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Sample records for rhodium sesquioxide reduction

  1. Rhodium Nanoparticle Shape Dependence in the Reduction of NO by CO

    Energy Technology Data Exchange (ETDEWEB)

    Renzas, J.R.; Zhang, Y.; Huang, W.; Somorjai, G.A.

    2009-07-13

    The shape dependence of the catalytic reduction of NO by CO on Rhodium nanopolyhedra and nanocubes was studied from 230-270 C. The nanocubes are found to exhibit higher turnover frequency and lower activation energy than the nanopolyhedra. These trends are compared to previous studies on Rh single crystals.

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

    Science.gov (United States)

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

    2015-02-01

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

  3. The Key Technique of Manufacture of Dense Chromium Sesquioxide Refractories

    Institute of Scientific and Technical Information of China (English)

    LIMaoqiang; ZHANGShuying; 等

    1998-01-01

    Dense chromium sesquioxide refractories have widely been used in the kilns for making alkai-free and anti-alkali glass fibers due to their excellent re-sistance to molten glasses.Densifications of chromium sesquioxide during sintering can be blocked by evaporation of chromium trioxide derived from oxidation at high temperature,In this paper the mech-anism of sintering chromium oxide and the process-ing technique for making dense chromium sesquiox-ide refractories are discussed .A process in laboratory scale for making dense chromium sesquioxide bricks is demonstrated.

  4. Rhodium-catalysed hydroacylation or reductive aldol reactions: a ligand dependent switch of reactivity.

    Science.gov (United States)

    Osborne, James D; Willis, Michael C

    2008-10-28

    The pathway for the combination of enones and beta-S-substituted aldehydes using Rh-catalysis can be switched between a hydroacylation reaction or a reductive aldol reaction by simple choice of the phosphine ligand; this catalyst controlled switch allows access to new ketone hydroacylation products; useful 1,4-diketone intermediates for the synthesis of N-, S- and O-heterocycles.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2008-07-01

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

  6. Rhodium-Coordinated Poly(arylene-ethynylene)-alt-Poly(arylene-vinylene) Copolymer Acting as Photocatalyst for Visible-Light-Powered NAD+/NADH Reduction

    Science.gov (United States)

    2014-01-01

    A 2,2′-bipyridyl-containing poly(arylene-ethynylene)-alt-poly(arylene-vinylene) polymer, acting as a light-harvesting ligand system, was synthesized and coupled to an organometallic rhodium complex designed for photocatalytic NAD+/NADH reduction. The material, which absorbs over a wide spectral range, was characterized by using various analytical techniques, confirming its chemical structure and properties. The dielectric function of the material was determined from spectroscopic ellipsometry measurements. Photocatalytic reduction of nucleotide redox cofactors under visible light irradiation (390–650 nm) was performed and is discussed in detail. The new metal-containing polymer can be used to cover large surface areas (e.g. glass beads) and, due to this immobilization step, can be easily separated from the reaction solution after photolysis. Because of its high stability, the polymer-based catalyst system can be repeatedly used under different reaction conditions for (photo)chemical reduction of NAD+. With this concept, enzymatic, photo-biocatalytic systems for solar energy conversion can be facilitated, and the precious metal catalyst can be recycled. PMID:25130570

  7. Extreme electron-phonon coupling in magnetic rubidium sesquioxide

    Science.gov (United States)

    de Groot, Robert; Attema, Jisk; Riyadi, S.; Blake, Greame; de Wijs, Gilles; Palstra, Thomas

    2008-03-01

    Rb2O3 is a black, opaque oxide. Early work suggests that the stability range of the sesquioxide phase in the rubidium-oxygen phase diagram is rather broad. Rb2O3 remains cubic down to the lowest temperature measured (5 K). The oxygens form dumbbells with interatomic distances in between those of peroxide and superoxide anions, and strong athermal motion persists down to low temperatures. [1] Electronic-structure calculations show that the dynamics at low temperature is caused by 6 phonon modes of zero frequency, which induce a very strong electron-phonon interaction. The softness of half of these modes is suppressed by the application of pressure. Calculated using the average oxygen positions, rubidium sesquioxide is a half-metallic ferromagnet. [2] [1] CR CHIM (11-13): 591-594 NOV 1999[2] JACS 127 (46): 16325-16328 NOV 23 2005

  8. Development of Sesquioxide Ceramic for High Energy Lasers

    Science.gov (United States)

    2015-05-25

    Final 3. DATES COVERED (From - To) 28 Mar 13 – 27 Mar 15 4. TITLE AND SUBTITLE Development of Sesquioxide Ceramic for High Energy Lasers ...the findings include, the relationship between the appropriate evaluation process for the performance of materials and laser oscillation performance...homogeneity was lowered by adding laser active ions into the above host materials. 4) Optical heterogeneity was caused by the inhomogeneous

  9. Hollow-shell-structured nanospheres: a recoverable heterogeneous catalyst for rhodium-catalyzed tandem reduction/lactonization of ethyl 2-acylarylcarboxylates to chiral phthalides.

