotic pathway, rather than the necrotic pathway induced by rhodium metalloinsertors.

  12. Insights into finding a mismatch through the structure of a mispaired DNA bound by a rhodium intercalator

    Science.gov (United States)

    Pierre, Valérie C.; Kaiser, Jens T.; Barton, Jacqueline K.

    2007-01-01

    We report the 1.1-Å resolution crystal structure of a bulky rhodium complex bound to two different DNA sites, mismatched and matched in the oligonucleotide 5′-(dCGGAAATTCCCG)2-3′. At the AC mismatch site, the structure reveals ligand insertion from the minor groove with ejection of both mismatched bases and elucidates how destabilized mispairs in DNA may be recognized. This unique binding mode contrasts with major groove intercalation, observed at a matched site, where doubling of the base pair rise accommodates stacking of the intercalator. Mass spectral analysis reveals different photocleavage products associated with the two binding modes in the crystal, with only products characteristic of mismatch binding in solution. This structure, illustrating two clearly distinct binding modes for a molecule with DNA, provides a rationale for the interrogation and detection of mismatches. PMID:17194756

  13. Rhodium(II) metallopeptide catalyst design enables fine control in selective functionalization of natural SH3 domains.

    Science.gov (United States)

    Vohidov, Farrukh; Coughlin, Jane M; Ball, Zachary T

    2015-04-07

    Chemically modified proteins are increasingly important for use in fundamental biophysical studies, chemical biology, therapeutic protein development, and biomaterials. However, chemical methods typically produce heterogeneous labeling and cannot approach the exquisite selectivity of enzymatic reactions. While bioengineered methods are sometimes an option, selective reactions of natural proteins remain an unsolved problem. Here we show that rhodium(II) metallopeptides combine molecular recognition with promiscuous catalytic activity to allow covalent decoration of natural SH3 domains, depending on choice of catalyst but independent of the specific residue present. A metallopeptide catalyst succeeds in modifying a single SH3-containing kinase at endogenous concentrations in prostate cancer (PC-3) cell lysate. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Regioconvergent and Enantioselective Rhodium-Catalyzed Hydroamination of Internal and Terminal Alkynes: A Highly Flexible Access to Chiral Pyrazoles.

    Science.gov (United States)

    Haydl, Alexander M; Hilpert, Lukas J; Breit, Bernhard

    2016-05-04

    The rhodium-catalyzed asymmetric N-selective coupling of pyrazole derivatives with internal and terminal alkynes features an utmost chemo-, regio-, and enantioselective access to enantiopure allylic pyrazoles, readily available for incorporation in small-molecule pharmaceuticals. This methodology is distinguished by a broad substrate scope, resulting in a remarkable compatability with a variety of different functional groups. It furthermore exhibits an intriguing case of regio-, position-, and enantioselectivity in just one step, underscoring the sole synthesis of just one out of up to six possible products in a highly flexible approach to allylated pyrazoles by emanating from various internal and terminal alkynes. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Characteristics of soft x-ray and extreme ultraviolet (XUV) emission from laser-produced highly charged rhodium ions

    Science.gov (United States)

    Barte, Ellie Floyd; Hara, Hiroyuki; Tamura, Toshiki; Gisuji, Takuya; Chen, When-Bo; Lokasani, Ragava; Hatano, Tadashi; Ejima, Takeo; Jiang, Weihua; Suzuki, Chihiro; Li, Bowen; Dunne, Padraig; O'Sullivan, Gerry; Sasaki, Akira; Higashiguchi, Takeshi; Limpouch, Jiří

    2018-05-01

    We have characterized the soft x-ray and extreme ultraviolet (XUV) emission of rhodium (Rh) plasmas produced using dual pulse irradiation by 150-ps or 6-ns pre-pulses, followed by a 150-ps main pulse. We have studied the emission enhancement dependence on the inter-pulse time separation and found it to be very significant for time separations less than 10 ns between the two laser pulses when using 6-ns pre-pulses. The behavior using a 150-ps pre-pulse was consistent with such plasmas displaying only weak self-absorption effects in the expanding plasma. The results demonstrate the advantage of using dual pulse irradiation to produce the brighter plasmas required for XUV applications.

  16. Rhodium(III)-Catalyzed Activation of C(sp3)-H Bonds and Subsequent Intermolecular Amidation at Room Temperature.

    Science.gov (United States)

    Huang, Xiaolei; Wang, Yan; Lan, Jingbo; You, Jingsong

    2015-08-03

    Disclosed herein is a Rh(III)-catalyzed chelation-assisted activation of unreactive C(sp3)-H bonds, thus enabling an intermolecular amidation to provide a practical and step-economic route to 2-(pyridin-2-yl)ethanamine derivatives. Substrates with other N-donor groups are also compatible with the amidation. This protocol proceeds at room temperature, has a relatively broad functional-group tolerance and high selectivity, and demonstrates the potential of rhodium(III) in the promotive functionalization of unreactive C(sp3)-H bonds. A rhodacycle having a SbF6(-) counterion was identified as a plausible intermediate. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Mixed N-Heterocyclic Carbene-Bis(oxazolinyl)borato Rhodium and Iridium Complexes in Photochemical and Thermal Oxidative Addition Reactions

    Energy Technology Data Exchange (ETDEWEB)

    Xu, Songchen [Ames Laboratory; Manna, Kuntal [Ames Laboratory; Ellern, Arkady [Ames Laboratory; Sadow, Aaron D [Ames Laboratory

    2014-12-08

    In order to facilitate oxidative addition chemistry of fac-coordinated rhodium(I) and iridium(I) compounds, carbene–bis(oxazolinyl)phenylborate proligands have been synthesized and reacted with organometallic precursors. Two proligands, PhB(OxMe2)2(ImtBuH) (H[1]; OxMe2 = 4,4-dimethyl-2-oxazoline; ImtBuH = 1-tert-butylimidazole) and PhB(OxMe2)2(ImMesH) (H[2]; ImMesH = 1-mesitylimidazole), are deprotonated with potassium benzyl to generate K[1] and K[2], and these potassium compounds serve as reagents for the synthesis of a series of rhodium and iridium complexes. Cyclooctadiene and dicarbonyl compounds {PhB(OxMe2)2ImtBu}Rh(η4-C8H12) (3), {PhB(OxMe2)2ImMes}Rh(η4-C8H12) (4), {PhB(OxMe2)2ImMes}Rh(CO)2 (5), {PhB(OxMe2)2ImMes}Ir(η4-C8H12) (6), and {PhB(OxMe2)2ImMes}Ir(CO)2 (7) are synthesized along with ToMM(η4-C8H12) (M = Rh (8); M = Ir (9); ToM = tris(4,4-dimethyl-2-oxazolinyl)phenylborate). The spectroscopic and structural properties and reactivity of this series of compounds show electronic and steric effects of substituents on the imidazole (tert-butyl vs mesityl), effects of replacing an oxazoline in ToM with a carbene donor, and the influence of the donor ligand (CO vs C8H12). The reactions of K[2] and [M(μ-Cl)(η2-C8H14)2]2 (M = Rh, Ir) provide {κ4-PhB(OxMe2)2ImMes'CH2}Rh(μ-H)(μ-Cl)Rh(η2-C8H14)2 (10) and {PhB(OxMe2)2ImMes}IrH(η3-C8H13) (11). In the former compound, a spontaneous oxidative addition of a mesityl ortho-methyl to give a mixed-valent dirhodium species is observed, while the iridium compound forms a monometallic allyl hydride. Photochemical reactions of dicarbonyl compounds 5 and 7 result in C–H bond oxidative addition providing the compounds {κ4-PhB(OxMe2)2ImMes'CH2}RhH(CO) (12) and {PhB(OxMe2)2ImMes}IrH(Ph)CO (13). In 12, oxidative addition results in cyclometalation of the mesityl ortho-methyl similar to 10, whereas the iridium compound reacts with the benzene solvent to give a rare crystallographically characterized cis

  18. Development of inductively coupled plasma atomic emission spectrometry for palladium and Rhodium determination in platinum-based alloy

    International Nuclear Information System (INIS)

    Kovacevic, R.; Todorovic, M.; Manojlovic, D.; Mutic, J.

    2008-01-01

    Inductively coupled plasma atomic emission spectroscopy with internal standardization was applied for the analysis of an in-house reference platinum alloy containing palladium and rhodium (approximately 5% by weight). In order to compensate for variations in signal recovery due to matrix interferences, and therefore to improve the precision, platinum. the major component, was chosen as an internal standard. Quantitative analysis was based on calibration using a set of matrix-matched calibration standards with and without employing the internal standard. These results were compared with those obtained by X-ray fluorescence spectroscopy. The results for both techniques were in a good agreement, although the precision was slightly better in the inductively coupled plasma atomic emission spectroscopy technique, with or without the internal standard

  19. Rhodium-rich silicides RERh{sub 6}Si{sub 4} (RE=La, Nd, Tb, Dy, Er, Yb)

    Energy Technology Data Exchange (ETDEWEB)

    Vosswinkel, Daniel; Poettgen, Rainer [Muenster Univ. (Germany). Inst. fuer Anorganische und Analytische Chemie

    2017-07-01

    Polycrystalline RERh{sub 6}Si{sub 4} (RE=La, Nd, Tb, Dy, Er, Yb) samples can be synthesized by arc-melting of the elements. Single crystals of LaRh{sub 6}Si{sub 4}, NdRh{sub 6}Si{sub 4} and YbRh{sub 6}Si{sub 4} were synthesized from the elements in bismuth fluxes (non-reactive flux medium). The structures were refined on the basis of single-crystal X-ray diffractometer data: LiCo{sub 6}P{sub 4} type, P anti 6m2, a=700.56(3), c=380.55(1) pm, wR2=0.0257, 317 F{sup 2} values, 19 variables for LaRh{sub 6}Si{sub 4}, a=698.4(5), c=377.7(2) pm, wR2=0.0578, 219 F{sup 2} values, 19 variables for NdRh{sub 6}Si{sub 4} and a=696.00(3), c=371.97(1) pm, wR2=0.0440, 309 F{sup 2} values, 19 variables for YbRh{sub 6}Si{sub 4}. The rhodium and silicon atoms build up three-dimensional, covalently bonded [Rh{sub 6}Si{sub 4}]{sup δ-} polyanionic networks with Rh-Si distances ranging from 239 to 249 pm. The rare earth atoms fill larger cavities within channels of these networks and they are coordinated by six silicon and twelve rhodium atoms in the form of hexa-capped hexagonal prisms.

  20. Synthesis and application of Amberlite xad-4 functionalized with alizarin red-s for preconcentration and adsorption of rhodium (III

    Directory of Open Access Journals (Sweden)

    Sid Kalal Hossein

    2012-09-01

    Full Text Available Abstract A new chelating resin was prepared by coupling Amberlite XAD-4 with alizarin red-s through an azo spacer, characterized by infra-red spectroscopy and thermal analysis and studied for Rh(III preconcentration using inductively coupled plasma atomic emission spectroscopy (ICP-AES for rhodium monitoring in the environment. The optimum pH for sorption of the metal ion was 6.5. The sorption capacity was found 2.1 mg/g of resin for Rh(III. A recovery of 88% was obtained for the metal ion with 1.5 M HCl as eluting agent. Kinetic adsorption data were analyzed by adsorption and desorption times of Rh(III on modified resin. Scat chard analysis revealed that the homogeneous binding sites were formed in the polymers. The linear regression equation was Q/C = –1.3169Q + 27.222 (R2 = 0.9239, for Rh were formed in the SPE sorbent,Kd and Qmax for the affinity binding sites were calculated to be 0.76 μmol/mL and 20.67 μmol/g, respectively. The equilibrium data and parameters of Rh(III adsorption on modified resin were analyzed by Langmuir, Freundlich, Temkin and Redlich–Peterson models. The experimental adsorption isotherm was in good concordance with Langmuir and Freundlich models (R2 > 0.998 and based on the Langmuir isotherm the maximum amount of adsorption (qmax was 4.842 mg/g. The method was applied for rhodium ions determination in environmental samples. with high recovery (>80%.

  1. Assessment of sublethal endpoints after chronic exposure of the nematode Caenorhabditis elegans to palladium, platinum and rhodium.

    Science.gov (United States)

    Schertzinger, Gerhard; Zimmermann, Sonja; Grabner, Daniel; Sures, Bernd

    2017-11-01

    The aim of this study was to investigate chronic effects of the platinum-group elements (PGE) palladium (Pd), platinum (Pt) and rhodium (Rh) on the nematode Caenorhabditis elegans. Aquatic toxicity testing was carried out according to ISO 10872 by determining 96 h EC 50 values for sublethal endpoints, including growth, fertility and reproduction. Single PGE standard solutions were used as metal source. Based on the EC 50 values for Pt, reproduction (96 h EC 50  = 497 μg/L) was the most sensitive endpoint followed by fertility (96 h EC 50  = 726 μg/L) and growth (96 h EC 50  = 808 μg/L). For Pd, no precise EC 50 values could be calculated due to bell-shaped concentration response curves, but the 96 h EC 50 for reproduction ranged between 10 and 100 μg/L. Pd and Pt had effects on all endpoints. With raising element concentrations reproduction was inhibited first. At a certain concentration, fertility was also affected, which in turn had an additional effect on reproduction. Growth inhibition can also lead to a loss of fertility if the worms do not reach an appropriate body size to become fertile. Rhodium showed no inhibition of any endpoint between concentrations of 100 to 10,000 μg Rh/L. The results of this study allow the following order of PGE with respect to decreasing toxicity to C. elegans: Pd > Pt » Rh. Copyright © 2017 Elsevier Ltd. All rights reserved.

  2. 29 CFR 99.320 - Report submission.

    Science.gov (United States)

    2010-07-01

    ... 29 Labor 1 2010-07-01 2010-07-01 true Report submission. 99.320 Section 99.320 Labor Office of the Secretary of Labor AUDITS OF STATES, LOCAL GOVERNMENTS, AND NON-PROFIT ORGANIZATIONS Auditees § 99.320... package pursuant to § 99.320(d)(2). (vii) A yes or no statement as to whether the auditee qualified as a...

  3. 14 CFR 99.49 - Hawaii ADIZ.

    Science.gov (United States)

    2010-01-01

    ... 14 Aeronautics and Space 2 2010-01-01 2010-01-01 false Hawaii ADIZ. 99.49 Section 99.49 Aeronautics and Space FEDERAL AVIATION ADMINISTRATION, DEPARTMENT OF TRANSPORTATION (CONTINUED) AIR TRAFFIC... Zones § 99.49 Hawaii ADIZ. (a) Outer boundary. The area included in the irregular octagonal figure...

  4. Diversification of 99Mo/99mTc separation: non–fission reactor production of 99Mo as a strategy for enhancing 99mTc availability.

    Science.gov (United States)

    Pillai, Maroor R A; Dash, Ashutosh; Knapp, Furn F Russ

    2015-01-01

    This paper discusses the benefits of obtaining (99m)Tc from non-fission reactor-produced low-specific-activity (99)Mo. This scenario is based on establishing a diversified chain of facilities for the distribution of (99m)Tc separated from reactor-produced (99)Mo by (n,γ) activation of natural or enriched Mo. Such facilities have expected lower investments than required for the proposed chain of cyclotrons for the production of (99m)Tc. Facilities can receive and process reactor-irradiated Mo targets then used for extraction of (99m)Tc over a period of 2 wk, with 3 extractions on the same day. Estimates suggest that a center receiving 1.85 TBq (50 Ci) of (99)Mo once every 4 d can provide 1.48-3.33 TBq (40-90 Ci) of (99m)Tc daily. This model can use research reactors operating in the United States to supply current (99)Mo needs by applying natural (nat)Mo targets. (99)Mo production capacity can be enhanced by using (98)Mo-enriched targets. The proposed model reduces the loss of (99)Mo by decay and avoids proliferation as well as waste management issues associated with fission-produced (99)Mo.

  5. Process for producing radioactive technetium 99 m

    International Nuclear Information System (INIS)

    Karageozian, H.L.

    1979-01-01

    Active aluminium oxide containing Molybdenum 99 and technetium 99 m is treated with a neutral solvent consisting of water, methylethylketone and ethanol. Technetium 99 m remains on the chromatographic material after drying, in the form of a dry powder. Other aliphatic alcohols can also be utilised. (DG) [de

  6. 45 CFR 99.25 - Evidence.

    Science.gov (United States)

    2010-10-01

    ... 45 Public Welfare 1 2010-10-01 2010-10-01 false Evidence. 99.25 Section 99.25 Public Welfare DEPARTMENT OF HEALTH AND HUMAN SERVICES GENERAL ADMINISTRATION PROCEDURE FOR HEARINGS FOR THE CHILD CARE AND DEVELOPMENT FUND Hearing Procedures § 99.25 Evidence. (a) Testimony. Testimony shall be given orally under...

  7. 21 CFR 99.1 - Scope.

    Science.gov (United States)

    2010-04-01

    ... 21 Food and Drugs 1 2010-04-01 2010-04-01 false Scope. 99.1 Section 99.1 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES GENERAL DISSEMINATION OF INFORMATION ON UNAPPROVED/NEW USES FOR MARKETED DRUGS, BIOLOGICS, AND DEVICES General Information § 99.1 Scope. (a) This...

  8. 7 CFR 27.99 - Values; expression.

    Science.gov (United States)

    2010-01-01

    ... 7 Agriculture 2 2010-01-01 2010-01-01 false Values; expression. 27.99 Section 27.99 Agriculture Regulations of the Department of Agriculture AGRICULTURAL MARKETING SERVICE (Standards, Inspections, Marketing... CLASSIFICATION UNDER COTTON FUTURES LEGISLATION Regulations Price Quotations and Differences § 27.99 Values...

  9. 45 CFR 99.24 - Evidentiary purpose.

    Science.gov (United States)

    2010-10-01

    ... 45 Public Welfare 1 2010-10-01 2010-10-01 false Evidentiary purpose. 99.24 Section 99.24 Public Welfare DEPARTMENT OF HEALTH AND HUMAN SERVICES GENERAL ADMINISTRATION PROCEDURE FOR HEARINGS FOR THE CHILD CARE AND DEVELOPMENT FUND Hearing Procedures § 99.24 Evidentiary purpose. The purpose of the...

  10. 14 CFR 99.41 - General.

    Science.gov (United States)

    2010-01-01

    ... 14 Aeronautics and Space 2 2010-01-01 2010-01-01 false General. 99.41 Section 99.41 Aeronautics and Space FEDERAL AVIATION ADMINISTRATION, DEPARTMENT OF TRANSPORTATION (CONTINUED) AIR TRAFFIC AND GENERAL OPERATING RULES SECURITY CONTROL OF AIR TRAFFIC Designated Air Defense Identification Zones § 99...

  11. 45 CFR 99.13 - Place.

    Science.gov (United States)

    2010-10-01

    ... 45 Public Welfare 1 2010-10-01 2010-10-01 false Place. 99.13 Section 99.13 Public Welfare DEPARTMENT OF HEALTH AND HUMAN SERVICES GENERAL ADMINISTRATION PROCEDURE FOR HEARINGS FOR THE CHILD CARE AND DEVELOPMENT FUND Preliminary Matters-Notice and Parties § 99.13 Place. The hearing shall be held in the city...

  12. 45 CFR 99.2 - Presiding officer.

    Science.gov (United States)

    2010-10-01

    ... 45 Public Welfare 1 2010-10-01 2010-10-01 false Presiding officer. 99.2 Section 99.2 Public Welfare DEPARTMENT OF HEALTH AND HUMAN SERVICES GENERAL ADMINISTRATION PROCEDURE FOR HEARINGS FOR THE CHILD CARE AND DEVELOPMENT FUND General § 99.2 Presiding officer. (a) (1) The presiding officer at a...

  13. 14 CFR 99.5 - Emergency situations.

