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Sample records for rhodium 89

  1. Mesoporous metallic rhodium nanoparticles

    NASA Astrophysics Data System (ADS)

    Jiang, Bo; Li, Cuiling; Dag, Ömer; Abe, Hideki; Takei, Toshiaki; Imai, Tsubasa; Hossain, Md. Shahriar A.; Islam, Md. Tofazzal; Wood, Kathleen; Henzie, Joel; Yamauchi, Yusuke

    2017-05-01

    Mesoporous noble metals are an emerging class of cutting-edge nanostructured catalysts due to their abundant exposed active sites and highly accessible surfaces. Although various noble metal (e.g. Pt, Pd and Au) structures have been synthesized by hard- and soft-templating methods, mesoporous rhodium (Rh) nanoparticles have never been generated via chemical reduction, in part due to the relatively high surface energy of rhodium (Rh) metal. Here we describe a simple, scalable route to generate mesoporous Rh by chemical reduction on polymeric micelle templates [poly(ethylene oxide)-b-poly(methyl methacrylate) (PEO-b-PMMA)]. The mesoporous Rh nanoparticles exhibited a ~2.6 times enhancement for the electrocatalytic oxidation of methanol compared to commercially available Rh catalyst. Surprisingly, the high surface area mesoporous structure of the Rh catalyst was thermally stable up to 400 °C. The combination of high surface area and thermal stability also enables superior catalytic activity for the remediation of nitric oxide (NO) in lean-burn exhaust containing high concentrations of O2.

  2. Formation of supported rhodium clusters from mononuclear rhodium complexes controlled by the support and ligands on rhodium.

    PubMed

    Serna, Pedro; Yardimci, Dicle; Kistler, Joseph D; Gates, Bruce C

    2014-01-21

    Extremely small supported rhodium clusters were prepared from rhodium complexes on the surfaces of solids with contrasting electron-donor properties. The samples were characterized by infrared and extended X-ray absorption fine structure spectroscopies to determine the changes occurring in the rhodium species resulting from treatments in hydrogen. Rhodium cluster formation occurred in the presence of H2, and the first steps are controlled by the electron-donor properties of the support--which acts as a ligand--and the other ligands bonded to the rhodium. The cluster formation begins at a lower temperature when the support is zeolite HY than when it is the better electron-donor MgO, provided that the other ligands on rhodium are ethene. In contrast, when these other ligands are CO, the pattern is reversed. The choice of ligands including the support also allows regulation of the stoichiometry of the surface transformations in H2 and the stability of the structures formed in the presence of other reactants. The combination of MgO as the support and ethene as a ligand allows restriction of the rhodium cluster size to the smallest possible-and these were formed in high yields. The data presented here are among the first characterizing the first steps of metal cluster formation.

  3. Rhodium nanoparticles for ultraviolet plasmonics.

    PubMed

    Watson, Anne M; Zhang, Xiao; Alcaraz de la Osa, Rodrigo; Marcos Sanz, Juan; González, Francisco; Moreno, Fernando; Finkelstein, Gleb; Liu, Jie; Everitt, Henry O

    2015-02-11

    The nonoxidizing catalytic noble metal rhodium is introduced for ultraviolet plasmonics. Planar tripods of 8 nm Rh nanoparticles, synthesized by a modified polyol reduction method, have a calculated local surface plasmon resonance near 330 nm. By attaching p-aminothiophenol, local field-enhanced Raman spectra and accelerated photodamage were observed under near-resonant ultraviolet illumination, while charge transfer simultaneously increased fluorescence for up to 13 min. The combined local field enhancement and charge transfer demonstrate essential steps toward plasmonically enhanced ultraviolet photocatalysis.

  4. Superconductivity in zirconium-rhodium alloys

    NASA Technical Reports Server (NTRS)

    Zegler, S. T.

    1969-01-01

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

  5. 103Rh NMR spectroscopy and its application to rhodium chemistry.

    PubMed

    Ernsting, Jan Meine; Gaemers, Sander; Elsevier, Cornelis J

    2004-09-01

    Rhodium is used for a number of large processes that rely on homogeneous rhodium-catalyzed reactions, for instance rhodium-catalyzed hydroformylation of alkenes, carbonylation of methanol to acetic acid and hydrodesulfurization of thiophene derivatives (in crude oil). Many laboratory applications in organometallic chemistry and catalysis involve organorhodium chemistry and a wealth of rhodium coordination compounds is known. For these and other areas, 103Rh NMR spectroscopy appears to be a very useful analytical tool. In this review, most of the literature concerning 103Rh NMR spectroscopy published from 1989 up to and including 2003 has been covered. After an introduction to several experimental methods for the detection of the insensitive 103Rh nucleus, a discussion of factors affecting the transition metal chemical shift is given. Computational aspects and calculations of chemical shifts are also briefly addressed. Next, the application of 103Rh NMR in coordination and organometallic chemistry is elaborated in more detail by highlighting recent developments in measurement and interpretation of 103Rh NMR data, in relation to rhodium-assisted reactions and homogeneous catalysis. The dependence of the 103Rh chemical shift on the ligands at rhodium in the first coordination sphere, on the complex geometry, oxidation state, temperature, solvent and concentration is treated. Several classes of compounds and special cases such as chiral rhodium compounds are reviewed. Finally, a section on scalar coupling to rhodium is provided. 2004 John Wiley & Sons, Ltd.

  6. Rhodium-rhodium interactions in [Rh(β-diketonato)(CO)2] complexes

    NASA Astrophysics Data System (ADS)

    Conradie, Marrigje Marianne; van Rooyen, Petrus H.; Pretorius, Carla; Roodt, Andreas; Conradie, Jeanet

    2017-09-01

    The solid state single crystal structures of [Rh(β-diketonato)(CO)2], where β-diketonato = (R1COCHCOR2)-, with R1, R2 = CF3, C4H3S (1), C4H3S, C4H3S (2), Ph, C4H3S (3) and CF3, Ph (4), show that these complexes in some cases form dinuclear units, which stack in chains with weak metallophilic rhodium-rhodium interactions, while in other cases they produce continuous polymeric units, with equal intermolecular Rh⋯Rh distances. Different solid state structural data is reported herein for these four complexes, including a low temperature comparison with ambient data for (4). In the latter case, weak intermolecular halogen bonding has also been identified, which additionally contributes to the stability of (4) in the solid state. Computational evaluation of the frontier molecular orbitals of both dinuclear and tetranuclear models of complexes (1)-(4), show Rh(dz2)-Rh(dz2) σ bonding and σ* anti-bonding orbitals. An NBO analysis of the dinuclear units, revealed a donor-acceptor interaction between the two rhodium atoms in such a unit, while a QTAIM study identified a bonding path between the two rhodium atoms therein.

  7. Rhodium oxides in unusual oxidation states

    NASA Astrophysics Data System (ADS)

    Reisner, Barbara Alice

    Mixed valence RhIII/RhIV oxides have been proposed as a promising class of candidate compounds for superconductivity. Unfortunately, it is difficult to stabilize rhodates with a formal oxidation state approaching RhIV, as other techniques used for the synthesis of rhodium. oxides favor the most commonly observed formal oxidation state, RhIII. One technique which has been used to stabilize metal oxides in high formal oxidation states is crystallization from molten hydroxides. This thesis explores the use of molten hydroxides to enhance the reactivity of rhodium oxides in order to synthesize rhodates with high formal oxidation states. K0.5RhO2, Rb0.2RhO2, and CsxRhO2 were synthesized from pure alkali metal hydroxides. All crystallized with a previously unobserved polytype in the alkali metal rhodate system. Due to the low activity of dissolved oxygen species in LiOH and NaOH, LiRhO2 and NaRhO2 cannot be crystallized. The formal oxidation state of rhodium in AxRhO2 (A = K, Rb, Cs) is a function of the alkali metal hydroxide used to synthesize these oxides. These materials exhibit remarkable stability for layered metal oxides containing the heavier alkali metals, but all phases are susceptible to intercalation by water. The synthesis, structural characterization, magnetic susceptibility, and reactivity of these oxides are reported. Sr2RhO4 and a new rhodate were crystallized from a KOH-Sr(OH)2 flux. The synthesis and characterization of these materials is reported. Efforts to substitute platinum for rhodium in Sr 2RhO4 are also discussed. Mixed alkali metal-alkaline earth metal hydroxide fluxes were used to crystallize LiSr3RhO6, and NaSr3RhO 6. The synthesis of LiSr3RhO6 and NaSr3RhO 6 represents the first example of the stabilization of a rhodium oxide with a formal oxidation state approaching RhV. X-ray diffraction, electron beam microprobe analysis, thermogravimetric analysis, potentiometric titrations, X-ray photoelectron spectroscopy, and magnetic susceptibility

  8. Overgrowth of Rhodium on Gold Nanorods

    PubMed Central

    2012-01-01

    This study focuses on the deposition and growth mode of rhodium (Rh) on gold (Au) seed nanorods (NRs). Using a combination of scanning transmission electron microscopy imaging, energy-dispersive X-ray spectroscopy, and UV–visible absorption spectroscopy, we show that Rh deposition results in an uneven overlayer morphology on the Au NR seeds, with a tendency for Rh deposition to occur preferentially on the Au NR ends. The results suggest that complex and kinetically driven metal–metal interactions take place in this system. PMID:22582111

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

    PubMed

    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.

  10. Structural properties of small rhodium clusters

    SciTech Connect

    Soon, Yee Yeen; Yoon, Tiem Leong; Lim, Thong Leng

    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.

  11. Oxidation-promoted activation of a ferrocene C-H bond by a rhodium complex.

    PubMed

    Labande, Agnès; Debono, Nathalie; Sournia-Saquet, Alix; Daran, Jean-Claude; Poli, Rinaldo

    2013-05-14

    The oxidation of a rhodium(I) complex containing a ferrocene-based heterodifunctional phosphine N-heterocyclic carbene (NHC) ligand produces a stable, planar chiral rhodium(III) complex with an unexpected C-H activation on ferrocene. The oxidation of rhodium(I) to rhodium(III) may be accomplished by initial oxidation of ferrocene to ferrocenium and subsequent electron transfer from rhodium to ferrocenium. Preliminary catalytic tests showed that the rhodium(III) complex is active for the Grignard-type arylation of 4-nitrobenzaldehyde via C-H activation of 2-phenylpyridine.

  12. Examination of a low-temperature rhodium oxidation mechanism

    SciTech Connect

    Salanov, A.N.; Savchenko, V.I.

    1994-09-01

    The interaction of O{sub 2} with Rh(100) and polycrystalline rhodium at O{sub 2} pressures of 10{sup {minus}5} - 10{sup 3} Pa at 400-600 K is studied by thermodesorption and Auger electron spectroscopy. At P{sub O{sub 2}} = 10{sup {minus}5} - 10{sup {minus}1} Pa, a surface rhodium oxide is formed, whereas at P{sub O{sub 2}} {ge} 10{sup {minus}1} Pa, a bulk rhodium oxide (Rh{sub 2}O{sub 3}) is produced. The bulk oxide film grows by the Cabrera-Mott mechanism of low-temperature metal oxidation. The film growth is dependent on P{sub O{sub 2}} and the sample temperature. The data obtained indicates that the rhodium surface structure has a minor influence on the oxidation process.

  13. Rhodium-Catalyzed Dehydrogenative Borylation of Cyclic Alkenes

    PubMed Central

    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

  14. Enantioselective rhodium(I)-catalyzed hydrogenation of trifluoromethyl ketones.

    PubMed

    Kuroki, Y; Sakamaki, Y; Iseki, K

    2001-02-08

    [figure: see text] The asymmetric hydrogenation of trifluoromethyl ketones to yield chiral alpha-trifluoromethyl alcohols with enantiomeric excesses up to 98% was achieved in the presence of chiral rhodium-(amidephosphine-phosphinite) complexes.

  15. Polyethylene-bound rhodium(I) hydrogenation catalysts

    SciTech Connect

    Bergbreiter, D.E.; Chandran, R.

    1987-01-07

    Homogeneous, recoverable hydrogenation catalysts were prepared with use of functionalized ethylene oligomers as ligands. Phosphine groups were introduced onto ethylene oligomers following anionic oligomerization of ethylene. The product polyethylenediphenylphosphine ligands were then exchanged with triphenylphosphine or ethylene ligands to prepare ethylene oligomer ligated rhodium(I) complexes. These Rh(I) complexes had the solubility of polyethylene and dissolved at 90-110/sup 0/C in hydrocarbon solvents but quantitatively precipitated at 25/sup 0/C. Less than 0.1% of the charged rhodium was lost in each dissolution precipitation cycle. The rhodium(I) complexes so prepared were shown to have about 80% of the activity of tris(triphenylphosphine)rhodium chloride in hydrogenation of various alkenes including 1-octene, ..delta../sup 2/-cholestene, cyclooctene, cyclododecene, styrene, and ..cap alpha..-methylstyrene. /sup 31/P NMR spectroscopy and reactivity studies were used to characterize these catalysts.

  16. Low gravity containerless processing of immiscible gold rhodium alloys

    NASA Technical Reports Server (NTRS)

    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.

  17. Rhodium-Catalyzed Transannulation of 1,2,3-Triazoles with Nitriles

    PubMed Central

    Horneff, Tony; Chuprakov, Stepan; Chernyak, Natalia

    2009-01-01

    Stable and readily available 1-sulfonyl triazoles are converted to the corresponding imidazoles in good to excellent yields via a rhodium(II)-catalyzed reaction with nitriles. Rhodium iminocarbenoids are proposed intermediates. PMID:18855475

  18. Strontium-89 Chloride

    MedlinePlus

    ... ever had bone marrow disease, blood disorders, or kidney disease.you should know that strontium-89 chloride may interfere with the normal menstrual cycle (period) in women and may stop sperm production ...

  19. Rhodium(NHC)-catalyzed O-arylation of aryl bromides.

    PubMed

    Kim, Hyun Jin; Kim, Min; Chang, Sukbok

    2011-05-06

    The first example of the rhodium-catalyzed O-arylation of aryl bromides is reported. While the right combination of rhodium species and N-heterocyclic carbene (NHC) offered an effective catalytic system enabling the arylation to proceed, the choice of NHC was determined to be most important. The developed O-arylation protocol has a wide range of substrate scope, high functional group tolerance, and flexibility allowing a complementary route to either N- or O-arylation depending on the choice of NHC.

  20. High pressure synthesis of marcasite-type rhodium pernitride.

    PubMed

    Niwa, Ken; Dzivenko, Dmytro; Suzuki, Kentaro; Riedel, Ralf; Troyan, Ivan; Eremets, Mikhail; Hasegawa, Masashi

    2014-01-21

    Marcasite-type rhodium nitride was successfully synthesized in a direct chemical reaction between a rhodium metal and molecular nitrogen at 43.2 GPa using a laser-heated diamond-anvil cell. This material shows a low zero-pressure bulk modulus of K0 = 235(13) GPa, which is much lower than those of other platinum group nitrides. This finding is due to the weaker bonding interaction between metal atoms and quasi-molecular dinitrogen units in the marcasite-type structure, as proposed by theoretical studies.

  1. Radioiodinated and astatinated NHC rhodium complexes: synthesis.

    PubMed

    Rajerison, Holisoa; Guérard, François; Mougin-Degraef, Marie; Bourgeois, Mickael; Da Silva, Isidro; Chérel, Michel; Barbet, Jacques; Faivre-Chauvet, Alain; Gestin, Jean-François

    2014-05-01

    The clinical development of radioimmunotherapy with astatine-211 is limited by the lack of a stable radiolabeling method for antibody fragments. An astatinated N-heterocyclic carbene (NHC) Rhodium complex was assessed for the improvement of radiolabeling methodologies with astatine. Wet harvested astatine-211 in diisopropyl ether was used. Astatine was first reduced with cysteine then was reacted with a chlorinated Rh-NHC precursor to allow the formation of the astatinated analogue. Reaction conditions have been optimized. Astatine and iodine reactivity were also compared. Serum stability of the astatinated complex has been evaluated. Quantitative formation of astatide was observed when cysteine amounts higher than 46.2 nmol/μl of astatine solution were added. Nucleophilic substitution kinetics showed that high radiolabeling yields were obtained within 15 min at 60°C (88%) or within 5 min at 100°C (95%). Chromatographic characteristics of this new astatinated compound have been correlated with the cold iodinated analog ones. The radioiodinated complex was also synthesized from the same precursor (5 min. at 100°C, up to 85%) using [(125)I]NaI as a radiotracer. In vitro stability of the astatinated complex was controlled after 15 h incubation in human serum at 4°C and 37°C. No degradation was observed, indicating the good chemical and enzymatic stability. The astatinated complex was obtained in good yield and exhibited good chemical and enzymatic stability. These preliminary results demonstrate the interest of this new radiolabeling methodology, and further functionalizations should open new possibilities in astatine chemistry. Although there are many steps and pitfalls before clinical use for a new prosthetic group from the family of NHC complexes, this work may open a new path for astatine-211 targeting. Copyright © 2014 Elsevier Inc. All rights reserved.

  2. Electronic and magnetic properties of small rhodium clusters

    SciTech Connect

    Soon, Yee Yeen; Yoon, Tiem Leong; Lim, Thong Leng

    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.

  3. Recent advances in rhodium-catalyzed asymmetric synthesis of heterocycles.

    PubMed

    Chen, Wen-Wen; Xu, Ming-Hua

    2017-02-01

    Heterocycles are crucial structural motifs that are ubiquitously present in biologically active natural products and pharmaceutically important compounds. Over the past few decades, great attention has been paid to develop efficient methodologies for the construction of diverse enantioenriched heterocyclic frameworks. This review focuses on the recent impressive progress and advances in the asymmetric synthesis of heterocycles under rhodium catalysis.

  4. Discovery of rubidium, strontium, molybdenum, and rhodium isotopes

    SciTech Connect

    Parker, A.M.; Thoennessen, M.

    2012-07-15

    Currently, 31 rubidium, 35 strontium, 35 molybdenum, and 38 rhodium isotopes have been observed and the discovery of these isotopes is described here. For each isotope a brief synopsis of the first refereed publication, including the production and identification method, is presented.

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

    PubMed

    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.

  6. Rhodium complexes bearing tetradentate diamine-bis(phenolate) ligands

    SciTech Connect

    Liu, Xiang Y; Lokare, Kapil S; Ganesh, Somesh K; Gonzales, Jason M; Oxgaard, Jonas; Goddard, William A; Periana, Roy A

    2011-01-01

    Using tetradentate, dianionic ligands, several new rhodium complexes have been prepared. Some of these diamine-bis(phenolate) compounds, are active for C–H activation of benzene. These complexes are air and thermally stable. All four complexes were characterized by X-ray diffraction.

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

    PubMed

    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.

  8. Plasmonics in the UV range with Rhodium nanocubes

    NASA Astrophysics Data System (ADS)

    Zhang, X.; Gutiérrez, Y.; Li, P.; Barreda, Á. I.; Watson, A. M.; Alcaraz de la Osa, R.; Finkelstein, G.; González, F.; Ortiz, D.; Saiz, J. M.; Sanz, J. M.; Everitt, H. O.; Liu, J.; Moreno, F.

    2016-04-01

    Plasmonics in the UV-range constitutes a new challenge due to the increasing demand to detect, identify and destroy biological toxins, enhance biological imaging, and characterize semiconductor devices at the nanometer scale. Silver and aluminum have an efficient plasmonic performance in the near UV region, but oxidation reduces its performance in this range. Recent studies point out rhodium as one of the most promising metals for this purpose: it has a good plasmonic response in the UV and, as gold in the visible, it presents a low tendency to oxidation. Moreover, its easy fabrication through chemical means and its potential for photocatalytic applications, makes this material very attractive for building plasmonic tools in the UV. In this work, we will show an overview of our recent collaborative research with rhodium nanocubes (NC) for Plasmonics in the UV.

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

    PubMed

    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

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

    PubMed Central

    2013-01-01

    Background 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. Methods 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. Results 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. Conclusions 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

  11. Asymmetric Arylation of Imines Catalyzed by Heterogeneous Chiral Rhodium Nanoparticles.

    PubMed

    Yasukawa, Tomohiro; Kuremoto, Tatsuya; Miyamura, Hiroyuki; Kobayashi, Shu̅

    2016-06-03

    Asymmetric arylation of aldimines catalyzed by heterogeneous chiral rhodium nanoparticles has been developed. The reaction proceeded in aqueous media without significant decomposition of the imines by hydrolysis to afford chiral (diarylmethyl)amines in high yields with outstanding enantioselectivities. This catalyst system exhibited the highest turnover number (700) in heterogeneous catalysts reported to date for these reactions. The reusability of the catalyst was also demonstrated.

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

    PubMed Central

    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

  13. Recovery of rhodium(III) from solutions and industrial wastewaters by a sulfate-reducing bacteria consortium.

    PubMed

    Ngwenya, Nonhlanhla; Whiteley, Chris G

    2006-01-01

    A quantitative analysis of the rate of removal of rhodium(III) by a resting sulfate-reducing bacteria (SRB) consortium under different initial rhodium and biomass concentrations, pH, temperature, and electron donor was studied. Rhodium speciation was found to be the main factor controlling the rate of its removal from solution. SRB cells were found to have a higher affinity for anionic rhodium species, as compared to both cationic and neutral species, which become abundant when speciation equilibrium was reached. Consequently, a pH-dependent rate of rhodium removal from solution was observed. The maximum SRB uptake capacity for rhodium was found to be 66 mg of rhodium per gram of resting SRB biomass. Electron microscopy studies revealed a time-dependent localization and distribution of rhodium precipitates, initially intracellularly and then extracellularly, suggesting the involvement of an enzymatic reductive precipitation process. When a purified hydrogenase enzyme was incubated with rhodium chloride solution under hydrogen, 88% of the rhodium was removed within 1 h, whereas with a soluble extract from SRB 77% was removed within 10 min. Due to the low pH of the industrial effluent (1.31), the enzymatic reduction of rhodium by the purified hydrogenase was greatly limited, and it was apparent that an industrial effluent pretreatment was necessary before the application of an enzymatic treatment. In the present study, however, it was established that SRB are good candidates for the enzymatic recovery of rhodium from both aqueous solution and industrial effluent.

  14. Electronic structure of ternary rhodium hydrides with lithium and magnesium.

    PubMed

    Becker, Jonas Nils; Bauer, Jessica; Giehr, Andreas; Chu, Pui Ieng; Kunkel, Nathalie; Springborg, Michael; Kohlmann, Holger

    2014-01-21

    Chemical bonding in and electronic structure of lithium and magnesium rhodium hydrides are studied theoretically using DFT methods. For Li3RhH4 with planar complex RhH4 structural units, Crystal Orbital Hamilton Populations reveal significant Rh−Rh interactions within infinite one-dimensional ∞ 1 [RhH4] stacks in addition to strong rhodium−hydrogen bonding. These metal−metal interactions are considerably weaker in the hypothetical, heavier homologue Na3RhH4. Both compounds are small-band gap semiconductors. The electronic structures of Li3RhH6 and Na3RhH6 with rhodium surrounded octahedrally by hydrogen, on the other hand, are compatible with a classical complex hydride model according to the limiting ionic formula (M+)3[RhH6]3− without any metal−metal interaction between the 18-electron hydridorhodate complexes. In MgRhH, building blocks of the composition (RhH2)4 are formed with strong rhodium−hydrogen and significant rhodium−rhodium bonding (bond lengths of 298 pm within Rh4 squares). These units are linked together to infinite two-dimensional layers ∞ 2 [(RhH2/2)4] via common hydrogen atoms. Li3RhH4 and MgRhH are accordingly examples for border cases of chemical bonding where the classical picture of hydridometalate complexes in complex hydrides is not sufficient to properly describe the chemical bonding situation.

  15. STS-89 landing views

    NASA Image and Video Library

    1998-03-30

    STS089-S-013 (31 Jan. 1998) --- Interesting vortices at the wingtips of the space shuttle Endeavour tell-tale the spacecraft's landing on Runway 15 of the Shuttle Landing Facility (SLF), at the Kennedy Space Center (KSC). Main gear touchdown for the almost nine-day flight was at 5:35:09 p.m. (EST) Jan. 31, 1998. Complete wheel stop occurred at 5:36:19 p.m., making a total mission elapsed time of eight days, 19 hours, 48 minutes and four seconds. The 89th space shuttle mission marked the 42nd (and 13th consecutive) landing of a space shuttle at KSC. Onboard were astronauts Terrence W. Wilcutt, Joe F. Edwards Jr., Bonnie J. Dunbar, David A. Wolf, James F. Reilly and Michael P. Anderson; and the Russian Space Agency's (RSA) cosmonaut Salizhan S. Sharipov. Andrew S. W. Thomas had earlier gone into space aboard the Endeavour to replace Wolf aboard Russia's Mir Space Station. The ninth and final shuttle/Mir docking mission in the spring of this year will retrieve Thomas from the Mir complex. Photo credit: NASA

  16. STS-89 landing view

    NASA Image and Video Library

    1998-03-30

    STS089-S-012 (31 Jan. 1998) --- The drag chute on the space shuttle Endeavour is deployed as the spacecraft rolls down Runway 15 of the Shuttle Landing Facility (SLF) to successfully complete an almost-nine-day mission in Earth orbit. Main gear touchdown was at 5:35:09 p.m. (EST) Jan. 31, 1998. Complete wheel stop occurred at 5:36:19 p.m., making a total mission elapsed time of eight days, 19 hours, 48 minutes and four seconds. The 89th space shuttle mission marked the 42nd (and 13th consecutive) landing of a shuttle at Kennedy Space Center (KSC). Onboard were astronauts Terrence W. Wilcutt, Joe F. Edwards Jr., Bonnie J. Dunbar, David A. Wolf, James F. Reilly and Michael P. Anderson; and the Russian Space Agency's (RSA) cosmonaut Salizhan S. Sharipov. Andrew S. W. Thomas had earlier gone into space aboard the Endeavour to replace Wolf aboard Russia's Mir Space Station. The ninth and final shuttle/Mir docking mission in the spring of this year will retrieve Thomas from the Mir complex. Photo credit: NASA

  17. STS-89 landing views

    NASA Image and Video Library

    1998-04-22

    STS089-S-016 (31 Jan. 1998) --- The space shuttle Endeavour is just about to touch down on Runway 15 of the Shuttle Landing Facility (SLF), at Kennedy Space Center (KSC), to successfully complete an almost-nine-day mission in Earth orbit. Main gear touchdown was at 5:35:09 p.m. (EST) Jan. 31, 1998. Complete wheel stop occurred at 5:36:19 p.m., making a total mission elapsed time of eight days, 19 hours, 48 minutes and four seconds. The 89th space shuttle mission marked the 42nd (and 13th consecutive) landing of a space shuttle at KSC. Onboard were astronauts Terrence W. Wilcutt, Joe F. Edwards Jr., Bonnie J. Dunbar, David A. Wolf, James F. Reilly and Michael P. Anderson and the Russian Space Agency's (RSA) cosmonaut Salizhan S. Sharipov. Andrew S. W. Thomas had earlier gone into space aboard the Endeavour to replace Wolf aboard Russia's Mir Space Station. The ninth and final shuttle/Mir docking mission in the spring of this year will retrieve Thomas from the Mir complex. Photo credit: NASA

  18. The adsorption of acetylene on rhodium-modified colloidal silver, a surface-enhanced Raman study

    NASA Astrophysics Data System (ADS)

    Feilchenfeld, Hannah; Luckier, Miguel; Efron, Leah; Willner, Bilha

    Surface-enhanced Raman scattering (SERS) from molecules adsorbed on rhodium-modified colloidal silver particles is reported for the first time. Deposition of thin layers of metallic rhodium on the silver surface led to fast aggregation of the sol and to modifications of its SERS spectrum. An intense new band, assigned to the RhO stretching vibration of citrate ions bound to rhodium sites, appeared at 530 cm -1 in the Raman spectrum after rhodium addition to the suspension. The spectra of acetylene adsorbed on both unmodified silver particles and silver modified by an overlayer of rhodium indicated that acetylene displaced the citrate ions from their adsorption sites. All acetylene spectra were characterized by weak bands at 1990, 2050 and 2150 cm -1 assigned to σ π-complexes between acetylene and silver, by a silver acetylide peak at 1800 cm -1 and by an intense band at 1550 cm -1 due to C=C containing species formed on the surface. However, on the rhodium-modified colloid an additional band, attributed to acetylene σ π-bound to rhodium sites, was observed at 1910-1920 cm -1. The intensity of the new band was a direct function of the amount of rhodium deposited on the silver. It increased immediately after acetylene adsorption, and later slowly diminished, while simultaneously the 1550 cm -1 peak became more important. This time evolution was ascribed to a reaction taking place on the surface.

  19. Homogeneous hydrogenation of unsaturated organic compounds catalyzed by rhodium complexes containing trioctylamine as a ligand

    SciTech Connect

    Frolov, V.M.; Shuikina, L.P.; Turisbekova, K.K.; Bondarenko, G.N.

    1994-11-01

    Two new types of toluene-soluble rhodium-complex catalysts for hydrogenation of multiple carbon-carbon bonds are synthesized by the reaction of rhodium salts with trioctylamine. The productivity of these catalysts reaches 26000 moles of substrate per gram-atom of rhodium per hour at 20{degrees}C and at a hydrogen pressure of 0.1 MPa. The promoting effect of molecular oxygen and water on homogeneous rhodium-complex catalysts prepared by direct interaction of rhodium trichloride with trioctylamine is established. A scheme for catalyst activation involving the reversible chemisorption of oxygen by the complex is proposed on the basis of IR-spectroscopic data. The kinetics of hydrogenation of unsaturated hydrocarbons is studied.

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

    PubMed

    Carneiro, Marcella L B; Nunes, Eloiza S; Peixoto, Raphael C A; Oliveira, Ricardo G S; Lourenço, Luiza H M; da Silva, Izabel C R; Simioni, Andreza R; Tedesco, Antônio C; de Souza, Aparecido R; Lacava, Zulmira G M; Báo, Sônia N

    2011-03-28

    Rhodium (II) citrate (Rh(2)(H(2)cit)(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 (Rh(2)(H(2)cit)(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 Rh(2)(H(2)cit)(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 (Rh(2)(H(2)cit)(4)) and rhodium (II) citrate-loaded maghemite nanoparticles or magnetoliposomes, used as drug delivery systems, on both normal and carcinoma breast cell cultures. Treatment with free Rh(2)(H(2)cit)(4) induced cytotoxicity that was dependent on dose, time, and cell line. The IC(50) 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 Rh(2)(H(2)cit)(4)-loaded maghemite nanoparticles (Mag(h)-Rh(2)(H(2)cit)(4)) and Rh(2)(H(2)cit)(4)-loaded magnetoliposomes (Lip-Magh-Rh(2)(H(2)cit)(4)) induced a higher cytotoxicity on MCF-7 and 4T1 than on MCF-10A (p < 0.05). These treatments enhanced cytotoxicity up to 4.6 times. These cytotoxic effects, induced by free Rh(2)(H(2)cit)(4), were evidenced by morphological alterations such as nuclear fragmentation, membrane blebbing and phosphatidylserine exposure, reduction of actin filaments, mitochondrial condensation and an increase in number of vacuoles, suggesting that Rh(2)(H(2)cit)(4) induces cell death by apoptosis. The treatment with rhodium (II) citrate-loaded maghemite nanoparticles and magnetoliposomes induced more specific cytotoxicity

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

    PubMed

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

    2016-01-07

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

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

    NASA Technical Reports Server (NTRS)

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

    1973-01-01

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

  3. Rhodium-catalyzed enantioselective cyclopropanation of electron deficient alkenes

    PubMed Central

    Wang, Hengbin; Guptill, David M.; Alvarez, Adrian Varela

    2013-01-01

    The rhodium-catalyzed reaction of electron-deficient alkenes with substituted aryldiazoacetates and vinyldiazoacetates results in highly stereoselective cyclopropanations. With adamantylglycine derived catalyst Rh2(S-TCPTAD)4, high asymmetric induction (up to 98% ee) can be obtained with a range of substrates. Computational studies suggest that the reaction is facilitated by weak interaction between the carbenoid and the substrate carbonyl but subsequently proceeds via different pathways depending on the nature of the carbonyl.. Acrylates and acrylamides result in the formation of cyclopropanation products while the use of unsaturated aldehydes and ketones results in the formation of epoxides. PMID:24049630

  4. Structure of adsorbed organometallic rhodium: model single atom catalysts.

    PubMed

    Bennett, R A; McCavish, N D; Basham, M; Dhanak, V R; Newton, M A

    2007-02-02

    We have determined the structure of a complex rhodium carbonyl chloride [Rh(CO)2Cl] molecule adsorbed on the TiO2(110) surface by the normal incidence x-ray standing wave technique. The data show that the technique is applicable to reducible oxide systems and that the dominant adsorbed species is undissociated with Rh binding atop bridging oxygen and to the Cl found close to the fivefold coordinated Ti ions in the surface. A minority geminal dicarbonyl species, where Rh-Cl bond scission has occurred, is found bridging the bridging oxygen ions forming a high-symmetry site.

  5. Atomic-absorption determination of rhodium in chromite concentrates

    USGS Publications Warehouse

    Schnepfe, M.M.; Grimaldi, F.S.

    1969-01-01

    Rhodium is determined in chromite concentrates by atomic absorption after concentration either by co-precipitation with tellurium formed by the reduction of tellurite with tin(II) chloride or by fire assay into a gold bead. Interelement interferences in the atomic-absorption determination are removed by buffering the solutions with lanthanum sulphate (lanthanum concentration 1%). Substantial amounts of Ag, Al, Au, Bi, Ca, Cd, Co, Cr, Cu, Fe, Ho, Hg, K, La, Mg, Mn, Mo, Na, Ni, Pb, Te, Ti, V, Y, Zn and platinum metals can be tolerated. A lower limit of approximately 0.07 ppm Rh can be determined in a 3-g sample. ?? 1969.

  6. Degradation of nonmodified and rhodium modified aluminide coating deposited on CMSX 4 superalloy.

    PubMed

    Zagula-Yavorska, Maryana; Wierzbińska, Małgorzata; Gancarczyk, Kamil; Sieniawski, Jan

    2016-07-01

    The Ni-base superalloy CMSX 4 used in the turbine blades of aircraft engines was coated with rhodium layer (0.5-μm thick). Next coated CMSX 4 superalloy was aluminized by the CVD method. The rhodium modified aluminide coating and nonmodified aluminide coating were oxidized at 1100°C at the air atmosphere. The rhodium modified aluminide coating showed about twice better oxidation resistance than the nonmodified one. The spallation equal 62% of the total area was observed on the surface of the nonmodified coating whereas only 36% spallation area was observed on the surface of the rhodium modified aluminide coating after the oxidation test. The oxide layer formed on the surface of the nonmodified coating was composed of nonprotective (Ni,Cr)Al2 O4 and (Ni,Cr)O phases. Aluminium in the coating reacts with oxygen, forming a protective α-Al2 O3 oxide on the surface of the rhodium modified aluminide coating. When the oxide cracks and spalls due to oxidation, additional aluminium from the coating diffuses to the surface to form the oxide. The presence of protective Al2 O3 oxide on the surface of the rhodium modified aluminide coating slows coating degradation. Therefore, rhodium modified aluminide coating has better oxidation resistance than the nonmodified one. © 2016 The Authors Journal of Microscopy © 2016 Royal Microscopical Society.

  7. Recyclable rhodium nanoparticles: green hydrothermal synthesis, characterization, and highly catalytic performance in reduction of nitroarenes.

    PubMed

    Lee, Yohan; Jang, Seongwan; Cho, Chang-Woo; Bae, Jong-Seong; Park, Sungkyun; Park, Kang Hyun

    2013-11-01

    In this work, rhodium nanoparticles were synthesized using hydrothermal method that is simple and easy to manipulate reaction and use nontoxic supercritical water. The rhodium nanoparticles were formed in uniform size and shape. These Rh NPs also acted as a efficient heterogenous catalyst in reduction of 4-nitrophenol to 4-aminophenol. Moreover, the rhodium nanoparticles can be recycled without any loss in catalytic activity, and showed highly catalytic activity for various nitroarenes. Therefore, this method will contribute greatly to the development of environmental field and be suitable for use in the industry.