    Science.gov (United States)

    Liu, Rui; Jin, Ronghua; An, Juzeng; Zhao, Qiankun; Cheng, Tanyu; Liu, Guohua

    2014-05-01

    Chiral organorhodium-functionalized hollow-shell-structured nanospheres were prepared by immobilization of a chiral N-sulfonylated diamine-based organorhodium complex within an ethylene-bridged organosilicate shell. Structural analysis and characterization reveal its well-defined single-site rhodium active center, and transmission electron microscopy images reveal a uniform dispersion of hollow-shell-structured nanospheres. As a heterogenous catalyst, it exhibits excellent catalytic activity and enantioselectivity in synthesis of chiral phthalides by a tandem reduction/lactonization of ethyl 2-acylarylcarboxylates in aqueous medium. The high catalytic performance is attributed to the synergistic effect of the high hydrophobicity and the confined chiral organorhodium catalytic nature. The organorhodium-functionalized nanospheres could be conveniently recovered and reused at least 10 times without loss of catalytic activity. This feature makes it an attractive catalyst in environmentally friendly organic reactions. The results of this study offer a new approach to immobilize chiral organometal functionalities within the hollow-shell-structured nanospheres to prepare materials with high activity in heterogeneous asymmetric catalysis.

  10. Phosphinoureas: cooperative ligands in rhodium-catalyzed hydroformylation? On the possibility of a ligand-assisted reductive elimination of the aldehyde

    NARCIS (Netherlands)

    Meeuwissen, J.; Sandee, A.J.; de Bruin, B.; Siegler, M.A.; Spek, A.L.; Reek, J.N.H.

    2010-01-01

    We report the synthesis of a novel type of phosphinourea ligand, its coordination chemistry with rhodium, its use in the asymmetric hydroformylation of styrene, and investigations on the hydroformylation reaction mechanism. Complex studies on the 2:1 complex of phosphinourea to [Rh(acac)(CO)(2)] sho

  11. Phosphinoureas: cooperative ligands in rhodium-catalyzed hydroformylation? on the possibility of a ligand-assisted reductive elimination of the aldehyde

    NARCIS (Netherlands)

    Meeuwissen, J.; Sandee, A. J.; de Bruin, B.; Siegler, M. A.; Spek, A.L.; Reek, J.N.H.

    2010-01-01

    We report the synthesis of a novel type of phosphinourea ligand, its coordination chemistry with rhodium, its use in the asymmetric hydroformylation of styrene, and investigations on the hydroformylation reaction mechanism. Complex studies on the 2:1 complex of phosphinourea to [Rh(acac)(CO)2] showe

  12. Cryogenic temperature characteristics of Verdet constant of terbium sesquioxide ceramics

    Science.gov (United States)

    Snetkov, I. L.; Palashov, O. V.

    2016-12-01

    The dependence of the Verdet constant on temperature in the (80-300 K) range for a promising magneto-active material terbium sesquioxide Tb2O3 at the wavelengths of 405-1064 nm is considered. For each of the studied wavelengths, the Verdet constant of the material cooled down to the liquid nitrogen temperature increased by more than a factor of 3.2 as compared to the room temperature value. Similarly to the other paramagnetics, the increase follows the law ∼1/T. Approximations for the temperature dependence of the Verdet constant have been obtained and the value of 1/V·(dV/dT) has been estimated. This information is needed to determine the angle of rotation as well as the variation of the extinction ratio of a Faraday isolator with temperature and extremely important at creation a cryogenic Faraday devices.

  13. Rhodium platings – experimental study

    Directory of Open Access Journals (Sweden)

    R. Rudolf

    2013-07-01

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

  14. The synthesis and cytotoxic activity of novel organogermanium sesquioxides with anthraquinone or naphthalene moiety

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    Four novel organogermanium sesquioxides with anthraquinone or naphthalene moiety were synthesized. The structures were characterized by IR, NMR and elemental analysis, and their cytotoxicities were evaluated against human chronic myeloid leukemia K562 cell lines. The cytotoxicity could be improved by the introduction of planar aromatic chromophore moiety to the parent compound, Ge-132.

  15. Selected Soil Morphological, Mineralogical and Sesquioxide Properties of Rehabilitated and Secondary Forests

    Directory of Open Access Journals (Sweden)

    B. T. Saga

    2010-01-01

    Full Text Available Problem statement: The tropical rain forests in Southeast Asia have been characterized by several researchers. However empirical data on soil characteristics under degraded forest land in tropical rain forest and rehabilitated program are limited. A study was conducted to evaluate the soil morphology, mineralogical and sesquioxide properties of a rehabilitated degraded forest land (19 years after it was planted with various indigenous species in comparison with an adjacent secondary forest. Approach: Soil samples were air-dried and pass through a 2 mm sieve. Soil morphology was determined based on field observation. The non-crystalline (amorphous of Al, Fe and Si oxides and hydroxides (Alo, Feo and Sio were extracted with ammonium oxalate while the dithionate-citrate-bicarbonate (DCB method was used for extracting (crystalline the Al, Fe and Si oxides and hydroxides (Ald, Fed and Sid. The concentrations of extracted Al, Fe and Si were determined by atomic absorption spectroscopy. Mineralogical compositions were identified by X-ray diffraction method. Results: The A-horizon of secondary forest was darker and thicker than that of the rehabilitated forest. Root mat at the secondary forest was well-developed compared to the rehabilitated forest. The clay minerals were dominated with kaolinite and illite to a lesser extent of goethite and hematite accompanied with low values of activity ratio of Al and Fe oxides and hydroxides, indicating that the soils were highly weathered. Conclusion/Recommendations: The difference between rehabilitated and secondary forests was root abundance where secondary forest had most. Good root penetration in the secondary forest indicates that the soil texture there was not heavy. Soils in the rehabilitated and secondary forests were strongly weathered (high presence of kaolin minerals, but the low presence of sesquioxides suggests that they are yet to reached the ultimately weathered phase. The soil properties in terms