    Science.gov (United States)

    2010-01-01

    ... 14 Aeronautics and Space 2 2010-01-01 2010-01-01 false Emergency situations. 99.5 Section 99.5 Aeronautics and Space FEDERAL AVIATION ADMINISTRATION, DEPARTMENT OF TRANSPORTATION (CONTINUED) AIR TRAFFIC AND GENERAL OPERATING RULES SECURITY CONTROL OF AIR TRAFFIC General § 99.5 Emergency situations. In an...

  14. 22 CFR 99.3 - [Reserved

    Science.gov (United States)

    2010-04-01

    ... 22 Foreign Relations 1 2010-04-01 2010-04-01 false [Reserved] 99.3 Section 99.3 Foreign Relations DEPARTMENT OF STATE LEGAL AND RELATED SERVICES REPORTING ON CONVENTION AND NON-CONVENTION ADOPTIONS OF EMIGRATING CHILDREN § 99.3 [Reserved] ...

  15. 29 CFR 99.100 - Purpose.

    Science.gov (United States)

    2010-07-01

    ... 29 Labor 1 2010-07-01 2010-07-01 true Purpose. 99.100 Section 99.100 Labor Office of the Secretary of Labor AUDITS OF STATES, LOCAL GOVERNMENTS, AND NON-PROFIT ORGANIZATIONS General § 99.100 Purpose. This part sets forth standards for obtaining consistency and uniformity among Federal agencies for the...

  16. 14 CFR 99.47 - Guam ADIZ.

    Science.gov (United States)

    2010-01-01

    ... 14 Aeronautics and Space 2 2010-01-01 2010-01-01 false Guam ADIZ. 99.47 Section 99.47 Aeronautics and Space FEDERAL AVIATION ADMINISTRATION, DEPARTMENT OF TRANSPORTATION (CONTINUED) AIR TRAFFIC AND GENERAL OPERATING RULES SECURITY CONTROL OF AIR TRAFFIC Designated Air Defense Identification Zones § 99...

  17. 14 CFR 61.99 - Aeronautical experience.

    Science.gov (United States)

    2010-01-01

    ... 14 Aeronautics and Space 2 2010-01-01 2010-01-01 false Aeronautical experience. 61.99 Section 61.99 Aeronautics and Space FEDERAL AVIATION ADMINISTRATION, DEPARTMENT OF TRANSPORTATION (CONTINUED) AIRMEN CERTIFICATION: PILOTS, FLIGHT INSTRUCTORS, AND GROUND INSTRUCTORS Recreational Pilots § 61.99...

  18. 14 CFR 99.3 - Definitions.

    Science.gov (United States)

    2010-01-01

    ... 14 Aeronautics and Space 2 2010-01-01 2010-01-01 false Definitions. 99.3 Section 99.3 Aeronautics and Space FEDERAL AVIATION ADMINISTRATION, DEPARTMENT OF TRANSPORTATION (CONTINUED) AIR TRAFFIC AND GENERAL OPERATING RULES SECURITY CONTROL OF AIR TRAFFIC General § 99.3 Definitions. Aeronautical facility...

  19. 14 CFR 99.15 - Position reports.

    Science.gov (United States)

    2010-01-01

    ... 14 Aeronautics and Space 2 2010-01-01 2010-01-01 false Position reports. 99.15 Section 99.15 Aeronautics and Space FEDERAL AVIATION ADMINISTRATION, DEPARTMENT OF TRANSPORTATION (CONTINUED) AIR TRAFFIC AND GENERAL OPERATING RULES SECURITY CONTROL OF AIR TRAFFIC General § 99.15 Position reports. (a) The...

  20. 29 CFR 99.225 - Sanctions.

    Science.gov (United States)

    2010-07-01

    ... 29 Labor 1 2010-07-01 2010-07-01 true Sanctions. 99.225 Section 99.225 Labor Office of the Secretary of Labor AUDITS OF STATES, LOCAL GOVERNMENTS, AND NON-PROFIT ORGANIZATIONS Audits § 99.225 Sanctions. No audit costs may be charged to Federal awards when audits required by this part have not been...

  1. 14 CFR 99.9 - Radio requirements.

    Science.gov (United States)

    2010-01-01

    ... 14 Aeronautics and Space 2 2010-01-01 2010-01-01 false Radio requirements. 99.9 Section 99.9 Aeronautics and Space FEDERAL AVIATION ADMINISTRATION, DEPARTMENT OF TRANSPORTATION (CONTINUED) AIR TRAFFIC AND GENERAL OPERATING RULES SECURITY CONTROL OF AIR TRAFFIC General § 99.9 Radio requirements. (a) A...

  2. 45 CFR 99.31 - Posthearing briefs.

    Science.gov (United States)

    2010-10-01

    ... 45 Public Welfare 1 2010-10-01 2010-10-01 false Posthearing briefs. 99.31 Section 99.31 Public Welfare DEPARTMENT OF HEALTH AND HUMAN SERVICES GENERAL ADMINISTRATION PROCEDURE FOR HEARINGS FOR THE CHILD CARE AND DEVELOPMENT FUND Posthearing Procedures, Decisions § 99.31 Posthearing briefs. The...

  3. 45 CFR 99.27 - Official transcript.

    Science.gov (United States)

    2010-10-01

    ... 45 Public Welfare 1 2010-10-01 2010-10-01 false Official transcript. 99.27 Section 99.27 Public Welfare DEPARTMENT OF HEALTH AND HUMAN SERVICES GENERAL ADMINISTRATION PROCEDURE FOR HEARINGS FOR THE CHILD CARE AND DEVELOPMENT FUND Hearing Procedures § 99.27 Official transcript. The Department will...

  4. 22 CFR 99.1 - Definitions.

    Science.gov (United States)

    2010-04-01

    ... 22 Foreign Relations 1 2010-04-01 2010-04-01 false Definitions. 99.1 Section 99.1 Foreign Relations DEPARTMENT OF STATE LEGAL AND RELATED SERVICES REPORTING ON CONVENTION AND NON-CONVENTION ADOPTIONS OF EMIGRATING CHILDREN § 99.1 Definitions. As used in this part, the term: (a) Convention means...

  5. 14 CFR 99.12 - [Reserved

    Science.gov (United States)

    2010-01-01

    ... 14 Aeronautics and Space 2 2010-01-01 2010-01-01 false [Reserved] 99.12 Section 99.12 Aeronautics and Space FEDERAL AVIATION ADMINISTRATION, DEPARTMENT OF TRANSPORTATION (CONTINUED) AIR TRAFFIC AND GENERAL OPERATING RULES SECURITY CONTROL OF AIR TRAFFIC General § 99.12 [Reserved] ...

  6. 15 CFR 9.9 - Consumer education.

    Science.gov (United States)

    2010-01-01

    ... 15 Commerce and Foreign Trade 1 2010-01-01 2010-01-01 false Consumer education. 9.9 Section 9.9 Commerce and Foreign Trade Office of the Secretary of Commerce PROCEDURES FOR A VOLUNTARY LABELING PROGRAM FOR HOUSEHOLD APPLIANCES AND EQUIPMENT TO EFFECT ENERGY CONSERVATION § 9.9 Consumer education. The...

  7. 45 CFR 99.23 - Discovery.

    Science.gov (United States)

    2010-10-01

    ... 45 Public Welfare 1 2010-10-01 2010-10-01 false Discovery. 99.23 Section 99.23 Public Welfare... DEVELOPMENT FUND Hearing Procedures § 99.23 Discovery. The Department, the Lead Agency, and any individuals or groups recognized as parties shall have the right to conduct discovery (including depositions) against...

  8. 25 CFR 700.99 - Salvage value.

    Science.gov (United States)

    2010-04-01

    ... 25 Indians 2 2010-04-01 2010-04-01 false Salvage value. 700.99 Section 700.99 Indians THE OFFICE OF NAVAJO AND HOPI INDIAN RELOCATION COMMISSION OPERATIONS AND RELOCATION PROCEDURES General Policies and Instructions Definitions § 700.99 Salvage value. Salvage value means the probable sale price of an...

  9. Accuracy of 99Molybdenum assays in /sup 99m/Technetium solutions

    International Nuclear Information System (INIS)

    Williams, C.C.; Kereiakes, J.G.; Grossman, L.W.

    1981-01-01

    A study was performed to determine the accuracy of 99 Mo measurements using three commercial dose calibrators with their 99 Mo assay shields. One 99 Mo assay shield allowed excessive penetration by the lower energy /sup 99m/Tc photons, resulting in the calibrator's falsely high interpretation of the activity of 99 Mo present in the high-activity /sup 99m/Tc eluates. All three calibrators performed adequately with a National Bureau of Standards 99 Mo standard in equilibrium with /sup 99m/Tc. By using low-activity aliquots of 99 Mo and /sup 99m/Tc, a low-level linearity test was performed. Only one of the calibrators was found to reflect accurately the activity of 99 Mo present under all conditions tested

  10. Formation of acetals under rhodium-catalyzed hydroformylation conditions in alcohols

    NARCIS (Netherlands)

    Diebolt, O.H.; Müller, C.; Cruzeuil, C.; Vogt, D.

    2012-01-01

    Hydroformylation of terminal alkenes in alcohol solvents leads to the selective formation of the corresponding acetals. The Xantphos ligand gave the best results as well as acetal selectivities higher than 99% and linear/branched ratios of up to 52 were obtained. The scope of the reaction was

  11. Remarkable promoting effect of rhodium on the catalytic performance of Ag/Al2O3 for the selective reduction of NO with decane

    International Nuclear Information System (INIS)

    Sato, Kazuhito; Yoshinari, Tomohiro; Kintaichi, Yoshiaki; Haneda, Masaaki; Hamada, Hideaki

    2003-01-01

    The addition of small amounts of rhodium enhanced the activity of Ag/Al 2 O 3 catalyst for the selective reduction of NO with decane at low temperatures. The Rh-promoted Ag/Al 2 O 3 showed its high performance even in the presence of low concentrations of SO 2 . Based on the catalytic activity for elementary reactions, it was suggested that the role of added rhodium is to enhance the reaction between NO x and decane-derived species, leading to NO reduction. Catalyst characterization by UV-Vis spectroscopy indicated that the major silver species on Rh-promoted Ag/Al 2 O 3 is Ag nn δ+ clusters, which would be responsible for the high activity. FT-IR measurements revealed that the formation rate of isocyanate species, which is a major reaction intermediate, is higher on Rh-promoted Ag/Al 2 O 3

  12. (η2,η2-Cycloocta-1,5-diene[2-(diphenylphosphanylmethylpyridine-κ2N,P]rhodium(I tetrafluoridoborate 1,2-dichloroethane monosolvate

    Directory of Open Access Journals (Sweden)

    Siping Wei

    2016-08-01

    Full Text Available The title compound, [Rh(C8H12(C18H16NP]BF4 has been prepared as a precatalyst for applications in rhodium-catalysed additions of carbocyclic acids to terminal alkynes leading to anti-Markovnikov Z-enol esters. Here the triclinic pseudopolymorph of the title compound is presented. In contrast to the earlier reported pseudopolymorph (orthorhombic space group [Wei et al. (2013. Chem. Eur. J. 19, 12067–12076], the triclinic polymorph contains half a molecule of dichloromethane as solvent in the asymmetric unit. The rhodium(I atom exhibits a square-planar coordination. The estimated diffraction contribution of the disordered solvent (a half molecule of dichloroethane per asymmetric unit was subtracted from the observed diffraction data using the SQUEEZE [Spek (2015. Acta Cryst. C71, 9–16] routine in PLATON. The given chemical formula and other crystal data do not take the solvent into account.

  13. 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.

  14. Rhodium-catalyzed [(3+2)+2] carbocyclization of alkynylidenecyclopropanes with substituted allenes: stereoselective construction of tri- and tetrasubstituted exocyclic olefins.

    Science.gov (United States)

    Evans, P Andrew; Negru, Daniela E; Shang, Deju

    2015-04-13

    The development of the stereoselective rhodium-catalyzed [(3+2)+2] carbocyclization of alkynylidenecyclopropanes (ACPs) with substituted allenes is described. This work demonstrates that activated and unactivated allenes preferentially undergo carbometalation at the distal terminus to generate tri- and tetrasubstituted exocyclic olefins with a neutral rhodium catalyst. In addition, this method provides a strategy for the total synthesis of the guaiane family of sesquiterpenes, which are not directly accessible using alkynes as exogenous π-components. Finally, the preparation of the bicyclo[5.4.0]undecane ring system using a homologated ACP tether serves to further illustrate the versatility of this approach. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Method of producing radioactive technetium-99M

    International Nuclear Information System (INIS)

    Karageozian, H.L.

    1979-01-01

    A chromatographic process of producing high purity and high yield radioactive Technetium-99m. A solution containing Molybdenum-99m and Technetium-99m is placed on a chromatographic column and eluted with a neutral solvent system comprising an organic solvent and from about 0.1 to less than about 10% of water or from about 1 to less than about 70% of a solvent selected from the group consisting of aliphatic alcohols having 1 to 6 carbon atoms. The eluted solvent system containing the Technetium-99m is then removed leaving the Technetium-99m as a dry, particulate residue

  16. Rhodium(II)-Catalyzed and Thermally Induced Intramolecular Migration of N-Sulfonyl-1,2,3-triazoles: New Approaches to 1,2-Dihydroisoquinolines and 1-Indanones.

    Science.gov (United States)

    Sun, Run; Jiang, Yu; Tang, Xiang-Ying; Shi, Min

    2016-04-11

    New rhodium(II)-catalyzed or thermally induced intramolecular alkoxy group migration of N-sulfonyl-1,2,3-triazoles has been developed, affording divergent synthesis of 1,2-dihydroisoquinoline and 1-indanone derivatives according to different conditions. N-Sulfonyl keteneimine is the key intermediate for the synthesis of dihydroisoquinoline, whereas the aza-vinyl carbene intermediate results in the formation of 1-indanone. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Oligomeric complexes of some heteroaromatic ligands and aromatic diamines with rhodium and molybdenum tetracarboxylates: 13C and 15N CPMAS NMR and density functional theory studies.

    Science.gov (United States)

    Leniak, Arkadiusz; Kamieński, Bohdan; Jaźwiński, Jarosław

    2015-05-01

    Seven new oligomeric complexes of 4,4'-bipyridine; 3,3'-bipyridine; benzene-1,4-diamine; benzene-1,3-diamine; benzene-1,2-diamine; and benzidine with rhodium tetraacetate, as well as 4,4'-bipyridine with molybdenum tetraacetate, have been obtained and investigated by elemental analysis and solid-state nuclear magnetic resonance spectroscopy, (13)C and (15)N CPMAS NMR. The known complexes of pyrazine with rhodium tetrabenzoate, benzoquinone with rhodium tetrapivalate, 4,4'-bipyridine with molybdenum tetrakistrifluoroacetate and the 1 : 1 complex of 2,2'-bipyridine with rhodium tetraacetate exhibiting axial-equatorial ligation mode have been obtained as well for comparison purposes. Elemental analysis revealed 1 : 1 complex stoichiometry of all complexes. The (15)N CPMAS NMR spectra of all new complexes consist of one narrow signal, indicating regular uniform structures. Benzidine forms a heterogeneous material, probably containing linear oligomers and products of further reactions. The complexes were characterized by the parameter complexation shift Δδ (Δδ = δcomplex  - δligand). This parameter ranged from around -40 to -90 ppm in the case of heteroaromatic ligands, from around -12 to -22 ppm for diamines and from -16 to -31 ppm for the complexes of molybdenum tetracarboxylates with 4,4'-bipyridine. The experimental results have been supported by a density functional theory computation of (15)N NMR chemical shifts and complexation shifts at the non-relativistic Becke, three-parameter, Perdew-Wang 91/[6-311++G(2d,p), Stuttgart] and GGA-PBE/QZ4P levels of theory and at the relativistic scalar and spin-orbit zeroth order regular approximation/GGA-PBE/QZ4P level of theory. Nucleus-independent chemical shifts have been calculated for the selected compounds. Copyright © 2015 John Wiley & Sons, Ltd.

  18. Rhodium-catalyzed NH insertion of pyridyl carbenes derived from pyridotriazoles: a general and efficient approach to 2-picolylamines and imidazo[1,5-a]pyridines.

    Science.gov (United States)

    Shi, Yi; Gulevich, Anton V; Gevorgyan, Vladimir

    2014-12-15

    A general and efficient NH insertion reaction of rhodium pyridyl carbenes derived from pyridotriazoles was developed. Various NH-containing compounds, including amides, anilines, enamines, and aliphatic amines, smoothly underwent the NH insertion reaction to afford 2-picolylamine derivatives. The developed transformation was further utilized in a facile one-pot synthesis of imidazo[1,5-a]pyridines. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Enantioselective Synthesis of Aminodiols by Sequential Rhodium-Catalysed Oxyamination/Kinetic Resolution: Expanding the Substrate Scope of Amidine-Based Catalysis.

    Science.gov (United States)

    Guasch, Joan; Giménez-Nueno, Irene; Funes-Ardoiz, Ignacio; Bernús, Miguel; Matheu, M Isabel; Maseras, Feliu; Castillón, Sergio; Díaz, Yolanda

    2018-03-26

    Regio- and stereoselective oxyamination of dienes through a tandem rhodium-catalysed aziridination-nucleophilic opening affords racemic oxazolidinone derivatives, which undergo a kinetic resolution acylation process with amidine-based catalysts (ABCs) to achieve s values of up to 117. This protocol was applied to the enantioselective synthesis of sphingosine. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. A Rhodium(III) Complex as an Inhibitor of Neural Precursor Cell Expressed, Developmentally Down-Regulated 8-Activating Enzyme with in Vivo Activity against Inflammatory Bowel Disease.

    Science.gov (United States)

    Zhong, Hai-Jing; Wang, Wanhe; Kang, Tian-Shu; Yan, Hui; Yang, Yali; Xu, Lipeng; Wang, Yuqiang; Ma, Dik-Lung; Leung, Chung-Hang

    2017-01-12

    We report herein the identification of the rhodium(III) complex [Rh(phq) 2 (MOPIP)] + (1) as a potent and selective ATP-competitive neural precursor cell expressed, developmentally down-regulated 8 (NEDD8)-activating enzyme (NAE) inhibitor. Structure-activity relationship analysis indicated that the overall organometallic design of complex 1 was important for anti-inflammatory activity. Complex 1 showed promising anti-inflammatory activity in vivo for the potential treatment of inflammatory bowel disease.

  1. Technetium-99 m generator safety simulation

    International Nuclear Information System (INIS)

    Kang, Sang Koo; Kim, Chong Yeal

    2008-01-01

    Technetium ( 99m Tc) is one of the most widely used radioactive isotopes for diagnosis in the world. In general, 99m Tc is produced inside the so called technetium generator where 99Mo decays to 99m Tc. And the generator is usually made out of lead to shield relatively high energy radiation from 99m Tc and 99 Mo. In this paper, a GEANT4 simulation is carried out to test the safety of the 99m Tc generators, taking domestic and Japanese products with radioactivity of 18.50 GBq (500 mCi) for example. According to the domestic regulation on radiation safety, the dose at 10 cm and 100 cm away from the surface of radiation shielder should not exceed 2 mSv∙h -1 and 0.02 mSv∙h -1 , respectively. The simulated dose turned out about only 10% of the limit, satisfying the domestic regulation

  2. A modified {sup 99} Mo- {sup 99} Tc generator on Zirconium molybdo- phosphate-{sup 99} Mo gel. Vol. 3

    Energy Technology Data Exchange (ETDEWEB)

    El-Kolaly, M T; Talaat, H [Labelled Compounds Department, Cairo (Egypt); Botros, N [Radioistspe and Generator Department, Radioisotope Production and Sealed Source Division, Hot Laboratories Center, Atomic Energy Authority, Cairo (Egypt)

    1996-03-01

    A modified {sup 99} Mo - {sup 99} Tc gel generator is described. The new generator is based on the use of zirconium molybdophosphate - {sup 99} Mo gel in which {sup 99} Mo chemically combined in the gel structure, where {sup 99m}Tc can be easily eluted with distilled water or saline. The gel was prepared via chemical reaction between zirconyl chloride and molybdophosphate - {sup 99} Mo solution. The PH of the reaction mixture was adjusted with NaOH. Different gels have been prepared by varying the molar ratio of Mo:Zr:p. The PH and time of digeston on complete gel formation was also investigated in order to optimize the condition of gel preparation. Molybdophosphate {sup 32} P solution was used to determine the phosphorous content in the gel and in the {sup 99m}Tc eluate. The temperature and time of drying of the gel and their effect on {sup 99m}Tc elution efficiency were also studied. From the data obtained, the optimum conditions for routine production of {sup 99} Mo - {sup 99m}Tc generator are presented and discussed. 2 figs., 6 tabs.