  8. Structural Evolution of a Recoverable Rhodium Hydrogenation Catalyst

    SciTech Connect

    Shaw, Wendy J.; Chen, Yongsheng; Fulton, John L.; Linehan, John C.; Gutowska, Anna; Bitterwolf, Thomas E.

    2008-06-01

    N-isopropylacrylamide was utilized as a ligand to affect recoverability into a rhodium hydrogenation catalyst. The catalyst ligand structure was characterized in situ using NMR, XAFS and IR. Model compounds including glycine, cysteamine and methionine methyl ester were also investigated to aid in the interpretation. The investigation revealed a ligand switch from RNH2 to RSR’ when the catalyst is placed in water as opposed to organic solvents. The catalyst continued to transform with time, creating Rh clusters of up to 4 rhodium atoms, with no Rh metal detected. Over the time and solvents investigated, the catalyst ligands evolve from 1-Cl, 1-NH2, and 2-CO’s to 3-Rh, 1-RSR’ and 1-CO. Upon introduction of the alkene for hydrogenation catalysis, the Rh cluster is lost, favoring instead the interaction with the reactant. The kinetics of the hydrogenation reaction were measured using a novel high pressure flow through NMR system and the catalyst was found to have a TOF of 3000/hr at 25 ºC. This work was supported by the Laboratory Directed Research and Development Program at the Pacific Northwest National Laboratory operated by Battelle for the U.S. Department of Energy.

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

    PubMed

    Merola, Joseph S; Franks, Marion A

    2015-02-01

    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 between the rhodium and iridium compounds, highlighting their isostructural relationships.

  10. Chloride-Bridged Dinuclear Rhodium(III) Complexes Bearing Chiral Diphosphine Ligands: Catalyst Precursors for Asymmetric Hydrogenation of Simple Olefins.

    PubMed

    Kita, Yusuke; Hida, Shoji; Higashihara, Kenya; Jena, Himanshu Sekhar; Higashida, Kosuke; Mashima, Kazushi

    2016-07-11

    Efficient rhodium(III) catalysts were developed for asymmetric hydrogenation of simple olefins. A new series of chloride-bridged dinuclear rhodium(III) complexes 1 were synthesized from the rhodium(I) precursor [RhCl(cod)]2 , chiral diphosphine ligands, and hydrochloric acid. Complexes from the series acted as efficient catalysts for asymmetric hydrogenation of (E)-prop-1-ene-1,2-diyldibenzene and its derivatives without any directing groups, in sharp contrast to widely used rhodium(I) catalytic systems that require a directing group for high enantioselectivity. The catalytic system was applied to asymmetric hydrogenation of allylic alcohols, alkenylboranes, and unsaturated cyclic sulfones. Control experiments support the superiority of dinuclear rhodium(III) complexes 1 over typical rhodium(I) catalytic systems. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

    SciTech Connect

    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.

  12. Rhodium-Catalyzed Ketone Methylation Using Methanol Under Mild Conditions: Formation of α-Branched Products**

    PubMed Central

    Chan, Louis K M; Poole, Darren L; Shen, Di; Healy, Mark P; Donohoe, Timothy J

    2014-01-01

    The rhodium-catalyzed methylation of ketones has been accomplished using methanol as the methylating agent and the hydrogen-borrowing method. The sequence is notable for the relatively low temperatures that are required and for the ability of the reaction system to form α-branched products with ease. Doubly alkylated ketones can be prepared from methyl ketones and two different alcohols by using a sequential one-pot iridium- and rhodium-catalyzed process. PMID:24288297

  13. Rhodium Complex and Enzyme Couple Mediated Electrochemical Detection of Adenosine.

    PubMed

    Han, Dawoon; Kim, Hyeong-Mook; Chand, Rohit; Kim, Gyumin; Shin, Ik-Soo; Kim, Yong-Sang

    2015-10-01

    Adenosine is one of the nucleoside which plays an important role in signal transduction and neuromodulation. This work proposes a simple electrochemical assay, comprising two enzymes and rhodium complex based electron transfer mediator, for the detection of adenosine. Sequential reaction of adenosine deaminase and L-glutamic dehydrogenase and the supporting cycle between β-NADH and mediator enable quantitative analysis of adenosine. Role of electron transfer mediator is the conveyance of proton from electrode to β-NAD(+) for regeneration of β-NADH. The electrochemical characteristics of electron transfer mediator were also studied. Real-time adenosine detection was carried out using this multiple enzyme based chronoamperometric assay. The analysis results show a low limit of detection (140 μM) and good correspondence between current signal and the adenosine concentration (R (2) = 0.997).

  14. Thermal effects on Rhodium nanoparticles supported on carbon

    NASA Astrophysics Data System (ADS)

    Agostini, G.; Grisenti, R.; Lamberti, C.; Piovano, A.; Fornasini, P.

    2013-04-01

    EXAFS measurements have been made in the temperature range 5 - 300 K on rhodium nano-clusters of average diameters 15.9 and 11.5 Å (rms dispersion 7.2 and 4.7 Å, respectively) supported on carbon, as well as on a Rh reference foil. The preliminary results of the first shell analysis are presented. The Debye temperature is slightly smaller in n-Rh with respect to bulk and decreases when the cluster size decreases. The results of amplitude analysis (coordination number and static DW) are sensitive to the inclusion of the 4th cumulant. In going from bulk Rh to n-Rh and decreasing the nanocluster size the average coordination number decreases and the static disorder increases. A contraction of the average nearest-neighbour distance is observed at 5 K, -0.004 Å and -0.009 Å for the larger and smaller clusters, respectively, accompanied by a very slight thermal expansion.

  15. Nuclear Data Sheets for A = 89

    SciTech Connect

    Singh, Balraj

    2013-01-15

    The evaluated experimental data are presented for 14 known nuclides of mass 89 (Ge, As, Se, Br, Kr, Rb, Sr, Y, Zr, Nb, Mo, Tc, Ru, Rh). New data on high–spin excitations are available for {sup 89}Kr, {sup 89}Rb, {sup 89}Sr, {sup 89}Tc and {sup 89}Ru, including a superdeformed structure in {sup 89}Tc. Fluorescence studies in {sup 89}Y have revealed a large number of new levels in 7–11 MeV range. New two–neutron transfer data are available for {sup 89}Zr. New direct and precise measurement of atomic masses of {sup 89}Se, {sup 89}Br, 89{sup K}r, {sup 89}Rb, {sup 89}Mo and {sup 89}Tc have greatly improved the Q value landscape in this mass region. This work supersedes previous A=89 evaluation published in 1998Si31, and also the older ones 1989Si20, 1975Ko21, and M.W. Johns et al., Nuclear Data Tables A 8, 373 (1970). In spite of extensive experimental work on the isobaric nuclei of this mass chain several deficiencies remain. The identification of {sup 89}Rh isotope remains unconfirmed. The half–lives of ground states of {sup 89}Ge, {sup 89}As and {sup 89}Rh have not been measured, only the lower limits are estimated from time–of–flight in a reaction and experimental arrangement, where produced and identified. The decay schemes of {sup 89}Ge, {sup 89}As, {sup 89}Se, {sup 89}Ru and {sup 89}Rh are not known, and those for {sup 89}Tc and {sup 89}Mo are incomplete. High–lying (neutron unbound) levels in {sup 89}Kr, expected to be populated in the decay of {sup 89}Br, have not been investigated. The spins and parities for levels in {sup 89}Kr are largely unassigned, while for {sup 89}Tc and {sup 89}Ru, only few low–spin excitations are established. For {sup 89}Rb, little information is available for high–spin structures. Detailed gamma–ray data are available for {sup 88}Sr(n,γ){sup 89}Sr reaction, but most of these γ rays remain unassigned in a level scheme. Excited state data are nonexistent for {sup 89}Ge, {sup 89}As, {sup 89}Se, {sup 89}Br and {sup

  16. Strong Metal-Support Interactions (smsi) in Model Titania-Supported Rhodium Catalysts.

    NASA Astrophysics Data System (ADS)

    Sadeghi, Hassan Roger

    Model catalysts consisting of rhodium particles supported on well characterized, single crystal rutile substrates were used to study the nature of strong metal -support interactions (SMSI) in supported catalyst systems. The use of single crystal supports eliminates many of the complications inherent with powder supported catalysts and greatly simplifies the interpretation of experimental data. A variety of surface sensitive electron spectroscopic techniques, including ultraviolet and x-ray photoemission (UPS and XPS), electron energy loss (ELS) and Auger spectroscopies, low energy electron diffraction (LEED), combined with chemisorption measurements were applied to rhodium on titania model catalysts in order to separate the various phenomena that contribute to SMSI. The properties of the clean titania supports have been determined, including the dynamics of oxidation of reduced surfaces. Model catalysts were then prepared by thermal evaporation of rhodium onto these supports. The high temperature reduction procedures that produce the SMSI state on powder supported catalysts have been used on the model catalysts, and Auger sputter profiles indicate that during high temperature reduction (HTR) a suboxide of titanium migrates onto the rhodium particles, thus blocking carbon monoxide chemisorption. Removal of the suboxide layer by ion bombardment restores the normal chemisorption properties of the catalyst. Model rhodium on titania catalysts fabricated on both fully oxidized and on partially reduced single crystal supports have also been used. In this way it is possible to observe support-to-metal charge transfer in the absence of the encapsulation that accompanies HTR. The experimental results show that reduced titania species and rhodium interact with each other through a partially ionic bond, with electronic charge transferred from the reduced titanium cations to the rhodium. This bonding interaction is part of the driving force that leads to encapsulation of the

  17. Level structure of 89Mo

    NASA Astrophysics Data System (ADS)

    García-Bermúdez, G.; Cardona, M. A.; Ribas, R. V.; Filevich, A.; Achterberg, E.; Szybisz, L.

    1993-10-01

    The level structure of 89Mo has been studied with the 60Ni(32S,2pn) reaction at 110 MeV beam energy. Mainly two bands of γ rays depopulating states of probable spin-parity values ranging up to (27/2)+ were determined from the excitation function, neutron and γ-γ coincidences, and γ-ray angular distributions. The high-spin states of 89Mo show a scheme very similar to that of the 87Zr isotone. The interpretation of these states in terms of the three neutron-hole configuration (νg9/2)-3 and core-excited states is discussed.

  18. Structure and transport behavior of In-filled cobalt rhodium antimonide skutterudites

    SciTech Connect

    Eilertsen, James; Berthelot, Romain; Sleight, Arthur W.; Subramanian, M.A.

    2012-06-15

    The effect of indium icosahedral void-site filling on the transport properties of cobalt and rhodium antimonide solid solutions is investigated. Co{sub 4-x}Rh{sub x}Sb{sub 12} and indium-filled In{sub 0.1}Co{sub 4-x}Rh{sub x}Sb{sub 12} solid solutions were synthesized. Partial rhodium substitution produces a distinct clustering-induced lattice strain that is partly relieved upon indium substitution into the skutterudite icosahedral void-sites. Indium lowers the thermal conductivity of all samples near room temperature. A distinct increase in thermal conductivity is observed in all indium-filled rhodium substituted samples at elevated temperatures and is attributed to bipolar thermal conductivity. In addition, the indium-filled samples were subjected to a 6-day heat treatment at 673 K. Void-site filled indium was found to be metastable at this temperature, and was found to partially precipitate during the 6-day heat treatment; thereby presenting concerns over the long-term stability of thermoelectric devices based on indium-filled skutterudites. - Graphical Abstract: Strain in the cobalt rhodium skutterudite solid solutions decreases upon indium filling. Highlights: Black-Right-Pointing-Pointer Unfilled and indium-filled cobalt and rhodium skutterudite solid solutions were synthesized. Black-Right-Pointing-Pointer Indium filling stabilizes the cobalt and rhodium skutterudite solid solutions. Black-Right-Pointing-Pointer The thermoelectric properties of all compositions are reported. Black-Right-Pointing-Pointer The thermal conductivity of rhodium-rich compositions is strongly affected by indium filling. Black-Right-Pointing-Pointer Void-site filled indium was found to be metastable.

  19. 1988-89 Basic Agenda.

    ERIC Educational Resources Information Center

    Randall, John D.; And Others

    The "Basic Agenda" of the Board of Governors of the California Community Colleges (CCC) is developed annually to establish priorities for the community college system and act as the Board's chief policy-making document. The 1988-89 agenda identifies 20 major issues facing the colleges and offers concrete solutions for their resolution…

  20. Zeolite-supported rhodium complexes and clusters: switching catalytic selectivity by controlling structures of essentially molecular species.

    PubMed

    Serna, Pedro; Gates, B C

    2011-04-06

    Precise synthesis and characterization of site-isolated rhodium complexes and extremely small rhodium clusters supported on zeolite HY allow control of the catalyst selectivity in the conversion of ethene to n-butene or ethane, respectively, as a result of tuning the structure of the active sites at a molecular level.

  1. 40 CFR 89.6 - Reference materials.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ...” 89.120; 89.207; 89.509. (2) SAE material. The following table sets forth material from the Society of... Commonwealth Dr., Warrendale, PA 15096-0001. Document number and name 40 CFR part 89 reference SAE J244 June 83: Recommended Practice for Measurement of Intake Air or Exhaust Gas Flow of Diesel Engines 89.416-96 SAE...

  2. Rhodium mediated bond activation: from synthesis to catalysis

    SciTech Connect

    Ho, Hung-An

    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

  3. X-ray photoelectron spectroscopy as a probe of rhodium-ligand interaction in ionic liquids

    NASA Astrophysics Data System (ADS)

    Men, Shuang; Lovelock, Kevin R. J.; Licence, Peter

    2016-02-01

    We use X-ray photoelectron spectroscopy (XPS) to identify the interaction between the rhodium atom and phosphine ligands in six 1-octyl-3-methylimidazolium-based ionic liquids ([C8C1Im][X]). The formation of a mono-phosphine rhodium complex based upon addition of triphenylphosphine (PPh3) is confirmed by XPS in all ionic liquids studied herein. Due to the electron donation effect of the ligand, the rhodium atom becomes more negatively charged and thus exhibits a lower measured binding energy. The influence of the anion basicity on the formation of different types of rhodium complexes is also investigated. By introducing a biphosphine ligand, a chelated diphosphine rhodium complex is formed in ionic liquids with more basic anions and verified by both XPS and Infrared Spectroscopy (IR). The measured Rh 3d binding energies are correlated to the reaction selectivity of a hydroformylation reaction which inspires a method to design a metal catalyst to control the chemical reaction towards desired products in the future.

  4. Rhodium chemzymes: Michaelis-Menten kinetics in dirhodium(II) carboxylate-catalyzed carbenoid reactions.

    PubMed

    Pirrung, Michael C; Liu, Hao; Morehead, Andrew T

    2002-02-13

    Rhodium carboxylate-mediated reactions of diazoketones involving cyclopropanation, C-H insertion, and aromatic C-C double bond addition/electrocyclic ring opening obey saturation (Michaelis-Menten) kinetics. Axial ligands for rhodium, including aromatic hydrocarbons and Lewis bases such as nitriles, ethers, and ketones, inhibit these reactions by a mixed kinetic inhibition mechanism, meaning that they can bind both to the free catalyst and to the catalyst-substrate complex. Substrate inhibition can also be exhibited by diazocompounds bearing these groupings in addition to the diazo group. The analysis of inhibition shows that the active catalyst uses only one of its two coordination sites at a time for catalysis. Some ketones exhibit the interesting property that they selectively bind to the catalyst-substrate complex. The similarity of the kinetic constants from different types of reactions with similar diazoketones, regardless of the linking unit or the environment of the reacting alkene, suggests that the rate-determining step is the generation of the rhodium carbenoid. A very useful rhodium carboxylate catalyst for asymmetric synthesis, Rh(2)(DOSP)(4), shows slightly slower kinetic parameters than the achiral catalysts, implying that enantioselectivity of this catalyst is based on slowing reactions from one of the enantiotopic faces of the reactant, rather than any type of ligand-accelerated catalysis. A series of rhodium catalysts derived from acids with pK(a)s spanning 4 orders of magnitude give very similar kinetic constants.

  5. Synthesis of phthalocyanine stabilized rhodium nanoparticles and their application in biosensing of cytochrome c.

    PubMed

    Lokesh, K S; Shivaraj, Y; Dayananda, B P; Chandra, Sudeshna

    2009-06-01

    A single step synthesis route is described for the preparation of rhodium nanoparticles using a cobalt aminophthalocyanine macrocyclic complex as a stabilizer. The results of nanoparticles characterization using electronic absorption, Raman and X-ray spectroscopes as well as transmission electron microscopy are reported. Rhodium nanoparticle modified electrode behavior as examined by cyclic and differential pulse voltammetry is also provided. The nanoparticles were found to be well dispersed and stabilized throughout the macromolecular matrix. TEM studies showed that they have an average diameter of 3 to 5 nm with spherical shape. The colloidal rhodium was then used for electrochemical sensing of cytochrome c using glassy carbon electrode. The results showed that the colloidal rhodium nanoparticles enhanced the electron transfer process between cytochrome c and the electrode. Differential pulse voltammetric measurements of cytochrome c at the colloidal rhodium nanoparticles modified glassy carbon electrode showed a linear relationship with the oxidation peak currents in the concentration range of 100 nM to 3 microM of cytochrome c.

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

    NASA Astrophysics Data System (ADS)

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

    The interactions of rhodium complex RhCl(CO)(TPPTS)2 [TPPTS = P(m-C6H4SO3Na)3] with cationic, nonionic, and anionic surfactants have been investigated by UV-vis, fluorescence and 1H 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.

  7. 10 CFR 52.89 - [Reserved

    Code of Federal Regulations, 2010 CFR

    2010-01-01

    ... 10 Energy 2 2010-01-01 2010-01-01 false 52.89 Section 52.89 Energy NUCLEAR REGULATORY COMMISSION (CONTINUED) LICENSES, CERTIFICATIONS, AND APPROVALS FOR NUCLEAR POWER PLANTS Combined Licenses § 52.89...

  8. 10 CFR 52.89 - [Reserved

    Code of Federal Regulations, 2014 CFR

    2014-01-01

    ... 10 Energy 2 2014-01-01 2014-01-01 false 52.89 Section 52.89 Energy NUCLEAR REGULATORY COMMISSION (CONTINUED) LICENSES, CERTIFICATIONS, AND APPROVALS FOR NUCLEAR POWER PLANTS Combined Licenses § 52.89 ...

  9. 10 CFR 52.89 - [Reserved

    Code of Federal Regulations, 2013 CFR

    2013-01-01

    ... 10 Energy 2 2013-01-01 2013-01-01 false 52.89 Section 52.89 Energy NUCLEAR REGULATORY COMMISSION (CONTINUED) LICENSES, CERTIFICATIONS, AND APPROVALS FOR NUCLEAR POWER PLANTS Combined Licenses § 52.89 ...

  10. 10 CFR 52.89 - [Reserved

    Code of Federal Regulations, 2011 CFR

    2011-01-01

    ... 10 Energy 2 2011-01-01 2011-01-01 false 52.89 Section 52.89 Energy NUCLEAR REGULATORY COMMISSION (CONTINUED) LICENSES, CERTIFICATIONS, AND APPROVALS FOR NUCLEAR POWER PLANTS Combined Licenses § 52.89 ...

  11. 10 CFR 52.89 - [Reserved

    Code of Federal Regulations, 2012 CFR

    2012-01-01

    ... 10 Energy 2 2012-01-01 2012-01-01 false 52.89 Section 52.89 Energy NUCLEAR REGULATORY COMMISSION (CONTINUED) LICENSES, CERTIFICATIONS, AND APPROVALS FOR NUCLEAR POWER PLANTS Combined Licenses § 52.89 ...

  12. Microstructure and oxidation behaviour investigation of rhodium modified aluminide coating deposited on CMSX 4 superalloy.

    PubMed

    Zagula-Yavorska, Maryana; Morgiel, Jerzy; Romanowska, Jolanta; Sieniawski, Jan

    2016-03-01

    The CMSX 4 superalloy was coated with rhodium 0.5-μm thick layer and next aluminized by the CVD method. The coating consisted of two layers: the additive and the interdiffusion one. The outward diffusion of nickel from the substrate turned out to be a coating growth dominating factor. The additive layer consists of the β-NiAl phase, whereas the interdiffusion layer consists of the β-NiAl phase with precipitates of σ and μ phases. Rhodium has dissolved in the coating up to the same level in the matrix and in the precipitates. The oxidation test proved that the rhodium modified aluminide coating showed about twice better oxidation resistance than the nonmodified one.

  13. Inhibition of carrageenin paw edema by pyridinalalkylimine rhodium(I) complexes.

    PubMed

    Sava, G; Pacor, S; Ceschia, V; Zassinovich, G; Mestroni, G

    1989-01-01

    The effects of a series of pyridinalalkyl-1,5-cyclooctadiene Rhodium(I) complexes were studied on the carrageenin paw edema model, using Sprague-Dawley rats. The series of compounds used were administered at 35, 70 and 140 mumol/kg i.p. 1hr before carrageenin application, and the effect was measured 4hr after carrageenin. The 1,5-cyclooctadienepyridinalaldoxime Rhodium(I) complex proved to be the most active compound, effective also when administered 1hr after carrageenin induction of paw swelling. However, the effects of this complex are not superior to those reported for the methyl derivative, and the overall antiinflammatory activity is inferior to that of this latter compound, particularly when the number of dosages causing at least 80% inhibition are compared. These data are consistent with those obtained in a previous investigation indicating that Rhodium(I) complexes have potential antiinflammatory properties, susceptible of further investigations extended also to other models of inflammatory disease.

  14. Monodisperse Platinum and Rhodium Nanoparticles as Model Heterogeneous Catalysts

    SciTech Connect

    Grass, Michael Edward

    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.

  15. Rhodium pair-sites on magnesium oxide: Synthesis, characterization, and catalysis of ethylene hydrogenation

    SciTech Connect

    Yang, Dong; Xu, Pinghong; Guan, Erjia; Browning, Nigel D.; Gates, Bruce C.

    2016-06-01

    Supported rhodium acetate dimers were prepared by the reaction of Rh2(OAc)4 (OAc is acetate) with highly dehydroxylated MgO powder and characterized by extended X-ray absorption fine structure and infrared (IR) spectra, which show that the supported species were well represented as Rh2(OAc)3, with each Rh atom on average bonded to one oxygen atom of the MgO surface. Aberration-corrected scanning transmission electron microscopy gave images of Rh atoms in pairs on the MgO. The supported rhodium dimers were probed with a pulse of CO, and the IR spectra indicate a Rh(II) species with weakly bonded carbonyl ligands; the sharpness of the νCO band indicates highly uniform surface species. Further treatment in CO led to breakup of the rhodium dimers into mononuclear species; such fragmentation took place in other treatment gases as well, with the degree of fragmentation decreasing in the order CO > C2H4 > helium. The fragmentation is inferred on the basis of IR spectra to have proceeded through intermediate Rh2 species without acetate ligands. In contrast, rhodium dimers were reduced and not fragmented in the presence of H2 at 353 K, but at higher temperatures the rhodium aggregated to give larger clusters. The supported species catalyzed ethylene hydrogenation at 298 K and 1 bar at a H2 to ethylene molar ratio of 4; after 27 h of catalysis in a once-through flow reactor, acetate ligands were removed from the dimers, and some of them fragmented, as shown by IR spectroscopy. The intermediate dirhodium species without acetate ligands are two or three orders of magnitude more active as catalysts than the supported mononuclear rhodium species or those present predominantly as Rh2(OAc)3, respectively.

  16. Formation of Hexagonal-Close Packed (HCP) Rhodium as a Size Effect.

    PubMed

    Huang, Jing Lu; Li, Zhi; Duan, Hao Hong; Cheng, Zhi Ying; Li, Ya Dong; Zhu, Jing; Yu, Rong

    2017-01-18

    Previous studies on the structural and functional properties of rhodium are based on the face-centered-cubic (fcc) structure in the bulk form. Here we report the first discovery of the hexagonal-close packed (hcp) rhodium in the nanoparticle form. The hcp Rh can be directly synthesized by solvothermal reaction or by electron-beam induced decomposition of Rh monolayers. The hcp Rh nanoparticles are stable under electron beam irradiation. Compared with the fcc structure, the hcp Rh nanoparticles show a large lattice expansion (6% larger atomic volume). The first-principles calculations suggest that the lower surface energy of hcp Rh leads to the size effect in the crystal structure.

  17. Electrochemical Behavior and Electrodeposition of Nanostructured Rhodium from Low-Temperature Carbamide and Acetamide Containing Melts

    NASA Astrophysics Data System (ADS)

    Kochetova, Svetlana; Savchuk, Anastasiya; Shakhnin, Dmytro; Malyshev, Viktor

    2017-05-01

    The electrochemical behavior of rhodium at low-temperature carbamide-chloride and acetamide-chloride melts was investigated. It was found that, during rhodium anodic dissolution in carbamide and acetamide containing chloride melts, mixed complexes [Rh(NH3)4Cl2]+ of quasi-octahedral symmetry D4h are produced. The composition and structure of nascent complex ions have been studied. During electrochemical reduction of [Rh(NH3)4Cl2]+ complexes, the synthesis of Rh nanoparticles, as well as Fe, Cu, and Mo nanocoatings, were realized.

  18. Thermoelectric homogeneity and stability of platinum-rhodium alloyed thermoelements of different compositions

    NASA Astrophysics Data System (ADS)

    Edler, F.; Ederer, P.

    2013-09-01

    This paper discusses the different oxidation behavior of platinum and rhodium and their alloys usable as thermocouple materials. A specially prepared thermocouple containing thermoelements of different platinum-rhodium alloys (Pt-5%Rh, Pt-6%Rh, Pt-13%Rh, Pt-17%Rh and Pt-20%Rh) and a Pt-67 thermoelement was investigated. It was annealed at different temperatures in air. The thermoelectric homogeneity and stability of the thermocouple was tested by measurements of immersion profiles at 400 °C in a salt bath. The alloys of Pt-17%Rh and Pt-20%Rh were found to be the most suitable compositions with regard to thermoelectric homogeneity and stability.

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

    PubMed

    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.

  20. Phosphabarrelenes as ligands in rhodium-catalyzed hydroformylation of internal alkenes essentially free of alkene isomerization.

    PubMed

    Fuchs, Evelyn; Keller, Manfred; Breit, Bernhard

    2006-09-06

    Despite significant research efforts in the past, one of the remaining problems to be solved in industrially important hydroformylation is the chemoselective low-pressure hydroformylation of internal alkenes. We report here on a new class of phosphabarrelene/rhodium catalysts 2 that display very high activity towards hydroformylation of internal alkenes with an unusually low tendency towards alkene isomerization. Preparation of new phosphabarrelene ligands, studies of their coordination properties, as well as results obtained in the rhodium-catalyzed hydroformylation of cyclic and acyclic internal alkenes are reported.

  1. Probing the structures of gas-phase rhodium cluster cations by far-infrared spectroscopy

    SciTech Connect

    Harding, D. J.; Gruene, P.; Haertelt, M.; Meijer, G.; Fielicke, A.; Hamilton, S. M.; Hopkins, W. S.; Mackenzie, S. R.; Neville, S. P.; Walsh, T. R.

    2010-12-07

    The geometric structures of small cationic rhodium clusters Rh{sub n}{sup +} (n = 6-12) are investigated by comparison of experimental far-infrared multiple photon dissociation spectra with spectra calculated using density functional theory. The clusters are found to favor structures based on octahedral and tetrahedral motifs for most of the sizes considered, in contrast to previous theoretical predictions that rhodium clusters should favor cubic motifs. Our findings highlight the need for further development of theoretical and computational methods to treat these high-spin transition metal clusters.

  2. Production of 89Sr in solution reactor.

    PubMed

    Chuvilin, D Yu; Khvostionov, V E; Markovskij, D V; Pavshook, V A; Ponomarev-Stepnoy, N N; Udovenko, A N; Shatrov, A V; Vereschagin, Yu I; Rice, J; Tome, L A

    2007-10-01

    The new method for medical (89)Sr production in a reactor with solution fuel is proposed which is characterized by simplicity, high production efficiency and low buildup of radioactive waste. The main advantages of the new technology were validated by numerous experiments. The proposed new technology selectively extracts (89)Sr from a fuel of solution reactor and precludes penetration of (90)Sr into the final product. This method is based on the presence of gaseous radionuclide (89)Kr (T(1/2)=190.7s) in the decay chain (89)Se-->(89)Br-->(89)Kr-->(89)Rb-->(89)Sr. The performed experiments on taking the gas probes from internal volume of the solution 20 kW mini-reactor "Argus" have confirmed that the mechanism for (89)Sr delivery to the sorption volume of the reactor experimental loop is based on transport of gaseous (89)Sr predecessor-radionuclide (89)Kr. According to the measurements of radioactive impurities in a final (89)SrCl(2) solution, the filtration of the gas flow with cermet filters followed by cleaning of (89)Sr chloride solution in chromatographic columns with DOWEX-50 x 8 or Sr-Resin ensures reception of (89)Sr fully meeting the requirements for medical application. The experimental estimations have shown that the proposed new technology is multiply more productive than the traditional industrial methods of (89)Sr reception.

  3. N-tosyloxycarbamates as a source of metal nitrenes: rhodium-catalyzed C-H insertion and aziridination reactions.

    PubMed

    Lebel, Hélène; Huard, Kim; Lectard, Sylvain

    2005-10-19

    The rhodium-catalyzed decomposition of N-tosyloxycarbamates to generate metal nitrenes which undergo intramolecular C-H insertion or aziridination reaction is described. Aliphatic N-tosyloxycarbamates produce oxazolidinones with high yields and stereospecificity through insertion in benzylic, tertiary, and secondary C-H bonds. Intramolecular aziridination occurs with allylic N-tosyloxycarbamates to produce aziridines as single diastereomers. The reaction proceeds at room temperature using a rhodium catalyst and an excess of potassium carbonate and does not require the use of strong oxidant, such as hypervalent iodine reagents. A rhodium nitrene species is presumably involved, as both reactions are stereospecific.

  4. Rhodium dihydride (RhH2) with high volumetric hydrogen density.

    PubMed

    Li, Bing; Ding, Yang; Kim, Duck Young; Ahuja, Rajeev; Zou, Guangtian; Mao, Ho-Kwang

    2011-11-15

    Materials with very high hydrogen density have attracted considerable interest due to a range of motivations, including the search for chemically precompressed metallic hydrogen and hydrogen storage applications. Using high-pressure synchrotron X-ray diffraction technique and theoretical calculations, we have discovered a new rhodium dihydride (RhH(2)) with high volumetric hydrogen density (163.7 g/L). Compressing rhodium in fluid hydrogen at ambient temperature, the fcc rhodium metal absorbs hydrogen and expands unit-cell volume by two discrete steps to form NaCl-typed fcc rhodium monohydride at 4 GPa and fluorite-typed fcc RhH(2) at 8 GPa. RhH(2) is the first dihydride discovered in the platinum group metals under high pressure. Our low-temperature experiments show that RhH(2) is recoverable after releasing pressure cryogenically to 1 bar and is capable of retaining hydrogen up to 150 K for minutes and 77 K for an indefinite length of time.

  5. Carbinol derivatives via rhodium-catalyzed addition of potassium trifluoro(organo)borates to aldehydes.

    PubMed

    Pucheault, Mathieu; Darses, Sylvain; Genet, Jean-Pierre

    2005-10-07

    Reaction of potassium aryltrifluoroborates with aldehydes, in the presence of a rhodium catalyst, afforded carbinol derivatives in high yields under mild aqueous conditions; this efficient reaction proved to be general, allowing the production of highly hindered diarylmethanols and aliphatic aldehydes were also reactive under these conditions.

  6. Activating Group Recycling in Action: A Rhodium-Catalyzed Carbothiolation Route to Substituted Isoquinolines

    PubMed Central

    2013-01-01

    A new rhodium(I) catalyst allows practical and efficient alkyne carbothiolation reactions to be achieved on synthetically useful ketone-bearing aryl methyl sulfides. The carbothiolation adducts, featuring a ‘recycled methyl sulfide’ activating group, are convenient precursors to highly substituted isoquinolines. PMID:24083625

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

    PubMed Central

    Selander, Nicklas; Fokin, Valery V.

    2013-01-01

    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. PMID:22233190

  8. A Rhodium Nanoparticle-Lewis Acidic Ionic Liquid Catalyst for the Chemoselective Reduction of Heteroarenes.

    PubMed

    Karakulina, Alena; Gopakumar, Aswin; Akçok, İsmail; Roulier, Bastien L; LaGrange, Thomas; Katsyuba, Sergey A; Das, Shoubhik; Dyson, Paul J

    2016-01-04

    We describe a catalytic system composed of rhodium nanoparticles immobilized in a Lewis acidic ionic liquid. The combined system catalyzes the hydrogenation of quinolines, pyridines, benzofurans, and furan to access the corresponding heterocycles, important molecules present in fine chemicals, agrochemicals, and pharmaceuticals. The catalyst is highly selective, acting only on the heteroaromatic ring, and not interfering with other reducible functional groups.

  9. The rhodium catalyzed three-component reaction of diazoacetates, titanium(IV) alkoxides and aldehydes.

    PubMed

    Lu, Chong-Dao; Liu, Hui; Chen, Zhi-Yong; Hu, Wen-Hao; Mi, Ai-Qiao

    2005-05-28

    The rhodium(II)-catalyzed three-component reaction of diazoacetates, titanium alkoxides and aldehydes is shown to give alpha-alkoxyl-beta-hydroxyl acid derivatives; the novel C-C bond formation reaction is proposed to occur through oxonium ylides derived from diazo compounds and titanium alkoxides, and followed by intermolecular trapping by aldehydes.

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

    PubMed

    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.

  11. Toward the Synthesis of Nuphar Sesquiterpene Thioalkaloids: Stereodivergent Rhodium-Catalyzed Synthesis of the Thiolane Subunit.

    PubMed

    Lu, Ping; Herrmann, Aaron T; Zakarian, Armen

    2015-08-07

    A stereodivergent approach to the central thiolane subunit of Nuphar sesquiterpene thioalkaloids has been developed. This approach features a rhodium-catalyzed Stevens-type rearrangement in conjunction with an enzyme resolution reaction. Further elaboration into a polycyclic ring system via alcohol oxidation and ring-closing metathesis is also described.

  12. Rhodium phosphine-π-arene intermediates in the hydroamination of alkenes.

    PubMed

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

    2011-03-02

    A detailed mechanistic study of the intramolecular hydroamination of alkenes with amines catalyzed by rhodium complexes of a biaryldialkylphosphine is reported. The active catalyst is shown to contain the phosphine ligand bound in a κ(1), η(6) 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.

  13. Rhodium dihydride (RhH[subscript 2]) with high volumetric hydrogen density

    SciTech Connect

    Li, Bing; Ding, Yang; Kim, Duck Young; Ahuja, Rajeev; Zou, Guangtian; Mao, Ho-Kwang

    2012-03-14

    Materials with very high hydrogen density have attracted considerable interest due to a range of motivations, including the search for chemically precompressed metallic hydrogen and hydrogen storage applications. Using high-pressure synchrotron X-ray diffraction technique and theoretical calculations, we have discovered a new rhodium dihydride (RhH{sub 2}) with high volumetric hydrogen density (163.7 g/L). Compressing rhodium in fluid hydrogen at ambient temperature, the fcc rhodium metal absorbs hydrogen and expands unit-cell volume by two discrete steps to form NaCl-typed fcc rhodium monohydride at 4 GPa and fluorite-typed fcc RhH{sub 2} at 8 GPa. RhH{sub 2} is the first dihydride discovered in the platinum group metals under high pressure. Our low-temperature experiments show that RhH{sub 2} is recoverable after releasing pressure cryogenically to 1 bar and is capable of retaining hydrogen up to 150 K for minutes and 77 K for an indefinite length of time.