  16. Study on the Recovery of Rhodium from Spent Organic Rhodium Catalysts of Acetic Acid Industry Using Pyrometallurgical Process

    Institute of Scientific and Technical Information of China (English)

    HE Xiaotang; WANG Huan; WU Xilong; LI Yong; ZHAO Yu; HAN Shouli; LI Kun; GUO Junmei

    2012-01-01

    A new process recycling rhodium from organic waste containing rhodium in acetic acid industry is developed.Use the special affinity of base metal sulfides (FeS,Ni2S3,CuS,etc.) on platinum group metals,adopting high nickel matte trapping-aluminothermic activation method to recovery rhodium from incinerator residue of organic rhodium waste.The method is shorter process,lower equipment requirement,and the higher activity of rhodium black.In pyrometallurgy enrichment process,the recovery rate of rhodium reached 94.65%,the full flow of rhodium recovery rate was 92.04%.

  17. Ab initio LSDA and LSDA+U study of pure and Cd-doped cubic lanthanide sesquioxides

    DEFF Research Database (Denmark)

    Richard, D.; Muñoz, E.L.; Rentería, M.

    2013-01-01

    The electronic, structural, and hyperfine properties of pure and Cd-doped lanthanide (Ln) sesquioxides with the cubic bixbyite structure (Ln2O3, Ln ranging from La to Lu) have been studied using the full-potential augmented plane wave plus local orbital (APW+lo) method within the local spin density...

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

    Science.gov (United States)

    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.

  19. Er-doped sesquioxides for 1.5-micron lasers - spectroscopic comparisons

    Science.gov (United States)

    Merkle, Larry D.; Ter-Gabrielyan, Nikolay

    2013-05-01

    Due to the favorable thermal properties of sesquioxides as hosts for rare earth laser ions, we have recently studied the spectroscopy of Er:Lu2O3 in the 1400-1700 nm wavelength range, and here report its comparison with our earlier results on Er:Y2O3 and Er:Sc2O3. These studies include absorption and fluorescence spectra, fluorescence lifetimes, and inference of absorption and stimulated emission cross sections, all as a function of temperature. At room temperature, optical absorption limits practical laser operation to wavelengths longer than about 1620 nm. In that spectral range, the strongest stimulated emission peak is that at 1665 nm in Er:Sc2O3, with an effective cross section considerably larger than those of Er:Y2O3 and Er:Lu2O3. At 77K, the absorption is weak enough for efficient laser operation at considerably shorter wavelengths, where there are peaks with much larger stimulated emission cross sections. The three hosts all have peaks near 1575-1580 nm with comparably strong cross sections. As we have reported earlier, it is possible to lase even shorter wavelengths efficiently at this temperature, in particular the line at 1558 nm in Er:Sc2O3. Our new spectroscopic studies of Er:Lu2O3 indicate that its corresponding peak, like that of Er:Sc2O3, has a less favorable ratio of stimulated emission to absorption cross sections. Reasons for the differences will be discussed. We conclude that for most operating scenarios, Er:Sc2O3 is the most promising of the Er-doped sesquioxides studied for laser operation around 1.5-1.6 microns.

  20. Study of cerium-promoted rhodium alumina catalyst as a steam reforming catalyst for treatment of spent solvents

    Institute of Scientific and Technical Information of China (English)

    Hee-Chul Yang; Min-Woo Lee; Ho-Sang Hwang; Jei-Kwon Moon; Dong-Yong Chung

    2014-01-01

    This study attempted to develop an appropriate catalyst used for the steam reforming of gasified spent solvents. Rh2O3/ CeO2-Al2O3 catalysts with various CeO2 loadings were prepared and heated at different temperatures of 500 and 800 ºC, and their surface properties were studied using X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), transmission electron mi-croscopy (TEM), temperature programmed reduction (TPR) and Brumauer-Emmett-Teller (BET) analyses. Rhodium existed in the form of Rh2O3, regardless of the sample composition as well as the heating temperature. In the tested range of cerium addition (up to 12 times the rhodium mass), no significant changes in BET surface areas and binding energy corresponding to Rh 3d5/2were observed. Instead, the addition of cerium led to a greatly enhanced dispersion of rhodium nanoparticles, and no agglomeration of rhodium was observed for samples heated even at 800 ºC. Honeycomb monolith rhodium catalysts promoted with cerium were fabricated and tested for the steam reforming of a gasified spent solvent, mainly consisting of butylene (C4H8). The test results suggested that a ce-rium-promoted rhodium catalyst could be used as an appropriate reforming catalyst for treating low-quality non-methane hydrocar-bons without the formation of coke at high temperatures of up to 900 ºC.

  1. Thermal and chemical stabilities of group-III sesquioxides in a flow of either N2 or H2

    Science.gov (United States)

    Togashi, Rie; Kisanuki, Yumi; Goto, Ken; Murakami, Hisashi; Kuramata, Akito; Yamakoshi, Shigenobu; Monemar, Bo; Koukitu, Akinori; Kumagai, Yoshinao

    2016-12-01

    The thermal and chemical stabilities of group-III sesquioxides (Al2O3, Ga2O3, and In2O3) were comparatively investigated at an atmospheric pressure at heat treatment temperatures ranging from 250 to 1450 °C in a flow of either N2 or H2. In a flow of N2, the thermal decomposition of α-Al2O3 was not observed at the temperatures investigated, while the decompositions of β-Ga2O3 and c-In2O3 occurred above 1150 and 1000 °C, respectively, with no generation of group-III metal droplets on the surfaces. In contrast, the chemical reactions of α-Al2O3, β-Ga2O3, and c-In2O3 began at low temperatures of 1150, 550, and 300 °C in a flow of H2. Thus, the presence of H2 in the gas flow significantly promotes the decomposition of group-III sesquioxides. The order of thermal and chemical stabilities (α-Al2O3 ≫ β-Ga2O3 > c-In2O3) obtained experimentally was verified by thermodynamic analysis, which also clarified dominant decomposition reactions of group-III sesquioxides.