  3. 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

  4. Rhodium, iridium and nickel complexes with a 1,3,5-triphenylbenzene tris-MIC ligand. Study of the electronic properties and catalytic activities

    Directory of Open Access Journals (Sweden)

    Carmen Mejuto

    2015-12-01

    Full Text Available The coordination versatility of a 1,3,5-triphenylbenzene-tris-mesoionic carbene ligand is illustrated by the preparation of complexes with three different metals: rhodium, iridium and nickel. The rhodium and iridium complexes contained the [MCl(COD] fragments, while the nickel compound contained [NiCpCl]. The preparation of the tris-MIC (MIC = mesoionic carbene complex with three [IrCl(CO2] fragments, allowed the estimation of the Tolman electronic parameter (TEP for the ligand, which was compared with the TEP value for a related 1,3,5-triphenylbenzene-tris-NHC ligand. The electronic properties of the tris-MIC ligand were studied by cyclic voltammetry measurements. In all cases, the tris-MIC ligand showed a stronger electron-donating character than the corresponding NHC-based ligands. The catalytic activity of the tri-rhodium complex was tested in the addition reaction of arylboronic acids to α,β-unsaturated ketones.

  5. Cyclotron Production of Technetium-99m

    Science.gov (United States)

    Gagnon, Katherine M.

    Technetium-99m (99mTc) has emerged as the most widely used radionuclide in medicine and is currently obtained from a 99Mo/ 99mTc generator system. At present, there are only a handful of ageing reactors worldwide capable of producing large quantities of the parent isotope, 99Mo, and owing to the ever growing shutdown periods for maintenance and repair of these ageing reactors, the reliable supply 99mTc has been compromised in recent years. With an interest in alternative strategies for producing this key medical isotope, this thesis focuses on several technical challenges related to the direct cyclotron production of 99mTc via the 100Mo(p,2n)99mTc reaction. In addition to evaluating the 100Mo(p,2n)99mTc and 100Mo(p,x)99Mo reactions, this work presented the first experimental evaluation of the 100Mo(p,2n) 99gTc excitation function in the range of 8-18 MeV. Thick target calculations suggested that large quantities of cyclotron-produced 99mTc may be possible. For example, a 6 hr irradiation at 500 μA with an energy window of 18→10 MeV is expected to yield 1.15 TBq of 99mTc. The level of coproduced 99gTc contaminant was found to be on par with the current 99Mo/99mTc generator standard eluted with a 24 hr frequency. Highly enriched 100Mo was required as the target material for 99mTc production and a process for recycling of this expensive material is presented. An 87% recovery yield is reported, including metallic target preparation, irradiation, 99mTc extraction, molybdate isolation, and finally hydrogen reduction to the metal. Further improvements are expected with additional optimization experiments. A method for forming structurally stable metallic molybdenum targets has also been developed. These targets are capable of withstanding more than a kilowatt of beam power and the reliable production and extraction of Curie quantities of 99mTc has been demonstrated. With the end-goal of using the cyclotron-produced 99mTc clinically, the quality of the cyclotron

  6. 99Mo production by 100Mo(n,2n)99Mo using accelerator neutrons

    International Nuclear Information System (INIS)

    Sato, Nozomi; Kawabata, Masako; Nagai, Yasuki; Hashimoto, Kazuyuki; Hatsukawa, Yuichi; Saeki, Hideya; Motoishi, Shoji; Kin, Tadahiro; Konno, Chikara; Ochiai, Kentaro; Takakura, Kosuke; Minato, Futoshi; Iwamoto, Osamu; Iwamoto, Nobuyuki; Hashimoto, Shintaro

    2013-01-01

    We proposed a new route to produce a medical radioisotope 99 Mo by the 100 Mo(n,2n) 99 Mo reaction using accelerator neutrons. A high-quality 99 Mo with a minimum level of radioactive waste can be obtained by the proposed reaction. The decay product of 99 Mo, 99m Tc, is separated from 99 Mo by the sublimation method. The proposed route could bring a major breakthrough in the solution of ensuring a constant and reliable supply of 99 Mo. (author)

  7. Altered [99mTc]Tc-MDP biodistribution from neutron activation sourced 99Mo.

    Science.gov (United States)

    Demeter, Sandor; Szweda, Roman; Patterson, Judy; Grigoryan, Marine

    2018-01-01

    Given potential worldwide shortages of fission sourced 99 Mo/ 99m Tc medical isotopes there is increasing interest in alternate production strategies. A neutron activated 99 Mo source was utilized in a single center phase III open label study comparing 99m Tc, as 99m Tc Methylene Diphosphonate ([ 99m Tc]Tc-MDP), obtained from solvent generator separation of neutron activation produced 99 Mo, versus nuclear reactor produced 99 Mo (e.g., fission sourced) in oncology patients for which an [ 99m Tc]Tc-MDP bone scan would normally have been indicated. Despite the investigational [ 99m Tc]Tc-MDP passing all standard, and above standard of care, quality assurance tests, which would normally be sufficient to allow human administration, there was altered biodistribution which could lead to erroneous clinical interpretation. The cause of the altered biodistribution remains unknown and requires further research.

  8. Study of methodologies for quality control of 99Mo used in 99Mo/99mTc generators

    International Nuclear Information System (INIS)

    Said, Daphne de Souza

    2016-01-01

    99m Tc is the most used radionuclide in nuclear medicine. In Brazil, the 99 Mo/ 99m Tc generators are exclusively produced by Radiopharmacy Center at IPEN-CNEN/ SP, by importing 99 Mo from different suppliers. 99 Mo (t 1/2 = 66 h) is a fission product of 235 U and it can have radionuclidic impurities that are prejudicial for human health. For safe use of generators, it is necessary to perform the evaluation of 99 Mo by quality control tests in order to assess if 99 Mo complies with the specifications. The European Pharmacopoeia (EP) presents a monograph for evaluation of the quality of the [ 99 Mo] solution as sodium molybdate,that is used as raw material for 99 Mo/ 99m Tc generators production, including specification parameters (identification, radiochemical purity and radionuclidic purity), analysis methods and limits. However, it has been observed difficulties on the execution and implementation of these methods by the generators producers, with a few literature about this subject, probably due to complexity of the proposed methods. In this work, many quality control parameters of 99 Mo described in the EP monograph were evaluated. Separation methods for 99M o from its radionuclidic impurities by solid phase extraction (SPE) and TLC were studied. After SPE separation, the quantification of metals by ICP-OES to evaluate the percentage of retention of Mo and the percentage of recovery of Ru, Te and Sr using different types of cartridges were proposed, replacing radiotracers use. It was observed that the specific type of SPE cartridge recommended by the EP for separation of 99 Mo presented low recoveries for Ru, compared to other available anion exchange SPE cartridges. 99 Mo samples from different worldwide suppliers were analyzed. It was observed that quantification of 103 Ru in 99 Mo samples with decay time higher than 4 weeks is possible. An alternative method for separation of 131 I from 99 Mo showed promising results by TLC. The quantification of beta and

  9. Development of fission Mo-99 production technology

    Energy Technology Data Exchange (ETDEWEB)

    Park, Jin Ho; Choung, W. M.; Lee, K. I. and others

    2000-05-01

    Fission Mo-99 is the only parent nuclide of Tc-99m, an extremely useful tool for mdeical diagnosis, with an estimated usage of greater than 80% of nuclear medicine applicatons. HEU and LEU targets to optimize in HANARO irradiation condition suggested and designed for domestic production of fission Mo-99. The optimum process conditions are established in each unit process to meet quality requirements of fission Mo-99 products, and the results of performance test in combined process show Mo separation and purification yield of the above 97%. The concept of Tc generator production process is established, and the result of performance test show Tc production yield of 98.4% in Tc generator procuction process. The drafts is prepared for cooperation of technical cooperation and business investment with foreign country. Evaluation on economic feasibility is accompanied for fission Mo-99 and Tc-99m generator production.

  10. Development of fission Mo-99 production technology

    International Nuclear Information System (INIS)

    Park, Jin Ho; Choung, W. M.; Lee, K. I. and others

    2000-05-01

    Fission Mo-99 is the only parent nuclide of Tc-99m, an extremely useful tool for mdeical diagnosis, with an estimated usage of greater than 80% of nuclear medicine applicatons. HEU and LEU targets to optimize in HANARO irradiation condition suggested and designed for domestic production of fission Mo-99. The optimum process conditions are established in each unit process to meet quality requirements of fission Mo-99 products, and the results of performance test in combined process show Mo separation and purification yield of the above 97%. The concept of Tc generator production process is established, and the result of performance test show Tc production yield of 98.4% in Tc generator procuction process. The drafts is prepared for cooperation of technical cooperation and business investment with foreign country. Evaluation on economic feasibility is accompanied for fission Mo-99 and Tc-99m generator production

  11. Problems in clinical practice of domestic supply of 99Mo/99mTc. Considerations on the domestic production of 99Mo/99mTc

    International Nuclear Information System (INIS)

    Yamabayashi, Hisamichi

    2012-01-01

    At present, a bulky import product, 99 Mo supplied in Japan is produced by a nuclear fission method which enables to produce a generator system with no need of commercially preparing 99m Tc-labeled radiopharmaceuticals due to its high specific activity. However its usage of enriched uranium target leads to avoiding the fission method from the option of domestic production. In order to secure the domestic supply of 99 Mo/ 99m Tc, the neutron activation method, aiming to meet about 20% of domestic demand, is under development along with the re-start program of JMTR. Development of various production methods using accelerators are also in progress. In those non-fission methods with reactors or accelerators, rapid and effective procedures for concentration and refinement of 99m Tc solution eluted from 99 Mo of low specific activity are the subjects to be considered for attaining the stable labeling performances. (author)

  12. Determination of Tc-99 in radioactive wastes

    International Nuclear Information System (INIS)

    Rivera S, A. A.

    2015-01-01

    Tc-99 is a fission product and one of the most important radionuclides from the view point of safety assessment for the disposal of radioactive waste because of its long half-life (2.1 x 10 5 years) and high mobility in soil-water systems, if this is released into the environment in significant quantities can concentrate on plants and animals. Tc-99 is a pure beta emitter with a maximum energy of 292 KeV, so their quantification imposes destructive methods to be analyzed by liquid scintillation. Therefore the quantification of Tc-99 in ion exchange resins requires of the mineralization of these and separation of Tc-99 of other radioisotopes present in the resin. Therefore the object of this thesis is to develop a quantification method of Tc-99 content in spent exchange resins. So in order to track the behavior of technetium during digestion exchange resins and radiochemical separation, given its high volatility, in this work the 99m Tc is used. To determine the degree of mineralization of the resins, an analysis was performed by chromatography. Subsequently the method used to determine the percentage of 99m Tc aerosolized during mineralization of resin is described. After the method for the radiochemical separation of 99m Tc is presented by liquid-liquid extraction using crown ether as extractant; for this testing was performed by varying the molarity of the extractant, the ratio of solvent extractant, type of digestion of the resin and the presence of Sr-85, in order to study the behavior of 99m Tc in the presence of this radioisotope. Finally, a track beta spectra of a sample of 99m Tc eluted from a generator 99 Mo/ 99m Tc function of time was performed. (Author)

  13. 14 CFR 99.45 - Alaska ADIZ.

    Science.gov (United States)

    2010-01-01

    ... 14 Aeronautics and Space 2 2010-01-01 2010-01-01 false Alaska ADIZ. 99.45 Section 99.45 Aeronautics and Space FEDERAL AVIATION ADMINISTRATION, DEPARTMENT OF TRANSPORTATION (CONTINUED) AIR TRAFFIC... Zones § 99.45 Alaska ADIZ. The area is bounded by a line from 54°00′N; 136°00′W; 56°57′N; 144°00′W; 57...

  14. Radiopharmaceuticals to 99mTc

    International Nuclear Information System (INIS)

    Leon Cabana, Alba

    1994-01-01

    Studies about 99m Tc had demonstrated that have favorable properties for support diagnostic proceedings in nuclear medicine. This physical and chemical properties used for obtain another radiopharmaceuticals have been employed through re actives kits labelled with Tc 99m . A brief description was given about 99m utilities in diagnostic techniques such as endothelium reticular system,renal and hepatic studies,bone scintillators,cardiac diagnostic and cerebral perfusion

  15. '99Mo/99mTc Generator Based on High Radionuclidic Pure Zirconium Molybdate Gel

    International Nuclear Information System (INIS)

    Amin, M.; Mostafa, M.; El-Amir, M.A.; El-Absy, M.A.; Mohamed, O.I.; Farag, A.B.

    2014-01-01

    99 Mo / 99 mTc radioisotope generator was prepared using in-situ precipitated zirconium molybdate chromatographic column. Zirconium molybdate gel matrix was synthesized by precipitation of neutron activation molybdenum-99 from its solution after variety purification processes to prevent contamination of the 99m Tc eluate with cross-contaminants. Greeter than 82.7 ± 0.4 % of the generated 99m Tc was immediately and reproducible eluted by passing 10 ml 0.9 % NaCl solution through the 1 g zirconium molybdate- 99 Mo column matrix at a flow rate of 0.5 ml / min and room temperature with high chemical, radionuclide ( ≥ 99.9 % 99m Tc) and radiochemical purity ( ≥ 97.7 % % as 99 mTcO 4 - ) with ph value suitable for medical uses.

  16. Separation of rhodium(III and iridium(IV chlorido species by quaternary diammonium centres hosted on silica microparticles

    Directory of Open Access Journals (Sweden)

    A. Majavu

    2017-12-01

    Full Text Available Silica gel was functionalized with six different quaternary diammonium centres derived from ethylenediamine (EDA, tetramethylenediamine (TMDA, hexamethylenediamine (HMDA, 1,8-diaminooctane (OMDA, 1,10-diaminodecane (DMDA and 1,12-diaminododecane (DDMDA to produce Si-QUAT EDA, Si-QUAT TMDA, Si-QUAT HMDA, Si-QUAT OMDA, Si-QUAT DMDA and Si-QUAT DDMDA, respectively. The synthesized silica-based resins were characterized by means of FTIR, XPS, SEM, BET surface area, thermogravimetric analysis and elemental analysis. The materials were used to investigate the adsorption and separation of [RhCl5(H2O]2− and [IrCl6]2−. Batch studies (equilibrium and kinetic studies were conducted to study the adsorption of [RhCl5(H2O]2− and [IrCl6]2− onto Si-QUAT EDA, Si-QUAT TMDA, Si-QUAT HMDA, Si-QUAT OMDA, Si-QUAT DMDA and Si-QUAT DDMDA using single metal aqueous solutions. The Freundlich isotherm confirmed multilayer adsorption and the Freundlich constant (kf displayed the following ascending order; Si-QUAT EDA, Si-QUAT TMDA, Si-QUAT HMDA, Si-QUAT OMDA and Si-QUAT DMDA, and a decrease in kf for Si-QUAT DDMDA. Kinetic studies suggest a pseudo-first order kinetic model. Column studies were also conducted for a binary mixture of these metal ion chlorido species ([RhCl5(H2O]2− and [IrCl6]2−. The iridium loading capacities increased as the carbon spacer between the diammonium centres increased in the following order; Si-QUAT EDA, Si-QUAT TMDA, Si-QUAT HMDA, Si-QUAT OMDA and Si-QUAT DMDA (4.56 mg/g, 6.88 mg/g, 14.63 mg/g, 19.01 mg/g and 29.35 mg/g, respectively. It was observed that the iridium loading capacity of Si-QUAT DDMDA decreased to 8.90 mg/g. This paper presents iridium-specific materials that could be applied in solutions of secondary PGMs sources containing rhodium and iridium as well as in feed solutions from ore processing. Keywords: Silica gel, Quaternary diammonium centres, Rhodium, Iridium, Separation

  17. 99Mo-99mTc production development by (n, γ) reaction

    International Nuclear Information System (INIS)

    Izumo, Hironobu; Nishikata, Kaori; Kimura, Akihiro; Tanimoto, Masataka; Tsuchiya, Kunihiko; Ishihara, Masahiro; Kaminaga, Masanori

    2012-01-01

    The renewed JMTR will be started from the later half of JFY2012, and it is expected to various fields. Supply of 99 Mo in Japan depends only on imports from foreign countries. JAEA has a plan to produce 99 Mo, a parent nuclide of 99m Tc. JMTR will contribute to produce 99 Mo by (n, r) method as one of effective uses of the JMTR. In this paper, outline of the technical study items for production method of 99 Mo- 99m Tc in JMTR will be described. (author)

  18. 42 CFR 9.9 - Facility staffing.

    Science.gov (United States)

    2010-10-01

    ... 42 Public Health 1 2010-10-01 2010-10-01 false Facility staffing. 9.9 Section 9.9 Public Health PUBLIC HEALTH SERVICE, DEPARTMENT OF HEALTH AND HUMAN SERVICES GENERAL PROVISIONS STANDARDS OF CARE FOR... Biosafety Officer must have experience in developing and monitoring biohazards and dealing with biosafety...

  19. 30 CFR 7.99 - Critical characteristics.

    Science.gov (United States)

    2010-07-01

    ... 30 Mineral Resources 1 2010-07-01 2010-07-01 false Critical characteristics. 7.99 Section 7.99 Mineral Resources MINE SAFETY AND HEALTH ADMINISTRATION, DEPARTMENT OF LABOR TESTING, EVALUATION, AND... characteristics. The following critical characteristics shall be inspected or tested on each diesel power package...

  20. 29 CFR 99.305 - Auditor selection.

    Science.gov (United States)

    2010-07-01

    ... 29 Labor 1 2010-07-01 2010-07-01 true Auditor selection. 99.305 Section 99.305 Labor Office of the... Auditor selection. (a) Auditor procurement. In procuring audit services, auditees shall follow the... reviews, and price. (b) Restriction on auditor preparing indirect cost proposals. An auditor who prepares...

  1. 99Mo production for using in the nuclear medicine in 99mTc generators

    International Nuclear Information System (INIS)

    Kurenkov, N.V.; Chuvilin, D.Yu.

    1999-01-01

    The review of methods and advanced technologies for obtaining 99 Mo in nuclear reactors is presented. The 99 Mo isotope is used for preparing the 99m Tc generators, widely applied in nuclear medicine. The reactor method for obtaining 99 Mo is based on the 98 Mo(n, γ) 99 Mo radiation capture reaction and 235 U fission reaction under the effect of the 235 U (n, f) 99 Mo reaction. The results of studies on obtaining 99 Mo on the charged particles accelerators, mainly, on the proton beam and under the effect of photonuclear reaction is also described. The data on the 99 Mo real consumption and forecast for its application in different regions of the world from 1994 up to 2006 are presented [ru

  2. Separation of sup(99m)Tc from 99Mo through a hydrous zirconium oxide column

    International Nuclear Information System (INIS)

    Mengatti, J.