  14. Rhodium dihydride (RhH2) with high volumetric hydrogen density

    PubMed Central

    Li, Bing; Ding, Yang; Kim, Duck Young; Ahuja, Rajeev; Zou, Guangtian; Mao, Ho-Kwang

    2011-01-01

    Materials with very high hydrogen density have attracted considerable interest due to a range of motivations, including the search for chemically precompressed metallic hydrogen and hydrogen storage applications. Using high-pressure synchrotron X-ray diffraction technique and theoretical calculations, we have discovered a new rhodium dihydride (RhH2) with high volumetric hydrogen density (163.7 g/L). Compressing rhodium in fluid hydrogen at ambient temperature, the fcc rhodium metal absorbs hydrogen and expands unit-cell volume by two discrete steps to form NaCl-typed fcc rhodium monohydride at 4 GPa and fluorite-typed fcc RhH2 at 8 GPa. RhH2 is the first dihydride discovered in the platinum group metals under high pressure. Our low-temperature experiments show that RhH2 is recoverable after releasing pressure cryogenically to 1 bar and is capable of retaining hydrogen up to 150 K for minutes and 77 K for an indefinite length of time. PMID:22039219

  15. Rhodium-catalyzed, efficient deutero- and tritiosilylation of carbonyl compounds from hydrosilanes and deuterium or tritium.

    PubMed

    Rubio, Miguel; Campos, Jesús; Carmona, Ernesto

    2011-10-07

    A cationic rhodium compound which is an active catalyst for both the hydrogen isotope exchange in hydrosilanes and the hydrosilylation of carbonyl compounds permits, in a one-flask, two-step procedure, efficient deutero- and tritiosilylations using SiEt(3)H under D(2) (0.5 bar) or T(2), at low catalyst loadings (0.1-0.5 mol %).

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

    PubMed Central

    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

  17. Ligand Fluorination to Optimize Preferential Oxidation (PROX) of Carbon Monoxide by Water-Soluble Rhodium Porphyrins.

    PubMed

    Biffinger, Justin C; Uppaluri, Shriharsha; Sun, Haoran; Dimagno, Stephen G

    2011-05-18

    Catalytic, low temperature preferential oxidation (PROX) of carbon monoxide by aqueous [5,10,15,20-tetrakis(4-sulfonatophenyl)-2,3,7,8,12,13,17,18-octafluoroporphyrinato]rhodium(III) tetrasodium salt, (1[Rh(III)]) and [5,10,15,20-tetrakis(3-sulfonato-2,6-difluorophenyl)-2,3,7,8,12,13,17,18-octafluoroporphyrinato]rhodium(III) tetrasodium salt, (2[Rh(III)]) is reported. The PROX reaction occurs at ambient temperature in buffered (4 ≤ pH ≤ 13) aqueous solutions. Fluorination on the porphyrin periphery is shown to increase the CO PROX reaction rate, shift the metal centered redox potentials, and acidify ligated water molecules. Most importantly, β-fluorination increases the acidity of the rhodium hydride complex (pK(a) = 2.2 ± 0.2 for 2[Rh-D]); the dramatically increased acidity of the Rh(III) hydride complex precludes proton reduction and hydrogen activation near neutral pH, thereby permitting oxidation of CO to be unaffected by the presence of H(2). This new fluorinated water-soluble rhodium porphyrin-based homogenous catalyst system permits preferential oxidation of carbon monoxide in hydrogen gas streams at 308 °K using dioxygen or a sacrificial electron acceptor (indigo carmine) as the terminal oxidant.

  18. Synthesis of 1H-Indazoles from Imidates and Nitrosobenzenes via Synergistic Rhodium/Copper Catalysis.

    PubMed

    Wang, Qiang; Li, Xingwei

    2016-05-06

    Nitrosobenzenes have been used as a convenient aminating reagent for the efficient synthesis of 1H-indazoles via rhodium and copper catalyzed C-H activation and C-N/N-N coupling. The reaction occurred under redox-neutral conditions with high efficiency and functional group tolerance. Moreover, a rhodacyclic imidate complex has been identified as a key intermediate.

  19. Transmetallation between metal-only Lewis pairs: a new rhodium alane complex.

    PubMed

    Bauer, Jürgen; Braunschweig, Holger; Radacki, Krzysztof

    2012-10-28

    In this communication, synthesis of a rhodium alane Lewis adduct, [Cp(Me(3)P)(2)Rh→AlCl(3)], is reported. Given that direct synthesis using aluminium trichloride failed, a convenient transmetallation reaction was applied. The new MOLP was analysed by single crystal X-ray diffraction, multinuclear NMR spectroscopy and density functional theory calculations.

  20. Ligand Fluorination to Optimize Preferential Oxidation (PROX) of Carbon Monoxide by Water-Soluble Rhodium Porphyrins

    PubMed Central

    Biffinger, Justin C.; Uppaluri, ShriHarsha; Sun, Haoran

    2011-01-01

    Catalytic, low temperature preferential oxidation (PROX) of carbon monoxide by aqueous [5,10,15,20-tetrakis(4-sulfonatophenyl)-2,3,7,8,12,13,17,18-octafluoroporphyrinato]rhodium(III) tetrasodium salt, (1[Rh(III)]) and [5,10,15,20-tetrakis(3-sulfonato-2,6-difluorophenyl)-2,3,7,8,12,13,17,18-octafluoroporphyrinato]rhodium(III) tetrasodium salt, (2[Rh(III)]) is reported. The PROX reaction occurs at ambient temperature in buffered (4 ≤ pH ≤ 13) aqueous solutions. Fluorination on the porphyrin periphery is shown to increase the CO PROX reaction rate, shift the metal centered redox potentials, and acidify ligated water molecules. Most importantly, β-fluorination increases the acidity of the rhodium hydride complex (pKa = 2.2 ± 0.2 for 2[Rh-D]); the dramatically increased acidity of the Rh(III) hydride complex precludes proton reduction and hydrogen activation near neutral pH, thereby permitting oxidation of CO to be unaffected by the presence of H2. This new fluorinated water-soluble rhodium porphyrin-based homogenous catalyst system permits preferential oxidation of carbon monoxide in hydrogen gas streams at 308 °K using dioxygen or a sacrificial electron acceptor (indigo carmine) as the terminal oxidant. PMID:21949596

  1. Anisotropic etching of rhodium and gold as the onset of nanoparticle formation by cathodic corrosion.

    PubMed

    Hersbach, Thomas J P; Mints, Vladislav A; Calle-Vallejo, Federico; Yanson, Alexei I; Koper, Marc T M

    2016-12-12

    Cathodic corrosion is a phenomenon in which negatively polarized metal electrodes are degraded by cathodic etching and nanoparticle formation. Though these changes are dramatic and sometimes even visible by eye, the exact mechanisms underlying cathodic corrosion are still unclear. This work aims to improve the understanding of cathodic corrosion by studying its onset on rhodium and gold electrodes, which are subjected to various constant cathodic potentials in 10 M NaOH. After this polarization, the electrodes are studied using cyclic voltammetry and scanning electron microscopy, allowing a corrosion onset potential of -1.3 V vs. NHE for rhodium and -1.6 V vs. NHE for gold to be defined. The mildness of the potentials on both metals suggests that cathodic corrosion is less extreme and more ubiquitous than expected. Furthermore, we are able to observe well-defined rectangular etch pits on rhodium. Combined with rhodium cyclic voltammetry, this indicates a strong preference for forming (100) sites during corrosion. In contrast, a (111) preference is indicated on gold by voltammetry and the presence of well-oriented quasi-octahedral nanoparticles. This different etching behavior is suggested to be caused by preferential adsorption of sodium ions to surface defects, as is confirmed by density functional theory calculations.

  2. Cyto- and genotoxic effects of coordination complexes of platinum, palladium and rhodium in vitro.

    PubMed

    Bünger, J; Stork, J; Stalder, K

    1996-01-01

    The growing industrial use of platinum group elements as catalysts, especially in automobile exhaust detoxification (trimetal catalytic converters), is causing increasing occupational and environmental pollution. The cytotoxic and mutagenic properties of industrially used coordination complexes of platinum, palladium and rhodium were investigated using the neutral red cytotoxicity assay on two established cell lines and the Salmonella typhimurium/microsome test system (Ames test). Cytotoxic effects of the platinum complexes, measured as ED50, occurred at test concentrations of 0.2 mM. The analogous palladium salts tested were 3 times less toxic with ED50 being 0.6 mM, while the rhodium salts proved to be 30 times less toxic (ED50 = 6 mM). Levels of toxicity of the different complexes of a particular metal did not differ significantly from each other, which indicates that the metal itself is responsible for the toxic effects. In the Ames test, the spontaneous mutation rates increased by factors of 3 to 20 when the four tester strains were exposed to the platinum complexes. The analogous rhodium compounds proved to be considerably less mutagenic, and palladium demonstrated no mutagenic potential. As all of the four tester strains contain different mutations, the mutagenic potential of platinum and rhodium complexes appears to be based on a variety of mechanisms that damage DNA. From these in vitro experiments, it can be concluded that water-soluble complex salts of rhodium are less toxic and have a smaller mutagenic potential than the analogous platinum complexes. For palladium there is no evidence of any mutagenic property. From this point of view, the development of a catalytic converter containing predominantly palladium may be a possible means of minimizing potential health risks from this exhaust detoxification technique.

  3. Determination of phenolic compounds using spectral and color transitions of rhodium nanoparticles.

    PubMed

    Gatselou, Vasiliki; Christodouleas, Dionysios C; Kouloumpis, Antonios; Gournis, Dimitrios; Giokas, Dimosthenis L

    2016-08-17

    This work reports a new approach for the determination of phenolic compounds based on their interaction with citrate-capped rhodium nanoparticles. Phenolic compounds (i.e., catechins, gallates, cinnamates, and dihydroxybenzoic acids) were found to cause changes in the size and localized surface plasmon resonance of rhodium nanoparticles, and therefore, give rise to analyte-specific spectral and color transitions in the rhodium nanoparticle suspensions. Upon reaction with phenolic compounds (mainly dithydroxybenzoate derivatives, and trihydroxybenzoate derivatives), new absorbance peaks at 350 nm and 450 nm were observed. Upon reaction with trihydroxybenzoate derivatives, however, an additional absorbance peak at 580 nm was observed facilitating the speciation of phenolic compounds in the sample. Both absorbance peaks at 450 nm and 580 nm increased with increasing concentration of phenolic compounds over a linear range of 0-500 μM. Detection limits at the mid-micromolar levels were achieved, depending on the phenolic compound involved, and with satisfactory reproducibility (<7.3%). On the basis of these findings, two rhodium nanoparticles-based assays for the determination of the total phenolic content and total catechin content were developed and applied in tea samples. The obtained results correlated favorably with commonly used methods (i.e., Folin-Ciocalteu and aluminum complexation assay). Not the least, the finding that rhodium nanoparticles can react with analytes and exhibit unique localized surface plasmon resonance bands in the visible region, can open new opportunities for developing new optical and sensing analytical applications.

  4. Burnup of rhodium SPND in VVER-1000: Method for determination of linear energy release by SPND readings

    SciTech Connect

    Kurchenkov, A. Yu.

    2011-12-15

    A method for determination of linear energy release of a VVER fuel assembly near a rhodium self-powered neutron detector (SPND) is described. The dependence of SPND burnup on the charge passing through it is specified.

  5. Asymmetric synthesis of gem-diaryl substituted cyclic sulfamidates and sulfamides by rhodium-catalyzed arylation of cyclic ketimines.

    PubMed

    Nishimura, Takahiro; Ebe, Yusuke; Fujimoto, Hiroto; Hayashi, Tamio

    2013-06-18

    Asymmetric addition of arylboronates to aryl-substituted cyclic ketimines proceeded in the presence of a rhodium catalyst coordinated with a chiral diene ligand to give high yields of sulfamidates and sulfamides with high enantioselectivity (up to 99% ee).

  6. Double hydrophosphination of alkynes promoted by rhodium: the key role of an N-heterocyclic carbene ligand.

    PubMed

    Di Giuseppe, Andrea; De Luca, Roberto; Castarlenas, Ricardo; Pérez-Torrente, Jesús J; Crucianelli, Marcello; Oro, Luis A

    2016-04-25

    The regioselective double hydrophosphination of alkynes mediated by rhodium catalysts is presented. The distinctive stereoelectronic properties of the NHC ligand prevent the catalyst deactivation by diphosphine coordination thereby allowing for the closing of a productive catalytic cycle.

  7. Stabilized rhodium(0) nanoparticles: a reusable hydrogenation catalyst for arene derivatives in a biphasic water-liquid system.

    PubMed

    Schulz, J; Roucoux, A; Patin, H

    2000-02-18

    A colloidal system based on an aqueous suspension of rhodium(o) nanoparticles proved to be an efficient catalyst for the hydrogenation of arene derivatives under biphasic conditions. The rhodium nanoparticles (2-2.5 nm) were synthesized by the reduction of RhCl3 x 3H2O with sodium borohydride and were stabilized by highly water-soluble N-alkyl-N-(2-hydroxyethyl)ammonium salts (HEA-Cn). These surfactant molecules were characterized by measurements of the surface tension and the aqueous dispersions with rhodium were observed by transmission electron cryomicroscopy. The catalytic system is efficient under ultramild conditions, namely room temperature and 1 atm H2 pressure. The aqueous phase which contains the protected rhodium(0) colloids can be reused without significant loss of activity. The microheterogeneous behavior of this catalytic system was confirmed on a mercury poisoning experiment.

  8. 10 CFR 71.89 - Opening instructions.

    Code of Federal Regulations, 2010 CFR

    2010-01-01

    ... 10 Energy 2 2010-01-01 2010-01-01 false Opening instructions. 71.89 Section 71.89 Energy NUCLEAR REGULATORY COMMISSION (CONTINUED) PACKAGING AND TRANSPORTATION OF RADIOACTIVE MATERIAL Operating Controls and Procedures § 71.89 Opening instructions. Before delivery of a package to a carrier for transport,...

  9. 40 CFR 89.106 - Prohibited controls.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 20 2010-07-01 2010-07-01 false Prohibited controls. 89.106 Section 89...) CONTROL OF EMISSIONS FROM NEW AND IN-USE NONROAD COMPRESSION-IGNITION ENGINES Emission Standards and Certification Provisions § 89.106 Prohibited controls. (a) An engine may not be equipped with an...

  10. 7 CFR 301.89-13 - Treatments.

    Code of Federal Regulations, 2010 CFR

    2010-01-01

    ... 7 Agriculture 5 2010-01-01 2010-01-01 false Treatments. 301.89-13 Section 301.89-13 Agriculture..., DEPARTMENT OF AGRICULTURE DOMESTIC QUARANTINE NOTICES Karnal Bunt § 301.89-13 Treatments. All conveyances... this section, unless a particular treatment is designated by an inspector. The treatment used must...

  11. 21 CFR 1250.89 - Swimming pools.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 21 Food and Drugs 8 2010-04-01 2010-04-01 false Swimming pools. 1250.89 Section 1250.89 Food and... SANITATION Sanitation Facilities and Conditions on Vessels § 1250.89 Swimming pools. (a) Fill and draw swimming pools shall not be installed or used. (b) Swimming pools of the recirculation type shall be...

  12. 40 CFR 89.423 - [Reserved

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 20 2010-07-01 2010-07-01 false 89.423 Section 89.423 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) AIR PROGRAMS (CONTINUED) CONTROL OF EMISSIONS FROM NEW AND IN-USE NONROAD COMPRESSION-IGNITION ENGINES Exhaust Emission Test Procedures § 89.423 ...

  13. 40 CFR 89.423 - [Reserved

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 20 2011-07-01 2011-07-01 false 89.423 Section 89.423 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) AIR PROGRAMS (CONTINUED) CONTROL OF EMISSIONS FROM NEW AND IN-USE NONROAD COMPRESSION-IGNITION ENGINES Exhaust Emission Test Procedures § 89.423 ...

  14. 40 CFR 89.425 - [Reserved

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 20 2010-07-01 2010-07-01 false 89.425 Section 89.425 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) AIR PROGRAMS (CONTINUED) CONTROL OF EMISSIONS FROM NEW AND IN-USE NONROAD COMPRESSION-IGNITION ENGINES Exhaust Emission Test Procedures § 89.425 ...

  15. 40 CFR 89.302 - Definitions.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 20 2010-07-01 2010-07-01 false Definitions. 89.302 Section 89.302 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) AIR PROGRAMS (CONTINUED) CONTROL OF EMISSIONS FROM NEW AND IN-USE NONROAD COMPRESSION-IGNITION ENGINES Emission Test Equipment Provisions § 89...

  16. 40 CFR 89.402 - Definitions.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 20 2010-07-01 2010-07-01 false Definitions. 89.402 Section 89.402 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) AIR PROGRAMS (CONTINUED) CONTROL OF EMISSIONS FROM NEW AND IN-USE NONROAD COMPRESSION-IGNITION ENGINES Exhaust Emission Test Procedures § 89.402...

  17. 40 CFR 89.327 - Charge cooling.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 20 2010-07-01 2010-07-01 false Charge cooling. 89.327 Section 89.327 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) AIR PROGRAMS (CONTINUED) CONTROL OF EMISSIONS FROM NEW AND IN-USE NONROAD COMPRESSION-IGNITION ENGINES Emission Test Equipment Provisions § 89...

  18. 40 CFR 89.302 - Definitions.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 20 2011-07-01 2011-07-01 false Definitions. 89.302 Section 89.302 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) AIR PROGRAMS (CONTINUED) CONTROL OF EMISSIONS FROM NEW AND IN-USE NONROAD COMPRESSION-IGNITION ENGINES Emission Test Equipment Provisions § 89...

  19. 40 CFR 89.402 - Definitions.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 20 2011-07-01 2011-07-01 false Definitions. 89.402 Section 89.402 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) AIR PROGRAMS (CONTINUED) CONTROL OF EMISSIONS FROM NEW AND IN-USE NONROAD COMPRESSION-IGNITION ENGINES Exhaust Emission Test Procedures § 89.402...

  20. 40 CFR 89.327 - Charge cooling.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 20 2011-07-01 2011-07-01 false Charge cooling. 89.327 Section 89.327 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) AIR PROGRAMS (CONTINUED) CONTROL OF EMISSIONS FROM NEW AND IN-USE NONROAD COMPRESSION-IGNITION ENGINES Emission Test Equipment Provisions § 89...

  1. 40 CFR 89.425 - [Reserved

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 20 2011-07-01 2011-07-01 false 89.425 Section 89.425 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) AIR PROGRAMS (CONTINUED) CONTROL OF EMISSIONS FROM NEW AND IN-USE NONROAD COMPRESSION-IGNITION ENGINES Exhaust Emission Test Procedures § 89.425 ...

  2. 40 CFR 89.1003 - Prohibited acts.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 20 2011-07-01 2011-07-01 false Prohibited acts. 89.1003 Section 89... Provisions and Prohibited Acts § 89.1003 Prohibited acts. (a) The following acts and the causing thereof are... ultimate purchaser or a subsequent purchaser that the coverage of a warranty under the Act is conditioned...

  3. 40 CFR 89.116 - Engine families.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 20 2010-07-01 2010-07-01 false Engine families. 89.116 Section 89.116... Provisions § 89.116 Engine families. (a) A manufacturer's product line is divided into engine families that... life periods. (b) The following characteristics distinguish engine families: (1) Fuel; (2)...

  4. 7 CFR 3570.89 - [Reserved

    Code of Federal Regulations, 2014 CFR

    2014-01-01

    ... 7 Agriculture 15 2014-01-01 2014-01-01 false 3570.89 Section 3570.89 Agriculture Regulations of the Department of Agriculture (Continued) RURAL HOUSING SERVICE, DEPARTMENT OF AGRICULTURE COMMUNITY PROGRAMS Community Facilities Grant Program § 3570.89 ...

  5. 25 CFR 700.89 - Relocation contract.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... 25 Indians 2 2014-04-01 2014-04-01 false Relocation contract. 700.89 Section 700.89 Indians THE... Policies and Instructions Definitions § 700.89 Relocation contract. The Relocation Contract is that contract signed by the head of household in which he/she agrees to purchase an existing house or to...

  6. 25 CFR 700.89 - Relocation contract.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... 25 Indians 2 2012-04-01 2012-04-01 false Relocation contract. 700.89 Section 700.89 Indians THE... Policies and Instructions Definitions § 700.89 Relocation contract. The Relocation Contract is that contract signed by the head of household in which he/she agrees to purchase an existing house or to...

  7. 14 CFR 33.89 - Operation test.

    Code of Federal Regulations, 2010 CFR

    2010-01-01

    ... 14 Aeronautics and Space 1 2010-01-01 2010-01-01 false Operation test. 33.89 Section 33.89... STANDARDS: AIRCRAFT ENGINES Block Tests; Turbine Aircraft Engines § 33.89 Operation test. (a) The operation test must include testing found necessary by the Administrator to demonstrate— (1) Starting,...

  8. 40 CFR 89.331 - Test conditions.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 20 2014-07-01 2013-07-01 true Test conditions. 89.331 Section 89.331... EMISSIONS FROM NEW AND IN-USE NONROAD COMPRESSION-IGNITION ENGINES Emission Test Equipment Provisions § 89.331 Test conditions. (a) General requirements. Calculate all volumes and volumetric flow rates...

  9. 14 CFR 33.89 - Operation test.

    Code of Federal Regulations, 2014 CFR

    2014-01-01

    ... 14 Aeronautics and Space 1 2014-01-01 2014-01-01 false Operation test. 33.89 Section 33.89... STANDARDS: AIRCRAFT ENGINES Block Tests; Turbine Aircraft Engines § 33.89 Operation test. (a) The operation test must include testing found necessary by the Administrator to demonstrate— (1) Starting,...

  10. 14 CFR 33.89 - Operation test.

    Code of Federal Regulations, 2013 CFR

    2013-01-01

    ... 14 Aeronautics and Space 1 2013-01-01 2013-01-01 false Operation test. 33.89 Section 33.89... STANDARDS: AIRCRAFT ENGINES Block Tests; Turbine Aircraft Engines § 33.89 Operation test. (a) The operation test must include testing found necessary by the Administrator to demonstrate— (1) Starting,...

  11. 40 CFR 89.331 - Test conditions.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 21 2013-07-01 2013-07-01 false Test conditions. 89.331 Section 89.331... EMISSIONS FROM NEW AND IN-USE NONROAD COMPRESSION-IGNITION ENGINES Emission Test Equipment Provisions § 89.331 Test conditions. (a) General requirements. Calculate all volumes and volumetric flow rates...

  12. 40 CFR 89.119 - Emission tests.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 20 2014-07-01 2013-07-01 true Emission tests. 89.119 Section 89.119... Provisions § 89.119 Emission tests. (a) Manufacturer testing. (1) Upon completion of service accumulation, the manufacturer must test each test engine using the specified test procedures, except as provided...

  13. 40 CFR 89.119 - Emission tests.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 21 2013-07-01 2013-07-01 false Emission tests. 89.119 Section 89.119... Provisions § 89.119 Emission tests. (a) Manufacturer testing. (1) Upon completion of service accumulation, the manufacturer must test each test engine using the specified test procedures, except as provided...

  14. 14 CFR 151.89 - Roads.

    Code of Federal Regulations, 2011 CFR

    2011-01-01

    ... 14 Aeronautics and Space 3 2011-01-01 2011-01-01 false Roads. 151.89 Section 151.89 Aeronautics and Space FEDERAL AVIATION ADMINISTRATION, DEPARTMENT OF TRANSPORTATION (CONTINUED) AIRPORTS FEDERAL AID TO AIRPORTS Project Programming Standards § 151.89 Roads. (a) Federal-aid Airport Program funds...

  15. 14 CFR 151.89 - Roads.

    Code of Federal Regulations, 2013 CFR

    2013-01-01

    ... 14 Aeronautics and Space 3 2013-01-01 2013-01-01 false Roads. 151.89 Section 151.89 Aeronautics and Space FEDERAL AVIATION ADMINISTRATION, DEPARTMENT OF TRANSPORTATION (CONTINUED) AIRPORTS FEDERAL AID TO AIRPORTS Project Programming Standards § 151.89 Roads. (a) Federal-aid Airport Program funds...

  16. 14 CFR 151.89 - Roads.

    Code of Federal Regulations, 2012 CFR

    2012-01-01

    ... 14 Aeronautics and Space 3 2012-01-01 2012-01-01 false Roads. 151.89 Section 151.89 Aeronautics and Space FEDERAL AVIATION ADMINISTRATION, DEPARTMENT OF TRANSPORTATION (CONTINUED) AIRPORTS FEDERAL AID TO AIRPORTS Project Programming Standards § 151.89 Roads. (a) Federal-aid Airport Program funds...

  17. 14 CFR 151.89 - Roads.

    Code of Federal Regulations, 2010 CFR

    2010-01-01

    ... 14 Aeronautics and Space 3 2010-01-01 2010-01-01 false Roads. 151.89 Section 151.89 Aeronautics and Space FEDERAL AVIATION ADMINISTRATION, DEPARTMENT OF TRANSPORTATION (CONTINUED) AIRPORTS FEDERAL AID TO AIRPORTS Project Programming Standards § 151.89 Roads. (a) Federal-aid Airport Program funds...

  18. 40 CFR 179.89 - Motions.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 25 2013-07-01 2013-07-01 false Motions. 179.89 Section 179.89... PUBLIC HEARING Hearing Procedures § 179.89 Motions. A motion, unless made in the course of a preliminary... by § 179.80 and include a draft order. A response may be filed within 10 days of service of a motion...

  19. 40 CFR 179.89 - Motions.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 24 2014-07-01 2014-07-01 false Motions. 179.89 Section 179.89... PUBLIC HEARING Hearing Procedures § 179.89 Motions. A motion, unless made in the course of a preliminary... by § 179.80 and include a draft order. A response may be filed within 10 days of service of a motion...

  20. 40 CFR 179.89 - Motions.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 23 2010-07-01 2010-07-01 false Motions. 179.89 Section 179.89... PUBLIC HEARING Hearing Procedures § 179.89 Motions. A motion, unless made in the course of a preliminary... by § 179.80 and include a draft order. A response may be filed within 10 days of service of a motion...

  1. 40 CFR 179.89 - Motions.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 25 2012-07-01 2012-07-01 false Motions. 179.89 Section 179.89... PUBLIC HEARING Hearing Procedures § 179.89 Motions. A motion, unless made in the course of a preliminary... by § 179.80 and include a draft order. A response may be filed within 10 days of service of a motion...

  2. 40 CFR 179.89 - Motions.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 24 2011-07-01 2011-07-01 false Motions. 179.89 Section 179.89... PUBLIC HEARING Hearing Procedures § 179.89 Motions. A motion, unless made in the course of a preliminary... by § 179.80 and include a draft order. A response may be filed within 10 days of service of a motion...

  3. 40 CFR 89.106 - Prohibited controls.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 21 2013-07-01 2013-07-01 false Prohibited controls. 89.106 Section 89...) CONTROL OF EMISSIONS FROM NEW AND IN-USE NONROAD COMPRESSION-IGNITION ENGINES Emission Standards and Certification Provisions § 89.106 Prohibited controls. (a) An engine may not be equipped with an emission...

  4. 40 CFR 89.106 - Prohibited controls.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 20 2014-07-01 2013-07-01 true Prohibited controls. 89.106 Section 89...) CONTROL OF EMISSIONS FROM NEW AND IN-USE NONROAD COMPRESSION-IGNITION ENGINES Emission Standards and Certification Provisions § 89.106 Prohibited controls. (a) An engine may not be equipped with an emission...

  5. 40 CFR 89.106 - Prohibited controls.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 20 2011-07-01 2011-07-01 false Prohibited controls. 89.106 Section 89...) CONTROL OF EMISSIONS FROM NEW AND IN-USE NONROAD COMPRESSION-IGNITION ENGINES Emission Standards and Certification Provisions § 89.106 Prohibited controls. (a) An engine may not be equipped with an emission...

  6. 40 CFR 89.106 - Prohibited controls.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 21 2012-07-01 2012-07-01 false Prohibited controls. 89.106 Section 89...) CONTROL OF EMISSIONS FROM NEW AND IN-USE NONROAD COMPRESSION-IGNITION ENGINES Emission Standards and Certification Provisions § 89.106 Prohibited controls. (a) An engine may not be equipped with an emission...

  7. 40 CFR 89.116 - Engine families.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 20 2011-07-01 2011-07-01 false Engine families. 89.116 Section 89.116... EMISSIONS FROM NEW AND IN-USE NONROAD COMPRESSION-IGNITION ENGINES Emission Standards and Certification Provisions § 89.116 Engine families. (a) A manufacturer's product line is divided into engine families that...

  8. 40 CFR 89.116 - Engine families.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 20 2014-07-01 2013-07-01 true Engine families. 89.116 Section 89.116... EMISSIONS FROM NEW AND IN-USE NONROAD COMPRESSION-IGNITION ENGINES Emission Standards and Certification Provisions § 89.116 Engine families. (a) A manufacturer's product line is divided into engine families that...

  9. 40 CFR 89.116 - Engine families.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 21 2013-07-01 2013-07-01 false Engine families. 89.116 Section 89.116... EMISSIONS FROM NEW AND IN-USE NONROAD COMPRESSION-IGNITION ENGINES Emission Standards and Certification Provisions § 89.116 Engine families. (a) A manufacturer's product line is divided into engine families that...

  10. 21 CFR 808.89 - Rhode Island.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... 21 Food and Drugs 8 2012-04-01 2012-04-01 false Rhode Island. 808.89 Section 808.89 Food and Drugs... and Local Exemptions § 808.89 Rhode Island. The following Rhode Island medical device requirements are... from preemption under section 521(b) of the act: Rhode Island General Laws, Section 5-49-2.1, and...

  11. 21 CFR 808.89 - Rhode Island.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 21 Food and Drugs 8 2010-04-01 2010-04-01 false Rhode Island. 808.89 Section 808.89 Food and Drugs... and Local Exemptions § 808.89 Rhode Island. The following Rhode Island medical device requirements are... from preemption under section 521(b) of the act: Rhode Island General Laws, Section 5-49-2.1, and...

  12. 21 CFR 808.89 - Rhode Island.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... 21 Food and Drugs 8 2014-04-01 2014-04-01 false Rhode Island. 808.89 Section 808.89 Food and Drugs... and Local Exemptions § 808.89 Rhode Island. The following Rhode Island medical device requirements are... from preemption under section 521(b) of the act: Rhode Island General Laws, Section 5-49-2.1, and...

  13. 21 CFR 808.89 - Rhode Island.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... 21 Food and Drugs 8 2013-04-01 2013-04-01 false Rhode Island. 808.89 Section 808.89 Food and Drugs... and Local Exemptions § 808.89 Rhode Island. The following Rhode Island medical device requirements are... from preemption under section 521(b) of the act: Rhode Island General Laws, Section 5-49-2.1, and...

  14. 21 CFR 808.89 - Rhode Island.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 21 Food and Drugs 8 2011-04-01 2011-04-01 false Rhode Island. 808.89 Section 808.89 Food and Drugs... and Local Exemptions § 808.89 Rhode Island. The following Rhode Island medical device requirements are... from preemption under section 521(b) of the act: Rhode Island General Laws, Section 5-49-2.1, and...

  15. 29 CFR 1960.89 - Organization.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 29 Labor 9 2014-07-01 2014-07-01 false Organization. 1960.89 Section 1960.89 Labor Regulations Relating to Labor (Continued) OCCUPATIONAL SAFETY AND HEALTH ADMINISTRATION, DEPARTMENT OF LABOR (CONTINUED... Field Federal Safety and Health Councils § 1960.89 Organization. (a) Field council officers...

  16. 29 CFR 1960.89 - Organization.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 29 Labor 9 2011-07-01 2011-07-01 false Organization. 1960.89 Section 1960.89 Labor Regulations Relating to Labor (Continued) OCCUPATIONAL SAFETY AND HEALTH ADMINISTRATION, DEPARTMENT OF LABOR (CONTINUED... Field Federal Safety and Health Councils § 1960.89 Organization. (a) Field council officers...

  17. 29 CFR 1960.89 - Organization.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 29 Labor 9 2012-07-01 2012-07-01 false Organization. 1960.89 Section 1960.89 Labor Regulations Relating to Labor (Continued) OCCUPATIONAL SAFETY AND HEALTH ADMINISTRATION, DEPARTMENT OF LABOR (CONTINUED... Field Federal Safety and Health Councils § 1960.89 Organization. (a) Field council officers...

  18. 29 CFR 1960.89 - Organization.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 29 Labor 9 2013-07-01 2013-07-01 false Organization. 1960.89 Section 1960.89 Labor Regulations Relating to Labor (Continued) OCCUPATIONAL SAFETY AND HEALTH ADMINISTRATION, DEPARTMENT OF LABOR (CONTINUED... Field Federal Safety and Health Councils § 1960.89 Organization. (a) Field council officers...

  19. 40 CFR 89.206 - Trading.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 20 2010-07-01 2010-07-01 false Trading. 89.206 Section 89.206... EMISSIONS FROM NEW AND IN-USE NONROAD COMPRESSION-IGNITION ENGINES Averaging, Banking, and Trading Provisions § 89.206 Trading. (a) Requirements for Tier 1 engines rated at or above 37 kW. (1) A...

  20. 9 CFR 89.5 - Feeding pens.

    Code of Federal Regulations, 2010 CFR

    2010-01-01

    ... 9 Animals and Animal Products 1 2010-01-01 2010-01-01 false Feeding pens. 89.5 Section 89.5... TWENTY-EIGHT HOUR LAW § 89.5 Feeding pens. (a) Stock pens and other enclosures for feeding, watering, and... same time, (2) properly designed facilities for feeding and watering the livestock, (3) reasonably well...

  1. 7 CFR 160.89 - Medicinal preparations.

    Code of Federal Regulations, 2012 CFR

    2012-01-01

    ... 7 Agriculture 3 2012-01-01 2012-01-01 false Medicinal preparations. 160.89 Section 160.89 Agriculture Regulations of the Department of Agriculture (Continued) AGRICULTURAL MARKETING SERVICE (Standards... STANDARDS FOR NAVAL STORES Sales and Shipments § 160.89 Medicinal preparations. A compound or...

  2. 7 CFR 160.89 - Medicinal preparations.

    Code of Federal Regulations, 2014 CFR

    2014-01-01

    ... 7 Agriculture 3 2014-01-01 2014-01-01 false Medicinal preparations. 160.89 Section 160.89 Agriculture Regulations of the Department of Agriculture (Continued) AGRICULTURAL MARKETING SERVICE (Standards... STANDARDS FOR NAVAL STORES Sales and Shipments § 160.89 Medicinal preparations. A compound or...

  3. 7 CFR 160.89 - Medicinal preparations.

    Code of Federal Regulations, 2013 CFR

    2013-01-01

    ... 7 Agriculture 3 2013-01-01 2013-01-01 false Medicinal preparations. 160.89 Section 160.89 Agriculture Regulations of the Department of Agriculture (Continued) AGRICULTURAL MARKETING SERVICE (Standards... STANDARDS FOR NAVAL STORES Sales and Shipments § 160.89 Medicinal preparations. A compound or...

  4. 40 CFR 89.312 - Analytical gases.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 20 2011-07-01 2011-07-01 false Analytical gases. 89.312 Section 89.312 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) AIR PROGRAMS (CONTINUED... Provisions § 89.312 Analytical gases. (a) The shelf life of all calibration gases must not be exceeded....

  5. 7 CFR 993.89 - Effective time.

    Code of Federal Regulations, 2011 CFR

    2011-01-01

    ... 7 Agriculture 8 2011-01-01 2011-01-01 false Effective time. 993.89 Section 993.89 Agriculture... Order Regulating Handling Miscellaneous Provisions § 993.89 Effective time. The provisions of this subpart, as well as any amendments to this subpart, shall become effective at such time as the Secretary...