  2. Tuning Eu{sup 3+} emission in europium sesquioxide films by changing the crystalline phase

    Energy Technology Data Exchange (ETDEWEB)

    Mariscal, A., E-mail: antonio.mariscal@csic.es [Laser Processing Group, Instituto de Óptica, CSIC, C/ Serrano 121, 28006 Madrid (Spain); Quesada, A. [Ceramics for Smart Systems Group, Instituto de Cerámica y Vidrio, C/ Kelsen 5, 28049 Madrid (Spain); Camps, I. [Laser Processing Group, Instituto de Óptica, CSIC, C/ Serrano 121, 28006 Madrid (Spain); Palomares, F.J. [Instituto de Ciencia de Materiales de Madrid, C/ Sor Juana Inés de la Cruz 3, 28049 Madrid (Spain); Fernández, J.F. [Ceramics for Smart Systems Group, Instituto de Cerámica y Vidrio, C/ Kelsen 5, 28049 Madrid (Spain); Serna, R. [Laser Processing Group, Instituto de Óptica, CSIC, C/ Serrano 121, 28006 Madrid (Spain)

    2016-06-30

    Highlights: • PLD production of high quality europium sesquioxide (Eu{sub 2}O{sub 3}) films. • The deposition of Al{sub 2}O{sub 3} capping and/or buffer layers modifies the crystallization for Eu{sub 2}O{sub 3} films upon annealing. • The formation of cubic or monoclinic phases can be favored. • Eu{sup 3+} emission tuning is achieved as a consequence of crystal field effects. - Abstract: We report the growth of europium sesquioxide (Eu{sub 2}O{sub 3}) thin films by pulsed laser deposition (PLD) in vacuum at room temperature from a pure Eu{sub 2}O{sub 3} ceramic bulk target. The films were deposited in different configurations formed by adding capping and/or buffer layers of amorphous aluminum oxide (a-Al{sub 2}O{sub 3}). The optical properties, refractive index and extinction coefficient of the as deposited Eu{sub 2}O{sub 3} layers were obtained. X-ray photoelectron spectroscopy (XPS) measurements were done to assess its chemical composition. Post-deposition annealing was performed at 500 °C and 850 °C in air in order to achieve the formation of crystalline films and to accomplish photoluminescence emission. According to the analysis of X-ray diffraction (XRD) spectra, cubic and monoclinic phases were formed. It is found that the relative amount of the phases is related to the different film configurations, showing that the control over the crystallization phase can be realized by adequately designing the structures. All the films showed photoluminescence emission peaks (under excitation at 355 nm) that are attributed to the intra 4f-transitions of Eu{sup 3+} ions. The emission spectral shape depends on the crystalline phase of the Eu{sub 2}O{sub 3} layer. Specifically, changes in the hypersensitive {sup 5}D{sub 0} → {sup 7}F{sub 2} emission confirm the strong influence of the crystal field effect on the Eu{sup 3+} energy levels.

  3. Self-irradiation and oxidation effects on americium sesquioxide and Raman spectroscopy studies of americium oxides

    Energy Technology Data Exchange (ETDEWEB)

    Horlait, Denis [CEA, DEN, DTEC/SDTC/LEMA, F-30207 Bagnols-sur-Cèze Cedex (France); Caraballo, Richard [CEA, DEN, DTCD/SECM/LMPA, F-30207 Bagnols-sur-Cèze Cedex (France); Lebreton, Florent [CEA, DEN, DTEC/SDTC/LEMA, F-30207 Bagnols-sur-Cèze Cedex (France); Jégou, Christophe [CEA, DEN, DTCD/SECM/LMPA, F-30207 Bagnols-sur-Cèze Cedex (France); Roussel, Pascal [Unité de Catalyse et Chimie du Solide, UMR 8012 CNRS, Ecole Nationale Supérieure de Chimie de Lille BP 90108, 59652 Villeneuve d’Ascq Cedex (France); Delahaye, Thibaud, E-mail: thibaud.delahaye@cea.fr [CEA, DEN, DTEC/SDTC/LEMA, F-30207 Bagnols-sur-Cèze Cedex (France)