    1980-01-01

    The preparation of 99 Mo-,sup(99m)Tc generator based on the adsorption of 99 Mo on hydrous zirconium oxide column, employing the in exchange technique, is described. The adsorption of 99 Mo on hydrous zirconium oxide (HZO) and the separation of sup(99m)Tc, generated by the decay of 99 Mo with saline solution, are analised. The sup(99m)Tc separation yield, pH of the eluted solution, aspect of the elution curve and the adsorption of 99 Mo on hydrous zirconium oxide calcined at 800 0 C are studied. The chemical and radioactive purities of the final product are analysed and the variation of the elution yield for successive elutions is studied. (Author) [pt

  3. Under used technetium-99m generators

    International Nuclear Information System (INIS)

    Mushtaq, A.

    2001-01-01

    Health care reform truly has become a global issue and it will undoubtedly have a dramatic impact on the future of nuclear medicine business in particular. A bigger concern within the nuclear medicine community is its competitiveness with other modalities and cost effectiveness.Technetium-99m and its generators are playing key role for the majority of diagnostic scans performed in the world today. Availability of ''9''9''mTc can be increased if it is separated from ''9''9Mo after much shorter growth times. After proper planning with the extra ''9''9''mTc, a significant number of scans can be performed or we would be able to order approximately 30% low activity ''9''9Tc generators to fulfill our requirements

  4. Complexes of rhodium (I) and iridium (I) with mixed phosphorus-oxygen and phosphorus-nitrogen glands

    International Nuclear Information System (INIS)

    Meintjies, E.; Singleton, E.; Schmutzler, R.; Sell, M.

    1985-01-01

    A series of four- and five-coordinate rhodium(I) and iridium(I) complexes of the type [MCl(cod)L] and [M(COD)L 2 ] sup(+)[M = Rh or Ir;cod = cycloocta-1,5-diene; L = P(C 6 H 4 OMe-o) 3 ,PMe 2 (C 6 H 4 OMe-o), PPh 2 (C 6 H 4 OMe-o),PPh 2 -(C 6 H 4 NMe 2 -o),PMe(C 6 H 4 OMe-o) 2 and PPh 2 (C 6 H 4 OPr sup(i)-o)] have been prepared from the reactions of [(MCl(cod)) 2 ] (M = Rh or Ir) with the appropriate stoichiometric amount of L in diethyl ether or methanol solution. N.m.r. evidence ( 1 H and 13 C) is presented for non-chelation in the case of the ether ligands and chelation for the amine ligand. Thus, the complexes [MCl(cod)L](L = ether ligand) are mononuclear square-planar species, whereas the amine ligand chelates to the metal atom, and a distorted trigonal bipyramidal structure is proposed. Attempts at displacing cod from the complexes [MCl(cod)L] with these ether and amine ligands, or with small phosphines, were unsuccessful. However, treatment of [MCl(cod)[P(C 6 H 4 OMe-o) 3

  5. Glucose biosensor based on a platinum electrode modified with rhodium nanoparticles and with glucose oxidase immobilized on gold nanoparticles

    International Nuclear Information System (INIS)

    Guo, Xishan; Jian, Jinming; Liang, Bo; Ye, Xuesong; Zhang, Yelei

    2014-01-01

    We have developed an enzymatic glucose biosensor that is based on a flat platinum electrode which was covered with electrophoretically deposited rhodium (Rh) nanoparticles and then sintered to form a large surface area. The biosensor was obtained by depositing glucose oxidase (GOx), Nafion, and gold nanoparticles (AuNPs) on the Rh electrode. The electrical potential and the fractions of Nafion and GOx were optimized. The resulting biosensor has a very high sensitivity (68.1 μA mM −1 cm −2 ) and good linearity in the range from 0.05 to 15 mM (r = 0.989). The limit of detection is as low as 0.03 mM (at an SNR of 3). The glucose biosensor also is quite selective and is not interfered by electroactive substances including ascorbic acid, uric acid and acetaminophen. The lifespan is up to 90 days. It was applied to the determination of glucose in blood serum, and the results compare very well with those obtained with a clinical analyzer. (author)

  6. Preparation, Characterization and NO-CO Redox Reaction Studies over Palladium and Rhodium Oxides Supported on Manganese Dioxide

    Directory of Open Access Journals (Sweden)

    M.S. Fal Desai

    2015-03-01

    Full Text Available The catalytic activity of PdO/MnO2 and Rh2O3/MnO2 is investigated for NO-CO redox reaction. Supported catalysts are prepared by wet impregnation method. Among the tested catalysts, PdO/MnO2 shows higher activity for this reaction. Active metal dispersion on MnO2 enhances the selectivity for N2 over N2O in this reaction. The XRD substantiate the formation of MnO2 monophasic phase. SEM images show the formation of elongated particles. TEM images indicate nano-size rod-like morphologies. An increase in the catalytic activity is observed on supported Pd and Rh oxides on MnO2. Temperature programed desorption studies with NO and CO are undertaken to investigate the catalytic surface studies. © 2015 BCREC UNDIP. All rights reservedReceived: 22nd November 2014; Revised: 31st December 2014; Accepted: 2nd January 2015How to Cite: Fal Desai, M.S., Kunkalekar, R.K., Salker, A.V. (2015. Preparation, Characterization and NO-CO Redox Reaction Studies over Palladium and Rhodium Oxides Supported on Manganese Dioxide. Bulletin of Chemical Reaction Engineering & Catalysis, 10 (1: 98-103. (doi:10.9767/bcrec.10.1.7802.98-103Permalink/DOI: http://dx.doi.org/10.9767/bcrec.10.1.7802.98-103 

  7. 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)

  8. 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.

  9. A Bulky Rhodium Complex Bound to an Adenosine-Adenosine DNA Mismatch: General Architecture of the Metalloinsertion Binding Mode†

    Science.gov (United States)

    Zeglis, Brian M.; Pierre, Valérie C.; Kaiser, Jens T.; Barton, Jacqueline K.

    2009-01-01

    Two crystal structures are determined for Δ-Rh(bpy)2(chrysi)3+ (chrysi = 5,6-chrysenequinone diimine) bound to the oligonucleotide duplex 5′-CGGAAATTACCG-3′ containing two adenosine-adenosine mismatches (italics) through metalloinsertion. Diffraction quality crystals with two different space groups (P3221 and P43212) were obtained under very similar crystallization conditions. In both structures, the bulky rhodium complex inserts into the two mismatched sites from the minor groove side, ejecting the mismatched bases into the major groove. The conformational changes are localized to the mismatched site; the metal complex replaces the mismatched base pair without an increase in base pair rise. The expansive metal complex is accommodated in the duplex by a slight opening in the phosphodiester backbone; all sugars retain a C2′-endo puckering, and flanking base pairs neither stretch nor shear. The structures differ, however, in that in one of the structures, an additional metal complex is bound by intercalation from the major groove at the central 5′-AT-3′ step. We conclude that this additional metal complex is intercalated into this central step because of crystal packing forces. The structures described here of Δ-Rh(bpy)2(chrysi)3+ bound to thermodynamically destabilized AA mismatches share critical features with binding by metalloinsertion in two other oligonucleotides containing different single base mismatches. These results underscore the generality of the metalloinsertion as a new mode of non-covalent binding by small molecules with a DNA duplex. PMID:19374348

  10. Acute and subchronic toxicity of the antitumor agent rhodium (II citrate in Balb/c mice after intraperitoneal administration

    Directory of Open Access Journals (Sweden)

    Marcella L.B. Carneiro

    2015-01-01

    Full Text Available This study aimed to investigate potential acute and subchronic toxicity of rhodium (II citrate in female Balb/c mice after intraperitoneal injections. In the acute test, independent groups received five doses; the highest dose (107.5 mg/kg was equivalent to 33 times that used in our previous reports. The other doses were chosen as proportions of the highest, being 80.7 (75%, 53.8 (50%, 26.9 (25% or 13.8 mg/kg (12.5%. Animals were monitored over 38 days and no severe signs of toxicity were observed, according to mortality, monitoring of adverse symptoms, hematological, biochemical and genotoxic parameters. We conclude that the median lethal dose (LD50 could be greater than 107.5 mg/kg. In the subchronic test, five doses of Rh2Cit (80, 60, 40, 20 or 10 mg/kg were evaluated and injections were conducted on alternate days, totaling five applications per animal. Paclitaxel (57.5 mg/kg and saline solution were controls. Clinical observations, histopathology of liver, lung and kidneys and effects on hematological, biochemistry and genotoxic records indicated that Rh2Cit induced no severe toxic effects, even at an accumulated dose up to 400 mg/kg.We suggest Rh2Cit has great potential as an antitumor drug without presenting acute and subchronic toxicity.

  11. A preliminary study of factors affecting the calibration stability of the iridium versus iridium-40 percent rhodium thermocouple

    Science.gov (United States)

    Ahmed, Shaffiq; Germain, Edward F.; Daryabeigi, Kamran; Alderfer, David W.; Wright, Robert E.

    1987-01-01

    An iridium versus iridium-40% rhodium thermocouple was studied. Problems associated with the use of this thermocouple for high temperature applications (up to 2000 C) were investigated. The metallurgical studies included X-ray, macroscopic, resistance, and metallographic studies. The thermocouples in the as-received condition from the manufacturer revealed large amounts of internal stress caused by cold working during manufacturing. The thermocouples also contained a large amount of inhomogeneities and segregations. No phase transformations were observed in the alloy up to 1100 C. It was found that annealing the thermocouple at 1800 C for two hours, and then at 1400 C for 2 to 3 hours yielded a fine grain structure, relieving some of the strains, and making the wire more ductile. It was also found that the above annealing procedure stabilized the thermal emf behavior of the thermocouple for application below 1800 C (an improvement from + or - 1% to + or - 0.02% within the range of the test parameters used).

  12. A {sup 99m}Tc Generator using PZC for (n,{gamma}) {sup 99}Mo

    Energy Technology Data Exchange (ETDEWEB)

    Adang, H G; Mutalib, A; Suparman, I; Hamid,; Purwadi, B; Pancoko, M; Setiowati, S; Yulianti, V; Robertus, D H [Radioisotope Production Center, National Atomic Energy Agency Kawasan PUSPIPTEK, Serpong (Indonesia)

    1998-10-01

    The high performance adsorbent Poly Zirconium Compound (PZC) was produced by Department of Radioisotope, Japan Atomic Energy Research Institute. This compound was developed as an adsorbent for natural Mo (n,{gamma}) {sup 99}Mo-{sup 99m}Tc Generator. In the present paper, we report the performance of the PZC for a {sup 99m}Tc Generator which was focused on the yield, on elution profile and {sup 99}Mo breakthrough. (author)

  13. Device for neutron flux monitoring in IEA-R1 reactor using rhodium self powered neutron detector; Dispositivo de mapeamento de fluxo de neutron atraves do SPN/Rodio no IEA-R1

    Energy Technology Data Exchange (ETDEWEB)

    Ricci Filho, Walter; Fernando, Alberto de Jesus; Jerez, Rogerio; Tondin, Julio B.M.; Pasqualetto, Hertz [Instituto de Pesquisas Energeticas e Nucleares (IPEN), Sao Paulo, SP (Brazil)

    2000-07-01

    The IEA-R1 reactor has undergone a modernization tio increase its operating power to 5 MW, in order to allow a more efficient production of radioisotopes. The objective of this work is to provide the reactor with flux monitoring device using a rhodium self powered neutron detector. Self powered detectors are rugged miniature devices with are increasingly being used for fixed in core reactor monitoring both for safety purposes and flux mapping. The work presents the results obtained with Rhodium-SPND in several irradiation position inside the reactor core. (author)

  14. Crystal structures of fac-trichloridotris(trimethylphosphane-κPrhodium(III monohydrate and fac-trichloridotris(trimethylphosphane-κPrhodium(III methanol hemisolvate: rhodium structures that are isotypic with their iridium analogs

    Directory of Open Access Journals (Sweden)

    Joseph S. Merola

    2015-02-01

    Full Text Available The crystal structures of two solvates of fac-trichloridotris(trimethylphosphane-κPrhodium(III are reported, i.e. one with water in the crystal lattice, fac-[RhCl3(Me3P3]·H2O, and one with methanol in the crystal lattice, fac-[RhCl3(Me3P3]·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 between the rhodium and iridium compounds, highlighting their isostructural relationships.

  15. 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...

  16. Technetium-99m Sestamibi in Multiple Myeloma

    International Nuclear Information System (INIS)

    Saber, R.A.

    2002-01-01

    Technetium-99m 2-methoxy - isobutyl - isonitrile (99mTc-MIBI) has been reported to be useful in evaluating patients with multiple myeloma. The aim of this study is to evaluate the role of technetium-99m sestamibi (99mTc-MIBI) scintigraphy in the diagnosis. staging and follow-up of patients with multiple myeloma. Methods and Materials: twenty-five consecutive patients with multiple myeloma were studied using 99mTc- MIBI. Of the 25 patients included in this study, 6 were in stage I, II in stage II and 8 in stage III. Anterior and posterior whole-body imaging were obtained 20 min after I.V. injection of 740 MBq of 99mTc-MIBI. Four different MIBI patterns could be described in our patients: physiological (P), diffuse (D), focal (F) and combined diffuse and focal (D+F). All patients in stages II and III as well as 3 patients in stage I were treated with chemotherapy (cyclophosphamide and prednisone) then 99mTc-MlBI scans were repeated after 6 courses. Results: in comparison to conventional X-ray skeletal survey, 99mTc-MIBI scans showed a higher number of myeloma bone disease at diagnosis. All patients with stage II and III multiple myeloma were positive with 99mTc-MlBl scans at diagnosis. The pattern of positive MIBI accumulation was diffuse in 13 (52%) patients, focal in 4 (16%) and combined focal and diffuse in 6 (24%) patients. The intensity of 99mTc-MIBI correlated with disease activity as determined by lactate dehydrogenase (LDH), number of plasma cells in bone marrow and serum electrophoresis. There was a direct correlation between 99mTc-MIBI scan result and clinical outcome of patients following 6 courses of chemotherapy. Sensitivity and specificity of 99mTc-MIBI scintigraphy in detecting myeloma bone lesions were 92% and 90% respectively. Conclusion: 99mTc-MIBI scintigraphy is a reliable method to evaluate bone marrow activity in patients with multiple myeloma and follow-up of myeloma bone lesions

  17. Technetium-99 in the Irish marine environment

    Energy Technology Data Exchange (ETDEWEB)

    Smith, V.; Fegan, M.; Pollard, D.; Long, S.; Hayden, E.; Ryan, T.P

    2001-07-01

    Technetium-99 activity concentrations in seawater and biota from Irish coastal waters are presented. Time series measurements of {sup 99}Tc in seawater and Fucus vesiculosus from the western Irish Sea show that activity concentrations have increased in line with the increase in discharges of {sup 99}Tc from Sellafield. The peak in activity concentrations in both seawater and Fucus vesiculosus occurred in 1997 approximately two years after the peak in {sup 99}Tc discharges. The highest activity concentration recorded in Fucus vesiculosus showed a 29-fold increase over the mean concentration for the period 1988-1993. Technetium-99 activity concentrations were measured in fish, lobsters, prawns, mussels and oysters landed at major fishing ports on the east and northeast coasts of Ireland between 1996 and 1998. Concentration factors for {sup 99}Tc in the brown seaweed Fucus vesiculosus and certain species of fish, crustaceans and molluscs from the Irish Sea were estimated. In general, these concentration factors were higher than those in the literature which were derived from laboratory studies, but agreed well with values which were based on field studies. The mean committed effective doses to Irish typical and heavy seafood consumers due to {sup 99}Tc in the period 1996-1998 were 0.061 and 0.24 {mu}Sv, respectively.

  18. Biodistribution of 99Mo in rats

    International Nuclear Information System (INIS)

    Souza, Raphael Sancho Sisley de; Ribeiro, Bianca da Silva; Dantas, Ana Leticia Almeida; Dantas, Bernardo Maranhao; Bernardo Filho, Mario

    2009-01-01

    The modification of 99 Mo standard metabolism in the presence of MDP would alter the dosimetry of this radionuclide in nuclear medicine patients. Therefore, the objective of this work is to evaluate the influence of MDP in the biodistribution of 99 Mo. Wistar rats were divided in two groups of six animals, being inoculated respectively 99 Molibdate and 99 Mo+MDP via plex ocular. The biodistribution study was carried out after 10 and 120 minutes respectively. The organs were counted with a NaI(Tl) detector. The uptake values did not present significant differences among the groups. An in vitro study through planar chromatography was carried out to determine the affinity between molybdenum and MDP. The results show that 99 Mo has low affinity both to propanone and NaCl-0.9% solution. However, 99 Mo in the presence of MDP presented affinity to NaCl-0.9% solution and low affinity to propanone suggesting that 99 Mo was bound to MDP under the conditions of the experiment. (author)

  19. Development of fission Mo-99 production technology

    Energy Technology Data Exchange (ETDEWEB)

    Park, Jin Ho; Choung, W. M.; Lee, K. I. and others

    2001-05-01

    This R and D project is planed to supply domestic demands of Mo-99 through fission route, and consequently this project will be expected to rise up utilization of HANARO and KAERI's capability for marketing extension into domestic and oversea radiopharmaceutical market. HEU and LEU target types are decided and designed for fission Mo-99 production in domestic. Experimental study of target fabrication technology was performed and developed processing equipments. And conceptual design of target loading/unloading in/from HANARO device are performed. Tracer test of Mo-99 separation and purification process was performed, test results reach to Mo-99 recovery yield above 80% and decontamination factor above 1600. Combined Mo-99 separation and purification process was decided for hot test scheduled from next year, and performance test was performed. Conceptual design for modification of existing hot cell for fission Mo-99 production facility was performed and will be used for detail design. Assumption for the comparison of LEU and HEU target in fission Mo-99 production process were suggested and compared of merits and demerits in view of fabrication technology and economy feasibility.

  20. Development of fission Mo-99 production technology

    International Nuclear Information System (INIS)

    Park, Jin Ho; Choung, W. M.; Lee, K. I. and others

    2001-05-01

    This R and D project is planed to supply domestic demands of Mo-99 through fission route, and consequently this project will be expected to rise up utilization of HANARO and KAERI's capability for marketing extension into domestic and oversea radiopharmaceutical market. HEU and LEU target types are decided and designed for fission Mo-99 production in domestic. Experimental study of target fabrication technology was performed and developed processing equipments. And conceptual design of target loading/unloading in/from HANARO device are performed. Tracer test of Mo-99 separation and purification process was performed, test results reach to Mo-99 recovery yield above 80% and decontamination factor above 1600. Combined Mo-99 separation and purification process was decided for hot test scheduled from next year, and performance test was performed. Conceptual design for modification of existing hot cell for fission Mo-99 production facility was performed and will be used for detail design. Assumption for the comparison of LEU and HEU target in fission Mo-99 production process were suggested and compared of merits and demerits in view of fabrication technology and economy feasibility

  1. sup(99m)Tc-2-mercaptopropionylglycine

    International Nuclear Information System (INIS)

    Saji, Hideo; Odori, Teruo; Morita, Rikushi; Yokoyama, Akira; Tanaka, Hisashi.

    1979-01-01

    Labeling of 2-mercaptopropionylglycine (2-MPG) with sup(99m)Tc, was studied and its chemical characteristics were examined. Further, biliary excretion behavior of this complex was comparatively estimated in mice, rats and rabbits. sup(99m)Tc-2-MPG was rapidly excreted in large quantities into the bile in mice and rats: within 1 hr after injection, 51% of the injected dose was recovered from the bile in rats. On the other hand, the ligand exchange reaction between this complex and penicillamine indicates that a low hydrolyzed sup(99m)Tc species is coordinated with 2-MPG. These results suggest that a low hydrolyzed sup(99m)Tc state is an effective feature in biliary excretion behavior of sup(99m)Tc compounds. Another interesting in vivo behavior of sup(99m)Tc-2-MPG is the difference observed in mice and rabbits: in mice, very high sup(99m)Tc activity is concentrated in the gallbladder and the clearance from tissues other than the gallbladder is rapid, whereas in rabbits, although a rapid and high excretion into the gallbladder is observed, a considerable high sup(99m)Tc activity is retained in the liver and the kidney. One reason for this different in vivo behavior is the low stability of this complex at high dilution: a big animal has the large dilution volume which lead to higher decomposition estimated by the higher liver and kidney retention or the lower bile excretion. In conclusion, studies carried on sup(99m)Tc-2-MPG showed a good biliary excretion behavior but an in vivo unstableness in big animals. (author)

  2. Synthesis and characterization of zirconium molybdates of 99 Mo/99m Tc generators

    International Nuclear Information System (INIS)

    Contreras R, A.; Monroy G, F.; Diaz A, L.V.