  6. 7 CFR 993.89 - Effective time.

    Code of Federal Regulations, 2010 CFR

    2010-01-01

    ... 7 Agriculture 8 2010-01-01 2010-01-01 false Effective time. 993.89 Section 993.89 Agriculture... Order Regulating Handling Miscellaneous Provisions § 993.89 Effective time. The provisions of this subpart, as well as any amendments to this subpart, shall become effective at such time as the Secretary...

  7. 42 CFR 32.89 - Discharge.

    Code of Federal Regulations, 2014 CFR

    2014-10-01

    ... 42 Public Health 1 2014-10-01 2014-10-01 false Discharge. 32.89 Section 32.89 Public Health PUBLIC HEALTH SERVICE, DEPARTMENT OF HEALTH AND HUMAN SERVICES MEDICAL CARE AND EXAMINATIONS MEDICAL CARE FOR PERSONS WITH HANSEN'S DISEASE AND OTHER PERSONS IN EMERGENCIES Persons with Hansen's Disease § 32.89...

  8. 42 CFR 32.89 - Discharge.

    Code of Federal Regulations, 2013 CFR

    2013-10-01

    ... 42 Public Health 1 2013-10-01 2013-10-01 false Discharge. 32.89 Section 32.89 Public Health PUBLIC HEALTH SERVICE, DEPARTMENT OF HEALTH AND HUMAN SERVICES MEDICAL CARE AND EXAMINATIONS MEDICAL CARE FOR PERSONS WITH HANSEN'S DISEASE AND OTHER PERSONS IN EMERGENCIES Persons with Hansen's Disease § 32.89...

  9. 7 CFR 993.89 - Effective time.

    Code of Federal Regulations, 2012 CFR

    2012-01-01

    ... 7 Agriculture 8 2012-01-01 2012-01-01 false Effective time. 993.89 Section 993.89 Agriculture... Order Regulating Handling Miscellaneous Provisions § 993.89 Effective time. The provisions of this subpart, as well as any amendments to this subpart, shall become effective at such time as the Secretary...

  10. 7 CFR 993.89 - Effective time.

    Code of Federal Regulations, 2014 CFR

    2014-01-01

    ... 7 Agriculture 8 2014-01-01 2014-01-01 false Effective time. 993.89 Section 993.89 Agriculture... Order Regulating Handling Miscellaneous Provisions § 993.89 Effective time. The provisions of this subpart, as well as any amendments to this subpart, shall become effective at such time as the Secretary...

  11. 7 CFR 993.89 - Effective time.

    Code of Federal Regulations, 2013 CFR

    2013-01-01

    ... 7 Agriculture 8 2013-01-01 2013-01-01 false Effective time. 993.89 Section 993.89 Agriculture... Order Regulating Handling Miscellaneous Provisions § 993.89 Effective time. The provisions of this subpart, as well as any amendments to this subpart, shall become effective at such time as the Secretary...

  12. 21 CFR 1250.89 - Swimming pools.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 21 Food and Drugs 8 2011-04-01 2011-04-01 false Swimming pools. 1250.89 Section 1250.89 Food and... SANITATION Sanitation Facilities and Conditions on Vessels § 1250.89 Swimming pools. (a) Fill and draw swimming pools shall not be installed or used. (b) Swimming pools of the recirculation type shall...

  13. 21 CFR 1250.89 - Swimming pools.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... 21 Food and Drugs 8 2014-04-01 2014-04-01 false Swimming pools. 1250.89 Section 1250.89 Food and... SANITATION Sanitation Facilities and Conditions on Vessels § 1250.89 Swimming pools. (a) Fill and draw swimming pools shall not be installed or used. (b) Swimming pools of the recirculation type shall...

  14. 40 CFR 89.702 - Definitions.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 21 2013-07-01 2013-07-01 false Definitions. 89.702 Section 89.702 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) AIR PROGRAMS (CONTINUED) CONTROL OF EMISSIONS FROM NEW AND IN-USE NONROAD COMPRESSION-IGNITION ENGINES Recall Regulations § 89.702...

  15. 40 CFR 89.4 - [Reserved

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 21 2012-07-01 2012-07-01 false 89.4 Section 89.4 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) AIR PROGRAMS (CONTINUED) CONTROL OF EMISSIONS FROM NEW AND IN-USE NONROAD COMPRESSION-IGNITION ENGINES General § 89.4...

  16. 40 CFR 89.702 - Definitions.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 20 2010-07-01 2010-07-01 false Definitions. 89.702 Section 89.702 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) AIR PROGRAMS (CONTINUED) CONTROL OF EMISSIONS FROM NEW AND IN-USE NONROAD COMPRESSION-IGNITION ENGINES Recall Regulations § 89.702...

  17. 40 CFR 89.701 - Applicability.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 20 2014-07-01 2013-07-01 true Applicability. 89.701 Section 89.701 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) AIR PROGRAMS (CONTINUED) CONTROL OF EMISSIONS FROM NEW AND IN-USE NONROAD COMPRESSION-IGNITION ENGINES Recall Regulations § 89.701...

  18. 40 CFR 89.701 - Applicability.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 20 2010-07-01 2010-07-01 false Applicability. 89.701 Section 89.701 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) AIR PROGRAMS (CONTINUED) CONTROL OF EMISSIONS FROM NEW AND IN-USE NONROAD COMPRESSION-IGNITION ENGINES Recall Regulations § 89.701...

  19. 40 CFR 89.701 - Applicability.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 21 2013-07-01 2013-07-01 false Applicability. 89.701 Section 89.701 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) AIR PROGRAMS (CONTINUED) CONTROL OF EMISSIONS FROM NEW AND IN-USE NONROAD COMPRESSION-IGNITION ENGINES Recall Regulations § 89.701...

  20. 40 CFR 89.4 - [Reserved

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 20 2011-07-01 2011-07-01 false 89.4 Section 89.4 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) AIR PROGRAMS (CONTINUED) CONTROL OF EMISSIONS FROM NEW AND IN-USE NONROAD COMPRESSION-IGNITION ENGINES General § 89.4...

  1. 40 CFR 89.4 - [Reserved

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 20 2014-07-01 2013-07-01 true 89.4 Section 89.4 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) AIR PROGRAMS (CONTINUED) CONTROL OF EMISSIONS FROM NEW AND IN-USE NONROAD COMPRESSION-IGNITION ENGINES General § 89.4...

  2. 40 CFR 89.902 - Definitions.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 20 2014-07-01 2013-07-01 true Definitions. 89.902 Section 89.902 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) AIR PROGRAMS (CONTINUED) CONTROL OF EMISSIONS FROM NEW AND IN-USE NONROAD COMPRESSION-IGNITION ENGINES Exemption Provisions § 89.902...

  3. 40 CFR 89.4 - [Reserved

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 20 2010-07-01 2010-07-01 false 89.4 Section 89.4 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) AIR PROGRAMS (CONTINUED) CONTROL OF EMISSIONS FROM NEW AND IN-USE NONROAD COMPRESSION-IGNITION ENGINES General § 89.4...

  4. 40 CFR 89.4 - [Reserved

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 21 2013-07-01 2013-07-01 false 89.4 Section 89.4 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) AIR PROGRAMS (CONTINUED) CONTROL OF EMISSIONS FROM NEW AND IN-USE NONROAD COMPRESSION-IGNITION ENGINES General § 89.4...

  5. 40 CFR 89.902 - Definitions.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 21 2013-07-01 2013-07-01 false Definitions. 89.902 Section 89.902 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) AIR PROGRAMS (CONTINUED) CONTROL OF EMISSIONS FROM NEW AND IN-USE NONROAD COMPRESSION-IGNITION ENGINES Exemption Provisions § 89.902...

  6. 40 CFR 89.702 - Definitions.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 20 2014-07-01 2013-07-01 true Definitions. 89.702 Section 89.702 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) AIR PROGRAMS (CONTINUED) CONTROL OF EMISSIONS FROM NEW AND IN-USE NONROAD COMPRESSION-IGNITION ENGINES Recall Regulations § 89.702...

  7. 9 CFR 89.4 - Watering.

    Code of Federal Regulations, 2014 CFR

    2014-01-01

    ... 9 Animals and Animal Products 1 2014-01-01 2014-01-01 false Watering. 89.4 Section 89.4 Animals and Animal Products ANIMAL AND PLANT HEALTH INSPECTION SERVICE, DEPARTMENT OF AGRICULTURE INTERSTATE... LAW § 89.4 Watering. Livestock should be furnished an ample supply of potable water. Water treated...

  8. 7 CFR 945.89 - Personal liability.

    Code of Federal Regulations, 2011 CFR

    2011-01-01

    ... 7 Agriculture 8 2011-01-01 2011-01-01 false Personal liability. 945.89 Section 945.89 Agriculture Regulations of the Department of Agriculture (Continued) AGRICULTURAL MARKETING SERVICE (Marketing Agreements... § 945.89 Personal liability. No member or alternate of the committee, nor any employee or agent thereof...

  9. 7 CFR 930.89 - Personal liability.

    Code of Federal Regulations, 2011 CFR

    2011-01-01

    ... 7 Agriculture 8 2011-01-01 2011-01-01 false Personal liability. 930.89 Section 930.89 Agriculture Regulations of the Department of Agriculture (Continued) AGRICULTURAL MARKETING SERVICE (Marketing Agreements... Miscellaneous Provisions § 930.89 Personal liability. No member or alternate member of the Board and no employee...

  10. 14 CFR 151.89 - Roads.

    Code of Federal Regulations, 2014 CFR

    2014-01-01

    ... 14 Aeronautics and Space 3 2014-01-01 2014-01-01 false Roads. 151.89 Section 151.89 Aeronautics... AID TO AIRPORTS Project Programming Standards § 151.89 Roads. (a) Federal-aid Airport Program funds may not be used to resolve highway problems. Only those airport entrance roads that are definitely...

  11. 49 CFR 89.45 - Department determination.

    Code of Federal Regulations, 2010 CFR

    2010-10-01

    ... 49 Transportation 1 2010-10-01 2010-10-01 false Department determination. 89.45 Section 89.45... Referral of Debts to IRS for Tax Refund Offset § 89.45 Department determination. (a) Following review of... supporting rationale. (b) If the Department either sustains or amends its determination, it shall notify the...

  12. 7 CFR 989.89 - Agents.

    Code of Federal Regulations, 2012 CFR

    2012-01-01

    ... 7 Agriculture 8 2012-01-01 2012-01-01 false Agents. 989.89 Section 989.89 Agriculture Regulations... CALIFORNIA Order Regulating Handling Miscellaneous Provisions § 989.89 Agents. The Secretary may, by a... name any bureau or division in the United States Department of Agriculture, to act as his agent or...

  13. 7 CFR 989.89 - Agents.

    Code of Federal Regulations, 2013 CFR

    2013-01-01

    ... 7 Agriculture 8 2013-01-01 2013-01-01 false Agents. 989.89 Section 989.89 Agriculture Regulations... CALIFORNIA Order Regulating Handling Miscellaneous Provisions § 989.89 Agents. The Secretary may, by a... name any bureau or division in the United States Department of Agriculture, to act as his agent or...

  14. 7 CFR 989.89 - Agents.

    Code of Federal Regulations, 2010 CFR

    2010-01-01

    ... 7 Agriculture 8 2010-01-01 2010-01-01 false Agents. 989.89 Section 989.89 Agriculture Regulations... CALIFORNIA Order Regulating Handling Miscellaneous Provisions § 989.89 Agents. The Secretary may, by a... name any bureau or division in the United States Department of Agriculture, to act as his agent or...

  15. 7 CFR 989.89 - Agents.

    Code of Federal Regulations, 2014 CFR

    2014-01-01

    ... 7 Agriculture 8 2014-01-01 2014-01-01 false Agents. 989.89 Section 989.89 Agriculture Regulations... CALIFORNIA Order Regulating Handling Miscellaneous Provisions § 989.89 Agents. The Secretary may, by a... name any bureau or division in the United States Department of Agriculture, to act as his agent or...

  16. 7 CFR 989.89 - Agents.

    Code of Federal Regulations, 2011 CFR

    2011-01-01

    ... 7 Agriculture 8 2011-01-01 2011-01-01 false Agents. 989.89 Section 989.89 Agriculture Regulations... CALIFORNIA Order Regulating Handling Miscellaneous Provisions § 989.89 Agents. The Secretary may, by a... name any bureau or division in the United States Department of Agriculture, to act as his agent or...

  17. 36 CFR 9.89 - Appeals.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 36 Parks, Forests, and Public Property 1 2010-07-01 2010-07-01 false Appeals. 9.89 Section 9.89 Parks, Forests, and Public Property NATIONAL PARK SERVICE, DEPARTMENT OF THE INTERIOR MINERALS MANAGEMENT Alaska Mineral Resource Assessment Program § 9.89 Appeals. Written appeals made within 30 days...

  18. 40 CFR 89.209 - Certification.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 20 2011-07-01 2011-07-01 false Certification. 89.209 Section 89.209... Provisions § 89.209 Certification. (a) In the application for certification a manufacturer must: (1) Declare...) Submit a statement that the engines for which certification is requested will not, to the best of the...

  19. 40 CFR 89.122 - Certification.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 20 2011-07-01 2011-07-01 false Certification. 89.122 Section 89.122... EMISSIONS FROM NEW AND IN-USE NONROAD COMPRESSION-IGNITION ENGINES Emission Standards and Certification Provisions § 89.122 Certification. (a) If, after a review of the manufacturer's application, request for...

  20. 40 CFR 89.122 - Certification.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 20 2010-07-01 2010-07-01 false Certification. 89.122 Section 89.122... EMISSIONS FROM NEW AND IN-USE NONROAD COMPRESSION-IGNITION ENGINES Emission Standards and Certification Provisions § 89.122 Certification. (a) If, after a review of the manufacturer's application, request for...

  1. 20 CFR 632.89 - Performance standards.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 20 Employees' Benefits 3 2011-04-01 2011-04-01 false Performance standards. 632.89 Section 632.89 Employees' Benefits EMPLOYMENT AND TRAINING ADMINISTRATION, DEPARTMENT OF LABOR INDIAN AND NATIVE AMERICAN EMPLOYMENT AND TRAINING PROGRAMS Program Design and Management § 632.89 Performance standards. The...

  2. 20 CFR 632.89 - Performance standards.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 20 Employees' Benefits 3 2010-04-01 2010-04-01 false Performance standards. 632.89 Section 632.89 Employees' Benefits EMPLOYMENT AND TRAINING ADMINISTRATION, DEPARTMENT OF LABOR INDIAN AND NATIVE AMERICAN EMPLOYMENT AND TRAINING PROGRAMS Program Design and Management § 632.89 Performance standards. The...

  3. 40 CFR 89.502 - Definitions.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 20 2011-07-01 2011-07-01 false Definitions. 89.502 Section 89.502 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) AIR PROGRAMS (CONTINUED) CONTROL OF EMISSIONS FROM NEW AND IN-USE NONROAD COMPRESSION-IGNITION ENGINES Selective Enforcement Auditing § 89.502...

  4. 40 CFR 89.501 - Applicability.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 20 2011-07-01 2011-07-01 false Applicability. 89.501 Section 89.501 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) AIR PROGRAMS (CONTINUED) CONTROL OF EMISSIONS FROM NEW AND IN-USE NONROAD COMPRESSION-IGNITION ENGINES Selective Enforcement Auditing § 89.501...

  5. 32 CFR 552.89 - Activities.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 32 National Defense 3 2010-07-01 2010-07-01 true Activities. 552.89 Section 552.89 National... CEMETERIES REGULATIONS AFFECTING MILITARY RESERVATIONS Fort Lewis Land Use Policy § 552.89 Activities. (a) Examples of authorized activities are listed in appendix C. (b) Activities listed in appendix D are not...

  6. 40 CFR 89.119 - Emission tests.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 20 2010-07-01 2010-07-01 false Emission tests. 89.119 Section 89.119... EMISSIONS FROM NEW AND IN-USE NONROAD COMPRESSION-IGNITION ENGINES Emission Standards and Certification Provisions § 89.119 Emission tests. (a) Manufacturer testing. (1) Upon completion of service...

  7. 40 CFR 89.119 - Emission tests.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 20 2011-07-01 2011-07-01 false Emission tests. 89.119 Section 89.119... EMISSIONS FROM NEW AND IN-USE NONROAD COMPRESSION-IGNITION ENGINES Emission Standards and Certification Provisions § 89.119 Emission tests. (a) Manufacturer testing. (1) Upon completion of service...

  8. 40 CFR 89.119 - Emission tests.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 21 2012-07-01 2012-07-01 false Emission tests. 89.119 Section 89.119... EMISSIONS FROM NEW AND IN-USE NONROAD COMPRESSION-IGNITION ENGINES Emission Standards and Certification Provisions § 89.119 Emission tests. (a) Manufacturer testing. (1) Upon completion of service...

  9. 14 CFR 33.89 - Operation test.

    Code of Federal Regulations, 2011 CFR

    2011-01-01

    ... 14 Aeronautics and Space 1 2011-01-01 2011-01-01 false Operation test. 33.89 Section 33.89 Aeronautics and Space FEDERAL AVIATION ADMINISTRATION, DEPARTMENT OF TRANSPORTATION AIRCRAFT AIRWORTHINESS STANDARDS: AIRCRAFT ENGINES Block Tests; Turbine Aircraft Engines § 33.89 Operation test. (a) The...

  10. 9 CFR 89.5 - Feeding pens.

    Code of Federal Regulations, 2014 CFR

    2014-01-01

    ... 9 Animals and Animal Products 1 2014-01-01 2014-01-01 false Feeding pens. 89.5 Section 89.5... TWENTY-EIGHT HOUR LAW § 89.5 Feeding pens. (a) Stock pens and other enclosures for feeding, watering, and... pens are located. (b) Care should be taken to protect livestock unloaded en route at a point having...

  11. 40 CFR 146.89 - Mechanical integrity.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 23 2011-07-01 2011-07-01 false Mechanical integrity. 146.89 Section 146.89 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) WATER PROGRAMS (CONTINUED... Wells § 146.89 Mechanical integrity. (a) A Class VI well has mechanical integrity if: (1) There is...

  12. 40 CFR 89.205 - Banking.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 20 2010-07-01 2010-07-01 false Banking. 89.205 Section 89.205... EMISSIONS FROM NEW AND IN-USE NONROAD COMPRESSION-IGNITION ENGINES Averaging, Banking, and Trading Provisions § 89.205 Banking. (a) Requirements for Tier 1 engines rated at or above 37 kW. (1) A...

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

    DOEpatents

    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.

  14. Ion exchange equilibria in simultaneous extraction of platinum(II, IV) and rhodium(III) from hydrochloric solutions

    NASA Astrophysics Data System (ADS)

    Mel'nikov, A. M.; Kononova, O. N.; Pavlenko, N. I.; Krylov, A. S.

    2012-06-01

    Regularities of sorption extraction of platinum(II, IV) and rhodium(III) by anion exchangers of various physical and chemical structure in the presence of hydrochloric media were studied. It is established that AM-2B, Purolite A 500, and Purolite S 985 ionites adsorb complex anions of platinum metals employing mixed mechanism. A high affinity of the studied anionites for the studied complex anions of platinum and rhodium is established.

  15. Enantioselective Synthesis of Spiroindenes by Enol-Directed Rhodium(III)-Catalyzed C–H Functionalization and Spiroannulation

    PubMed Central

    Reddy Chidipudi, Suresh; Burns, David J; Khan, Imtiaz; Lam, Hon Wai

    2015-01-01

    Chiral cyclopentadienyl rhodium complexes promote highly enantioselective enol-directed C(sp2)-H functionalization and oxidative annulation with alkynes to give spiroindenes containing all-carbon quaternary stereocenters. High selectivity between two possible directing groups, as well as control of the direction of rotation in the isomerization of an O-bound rhodium enolate into the C-bound isomer, appear to be critical for high enantiomeric excesses. PMID:26404643

  16. Intrinsic selectivity and structure sensitivity of Rhodium catalysts for C2+ oxygenate production [On the intrinsic selectivity and structure sensitivity of Rhodium catalysts for C2+ oxygenate production

    DOE PAGES

    Yang, Nuoya; Medford, Andrew J.; Liu, Xinyan; ...

    2016-01-31

    Synthesis gas (CO + H2) conversion is a promising route to converting coal, natural gas, or biomass into synthetic liquid fuels. Rhodium has long been studied as it is the only elemental catalyst that has demonstrated selectivity to ethanol and other C2+ oxygenates. However, the fundamentals of syngas conversion over rhodium are still debated. In this work a microkinetic model is developed for conversion of CO and H2 into methane, ethanol, and acetaldehyde on the Rh (211) and (111) surfaces, chosen to describe steps and close-packed facets on catalyst particles. The model is based on DFT calculations using the BEEF-vdWmore » functional. The mean-field kinetic model includes lateral adsorbate–adsorbate interactions, and the BEEF-vdW error estimation ensemble is used to propagate error from the DFT calculations to the predicted rates. The model shows the Rh(211) surface to be ~6 orders of magnitude more active than the Rh(111) surface, but highly selective toward methane, while the Rh(111) surface is intrinsically selective toward acetaldehyde. A variety of Rh/SiO2 catalysts are synthesized, tested for catalytic oxygenate production, and characterized using TEM. The experimental results indicate that the Rh(111) surface is intrinsically selective toward acetaldehyde, and a strong inverse correlation between catalytic activity and oxygenate selectivity is observed. Furthermore, iron impurities are shown to play a key role in modulating the selectivity of Rh/SiO2 catalysts toward ethanol. The experimental observations are consistent with the structure-sensitivity predicted from theory. As a result, this work provides an improved atomic-scale understanding and new insight into the mechanism, active site, and intrinsic selectivity of syngas conversion over rhodium catalysts and may also guide rational design of alloy catalysts made from more abundant elements.« less

  17. Terminal phosphanido rhodium complexes mediating catalytic P-P and P-C bond formation.

    PubMed

    Geer, Ana M; Serrano, Ángel L; de Bruin, Bas; Ciriano, Miguel A; Tejel, Cristina

    2015-01-07

    Complexes with terminal phosphanido (M-PR2) functionalities are believed to be crucial intermediates in new catalytic processes involving the formation of P-P and P-C bonds. We showcase here the isolation and characterization of mononuclear phosphanide rhodium complexes ([RhTp(H)(PR2)L]) that result from the oxidative addition of secondary phosphanes, a reaction that was also explored computationally. These compounds are active catalysts for the dehydrocoupling of PHPh2 to Ph2P-PPh2. The hydrophosphination of dimethyl maleate and the unactivated olefin ethylene is also reported. Reliable evidence for the prominent role of mononuclear phosphanido rhodium species in these reactions is also provided. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Rhodium-catalyzed ketone methylation using methanol under mild conditions: formation of α-branched products.

    PubMed

    Chan, Louis K M; Poole, Darren L; Shen, Di; Healy, Mark P; Donohoe, Timothy J

    2014-01-13

    The rhodium-catalyzed methylation of ketones has been accomplished using methanol as the methylating agent and the hydrogen-borrowing method. The sequence is notable for the relatively low temperatures that are required and for the ability of the reaction system to form α-branched products with ease. Doubly alkylated ketones can be prepared from methyl ketones and two different alcohols by using a sequential one-pot iridium- and rhodium-catalyzed process. © 2014 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.

  19. Nanostructured rhodium films produced by pulsed laser deposition for nuclear fusion applications

    NASA Astrophysics Data System (ADS)

    Passoni, M.; Dellasega, D.; Grosso, G.; Conti, C.; Ubaldi, M. C.; Bottani, C. E.

    2010-09-01

    In this paper the possibilities offered by pulsed laser deposition (PLD) for the production of nanostructured rhodium films with improved properties are explored. Thanks to its high reflectivity and low sputtering yield, rhodium is one of the best candidates for the development of thin films to be used in first mirrors, which are crucial components in many diagnostic systems of thermonuclear magnetic fusion machines, like tokamaks. Due to the features of PLD, by varying the process parameters it is possible to tailor both the structure, i.e. the nanocrystalline domain size of the deposited films, down to less than 5 nm and separately control the other relevant physical properties. This leads to modifications in growth regime and annealing dynamics, in such a way that both morphology and reflectivity achieve the properties demanded to use these films as mirrors for fusion applications, opening at the same time new possibilities for the future improvement of thermo-mechanical and adhesion properties.

  20. Allenols versus Allenones: Rhodium-Catalyzed Regiodivergent and Tunable Allene Reactivity with Triazoles.

    PubMed

    Alcaide, Benito; Almendros, Pedro; Cembellín, Sara; Martínez Del Campo, Teresa; Palop, Guillermo

    2017-10-04

    2-Pyrrolines and 6-oxo-hexa-2,4-dienals have been prepared through the divergent reactions of 1-benzenesulfonyl-4-aryl-1,2,3-triazoles with functionalized allenes. The rhodium-catalyzed reactions between allenols and 1-benzenesulfonyl-4-aryl-1,2,3-triazoles yielded 2-pyrrolines. This transformation is compatible with the presence of aliphatic, aromatic, heterocyclic, amide, and halogen functional groups. Interestingly, a reactivity switch took place when the allene-tethered alcohol substrate was replaced by its ketone counterpart. When the rhodium-catalyzed reaction of 1-benzenesulfonyl-4-phenyl-1,2,3-triazole was performed with allenones, acyclic 6-oxo-hexa-2,4-dienals were stereoselectively formed as (2Z,4E) isomers. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. 40 CFR 89.203 - General provisions.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... greater than or equal to zero, as determined under § 89.207(a). A manufacturer may certify one or more... zero, as determined under § 89.207(b). (A) FELs for NMHC+NOX and FELs for PM may not exceed the upper... transactions in a given model year, as determined under § 89.207(b), are each allowed to be less than zero...

  2. 40 CFR 89.6 - Reference materials.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 20 2010-07-01 2010-07-01 false Reference materials. 89.6 Section 89.6... EMISSIONS FROM NEW AND IN-USE NONROAD COMPRESSION-IGNITION ENGINES General § 89.6 Reference materials. (a... information on the availability of this material at NARA, call 202-741-6030, or go to: http://www.archives.gov...

  3. Aerobic C-H Oxidation of Arenes Using a Recyclable, Heterogeneous Rhodium Catalyst.

    PubMed

    Matsumoto, Kenji; Tachikawa, Shohei; Hashimoto, Noriko; Nakano, Rina; Yoshida, Masahiro; Shindo, Mitsuru

    2017-04-21

    A novel, practical protocol for the aerobic direct C-H acetoxylation of arenes, employing a recyclable heterogeneous rhodium catalyst, is reported herein. The trifluoroacetoxylation of 2-amido-substituted anthracenes proceeded at the 9-position with exclusive regioselectivity. The oxidation of variously substituted anthracenes and other polycyclic aromatics with molecular oxygen as a terminal oxidant proceeded under mild conditions, providing products in good to excellent yields.

  4. Long Range Materials Research. Appendix 1. Synthesis and Characterization of Supported Organometallic Rhodium (I) Catalysts

    DTIC Science & Technology

    1974-06-30

    support organo - metallic homogeneous catalysts on inert supports. This thesis describes the synthesis of a new chelating ligand for binding...homogeneous catalysts to silica surfaces, a now method using poisons for distinguishing con- ventional heterogeneous catal’,sts from the newer supported organo ...Homogeneous HIydrogenation by Rhodium(l) Complexes Homogeneous catalysts have both served and plagued alchemists and chemists since work began with solutions

  5. Drift as a Function of Temperature in Platinum-Rhodium-Alloyed Thermoelements

    NASA Astrophysics Data System (ADS)

    Webster, E. S.; Edler, F.

    2017-02-01

    Platinum-rhodium-alloyed thermocouples are the most commonly used high-temperature reference thermometer in national measurement institutes, second tier laboratories and industry. Despite the common use of these thermocouples, there is still a great deal that is not known about the drift processes that occur in them. Drift processes in these alloys are known to be made up of three main components: crystallographic changes, rhodium oxidation and migration, and contamination. Through careful use, contamination can be largely avoided; however, the other two processes often cannot. Research on drift in the different platinum-rhodium alloys is important because the largest uncertainty component during calibration of these thermocouple types is due to inhomogeneity, and the same mechanisms responsible for inhomogeneity are responsible for the drift. This study investigates the drift processes as a function of temperature and time for the 5 %, 13 %, 17 %, 20 %, 30 % and 40 % Rh alloys when paired with pure platinum. The use of a linear gradient furnace and high-resolution homogeneity scanner has enabled identification of drift characteristics in the temperature range 100°C to 950°C, where the bulk of reversible drift occurs. The experiments have quantified the drift rates and magnitude for thermoelements given two commonly used annealing procedures: the high-temperature quench anneal and the low-temperature vacancy anneal. Consequently, this study provides users of platinum-rhodium thermoelements with guidance on what levels of drift they should expect and exposure times before re-annealing is required. It also shows that a Pt-Rh alloy of 20 % Rh is by far the most stable and has properties comparable to the Pt-Pd thermocouple.

  6. Catalytic asymmetric synthesis of pyrroloindolines via a rhodium(II)-catalyzed annulation of indoles.

    PubMed

    Spangler, Jillian E; Davies, Huw M L

    2013-05-08

    Herein we report the synthesis of pyrroloindolines via a catalytic enantioselective formal [3+2] cycloaddition of C(3)-substituted indoles. This methodology utilizes 4-aryl-1-sulfonyl-1,2,3-triazoles as carbenoid precursors and the rhodium(II)-tetracarboxylate catalyst Rh2(S-PTAD)4. A variety of aryl-substituted pyrroloindolines were prepared in good yields and with high levels of enantioinduction.

  7. Neutron activation determination of rhodium with preliminary micro-fire-assay concentration into a bismuth collector

    SciTech Connect

    Artem'ev, O.I.; Kabirova, G.M.; Stepanov, V.M.

    1987-09-10

    The authors investigated the possibility of neutron activation determination of rhodium with micro-fire-assay preconcentration (MFAP) in conventional laboratory muffle furnaces or tube furnaces. Lead and bismuth were investigated as collectors. Lead or bismuth alloys obtained by MFAP of the test samples and reference samples (RS) with subsequent cupellation were irradiated along with monitors in the thermal channel of the VVR-K reactor at the Institute of Nuclear Physics (Academy of Sciences of the Kazakh SSR), equipped with a pneumatic transport system, in a flux of approximately 1 x 10/sup 13/ neutrons per square centimeter per second. The monitors were comparison samples of manganese with a concentration of 2 x 10/sup -5/ g. The sample irradiation time was 1 min, measurement time 5 min. The measurements were performed 1.5 min and 1 h after irradiation in a gamma-ray spectrometer with a germanium-lithium detector with a volume of 40 cm/sup 3/. The resolution of the spectrometer was 4.5 keV for the 1332-keV gamma line (/sup 60/Co). The spectra of the monitors were taken under fixed conditions for 3 min, starting 10 min after irradiation. The rhodium content was determined from the area of the photopeak of the gamma line with an energy of 556 keV (/sup 104/Rh + /sup 104m/Rh). With a rhodium content of 10/sup -1/% by weight (concentrates and slimes from copper-nickel ores), when using the cadmium channel (thickness 0.7 mm) with certain samples, rhodium can also be determined by purely instrumental NAA without preconcentration.

  8. Cyclic (Alkyl)(Amino)Carbene Complexes of Rhodium and Nickel and Their Steric and Electronic Parameters.

    PubMed

    Paul, Ursula S D; Sieck, Carolin; Haehnel, Martin; Hammond, Kai; Marder, Todd B; Radius, Udo

    2016-07-25

    N-heterocyclic carbenes (NHCs) and cyclic (alkyl)(amino)carbenes (CAACs) are of great interest, as their electronic and steric properties provide a unique class of ligands and organocatalysts. Herein, substitution reactions involving novel carbonyl complexes of rhodium and nickel were studied to provide a deeper understanding of the fundamental electronic factors characterizing CAAC(methyl) , which were compared with the large array of data available for NHC and sterically more demanding CAAC ligands.

  9. Particle size, precursor, and support effects in the hydrogenolysis of alkanes over supported rhodium catalysts

    SciTech Connect

    Coq, B.; Dutartre, R.; Figueras, F.; Tazi, T. )

    1990-04-01

    A series of Rh catalysts of widely varying dispersion has been prepared using {gamma}-alumina as support and Rh acetylacetonate (Rh(acac){sub 3}) as precursor. The hydrogenolyses of n-hexane (nH), methylcyclopentane (MCP), and 2,2,3,3-tetramethylbutane (TeMB) were investigated as model reactions. Clear dependence of turnover frequency on Rh particle size is observed for nH and MCP hydrogenolysis, but only slight changes of selectivities occur with these alkanes. By contrast, large modifications of both specific activity and selectivity appear when TeMB is reacted. TeMB hydrogenolysis is thus a reliable tool for studying modifications of the surface structure of rhodium particles. This probe was used to investigate the effects of precursor and support on rhodium catalysts. The effect of chlorine is appreciable and shifts the selectivity of TeMB hydrogenolysis toward that of large particles. This is attributed to a different morphology of the rhodium particles. When the effect of dispersion of the metal is taken into account, no support effect is observed when SiO{sub 2} or ZrO{sub 2} is used as support. The different properties of rhodium on MgO can also be attributed to a different morphology of the particles. For Rh/TiO{sub 2} prepared from RhCl{sub 3} {center dot} 3H{sub 2}O, the catalytic properties are similar to those of Rh/Al{sub 2}O{sub 3} of moderate dispersion whatever temperature is used for reduction. Rh/TiO{sub 2} prepared from Rh(acac){sub 3} and reduced at 573 and 773 K simulates the catalytic properties of particles smaller than indeed observed. This effect can be interpreted by a partial coverage of the Rh surface by TiO{sub x} species (SMSI). This SMSI effect disappears upon reduction at 873 K.

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

    SciTech Connect

    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.

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

    PubMed

    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.

  12. Catalytic activity of rhodium complex immobilized on AN-31 ion exchanger

    SciTech Connect

    Parshikova, G.N.; Korneva, L.I.; Kononov, Yu.S.

    1995-08-10

    Immobilized platinum-metal complexes are of interest as heterogeneous catalysts. Ion-exchange resins may be used as supports for catalytically active complexes. However, immobilized metal complexes are often unstable, are washed out from supports, and are lost with reaction products. Secure immobilization of metal complexes on supports is possible, for example, via coordination of the central metal by electron-donor groups of the support. This is the case when platinum metals are sorbed from solutions by nitrogen-containing ion exchangers. Complexes thus immobilized have high catalytic activity. Previously the authors demonstrated that rhodium(III) is sorbed from solutions containing rhodium aqua-chloro complexes as stable complexes with AN-31. These complexes were not desorbed with 10 M hydrochloric acid. Stable amino complexes of transition metals sorbed on ion exchangers are known to be active in decomposition of hydrogen peroxide. In this work, the authors have studied catalytic properties of rhodium complex with the ion exchanger under atmospheric pressure at 25-80{degrees}C.

  13. Mild partial deoxygenation of esters catalyzed by an oxazolinylborate-coordinated rhodium silylene

    DOE PAGES

    Xu, Songchen; Boschen, Jeffery S.; Biswas, Abhranil; ...