    2014-09-15

    Americium oxides samples were characterized by X-ray diffraction (XRD) and Raman spectroscopy, with an emphasis on their structural behavior under oxidation and self-irradiation. Raman spectra of americium dioxide (AmO{sub 2}) and sesquioxide (Am{sub 2}O{sub 3}) were obtained for the first time. With the help of literature data on isostructural oxides, Raman signatures of Ia-3 C-type Am{sub 2}O{sub 3} and P-3m1 A-type Am{sub 2}O{sub 3} are identified. For AmO{sub 2,} a clear band is noted at 390 cm{sup −1}. Its nature is compared to that of the other actinide dioxides. Am{sub 2}O{sub 3} evolution under ambient conditions and against {sup 241}Am α self-irradiation was monitored by powder XRD. The sample, initially composed of A-type Am{sub 2}O{sub 3} as major phase as well as C2/m B-type and C-type structures as minor phases, progressively oxidizes to Fm-3m AmO{sub 2−δ} over a few months. On the basis of diffractogram refinements, evolutions of unit cell volumes caused by self-irradiation are also determined and discussed. - Graphical abstract: The evolution of americium oxide under ambient conditions was monitored using XRD (X-ray diffraction) and Raman spectroscopy. After a thermal treatment under reducing conditions, a polyphasic sample mainly composed of A- and C-type americium sesquioxides is evidenced by XRD and Raman spectroscopy. The sample then evolves through two processes: oxidation and self-irradiation. The first one provokes the progressive appearance of F-type americium dioxide while the initial phases disappear, whereas the main effect of the second is a structural swelling with time. - Highlights: • The first Raman spectroscopy measurements on americium oxides were performed. • Observed Am{sub 2}O{sub 3} Raman bands were identified thanks to data on analogue compounds. • AmO{sub 2} assumed T{sub 2g} band presents a shift compared to the actinide dioxide series. • Am{sub 2}O{sub 3} evolution under self-irradiation and oxidation was also

  4. Study of electrocatalytic properties of iridium carbonyl cluster and rhodium carbonyl cluster compounds for the oxygen reduction and hydrogen oxidation reactions in 0.5 MH{sub 2}SO{sub 4} in presence and absence of methanol and carbon monoxide, respectively

    Energy Technology Data Exchange (ETDEWEB)

    Uribe-Godinez, J.; Borja-Arco, E.; Castellanos, R.H. [Centro de Investigacion y Desarrollo Tecnologico en Electroquimica, Escobedo (Mexico); Jimenez-Sandoval, O. [Centro de Investigacion y de Estudios Avanzados del Inst. Politecnico Nacional, Querataro (Mexico)

    2006-07-01

    The suitability of carbonyl cluster compounds as a substitute to platinum (Pt) in fuel cell catalysts was investigated. Iridium (Ir{sub 4}(CO){sub 12} and rhodium (Rh{sub 6}(CO){sub 116}) cluster compounds were investigated as potential new electrocatalysts for oxygen reduction reaction (ORR) in the presence and absence of methanol at different concentrations, as well as for the hydrogen oxidation reaction (HOR) with pure hydrogen and a hydrogen/carbon monoxide mixture. The materials were studied using room temperature rotating disk electrode (RDE) measurements and cyclic and linear sweep voltammetry techniques (LSV). Tafel slope and exchange current density were calculated using the LSV polarization curves. Cyclic voltamperometry results suggested that the electrocatalysts were tolerant to methanol. However, electrochemical behaviour of the materials altered in the presence of CO, and peaks corresponding to CO oxidation were observed in both cases. The rhodium carbonyl showed a higher current density for the ORR than the iridium carbonyl. The current potential curves in the presence of methanol were similar to those obtained without methanol. Results confirmed the tolerance properties of the materials to perform the ORR. Decreased current density values were observed during HOR, and were attributed to changes in the hydrogen solubility and diffusion coefficient due to the presence of CO. The Tafel slopes indicated that the mechanics of the HOR were Heyrovsky-Volmer. Results showed that the materials are capable of performing both ORR and HOR in an acid medium. It was noted that the iridium carbonyl cluster followed a 4-electron transfer mechanism towards the formation of water. It was concluded that the compounds are suitable for use as both cathodes and anodes in proton exchange membrane fuel cells (PEMFCs) and as cathodes in direct methanol fuel cells (DMFCs). 3 refs., 2 tabs., 3 figs.

  5. Evidence for 5d-σ and 5d-π covalency in lanthanide sesquioxides from oxygen K-edge X-ray absorption spectroscopy.

    Science.gov (United States)

    Altman, Alison B; Pacold, Joseph I; Wang, Jian; Lukens, Wayne W; Minasian, Stefan G

    2016-06-14

    The electronic structure in the complete series of stable lanthanide sesquioxides, Ln2O3 (Ln = La to Lu, except radioactive Pm), has been evaluated using oxygen K-edge X-ray absorption spectroscopy (XAS) with a scanning transmission X-ray microscope (STXM). The experimental results agree with recent synthetic, spectroscopic and theoretical investigations that provided evidence for 5d orbital involvement in lanthanide bonding, while confirming the traditional viewpoint that there is little Ln 4f and O 2p orbital mixing. However, the results also showed that changes in the energy and occupancy of the 4f orbitals can impact Ln 5d and O 2p mixing, leading to several different bonding modes for seemingly identical Ln2O3 structures. On moving from left to right in the periodic table, abrupt changes were observed for the energy and intensity of transitions associated with Ln 5d and O 2p antibonding states. These changes in peak intensity, which were directly related to the amounts of O 2p and Ln 5d mixing, were closely correlated to the well-established trends in the chemical accessibility of the 4f orbitals towards oxidation or reduction. The unique insight provided by the O K-edge XAS is discussed in the context of several recent theoretical and physical studies on trivalent lanthanide compounds.

  6. Rhodium-Catalyzed Decarbonylation of Aldoses

    DEFF Research Database (Denmark)

    Monrad, Rune; Madsen, Robert

    2007-01-01

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

  7. Carbon nanofiber growth on thin rhodium layers

    NARCIS (Netherlands)

    Chinthaginjala, J.K.; Unnikrishnan, S.; Smithers, M.A.; Kip, G.A.M.; Lefferts, L.