    2002-01-01

    The zirconium molybdates are gels which are used as cation exchangers in the production of 99 Mo/ 99m Tc generators. The synthesis method and the characterization of these gels by thermogravimetry, infrared spectroscopy and X-ray diffraction is presented with the purpose of finding which the factors are that influence in the efficiency of the 99m Tc production. The results show that the quantity of molecular water contained in gel, is possibly the cause of variations of the efficiencies of the 99 Mo/ 99m Tc generator. (Author)

  3. Ionic liquid ultrasound assisted dispersive liquid-liquid microextraction method for preconcentration of trace amounts of rhodium prior to flame atomic absorption spectrometry determination

    Energy Technology Data Exchange (ETDEWEB)

    Molaakbari, Elaheh [Chemistry Department, Shahid Bahonar University of Kerman, Kerman (Iran, Islamic Republic of); Young Research Society, Shahid Bahonar University of Kerman, Kerman (Iran, Islamic Republic of); Mostafavi, Ali, E-mail: mostafavi.ali@gmail.com [Chemistry Department, Shahid Bahonar University of Kerman, Kerman (Iran, Islamic Republic of); Afzali, Daryoush [Environment and Nanochemistry Department, Research Institute of Environmental Science, International Center for Science, High Technology and Environmental Science, Kerman (Iran, Islamic Republic of); Mineral Industries Research Center, Shahid Bahonar University of Kerman, Kerman (Iran, Islamic Republic of)

    2011-01-30

    In this article, we consider ionic liquid based ultrasound-assisted dispersive liquid-liquid microextraction of trace amounts of rhodium from aqueous samples and show that this is a fast and reliable sample pre-treatment for the determination of rhodium ions by flame atomic absorption spectrometry. The Rh(III) was transferred into its complex with 2-(5-bromo-2-pyridylazo)-5-diethylamino phenol as a chelating agent, and an ultrasonic bath with the ionic liquid, 1-octyl-3-methylimidazolium bis (trifluoromethylsulfonyl) imide at room temperature was used to extract the analyte. The centrifuged rhodium complex was then enriched in the form of ionic liquid droplets and prior to its analysis by flame atomic absorption spectrometry, 300 {mu}L ethanol was added to the ionic liquid-rich phase. Finally, the influence of various parameters on the recovery of Rh(III) was optimized. Under optimum conditions, the calibration graph was linear in the range of 4.0-500.0 ng mL{sup -1}, the detection limit was 0.37 ng mL{sup -1} (3S{sub b}/m, n = 7) and the relative standard deviation was {+-}1.63% (n = 7, C = 200 ng mL{sup -1}). The results show that ionic liquid based ultrasound assisted dispersive liquid-liquid microextraction, combined with flame atomic absorption spectrometry, is a rapid, simple, sensitive and efficient analytical method for the separation and determination of trace amounts of Rh(III) ions with minimum organic solvent consumption.

  4. First-principle study of silicon cluster doped with rhodium: Rh{sub 2}Si{sub n} (n = 1–11) clusters

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Shuai; Luo, Chang Geng; Li, Hua Yang [Department of Physics, Nanyang Normal University, Nanyang 473061 (China); Lu, Cheng, E-mail: lucheng@calypso.cn [Department of Physics, Nanyang Normal University, Nanyang 473061 (China); State Key Laboratory of Superhard Materials, Jilin University, Changchun 130012 (China); Li, Gen Quan; Lu, Zhi Wen [Department of Physics, Nanyang Normal University, Nanyang 473061 (China)

    2015-06-15

    The geometries, stabilities and electronic properties of rhodium-doped silicon clusters Rh{sub 2}Si{sub n} (n = 1–11) have been systematically studied by using density functional calculations at the B3LYP/GENECP level. The optimized results show that the lowest-energy isomers of Rh{sub 2}Si{sub n} clusters favor three-dimensional structures for n = 2–11. Based on the averaged binding energy, fragmentation energy, second-order energy difference and HOMO-LUMO energy gap, the stabilities of Rh{sub 2}Si{sub n} (n = 1–11) clusters have been analyzed. The calculated results suggest that the Rh{sub 2}Si{sub 6} cluster has the strongest relative stability and the doping with rhodium atoms can reduce the chemical stabilities of Si{sub n} clusters. The natural population and natural electron configuration analysis indicate that there is charge transfer from the Si atoms and 5s orbital of the Rh atoms to the 4d and 5p orbitals of Rh atoms. The analysis of electron localization function reveal that the Si–Si bonds are mainly covalent bonds and the Si–Rh bonds are almost ionic bonds. Moreover, the vertical ionization potential, vertical electron affinity, chemical hardness, chemical potential, vibrational spectrum and polarizability are also discussed. - Highlights: • The geometric structures of Rh{sub 2}Si{sub n} (n = 1–11) clusters are determined. • The stabilities and electronic properties of Rh{sub 2}Si{sub n} clusters are discussed. • The Rh{sub 2}Si{sub 6} cluster has the higher stability than other clusters. • The doped rhodium atoms can reduce the chemical stabilities of Si{sub n} clusters.

  5. Pentamethylcyclopentadienyl-rhodium and iridium complexes containing (N^N and N^O) bound chloroquine analogue ligands: synthesis, characterization and antimalarial properties.

    Science.gov (United States)

    Ekengard, Erik; Kumar, Kamlesh; Fogeron, Thibault; de Kock, Carmen; Smith, Peter J; Haukka, Matti; Monari, Magda; Nordlander, Ebbe

    2016-03-07

    The synthesis and characterization of twenty new pentamethylcyclopentadienyl-rhodium and iridium complexes containing N^N and N^O-chelating chloroquine analogue ligands are described. The in vitro antimalarial activity of the new ligands as well as the complexes was evaluated against the chloroquine sensitive (CQS) NF54 and the chloroquine resistant (CQR) Dd2 strains of Plasmodium falciparum. The antimalarial activity was found to be good to moderate; although all complexes are less active than artesunate, some of the ligands and complexes showed better activity than chloroquine (CQ). In particular, rhodium complexes were found to be considerably more active than iridium complexes against the CQS NF54 strain. Salicylaldimine Schiff base ligands having electron-withdrawing groups (F, Cl, Br, I and NO2) in para position of the salicyl moiety and their rhodium complexes showed good antiplasmodial activity against both the CQS-NF54 and the CQR-Dd2 strains. The crystal structures of (η(5)-pentamethylcyclopentadienyl){N(1)-(7-chloroquinolin-4-yl)-N(2)-(pyridin-2-ylmethyl)ethane-1,2-diamine)} chlororhodium(III) chloride and (η(5)-pentamethylcyclopentadienyl){(4-chloro-2-(((2-((7-chloroquinolin-4-yl)amino)ethyl)imino)methyl)phenolate)}chlororhodium(III) chloride are reported. The crystallization of the amino-pyridyl complex (η(5)-pentamethylcyclopentadienyl){(N(1)-(7-chloroquinolin-4-yl)-N(2)-(pyridin-2-ylmethyl)ethane-1,2-diamine)}chloroiridium(III) chloride in acetone resulted in the formation of the imino-pyridyl derivative (η(5)-pentamethylcyclopentadienyl){(N1-(7-chloroquinolin-4-yl)-N2-(pyridin-2-ylmethylene)ethane-1,2-diamine)}chloroiridium(III) chloride, the crystal structure of which is also reported.

  6. Determination of technetium-99 from complex matrix

    International Nuclear Information System (INIS)

    Lixiong Wang; Lei Tang; Tongzai Yang; Yanqiu Yang; Liang Yang

    2013-01-01

    This paper reports an approach that can be used for efficient separation and determination of 99 Tc (as pertechnetate) after contamination of the environment by nuclear materials. The samples were decomposed by fusion in a mixture of potassium hydroxide and potassium nitrate. After fusion, technetium remains as the pertechnetate anion (TcO 4 - ). The technetium was isolated from the sample by technique combining solvent extraction, anion exchange, then, again, solvent extraction. After separation, 99 Tc was measured by isotope-dilution mass spectrometry with 97 Tc as spike. This method yielded nanogram detection limits for 99 Tc. (author)

  7. Intermediate Energy Activation File (IEAF-99)

    International Nuclear Information System (INIS)

    Korovin, Yu.; Konobeev, A.; Pereslavtsev, P.; Stankovskij, A.; Fischer, U.; Moellendorff, U. von

    1999-01-01

    Nuclear data library IEAF-99, elaborated to study processes of interactions of intermediate energy neutrons with materials in accelerator driven systems, is described. The library is intended for activation and transmutation studies for materials irradiated by neutrons. IEAF-99 contains evaluated neutron induced reaction cross sections at the energies 0-150 MeV for 665 stable and unstable nuclei from C to Po. Approximately 50,000 excitation functions are included in the library. The IEAF-99 data are written in the ENDF-6 format combining MF = 3,6 MT = 5 data recording. (author)

  8. 99mTechnetium labelled Escherichia coli

    International Nuclear Information System (INIS)

    Diniz, S.O.F.; Cardoso, V.N.; Resende, B.M.; Nunan, E.A.; Simal, C.J.R.

    1999-01-01

    Samples of a culture of unlabeled Escherichia coli were incubated with different concentrations of stannous chloride for various time periods. 99m Tc (26.0 MBq) was added to each preparation and the results showed a labelling yield of 98% for E. coli. Since the bacterial viability of 99m Tc-E. coli and E. coli did not show any statistical differences, these results demonstrate that labelling of E. coli with 99m Tc does not modify the bacterial viability, and the radiolabelled bacteria may be a good model to study bacterial translocation

  9. Theoretical study of the adsorption of rhodium on a TiO2 (1 1 0)-1 × 1 surface

    Czech Academy of Sciences Publication Activity Database

    Mutombo, Pingo; Balázs, N.; Majzik, Zsolt; Berkó, A.; Cháb, Vladimír

    2012-01-01

    Roč. 258, č. 10 (2012), s. 4478-4482 ISSN 0169-4332 R&D Projects: GA MŠk MEB040921 Grant - others:Czech-Hungarian Intergovernmental Science&Technology Program(HU) CZ-06/2008 TET Institutional research plan: CEZ:AV0Z10100521 Keywords : density functional theory * rhodium * oxide surface * scanning tunneling spectroscopy Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 2.112, year: 2012 http://www.sciencedirect.com/science/article/pii/S0169433212000232

  10. Influence of epoxy, polytetrafluoroethylene (PTFE) and rhodium surface coatings on surface roughness, nano-mechanical properties and biofilm adhesion of nickel titanium (Ni-Ti) archwires

    Science.gov (United States)

    Asiry, Moshabab A.; AlShahrani, Ibrahim; Almoammar, Salem; Durgesh, Bangalore H.; Kheraif, Abdulaziz A. Al; Hashem, Mohamed I.

    2018-02-01

    Aim. To investigate the effect of epoxy, polytetrafluoroethylene (PTFE) and rhodium surface coatings on surface roughness, nano-mechanical properties and biofilm adhesion of nickel titanium (Ni-Ti) archwires Methods. Three different coated (Epoxy, polytetrafluoroethylene (PTFE) and rhodium) and one uncoated Ni-Ti archwires were evaluated in the present study. Surface roughness (Ra) was assessed using a non-contact surface profilometer. The mechanical properties (nano-hardness and elastic modulus) were measured using a nanoindenter. Bacterial adhesion assays were performed using Streptococcus mutans (MS) and streptococcus sobrinus (SS) in an in-vitro set up. The data obtained were analyzed using analyses of variance, Tukey’s post hoc test and Pearson’s correlation coefficient test. Result. The highest Ra values (1.29 ± 0.49) were obtained for epoxy coated wires and lowest Ra values (0.29 ± 0.16) were obtained for the uncoated wires. No significant differences in the Ra values were observed between the rhodium coated and uncoated archwires (P > 0.05). The highest nano-hardness (3.72 ± 0.24) and elastic modulus values (61.15 ± 2.59) were obtained for uncoated archwires and the lowest nano-hardness (0.18 ± 0.10) and elastic modulus values (4.84 ± 0.65) were observed for epoxy coated archwires. No significant differences in nano-hardness and elastic modulus values were observed between the coated archwires (P > 0.05). The adhesion of Streptococcus mutans (MS) to the wires was significantly greater than that of streptococcus sobrinus (SS). The epoxy coated wires demonstrated an increased adhesion of MS and SS and the uncoated wires demonstrated decreased biofilm adhesion. The Spearman correlation test showed that MS and SS adhesion was positively correlated with the surface roughness of the wires. Conclusion. The different surface coatings significantly influence the roughness, nano-mechanical properties and biofilm adhesion parameters of the archwires. The

  11. A Rhodium(III)-Based Inhibitor of Lysine-Specific Histone Demethylase 1 as an Epigenetic Modulator in Prostate Cancer Cells.

    Science.gov (United States)

    Yang, Chao; Wang, Wanhe; Liang, Jia-Xin; Li, Guodong; Vellaisamy, Kasipandi; Wong, Chun-Yuen; Ma, Dik-Lung; Leung, Chung-Hang

    2017-03-23

    We report herein a novel rhodium(III) complex 1 as a new LSD1 targeting agent and epigenetic modulator. Complex 1 disrupted the interaction of LSD1-H3K4me2 in human prostate carcinoma cells and enhanced the amplification of p21, FOXA2, and BMP2 gene promoters. Complex 1 was selective for LSD1 over other histone demethylases, such as KDM2b, KDM7, and MAO activities, and also showed antiproliferative activity toward human cancer cells. To date, complex 1 is the first metal-based inhibitor of LSD1 activity.

  12. Neutron capture cross sections of rhodium, thulium, iridium, and gold between 0.5 and 3.0 MeV

    International Nuclear Information System (INIS)

    Joly, S.; Voignier, J.; Grenier, G.; Drake, D.M.; Nilsson, L.

    1979-01-01

    Measurements of the neutron capture cross sections of rhodium, thulium, gold, and iridium were carried out in the 0.5- to 3.0-MeV energy range. The cross sections are deduced from the capture gamma-ray spectra recorded by a NaI spectrometer consisting of central and annulus detectors. Time-of-flight techniques are used to improve the signal-to-background ratio. When comparison is possible, the present results are found to be in general agreement with the previous data. 5 figures, 3 tables

  13. Rhodium-Catalyzed Asymmetric N-H Functionalization of Quinazolinones with Allenes and Allylic Carbonates: The First Enantioselective Formal Total Synthesis of (-)-Chaetominine.

    Science.gov (United States)

    Zhou, Yirong; Breit, Bernhard

    2017-12-22

    An unprecedented asymmetric N-H functionalization of quinazolinones with allenes and allylic carbonates was successfully achieved by rhodium catalysis with the assistance of chiral bidentate diphosphine ligands. The high efficiency and practicality of this method was demonstrated by a low catalyst loading of 1 mol % as well as excellent chemo-, regio-, and enantioselectivities with broad functional group compatibility. Furthermore, this newly developed strategy was applied as key step in the first enantioselective formal total synthesis of (-)-chaetominine. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Expedient synthesis of fused azepine derivatives using a sequential rhodium(II)-catalyzed cyclopropanation/1-aza-Cope rearrangement of dienyltriazoles.

    Science.gov (United States)

    Schultz, Erica E; Lindsay, Vincent N G; Sarpong, Richmond

    2014-09-08

    A general method for the formation of fused dihydroazepine derivatives from 1-sulfonyl-1,2,3-triazoles bearing a tethered diene is reported. The process involves an intramolecular cyclopropanation of an α-imino rhodium(II) carbenoid, leading to a transient 1-imino-2-vinylcyclopropane intermediate which rapidly undergoes a 1-aza-Cope rearrangement to generate fused dihydroazepine derivatives in moderate to excellent yields. The reaction proceeds with similar efficiency on gram scale. The use of catalyst-free conditions leads to the formation of a novel [4.4.0] bicyclic heterocycle. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Rhodium(II) Proximity-Labeling Identifies a Novel Target Site on STAT3 for Inhibitors with Potent Anti-Leukemia Activity.

    Science.gov (United States)

    Minus, Matthew B; Liu, Wei; Vohidov, Farrukh; Kasembeli, Moses M; Long, Xin; Krueger, Michael J; Stevens, Alexandra; Kolosov, Mikhail I; Tweardy, David J; Sison, Edward Allan R; Redell, Michele S; Ball, Zachary T

    2015-10-26

    Nearly 40 % of children with acute myeloid leukemia (AML) suffer relapse arising from chemoresistance, often involving upregulation of the oncoprotein STAT3 (signal transducer and activator of transcription 3). Herein, rhodium(II)-catalyzed, proximity-driven modification identifies the STAT3 coiled-coil domain (CCD) as a novel ligand-binding site, and we describe a new naphthalene sulfonamide inhibitor that targets the CCD, blocks STAT3 function, and halts its disease-promoting effects in vitro, in tumor growth models, and in a leukemia mouse model, validating this new therapeutic target for resistant AML. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Crystal structures of bis[2-(pyridin-2-ylphenyl-κ2N,C1]rhodium(III complexes containing an acetonitrile or monodentate thyminate(1− ligand

    Directory of Open Access Journals (Sweden)

    Mika Sakate

    2016-04-01

    Full Text Available The crystal structures of bis[2-(pyridin-2-ylphenyl]rhodium(III complexes with the metal in an octahedral coordination containing chloride and acetonitrile ligands, namely (OC-6-42-acetonitrilechloridobis[2-(pyridin-2-ylphenyl-κ2N,C1]rhodium(III, [RhCl(C11H8N2(CH3CN] (1, thyminate(1− and methanol, namely (OC-6-42-methanol(5-methyl-2,4-dioxo-1,2,3,4-tetrahydropyrimidin-1-ido-κN1bis[2-(pyridin-2-ylphenyl-κ2N,C1]rhodium(III, [Rh(C11H8N2(C5H5N2O2(CH3OH]·CH3OH·0.5H2O (2, and thyminate(1− and ethanol, namely (OC-6-42-ethanol(5-methyl-2,4-dioxo-1,2,3,4-tetrahydropyrimidin-1-ido-κN1bis[2-(pyridin-2-ylphenyl-κ2N,C1]rhodium(III, [Rh(C11H8N2(C5H5N2O2(C2H5OH]·C2H5OH (3, are reported. The acetonitrile complex, 1, is isostructural with the IrIII analog. In complexes 2 and 3, the monodeprotonated thyminate (Hthym− ligand coordinates to the RhIII atom through the N atom, and the resulting Rh—N(Hthym bond lengths are relatively long [2.261 (2 and 2.252 (2 Å for 2 and 3, respectively] as compared to the Rh—N bonds in the related thyminate complexes. In each of the crystals of 2 and 3, the complexes are linked via a pair of intermolecular N—H...O hydrogen bonds between neighbouring Hthym− ligands, forming an inversion dimer. A strong intramolecular O—H...O hydrogen bond between the thyminate(1− and alcohol ligands in mutually cis positions to each other is also observed.

  17. Rhodium-Catalyzed Denitrogenative [3+2] Cycloaddition: Access to Functionalized Hydroindolones and the Framework of Montanine-Type Amaryllidaceae Alkaloids.