    2015-08-17

    An electrophilic, coordinatively unsaturated rhodium complex supported by borate-linked oxazoline, oxazoline-coordinated silylene, and N-heterocyclic carbene donors [{κ³-N,Si,C-PhB(OxMe²)(OxMe²SiHPh)ImMes}Rh(H)CO][HB(C₆F₅)₃] (2, OxMe² = 4,4-dimethyl-2-oxazoline; ImMes = 1-mesitylimidazole) is synthesized from the neutral rhodium silyl {PhB(OxMe²)₂ImMes}RhH(SiH2Ph)CO (1) and B(C6F5)3. The unusual oxazoline-coordinated silylene structure in 2 is proposed to form by rearrangement of an unobserved isomeric cationic rhodium silylene species [{PhB(OxMe²)₂ImMes}RhH(SiHPh)CO][HB(C₆F₅)₃] generated by H abstraction. Complex 2 catalyzes reductions of organic carbonyl compounds with silanes to give hydrosilylation products or deoxygenation products. The pathway to these reactions is primarily influenced by the degree of substitution of the organosilane. Reactions with primary silanes give deoxygenationmore » of esters to ethers, amides to amines, and ketones and aldehydes to hydrocarbons, whereas tertiary silanes react to give 1,2-hydrosilylation of the carbonyl functionality. In contrast, the strong Lewis acid B(C₆F₅)₃ catalyzes the complete deoxygenation of carbonyl compounds to hydrocarbons with PhSiH₃ as the reducing agent.« less

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

    PubMed Central

    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

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

    PubMed Central

    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

  16. 45 CFR 89.2 - Definitions.

    Code of Federal Regulations, 2010 CFR

    2010-10-01

    ... 45 Public Welfare 1 2010-10-01 2010-10-01 false Definitions. 89.2 Section 89.2 Public Welfare DEPARTMENT OF HEALTH AND HUMAN SERVICES GENERAL ADMINISTRATION ORGANIZATIONAL INTEGRITY OF ENTITIES... Leadership Act funds for HIV/AIDS programs directly or indirectly from HHS. Sex trafficking means...

  17. 40 CFR 745.89 - Firm certification.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Firm certification. 745.89 Section 745.89 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) TOXIC SUBSTANCES CONTROL ACT LEAD-BASED PAINT POISONING PREVENTION IN CERTAIN RESIDENTIAL STRUCTURES Residential Property...

  18. 40 CFR 745.89 - Firm certification.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Firm certification. 745.89 Section 745.89 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) TOXIC SUBSTANCES CONTROL ACT LEAD-BASED PAINT POISONING PREVENTION IN CERTAIN RESIDENTIAL STRUCTURES Residential Property...

  19. 40 CFR 745.89 - Firm certification.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Firm certification. 745.89 Section 745.89 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) TOXIC SUBSTANCES CONTROL ACT LEAD-BASED PAINT POISONING PREVENTION IN CERTAIN RESIDENTIAL STRUCTURES Residential Property...

  20. 40 CFR 745.89 - Firm certification.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Firm certification. 745.89 Section 745.89 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) TOXIC SUBSTANCES CONTROL ACT LEAD-BASED PAINT POISONING PREVENTION IN CERTAIN RESIDENTIAL STRUCTURES Residential Property...

  1. 24 CFR 242.89 - Supplemental loans.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... 24 Housing and Urban Development 2 2012-04-01 2012-04-01 false Supplemental loans. 242.89 Section... DEVELOPMENT MORTGAGE AND LOAN INSURANCE PROGRAMS UNDER NATIONAL HOUSING ACT AND OTHER AUTHORITIES MORTGAGE INSURANCE FOR HOSPITALS Miscellaneous Requirements § 242.89 Supplemental loans. A loan, advance of...

  2. 24 CFR 242.89 - Supplemental loans.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... 24 Housing and Urban Development 2 2014-04-01 2014-04-01 false Supplemental loans. 242.89 Section... DEVELOPMENT MORTGAGE AND LOAN INSURANCE PROGRAMS UNDER NATIONAL HOUSING ACT AND OTHER AUTHORITIES MORTGAGE INSURANCE FOR HOSPITALS Miscellaneous Requirements § 242.89 Supplemental loans. A loan, advance of...

  3. 24 CFR 242.89 - Supplemental loans.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 24 Housing and Urban Development 2 2010-04-01 2010-04-01 false Supplemental loans. 242.89 Section... DEVELOPMENT MORTGAGE AND LOAN INSURANCE PROGRAMS UNDER NATIONAL HOUSING ACT AND OTHER AUTHORITIES MORTGAGE INSURANCE FOR HOSPITALS Miscellaneous Requirements § 242.89 Supplemental loans. A loan, advance of...

  4. 24 CFR 242.89 - Supplemental loans.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... 24 Housing and Urban Development 2 2013-04-01 2013-04-01 false Supplemental loans. 242.89 Section... DEVELOPMENT MORTGAGE AND LOAN INSURANCE PROGRAMS UNDER NATIONAL HOUSING ACT AND OTHER AUTHORITIES MORTGAGE INSURANCE FOR HOSPITALS Miscellaneous Requirements § 242.89 Supplemental loans. A loan, advance of...

  5. 40 CFR 89.409 - Data logging.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 20 2010-07-01 2010-07-01 false Data logging. 89.409 Section 89.409... Data logging. (a) A computer or any other automatic data processing device(s) may be used as long as the system meets the requirements of this subpart. (b) Determine from the data collection records the...

  6. 40 CFR 89.409 - Data logging.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 21 2013-07-01 2013-07-01 false Data logging. 89.409 Section 89.409... Data logging. (a) A computer or any other automatic data processing device(s) may be used as long as the system meets the requirements of this subpart. (b) Determine from the data collection records the...

  7. 40 CFR 89.409 - Data logging.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 20 2014-07-01 2013-07-01 true Data logging. 89.409 Section 89.409... Data logging. (a) A computer or any other automatic data processing device(s) may be used as long as the system meets the requirements of this subpart. (b) Determine from the data collection records the...

  8. 40 CFR 89.409 - Data logging.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 20 2011-07-01 2011-07-01 false Data logging. 89.409 Section 89.409... Data logging. (a) A computer or any other automatic data processing device(s) may be used as long as the system meets the requirements of this subpart. (b) Determine from the data collection records the...

  9. 40 CFR 89.409 - Data logging.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 21 2012-07-01 2012-07-01 false Data logging. 89.409 Section 89.409... Data logging. (a) A computer or any other automatic data processing device(s) may be used as long as the system meets the requirements of this subpart. (b) Determine from the data collection records the...

  10. 7 CFR 930.89 - Personal liability.

    Code of Federal Regulations, 2010 CFR

    2010-01-01

    ... 7 Agriculture 8 2010-01-01 2010-01-01 false Personal liability. 930.89 Section 930.89 Agriculture Regulations of the Department of Agriculture (Continued) AGRICULTURAL MARKETING SERVICE (Marketing Agreements and Orders; Fruits, Vegetables, Nuts), DEPARTMENT OF AGRICULTURE TART CHERRIES GROWN IN THE STATES...

  11. 40 CFR 89.1003 - Prohibited acts.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... REQUIREMENTS. SALE OR INSTALLATION OF THIS ENGINE FOR ANY PURPOSE OTHER THAN AS A REPLACEMENT ENGINE FOR AN... engine unless the manufacturer has complied with the requirements of § 89.1007. (ii) To sell, offer for... engine in accordance with § 89.110. (iii) To fail or refuse to comply with the requirements of §...

  12. 40 CFR 89.907 - Display exemption.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 20 2011-07-01 2011-07-01 false Display exemption. 89.907 Section 89....907 Display exemption. Where an uncertified nonroad engine is a display engine to be used solely for display purposes, will only be operated incident and necessary to the display purpose, and will not...

  13. 40 CFR 89.907 - Display exemption.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 21 2013-07-01 2013-07-01 false Display exemption. 89.907 Section 89....907 Display exemption. Where an uncertified nonroad engine is a display engine to be used solely for display purposes, will only be operated incident and necessary to the display purpose, and will not...

  14. 40 CFR 89.907 - Display exemption.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 20 2010-07-01 2010-07-01 false Display exemption. 89.907 Section 89....907 Display exemption. Where an uncertified nonroad engine is a display engine to be used solely for display purposes, will only be operated incident and necessary to the display purpose, and will not...

  15. 40 CFR 89.907 - Display exemption.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 21 2012-07-01 2012-07-01 false Display exemption. 89.907 Section 89....907 Display exemption. Where an uncertified nonroad engine is a display engine to be used solely for display purposes, will only be operated incident and necessary to the display purpose, and will not...

  16. 40 CFR 89.907 - Display exemption.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 20 2014-07-01 2013-07-01 true Display exemption. 89.907 Section 89....907 Display exemption. Where an uncertified nonroad engine is a display engine to be used solely for display purposes, will only be operated incident and necessary to the display purpose, and will not...

  17. 40 CFR 141.89 - Analytical methods.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ....89 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) WATER PROGRAMS (CONTINUED) NATIONAL PRIMARY DRINKING WATER REGULATIONS Control of Lead and Copper § 141.89 Analytical methods. (a) Analyses for lead, copper, pH, conductivity, calcium, alkalinity, orthophosphate, silica, and...

  18. 40 CFR 141.89 - Analytical methods.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ....89 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) WATER PROGRAMS (CONTINUED) NATIONAL PRIMARY DRINKING WATER REGULATIONS Control of Lead and Copper § 141.89 Analytical methods. (a) Analyses for lead, copper, pH, conductivity, calcium, alkalinity, orthophosphate, silica, and...

  19. 40 CFR 89.503 - Test orders.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 20 2014-07-01 2013-07-01 true Test orders. 89.503 Section 89.503... Test orders. (a) A test order addressed to the manufacturer is required for any testing under this subpart. (b) The test order is signed by the Assistant Administrator for Air and Radiation or his or...

  20. 40 CFR 89.508 - Test procedures.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 21 2013-07-01 2013-07-01 false Test procedures. 89.508 Section 89.508... Test procedures. (a)(1) For nonroad engines subject to the provisions of this subpart, the prescribed test procedures are the nonroad engine 8-mode test procedure as described in subpart E of this...

  1. 40 CFR 89.503 - Test orders.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 21 2013-07-01 2013-07-01 false Test orders. 89.503 Section 89.503... Test orders. (a) A test order addressed to the manufacturer is required for any testing under this subpart. (b) The test order is signed by the Assistant Administrator for Air and Radiation or his or...

  2. 47 CFR 80.89 - Unauthorized transmissions.

    Code of Federal Regulations, 2013 CFR

    2013-10-01

    ... 47 Telecommunication 5 2013-10-01 2013-10-01 false Unauthorized transmissions. 80.89 Section 80.89... transmissions. Stations must not: (a) Engage in superfluous radio-communication. (b) Use telephony on 243 MHz... transmission of distress, alarm, urgency, or safety signals or messages, or to test transmissions. (e)...

  3. 47 CFR 80.89 - Unauthorized transmissions.

    Code of Federal Regulations, 2014 CFR

    2014-10-01

    ... 47 Telecommunication 5 2014-10-01 2014-10-01 false Unauthorized transmissions. 80.89 Section 80.89... transmissions. Stations must not: (a) Engage in superfluous radio-communication. (b) Use telephony on 243 MHz... transmission of distress, alarm, urgency, or safety signals or messages, or to test transmissions. (e)...

  4. 47 CFR 80.89 - Unauthorized transmissions.

    Code of Federal Regulations, 2011 CFR

    2011-10-01

    ... 47 Telecommunication 5 2011-10-01 2011-10-01 false Unauthorized transmissions. 80.89 Section 80.89... transmissions. Stations must not: (a) Engage in superfluous radio-communication. (b) Use telephony on 243 MHz... transmission of distress, alarm, urgency, or safety signals or messages, or to test transmissions. (e)...

  5. 47 CFR 80.89 - Unauthorized transmissions.

    Code of Federal Regulations, 2012 CFR

    2012-10-01

    ... 47 Telecommunication 5 2012-10-01 2012-10-01 false Unauthorized transmissions. 80.89 Section 80.89... transmissions. Stations must not: (a) Engage in superfluous radio-communication. (b) Use telephony on 243 MHz... transmission of distress, alarm, urgency, or safety signals or messages, or to test transmissions. (e)...

  6. 9 CFR 89.4 - Watering.

    Code of Federal Regulations, 2010 CFR

    2010-01-01

    ... 9 Animals and Animal Products 1 2010-01-01 2010-01-01 false Watering. 89.4 Section 89.4 Animals and Animal Products ANIMAL AND PLANT HEALTH INSPECTION SERVICE, DEPARTMENT OF AGRICULTURE INTERSTATE TRANSPORTATION OF ANIMALS (INCLUDING POULTRY) AND ANIMAL PRODUCTS STATEMENT OF POLICY UNDER THE TWENTY-EIGHT...

  7. 42 CFR 84.89 - Weight requirement.

    Code of Federal Regulations, 2014 CFR

    2014-10-01

    ... 42 Public Health 1 2014-10-01 2014-10-01 false Weight requirement. 84.89 Section 84.89 Public Health PUBLIC HEALTH SERVICE, DEPARTMENT OF HEALTH AND HUMAN SERVICES OCCUPATIONAL SAFETY AND HEALTH RESEARCH AND RELATED ACTIVITIES APPROVAL OF RESPIRATORY PROTECTIVE DEVICES Self-Contained...

  8. 42 CFR 84.89 - Weight requirement.

    Code of Federal Regulations, 2012 CFR

    2012-10-01

    ... 42 Public Health 1 2012-10-01 2012-10-01 false Weight requirement. 84.89 Section 84.89 Public Health PUBLIC HEALTH SERVICE, DEPARTMENT OF HEALTH AND HUMAN SERVICES OCCUPATIONAL SAFETY AND HEALTH RESEARCH AND RELATED ACTIVITIES APPROVAL OF RESPIRATORY PROTECTIVE DEVICES Self-Contained...

  9. 42 CFR 84.89 - Weight requirement.

    Code of Federal Regulations, 2013 CFR

    2013-10-01

    ... 42 Public Health 1 2013-10-01 2013-10-01 false Weight requirement. 84.89 Section 84.89 Public Health PUBLIC HEALTH SERVICE, DEPARTMENT OF HEALTH AND HUMAN SERVICES OCCUPATIONAL SAFETY AND HEALTH RESEARCH AND RELATED ACTIVITIES APPROVAL OF RESPIRATORY PROTECTIVE DEVICES Self-Contained...

  10. 42 CFR 84.89 - Weight requirement.

    Code of Federal Regulations, 2010 CFR

    2010-10-01

    ... 42 Public Health 1 2010-10-01 2010-10-01 false Weight requirement. 84.89 Section 84.89 Public Health PUBLIC HEALTH SERVICE, DEPARTMENT OF HEALTH AND HUMAN SERVICES OCCUPATIONAL SAFETY AND HEALTH RESEARCH AND RELATED ACTIVITIES APPROVAL OF RESPIRATORY PROTECTIVE DEVICES Self-Contained...

  11. 42 CFR 84.89 - Weight requirement.

    Code of Federal Regulations, 2011 CFR

    2011-10-01

    ... 42 Public Health 1 2011-10-01 2011-10-01 false Weight requirement. 84.89 Section 84.89 Public Health PUBLIC HEALTH SERVICE, DEPARTMENT OF HEALTH AND HUMAN SERVICES OCCUPATIONAL SAFETY AND HEALTH RESEARCH AND RELATED ACTIVITIES APPROVAL OF RESPIRATORY PROTECTIVE DEVICES Self-Contained...

  12. 36 CFR 251.89 - Time extensions.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 36 Parks, Forests, and Public Property 2 2010-07-01 2010-07-01 false Time extensions. 251.89... Appeal of Decisions Relating to Occupancy and Use of National Forest System Lands § 251.89 Time extensions. (a) Filing of notice of appeal. Time for filing a notice of appeal is not extendable. (b) All...

  13. 33 CFR 401.89 - Transit refused.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 33 Navigation and Navigable Waters 3 2011-07-01 2011-07-01 false Transit refused. 401.89 Section... TRANSPORTATION SEAWAY REGULATIONS AND RULES Regulations General § 401.89 Transit refused. (a) An officer may refuse to allow a vessel to transit when, (1) The vessel is not equipped in accordance with §§ 401.5...

  14. 33 CFR 401.89 - Transit refused.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 33 Navigation and Navigable Waters 3 2012-07-01 2012-07-01 false Transit refused. 401.89 Section... TRANSPORTATION SEAWAY REGULATIONS AND RULES Regulations General § 401.89 Transit refused. (a) An officer may refuse to allow a vessel to transit when, (1) The vessel is not equipped in accordance with §§ 401.5...

  15. 33 CFR 401.89 - Transit refused.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 33 Navigation and Navigable Waters 3 2014-07-01 2014-07-01 false Transit refused. 401.89 Section... TRANSPORTATION SEAWAY REGULATIONS AND RULES Regulations General § 401.89 Transit refused. (a) An officer may refuse to allow a vessel to transit when, (1) The vessel is not equipped in accordance with §§ 401.5...

  16. 33 CFR 401.89 - Transit refused.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 33 Navigation and Navigable Waters 3 2010-07-01 2010-07-01 false Transit refused. 401.89 Section... TRANSPORTATION SEAWAY REGULATIONS AND RULES Regulations General § 401.89 Transit refused. (a) An officer may refuse to allow a vessel to transit when, (1) The vessel is not equipped in accordance with §§ 401.5...

  17. 33 CFR 401.89 - Transit refused.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 33 Navigation and Navigable Waters 3 2013-07-01 2013-07-01 false Transit refused. 401.89 Section... TRANSPORTATION SEAWAY REGULATIONS AND RULES Regulations General § 401.89 Transit refused. (a) An officer may refuse to allow a vessel to transit when, (1) The vessel is not equipped in accordance with §§ 401.5...

  18. 36 CFR 251.89 - Time extensions.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 36 Parks, Forests, and Public Property 2 2012-07-01 2012-07-01 false Time extensions. 251.89... Appeal of Decisions Relating to Occupancy and Use of National Forest System Lands § 251.89 Time extensions. (a) Filing of notice of appeal. Time for filing a notice of appeal is not extendable. (b) All...

  19. 7 CFR 981.89 - Agents.

    Code of Federal Regulations, 2014 CFR

    2014-01-01

    ... 7 Agriculture 8 2014-01-01 2014-01-01 false Agents. 981.89 Section 981.89 Agriculture Regulations of the Department of Agriculture (Continued) AGRICULTURAL MARKETING SERVICE (MARKETING AGREEMENTS AND ORDERS; FRUITS, VEGETABLES, NUTS), DEPARTMENT OF AGRICULTURE ALMONDS GROWN IN CALIFORNIA Order Regulating...

  20. 7 CFR 981.89 - Agents.

    Code of Federal Regulations, 2012 CFR

    2012-01-01

    ... 7 Agriculture 8 2012-01-01 2012-01-01 false Agents. 981.89 Section 981.89 Agriculture Regulations of the Department of Agriculture (Continued) AGRICULTURAL MARKETING SERVICE (Marketing Agreements and Orders; Fruits, Vegetables, Nuts), DEPARTMENT OF AGRICULTURE ALMONDS GROWN IN CALIFORNIA Order Regulating...

  1. 7 CFR 981.89 - Agents.

    Code of Federal Regulations, 2010 CFR

    2010-01-01

    ... 7 Agriculture 8 2010-01-01 2010-01-01 false Agents. 981.89 Section 981.89 Agriculture Regulations of the Department of Agriculture (Continued) AGRICULTURAL MARKETING SERVICE (Marketing Agreements and Orders; Fruits, Vegetables, Nuts), DEPARTMENT OF AGRICULTURE ALMONDS GROWN IN CALIFORNIA Order Regulating...

  2. 7 CFR 981.89 - Agents.

    Code of Federal Regulations, 2013 CFR

    2013-01-01

    ... 7 Agriculture 8 2013-01-01 2013-01-01 false Agents. 981.89 Section 981.89 Agriculture Regulations of the Department of Agriculture (Continued) AGRICULTURAL MARKETING SERVICE (MARKETING AGREEMENTS AND ORDERS; FRUITS, VEGETABLES, NUTS), DEPARTMENT OF AGRICULTURE ALMONDS GROWN IN CALIFORNIA Order Regulating...

  3. 7 CFR 981.89 - Agents.

    Code of Federal Regulations, 2011 CFR

    2011-01-01

    ... 7 Agriculture 8 2011-01-01 2011-01-01 false Agents. 981.89 Section 981.89 Agriculture Regulations of the Department of Agriculture (Continued) AGRICULTURAL MARKETING SERVICE (Marketing Agreements and Orders; Fruits, Vegetables, Nuts), DEPARTMENT OF AGRICULTURE ALMONDS GROWN IN CALIFORNIA Order Regulating...

  4. 40 CFR 89.902 - Definitions.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... EMISSIONS FROM NEW AND IN-USE NONROAD COMPRESSION-IGNITION ENGINES Exemption Provisions § 89.902 Definitions... an exemption granted under § 89.1004(b) for the purpose of exporting new nonroad engines. National... piece of equipment employed from year to year in the ordinary course of business for product development...

  5. 44 CFR 5.89 - Waiver.

    Code of Federal Regulations, 2010 CFR

    2010-10-01

    ... 44 Emergency Management and Assistance 1 2010-10-01 2010-10-01 false Waiver. 5.89 Section 5.89 Emergency Management and Assistance FEDERAL EMERGENCY MANAGEMENT AGENCY, DEPARTMENT OF HOMELAND SECURITY GENERAL PRODUCTION OR DISCLOSURE OF INFORMATION Subpoenas or Other Legal Demands for Testimony or the...

  6. 20 CFR 632.89 - Performance standards.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... 20 Employees' Benefits 3 2012-04-01 2012-04-01 false Performance standards. 632.89 Section 632.89 Employees' Benefits EMPLOYMENT AND TRAINING ADMINISTRATION, DEPARTMENT OF LABOR INDIAN AND NATIVE AMERICAN... the Program Years 1985-1986. Performance results will be a factor in grantee designations for...

  7. 40 CFR 89.1 - Applicability.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... EMISSIONS FROM NEW AND IN-USE NONROAD COMPRESSION-IGNITION ENGINES General § 89.1 Applicability. (a) This part applies for all compression-ignition nonroad engines (see definition of “nonroad engine” in § 89.2... applies include but are not limited to the following: (1) Compression-ignition engines exempted from...

  8. 40 CFR 89.501 - Applicability.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 20 2014-07-01 2013-07-01 true Applicability. 89.501 Section 89.501 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) AIR PROGRAMS (CONTINUED) CONTROL OF EMISSIONS FROM NEW AND IN-USE NONROAD COMPRESSION-IGNITION ENGINES Selective Enforcement Auditing §...

  9. 40 CFR 89.514 - Hearing procedures.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 21 2013-07-01 2013-07-01 false Hearing procedures. 89.514 Section 89.514 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) AIR PROGRAMS (CONTINUED) CONTROL OF EMISSIONS FROM NEW AND IN-USE NONROAD COMPRESSION-IGNITION ENGINES Selective...

  10. 40 CFR 89.1 - Applicability.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... EMISSIONS FROM NEW AND IN-USE NONROAD COMPRESSION-IGNITION ENGINES General § 89.1 Applicability. (a) This part applies for all compression-ignition nonroad engines (see definition of “nonroad engine” in § 89.2... applies include but are not limited to the following: (1) Compression-ignition engines exempted from...

  11. 40 CFR 89.514 - Hearing procedures.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 20 2014-07-01 2013-07-01 true Hearing procedures. 89.514 Section 89.514 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) AIR PROGRAMS (CONTINUED) CONTROL OF EMISSIONS FROM NEW AND IN-USE NONROAD COMPRESSION-IGNITION ENGINES Selective...

  12. 40 CFR 89.1 - Applicability.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... EMISSIONS FROM NEW AND IN-USE NONROAD COMPRESSION-IGNITION ENGINES General § 89.1 Applicability. (a) This part applies for all compression-ignition nonroad engines (see definition of “nonroad engine” in § 89.2... applies include but are not limited to the following: (1) Compression-ignition engines exempted from...

  13. 40 CFR 89.501 - Applicability.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 20 2010-07-01 2010-07-01 false Applicability. 89.501 Section 89.501 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) AIR PROGRAMS (CONTINUED) CONTROL OF EMISSIONS FROM NEW AND IN-USE NONROAD COMPRESSION-IGNITION ENGINES Selective Enforcement Auditing §...

  14. 40 CFR 89.1 - Applicability.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... EMISSIONS FROM NEW AND IN-USE NONROAD COMPRESSION-IGNITION ENGINES General § 89.1 Applicability. (a) This part applies for all compression-ignition nonroad engines (see definition of “nonroad engine” in § 89.2... applies include but are not limited to the following: (1) Compression-ignition engines exempted from...

  15. 40 CFR 89.909 - Export exemptions.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 20 2014-07-01 2013-07-01 true Export exemptions. 89.909 Section 89.909 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) AIR PROGRAMS (CONTINUED) CONTROL OF EMISSIONS FROM NEW AND IN-USE NONROAD COMPRESSION-IGNITION ENGINES Exemption Provisions §...

  16. 40 CFR 89.905 - Testing exemption.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 20 2010-07-01 2010-07-01 false Testing exemption. 89.905 Section 89.905 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) AIR PROGRAMS (CONTINUED) CONTROL OF EMISSIONS FROM NEW AND IN-USE NONROAD COMPRESSION-IGNITION ENGINES Exemption Provisions §...

  17. 40 CFR 89.1 - Applicability.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... EMISSIONS FROM NEW AND IN-USE NONROAD COMPRESSION-IGNITION ENGINES General § 89.1 Applicability. (a) This part applies for all compression-ignition nonroad engines (see definition of “nonroad engine” in § 89.2... applies include but are not limited to the following: (1) Compression-ignition engines exempted from...

  18. 40 CFR 89.901 - Applicability.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 20 2014-07-01 2013-07-01 true Applicability. 89.901 Section 89.901 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) AIR PROGRAMS (CONTINUED) CONTROL OF EMISSIONS FROM NEW AND IN-USE NONROAD COMPRESSION-IGNITION ENGINES Exemption Provisions §...

  19. 40 CFR 89.502 - Definitions.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 21 2013-07-01 2013-07-01 false Definitions. 89.502 Section 89.502 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) AIR PROGRAMS (CONTINUED) CONTROL OF EMISSIONS FROM NEW AND IN-USE NONROAD COMPRESSION-IGNITION ENGINES Selective Enforcement Auditing §...

  20. 40 CFR 89.901 - Applicability.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 20 2010-07-01 2010-07-01 false Applicability. 89.901 Section 89.901 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) AIR PROGRAMS (CONTINUED) CONTROL OF EMISSIONS FROM NEW AND IN-USE NONROAD COMPRESSION-IGNITION ENGINES Exemption Provisions §...

  1. 40 CFR 89.501 - Applicability.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 21 2013-07-01 2013-07-01 false Applicability. 89.501 Section 89.501 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) AIR PROGRAMS (CONTINUED) CONTROL OF EMISSIONS FROM NEW AND IN-USE NONROAD COMPRESSION-IGNITION ENGINES Selective Enforcement Auditing §...

  2. 40 CFR 89.901 - Applicability.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 21 2013-07-01 2013-07-01 false Applicability. 89.901 Section 89.901 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) AIR PROGRAMS (CONTINUED) CONTROL OF EMISSIONS FROM NEW AND IN-USE NONROAD COMPRESSION-IGNITION ENGINES Exemption Provisions §...

  3. 40 CFR 89.905 - Testing exemption.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 20 2014-07-01 2013-07-01 true Testing exemption. 89.905 Section 89.905 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) AIR PROGRAMS (CONTINUED) CONTROL OF EMISSIONS FROM NEW AND IN-USE NONROAD COMPRESSION-IGNITION ENGINES Exemption Provisions §...

  4. 40 CFR 89.514 - Hearing procedures.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 20 2010-07-01 2010-07-01 false Hearing procedures. 89.514 Section 89.514 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) AIR PROGRAMS (CONTINUED) CONTROL OF EMISSIONS FROM NEW AND IN-USE NONROAD COMPRESSION-IGNITION ENGINES Selective...

  5. 40 CFR 89.502 - Definitions.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 20 2014-07-01 2013-07-01 true Definitions. 89.502 Section 89.502 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) AIR PROGRAMS (CONTINUED) CONTROL OF EMISSIONS FROM NEW AND IN-USE NONROAD COMPRESSION-IGNITION ENGINES Selective Enforcement Auditing §...

  6. 40 CFR 146.89 - Mechanical integrity.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 24 2012-07-01 2012-07-01 false Mechanical integrity. 146.89 Section... Wells § 146.89 Mechanical integrity. (a) A Class VI well has mechanical integrity if: (1) There is no... may require any other test to evaluate mechanical integrity under paragraphs (a)(1) or (a)(2) of this...

  7. 40 CFR 146.89 - Mechanical integrity.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 23 2014-07-01 2014-07-01 false Mechanical integrity. 146.89 Section... Wells § 146.89 Mechanical integrity. (a) A Class VI well has mechanical integrity if: (1) There is no... may require any other test to evaluate mechanical integrity under paragraphs (a)(1) or (a)(2) of this...

  8. 40 CFR 146.89 - Mechanical integrity.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 24 2013-07-01 2013-07-01 false Mechanical integrity. 146.89 Section... Wells § 146.89 Mechanical integrity. (a) A Class VI well has mechanical integrity if: (1) There is no... may require any other test to evaluate mechanical integrity under paragraphs (a)(1) or (a)(2) of this...

  9. 7 CFR 945.89 - Personal liability.

    Code of Federal Regulations, 2010 CFR

    2010-01-01

    ... 7 Agriculture 8 2010-01-01 2010-01-01 false Personal liability. 945.89 Section 945.89 Agriculture Regulations of the Department of Agriculture (Continued) AGRICULTURAL MARKETING SERVICE (Marketing Agreements and Orders; Fruits, Vegetables, Nuts), DEPARTMENT OF AGRICULTURE IRISH POTATOES GROWN IN CERTAIN DESIGNATED COUNTIES IN IDAHO, AND...

  10. 40 CFR 89.909 - Export exemptions.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 20 2010-07-01 2010-07-01 false Export exemptions. 89.909 Section 89....909 Export exemptions. (a) A new nonroad engine intended solely for export, and so labeled or tagged..., 1200 Pennsylvania Ave., NW., Washington, DC 20460. New nonroad engines exported to such countries must...

  11. 9 CFR 89.5 - Feeding pens.

    Code of Federal Regulations, 2012 CFR

    2012-01-01

    ... 9 Animals and Animal Products 1 2012-01-01 2012-01-01 false Feeding pens. 89.5 Section 89.5 Animals and Animal Products ANIMAL AND PLANT HEALTH INSPECTION SERVICE, DEPARTMENT OF AGRICULTURE... resting livestock in transit should have (1) sufficient space for all of the livestock to lie down at the...

  12. 9 CFR 89.5 - Feeding pens.

    Code of Federal Regulations, 2013 CFR

    2013-01-01

    ... 9 Animals and Animal Products 1 2013-01-01 2013-01-01 false Feeding pens. 89.5 Section 89.5 Animals and Animal Products ANIMAL AND PLANT HEALTH INSPECTION SERVICE, DEPARTMENT OF AGRICULTURE... resting livestock in transit should have (1) sufficient space for all of the livestock to lie down at the...

  13. 36 CFR 251.89 - Time extensions.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 36 Parks, Forests, and Public Property 2 2011-07-01 2011-07-01 false Time extensions. 251.89... Appeal of Decisions Relating to Occupancy and Use of National Forest System Lands § 251.89 Time extensions. (a) Filing of notice of appeal. Time for filing a notice of appeal is not extendable. (b)...

  14. 9 CFR 89.5 - Feeding pens.

    Code of Federal Regulations, 2011 CFR

    2011-01-01

    ... 9 Animals and Animal Products 1 2011-01-01 2011-01-01 false Feeding pens. 89.5 Section 89.5 Animals and Animal Products ANIMAL AND PLANT HEALTH INSPECTION SERVICE, DEPARTMENT OF AGRICULTURE...-drained, clean, and safe floors of concrete, cinders, gravel, hard-packed earth, or other...

  15. 7 CFR 905.89 - Separability.

    Code of Federal Regulations, 2010 CFR

    2010-01-01

    ... 7 Agriculture 8 2010-01-01 2010-01-01 false Separability. 905.89 Section 905.89 Agriculture Regulations of the Department of Agriculture (Continued) AGRICULTURAL MARKETING SERVICE (Marketing Agreements and Orders; Fruits, Vegetables, Nuts), DEPARTMENT OF AGRICULTURE ORANGES, GRAPEFRUIT, TANGERINES, AND...

  16. 33 CFR 89.23 - Definitions.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 33 Navigation and Navigable Waters 1 2010-07-01 2010-07-01 false Definitions. 89.23 Section 89.23 Navigation and Navigable Waters COAST GUARD, DEPARTMENT OF HOMELAND SECURITY INLAND NAVIGATION RULES INLAND... Inland Navigational Rules Act of 1980 (Pub. L. 96-591, 33 U.S.C. 2001 et. seq.) and the technical annexes...

  17. 40 CFR 89.202 - Definitions.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 21 2013-07-01 2013-07-01 false Definitions. 89.202 Section 89.202 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) AIR PROGRAMS (CONTINUED) CONTROL OF...) uncovers problems or errors. Trading means the exchange of nonroad engine emission credits between...

  18. 7 CFR 966.89 - Derogation.

    Code of Federal Regulations, 2011 CFR

    2011-01-01

    ... 7 Agriculture 8 2011-01-01 2011-01-01 false Derogation. 966.89 Section 966.89 Agriculture Regulations of the Department of Agriculture (Continued) AGRICULTURAL MARKETING SERVICE (Marketing Agreements and Orders; Fruits, Vegetables, Nuts), DEPARTMENT OF AGRICULTURE TOMATOES GROWN IN FLORIDA Order...

  19. 7 CFR 966.89 - Derogation.

    Code of Federal Regulations, 2012 CFR

    2012-01-01

    ... 7 Agriculture 8 2012-01-01 2012-01-01 false Derogation. 966.89 Section 966.89 Agriculture Regulations of the Department of Agriculture (Continued) AGRICULTURAL MARKETING SERVICE (Marketing Agreements and Orders; Fruits, Vegetables, Nuts), DEPARTMENT OF AGRICULTURE TOMATOES GROWN IN FLORIDA Order...

  20. 7 CFR 966.89 - Derogation.

    Code of Federal Regulations, 2010 CFR

    2010-01-01

    ... 7 Agriculture 8 2010-01-01 2010-01-01 false Derogation. 966.89 Section 966.89 Agriculture Regulations of the Department of Agriculture (Continued) AGRICULTURAL MARKETING SERVICE (Marketing Agreements and Orders; Fruits, Vegetables, Nuts), DEPARTMENT OF AGRICULTURE TOMATOES GROWN IN FLORIDA Order...

  1. 7 CFR 966.89 - Derogation.

    Code of Federal Regulations, 2014 CFR

    2014-01-01

    ... 7 Agriculture 8 2014-01-01 2014-01-01 false Derogation. 966.89 Section 966.89 Agriculture Regulations of the Department of Agriculture (Continued) AGRICULTURAL MARKETING SERVICE (MARKETING AGREEMENTS AND ORDERS; FRUITS, VEGETABLES, NUTS), DEPARTMENT OF AGRICULTURE TOMATOES GROWN IN FLORIDA Order...

  2. 7 CFR 966.89 - Derogation.

    Code of Federal Regulations, 2013 CFR

    2013-01-01

    ... 7 Agriculture 8 2013-01-01 2013-01-01 false Derogation. 966.89 Section 966.89 Agriculture Regulations of the Department of Agriculture (Continued) AGRICULTURAL MARKETING SERVICE (MARKETING AGREEMENTS AND ORDERS; FRUITS, VEGETABLES, NUTS), DEPARTMENT OF AGRICULTURE TOMATOES GROWN IN FLORIDA Order...

  3. Enantioselective rhodium-catalyzed arylation of cyclic N-sulfamidate alkylketimines: a new access to chiral β-alkyl-β-aryl amino alcohols.

    PubMed

    Chen, Ya-Jing; Chen, Ya-Heng; Feng, Chen-Guo; Lin, Guo-Qiang

    2014-06-20

    The enantioselective rhodium-catalyzed 1,2-addition of arylboronates to cyclic N-sulfamidate alkylketimines was developed. With a rhodium/diene complex as catalyst, high enantioselectivity and broad functional group tolerance were observed. The resulting sulfamidates can easily be converted into chiral β-alkyl-β-aryl amino alcohols.