    2012-01-01

    A thinlayer of carbon nanofibers (CNFs) was synthesized on a thin polycrystalline rhodium (Rh) metal layer by decomposing ethylene in the presence of hydrogen. Interaction of Rh crystals with carbon results in fragmentation and formation of Rh-nanoparticles, facilitating CNF growth. CNFs are immobil

  8. Relaxation of polarized nuclei in superconducting rhodium

    DEFF Research Database (Denmark)

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

    2000-01-01

    Nuclear spin lattice relaxation rates were measured in normal and superconducting (sc) rhodium with nuclear polarizations up to p = 0.55. This was sufficient to influence the sc state of Rh, whose T, and B-c, are exceptionally low. Because B-c

  9. Rhodium olefin complexes of diiminate type ligands

    NARCIS (Netherlands)

    Willems, Sander Theodorus Hermanus

    2003-01-01

    The mono-anionic beta-diiminate ligand (ArNC(CH3)CHC(CH3)NAr) on several previous occasions proved useful in stabilising low coordination numbers for both early and late transition metals. In this thesis the reactivity of the rhodium olefin complexes of one of these beta-diiminate ligands (Ar = 2,6-

  10. EXAFS Determination of the Change in the Structure of Rhodium in Highly Dispersed Rhodium/gamma-Aluminum Oxide Catalysts after Carbon Monoxide and/or Hydrogen Adsorption at Different Temperatures

    NARCIS (Netherlands)

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

    1984-01-01

    Extended X-ray absorption spectroscopy (EXAFS) has been applied to study the Rh K-edge of two ultradisperse Rh/Al{2}O{3} catalysts containing 0.47 and 1.04 wt.% rhodium respectively. The structural properties of the Rh crystallites were determined after reduction with H{2}, evacuation at elevated te

  11. ASYMMETRIC HYDROSILYLATION CATALYZED BY POLYMER—SUPPORTED THIAZOLIDINE RHODIUM CATALYSTS

    Institute of Scientific and Technical Information of China (English)

    LEIYanohui; LIHong; 等

    1999-01-01

    Asymmetric hydrisilylation catalyzed by polymeric thiazolidine rhodium catalysts was conducted.Almost the same optical yields have been obtained when comb-shaped polymeric ligands and their corresponding monomer complexed rhodium cataltysts were used to asymmetric hydrosilylation of acetophenone.Optical yield of chiral 1-methylbenzyl alcohol reaches as high as 71.5%.Temperature dependence of enantioselective hydrosilylation of acetophenone was discussed.

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

    Science.gov (United States)

    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.

  13. A density-functional theory approach to the existence and stability of molybdenum and tungsten sesquioxide polymorphs

    Energy Technology Data Exchange (ETDEWEB)

    Becker, Nils; Dronskowski, Richard [RWTH Aachen Univ. (Germany). Inst. fuer Anorganische Chemie; RWTH Aachen Univ. (Germany). Juelich-Aachen Research Alliance; Reimann, Christoph; Bredow, Thomas [Bonn Univ. (Germany). Inst. fuer Physikalische und Theoretische Chemie; Weber, Dominik; Luedtke, Tobias; Lerch, Martin [Berlin Technische Univ. (Germany). Inst. fuer Chemie

    2017-03-01

    The sesquioxides of molybdenum and tungsten have been reported as thin films or on surfaces as early as 1971, but the preparation of bulk materials and their crystal structures are still unknown up to the present day. We present a systematic ab initio approach to their possible syntheses and crystal structures applying complementary methods and basis-set types. For both compounds, the corundum structure is the most stable and does not display any imaginary frequencies. Calculations targeted at a high-pressure synthesis starting from the stable oxides and metals predict a reaction pressure of 15 GPa for Mo{sub 2}O{sub 3} and over 60 GPa for W{sub 2}O{sub 3}.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2005-01-01

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

  15. Adhesion of rhodium films on metallic substrates

    Energy Technology Data Exchange (ETDEWEB)

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

    2008-09-01

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

  16. Electronic and magnetic properties of ultrathin rhodium nanowires

    CERN Document Server

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

    2003-01-01

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

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

    Science.gov (United States)

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

    2016-01-01

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

  18. Structural properties of small rhodium clusters

    Science.gov (United States)

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

    2015-04-01

    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.

  19. Structural properties of small rhodium clusters

    Energy Technology Data Exchange (ETDEWEB)

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

    2015-04-24

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

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

    Science.gov (United States)

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

    2015-05-01

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

  1. Ab initio study on the mechanism of rhodium-complexcatalyzed carbonylation of methanol to acetic acid

    Institute of Scientific and Technical Information of China (English)