    Science.gov (United States)

    Yang, Hongjian; Hou, Shengtai; Tao, Cheng; Liu, Zhao; Wang, Chao; Cheng, Bin; Li, Yun; Zhai, Hongbin

    2017-09-18

    Rhodium-catalyzed denitrogenative [3+2] cycloaddition of 1-sulfonyl-1,2,3-triazoles with cyclic silyl dienol ethers has been developed for the synthesis of functionalized hydroindolones or their corresponding silyl ethers. The present method has been employed to construct synthetically valuable bicyclo[3.3.1]alkenone derivatives and pyrrolidine-ring-containing bicyclic indole compounds. As a further synthetic application, a stereoselective synthesis of 5,11-methanomorphanthridin-3-one, which shares a key skeleton with montanine-type Amaryllidaceae alkaloids has been achieved by using this chemistry. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Uses of Tc99m complexes

    International Nuclear Information System (INIS)

    Kubiatowicz, D.O.; Bolles, T.F.

    1978-01-01

    The invention deals with the use of a complex of the radioactive metastable isotope Tcsup(99m) together with water-soluble mercaptane for the preparation of a parenterally administered renal diagnostic agent. (VJ/orig.) [de

  19. Transmutation of Tc-99 in fission reactors

    International Nuclear Information System (INIS)

    Kloosterman, J.L.; Li, J.M.

    1994-12-01

    Transmutation of Tc-99 in three different types of fission reactors is considered: A heavy water reactor, a fast reactor and a light water reactor. For the first type a CANDU reactor was chosen, for the second one the Superphenix reactor, and for the third one a PWR. The three most promising Tc-99 transmuters are the fast reactor with a moderated subassembly in the inner core, a fast reactor with a non-moderated subassembly in the inner core, and a heavy water reactor with Tc-99 target pins in the moderator between the fuel bundles. Transmutation half lives of 15 to 25 years can be achieved, with yearly transmuted Tc-99 masses of about 100 kg at a thermal reactor power of about 3000 MW. (orig.)

  20. Technetium-99m-human fibrinogen

    International Nuclear Information System (INIS)

    Wong, D.W.; Mishkin, F.S.

    1975-01-01

    Exogenous fibrinogen has been successfully labeled with /sup 99m/Tc using a modified electrolytic method. The exact labeling mechanism has not been determined. Experimental data suggest that the labeling process of /99m/Tc-fibrinogen is quite similar to that of /sup 99m/Tc-human serum albumin as reported earlier by Benjamin. Technetium-99m-fibrinogen is stable in human plasma or in 1 percent buffered human serum albumin. A binding efficiency of 76 percent has been achieved with approximately 25 percent clottable protein. The entire labeling procedure requires less than 1 hr of preparation time. This short labeling time in a closed system may allow development of a practical method for labeling autologous fibrinogen, thus eliminating the risk of hepatitis transmission. (U.S.)

  1. Labeling of creatinine with technetium-99m

    Energy Technology Data Exchange (ETDEWEB)

    Yurt Lambrecht, F. [Ege Univ., Bornova, Izmir (Turkey). Dept. of Nuclear Applications, Inst. of Nuclear Sciences; Durkan, K. [Dokuz Eylul Univ., Buca, Izmir (Turkey). Chemistry Technicianship Program, Izmir Vocational School; Soylu, A. [Dokuz Eylul Univ., Narlidere, Izmir (Turkey). Dept. of Pediatrics, Medical Faculty

    2004-07-01

    Creatinine is a clinically important index of renal glomerular filtration rate. Urine creatinine levels can be used as a screening test to evaluate kidney function or can be part of the creatinine clearance test. In case of kidney dysfunction or muscle disorders the creatinine concentration in serum/plasma may rise to a higher value than in healthy body. Technetium- 99m has been used in nuclear medicine and in biomedical research to label molecular and cellular structures employed as radiotracers. {sup 99m}Tc is utilized to label molecules and cells, used as radiopharmaceuticals, and also to label biological species. It presents many desirable characteristics. SnCl{sub 2} method is frequently used as a reducing agent in the {sup 99m}Tc- labeling process. Creatinine metabolism might be investigated by using labeled {sup 99m}Tc- creatinine in healthy or uremic rats. (orig.)

  2. Molybdenum-99 supply: a global issue

    International Nuclear Information System (INIS)

    Cote, R.V.

    2011-01-01

    This article discusses the global supply of Molybdenum 99 used in nuclear medicine. Following a disruption in supplies of isotopes in the last few years, a Canadian expert panel assessed the most viable options for securing a sustainable supply of Technitium 99 over the medium to long term. The general recommendations were to strive for diversity and redundancy throughout the supply chain, leverage multi-use infrastructure, continue with international coordination and seek processing standardization within North America.

  3. Radiation decomposition of technetium-99m radiopharmaceuticals

    International Nuclear Information System (INIS)

    Billinghurst, M.W.; Rempel, S.; Westendorf, B.A.

    1979-01-01

    Technetium-99m radiopharmaceuticals are shown to be subject to autoradiation-induced decomposition, which results in increasing abundance of pertechnetate in the preparation. This autodecomposition is catalyzed by the presence of oxygen, although the removal of oxygen does not prevent its occurrence. The initial appearance of pertechnetate in the radiopharmaceutical is shown to be a function of the amount of radioactivity, the quantity of stannous ion used, and the ratio of /sup 99m/Tc to total technetium in the preparation

  4. Distribution of technetium-99 in surface soils

    International Nuclear Information System (INIS)

    Tagami, Keiko; Uchida, Shigeo

    2000-01-01

    Technetium-99 ( 99 Tc) is an important fission product which has been widely distributed in the environment as a result of fallout from nuclear weapons testing. In order to improve our understanding of the behavior of 99 Tc in the environment, it is essential that we obtain more reliable information on the levels, distribution and fate of 99 Tc in the environment. In this study, the concentration of global fallout 99 Tc, in several surface soil samples (0 - 20 cm) collected in Japan, were determined by ICP-MS (inductively coupled plasma mass spectroscopy). The range of 99 Tc in rice paddy field, upland field and other soils determined in this study were 0.006 - 0.11, 0.004 - 0.008 and 0.007 - 0.02 Bq kg -1 dry, respectively. 137 Cs was used as a comparative indicator for the source of 99 Tc, because the fission yields from 235 U and 239 Pu were about the same (ca. 6%) for the two isotopes, and the behavior and distribution of 137 Cs in the environment is reasonably well understood. The 137 Cs contents in rice paddy field, upland field and other soils range between 1.7 - 28, 1.4 - 9.2 and -1 dry, respectively. The activity ratios of 99 Tc/ 137 Cs in all soil samples were (0.6 - 5.9) x 10 -3 . Most of the measured ratios were one order of magnitude higher than the theoretical one obtained from fission. However, this ratio in soil, presumably depends on not only both the characteristic of radionuclides and the soil, but also on their contents after deposition to the earth's surface. (author)

  5. Labelled Preformed liposomes with 99MTC-DTPA, 99 MTC-ECD, 99MTC-MDP and 99MTC-MIBI : Labelling procedures and stability studies

    International Nuclear Information System (INIS)

    Savio, E.O.; Teran, M.A.; Vales, M.E.; Frier, M.

    2004-01-01

    Liposomes labelled with gamma e miters like 99mTc, can be used for scintigraphic imaging to non-invasively track and quantify the distribution of liposomes in the body. In vitro studies were done to choose a suitable radiopharmaceutical (RF) to be attached to performed liposomes. 99mTc-Complexes (DTPA, ECD, MDP, MIBI) were used to label collagen liposomes. Commercial kits were labelled with 99mTc04-(TechnoNuclear). Quality controls of the RF were performed. Collagen liposomes suspended in saline 0.9% were incubated at 4.25.37 and 60 for 30 min. Efficiency of the labelling procedure was determined by gel filtration using Sephadex G25 (Pharmacia) and NaC10.9%. Samples of 100mL (74MBq), were seeded and fractions of 0.5mL were colleted and measured in an ionisation chamber (Capintec CRC). Stability of the labelled liposomes was assessed incubating 0.5mL, of the suspension with 1mL of human serum during 30 min at 37 . Dialysis was performed using dialysis bags of 64 K pore size and NaCI 0.9% at room temperature. Samples of the saline bath were collected at 30.60 and 90 min. and measured in a solid scintillation counter Ortec.Liposomes labelled with 99mTc-DTPA and 99mTcMIBI showed a labelling efficiency of 80%; liposomes incubated with 99mTc-MDP were labelled in a 50% and 99mTc-ECD did not bind to liposomes in the conditions of study. Incubation of labelled liposomes with human serum showed 50% of strong binding to the plasmatic proteins for 99mTc-DTPA but low values (5%) for the other specimens. Labelled liposomes were achieved, with different RF, showing a suitable in vitro stability to perform in vivo studies

  6. Improved processes of molybdenum-99 production

    International Nuclear Information System (INIS)

    Dadachova, K.; La Riviere, K.; Anderon, P.

    1997-01-01

    Two improved processes of Molybdenum-99 production have been developed at ANSTO on laboratory scale. The first one allows to purify Mo of natural isotopic composition from tungsten impurities by using preferential adsorption of tungsten on hydrated tin(IV) oxide SnO 2 x nH 2 O before irradiation in the nuclear reactor. Mo-99 obtained via this route can be used for production of i nstant Tc-99m. As the starting material MoO 3 contains considerable amounts of tungsten impurity (W > 60 ppm), 5-7 days irradiation results in generation of W-188 in amounts sufficient to contaminate the final Tc-99m product with rhenium-188 (Re-188, 16.8 h half-life) - radioactive daughter of W-188. To overcome this problem, a method of MoO 3 purification from W, based on preferential adsorption of W by hydrated tin (IV) oxide has been developed. The contents of W in MoO 3 purified by this technique became 3 and retaining of Mo-99 on a large alumina column. Mo-99 is stripped off the column with 200 mL 1M NH 4 OH followed by loading this solution onto the AG 1x8 column. The next steps are different for each version of separation process

  7. Development of 99mTc extraction techniques from 99Mo by (n,γ) reaction

    International Nuclear Information System (INIS)

    Kimura, Akihiro; Hori, Naohiko; Tsuchiya, Kunihiko; Ishihara, Masahiro; Yamabayashi, Hisamichi; Tanase, Masakazu; Fujisaki, Saburo; Sato, Yuichi

    2010-11-01

    Investigation of production method of 99 Mo by (n, γ) reaction, where the processing is relatively simple and generating less amount of radioactive waste, is conducted in the Neutron Irradiation and Testing Reactor Center. The 99 Mo is adsorbed to highly efficient adsorbent PZC after neutron irradiation and 99m Tc is eluted. However, radioactivity concentration of the 99m Tc solution obtained from PZC column loaded with 99 Mo derived by (n, γ) method is lower than that obtained from alumina column with 99 Mo by (n, f) method due to extremely low specific activity of (n, f) 99 Mo. Therefore, it is necessary to develop technique for increasing the amount of 99 Mo and the 99m Tc solution of high radioactivity concentration (minimum: 1Ci/ cm 3 ). In this study, the preliminary fabrication tests using high density MoO 3 pellets were carried out to increase the production of 99 Mo. The method of concentrating 99m Tc solution through solvent extraction with MEK was investigated and a device for this concentration process was also developed. In the preliminary tests of the MoO 3 pellets, the pellets having high density were successfully fabricated by the SPS method. Additionally, it was ascertained that the pellets can be dissolved with 6M-NaOH solution completely. The test for 99 Mo adsorption followed by 99m Tc elution using PZC was carried out. As the result, amount of Mo adsorbed to 1g-PZC was about 250mg, and 99m Tc yield was about 80%. In the concentration test using Re solution instead of 99m Tc solution, it was ascertained that the concentration efficiency is higher than 80% of the theoretical value. A concentration device for 99m Tc solution could be realized based on the method employed in the present experiments. The outcomes of development of 99m Tc extraction techniques from 99 Mo by (n,γ) reaction was reviewed in this paper, and the contents were presented in the 3rd International Symposium on Material Test Reactors. (author)

  8. Diversification in the Supply Chain of (99)Mo Ensures a Future for (99m)Tc.

    Science.gov (United States)

    Cutler, Cathy S; Schwarz, Sally W

    2014-07-01

    The uncertain availability of (99m)Tc has become a concern for nuclear medicine departments across the globe. An issue for the United States is that currently it is dependent on a supply of (99m)Tc (from (99)Mo) that is derived solely by production outside the United States. Since the United States uses half the world's (99)Mo production, the U.S. (99)Mo supply chain would be greatly enhanced if a producer were located within the United States. The fragility of the old (99)Mo supply chain is being addressed as new facilities are constructed and new processes are developed to produce (99)Mo without highly enriched uranium. The conversion to low-enriched uranium is necessary to minimize the potential misuse of highly enriched uranium in the world for nonpeaceful means. New production facilities, new methods for the production of (99)Mo, and a new generator elution system for the supply of (99m)Tc are currently being pursued. The progress made in all these areas will be discussed, as they all highlight the need to embrace diversity to ensure that we have a robust and reliable supply of (99m)Tc in the future. © 2014 by the Society of Nuclear Medicine and Molecular Imaging, Inc.

  9. An Unusual Ligand Coordination Gives Rise to a New Family of Rhodium Metalloinsertors with Improved Selectivity and Potency

    Science.gov (United States)

    2015-01-01

    Rhodium metalloinsertors are octahedral complexes that bind DNA mismatches with high affinity and specificity and exhibit unique cell-selective cytotoxicity, targeting mismatch repair (MMR)-deficient cells over MMR-proficient cells. Here we describe a new generation of metalloinsertors with enhanced biological potency and selectivity, in which the complexes show Rh–O coordination. In particular, it has been found that both Δ- and Λ-[Rh(chrysi)(phen)(DPE)]2+ (where chrysi =5,6 chrysenequinone diimmine, phen =1,10-phenanthroline, and DPE = 1,1-di(pyridine-2-yl)ethan-1-ol) bind to DNA containing a single CC mismatch with similar affinities and without racemization. This is in direct contrast with previous metalloinsertors and suggests a possible different binding disposition for these complexes in the mismatch site. We ascribe this difference to the higher pKa of the coordinated immine of the chrysi ligand in these complexes, so that the complexes must insert into the DNA helix with the inserting ligand in a buckled orientation; spectroscopic studies in the presence and absence of DNA along with the crystal structure of the complex without DNA support this assignment. Remarkably, all members of this new family of compounds have significantly increased potency in a range of cellular assays; indeed, all are more potent than cisplatin and N-methyl-N′-nitro-nitrosoguanidine (MNNG, a common DNA-alkylating chemotherapeutic agent). Moreover, the activities of the new metalloinsertors are coupled with high levels of selective cytotoxicity for MMR-deficient versus proficient colorectal cancer cells. PMID:25254630

  10. Technetium-99m ceftizoxime kit preparation

    International Nuclear Information System (INIS)

    Diniz, Simone Odilia Fernandes; Siqueira, Cristiano Ferrari; Nelson, David Lee; Cardoso, Valbert Nascimento

    2005-01-01

    The aim of this work was to prepare a kit of 99 m Tc-ceftizoxime ( 99m Tc-CFT), with stability and biological activity preserved, able to identify a septic focus (E. coli) in the experimental infection model in rats. The preparation of the CFT kit involved the use of lyophilized solutions containing the antibiotic ceftizoxime and the sodium dithionite reducing agent (6.0 mg/m L). After lyophilization, the kit was reconstituted with 1.0 mL of sodium 99m Tc pertechnetate solution (Na 99m Tc O 4- ) with an activity of 370 MBq. The solution was boiled for 10 min and filtered through a cellulose ester filter. The labeling efficiency was on the order of 92%, remaining stable for six hours and the kit remained stable for two months. The biological activity of the 99m Tc-CFT was evaluated by diffusion in agar impregnated with E.coli and S. aureus. Seven Wistar rats, weighing from 200 to 250 g, were used for the development of the septic focus. After 24 hours from the induction of the infectious site (E.coli), the animals were anesthetized and 0.1 mL of 99m Tc-CFT (37 MBq) was injected into the tail veins of the animals. The images were obtained with a gamma camera one, two and six hours after injection and the regions of interest (ROIs) were calculated. The diameters of the inhibition halos for 99 m Tc-CFT were 27.16 ± 0.23 and 27.17 ± 0.20 for S.aureus and E.coli, respectively, while those for the unlabeled CFT were 30.4 ± 0.33 and 29.43 ± 0.26, respectively. The results for the biodistribution of 99m Tc-CFT in infected animals furnished a ratio of 1.97 ± 0.31, 2.10 ± 0.42 and 2.01 ± 0.42 for cpm-target/cpm-no target for the one, two and six-hour periods, respectively. The images showed a clear uptake of labeled antibiotic ( 99m Tc-CFT) by the infectious site during the experiment. The results attest to the viability of producing a kit with 99m technetium-labeled ceftizoxime for the investigation of infectious processes. (author)

  11. Technetium-99m ceftizoxime kit preparation

    Energy Technology Data Exchange (ETDEWEB)

    Diniz, Simone Odilia Fernandes; Siqueira, Cristiano Ferrari; Nelson, David Lee; Cardoso, Valbert Nascimento [Minas Gerais Univ. Federal, Belo Horizonte, MG (Brazil). Faculdade de Farmacia]. E-mail: simone@farmacia.ufmg.br; Martin-Comin, Josep [Bellvitge Univ., Barcelona (Spain)

    2005-10-15

    The aim of this work was to prepare a kit of {sup 99}m Tc-ceftizoxime ({sup 99m} Tc-CFT), with stability and biological activity preserved, able to identify a septic focus (E. coli) in the experimental infection model in rats. The preparation of the CFT kit involved the use of lyophilized solutions containing the antibiotic ceftizoxime and the sodium dithionite reducing agent (6.0 mg/m L). After lyophilization, the kit was reconstituted with 1.0 mL of sodium {sup 99m} Tc pertechnetate solution (Na {sup 99m} Tc O{sub 4-}) with an activity of 370 MBq. The solution was boiled for 10 min and filtered through a cellulose ester filter. The labeling efficiency was on the order of 92%, remaining stable for six hours and the kit remained stable for two months. The biological activity of the {sup 99m} Tc-CFT was evaluated by diffusion in agar impregnated with E.coli and S. aureus. Seven Wistar rats, weighing from 200 to 250 g, were used for the development of the septic focus. After 24 hours from the induction of the infectious site (E.coli), the animals were anesthetized and 0.1 mL of {sup 99m} Tc-CFT (37 MBq) was injected into the tail veins of the animals. The images were obtained with a gamma camera one, two and six hours after injection and the regions of interest (ROIs) were calculated. The diameters of the inhibition halos for {sup 99}m Tc-CFT were 27.16 {+-} 0.23 and 27.17 {+-} 0.20 for S.aureus and E.coli, respectively, while those for the unlabeled CFT were 30.4 {+-} 0.33 and 29.43 {+-} 0.26, respectively. The results for the biodistribution of {sup 99m} Tc-CFT in infected animals furnished a ratio of 1.97 {+-} 0.31, 2.10 {+-} 0.42 and 2.01 {+-} 0.42 for cpm-target/cpm-no target for the one, two and six-hour periods, respectively. The images showed a clear uptake of labeled antibiotic ({sup 99m} Tc-CFT) by the infectious site during the experiment. The results attest to the viability of producing a kit with {sup 99m} technetium-labeled ceftizoxime for the

  12. Tetramethyl(perfluoroalkyl)cyclopentadienyl Rhodium(I) Complexes with Ethylene or Diene Ligands. Crystal Structure of [(eta-5-C5Me4C6F13)Rh(CO)2

    Czech Academy of Sciences Publication Activity Database

    Čermák, Jan; Krupková, Alena; Auerová, Kateřina; Zamrzla, M.; Nguyen Thi, T.H.; Vojtíšek, P.; Císařová, I.