  4. Enantioselective conjugate addition of phenylboronic acid to enones catalysed by a chiral tropos/atropos rhodium complex at the coalescence temperature.

    PubMed

    Monti, Chiara; Gennari, Cesare; Piarulli, Umberto

    2005-11-14

    A highly enantioselective rhodium-catalysed conjugate addition of phenylboronic acid to cyclic enones has been achieved using a dynamic library of chiral phosphorus ligands; the tropos/atropos nature of the ligands in the rhodium complex has been characterised via 31P-NMR.

  5. Determination of rhodium in metallic alloy and water samples using cloud point extraction coupled with spectrophotometric technique

    NASA Astrophysics Data System (ADS)

    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. Influence of particle size and support on the catalytic properties of rhodium for hydrogenolysis of hexanes and methylcyclopentane

    SciTech Connect

    Del Angel, G.; Coq, B.; Dutartre, R.; Figueras, F.

    1984-05-01

    The catalytic properties of rhodium for the hydrogenolysis of C/sub 6/ hydrocarbons have been investigated. Rhodium preferentially cleaves bisecondary and primary-secondary carbon-carbon bonds. Primary-tertiary C-C bonds react much more slowly. Methylcyclopentane (MCP) is converted to methyl-2-pentane, methyl-3-pentane, and n-hexane at temperatures lower than 503 K. The selectivity to n-hexane is low (10%) but measurable on well-dispersed Rh/Al/sub 2/O/sub 3/ catalysts and decreases when the dispersion decreases. Rh/SiO/sub 2/ catalysts have a low selectivity for the formation of n-hexane whatever the dispersion. The specific activity for MCP conversion changes as a function of the dispersion of rhodium and of the support: small rhodium particles are more active than large particles when the support is silica, but the reverse is true on alumina. These changes of activity are consistent with the results reported for C/sub 2/H/sub 6/ hydrogenolysis on Rh/SiO/sub 2/ and for C/sub 5/H/sub 10/ conversion on Rh/Al/sub 2/O/sub 3/. The variations of the catalytic properties for hydrogenolysis may be interpreted as due to the modification of the structure of the small rhodium particles observed on silica.

  7. The structures of the crystalline phase and columnar mesophase of rhodium (II) heptanoate and of its binary mixture with copper (II) heptanoate probed by EXAFS

    NASA Astrophysics Data System (ADS)

    Inb-Elhaj, M.; Guillon, D.; Skoulios, A.; Maldivi, P.; Giroud-Godquin, A. M.; Marchon, J.-C.

    1992-12-01

    EXAFS was used to investigate the local structure of the polar spines of rhodium (II) soaps in the columnar liquid crystalline state. It was also used to ascertain the degree of blending of the cores in binary mixtures of rhodium (II) and copper (II) soaps. For the pure rhodium soaps, the columns are shown to result from the stacking of binuclear metal-metal bonded dirhodium tetracarboxylate units bonded to one another by apical ligation of the metal atom of each complex with one of the oxygen atoms of the adjacent molecule. Mixtures of rhodium (II) and copper (II) soaps give a hexagonal columnar mesophase in which pure rhodium and pure copper columns are randomly distributed.

  8. PET Tracers Based on Zirconium-89

    PubMed Central

    Zhang, Yin; Hong, Hao; Cai, Weibo

    2011-01-01

    Positron emission tomography (PET) imaging with radiolabeled monoclonal antibodies has always been a dynamic area in molecular imaging. With decay half-life (3.3 d) well matched to the circulation half-lives of antibodies (usually on the order of days), 89Zr has been extensively studied over the last decade. This review article will give a brief overview on 89Zr isotope production, the radiochemistry generally used for 89Zr-labeling, and the PET tracers that have been developed using 89Zr. To date, 89Zr-based PET imaging has been investigated for a wide variety of cancer-related targets, which include human epidermal growth factor receptor 2, epidermal growth factor receptor, prostate-specific membrane antigen, splice variant v6 of CD44, vascular endothelial growth factor, carbonic anhydrase IX, insulin-like growth factor 1 receptor, among others. With well-developed radiochemistry, commercial availability of chelating agents for 89Zr labeling, increasingly widely available isotope supply, as well as successful proof-of-principle in pilot human studies, it is expected that PET imaging with 89Zr-based tracers will be a constantly evolving and highly vibrant field in the near future. PMID:22191652

  9. A rhodium/silicon co-electrocatalyst design concept to surpass platinum hydrogen evolution activity at high overpotentials

    PubMed Central

    Zhu, Lili; Lin, Haiping; Li, Youyong; Liao, Fan; Lifshitz, Yeshayahu; Sheng, Minqi; Lee, Shuit-Tong; Shao, Mingwang

    2016-01-01

    Currently, platinum-based electrocatalysts show the best performance for hydrogen evolution. All hydrogen evolution reaction catalysts should however obey Sabatier's principle, that is, the adsorption energy of hydrogen to the catalyst surface should be neither too high nor too low to balance between hydrogen adsorption and desorption. To overcome the limitation of this principle, here we choose a composite (rhodium/silicon nanowire) catalyst, in which hydrogen adsorption occurs on rhodium with a large adsorption energy while hydrogen evolution occurs on silicon with a small adsorption energy. We show that the composite is stable with better hydrogen evolution activity than rhodium nanoparticles and even exceeding those of commercial platinum/carbon at high overpotentials. The results reveal that silicon plays a key role in the electrocatalysis. This work may thus open the door for the design and fabrication of electrocatalysts for high-efficiency electric energy to hydrogen energy conversion. PMID:27447292

  10. 34 CFR 361.89 - Enforcement procedures.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... Standards and Performance Indicators § 361.89 Enforcement procedures. (a) If a DSU fails to meet the... satisfactory level on the compliance indicators. (Approved by the Office of Management and Budget under...

  11. 34 CFR 361.89 - Enforcement procedures.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... Standards and Performance Indicators § 361.89 Enforcement procedures. (a) If a DSU fails to meet the... satisfactory level on the compliance indicators. (Approved by the Office of Management and Budget under...

  12. 9 CFR 89.4 - Watering.

    Code of Federal Regulations, 2012 CFR

    2012-01-01

    ... and Animal Products ANIMAL AND PLANT HEALTH INSPECTION SERVICE, DEPARTMENT OF AGRICULTURE INTERSTATE... LAW § 89.4 Watering. Livestock should be furnished an ample supply of potable water. Water treated... weather, the water should be free from ice. ...

  13. 9 CFR 89.4 - Watering.

    Code of Federal Regulations, 2013 CFR

    2013-01-01

    ... and Animal Products ANIMAL AND PLANT HEALTH INSPECTION SERVICE, DEPARTMENT OF AGRICULTURE INTERSTATE... LAW § 89.4 Watering. Livestock should be furnished an ample supply of potable water. Water treated... weather, the water should be free from ice. ...

  14. 40 CFR 89.203 - General provisions.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ..., banking, and trading programs if they are exported or are sold as Blue Sky Series engines as described in... sold as Blue Sky Series engines as described in § 89.112(f). Nonroad engines certified on a...

  15. 40 CFR 89.203 - General provisions.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ..., banking, and trading programs if they are exported or are sold as Blue Sky Series engines as described in... sold as Blue Sky Series engines as described in § 89.112(f). Nonroad engines certified on a...

  16. 7 CFR 301.89-4 - Planting.

    Code of Federal Regulations, 2010 CFR

    2010-01-01

    ..., DEPARTMENT OF AGRICULTURE DOMESTIC QUARANTINE NOTICES Karnal Bunt § 301.89-4 Planting. Any wheat, durum wheat, or triticale that originates within a regulated area must be tested and found free from bunted...

  17. 9 CFR 89.4 - Watering.

    Code of Federal Regulations, 2011 CFR

    2011-01-01

    ... and Animal Products ANIMAL AND PLANT HEALTH INSPECTION SERVICE, DEPARTMENT OF AGRICULTURE INTERSTATE... LAW § 89.4 Watering. Livestock should be furnished an ample supply of potable water. Water treated... weather, the water should be free from ice....

  18. 40 CFR 89.503 - Test orders.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... EMISSIONS FROM NEW AND IN-USE NONROAD COMPRESSION-IGNITION ENGINES Selective Enforcement Auditing § 89.503... Selective Enforcement Auditing (SEA) test orders than an annual limit determined to be the larger of the...

  19. 7 CFR 160.89 - Medicinal preparations.

    Code of Federal Regulations, 2010 CFR

    2010-01-01

    ... Agriculture Regulations of the Department of Agriculture (Continued) AGRICULTURAL MARKETING SERVICE (Standards, Inspections, Marketing Practices), DEPARTMENT OF AGRICULTURE (CONTINUED) NAVAL STORES REGULATIONS AND STANDARDS FOR NAVAL STORES Sales and Shipments § 160.89 Medicinal preparations. A compound or...

  20. 7 CFR 160.89 - Medicinal preparations.

    Code of Federal Regulations, 2011 CFR

    2011-01-01

    ... Agriculture Regulations of the Department of Agriculture (Continued) AGRICULTURAL MARKETING SERVICE (Standards, Inspections, Marketing Practices), DEPARTMENT OF AGRICULTURE (CONTINUED) NAVAL STORES REGULATIONS AND STANDARDS FOR NAVAL STORES Sales and Shipments § 160.89 Medicinal preparations. A compound or...

  1. 40 CFR 89.203 - General provisions.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ..., banking, and trading programs if they are exported or are sold as Blue Sky Series engines as described in... sold as Blue Sky Series engines as described in § 89.112(f). Nonroad engines certified on a special...

  2. 40 CFR 89.203 - General provisions.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ..., banking, and trading programs if they are exported or are sold as Blue Sky Series engines as described in... sold as Blue Sky Series engines as described in § 89.112(f). Nonroad engines certified on a special...

  3. 7 CFR 301.89-4 - Planting.

    Code of Federal Regulations, 2011 CFR

    2011-01-01

    ..., DEPARTMENT OF AGRICULTURE DOMESTIC QUARANTINE NOTICES Karnal Bunt § 301.89-4 Planting. Any wheat, durum wheat, or triticale that originates within a regulated area must be tested and found free from bunted wheat...

  4. 7 CFR 301.89-4 - Planting.

    Code of Federal Regulations, 2014 CFR

    2014-01-01

    ..., DEPARTMENT OF AGRICULTURE DOMESTIC QUARANTINE NOTICES Karnal Bunt § 301.89-4 Planting. Any wheat, durum wheat, or triticale that originates within a regulated area must be tested and found free from bunted wheat...

  5. 7 CFR 301.89-4 - Planting.

    Code of Federal Regulations, 2012 CFR

    2012-01-01

    ..., DEPARTMENT OF AGRICULTURE DOMESTIC QUARANTINE NOTICES Karnal Bunt § 301.89-4 Planting. Any wheat, durum wheat, or triticale that originates within a regulated area must be tested and found free from bunted wheat...

  6. 7 CFR 301.89-4 - Planting.

    Code of Federal Regulations, 2013 CFR

    2013-01-01

    ..., DEPARTMENT OF AGRICULTURE DOMESTIC QUARANTINE NOTICES Karnal Bunt § 301.89-4 Planting. Any wheat, durum wheat, or triticale that originates within a regulated area must be tested and found free from bunted wheat...

  7. 49 CFR 230.89 - Reverse gear.

    Code of Federal Regulations, 2011 CFR

    2011-10-01

    ... Reversing Gear § 230.89 Reverse gear. (a) General provisions. Reverse gear, reverse levers, and quadrants shall be maintained in a safe and suitable condition for service. Reverse lever latch shall be so...

  8. 49 CFR 230.89 - Reverse gear.

    Code of Federal Regulations, 2013 CFR

    2013-10-01

    ... Reversing Gear § 230.89 Reverse gear. (a) General provisions. Reverse gear, reverse levers, and quadrants shall be maintained in a safe and suitable condition for service. Reverse lever latch shall be so...

  9. 49 CFR 230.89 - Reverse gear.

    Code of Federal Regulations, 2014 CFR

    2014-10-01

    ... Reversing Gear § 230.89 Reverse gear. (a) General provisions. Reverse gear, reverse levers, and quadrants shall be maintained in a safe and suitable condition for service. Reverse lever latch shall be so...

  10. 49 CFR 230.89 - Reverse gear.

    Code of Federal Regulations, 2010 CFR

    2010-10-01

    ... Reversing Gear § 230.89 Reverse gear. (a) General provisions. Reverse gear, reverse levers, and quadrants shall be maintained in a safe and suitable condition for service. Reverse lever latch shall be so...

  11. 49 CFR 230.89 - Reverse gear.

    Code of Federal Regulations, 2012 CFR

    2012-10-01

    ... Reversing Gear § 230.89 Reverse gear. (a) General provisions. Reverse gear, reverse levers, and quadrants shall be maintained in a safe and suitable condition for service. Reverse lever latch shall be so...

  12. Graphs for Isotopes of 89-Ac (Actinium)

    NASA Astrophysics Data System (ADS)

    Sukhoruchkin, S. I.; Soroko, Z. N.

    This document is part of the Supplement containing the complete sets of data of Subvolume B `Nuclei with Z = 55 - 100' of Volume 22 `Nuclear Binding Energies and Atomic Masses' of Landolt-Börnstein - Group I `Elementary Particles, Nuclei and Atoms', and additionally including data for nuclei with Z = 101 - 130. It provides a graphic representation of nucleon separation energies and residual interaction parameters for isotopes of the chemical element 89-Ac (Actinium, atomic number Z = 89).

  13. Mechanochemical Rhodium(III)-Catalyzed C-H Bond Functionalization of Acetanilides under Solventless Conditions in a Ball Mill.

    PubMed

    Hermann, Gary N; Becker, Peter; Bolm, Carsten

    2015-06-15

    In a proof-of-principle study, a planetary ball mill was applied to rhodium(III)-catalyzed C-H bond functionalization. Under solventless conditions and in the presence of a minute amount of Cu(OAc)2, the mechanochemical activation led to the formation of an active rhodium species, thus enabling an oxidative Heck-type cross-coupling reaction with dioxygen as the terminal oxidant. The absence of an organic solvent, the avoidance of a high reaction temperature, the possibility of minimizing the amount of the metallic mediator, and the simplicity of the protocol result in a powerful and environmentally benign alternative to the common solution-based standard protocol.

  14. Permeation of platinum and rhodium nanoparticles through intact and damaged human skin

    NASA Astrophysics Data System (ADS)

    Mauro, Marcella; Crosera, Matteo; Bianco, Carlotta; Adami, Gianpiero; Montini, Tiziano; Fornasiero, Paolo; Jaganjac, Morana; Bovenzi, Massimo; Filon, Francesca Larese

    2015-06-01

    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 Na2PtCl6 and RhCl3·3H2O 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.

  15. Synthesis, characterization, and reactivity of rhodium(I) acetylacetonato complexes containing pyridinecarboxaldimine ligands.

    PubMed

    Kanas, Diane A; Geier, Stephen J; Vogels, Christopher M; Decken, Andreas; Westcott, Stephen A

    2008-10-06

    Addition of o-C 6H 4NCHNAr to Rh(coe) 2(acac) (coe = cis-cyclooctene, acac = acetylacetonato) gave several new iminopyridine rhodium(I) complexes of the type Rh(acac)(kappa (2)- o-C 6H 4 NCH NAr) ( 1a Ar = 4-C 6H 4-OMe; 1b Ar = 2,6-C 6H 3-Me 2; 1c Ar = 2,6-C 6H 3-Et 2; 1d Ar = 2,6-C 6H 3- i-Pr 2). All new rhodium complexes have been characterized by a number of physical methods, including multinuclear NMR spectroscopy and X-ray diffraction studies for 1b and 1c. Addition of CHCl 3 to 1a afforded the corresponding rhodium(III) complex trans-Rh(kappa (2)- o-C 6H 4 NCH NAr)(CHCl 2)(Cl)(acac) ( 2). Addition of B 2cat 3 (cat = 1,2-O 2C 6H 4) to 1 gave zwitterionic Rh(eta (6)-catBcat)(kappa (2)- o-C 6H 4 NCH NAr) ( 3). The molecular structure of 3b has been confirmed by a single crystal X-ray diffraction study and shows that the N 2Rh fragment is bound to the catBcat anion via one of the catecholato groups in a eta (6)-fashion. These complexes have also been examined for their ability to catalyze the hydroboration of a series of vinylarenes. Reactions using catecholborane and pinacolborane seem to proceed largely through a dehydrogenative borylation mechanism to give a number of boronated products.

  16. Mild partial deoxygenation of esters catalyzed by an oxazolinylborate-coordinated rhodium silylene

    SciTech Connect

    Xu, Songchen; Boschen, Jeffery S.; Biswas, Abhranil; Kobayashi, Takeshi; Pruski, Marek; Windus, Theresa L.; Sadow, Aaron D.

    2015-08-17

    An electrophilic, coordinatively unsaturated rhodium complex supported by borate-linked oxazoline, oxazoline-coordinated silylene, and N-heterocyclic carbene donors [{κ³-N,Si,C-PhB(OxMe²)(OxMe²SiHPh)ImMes}Rh(H)CO][HB(C₆F₅)₃] (2, OxMe² = 4,4-dimethyl-2-oxazoline; ImMes = 1-mesitylimidazole) is synthesized from the neutral rhodium silyl {PhB(OxMe²)₂ImMes}RhH(SiH2Ph)CO (1) and B(C6F5)3. The unusual oxazoline-coordinated silylene structure in 2 is proposed to form by rearrangement of an unobserved isomeric cationic rhodium silylene species [{PhB(OxMe²)₂ImMes}RhH(SiHPh)CO][HB(C₆F₅)₃] generated by H abstraction. Complex 2 catalyzes reductions of organic carbonyl compounds with silanes to give hydrosilylation products or deoxygenation products. The pathway to these reactions is primarily influenced by the degree of substitution of the organosilane. Reactions with primary silanes give deoxygenation of esters to ethers, amides to amines, and ketones and aldehydes to hydrocarbons, whereas tertiary silanes react to give 1,2-hydrosilylation of the carbonyl functionality. In contrast, the strong Lewis acid B(C₆F₅)₃ catalyzes the complete deoxygenation of carbonyl compounds to hydrocarbons with PhSiH₃ as the reducing agent.

  17. A concise total synthesis of pyrovellerolactone using a rhodium-catalyzed [(3 + 2) + 2] carbocyclization reaction.

    PubMed

    Evans, P Andrew; Inglesby, Phillip A; Kilbride, Kathryn

    2013-04-19

    A concise and highly convergent three-step total synthesis of the lactarane natural product, pyrovellerolactone, is described. The key step involves a regio- and diastereoselective rhodium-catalyzed [(3 + 2) + 2] carbocyclization of an alkenylidenecyclopropane with a 4-hydroxybut-2-ynoate followed by an in situ intramolecular lactonization to generate the tricyclic core in a single operation. This represents the first example of a higher-order [3 + 2 + 2] carbocyclization reaction in total synthesis, which is likely to provide an important strategy for the construction of related targets within this sesquiterpene family.

  18. Hydrolysis of Letrozole catalyzed by macrocyclic Rhodium (I) Schiff-base complexes.

    PubMed

    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.

  19. Construction of a Chiral Silicon Center by Rhodium-Catalyzed Enantioselective Intramolecular Hydrosilylation.

    PubMed

    Naganawa, Yuki; Namba, Tomoya; Kawagishi, Mayu; Nishiyama, Hisao

    2015-06-22

    Rhodium-catalyzed enantioselective desymmetrizing intramolecular hydrosilylation of symmetrically disubstituted hydrosilanes is described. The original axially chiral phenanthroline ligand (S)-BinThro (Binol-derived phenanthroline) was found to work as an effective chiral catalyst for this transformation. A chiral silicon stereogenic center is one of the chiral motifs gaining much attention in asymmetric syntheses and the present protocol provides cyclic five-membered organosilanes incorporating chiral silicon centers with high enantioselectivities (up to 91 % ee). The putative active Rh(I) catalyst takes the form of an N,N,O-tridentate coordination complex, as determined by several complementary experiments.

  20. Oxidative addition of methane and benzene C--H bonds to rhodium center: A DFT study

    NASA Astrophysics Data System (ADS)

    Bi, Siwei; Zhang, Zhenwei; Zhu, Shufen

    2006-11-01

    A density functional theory study on mechanisms of the oxidative addition of methane and benzene C-H bonds to the rhodium center containing Cp and PMe 3 ligands has been performed. Our calculated results confirm that the C-H bond cleavage from a sigma complex to a hydride alkyl complex is the rate-determining step. Compared with the case of methane C-H bond, the oxidative addition of benzene C-H bond is more favorable kinetically and thermodynamically. Stronger backdonation from metal center to the σ ∗ antibonding orbital of benzene C-H bond is responsible for the observations.

  1. Platinum, palladium, and rhodium analyses of ultramafic and mafic rocks from the Stillwater Complex, Montana

    USGS Publications Warehouse

    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.

  2. AMTEC cell testing, optimization of rhodium/tungsten electrodes, and tests of other components

    NASA Technical Reports Server (NTRS)

    Williams, Roger M.; Ryan, Margaret A.; Jeffries-Nakamura, Barbara; Underwood, Mark L.; O'Connor, Dennis; Kikkert, Stan

    1991-01-01

    Electrodes, current collectors, ceramic to metal braze seals, and metallic components exposed to the high 'hot side' temperatures and sodium liquid and vapor environment have been tested and evaluated in laboratory cells running for hundreds of hours at 1100-1200 K. Rhodium/tungsten electrodes have been selected as the optimum electrodes based on performance parameters and durability. Current collectors have been evaluated under simulated and actual operating conditions. The microscopic effects of metal migration between electrode and current collector alloys as well as their thermal and electrical properties determined the suitability of current collector and lead materials. Braze seals suitable for long term application to AMTEC devices are being developed.

  3. The oxidation of carbon monoxide on polycrystalline rhodium under knudsen conditions. II. Reaction with nitrogen monoxide

    NASA Astrophysics Data System (ADS)

    Lintz, Hans-Günther; Weisker, Tilman

    1985-09-01

    The reaction between carbon monoxide and nitrogen monoxide on a polycrystalline rhodium ribbon under stationary conditions is followed by mass spectrometry. In the temperature range 300 to 1100 K the ratio of the partial pressures of the reactants varies between 0.1 < pNO/ pCO < 100 at values of the total pressure in the reactor from 10 -4 to 10 -5 Torr. The results can be interpreted qualitatively by a simple elementary reaction sequence. Simulation using literature values of the kinetic constants leads to semi-quantitative agreement with experimental results. No isothermal oscillations of the reaction rate could be observed under the stated conditions.

  4. Understanding Rate Acceleration and Stereoinduction of an Asymmetric Giese Reaction Mediated by a Chiral Rhodium Catalyst.

    PubMed

    Tutkowski, Brandon; Meggers, Eric; Wiest, Olaf

    2017-06-21

    The surprising acceleration of the addition of electron-rich radicals to α,β-unsaturated 2-acyl imidazoles by a chiral-at-metal rhodium catalyst is investigated. M06/Lanl2DZ (Rh),6-31G(d) calculations reproduce the observed rate acceleration and shed light on a catalyst design where a rigid chiral pocket with a steric interaction >5 Å from the chiral metal center leads to the observed high stereoinduction. Analysis of the molecular orbitals of two key addition transition states emphasize the role of the catalyst as a Lewis acid without significant charge transfer.

  5. Rhodium(III)-catalyzed indazole synthesis by C-H bond functionalization and cyclative capture.

    PubMed

    Lian, Yajing; Bergman, Robert G; Lavis, Luke D; Ellman, Jonathan A

    2013-05-15

    An efficient, one-step, and highly functional group-compatible synthesis of substituted N-aryl-2H-indazoles is reported via the rhodium(III)-catalyzed C-H bond addition of azobenzenes to aldehydes. The regioselective coupling of unsymmetrical azobenzenes was further demonstrated and led to the development of a new removable aryl group that allows for the preparation of indazoles without N-substitution. The 2-aryl-2H-indazole products also represent a new class of readily prepared fluorophores for which initial spectroscopic characterization has been performed.

  6. Associative Covalent Relay: An Oxadiazolone Strategy for Rhodium(III)-Catalyzed Synthesis of Primary Pyridinylamines.

    PubMed

    Yu, Xiaolong; Chen, Kehao; Wang, Qi; Guo, Shan; Zha, Shanke; Zhu, Jin

    2017-04-05

    A relay formalism is proposed herein for categorizing the interplay among reactants, target product, and catalytic center in transition-metal catalysis, an important factor that can dictate overall catalysis viability and efficiency. In this formalism, transition-metal catalysis can proceed by dissociative relay, associative covalent relay, and associative dative relay modes. An intriguing associative covalent relay process operates in rhodium(III)-catalyzed oxadiazolone-directed alkenyl C-H coupling with alkynes and allows efficient access to primary pyridinylamines. Although the primary pyridinylamine synthesis mechanism is posteriori rationalized, the relay formalism formulated herein can provide an important mechanistic conceptual framework for future catalyst design and reaction development.

  7. Thermodynamics of oxygen activation by macrocyclic complexes of rhodium.

    PubMed

    Szajna-Fuller, Ewa; Bakac, Andreja

    2007-12-10

    The oxidation of ABTS2- [2,2'-azino-bis(3-ethylbenzothiazoline-6-sulfonate)] with a superoxorhodium(III) complex, L2(H2O)RhOO2+ (L2 = meso-hexamethylcyclam) is characterized by an acid-dependent equilibrium constant, log(Ke/[H+]) = 4.91 +/- 0.10 in the pH range of 4.89-6.49. This equilibrium constant was used to calculate the reduction potential for the L2(H2O)RhOO2+/L2(H2O)RhOOH2+ couple, E0 = 0.97 V vs NHE. The pH dependence of the kinetics of the L2(H2O)RhOOH2+/I- reaction yielded the acid dissociation constant for the coordinated water in L2(H2O)RhOOH2+, pKa = 6.9. Spectrophotometric pH titrations provided pKa = 6.6 for the superoxo complex, L2(H2O)RhOO2+. The combination of the two pKa values with the reduction potential measured in acidic solutions yielded the reduction potential E0 = 0.95 V for the L2(HO)RhOO+/L2(HO)RhOOH+ couple. Thermochemical calculations yielded the bond-dissociation free energy of the L2(H2O)RhOO-H2+ bond as 315 kJ/mol at 298 K.

  8. 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

    SciTech Connect

    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.

  9. The role of macrocyclic compounds in the extraction and possible separation of platinum and rhodium from chloride solutions

    PubMed Central

    Jyothi, Rajesh Kumar; Lee, Jin-Young

    2016-01-01

    Macrocyclic compounds (crown ethers), specifically 18-crown-6 (18-C-6), benzo-15-crown-5 (B-15-C-5), di-benzo-18-crown-6 (DB-18-C-6) and di-cyclohexano-18-crown-6 (DC-18C-6), are used as extractants as well as synergists with amine-group extractants. Platinum and rhodium belong to platinum-group metals (PGMs) and have very similar ionic radii and similar properties. The separation of PGMs is most useful for the preparation of functional materials. Macrocyclic compounds are tested for platinum and rhodium separation and are found to achieve marginal separation. Amines (used as extractants) are paired with macrocyclic compounds (used as synergists), and the separation factor between platinum and rhodium is increased with synergistic enhancement from a chloride solution. The present study discusses extraction chemistry, separation factors and the synergy between platinum and rhodium from chloride solutions. To ensure accurate data, the aqueous samples in this study are analyzed using an inductively coupled plasma optical emission spectrometer (ICP-OES). PMID:27283394

  10. Direct access to ketones from aldehydes via rhodium-catalyzed cross-coupling reaction with potassium trifluoro(organo)borates.

    PubMed

    Pucheault, Mathieu; Darses, Sylvain; Genet, Jean-Pierre

    2004-12-01

    A direct cross-coupling reaction of aromatic aldehydes with potassium trifluoro(organo)borates afforded ketones in high yields and under mild conditions in the presence of a rhodium catalyst and acetone. This new reaction, involving a formal aldehyde C-H bond activation, is believed to proceed via a Heck-type mechanism followed by hydride transfer to acetone.

  11. The role of macrocyclic compounds in the extraction and possible separation of platinum and rhodium from chloride solutions

    NASA Astrophysics Data System (ADS)

    Jyothi, Rajesh Kumar; Lee, Jin-Young

    2016-06-01

    Macrocyclic compounds (crown ethers), specifically 18-crown-6 (18-C-6), benzo-15-crown-5 (B-15-C-5), di-benzo-18-crown-6 (DB-18-C-6) and di-cyclohexano-18-crown-6 (DC-18C-6), are used as extractants as well as synergists with amine-group extractants. Platinum and rhodium belong to platinum-group metals (PGMs) and have very similar ionic radii and similar properties. The separation of PGMs is most useful for the preparation of functional materials. Macrocyclic compounds are tested for platinum and rhodium separation and are found to achieve marginal separation. Amines (used as extractants) are paired with macrocyclic compounds (used as synergists), and the separation factor between platinum and rhodium is increased with synergistic enhancement from a chloride solution. The present study discusses extraction chemistry, separation factors and the synergy between platinum and rhodium from chloride solutions. To ensure accurate data, the aqueous samples in this study are analyzed using an inductively coupled plasma optical emission spectrometer (ICP-OES).

  12. Rhodium(III)-catalyzed C-H activation/annulation with vinyl esters as an acetylene equivalent.

    PubMed

    Webb, Nicola J; Marsden, Stephen P; Raw, Steven A

    2014-09-19

    The behavior of electron-rich alkenes in rhodium-catalyzed C-H activation/annulation reactions is investigated. Vinyl acetate emerges as a convenient acetylene equivalent, facilitating the synthesis of sixteen 3,4-unsubstituted isoquinolones, as well as select heteroaryl-fused pyridones. The complementary regiochemical preferences of enol ethers versus enol esters/enamides is discussed.

  13. Asymmetric cyclopropanation of alkenes catalyzed by a rhodium {open_quotes}chiral fortress{close_quotes} porphyrin

    SciTech Connect

    O`Malley, S.; Kodadek, T.

    1992-06-01

    The authors investigated the use of chiral rhodium porphyrin catalysts for the production of predominantly syn isomers in the cyclopropanation of alkenes. The reactions display good diastereoselectivity on some cases, but only modest enantioselectivities are observed. 15 refs., 3 figs., 1 tab.

  14. Development and testing of a compact basis set for use in effective core potential calculations on rhodium complexes.

    PubMed

    Roscioni, Otello M; Lee, Edmond P F; Dyke, John M

    2012-10-05

    We present a set of effective core potential (ECP) basis sets for rhodium atoms which are of reasonable size for use in electronic structure calculations. In these ECP basis sets, the Los Alamos ECP is used to simulate the effect of the core electrons while an optimized set of Gaussian functions, which includes polarization and diffuse functions, is used to describe the valence electrons. These basis sets were optimized to reproduce the ionization energy and electron affinity of atomic rhodium. They were also tested by computing the electronic ground state geometry and harmonic frequencies of [Rh(CO)(2) μ-Cl](2) , Rh(CO)(2) ClPy, and RhCO (neutral and its positive, and negative ions) as well as the enthalpy of the reaction of [Rh(CO)(2) μ-Cl](2) with pyridine (Py) to give Rh(CO)(2) ClPy, at different levels of theory. Good agreement with experimental values was obtained. Although the number of basis functions used in our ECP basis sets is smaller than those of other ECP basis sets of comparable quality, we show that the newly developed ECP basis sets provide the flexibility and precision required to reproduce a wide range of chemical and physical properties of rhodium compounds. Therefore, we recommend the use of these compact yet accurate ECP basis sets for electronic structure calculations on molecules involving rhodium atoms. Copyright © 2012 Wiley Periodicals, Inc.

  15. Ethylaluminum as an ethylene source for the Mizoroki-Heck-type reaction. Rhodium-catalyzed preparation of stilbene derivatives.

    PubMed

    Tanaka, Shota; Itami, Kazuki; Sunahara, Kazuhiro; Tatsuta, Go; Mori, Atsunori

    2015-02-04

    Treatment of an organoaluminum reagent bearing aryl and ethyl groups furnishes 1,2-diarylethene derivatives in good to excellent yields by the catalysis of a rhodium complex, in which the ethyl group of the aluminum reagent serves as an ethylene source in the product formation.

  16. Development of an improved rhodium catalyst for z-selective anti-markovnikov addition of carboxylic acids to terminal alkynes.

    PubMed

    Wei, Siping; Pedroni, Julia; Meißner, Antje; Lumbroso, Alexandre; Drexler, Hans-Joachim; Heller, Detlef; Breit, Bernhard

    2013-09-02

    To develop more active catalysts for the rhodium-catalyzed addition of carboxylic acids to terminal alkynes furnishing anti-Markovnikov Z enol esters, a thorough study of the rhodium complexes involved was performed. A number of rhodium complexes were characterized by NMR, ESI-MS, and X-ray analysis and applied as catalysts for the title reaction. The systematic investigations revealed that the presence of chloride ions decreased the catalyst activity. Conversely, generating and applying a mixture of two rhodium species, namely, [Rh(DPPMP)2][H(benzoate)2] (DPPMP=diphenylphosphinomethylpyridine) and [{Rh(COD)(μ2-benzoate)}2], provided a significantly more active catalyst. Furthermore, the addition of a catalytic amount of base (Cs2CO3) had an additional accelerating effect. This higher catalyst activity allowed the reaction time to be reduced from 16 to 1-4 h while maintaining high selectivity. Studies on the substrate scope revealed that the new catalysts have greater functional-group compatibility.

  17. New Fischer carbene complexes of rhodium(i): preparation and 2-cyclopentenone ring synthesis by annelation to alkynes.

    PubMed

    Barluenga, José; Vicente, Rubén; López, Luis A; Rubio, Eduardo; Tomás, Miguel; Alvarez-Rúa, Carmen

    2004-01-21

    A new type of metal carbene complexes of group 9, specifically a cationic Fischer carbene of rhodium(I), has been synthesized from chromium carbene complexes via double transfer of carbene and CO ligands. These complexes reveal a different reactivity than other transition metal carbenes, including their chromium precursors, toward neutral and electron-poor alkynes, giving selectively polysubstituted cyclopentenones.

  18. Development of Chinese Standard Type of Rhodium-Iron Resistance Thermometer

    NASA Astrophysics Data System (ADS)

    Lin, Peng; Li, Xingwei; Gao, Bo; Yu, Lihong; Huang, Rongjin; Li, Fuhong

    2017-02-01

    New rhodium alloy wires with 0.52 % atomic of iron have been drawn, and several batches of RhFe thermometer with strain-free construction and helium-filled platinum capsule have been made using these new alloy wires and old alloy wires which were made in the 1980s in China. In one of the constructions, the coil of wire is inserted into twisted glass tubes, and in the other, it is laid in grooves on a fused-silica crossed frame. The resistance versus temperature relationship and interpolating characteristic of Chinese RhFe thermometer are similar to those of Tinsley 5187U thermometer from 1.5 K to 27 K. The resistance changes of most thermometers are less than that of equivalent to 0.2 mK at 4.5 K after they are exposed to fifty thermal cycles from room temperature to liquid helium temperature. This standard type of rhodium-iron resistance thermometer is now commercially available. Instead of the regular annealing temperature, which is 750°C, two batches of RhFe thermometers are made with the annealing temperature of 850°C and 950°C. The interpolating characteristics of RhFe thermometers will be studied to find new calibration method.