    LEI; Ming

    2001-01-01

    [1]Thomas, R., Cundari, T. R., Computational studies of transition metal-main group multiple bonding, Chem. Rev., 2000,100: 807.[2]Maricel Torrent, Miquel Sola, Gernot Frenking, Theoretical studies of some transition-metal-mediated reactions of industrial and synthetic importance, Chem. Rev., 2000, 100: 439.[3]Paulik, F. E., Roth, J. F., Catalysts for the low-pressure carbonylation of menthanol to acetic acid, Chem. Commun., 1968,24: 1578.[4]Jiang Hua, Diao Kaisheng, Pan Pinglai et al., A new class of rhodium complexes containing free donor atoms and their intramolecular substitution reaction, Chin. J. Chem., 2000, 18: 752.[5]Jiang Dazhi, Li Xiaobao, Wang Enlai, Synthesis Chemistry ofCarbonylation, Beijing: Chemical Technology Press, 1996.[6]Adamson, G. W., Daly, J. J., Forster, D., Reduction of iolocarbonyl rhodium ions with methyl iodide, structure of the rho-dium acetyl complex: [Me3PhN+], [Rh2I6-(Me(O)2(CO)2)]2-, J. Organomet. Chem., 1974, 71: C 17.[7]Forster, D., On the mechanism of a rhodium-complex-catalyzed carbonylation of methanol to acetic acid, J. Am. Chem.Soc., 1976, 98: 846.[8]Hjortkjaer, J., Jensen, O. R., Rhodium complexes catalyzed methanol carbonylation, Ind. Eng. Chem. Prod. Dev., 1976, 15:46.[9]Jeffrey, P., Wadt, W. R., Ab initio effective core potentials for molecular calculations, Potentials for the transition metalatoms Sc to Hg, J. Chem. Phys., 1995, 82: 270.[10]Frisch, M. J., Trunks, G. W., Schlegel, H. B. et al., Gaussian 94, Pittsburgh PA: Gaussian, Inc., 1995.[11]Lei Ming, Feng Wenlin, Xu Zhenfeng et al., A theoretical study on the key reactions of hydroformylation cycle by modi-fied carbonyl cobalt, Chemical Journal of Chinese University, 2001, 22: 455.[12]Lei Ming, Feng Wenlin, Xu Zhenfeng, Ab initio MO study on the reaction mechanism for carbonyl insertion catalyzed by the carbonyl cobalt complex, Chemical Research in Chinese University, 2000, 19:31.

  2. Rhodium deposition onto a 4-mercaptopyridine SAM on Au(1 1 1)

    Energy Technology Data Exchange (ETDEWEB)

    Manolova, M. [Institute of Electrochemistry, University of Ulm, 89069 Ulm (Germany); Kayser, M. [Institute of Electrochemistry, University of Ulm, 89069 Ulm (Germany); Kolb, D.M. [Institute of Electrochemistry, University of Ulm, 89069 Ulm (Germany)]. E-mail: dieter.kolb@uni-ulm.de; Boyen, H.-G. [Institute of Solid State Physics, University of Ulm, 89069 Ulm (Germany); Ziemann, P. [Institute of Solid State Physics, University of Ulm, 89069 Ulm (Germany); Mayer, D. [BASF Electronic Materials GmbH, 67056 Ludwigshafen (Germany); Wirth, A. [BASF Electronic Materials GmbH, 67056 Ludwigshafen (Germany)

    2007-02-10

    The application of a recently developed method for the deposition of Pd and Pt on top of a SAM, has been successfully extended to Rh, thus proving the versatility of the new concept. Experimental evidence from cyclic voltammetry, in situ STM and ex situ X-ray photoemission spectroscopy is presented for the deposition of monoatomic high rhodium islands onto a 4-mercaptopyridine self-assembled monolayer on a Au(1 1 1) electrode. By repetitive complexation of the Rh ions to the ring-nitrogen and reduction in a Rh-ion free solution, an almost completely covered SAM is obtained. The consequences of making contacts for molecular electronics are briefly discussed.

  3. Rhodium mediated bond activation: from synthesis to catalysis

    Energy Technology Data Exchange (ETDEWEB)

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

    2012-01-01

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

  4. Monodisperse Platinum and Rhodium Nanoparticles as Model Heterogeneous Catalysts

    Energy Technology Data Exchange (ETDEWEB)

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

    2008-09-01

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

  5. A comparison of chromium sesquioxide and [51Cr]chromic chloride as inert markers in calcium balance studies.

    Science.gov (United States)

    Hesp, R; Williams, D; Rinsler, M; Reeve, J

    1979-07-01

    1. Chromium sesquioxide (Cr2O3; 1.5 g/day) and [51Cr]chromic chloride [51CrCl3 (0.3 muCi/day)] were compared as continuously administered non-absorbed markers for the correction of faecal recoveries in 14 calcium balance studies each lasting at least 18 days. 2. The mean recoveries of each, 98.4% for Cr2O3 and 101.9% for 51CrCl3, were not significantly different from 100%. 3. The two markers reduced the uncertainity in a typical 3 x 6 day calcium balance study to a similar extent (SD = 1.4 mmol/day for Cr2O3 and SD = 1.5 mmol/day for 51CrCl3. 4. 51CrCl3 is a convenient and satisfactorily alternative to Cr2O3 when the laboratory hazards associated with estimating the latter cannot easily be eliminated.

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

    Science.gov (United States)

    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

  7. X-ray photoelectron spectroscopy as a probe of the interaction between rhodium acetate and ionic liquids

    Science.gov (United States)

    Men, Shuang; Jiang, Jing

    2016-02-01

    X-ray photoelectron spectroscopy (XPS) is used as a probe of the interaction between rhodium acetate ([Rh2(OAc)4]) and ionic liquids. Due to the impact of the anion of ionic liquids on the electronic environment of the rhodium centre, the measured Rh 3d binding energies of [Rh2(OAc)4] dissolved in a series of ionic liquids were found to decrease along with the increasing of the basicity of anions. The reduction of Rh(II) to Rh(0) in 1-octyl-3methylimidazolium acetate ([C8C1Im][OAc]) under UHV condition was monitored by XPS. The intensity of the new formed metallic Rh(0) peak was found increased along with time. The surface enrichment of the new formed Rh(0) species in the system was also concluded.