    2010-01-01

    Roč. 695, č. 3 (2010), s. 375-381 ISSN 0022-328X R&D Projects: GA AV ČR IAA4072203; GA MŠk(CZ) LC06070 Institutional research plan: CEZ:AV0Z40720504 Keywords : fluorous cyclopentadienes * rhodium complexes * alkene complexes Subject RIV: CC - Organic Chemistry Impact factor: 2.205, year: 2010

  13. 99mTc-EDTA and 99mTc-DTPA complexes as hydrological tracers

    International Nuclear Information System (INIS)

    Dominguez, J.; Borroto, J.; Nazco, J.; Perez, E.; Gamboa, R.; Cruz, J.

    2002-01-01

    The [ 99m Tc-DTPA] 2- and [ 99m Tc-EDTA] 1- were evaluated as radiotracers for short time hydrological studies. Their complex stability after labelling with 9.25 GBq of 99m Tc, the behaviour against pH variations, from 5 to 9, in simulated solutions and in natural river waters and the sorption of these compounds on the river sediments, were tested in laboratory experiments. Finally field double tracing experiments were carried out for each of labelling complexes and Rhodamine WT. From recovery calculations not losses of the 99m Tc activity were observed. The shape of the RTD curves of the [ 99m Tc-DTPA] 2- and [ 99m Tc-EDTA] 1 were quite similar to the Rhodamine Wt ones. May be concluded that both complexes behaved conservatively on the studied environmental conditions. (author)

  14. sup(99)Tcsup(m)-ascorbate

    International Nuclear Information System (INIS)

    Persson, R.B.R.; Strand, S.E.; White, T.

    1975-01-01

    The sup(99)Tcsup(m)-ascorbate preparation used in this investigation contained FeCl 3 4mN, asorbic acid 110 mM and had an initial pH-value of 7.4 and a final pH-value of 6.8. Studies of the complex-formation were performed with gel-chromatography column-scanning (GCS), which is the analytical method to be preferred for this type of compound, indicated that the complex was formed in two steps. First reduced hydrolyzed sup(99)Tcsup(m) was formed rapidly and the sup(99)Tcsup(m)-ascorbate was formed by a slower reaction (k = 3, 10 -2 min -1 ). The renal uptake of sup(99)Tcsup(m)- was studied in 29 patients with a gamma-camera. The time-course of radio-activity in kidneys, 'tissue background'-areas and in blood suggested that optimal conditions for kidney-imaging were reached 3 to 6 hr after injection. About 20% of the sup(99)Tcsup(m)-ascorbate was bound to plasma-proteins, and only a small fraction to red blood-cells. The disappearance of the sup(99)Tcsup(m)-ascorbate from plasma followed a three-exponential curve: 40% with a half-life of 0.2 hr, 30% with a half-life of 20 hr. The absorbed radiation dose to the kidneys was about 200 (SE +- 60) mrad mCi -1 and to the whole-body 10 (SE +- 3) mrad mCi -1 of administered activity. There was a close correlation (r + 0.98) of the separate renal uptake (dx:(dx +sin)) of sup(99)Tcsup(m)-ascorbate to the separate renal function as determined with 131 I-Hippuran. (author)

  15. Potential Ways to Address Shortage Situations of 99Mo/99mTc.

    Science.gov (United States)

    Filzen, Leah M; Ellingson, Lacey R; Paulsen, Andrew M; Hung, Joseph C

    2017-03-01

    99m Tc, the most common radioisotope used in nuclear medicine, is produced in a nuclear reactor from the decay of 99 Mo. There are only a few aging nuclear reactors around the world that produce 99 Mo, and one of the major contributors, the National Research Universal (Canada), ceased production on October 31, 2016. The National Research Universal produced approximately 40% of the world's 99 Mo supply, so with its shut down, shortages of 99 Mo/ 99m Tc are expected. Methods: Nuclear pharmacies and nuclear medicine departments throughout the United States were contacted and asked to provide their strategies for coping with a shortage of 99 Mo/ 99m Tc. Each of these strategies was evaluated on the basis of its effectiveness for conserving 99m Tc while still meeting the needs of the patients. Results: From the responses, the following 6 categories of strategies, in order of importance, were compiled: contractual agreements with commercial nuclear pharmacies, alternative imaging protocols, changes in imaging schedules, software use, generator management, and reduction of ordered doses or elimination of backup doses. Conclusion: The supply chain of 99 Mo/ 99m Tc is quite fragile; therefore, being aware of the most appropriate coping strategies is crucial. It is essential to build a strong collaboration between the nuclear pharmacy and nuclear medicine department during a shortage situation. With both nuclear medicine departments and nuclear pharmacies implementing viable strategies, such as the ones proposed, the amount of 99m Tc available during a shortage situation can be maximized. © 2017 by the Society of Nuclear Medicine and Molecular Imaging.

  16. Determination of Tc-99 in radioactive wastes; Determinacion de Tc-99 en desechos radiactivos

    Energy Technology Data Exchange (ETDEWEB)

    Rivera S, A. A.

    2015-07-01

    Tc-99 is a fission product and one of the most important radionuclides from the view point of safety assessment for the disposal of radioactive waste because of its long half-life (2.1 x 10{sup 5} years) and high mobility in soil-water systems, if this is released into the environment in significant quantities can concentrate on plants and animals. Tc-99 is a pure beta emitter with a maximum energy of 292 KeV, so their quantification imposes destructive methods to be analyzed by liquid scintillation. Therefore the quantification of Tc-99 in ion exchange resins requires of the mineralization of these and separation of Tc-99 of other radioisotopes present in the resin. Therefore the object of this thesis is to develop a quantification method of Tc-99 content in spent exchange resins. So in order to track the behavior of technetium during digestion exchange resins and radiochemical separation, given its high volatility, in this work the {sup 99m}Tc is used. To determine the degree of mineralization of the resins, an analysis was performed by chromatography. Subsequently the method used to determine the percentage of {sup 99m}Tc aerosolized during mineralization of resin is described. After the method for the radiochemical separation of {sup 99m}Tc is presented by liquid-liquid extraction using crown ether as extractant; for this testing was performed by varying the molarity of the extractant, the ratio of solvent extractant, type of digestion of the resin and the presence of Sr-85, in order to study the behavior of {sup 99m}Tc in the presence of this radioisotope. Finally, a track beta spectra of a sample of {sup 99m}Tc eluted from a generator {sup 99}Mo/{sup 99m}Tc function of time was performed. (Author)

  17. Polymeric optical sensors for selective and sensitive nitrite detection using cobalt(III) corrole and rhodium(III) porphyrin as ionophores

    Energy Technology Data Exchange (ETDEWEB)

    Yang, Si; Wo, Yaqi; Meyerhoff, Mark E., E-mail: mmeyerho@umich.edu

    2014-09-16

    Highlights: • We examine cobalt(III) corroles and rhodium(III) porphyrins as ionophores in polymeric films for optical sensors to detect nitrite. • Different types of proton chromoionophores are evaluated to optimize nitrite response. • Selectivity over lipophilic anions such as perchlorate and thiocyanate is observed. • Both ionophores yield optical sensors that are fully reversible. • The cobalt(III) corrole based sensor is employed to determine nitric oxide emission rates from NO donor doped polymers with good accuracy. - Abstract: Cobalt(III) 5,10,15-tris(4-tert-butylphenyl) corrole with a triphenylphosphine axial ligand and rhodium(III) 5,10,15,20-tetra(p-tert-butylphenyl) porphyrin are incorporated into plasticized poly(vinyl chloride) films to fabricate nitrite-selective bulk optodes via absorbance measurements. The resulting films yield sensitive, fast and fully reversible response toward nitrite with significantly enhanced nitrite selectivity over other anions including lipophilic anions such as thiocyanate and perchlorate. The selectivity patterns differ greatly from the Hofmeister series based on anion lipophilicity and are consistent with selectivity obtained with potentiometric sensors based on the same ionophores. The optical nitrite sensors are shown to be useful for detecting rates of emission of nitric oxide (NO) from NO releasing polymers containing S-nitroso-N-acetyl-DL-penicillamine.

  18. Rhodium based clusters for oxygen reduction and hydrogen oxidation in 0.5 M H2SO4, tolerant to methanol and carbon monoxide, respectively

    Energy Technology Data Exchange (ETDEWEB)

    Uribe-Godinez, J.; Jimenez-Sandoval, O.; Borja-Arco, E.; Altamirano-Gutierrez, A. [Centro de Investigacion y de Estudios Avanzados del Instituto Politecnico Nacional, Queritaro (Mexico); Castellanos, R.H. [Centro de Investigacion en Ciencia Aplicada y Tecnologia Avanzada-Queretaro, Queretaro (Mexico)

    2008-07-01

    Rhodium (Rh6(CO)16) and novel Rh-based clusters were prepared using thermolysis techniques under different conditions in N2 and H2 reaction media, as well as in n-nonane, o-xylene, 1,2-dichlorobenzene and dimethylsulfoxide. The clusters were used as novel electrocatalysts for oxygen reduction reaction (ORR) in the absence and presence of 1.0 and 2.0 M methanol solutions. The catalysts were also used for hydrogen oxidation reaction (HOR) with pure hydrogen (H2) and in the presence of carbon monoxide (CO). Rotating disk electrode measurements were used to analyze the materials. The study showed that the electrocatalyst support ratio plays a significant role in the electrochemical behaviour of the materials. Rh6(CO)16 and Rh2(1,2-DCB) presented the best electrocatalytic behaviour for ORR and HOR in the absence and presence of methanol and CO. The study demonstrated that the rhodium-based materials are capable of performing ORR and HOR while being tolerant of both methanol and CO. 3 refs., 3 figs.

  19. Investigation of Gasochromic Rhodium Complexes Towards Their Reactivity to CO and Integration into an Optical Gas Sensor for Fire Gas Detection

    Directory of Open Access Journals (Sweden)

    Carolin Pannek

    2018-06-01

    Full Text Available The detection of the toxic gas carbon monoxide (CO in the low ppm range is required in different applications. We present a study of the reactivity of different gasochromic rhodium complexes towards the toxic gas carbon monoxide (CO. Therefore, variations of binuclear rhodium complexes with different ligands were prepared. They were characterized by FTIR spectroscopy, 1H NMR spectroscopy, and differential scanning calorimetry. All complexes are spectroscopically distinguishable and temperature stable up to at least 187 °C. The gasochromic behavior of all different compounds was tested. Therefore, the compounds were dissolved in toluene and exposed to 100 ppm CO for 10 min to investigate their gas sensitivity and reaction velocity. The changes in the transmission spectra were recorded by UV/vis spectroscopy. Furthermore, a significant influence of the solvent to the color dyes’ gasochromic reaction and behavior was observed. After characterization, one complex was transferred as sensing element into an optical gas sensor. Two different measurement principles (reflection- and waveguide-based were built up and tested towards their capability as gasochromic CO sensors. Finally, different gas-dependent measurements were carried out.

  20. Enantioselective Rhodium-Catalyzed [2+2+2] Cycloadditions of Terminal Alkynes and Alkenyl Isocyanates: Mechanistic Insights Lead to a Unified Model that Rationalizes Product Selectivity

    Science.gov (United States)

    Dalton, Derek M.; Oberg, Kevin M.; Yu, Robert T.; Lee, Ernest E.; Perreault, Stéphane; Oinen, Mark Emil; Pease, Melissa L.; Malik, Guillaume; Rovis, Tomislav

    2009-01-01

    This manuscript describes the development and scope of the asymmetric rhodium-catalyzed [2+2+2] cycloaddition of terminal alkynes and alkenyl isocyanates leading to the formation of indolizidine and quinolizidine scaffolds. The use of phosphoramidite ligands proved crucial for avoiding competitive terminal alkyne dimerization. Both aliphatic and aromatic terminal alkynes participate well, with product selectivity a function of both the steric and electronic character of the alkyne. Manipulation of the phosphoramidite ligand leads to tuning of enantio- and product selectivity, with a complete turnover in product selectivity seen with aliphatic alkynes when moving from Taddol-based to biphenol-based phosphoramidites. Terminal and 1,1-disubstituted olefins are tolerated with nearly equal efficacy. Examination of a series of competition experiments in combination with analysis of reaction outcome shed considerable light on the operative catalytic cycle. Through a detailed study of a series of X-ray structures of rhodium(cod)chloride/phosphoramidite complexes, we have formulated a mechanistic hypothesis that rationalizes the observed product selectivity. PMID:19817441

  1. Homogeneous SLOWPOKE reactors for Mo-99/Tc-99m production in North America

    Energy Technology Data Exchange (ETDEWEB)

    Hilborn, J.W., E-mail: hilbovanw@sympatico.ca [Deep River, Ontario (Canada); Bonin, H.W. [Royal Military College of Canada, Kingston, Ontario (Canada)

    2014-07-01

    The 15 month shutdown of NRU in 2009 - 2010 caused an overall isotope shortage of approximately 30%; and in North America, the annual Tc-99m demand decreased from an estimated 20 million unit doses to about 15 million unit doses. Mo-99/Tc-99m is produced from HEU targets, irradiated in NRU for 11 days, and after chemical removal of uranium it is shipped to Nordion in Kanata, Ontario. Nordion further purifies the material and sends it to Lantheus Medical Imaging in the USA for manufacture of Mo-99 generators, which are then distributed to hundreds of hospital radiopharmacies throughout North America. One other American company, Covidien, manufactures and distributes Mo-99 generators like Lantheus, but they import bulk Mo-99 from Europe or South Africa. At the hospitals, Tc-99m is chemically extracted daily from the Mo-99 generators and loaded into syringes for immediate clinical use. Fortuitously, the 66 hour half-life of Mo-99 allows the replenishment of Tc-99m in the generator over a growth period of about 20 hours; and a generator can be 'milked' daily for up to two weeks. A more efficient model is the direct production and distribution of Tc-99m unit doses to regional hospitals from 10 'industrial' radiopharmacies located at existing licensed reactor sites in North America. A 20 kW homogeneous SLOWPOKE reactor at each site would deliver 15 litres of irradiated uranyl sulphate fuel solution daily to industrial-scale hot cells for extraction of Mo-99, which would be incorporated in large Mo-99/Tc-99m generators for extraction of Tc-99m five days a week; and the Low Enriched Uranium (LEU) would be recycled. Each automated hot-cell facility would be designed to load up to 7,000 Tc-99m syringes daily, for courier delivery to all of the Nuclear Medicine hospitals within a 3 hour average range by road transport. Typically, the delivered doses would be in the range 10 to 30 mCi. Assuming an average unit dose of 25 mCi at the hospital and 5 x 52

  2. Performance tests on column materials for {sup 99}Mo-{sup 99m}Tc generator

    Energy Technology Data Exchange (ETDEWEB)

    Sombrito, E Z; Bulos, A D; Tangonan, M C [Chemistry Research Section, Atomic Research Div., Philippine Nuclear Research Inst., Quezon (Philippines)

    1998-10-01

    To meet the need of producing a {sup 99}Mo-{sup 99m}Tc generator, based on low specific activity reactor-produced {sup 99}Mo, different procedures for preparing zirconium molybdate gels were tested. Performance tests were done on molybdate gel columns prepared using the procedures developed by Vietnam and China, and recently, on a polyzirconium compound (PZC) prepared in Japan. The conditions for the batch drying of a large volume of the gel material were studied as well as the conditions in preparing a column to concentrate technetium-99m. The performance of PZC sample as column material for the generator was also evaluated. (author)

  3. Present status of Mo-99/Tc-99m generator in Thailand

    International Nuclear Information System (INIS)

    Khongpetch, Pranom

    2007-01-01

    Isotop Production Program, Office of Atoms for Peace had produced technetium-99m by MEK extraction of Mo-99 obtained from (n,γ) reaction in TRIGA Mark III reactor and supplied to nuclear medicine centers in Bangkok from 1980 to 1997. Because of the difficulty to meet the increased demand and limitation of reactor operation, the production of technetium-99m was stopped in 1997. Presently, there are 21 nuclear medicine centers with 25 SPECT, 7 gamma camera and 3 PET. All nuclear medicine centers are currently using imported Tc-99m generator. (author)

  4. Evaluation of '99Mo presence in eluates of 99mTc used in nuclear medicine

    International Nuclear Information System (INIS)

    Ribeiro, Bianca da Silva

    2010-01-01

    Tc-99m is used for diagnostic imaging in nuclear medicine through SPECT technique. It is obtained by the elution of 99 Mo/ 99m Tc generators. During the elution process 99 Mo can be extracted becoming a radionuclidic impurity. One of the quality parameters of the eluate is the radionuclidic purity, MBT (molybdenum break through), defined as the ratio between 99 Mo and 99m Tc activities in the eluate. The North-American and European pharmacopoeias restrict the 99 Mo content, respectively, in 0.015 e 0.1% and, according to the International Atomic Energy Agency (IAEA), the activity ratio at the moment of administration of the radiopharmaceutical to the patient, should not exceed 0.015%. In Brazil, the control of such parameter is not obliged in official regulations. Thus, the objective of this work is to evaluate the occurrence of 99 Mo in 99m Tc eluates. It was initially optimized a methodology to determine the activity of 99 Mo in eluate samples. Efficiency curves were obtained for a NaI (Tl) 8'' x 4'' scintillation detector installed at the In Vivo Monitoring Laboratory (LABMIV-IRD). The methodology has been validated through the measurement of a 99 Mo standard liquid source calibrated at the National Metrology Laboratory for Ionizing Radiation (LNMRI-IRD). The samples analyzed in this work were gently supplied by 5 Nuclear Medicine Clinics located in the city of Rio de Janeiro. The activities of 99 mTc and 99 Mo in those samples have been measured respectively at the clinics and at the LABMIV. By applying a standardized methodology, the ration between the activities were calculated. The results show that 147 out of 174 samples presented 99 Mo activities above the minimum detectable activity of the technique. On the other hand, only 2 out of 147 samples surpassed the MBT limit suggested by the IAEA and have been detected in samples eluted from generators of 750 mCi. In one of the samples, eluted from a generator of 1000 mCi, the calculated MBT value was very close

  5. Generator of 99m Tc with MnO2 as support of 99 Mo

    International Nuclear Information System (INIS)

    Granados C, F.; Serrano G, J.

    2002-01-01

    The generator of 99m Tc with MnO 2 as support of 99 Mo was studied. By mean of static experiments the retention of 99 Mo in MnO 2 in function of the stirring time and of the p H value of the solution of 99 Mo. It was found that the 99 Mo presents 100% of retention in MnO 2 in the rank of p H 3-11 and the balance was reached before of 10 minutes. In dynamic conditions the retention of 99 Mo in MnO 2 at p H=5 was also higher: 99.72%. The generated 99m Tc can be separated from 99 Mo, adsorbed in MnO 2 packed in the column, using distilled water at p H=5 or NaCl solution at 0.9%. With saline solution the elution yields were greater than 80% and only an aliquot of 5 ml was necessary for obtaining this yield. The better results were obtained when the column was packed with 1 g of MnO 2 . The water and the saline solution were passed through of the column with a flux of 1.25 ml/min. (Author)

  6. Technetium-99m ceftizoxime kit preparation

    Directory of Open Access Journals (Sweden)

    Simone Odília Fernandes Diniz

    2005-10-01

    Full Text Available The aim of this work was to prepare a kit of 99mTc-ceftizoxime (99mTc-CFT, with stability and biological activity preserved, able to identify a septic focus (E. coli in the experimental infection model in rats. The preparation of the CFT kit involved the use of lyophilized solutions containing the antibiotic ceftizoxime and the sodium dithionite reducing agent (6.0 mg/mL. After lyophilization, the kit was reconstituted with 1.0 mL of sodium 99mTc-pertechnetate solution (Na99mTcO4- with an activity of 370 MBq. The solution was boiled for 10 min and filtered through a cellulose ester filter. The labeling efficiency was on the order of 92%, remaining stable for six hours and the kit remained stable for two months. The biological activity of the 99mTc-CFT was evaluated by diffusion in agar impregnated with E.coli and S. aureus. Seven Wistar rats, weighing from 200 to 250 g, were used for the development of the septic focus. After 24 hours from the induction of the infectious site (E.coli, the animals were anesthetized and 0.1 mL of 99mTc-CFT (37 MBq was injected into the tail veins of the animals. The images were obtained with a gamma camera one, two and six hours after injection and the regions of interest (ROIs were calculated. The diameters of the inhibition halos for 99mTc-CFT were 27.16 ± 0.23 and 27.17 ± 0.20 for S.aureus and E.coli, respectively, while those for the unlabeled CFT were 30.4 ± 0.33 and 29.43 ± 0.26, respectively. The results for the biodistribution of 99mTc-CFT in infected animals furnished a ratio of 1.97 ± 0.31, 2.10 ± 0.42 and 2.01 ± 0.42 for cpm-target/cpm-no target for the one, two and six-hour periods, respectively. The images showed a clear uptake of labeled antibiotic (99mTc-CFT by the infectious site during the experiment. The results attest to the viability of producing a kit with 99m technetium-labeled ceftizoxime for the investigation of infectious processes.O objetivo deste trabalho foi preparar um kit de Tc

  7. Process modifications of obtaining Tc-99m by solvent extraction

    International Nuclear Information System (INIS)

    Leon, A.; Verdera, S.