  19. Mechanisms of catalytic dehydrogenation of alkanes by rhodium clusters Rhn+ probed by isotope labelling

    NASA Astrophysics Data System (ADS)

    Adlhart, Christian; Uggerud, Einar

    2006-03-01

    The regioselectivity for the dehydrogenation of alkanes by rhodium clusters was investigated by reacting Rhn+, n = 1-20, with the isotopically labelled alkanes ethane-1,1,1-d3 and propane-1,1,1,3,3,3-d6. For Rh+ reacting with propane a clear preference for a 1,2- over a 1,1- and 1,3-mechanism was observed. For larger clusters, hydrogen scrambling is faster than hydrogen elimination, which essentially leads to statistical formation of the neutrals H2, HD, and D2. Isotope scrambling with D2 was also used as a structural probe for the reaction products of rhodium clusters with ethane. The intactness of the CH bonds was demonstrated for (n > 6). The studies are completed with a detailed kinetic analysis for the reaction of Rh7+ with ethane and ethane/hydrogen and ethane/helium mixtures. An over-all picture with efficient CH bond activation and fast and reversible hydrogen rearrangements emerges on the basis of these experiments. Some of the dehydrogenation reactions appear to be reversible.

  20. Rhodium-catalyzed formation of stereocontrolled trisubstituted alkenes from Baylis-Hillman adducts.

    PubMed

    Gendrineau, Thomas; Demoulin, Nicolas; Navarre, Laure; Genet, Jean-Pierre; Darses, Sylvain

    2009-01-01

    Efficient and general conditions for the formation of stereodefined trisubstituted alkenes by using the rhodium-catalyzed reaction of unactivated Baylis-Hillman adducts with either organoboronic acids or potassium trifluoro(organo)borates are reported (see scheme).We report here efficient and general conditions for the formation of stereodefined trisubstituted alkenes using the rhodium-catalyzed reaction of unactivated Baylis-Hillman adducts with either organoboronic acids and potassium trifluoro(organo)borates. The use of the [{Rh(cod)OH}(2)] precursor gave very fast coupling reactions under low catalyst loading, very mild reaction conditions (from room temperature up to 50 degrees C) and without the need of additional phosphane ligands. Based on the new reaction conditions, the reaction, originally limited to Baylis-Hillman adducts derived from esters, could be extended to a large variety of Baylis-Hillman adducts, bearing either keto, cyano or amido functionalities. Moreover, the reaction of Baylis-Hillman adducts bearing esters functionality was improved and could be conducted at lower temperature using lower catalyst loading.

  1. The synthesis of rhodium/carbon dots nanoparticles and its hydrogenation application

    NASA Astrophysics Data System (ADS)

    Zhang, Jie; Chen, Yao; Tan, Jing; Sang, Haitao; Zhang, Liqun; Yue, Dongmei

    2017-02-01

    Rhodium (Rh) nanoparticles have been widely used as potent hydrogenation catalysts. Herein, a new convenient method has been developed to synthesize rhodium nanoparticles, in which carbon dots (CDs) were used both as stabilizing and reducing agents. The fluorescent CDs were prepared by microwave-assisted heating method using chitosan as raw material and the presences of hydroxyl and carbonyl on the surface of CDs were supported by FTIR spectra. Subsequently, CDs could directly reduce Rh3+ to Rh0 without additional reducing and stabilizing agents by heating Rh3+ with CDs for 1 h at 120 °C. The resulting Rh nanoparticles have an average size of about 2.8 nm and the Rh/CDs nanoparticles also retain the fluorescent property of CDs. The hydrogenation activities of Rh/CDs nanoparticles were investigated. The results demonstrated that the nanoparticles had highly catalytic activity in the hydrogenation reaction of hydroxyl-terminated polybutadiene (HTPB) and hydroxy-terminated butadiene-acrylonitrile (HTBN). Also, the presence of CDs could improve the fluorescent properties of rubbers after hydrogenation.

  2. Rhodium-catalysed syn-carboamination of alkenes via a transient directing group.

    PubMed

    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.

  3. Tracking the shape-dependent sintering of platinum-rhodium model catalysts under operando conditions

    NASA Astrophysics Data System (ADS)

    Hejral, Uta; Müller, Patrick; Balmes, Olivier; Pontoni, Diego; Stierle, Andreas

    2016-03-01

    Nanoparticle sintering during catalytic reactions is a major cause for catalyst deactivation. Understanding its atomic-scale processes and finding strategies to reduce it is of paramount scientific and economic interest. Here, we report on the composition-dependent three-dimensional restructuring of epitaxial platinum-rhodium alloy nanoparticles on alumina during carbon monoxide oxidation at 550 K and near-atmospheric pressures employing in situ high-energy grazing incidence x-ray diffraction, online mass spectrometry and a combinatorial sample design. For platinum-rich particles our results disclose a dramatic reaction-induced height increase, accompanied by a corresponding reduction of the total particle surface coverage. We find this restructuring to be progressively reduced for particles with increasing rhodium composition. We explain our observations by a carbon monoxide oxidation promoted non-classical Ostwald ripening process during which smaller particles are destabilized by the heat of reaction. Its driving force lies in the initial particle shape which features for platinum-rich particles a kinetically stabilized, low aspect ratio.

  4. Correlation between the Stereochemistry and Bioactivity in Octahedral Rhodium Prolinato Complexes.

    PubMed

    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.

  5. Immobilization of rhodium complexes in chiral organic-inorganic hybrid materials.

    PubMed

    Adima, A; Moreau, J J; Wong Chi Man, M

    2000-06-01

    Two new alkoxysilylated derivatives of (-)-(1R,2R)-1, 2-diaminocyclohexane: M = N-[(triethoxysilyl)propyl]-(-)-(1R,2R)-1, 2-diaminocyclohexane and B = N, N'-bis[(triethoxysilyl)propyl]-(-)-(1R,2R)-1,2-diaminocyclohexane have been synthesized. Their complexation with [Rh(cod)Cl]2 in the presence of TEOS = Si(OEt)4, followed by sol-gel hydrolysis-condensation, afforded new catalytic chiral hybrid materials. Evidence for the presence of the organic moieties complexed by rhodium in these solids was obtained by UV-visible spectroscopy, FT-IR studies, solid state 13C and 29Si CP-MAS NMR analysis, energy-dispersive X-ray (EDX) techniques, and elemental analysis. The nitrogen sorption studies and BET analyses ranged these solid gels from nonporous to highly porous materials. The catalytic activities and selectivities of the solid materials have been studied in the asymmetric hydrogen-transfer reduction of prochiral ketones and compared to that of the homogeneous rhodium complexes of the ligands M and B. The hybrid materials appeared interesting supports for enantioselective heterogeneous catalysis leading to chiral alcohols with ee up to 58% in the reduction of acetophenone and up to 98% in the case of the more hindered related ketones. The catalytic properties as a function of the nature of chiral hybrid solid are discussed.

  6. The Role of the Element Rhodium in the hyperbolic law of the Periodic Table of Elements

    NASA Astrophysics Data System (ADS)

    Khazan, Albert

    2009-03-01

    The method of equilateral hyperboles assumes that their tops should be certain with high accuracy by means of Lagrange's theorem. On this basis the scaling factor for transition from the coordinate system usual to mathematicians to that which is to be used in chemistry is calculated. Such an approach has allowed calculating parameters of the last element. The calculation can be checked by means of the first sequel from the hyperbolic law, proceeding only from the atomic mass of the element Rhodium. As it has appeared, the direct and adjacent hyperboles are crossed in a point with the coordinates 205.811; 0.5, which abscissa makes a half of the last element's atomic mass (the deviation is about 0.01%). The real axes of the hyperboles coincide with the tangents and normals, and the scaling factor differs from the first calculation as 0.001%. However these insignificant divergences are so small to the most important conclusion that the validity of the Hyperbolic Law, as calculation on Rhodium our data consists of (Progr. Physics, 2007, v.1, 38; v.2, 83; v.2, 104; 2008, v.3, 56).

  7. Tracking the shape-dependent sintering of platinum–rhodium model catalysts under operando conditions

    PubMed Central

    Hejral, Uta; Müller, Patrick; Balmes, Olivier; Pontoni, Diego; Stierle, Andreas

    2016-01-01

    Nanoparticle sintering during catalytic reactions is a major cause for catalyst deactivation. Understanding its atomic-scale processes and finding strategies to reduce it is of paramount scientific and economic interest. Here, we report on the composition-dependent three-dimensional restructuring of epitaxial platinum–rhodium alloy nanoparticles on alumina during carbon monoxide oxidation at 550 K and near-atmospheric pressures employing in situ high-energy grazing incidence x-ray diffraction, online mass spectrometry and a combinatorial sample design. For platinum-rich particles our results disclose a dramatic reaction-induced height increase, accompanied by a corresponding reduction of the total particle surface coverage. We find this restructuring to be progressively reduced for particles with increasing rhodium composition. We explain our observations by a carbon monoxide oxidation promoted non-classical Ostwald ripening process during which smaller particles are destabilized by the heat of reaction. Its driving force lies in the initial particle shape which features for platinum-rich particles a kinetically stabilized, low aspect ratio. PMID:26957204

  8. Tracking the shape-dependent sintering of platinum-rhodium model catalysts under operando conditions.

    PubMed

    Hejral, Uta; Müller, Patrick; Balmes, Olivier; Pontoni, Diego; Stierle, Andreas

    2016-03-09

    Nanoparticle sintering during catalytic reactions is a major cause for catalyst deactivation. Understanding its atomic-scale processes and finding strategies to reduce it is of paramount scientific and economic interest. Here, we report on the composition-dependent three-dimensional restructuring of epitaxial platinum-rhodium alloy nanoparticles on alumina during carbon monoxide oxidation at 550 K and near-atmospheric pressures employing in situ high-energy grazing incidence x-ray diffraction, online mass spectrometry and a combinatorial sample design. For platinum-rich particles our results disclose a dramatic reaction-induced height increase, accompanied by a corresponding reduction of the total particle surface coverage. We find this restructuring to be progressively reduced for particles with increasing rhodium composition. We explain our observations by a carbon monoxide oxidation promoted non-classical Ostwald ripening process during which smaller particles are destabilized by the heat of reaction. Its driving force lies in the initial particle shape which features for platinum-rich particles a kinetically stabilized, low aspect ratio.

  9. Bimetallic poly- and oligo-nuclear complexes based on a rhodium(III) metalloligand

    NASA Astrophysics Data System (ADS)

    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.

  10. 7 CFR 983.89 - Termination.

    Code of Federal Regulations, 2010 CFR

    2010-01-01

    ..., ARIZONA, AND NEW MEXICO Miscellaneous Provisions § 983.89 Termination. (a) The Secretary may at any time... producers who, during a representative period, have been engaged in the production of pistachios: Provided... representative period determined by the Secretary, have been engaged in the production for market of pistachios...

  11. City FLEX 89: Meeting the Challenge.

    ERIC Educational Resources Information Center

    Alfano, Kathy

    Information is provided on San Diego City College's Flex 89 Program, a 3-day staff development effort offered for the college's administrators, full-time and adjunct faculty, and classified staff. The packet includes the flyer sent to all participants, the Flex Catalog and registration form, an example of an enrollment confirmation, the program…

  12. 40 CFR 141.89 - Analytical methods.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ...) NATIONAL PRIMARY DRINKING WATER REGULATIONS Control of Lead and Copper § 141.89 Analytical methods. (a) Analyses for lead, copper, pH, conductivity, calcium, alkalinity, orthophosphate, silica, and temperature... State. Analyses under this section for lead and copper shall only be conducted by laboratories that...

  13. 40 CFR 89.301 - Scope; applicability.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ...) CONTROL OF EMISSIONS FROM NEW AND IN-USE NONROAD COMPRESSION-IGNITION ENGINES Emission Test Equipment... perform exhaust emission tests on new nonroad compression-ignition engines subject to the provisions of subpart B of part 89. (b) Exhaust gases, either raw or dilute, are sampled while the test engine is...

  14. 40 CFR 89.301 - Scope; applicability.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ...) CONTROL OF EMISSIONS FROM NEW AND IN-USE NONROAD COMPRESSION-IGNITION ENGINES Emission Test Equipment... perform exhaust emission tests on new nonroad compression-ignition engines subject to the provisions of subpart B of part 89. (b) Exhaust gases, either raw or dilute, are sampled while the test engine is...

  15. 40 CFR 89.307 - Dynamometer calibration.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... (CONTINUED) CONTROL OF EMISSIONS FROM NEW AND IN-USE NONROAD COMPRESSION-IGNITION ENGINES Emission Test... out system must be calibrated with weights at each test weight specified in § 89.306. The calibration... master load-cell for each in-use range used. (5) The in-use torque measurement must be within 2 percent...

  16. 47 CFR 101.89 - Negotiations.

    Code of Federal Regulations, 2010 CFR

    2010-10-01

    ... Band § 101.89 Negotiations. (a) The negotiation is triggered by the fixed-satellite service (FSS... faith, the FCC will consider, inter alia, the following factors: (1) Whether the FSS licensee has made a... with providing that facility to the incumbent licensee. (d) Negotiations will commence when the FSS...

  17. 47 CFR 101.89 - Negotiations.

    Code of Federal Regulations, 2011 CFR

    2011-10-01

    ... Band § 101.89 Negotiations. (a) The negotiation is triggered by the fixed-satellite service (FSS... faith, the FCC will consider, inter alia, the following factors: (1) Whether the FSS licensee has made a... with providing that facility to the incumbent licensee. (d) Negotiations will commence when the FSS...

  18. 40 CFR 89.1006 - Penalties.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) AIR PROGRAMS (CONTINUED) CONTROL OF...) constitutes a separate offense with respect to each nonroad engine. (4) A violation with respect to § 89.1003(a)(3)(ii) constitutes a separate offense with respect to each part or component. Each day of a...

  19. 40 CFR 89.307 - Dynamometer calibration.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... transducer, any lever arm used to convert a weight or a force through a distance into a torque must be in a... dynamometer manufacturer's specifications. (2) Determine the dynamometer calibration moment arm (a distance... specified in § 89.306 to the moment arm at the calibration distance determined in paragraph (b)(2) of this...

  20. 40 CFR 89.602 - Definitions.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    .... Model year for imported engines. The manufacturer's annual production period (as determined by the Administrator) which includes January 1 of the calendar year; provided, that if the manufacturer has no annual... course of nonroad engine production and required to be reported under § 89.123. United States....

  1. 40 CFR 89.1003 - Prohibited acts.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... access to or copying of records or to fail to make reports or provide information required under § 89... sale, or introduce or deliver into commerce, a nonroad engine unless a label or tag is affixed to the... subject to any emission standards under this part, the replacement engine must have a permanent label with...

  2. 40 CFR 89.503 - Test orders.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... EMISSIONS FROM NEW AND IN-USE NONROAD COMPRESSION-IGNITION ENGINES Selective Enforcement Auditing § 89.503... following factors: (i) Production factor, determined by dividing the projected nonroad engine sales in the... rounding to the nearest whole number. If the projected sales are less than 8,000, this factor is one....

  3. 40 CFR 89.503 - Test orders.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... EMISSIONS FROM NEW AND IN-USE NONROAD COMPRESSION-IGNITION ENGINES Selective Enforcement Auditing § 89.503... following factors: (i) Production factor, determined by dividing the projected nonroad engine sales in the... rounding to the nearest whole number. If the projected sales are less than 8,000, this factor is one....

  4. 40 CFR 89.508 - Test procedures.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... EMISSIONS FROM NEW AND IN-USE NONROAD COMPRESSION-IGNITION ENGINES Selective Enforcement Auditing § 89.508... procedure as adopted in the California Regulations for New 1996 and Later Heavy-Duty Off-Road Diesel Cycle... information needed to establish an alternate minimum idle speed. The Administrator, in making or specifying...

  5. 42 CFR 32.89 - Discharge.

    Code of Federal Regulations, 2010 CFR

    2010-10-01

    ... HEALTH SERVICE, DEPARTMENT OF HEALTH AND HUMAN SERVICES MEDICAL CARE AND EXAMINATIONS MEDICAL CARE FOR PERSONS WITH HANSEN'S DISEASE AND OTHER PERSONS IN EMERGENCIES Persons with Hansen's Disease § 32.89 Discharge. Patients with Hansen's disease will be discharged when, in the opinion of the medical staff...

  6. 42 CFR 32.89 - Discharge.

    Code of Federal Regulations, 2011 CFR

    2011-10-01

    ... HEALTH SERVICE, DEPARTMENT OF HEALTH AND HUMAN SERVICES MEDICAL CARE AND EXAMINATIONS MEDICAL CARE FOR PERSONS WITH HANSEN'S DISEASE AND OTHER PERSONS IN EMERGENCIES Persons with Hansen's Disease § 32.89 Discharge. Patients with Hansen's disease will be discharged when, in the opinion of the medical staff...

  7. 42 CFR 32.89 - Discharge.

    Code of Federal Regulations, 2012 CFR

    2012-10-01

    ... HEALTH SERVICE, DEPARTMENT OF HEALTH AND HUMAN SERVICES MEDICAL CARE AND EXAMINATIONS MEDICAL CARE FOR PERSONS WITH HANSEN'S DISEASE AND OTHER PERSONS IN EMERGENCIES Persons with Hansen's Disease § 32.89 Discharge. Patients with Hansen's disease will be discharged when, in the opinion of the medical staff...

  8. City FLEX 89: Meeting the Challenge.

    ERIC Educational Resources Information Center

    Alfano, Kathy

    Information is provided on San Diego City College's Flex 89 Program, a 3-day staff development effort offered for the college's administrators, full-time and adjunct faculty, and classified staff. The packet includes the flyer sent to all participants, the Flex Catalog and registration form, an example of an enrollment confirmation, the program…

  9. Reactions of Highly Uniform Zeolite H-Supported Rhodium Complexes: Transient Characterization by Infrared and X-ray Absorption Spectroscopies

    SciTech Connect

    Ogino, I.; Gates, B

    2010-01-01

    A zeolite H-{beta}-supported mononuclear rhodium diethene complex (Rh(C{sub 2}H{sub 4}){sub 2}{l_brace}O{sub 2}Al{r_brace}, where the braces indicate a part of the zeolite) was formed by the reaction of Rh(acac)({eta}{sub 2}-C{sub 2}H{sub 4}){sub 2} (acac = acetylacetonate, C{sub 5}H{sub 7}O{sub 2}{sup -}) with the zeolite. Transient characterization of the sample by X-ray absorption near edge structure (XANES) and infrared (IR) spectroscopies (combined with mass spectrometry of the effluent gas) while the sample was in contact with flowing CO indicates a simple stoichiometric conversion of the supported metal complex into another species, identified by the spectra as the zeolite-supported rhodium gem-dicarbonyl (Rh(CO){sub 2}{l_brace}O{sub 2}Al{r_brace}). The sharpness of the v{sub CO} bands in the IR spectrum indicates a high degree of uniformity of the supported rhodium gem-dicarbonyl, and isosbestic points in the XANES spectra as the transformation was occurring imply that the rhodium diethene complex was also highly uniform. Spectra similarly show that treatment of the supported rhodium gem-dicarbonyl with flowing C{sub 2}H{sub 4} resulted in another stoichiometrically simple transformation, giving a species suggested to be Rh(C{sub 2}H{sub 4})(CO){sub 2}{l_brace}O{sub 2}Al{r_brace}. The intermediate was ultimately transformed when the sample was purged with helium into another highly uniform supported species, inferred on the basis of IR spectra to be Rh(C{sub 2}H{sub 4})(CO){l_brace}O{sub 2}Al{r_brace}. Extended X-ray absorption fine structure spectra characterizing the supported rhodium diethene complex and the species formed from it show how the Rh-O bond distance at the Rh-support interface varied in response to the changes in the ligands bonded to the rhodium.

  10. Adsorptive separation of rhodium(III) using Fe(III)-templated oxine type of chemically modified chitosan

    SciTech Connect

    Alam, M.S.; Inoue, Katsutoshi; Yoshizuka, Kazuharu; Ishibashi, Hideaki

    1998-03-01

    The oxine type of chemically modified chitosan was prepared by the template crosslinking method using Fe(III) as a template ion. Batchwise adsorption of rhodium(III) on this chemically modified chitosan was examined from chloride media in the absence and presence of a large amount of tin(II). It was observed that the Fe(III)-templated oxine type of chemically modified chitosan shows better performance for rhodium adsorption than that of the original chitosan. When Sn(II) is absent from the solution, Rh(III) is hardly adsorbed on the modified chitosan and the order of selectivity of the adsorption of Rh(III), Pt(IV), and Cu(II) was found to be Pt(IV) > Cu(II) {approx} Rh(III). On the other hand, adsorption of rhodium is significantly increased in the presence of Sn(II) and the selectivity order of the adsorption was drastically changed to Rh(III) > Pt(IV) {much_gt} Cu(II), which ensures selective separation of Rh(III) from their mixture. Adsorption of Rh(III) increases with an increase in the concentration of Sn(II) in the aqueous solution, and maximum adsorption is achieved at a molar ratio, [Sn]/[Rh], of >6. The adsorption of Rh(III) decreases at a high concentration of hydrochloric acid. The maximum adsorption capacity was evaluated to be 0.92 mol/kg-dry adsorbent. Stripping tests of rhodium from the loaded chemically modified chitosan were carried out using different kinds of stripping agents containing some oxidizing agent. The maximum stripping of rhodium under these experimental conditions was found to be 72.5% by a single contact with 0.5 M HCl + 8 M HNO{sub 3}.

  11. MERCURY-NITRITE-RHODIUM-RUTHENIUM INTERACTIONS IN NOBLE METAL CATALYZED HYDROGEN GENERATION FROM FORMIC ACID DURING NUCLEAR WASTE PROCESSING AT THE SAVANNAH RIVER SITE - 136C

    SciTech Connect

    Koopman, D.; Pickenheim, B.; Lambert, D.; Newell, J; Stone, M.

    2009-09-02

    Chemical pre-treatment of radioactive waste at the Savannah River Site is performed to prepare the waste for vitrification into a stable waste glass form. During pre-treatment, compounds in the waste become catalytically active. Mercury, rhodium, and palladium become active for nitrite destruction by formic acid, while rhodium and ruthenium become active for catalytic conversion of formic acid into hydrogen and carbon dioxide. Nitrite ion is present during the maximum activity of rhodium, but is consumed prior to the activation of ruthenium. Catalytic hydrogen generation during pre-treatment can exceed radiolytic hydrogen generation by several orders of magnitude. Palladium and mercury impact the maximum catalytic hydrogen generation rates of rhodium and ruthenium by altering the kinetics of nitrite ion decomposition. New data are presented that illustrate the interactions of these various species.

  12. ORNL (Oak Ridge National Laboratory) 89

    SciTech Connect

    Anderson, T.D.; Appleton, B.R.; Jefferson, J.W.; Merriman, J.R.; Mynatt, F.R.; Richmond, C.R.; Rosenthal, M.W.

    1989-01-01

    This is the inaugural issues of an annual publication about the Oak Ridge National Laboratory. Here you will find a brief overview of ORNL, a sampling of our recent research achievements, and a glimpse of the directions we want to take over the next 15 years. A major purpose of ornl 89 is to provide the staff with a sketch of the character and dynamics of the Laboratory.

  13. 89 Herculis and HD 161796 in 1988

    SciTech Connect

    Fernie, J.D. )

    1990-04-01

    New UBV photometry of V441 Herculis (89 Herculis) and 814 Herculis (HD 161796) obtained with the automatic photoelectric telescope service is presented. These two stars are members of a class of variable known as UU Herculis stars, high-latitude F supergiants that have curious properties. The intention behind the ongoing photometry is to obtain sufficient data with which to study the systematics of the variability of the stars.

  14. Synergistic rhodium(II) carboxylate and brønsted acid catalyzed multicomponent reactions of enalcarbenoids: direct synthesis of α-pyrrolylbenzylamines.

    PubMed

    Dawande, Sudam Ganpat; Kanchupalli, Vinaykumar; Lad, Bapurao Sudam; Rai, Jyoti; Katukojvala, Sreenivas

    2014-07-18

    The design of a synergistic rhodium(II) carboxylate and BINOL phosphoric acid catalyzed efficient multicomponent reaction of enaldiazo compounds, arylamines, and aryl aldehydes leading to the first transition-metal-catalyzed direct synthesis of valuable α-pyrrolylbenzylamines is disclosed. The reaction is proposed to involve a transient ammonium ylide of a new class of electrophilic rhodium enalcarbenoid, its regioselective Mannich reaction, and a cyclocondensation cascade. The methodology was used in a highly diastereoselective synthesis of a binaphthyl based chiral pyrrole.

  15. 16 CFR 23.7 - Misuse of the words “platinum,” “iridium,” “palladium,” “ruthenium,” “rhodium,” and “osmium.”

    Code of Federal Regulations, 2013 CFR

    2013-01-01

    ... § 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... Platinum, Iridium, Palladium, Ruthenium, Rhodium, and Osmium. (b) The following are examples of markings or...

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

    Code of Federal Regulations, 2012 CFR

    2012-01-01

    ... § 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... Platinum, Iridium, Palladium, Ruthenium, Rhodium, and Osmium. (b) The following are examples of markings or...

  17. 16 CFR 23.7 - Misuse of the words “platinum,” “iridium,” “palladium,” “ruthenium,” “rhodium,” and “osmium.”

    Code of Federal Regulations, 2010 CFR

    2010-01-01

    ... § 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... Platinum, Iridium, Palladium, Ruthenium, Rhodium, and Osmium. (b) The following are examples of markings or...

  18. 16 CFR 23.7 - Misuse of the words “platinum,” “iridium,” “palladium,” “ruthenium,” “rhodium,” and “osmium.”

    Code of Federal Regulations, 2011 CFR

    2011-01-01

    ... § 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... Platinum, Iridium, Palladium, Ruthenium, Rhodium, and Osmium. (b) The following are examples of markings...

  19. 16 CFR 23.7 - Misuse of the words “platinum,” “iridium,” “palladium,” “ruthenium,” “rhodium,” and “osmium.”

    Code of Federal Regulations, 2014 CFR

    2014-01-01

    ... § 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... Platinum, Iridium, Palladium, Ruthenium, Rhodium, and Osmium. (b) The following are examples of markings...

  20. Heck-type coupling vs. conjugate addition in phosphine-rhodium catalyzed reactions of aryl boronic acids with alpha,beta-unsaturated carbonyl compounds: a systematic investigation.

    PubMed

    Zou, Gang; Guo, Jianping; Wang, Zhiyong; Huang, Wen; Tang, Jie

    2007-07-28

    The competition between Heck-type coupling and conjugate addition in phosphine-rhodium catalyzed reactions of aryl boronic acids with alpha,beta-unsaturated carbonyls has been systematically investigated in a toluene-H(2)O biphasic system. Aside from the intrinsic nature of rhodium and the enolization of carbonyls, the phosphine supporting ligand on rhodium, the ratio of aryl boronic acid to alpha,beta-unsaturated carbonyl and the pH value of the aqueous phase were found to affect the competition significantly. Highly selective rhodium-based catalyst systems have therefore been developed for both Heck-type coupling and conjugate addition by synergistically tuning the supporting ligand, the boronic acid to olefin ratio and other reaction conditions. Conjugate addition with selectivity >99% and Heck-type coupling with selectivity of up to 100%, 98% and 84% for acrylates, acrylamides and methyl vinyl ketone, respectively, could be achieved in the rhodium-catalyzed reactions of aryl boronic acids with alpha,beta-unsaturated carbonyls using the corresponding optimized rhodium-based catalyst systems.

  1. Catalytic partial oxidation of iso-octane over rhodium catalysts: An experimental, modeling, and simulation study

    SciTech Connect

    Hartmann, M.; Minh, H.D.; Maier, L.; Deutschmann, O.

    2010-09-15

    Catalytic partial oxidation of iso-octane over a rhodium/alumina coated honeycomb monolith is experimentally and numerically studied at short-contact times for varying fuel-to-oxygen ratios. A new experimental set-up with well-defined inlet and boundary conditions is presented. The conversion on the catalyst and in the gas-phase is modeled by detailed reaction mechanisms including 857 gas-phase and 17 adsorbed species. Elementary-step based heterogeneous and homogeneous reaction mechanisms are implemented into two-dimensional flow field description of a single monolith channel. Experiment and simulation provide new insights into the complex reaction network leading to varying product distribution as function of fuel-to-oxygen ratio. At fuel rich conditions, the formation of by-products that can serve as coke precursors is observed and interpreted. (author)

  2. Synthesis of Carbazoles and Carbazole-Containing Heterocycles via Rhodium-Catalyzed Tandem Carbonylative Benzannulations.

    PubMed

    Song, Wangze; Li, Xiaoxun; Yang, Ka; Zhao, Xian-liang; Glazier, Daniel A; Xi, Bao-min; Tang, Weiping

    2016-04-01

    Polycyclic aromatic compounds are important constituents of pharmaceuticals and other materials. We have developed a series of Rh-catalyzed tandem carbonylative benzannulations for the synthesis of tri-, tetra-, and pentacyclic heterocycles from different types of aryl propargylic alcohols. These tandem reactions provide efficient access to highly substituted carbazoles, furocarbazoles, pyrrolocarbazoles, thiophenocarbazoles, and indolocarbazoles. While tricyclic heterocycles could be derived from vinyl aryl propargylic alcohols, tetra- and pentacyclic heterocycles were synthesized from diaryl propargylic alcohols. The tandem carbonylative benzannulation is initiated by a π-acidic rhodium(I) catalyst-mediated nucleophilic addition to alkyne to generate a key metal-carbene intermediate, which is then trapped by carbon monoxide to form a ketene species for 6π electrocyclization. Overall, three bonds and two rings are formed in all of these tandem carbonylative benzannulation reactions.

  3. Synthesis, characterization and antibacterial study of cyclometalated rhodium(III) complex containing dithiocarbamate

    NASA Astrophysics Data System (ADS)

    Mansouri, Ghobad; Heidarizadi, Fateme; Naghipour, Ali; Notash, Behrouz

    2016-10-01

    The novel cyclometalated Rh(III) complex, [Rh(phpy)2(SˆS)], Where phpy is 2-phenylpyridine and (SˆS) is diethyldithiocarbamate, has been prepared and characterized by elemental analysis, IR, 13C and 1H NMR, electronic absorption and Fluorescence spectroscopies, cyclic voltammetry, and X-ray crystallography. The crystal structure of [Rh(phpy)2(SˆS)] shows that the coordination geometry around the Rh(III) is a distorted octahedron, with bite angles of 71.19-81.04° for all three bidentate ligands. Electrochemical analysis by cyclic voltammetry reveals irreversible redox behavior of the rhodium centre. Antibacterial activity of the complex has also been studied by agar disc diffusion method against three Gram-negative bacteria (Pseudomonas aeroginosa, Salmonella typhi and Escherichia coli) and two Gram-positive bacteria (Staphylococcus aureus and Corynebacterium renale).

  4. Determination of palladium, platinum and rhodium in geologic materials by fire assay and emission spectrography

    USGS Publications Warehouse

    Hapfty, J.; Riley, L.B.

    1968-01-01

    A method is described for the determination of palladium down to 4ppb (parts per billion, 109), platinum down to 10 ppb and rhodium down to 5 ppb in 15 g of sample. Fire-assay techniques are used to preconcentrate the platinum metals into a gold bead, then the bead is dissolved in aqua regia and diluted to volume with 1M hydrochloric acid. The solution is analysed by optical emission spectrography of the residue from 200 ??l of it evaporated on a pair of flat-top graphite electrodes. This method requires much less sample handling than most published methods for these elements. Data are presented for G-1, W-1, and six new standard rocks of the U.S. Geological Survey. The values for palladium in W-1 are in reasonable agreement with previously published data. ?? 1968.

  5. Optimization of Rhodium-Based Catalysts for Mixed Alcohol Synthesis – 2012 Progress Report

    SciTech Connect

    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.

  6. Optimization of Rhodium-Based Catalysts for Mixed Alcohol Synthesis -- 2011 Progress Report

    SciTech Connect

    Gerber, Mark A.; Gray, Michel J.; Albrecht, Karl O.; Rummel, Becky L.

    2011-10-01

    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. Research during FY 2011 continued to examine the performance of RhMn catalysts on alternative supports including selected zeolite, silica, and carbon supports. Catalyst optimization continued using both the Davisil 645 and Merck Grade 7734 silica supports. Research also was initiated in FY 2011, using the both Davisil 645 silica and Hyperion CS-02C-063 carbon supports, to evaluate the potential for further improving catalyst performance, through the addition of one or two additional metals as promoters to the catalysts containing Rh, Mn, and Ir.

  7. Optimization of Rhodium-Based Catalysts for Mixed Alcohol Synthesis -- 2009 Progress Report

    SciTech Connect

    Gerber, Mark A.; Gray, Michel J.; Stevens, Don J.; White, J. F.; Rummel, Becky L.

    2010-12-21

    Pacific Northwest National Laboratory (PNNL) has been conducting research for the United States Department of Energy, Energy Efficiency Renewable Energy, Biomass Program to investigate the feasibility of producing mixed alcohols from biomass-derived synthesis gas (syngas). This research has involved the screening of potential catalysts, and optimization of the more promising ones, using laboratory scale reactors. During 2009, the main goal of the testing program focused on optimizing selected supported catalysts containing rhodium (Rh) and manganese (Mn). Optimization involved examining different total concentrations and atomic ratios of Rh and Mn as well as that of the more promising promoters (Ir and Li) identified in the earlier screening studies. Evaluation of catalyst performance focused on attaining improvements with respect to the space-time-yield and converted carbon selectivity to C2+ oxygenates, with additional consideration given to the fraction of the oxygenates that were C2+ alcohols.

  8. Scanning tunneling microscopy studies of organic monolayers adsorbed on the rhodium(111) crystal surface

    SciTech Connect

    Cernota, Paul Davis

    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.

  9. Bifunctional rhodium intercalator conjugates as mismatch-directing DNA alkylating agents.

    PubMed

    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.

  10. Hydrogenation of aniline on a low-percentage, supported rhodium catalyst

    SciTech Connect

    Ualikhanova, A.; Temirbulatova, A.E.

    1992-01-10

    The products of hydrogenation of aniline and their derivatives exhibit biological activity and are used in the pharmaceutical industry for preparation of analgesic, antipyretic, and sulfanilamide drugs. Up to 30% of the total consumption of aniline is for synthesis of drugs. Hydrogenation of aniline on platinum metals supported on carbon was studied by Rylander et al. The authors investigated the catalytic properties of rhodium supported on oxides in saturation of aniline with hydrogen in water. In most cases, the amount of noble metal in the supported catalyst was 5%. Decreasing the concentration of active phase in the catalyst is economically advantageous. The features of hydrogenation of aniline in the presence of 1% Rh/MgO in solutions with wide variation of the technological parameters of the process were investigated in the present study. 19 refs., 3 figs., 2 tabs.

  11. Production of Palladium-103 ( 103Pd) from a thin rhodium foil target - Improved cooling concept

    NASA Astrophysics Data System (ADS)

    Silverman, I.; Lavie, E.; Arenshtam, A.; Kijel, D.; Vaknin, D.; Veinguer, M.; Nagler, A.

    2007-08-01

    Palladium-103 (103Pd) is one of the commonly used radioisotopes for prostate cancer treatment. The current irradiation technique used to produce this radioisotope suffers from several serious inherent drawbacks, of which one is the low beam current due to cooling limitation and the other is the electroplating process used to prepare the target. A liquid-metal jet impingement target cooling system developed at Soreq NRC demonstrated recently a cooling capacity of 8.4 kW/cm2 while the pressure of the cooling liquid on the target back was less than 1 bar. The latter value implies that the target can be made very thin and that the copper back-plate might be removed. Hence, we propose a new target design based on the use of a thin rhodium foil directly cooled by a liquid-metal such as gallium.

  12. Screen-Printed Carbon Electrodes Modified by Rhodium Dioxide and Glucose Dehydrogenase

    PubMed Central

    Polan, Vojtěch; Soukup, Jan; Vytřas, Karel

    2010-01-01

    The described glucose biosensor is based on a screen-printed carbon electrode (SPCE) modified by rhodium dioxide, which functions as a mediator. The electrode is further modified by the enzyme glucose dehydrogenase, which is immobilized on the electrode's surface through electropolymerization with m-phenylenediamine. The enzyme biosensor was optimized and tested in model glucose samples. The biosensor showed a linear range of 500–5000 mg L−1 of glucose with a detection limit of 210 mg L−1 (established as 3σ) and response time of 39 s. When compared with similar glucose biosensors based on glucose oxidase, the main advantage is that neither ascorbic and uric acids nor paracetamol interfere measurements with this biosensor at selected potentials. PMID:21528113

  13. Rhodium-catalyzed acyloxy migration of propargylic esters in cycloadditions, inspiration from the recent "gold rush".

    PubMed

    Shu, Xing-Zhong; Shu, Dongxu; Schienebeck, Casi M; Tang, Weiping

    2012-12-07

    Transition metal-catalyzed acyloxy migration of propargylic esters offers versatile entries to allene and vinyl carbene intermediates for various fascinating subsequent transformations. Most π-acidic metals (e.g. gold and platinum) are capable of facilitating these acyloxy migration events. However, very few of these processes involve redox chemistry, which are well-known for most other transition metals such as rhodium. The coupling of acyloxy migration of propargylic esters with oxidative addition, migratory insertion, and reductive elimination may lead to ample new opportunities for the design of new reactions. This tutorial review summarizes recent developments in Rh-catalyzed 1,3- and 1,2-acyloxy migration of propargylic esters in a number of cycloaddition reactions. Related Au- and Pt-catalyzed cycloadditions involving acyloxy migration are also discussed.

  14. Dimerisation, rhodium complex formation and rearrangements of N-heterocyclic carbenes of indazoles

    PubMed Central

    Guan, Zong; Namyslo, Jan C; Drafz, Martin H H; Nieger, Martin

    2014-01-01

    Summary 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. PMID:24778738

  15. Iminophosphanes: Synthesis, Rhodium Complexes, and Ruthenium(II)-Catalyzed Hydration of Nitriles

    PubMed Central

    2017-01-01

    Highly stable iminophosphanes, obtained from alkylating nitriles and reaction of the resulting nitrilium ions with secondary phosphanes, were explored as tunable P-monodentate and 1,3-P,N bidentate ligands in rhodium complexes. X-ray crystal structures are reported for both κ1 and κ2 complexes with the counterion in one of them being an unusual anionic coordination polymer of silver triflate. The iminophosphane-based ruthenium(II)-catalyzed hydration of benzonitrile in 1,2-dimethoxyethane (180 °C, 3 h) and water (100 °C, 24 h) and under solvent free conditions (180 °C, 3 h) results in all cases in the selective formation of benzamide with yields of up to 96%, thereby outperforming by far the reactions in which the common 2-pyridyldiphenylphosphane is used as the 1,3-P,N ligand. PMID:28316361

  16. Optimization of Rhodium-Based Catalysts for Mixed Alcohol Synthesis -- 2010 Progress Report

    SciTech Connect

    Gerber, Mark A.; Gray, Michel J.; Albrecht, Karl O.; White, J. F.; Rummel, Becky L.; Stevens, Don J.

    2010-10-01

    Pacific Northwest National Laboratory has been conducting research for the U.S. Department of Energy, Energy Efficiency Renewable Energy, Biomass Program to investigate the feasibility of producing mixed alcohols from biomass-derived synthesis gas. In recent years this research has primarily involved the further development of a silica-supported catalyst containing rhodium and manganese that was selected from earlier catalyst screening tests. A major effort during 2010 was to examine alternative catalyst supports to determine whether other supports, besides the Davisil 645 silica, would improve performance. Optimization of the Davisil 645 silica-supported catalyst also was continued with respect to candidate promoters iridium, platinum, and gallium, and examination of selected catalyst preparation and activation alternatives for the baseline RhMn/SiO2 catalyst.

  17. Gravimetric preparation and characterization of primary reference solutions of molybdenum and rhodium.

    PubMed

    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) < 0.05 %. To achieve this, a microwave-assisted digestion procedure for Rh and a hotplate digestion procedure for Mo were developed along with highly accurate and precise inductively coupled plasma optical emission spectrometry (ICP OES) and multicollector inductively coupled plasma mass spectrometry (MC-ICP-MS) methods required to assist with the preparation and as dissemination tools.

  18. Role of Ligand Protonation in Dihydrogen Evolution from a Pentamethylcyclopentadienyl Rhodium Catalyst.

    PubMed

    Johnson, Samantha I; Gray, Harry B; Blakemore, James D; Goddard, William A

    2017-09-01

    Recent work has shown that Cp*Rh(bpy) [Cp* = pentamethylcyclopentadienyl, bpy = 2,2'- bipyridine] undergoes endo protonation at the [Cp*] ligand in the presence of weak acid (Et3NH(+); pKa = 18.8 in MeCN). Upon exposure to stronger acid (e.g., DMFH(+); pKa = 6.1), hydrogen is evolved with unity yield. Here, we study the mechanisms by which this catalyst evolves dihydrogen using density functional theory (M06) with polarizable continuum solvation. The calculations show that the complex can be protonated by weak acid first at the metal center with a barrier of 3.2 kcal/mol; this proton then migrates to the ring to form the detected intermediate, a rhodium(I) compound bearing endo η(4)-Cp*H. Stronger acid is required to evolve hydrogen, which calculations show happens via a concerted mechanism. The acid approaches and protonates the metal, while the second proton simultaneously migrates from the ring with a barrier of ∼12 kcal/mol. Under strongly acidic conditions, we find that hydrogen evolution can proceed through a traditional metal-hydride species; protonation of the initial hydride to form an H-H bond occurs before migration of the hydride (in the form of a proton) to the [Cp*] ring (i.e., H-H bond formation is faster than hydride-proton tautomerization). This work demonstrates the role of acid strength in accessing different mechanisms of hydrogen evolution. Calculations also predict that modification of the bpy ligand by a variety of functional groups does not affect the preference for [Cp*] protonation, although the driving force for protonation changes. However, we predict that exchange of bpy for a bidentate phosphine ligand will stabilize a rhodium(III) hydride, reversing the preference for bound [Cp*H] found in all computed bpy derivatives and offering an appealing alternative ligand platform for future experimental and computational mechanistic studies of H2 evolution.

  19. 40 CFR 89.416 - Raw exhaust gas flow.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 20 2014-07-01 2013-07-01 true Raw exhaust gas flow. 89.416 Section 89... Procedures § 89.416 Raw exhaust gas flow. The exhaust gas flow shall be determined by one of the methods... procedure has been incorporated by reference. See § 89.6.) and calculation of the exhaust gas flow as...

  20. 49 CFR 89.7 - Exceptions to delegated authority.

    Code of Federal Regulations, 2010 CFR

    2010-10-01

    ... 49 Transportation 1 2010-10-01 2010-10-01 false Exceptions to delegated authority. 89.7 Section 89.7 Transportation Office of the Secretary of Transportation IMPLEMENTATION OF THE FEDERAL CLAIMS COLLECTION ACT General § 89.7 Exceptions to delegated authority. The authority delegated under § 89.5 does...

  1. Rhodium-catalyzed oxygenative [2 + 2] cycloaddition of terminal alkynes and imines for the synthesis of β-lactams.

    PubMed

    Kim, Insu; Roh, Sang Weon; Lee, Dong Gil; Lee, Chulbom

    2014-05-02

    A rhodium-catalyzed oxygenative [2 + 2] cycloaddition of terminal alkynes and imines has been developed, which gives β-lactams as products with high trans diastereoselectivity. In the presence of a Rh(I) catalyst and 4-picoline N-oxide, a terminal alkyne is converted to a rhodium ketene species via oxidation of a vinylidene complex and subsequently undergoes a [2 + 2] cycloaddition with an imine to give rise to the 2-azetidinone ring system. Mechanistic studies suggest that the reaction proceeds through a metalloketene rather than free ketene intermediate. The new method taking advantage of catalytic generation of a ketene species directly from a terminal alkyne provides a novel and efficient entry to the Staudinger synthesis of β-lactams under mild conditions.

  2. Dicarba-closo-dodecarborane-containing half-sandwich complexes of ruthenium, osmium, rhodium and iridium: biological relevance and synthetic strategies.

    PubMed

    Barry, Nicolas P E; Sadler, Peter J

    2012-04-21

    This review describes how the incorporation of dicarba-closo-dodecarboranes into half-sandwich complexes of ruthenium, osmium, rhodium and iridium might lead to the development of a new class of compounds with applications in medicine. Such a combination not only has unexplored potential in traditional areas such as Boron Neutron Capture Therapy agents, but also as pharmacophores for the targeting of biologically important proteins and the development of targeted drugs. The synthetic pathways used for the syntheses of dicarba-closo-dodecarboranes-containing half-sandwich complexes of ruthenium, osmium, rhodium and iridium are also reviewed. Complexes with a wide variety of geometries and characteristics can be prepared. Examples of addition reactions on the metal centre, B-H activation, transmetalation reactions and/or direct formation of metal-metal bonds are discussed (103 references).

  3. Photoinduced cleavage by a rhodium complex at G.U mismatches and exposed guanines in large and small RNAs.

    PubMed

    Chow, Christine S; Cunningham, Philip R; Lee, KangSeok; Meroueh, May; SantaLucia, John; Varma, Shikha

    2002-09-01

    Photoinduced cleavage reactions by the rhodium complex tris(4,7-diphenyl-1,10-phenanthroline)rhodium(III) [Rh(DIP)(3)(3+)] with three RNA hairpins, r(GGGGU UCGCUC CACCA) (16 nucleotide, tetraloop(Ala2)), r(GGGGCUAUAGCUCUAGCUC CACCA) (24 nucleotide, microhelix(Ala)), and r(GGCGGUUAGAUAUCGCC) (17 nucleotide, 790 loop), and full-length (1542 nucleotide) 16S rRNA from Escherichia coli were investigated. The cleavage reactions were monitored by gel electrophoresis and the sites of cleavage by Rh(DIP)(3)(3+) were determined by comparisons with chemical or enzymatic sequencing reactions. In general, RNA backbone scission by the metal complex was induced at G.U mismatches and at exposed G residues. The cleavage activity was observed on the three small RNA hairpins as well as on the isolated 1542-nucleotide ribosomal RNA.

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

    PubMed

    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.

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

    PubMed

    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.

  6. Rhodium-catalyzed [(3+2)+1] carbocyclization reactions of alkynylidenecyclopropanes with carbon monoxide: regiospecific construction of polysubstituted phenols.

    PubMed

    Evans, P Andrew; Burnie, Andrew J; Negru, Daniela E

    2014-09-05

    The development of the rhodium-catalyzed [(3+2)+1] carbocyclization reaction of alkynylidenecyclopropanes with carbon monoxide to construct polysubstituted phenols is described. This work offers a convenient method for the selective formation of tetra- and pentasubstituted phenols, which provide important intermediates for target directed synthesis. Finally, the ability to regiospecifically functionalize the phenols using conventional methods further illustrates the utility of this process.

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

    PubMed

    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.

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

    PubMed

    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.

  9. IN VIVO BIODISTRIBUTION AND ACCUMULATION OF 89Zr IN MICE

    PubMed Central

    Abou, D.S.; Ku, T.; Smith-Jones, P.M.

    2015-01-01

    Introduction The present investigation focuses on the chemical and biological fate of 89Zr in mice. Electrophoreses of 89Zr solvated or chelated in different conditions are here presented. The biological fate of mice injected with [89Zr]Zr-oxalate, [89Zr]Zr-chloride, [89Zr]Zr-phosphate, [89Zr]Zr-desferrioxamine and [89Zr]Zr-citrate is studied with the biodistribution, the clearances and PET images. A special focus is also given regarding the quality of 89Zr bone accumulation. Methods Electrophoreses were carried out on chromatography paper and read by gamma counting. Then, the solutions were intravenously injected in mice, imaged at different time points and sacrificed. The bones, the epiphysis and the marrow substance were separated and evaluated with gamma counts. Results The clearances of [89Zr]Zr-chloride and [89Zr]Zr-oxalate reached 20% of ID after 6 days whereas [89Zr]Zr-phosphate was only 5% of ID. [89Zr]Zr-citrate and [89Zr]Zr-DFO were noticeably excreted after the first day p.i.. [89Zr]Zr-chloride and [89Zr]Zr-oxalate resulted in a respective bone uptake of ~15% ID/g and~20% ID/g at 8 h p.i. with minor losses after 6 days. [89Zr]Zr-citrate bone uptake was also observed, but [89Zr]Zr-phosphate was absorbed in high amounts in the liver and the spleen. The marrow cells were insignificantly radioactive in comparison to the calcified tissues. Conclusion Despite the complexity of Zr coordination, the electrophoretic analyses provided detailed evidences of Zr charges either as salts or as complexes. This study also shows that weakly chelated, 89Zr is a bone seeker and has a strong affinity for phosphate. PMID:21718943

  10. Modeling and experimental data of zirconium-89 production yield.

    PubMed

    Sharifian, Mozhgan; Sadeghi, Mahdi; Alirezapour, Behrouz; Yarmohammadi, Mohammad; Ardaneh, Khosro

    2017-09-29

    The radionuclide zirconium-89 can be employed for the positron emission tomography (PET). In this study (89)Zr excitation function via (89)Y(p,n)(89)Zr reaction was calculated by the TALYS-1.8 code based on microscopic level density model. The formation of (89)Zr was simulated using the Monte Carlo simulation code MCNPX to calculate the integral yield in the (89)Y target body for threshold up to 40MeV incident-proton energy. The target thickness was based on calculation of the stopping power using the SRIM-2013 code matched to any incident-proton energy. The production yield of the (89)Zr simulated with the Monte Carlo method for the (89)Y(p,n)(89)Zr, (89)Y(d,2n)(89)Zr, (nat)Sr(α,xn)(89)Zr and (nat)Zr(p,pxn)(89)Zr reactions and the results were in good agreement with published experimental results for the optimum energy range. An experimental yield of 53.1MB/µA for the 15MeV proton-induced on Y2O3 powder as a disk-target obtained for 1h irradiation at the AMIRS cyclotron. Copyright © 2017 Elsevier Ltd. All rights reserved.

  11. The promotion of CO dissociation by molybdenum oxide overlayers on rhodium

    NASA Astrophysics Data System (ADS)

    Szenti, Imre; Bugyi, László; Kónya, Zoltán

    2017-03-01

    A considerable promotional effect of MoOx species observed at high pressures on the catalytic activity of rhodium initiated the present UHV model study. The MoOx overlayers formed on Rh films (0.15-20.0 ML) supported by TiO2(110) substrate were characterized by AES, TPD, work function (WF) measurements and CO adsorption. On the mixed oxide support produced by depositing 1.2 ML Mo onto TiO2(110), a new recombinative CO desorption state was observed with Tp=700 K, assigned as β-CO and related to the promotional effect of MoOx species diffused onto Rh particles of 1.0 ML coverage. The development of β-CO needs 0.5-0.7 ML threshold Rh coverage, attributable to particle size effect and geometric factors governing the CO adsorption. The β-CO state with Tp=725-742 K could also be detected on Rh films covered by MoOx moiety formed by the oxidation of Mo overlayers in O2. Remarkably, recombinative CO desorption with Tp=700 K could be observed on the Rh nanoparticles covered by MoOzCy produced from pure Mo deposits by CO adsorption, too. In harmony with the promotional effect of MoOx overlayer found at high pressures, it is established that the dissociation of CO is maximal at 0.2-0.3 ML Mo coverage, attributed to the presence of active sites at the oxide-metal interface. The low desorption peak temperature (700 K) of associative CO desorption observed in the presence of MoOx and MoOzCy overlayers indicates a low activation energy for the reactions of Oa and Ca atoms, allowing high reaction rates for these intermediates. The MoOx species exerted both promotion and inhibition effects on CO adsorption at sub-monolayer coverages, but above 1 ML it completely suppressed the reactivity of rhodium layers towards CO, suggesting that its surface concentration is a critical factor.

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

    PubMed

    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)(H2L(tBu))Cl3] (1) (H2L(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)(H2L(tBu))Cl3] (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)(H2L(tBu))Cl3] 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.

  13. A Possible 5th Planet in the Kepler-89 System

    NASA Astrophysics Data System (ADS)

    Mayo, Andrew; Deck, Katherine; Knutson, Heather; Batygin, Konstantin; Christiansen, Jessie

    2017-01-01

    Kepler-89 is a system with four known, transiting planets. We investigate a large discrepancy in the mass of the Jupiter-sized Kepler-89d between previous radial velocity (RV) and transit timing variation (TTV) measurements. We model the TTV data for the system and find evidence of a fifth planet, which we call Kepler-89f, inducing high amplitude TTVs on the outer transiting planet, Kepler-89e. We model the characteristics of this hypothetical planet and investigate how its presence may affect other system parameters, including the mass of Kepler-89d. We also analyze whether future transit observations of Kepler-89e could improve the characterization of Kepler-89f. Lastly, we explore how model results differ between fitting against TTV data versus fitting against raw transit times, and whether this could also be a contributing factor to the discrepancy between RV and TTV measurements of Kepler-89d.

  14. 36 CFR 8.9 - Posting of regulations.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 36 Parks, Forests, and Public Property 1 2011-07-01 2011-07-01 false Posting of regulations. 8.9 Section 8.9 Parks, Forests, and Public Property NATIONAL PARK SERVICE, DEPARTMENT OF THE INTERIOR LABOR STANDARDS APPLICABLE TO EMPLOYEES OF NATIONAL PARK SERVICE CONCESSIONERS § 8.9 Posting of regulations...

  15. 50 CFR 18.89 - Oral and written arguments.

    Code of Federal Regulations, 2012 CFR

    2012-10-01

    ... 50 Wildlife and Fisheries 9 2012-10-01 2012-10-01 false Oral and written arguments. 18.89 Section 18.89 Wildlife and Fisheries UNITED STATES FISH AND WILDLIFE SERVICE, DEPARTMENT OF THE INTERIOR... WILDLIFE AND PLANTS (CONTINUED) MARINE MAMMALS Notice and Hearing on Section 103 Regulations § 18.89 Oral...

  16. 25 CFR 89.42 - Factors to be considered.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 25 Indians 1 2011-04-01 2011-04-01 false Factors to be considered. 89.42 Section 89.42 Indians... TRIBES Payment of Tribal Attorney Fees with Appropriated Funds § 89.42 Factors to be considered. The following factors are to be considered in determining whether funds should be paid to provide private legal...

  17. 10 CFR 34.89 - Location of documents and records.

    Code of Federal Regulations, 2013 CFR

    2013-01-01

    ... 10 Energy 1 2013-01-01 2013-01-01 false Location of documents and records. 34.89 Section 34.89 Energy NUCLEAR REGULATORY COMMISSION LICENSES FOR INDUSTRIAL RADIOGRAPHY AND RADIATION SAFETY REQUIREMENTS FOR INDUSTRIAL RADIOGRAPHIC OPERATIONS Recordkeeping Requirements § 34.89 Location of...

  18. 10 CFR 34.89 - Location of documents and records.

    Code of Federal Regulations, 2012 CFR

    2012-01-01

    ... 10 Energy 1 2012-01-01 2012-01-01 false Location of documents and records. 34.89 Section 34.89 Energy NUCLEAR REGULATORY COMMISSION LICENSES FOR INDUSTRIAL RADIOGRAPHY AND RADIATION SAFETY REQUIREMENTS FOR INDUSTRIAL RADIOGRAPHIC OPERATIONS Recordkeeping Requirements § 34.89 Location of...

  19. 10 CFR 34.89 - Location of documents and records.

    Code of Federal Regulations, 2011 CFR

    2011-01-01

    ... 10 Energy 1 2011-01-01 2011-01-01 false Location of documents and records. 34.89 Section 34.89 Energy NUCLEAR REGULATORY COMMISSION LICENSES FOR INDUSTRIAL RADIOGRAPHY AND RADIATION SAFETY REQUIREMENTS FOR INDUSTRIAL RADIOGRAPHIC OPERATIONS Recordkeeping Requirements § 34.89 Location of...

  20. 18 CFR 401.89 - Action by the Commission.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 18 Conservation of Power and Water Resources 2 2011-04-01 2011-04-01 false Action by the Commission. 401.89 Section 401.89 Conservation of Power and Water Resources DELAWARE RIVER BASIN COMMISSION ADMINISTRATIVE MANUAL RULES OF PRACTICE AND PROCEDURE Administrative and Other Hearings § 401.89 Action by the...

  1. 21 CFR 114.89 - Deviations from scheduled processes.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 21 Food and Drugs 2 2011-04-01 2011-04-01 false Deviations from scheduled processes. 114.89 Section 114.89 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) FOOD FOR HUMAN CONSUMPTION ACIDIFIED FOODS Production and Process Controls § 114.89...

  2. 21 CFR 114.89 - Deviations from scheduled processes.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... 21 Food and Drugs 2 2012-04-01 2012-04-01 false Deviations from scheduled processes. 114.89 Section 114.89 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) FOOD FOR HUMAN CONSUMPTION ACIDIFIED FOODS Production and Process Controls § 114.89...

  3. 21 CFR 114.89 - Deviations from scheduled processes.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... 21 Food and Drugs 2 2014-04-01 2014-04-01 false Deviations from scheduled processes. 114.89 Section 114.89 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) FOOD FOR HUMAN CONSUMPTION ACIDIFIED FOODS Production and Process Controls § 114.89...

  4. 21 CFR 114.89 - Deviations from scheduled processes.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... 21 Food and Drugs 2 2013-04-01 2013-04-01 false Deviations from scheduled processes. 114.89 Section 114.89 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) FOOD FOR HUMAN CONSUMPTION ACIDIFIED FOODS Production and Process Controls § 114.89...

  5. 14 CFR 437.89 - Pre-flight reporting.

    Code of Federal Regulations, 2010 CFR

    2010-01-01

    ... 14 Aeronautics and Space 4 2010-01-01 2010-01-01 false Pre-flight reporting. 437.89 Section 437.89 Aeronautics and Space COMMERCIAL SPACE TRANSPORTATION, FEDERAL AVIATION ADMINISTRATION, DEPARTMENT OF TRANSPORTATION LICENSING EXPERIMENTAL PERMITS Terms and Conditions of an Experimental Permit § 437.89 Pre-flight...

  6. 36 CFR 7.89 - New River Gorge National River.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 36 Parks, Forests, and Public Property 1 2011-07-01 2011-07-01 false New River Gorge National River. 7.89 Section 7.89 Parks, Forests, and Public Property NATIONAL PARK SERVICE, DEPARTMENT OF THE INTERIOR SPECIAL REGULATIONS, AREAS OF THE NATIONAL PARK SYSTEM § 7.89 New River Gorge National River. (a...

  7. 36 CFR 8.9 - Posting of regulations.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 36 Parks, Forests, and Public Property 1 2010-07-01 2010-07-01 false Posting of regulations. 8.9 Section 8.9 Parks, Forests, and Public Property NATIONAL PARK SERVICE, DEPARTMENT OF THE INTERIOR LABOR STANDARDS APPLICABLE TO EMPLOYEES OF NATIONAL PARK SERVICE CONCESSIONERS § 8.9 Posting of regulations...

  8. 49 CFR 8.9 - Information Security Review Committee.

    Code of Federal Regulations, 2013 CFR

    2013-10-01

    ... 49 Transportation 1 2013-10-01 2013-10-01 false Information Security Review Committee. 8.9 Section 8.9 Transportation Office of the Secretary of Transportation CLASSIFIED INFORMATION: CLASSIFICATION/DECLASSIFICATION/ACCESS Classification/Declassification of Information § 8.9 Information Security Review Committee...

  9. 36 CFR 8.9 - Posting of regulations.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 36 Parks, Forests, and Public Property 1 2012-07-01 2012-07-01 false Posting of regulations. 8.9 Section 8.9 Parks, Forests, and Public Property NATIONAL PARK SERVICE, DEPARTMENT OF THE INTERIOR LABOR STANDARDS APPLICABLE TO EMPLOYEES OF NATIONAL PARK SERVICE CONCESSIONERS § 8.9 Posting of regulations...

  10. 36 CFR 8.9 - Posting of regulations.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 36 Parks, Forests, and Public Property 1 2014-07-01 2014-07-01 false Posting of regulations. 8.9 Section 8.9 Parks, Forests, and Public Property NATIONAL PARK SERVICE, DEPARTMENT OF THE INTERIOR LABOR STANDARDS APPLICABLE TO EMPLOYEES OF NATIONAL PARK SERVICE CONCESSIONERS § 8.9 Posting of regulations...

  11. 25 CFR 89.32 - Notice from the principal officer.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 25 Indians 1 2010-04-01 2010-04-01 false Notice from the principal officer. 89.32 Section 89.32... INDIAN TRIBES Five Civilized Tribes § 89.32 Notice from the principal officer. Notice of intention to negotiate with attorneys or with technical specialists shall be sent by the principal tribal officer to the...

  12. 25 CFR 89.32 - Notice from the principal officer.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 25 Indians 1 2011-04-01 2011-04-01 false Notice from the principal officer. 89.32 Section 89.32... INDIAN TRIBES Five Civilized Tribes § 89.32 Notice from the principal officer. Notice of intention to negotiate with attorneys or with technical specialists shall be sent by the principal tribal officer to the...

  13. 47 CFR 8.9 - Other Laws and Considerations.

    Code of Federal Regulations, 2011 CFR

    2011-10-01

    ... 47 Telecommunication 1 2011-10-01 2011-10-01 false Other Laws and Considerations. 8.9 Section 8.9 Telecommunication FEDERAL COMMUNICATIONS COMMISSION GENERAL PRESERVING THE OPEN INTERNET § 8.9 Other Laws and... Internet access service may have to address the needs of emergency communications or law enforcement...

  14. 47 CFR 8.9 - Other laws and considerations.

    Code of Federal Regulations, 2014 CFR

    2014-10-01

    ... 47 Telecommunication 1 2014-10-01 2014-10-01 false Other laws and considerations. 8.9 Section 8.9 Telecommunication FEDERAL COMMUNICATIONS COMMISSION GENERAL PRESERVING THE OPEN INTERNET § 8.9 Other laws and... Internet access service may have to address the needs of emergency communications or law enforcement...

  15. 47 CFR 8.9 - Other laws and considerations.

    Code of Federal Regulations, 2013 CFR

    2013-10-01

    ... 47 Telecommunication 1 2013-10-01 2013-10-01 false Other laws and considerations. 8.9 Section 8.9 Telecommunication FEDERAL COMMUNICATIONS COMMISSION GENERAL PRESERVING THE OPEN INTERNET § 8.9 Other laws and... Internet access service may have to address the needs of emergency communications or law enforcement...

  16. 18 CFR 401.89 - Action by the Commission.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 18 Conservation of Power and Water Resources 2 2010-04-01 2010-04-01 false Action by the Commission. 401.89 Section 401.89 Conservation of Power and Water Resources DELAWARE RIVER BASIN COMMISSION ADMINISTRATIVE MANUAL RULES OF PRACTICE AND PROCEDURE Administrative and Other Hearings § 401.89 Action by the...

  17. 40 CFR 89.311 - Analyzer calibration frequency.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 21 2013-07-01 2013-07-01 false Analyzer calibration frequency. 89.311 Section 89.311 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) AIR PROGRAMS... Equipment Provisions § 89.311 Analyzer calibration frequency. (a) Prior to initial use and after major...

  18. 40 CFR 89.311 - Analyzer calibration frequency.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 21 2012-07-01 2012-07-01 false Analyzer calibration frequency. 89.311 Section 89.311 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) AIR PROGRAMS... Equipment Provisions § 89.311 Analyzer calibration frequency. (a) Prior to initial use and after major...

  19. 40 CFR 89.311 - Analyzer calibration frequency.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 20 2014-07-01 2013-07-01 true Analyzer calibration frequency. 89.311 Section 89.311 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) AIR PROGRAMS... Equipment Provisions § 89.311 Analyzer calibration frequency. (a) Prior to initial use and after major...

  20. 40 CFR 89.311 - Analyzer calibration frequency.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 20 2010-07-01 2010-07-01 false Analyzer calibration frequency. 89.311 Section 89.311 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) AIR PROGRAMS... Equipment Provisions § 89.311 Analyzer calibration frequency. (a) Prior to initial use and after major...

  1. 49 CFR 229.89 - Jumpers; cable connections.

    Code of Federal Regulations, 2013 CFR

    2013-10-01

    ... 49 Transportation 4 2013-10-01 2013-10-01 false Jumpers; cable connections. 229.89 Section 229.89....89 Jumpers; cable connections. (a) Jumpers and cable connections between locomotives shall be so...) Cable and jumper connections between locomotive may not have any of the following conditions: (1) Broken...

  2. 49 CFR 229.89 - Jumpers; cable connections.

    Code of Federal Regulations, 2014 CFR

    2014-10-01

    ... 49 Transportation 4 2014-10-01 2014-10-01 false Jumpers; cable connections. 229.89 Section 229.89....89 Jumpers; cable connections. (a) Jumpers and cable connections between locomotives shall be so...) Cable and jumper connections between locomotive may not have any of the following conditions: (1) Broken...

  3. 49 CFR 229.89 - Jumpers; cable connections.

    Code of Federal Regulations, 2011 CFR

    2011-10-01

    ... 49 Transportation 4 2011-10-01 2011-10-01 false Jumpers; cable connections. 229.89 Section 229.89....89 Jumpers; cable connections. (a) Jumpers and cable connections between locomotives shall be so...) Cable and jumper connections between locomotive may not have any of the following conditions: (1) Broken...

  4. 49 CFR 229.89 - Jumpers; cable connections.

    Code of Federal Regulations, 2012 CFR

    2012-10-01

    ... 49 Transportation 4 2012-10-01 2012-10-01 false Jumpers; cable connections. 229.89 Section 229.89....89 Jumpers; cable connections. (a) Jumpers and cable connections between locomotives shall be so...) Cable and jumper connections between locomotive may not have any of the following conditions: (1) Broken...

  5. 49 CFR 229.89 - Jumpers; cable connections.

    Code of Federal Regulations, 2010 CFR

    2010-10-01

    ... 49 Transportation 4 2010-10-01 2010-10-01 false Jumpers; cable connections. 229.89 Section 229.89....89 Jumpers; cable connections. (a) Jumpers and cable connections between locomotives shall be so...) Cable and jumper connections between locomotive may not have any of the following conditions: (1) Broken...

  6. 40 CFR 89.416 - Raw exhaust gas flow.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 21 2012-07-01 2012-07-01 false Raw exhaust gas flow. 89.416 Section... Procedures § 89.416 Raw exhaust gas flow. The exhaust gas flow shall be determined by one of the methods... procedure has been incorporated by reference. See § 89.6.) and calculation of the exhaust gas flow as...

  7. 40 CFR 89.113 - Smoke emission standard.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 20 2011-07-01 2011-07-01 false Smoke emission standard. 89.113 Section 89.113 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) AIR PROGRAMS... and Certification Provisions § 89.113 Smoke emission standard. (a) Exhaust opacity from compression...

  8. 40 CFR 89.113 - Smoke emission standard.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 20 2010-07-01 2010-07-01 false Smoke emission standard. 89.113 Section 89.113 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) AIR PROGRAMS... and Certification Provisions § 89.113 Smoke emission standard. (a) Exhaust opacity from compression...

  9. 29 CFR 102.89 - Initiation of proceedings.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 29 Labor 2 2010-07-01 2010-07-01 false Initiation of proceedings. 102.89 Section 102.89 Labor Regulations Relating to Labor NATIONAL LABOR RELATIONS BOARD RULES AND REGULATIONS, SERIES 8 Procedure To Hear and Determine Disputes Under Section 10(k) of the Act § 102.89 Initiation of proceedings. Whenever it...

  10. 7 CFR 301.89-2 - Regulated articles.

    Code of Federal Regulations, 2014 CFR

    2014-01-01

    ... 7 Agriculture 5 2014-01-01 2014-01-01 false Regulated articles. 301.89-2 Section 301.89-2... SERVICE, DEPARTMENT OF AGRICULTURE DOMESTIC QUARANTINE NOTICES Karnal Bunt § 301.89-2 Regulated articles. The following are regulated articles: (a) Conveyances, including trucks, railroad cars, and...

  11. 7 CFR 301.89-2 - Regulated articles.

    Code of Federal Regulations, 2013 CFR

    2013-01-01

    ... 7 Agriculture 5 2013-01-01 2013-01-01 false Regulated articles. 301.89-2 Section 301.89-2... SERVICE, DEPARTMENT OF AGRICULTURE DOMESTIC QUARANTINE NOTICES Karnal Bunt § 301.89-2 Regulated articles. The following are regulated articles: (a) Conveyances, including trucks, railroad cars, and...

  12. 10 CFR 1040.89-3 - Information requirements.

    Code of Federal Regulations, 2013 CFR

    2013-01-01

    ... 10 Energy 4 2013-01-01 2013-01-01 false Information requirements. 1040.89-3 Section 1040.89-3... of Doe Recipients § 1040.89-3 Information requirements. Each recipient shall: (a) Upon request make available to DOE information necessary to determine whether the recipient is complying with the Act and...

  13. 40 CFR 89.911 - Submission of exemption requests.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 20 2014-07-01 2013-07-01 true Submission of exemption requests. 89.911 Section 89.911 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) AIR PROGRAMS... Provisions § 89.911 Submission of exemption requests. Requests for exemption or further information...

  14. 40 CFR 89.911 - Submission of exemption requests.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 21 2012-07-01 2012-07-01 false Submission of exemption requests. 89.911 Section 89.911 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) AIR PROGRAMS... Provisions § 89.911 Submission of exemption requests. Requests for exemption or further information...

  15. 40 CFR 89.911 - Submission of exemption requests.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 21 2013-07-01 2013-07-01 false Submission of exemption requests. 89.911 Section 89.911 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) AIR PROGRAMS... Provisions § 89.911 Submission of exemption requests. Requests for exemption or further information...

  16. 40 CFR 89.911 - Submission of exemption requests.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 20 2011-07-01 2011-07-01 false Submission of exemption requests. 89.911 Section 89.911 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) AIR PROGRAMS... Provisions § 89.911 Submission of exemption requests. Requests for exemption or further information...

  17. 40 CFR 89.911 - Submission of exemption requests.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 20 2010-07-01 2010-07-01 false Submission of exemption requests. 89.911 Section 89.911 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) AIR PROGRAMS... Provisions § 89.911 Submission of exemption requests. Requests for exemption or further information...

  18. 10 CFR 76.89 - Criticality accident requirements.

    Code of Federal Regulations, 2012 CFR

    2012-01-01

    ... 10 Energy 2 2012-01-01 2012-01-01 false Criticality accident requirements. 76.89 Section 76.89 Energy NUCLEAR REGULATORY COMMISSION (CONTINUED) CERTIFICATION OF GASEOUS DIFFUSION PLANTS Safety § 76.89 Criticality accident requirements. (a) The Corporation must maintain and operate a criticality monitoring and...

  19. 10 CFR 76.89 - Criticality accident requirements.

    Code of Federal Regulations, 2014 CFR

    2014-01-01

    ... 10 Energy 2 2014-01-01 2014-01-01 false Criticality accident requirements. 76.89 Section 76.89 Energy NUCLEAR REGULATORY COMMISSION (CONTINUED) CERTIFICATION OF GASEOUS DIFFUSION PLANTS Safety § 76.89 Criticality accident requirements. (a) The Corporation must maintain and operate a criticality monitoring and...

  20. 10 CFR 76.89 - Criticality accident requirements.

    Code of Federal Regulations, 2010 CFR

    2010-01-01

    ... 10 Energy 2 2010-01-01 2010-01-01 false Criticality accident requirements. 76.89 Section 76.89 Energy NUCLEAR REGULATORY COMMISSION (CONTINUED) CERTIFICATION OF GASEOUS DIFFUSION PLANTS Safety § 76.89 Criticality accident requirements. (a) The Corporation must maintain and operate a criticality monitoring and...