    1978-01-01

    This paper describes a modification in the process to obtaining Tc-99m by the extraction method of solvent from Mo-99 produced by irradiation. Tc-99m is considered an ideal radionuclide for medical and biological applications

  8. A comparative study of 99Tcm-tetrofosmin and 99Tcm-MIBI myocardial imaging

    International Nuclear Information System (INIS)

    Zhao Kui; Chen Peng; Zhang Furong; Shen Wenhua

    2001-01-01

    Objective: To evaluate the value of 99 Tc m -tetrofosmin myocardial imaging for detecting coronary artery disease. Methods: Twenty-seven patients underwent 99 Tc m -tetrofosmin SPECT, twenty-six patients underwent 99 Tc m -MIBI SPECT; coronary angiography was performed on patients included in both groups (≥50% luminal diameter stenosis was considered significant coronary stenosis). Results: 99 Tc m -tetrofosmin produced high quality myocardial images from 30 min to several hours postinjection, the outlines of myocardial perfusion images provided by 99 Tc m -tetrofosmin imaging were clearly discernible. One-day exercise/rest 99 Tc m -tetrofosmin myocardial perfusion imaging was feasible and had a high sensitivity for detection of coronary artery disease. Sensitivities of 99 Tc m -tetrofosmin SPECT and 99 Tc m -MIBI SPECT for detecting coronary artery disease were 90% and 94%, respectively. The 95% confidence limits of both sensitivities were 68.65% - 98.77% and 72.33% - 99.86%, respectively; the positive predictive values of both imaging agents were 90.0% and 89.5%, respectively, the 95% confidence limits of those were 68.38% - 98.77% and 72.33% - 99.86% respectively; the positive predictive values of both imaging agents were 90.0% and 89.5%, respectively, the 95% confidence limits of those were 68.38% - 98.77% and 66.38% - 98.70%, respectively; efficiencies of both imaging agents were 85.2% and 88.5%, respectively. The 95% confidence limits of both efficiencies were 65.81% - 95.78% and 69.44 - 98.70%, respectively. The specificity for both imaging agents was 71% and 75%. There was no significant difference among above results (P > 0.05). No ECG abnormalities were found following the injection of 99 Tc m -tetrofosmin SPECT. There were no drug-related effects on blood pressure, heart rate and body temperature. This experiment failed to provide the negative predictive value of the myocardial perfusion imaging with 99 Tc m -tetrofosmin because that few patients with

  9. Development of 99Mo/99mTc Generator System for Production of Medical Radionuclide 99mTc using a Neutron-activated 99Mo and Zirconium Based Material (ZBM as its Adsorbent

    Directory of Open Access Journals (Sweden)

    I. Saptiama

    2016-12-01

    Full Text Available Molybdenum produced from fission of U-235 is the most desirable precursor for 99Mo/99mTc generator system as it is non-carrier added and has high specific activity. However, in the last decade there has been short supply of 99Mo due to several constrains. Therefore, there have been many works performed for development of 99Mo/99mTc generator system using 99Mo which is not produced from either LEU or HEU. This report deals with development of 99Mo/99mTc generator system where zirconium-based material (ZBM is used as adsorbent of neutron-activated 99Mo. The system was prepared by firstly irradiating natural Mo in the G. A. Siwabessy reactor to produce neutron-activated 99Mo. The target was dissolved in NaOH 4N and then neutralized with 12 M HCl. The 99Mo solution was then mixed with a certain amount of ZBM followed by heating at 90°C for three hours to allow the 99Mo adsorbed on ZBM. The 99Mo-ZBM (9.36 GBq of 99Mo was Mo/ 4.2 g ZBM was packed on a fritz-glass column. This column was then fitted serially with an alumina column for trapping 99Mo breakthrough. The columns were then eluted daily with saline solution for up to one week. The yield of 99mTc was found to be between 53.7 – 74% (n= 5. All 99mTc eluates were clear solutions with pH of 5. Breakthrough of 99Mo in 99mTc eluates was found to be 0.031 ± 0.019 μCi 99Mo/ mCi 99mTc (n= 5 which was less than the maximum activity of 99Mo allowed in 99mTc solution ( 99%. Radiolabeling of this 99mTc towards methylene diphosphonate (MDP kit gave a radiolabelling efficiency of 99%. In summary, a new 99Mo/99mTc generator system that used neutron-activated 99Mo and ZBM as its adsorbent has been successfully prepared. The 99mTc produced from this new 99Mo/99mTc generator system attained the quality of 99mTc required for medical purposes.

  10. Can tumor uptake Tc-99m MDP

    International Nuclear Information System (INIS)

    Yang, Y.S.F.; Zeng, Z.J.; Yao, Y.M.; Shi, S.M.P.; Shi, S.Z.Y.

    2002-01-01

    Aim: To study a distribution of Tc-99m MDP in mice bearing tumor cell lines. Methods: The uptake of Tc-99m MDP was analyzed in seven human tumor cell lines (SPC-A1 adenocarcinoma of lung cancer, P37 Breast cancer, T24 Bladder cancer, SKOV2 Ovary carcinoma, Hela-229 Cervical carcinoma, Osteosarcoma, A375 Melanoma) and one mouse lung cancer cell line (Lewis). They were transplanted into 13, 4, 5, 5, 4, 5 athymic mice, 6 SCID nude mice and 4 C57 black mice, respectively. Approximately 10(7) cells of each cell line were injected subcutaneously into a right chest of mouse. After 5∼6 weeks, the Tc-99m MDP scintigraphy were determined 5-6 hours after i.v. injection of 74MBq in 0.05ml every mouse. Result: Biodistribution and tumor uptake MDP was different in the various cell types investigated. Region of interests (RIOs) placed on a small part of the tumor and horizontal copied to left chest or spine of mice in Tc-99m MDP imaging and the average count ratio (tumor to background ratio: T/B, tumor to spine ratio: T/NT) in each ROI was calculated. 13 nude mice bearing the adenocarcinoma (SPC-A1) were sacrificed and biodistribution was determined after Tc-99m MDP scintigraphy. Results were expressed as % injected dose/gram (%ID/g), mean±SD. T-ulcer=ulcer of tumor, T-round=surrounding of tumor, T-center=the center of tumor, Thor-sp=thoracic spine, Lum-ver=lumbar vertebra, LN=lymph node. Conclusions: Tumor can uptake Tc-99m MDP including adenocarcinoma. Higher uptake rate in the center tissue of tumor is than other part of tumor. It maybe connected with necrosis or fibrosis of tumor

  11. Use of 99mTc from a commercial 99Mo/9mTc generator as yield tracer for the determination of 99Tc at low levels

    DEFF Research Database (Denmark)

    Hou, Xiaolin; Jensen, Mikael; Nielsen, Sven Poul

    2007-01-01

    The concentrations of Tc-99 and impurity radionuclides in the Tc-99m tracer solution obtained from a commercial Mo-99/Tc-99m generator were measured by gamma spectrometry and liquid scintillation counting. Mo-99 and Ru-103 were found in the Tc-99m eluate. A simple separation using two extra alumina...... cartridges was investigated to purify the eluate to obtain a suitable Tc-99m tracer with low Tc-99 concentration. The activity ratio of Tc-99/Tc-99m in the prepared Tc-99m solution is lower than 15 x 10(-9), which is higher than the theoretical ratio of less than 10 x 10(-9). The possible reason is discussed....... The Tc-99 in the 20 kBq spiked Tc-99m tracer was found to be less than 0.3mBq, which is lower than the detection limit of the radiometric method used for environmental samples. The purified Tc-99m eluate is used as yield tracer for the determination of low levels of Tc-99 in environmental samples. (c...

  12. Current status of research and development of 99Mo/99mTc generator in Korea

    International Nuclear Information System (INIS)

    Park, U.J.; Lee, J.S.; Son, K.J.; Nam, S.S.; Kwak, S.I.; Han, H.S.

    2006-01-01

    To supply 99m Tc in stable and economical manner in Korea, a chromatographic generator has been under development at KAERI since late 1980's. The chromatographic type of technetium generator is preferred in hospital because it is more convenient and less time-restricted for applications. Hence, the demand of 99m Tc in medical applications is keep increasing. In Korea, there are more than 200 gamma cameras including SPECT in hospitals. For these applications, approximately 100 units/week of 99m Tc generators of which annual cost reached 3 million US dollars were required in 2002. Hence, the development of 99m Tc generators and technology of fission 99 Mo processing were started while installing the generator loading facility (GLF) at KAERI. This facility is currently on a trial run for the commercial production of 99m Tc generators and expected to produce more than 200 generators per week in 2004. For the fission 99 Mo production, an annulus U foil target was considered as the LEU target. The designed LEU target is being used for target manufacturing test and accident analysis. The develop gel type 99m Tc generators by using a poly zirconium complex (PZC) and alumina column, KAERI has cooperated with a Japanese company since late 1990's. In 2003, experimental studies for molybdate adsorption capacity and elution characteristics of the PZC samples from three different batches produced by Kaken Co. were carried out. (author)

  13. Gentc99m, computational system for the technetium-99m generator

    International Nuclear Information System (INIS)

    Suparman, I.

    1997-01-01

    The technetium-99m generator is one of the main products of the PPR, as the continuity of the technetium-99m generator production is important for supporting the development of nuclear medicine. GENTC99M has been made for computational for the technetium-99m generator and includes data processing, documentation and information GENTC99M is also very useful in quality control application especially for the determinations of yield and radionuclidic impurities which consume much time. microsoft visual basic for MS-DOS and visual basic for windows have been used for making GENTC99M. Microsoft visual basic has several features that make it an ideal development language for both MS-DOS and Microsoft Windows. These features not only increase productivity, they also provide all the tools and hooks needed to develop some very sophisticated applications. for a production centre like PPR, GENTC99M is very useful to support the data processing, documentation and information system of the technetium-99m generator and it can also be modified for other products

  14. 99Mo-99mTc generator - study of their performance and quality

    International Nuclear Information System (INIS)

    Acar, M.E.D.

    1987-01-01

    In this work the performance of the 99 Mo - 99m Tc generators produced at IPEN-CNEN/SP as well as the quality of the eluted solutions were analysed. The following parameters were studied: elution efficiency, chemical radiochemical, radionuclidic and microbiological purities and pH of the eluates. The 99m Tc yield ranged from 84,7 to 98,5%. The radioactivity due to the pertechnetate ion in the studied solutions was higher than 97,5%. The aluminium content in eluates, determined by spectrophotometry, was lower than 2,5 μg/ml and the pH of the solutions between 4,5 and 5,1. Radioactive impurities of the order of 10 -3 KBq 99 Mc/MBq 99m Tc and 10 -5 KBq 131 I/MBq 99m Tc were found in the eluates at the time of elution. Other γ emitting radioactive impurities were order of 10 -3 KBq/MBq 99m Tc. The eluates were sterile and pyrogen-free. From the results obtained in this work one can state that the IPEN-TEC generator is a reliable source of good quality 99m Tc-pertechnetate. (author) [pt

  15. Comparative study of 99Mo/99mTc generators at base of synthesized gels starting from 99Mo of activation and of fission

    International Nuclear Information System (INIS)

    Lopez M, I.Z.; Monroy G, F.; Rivero G, T.; Rojas N, P.

    2007-01-01

    At the present time the more used and diffused radionuclide in nuclear medicine it is the Technetium 99 metastable ( 99 mTc) it is used for diagnostic and therapy. It is produced starting from molybdenum 99 ( 99 Mo), which is absorbed in chromatographic columns, loaded with alumina that absorb only 0.2% of 99 Mo situation that forces to use high specific activities of 99 Mo that it is obtained starting from the fission of the 235 U. Given these conditions and limitations, new preparation procedures of 99 Mo/ 99m Tc generators, of low or medium specific activity, its have been developed, using gels of zirconium molybdates that incorporates until 30% in weight of 99 Mo in the gel, and also conserve similar characteristics of quality and purity that those obtained by the traditional generator; reducing by this way the cost of production of the 99m Tc, when using 99 Mo of low specific activity, in the preparation of 99 Mo/ 99m Tc generators. The radiochemical characteristics of the elution of 99m Tc, depends strongly on the gel preparation conditions. In particular, the present work has for object to determine the influence of the used type of 99 Mo, fission or activation product, during the gels synthesis, as well as the used air flow for the agitation in the gels preparation and its influence in the quality of the 99 Mo/ 99m Tc generators. When diminishing the agitation air flow the efficiency it increases and in the radionuclide purity of the eluates and when using 99 Mo of fission for the gels production it increases in an important way the elution efficiency, the radiochemical purity and radionuclide of the eluates of 99m Tc. (Author)

  16. Preparation of i.v. 99mTc radiopharmaceuticals from spent moly 99Mo

    International Nuclear Information System (INIS)

    Noronha, O.P.D.

    1998-01-01

    Full text: Expiry dating is an important quality assurance precept in (radio) pharmacy. There are occasions when for the sake of patient service one may be forced to continue using an over aged source of 99 Mo to generate 99m Tc beyond 7d, especially when there is short/no supply of 99 Mo, (In the early days the expiry date was 3 d or 3 extractions, whichever one was earlier). With the passage of time a few physico-chemical changes (apart from decay) do occur in the 99 Mo/ 99m Tc milieu. The cocktail also begins to contain traces of carried over MEK which is subjected to strong β-, γ irradiation. These impurity (in trace amounts) is soluble in MEK and even, to an extent, in aqueous media. Furthermore, the concentrated impurity tends to seemingly increase in the bulk 99m TcO 4 - since one is compelled to leach TcO 4 - in lower volume of saline. On many occasions we have been constrained to extend the use of 99 Mo beyond 7 - 14 d. Adequate activities were obtained by pooling the previous week's lot of 99 Mo with the current over aged lot. On a few occasions over the past 26 years we have used 99 Mo much beyond 14 d and 2 - 3 occasions for 26 - 28 d (i.e. >10 t 1 /2 of 99 Mo). On each of these occasions the purity of 99m TcO- 4 was ascertained by pharmacopoeial procedures. It was found that despite depleting activities, the purity was not compromised and the trace impurities, even if present, did not cause any interference. We have profitably utilised the bulk TcO- 4 to formulate a variety of i.v. dosage forms of 99m Tc radiodiagnostics. The following strategy was adopted for the patient services - the agents requiring larger activity levels/patients dose were made available in the earlier period, the other during the latter half. It is concluded that pure 99m TcO- 4 can be obtained over the entire useful life-period of 99 Mo, even > 10t l/2

  17. Utility of the Static-99 and Static-99R With Latino Sex Offenders.

    Science.gov (United States)

    Leguízamo, Alejandro; Lee, Seung C; Jeglic, Elizabeth L; Calkins, Cynthia

    2017-12-01

    The predictive validity of the Static-99 measures with ethnic minorities in the United States has only recently been assessed with mixed results. We assessed the predictive validity of the Static-99 and Static-99R with a sample of Latino sex offenders ( N = 483) as well as with two subsamples (U.S.-born, including Puerto Rico, and non-U.S.-born). The overall sexual recidivism rate was very low (1.9%). Both the Static-99 measures were able to predict sexual recidivism for offenders born in the United States and Puerto Rico, but neither was effective in doing so for other Latino immigrants. Calibration analyses ( N = 303) of the Static-99R were consistent with the literature and provided support for the potential use of the measure with Latinos born in the United States and Puerto Rico. These findings and their implications are discussed as they pertain to the assessment of Latino sex offenders.

  18. Preparation of 99Mo/99mTc generators based on 99Mo zirconium molybdates in the Gel Synthesis Device for Generators

    International Nuclear Information System (INIS)

    Lopez M, I. Z.; Monroy G, F.; Rivero G, T.; Rojas N, P.

    2008-01-01

    The 99m Tc is used for diagnosis and therapy. It is produced commercially from 99 Mo obtained from the fission of 235 U, which is retained in chromatographic columns filled with alumina whose maximum capacity is 0.2%. Given these constraints new methods of preparation 99 Mo/ 99m Tc generators have been developed using zirconium molybdates gels containing up to 30% of Mo, which is part of the generator matrix, and retaining quality and purity similar characteristics to those commercial generators. The present study aims to determine the flow of agitation, temperature and drying time optimal to prepare 99 Mo/ 99m Tc generators based on 99 Mo zirconium molybdates in the Gel Synthesis Device 99 Mo/ 99m Tc Generators designed and built by groups of the Radioactive Materials Research Laboratory and Automation and Instrumentation Department of the National Institute of Nuclear Research. (Author)

  19. Nanostructured metal oxides: promise opportunity and challenge to develop clinically useful 99Mo/99mTc generators using (n, gamma)99Mo

    International Nuclear Information System (INIS)

    Dash, Ashutosh

    2014-01-01

    The role of 99m Tc diagnostic nuclear medicine needs hardly to be reiterated. Today, it is the most widely used radionuclide for single photon emission computed tomography (SPECT) imaging procedures. The current strategy of availing 99m Tc is ensured from column chromatographic 99 Mo/ 99m Tc generators using a bed of acidic alumina. While the column chromatographic 99 Mo/ 99m Tc generator constitute a successful exemplar of availing 99m Tc, the limited capacity of alumina (2-20 mg Mo per g of alumina) for taking up molybdate ions necessitates the use of 99 Mo of the highest specific activity available, as can be found in fission produced 99 Mo (F 99 Mo). In order to reduce dependence of F 99 Mo, the scope of using low specific activity (n,γ) 99 Mo along with high capacity adsorbent is an interesting prospect. In this context, the scope of using nanomaterials as a viable adsorbent seemed attractive by virtue of their huge surface to volume ratios, altered physical properties, tailored surface chemistry, favorable adsorption characteristics, and enhanced surface reactivity resulting from the nanoscale dimensions. This emerging class of adsorbent represents an innovative paradigm and is expected to play an important role in the development of 99 Mo/ 99m Tc generators adaptable to the existing and foreseeable demands. This talk outlines a critical assessment on the role of nanostructured metal oxides, recent developments, the contemporary status, and key challenges and apertures to the near future. (author)

  20. MIBI-99mTc mammary scintigraphy

    International Nuclear Information System (INIS)

    Mayosky, Maria C.; Parma, Elvira P.; Armesto, Amparo M.; Zarlenga, Ana C.; Cresta, Carlos; Azar, Maria E.; Noblia, Cristina

    1999-01-01

    121 patients suspected of breast cancer were studied with MIBI- 99m Tc to evaluate the suitability of the mammary scintigraphy in patients with doubtful cancer diagnosis.The results show 93 % sensitivity and 95 % specificity and indicate the usefulness of this procedure to increase the accuracy of the diagnosis