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

    Energy Technology Data Exchange (ETDEWEB)

    Mauro, Marcella [University of Trieste, Clinical Unit of Occupational Medicine, Department of Medical Sciences (Italy); Crosera, Matteo; Bianco, Carlotta; Adami, Gianpiero; Montini, Tiziano; Fornasiero, Paolo [University of Trieste, Department of Chemical and Pharmaceutical Sciences (Italy); Jaganjac, Morana [Rudjer Boskovic Institute, Laboratory for Oxidative Stress, Department of Molecular Medicine (Croatia); Bovenzi, Massimo; Filon, Francesca Larese, E-mail: larese@units.it [University of Trieste, Clinical Unit of Occupational Medicine, Department of Medical Sciences (Italy)

    2015-06-15

    The aim of the study was to evaluate percutaneous penetration of platinum and rhodium nanoparticles (PtNPs: 5.8 ± 0.9 nm, RhNPs: 5.3 ± 1.9 nm) through human skin. Salts compounds of these metals are sensitizers and some also carcinogenic agents. In vitro permeation experiments were performed using Franz diffusion cells with intact and damaged skin. PtNPs and RhNPs, stabilized with polyvinylpyrrolidone, were synthesized by reduction of Na{sub 2}PtC{sub l6} and RhCl{sub 3}·3H{sub 2}O respectively. Suspensions with a concentration of 2.0 g/L of PtNPs and RhNPs were dispersed separately in synthetic sweat at pH 4.5 and applied as donor phases to the outer surface of the skin for 24 h. Measurements of the content of the metals in the receiving solution and in the skin were performed subsequently. Rhodium skin permeation was demonstrated through damaged skin, with a permeation flux of 0.04 ± 0.04 μg cm{sup −2} h{sup −1} and a lag time of 7.9 ± 1.1 h, while no traces of platinum were found in receiving solutions. Platinum and rhodium skin-analysis showed significantly higher concentrations of the metals in damaged skin. Rh and Pt applied as NPs can penetrate the skin barrier and Rh can be found in receiving solutions. These experiments pointed out the need for skin contamination prevention, since even a minor injury to the skin barrier can significantly increase penetration.

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

    Science.gov (United States)

    Hung, Chang-Mao

    2009-04-15

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

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

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    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.

  12. Rhodium catalyzed asymmetric Pauson-Khand reaction using SDP ligands

    Institute of Scientific and Technical Information of China (English)

    2006-01-01

    The activity and enantiocontrol ability of the chiral catalysts prepared from spiro diphosphine ligands, SDP, and rhodium precursor were investigated in the asymmetric catalytic Pauson-Khand reaction. The results showed that SDP ligands were very effective in Rh-catalyzed Pauson-Khand reaction, and their complexes with rhodium could convert a variety of 1,6-enyne compounds into bicyclopentone derivatives under CO atmosphere in high yields with good enantioselectivities. The SbF6- was found to be a suitable counter anion of the catalyst, and 1,2-dichloroethane was the best choice of the solvent for Pauson-Khand reaction.

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

    Science.gov (United States)

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

    2010-08-01

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

  14. Tris-(1,3-diaryltriazenide) complexes of rhodium - Synthesis, structure and, spectral and electrochemical properties

    Indian Academy of Sciences (India)

    Chhandasi Guharoy; Michael G B Drew; Samaresh Bhattacharya

    2009-05-01

    Reaction of 1,3-diaryltriazenes (abbreviated in general as HL-R, where R stands for the para-substituent in the aryl fragment and H stands for the dissociable hydrogen atom, R = OCH3, CH3, H, Cl, NO2) with [Rh(PPh3)2(CO)Cl] in ethanol in the presence of NEt3 produces a series of trisdiaryltriazenide complexes of rhodium of type [Rh(L-R)3], where the triazenes are coordinated to rhodium as monoanionic, bidentate N,N-donors. Structure of the [Rh(L-OCH3)3] complex has been determined by X-ray crystallography. The complexes are diamagnetic, and show characteristic 1H NMR signals and intense MLCT transitions in the visible region. They also fluoresce in the visible region under ambient condition while excited at around 400 nm. Cyclic voltammetry on these complexes shows a Rh(III)-Rh(IV) oxidation (within 0.84-1.67 V vs SCE), followed by an oxidation of the coordinated triazene ligand (except the R = NO2 complex). An irreversible reduction of the coordinated triazene is also observed for all the complexes below -1.03 V vs SCE.

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

    Science.gov (United States)

    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.

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

    Science.gov (United States)

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

    2014-12-01

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

  17. Rhodium catalyzed arylation of diazo compounds with aryl boronic acids.

    Science.gov (United States)

    Ghorai, Jayanta; Anbarasan, Pazhamalai

    2015-04-03

    A general and efficient synthesis of diarylacetate, a diarylmethine derivative, was accomplished through rhodium catalyzed direct arylation of diazo compounds with arylboronic acids. The reaction tolerates various boronic acid derivatives and functional groups. Notably, chemoselective arylation of diazo compounds over other electrophiles were demonstrated. The efficacy of the developed methodology is shown by the expeditious synthesis of the core structure of diclofensine.

  18. Electronic and magnetic properties of small rhodium clusters

    Energy Technology Data Exchange (ETDEWEB)

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

    2015-04-24

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

  19. Dimethylammonium hexanoate stabilized rhodium(0) nanoclusters identified as true heterogeneous catalysts with the highest observed activity in the dehydrogenation of dimethylamine-borane.

    Science.gov (United States)

    Zahmakiran, Mehmet; Ozkar, Saim

    2009-09-21

    Herein we report the discovery of a superior dimethylamine-borane dehydrogenation catalyst, more active than the prior best heterogeneous catalyst (Jaska, C. A.; Manners, I. J. Am. Chem. Soc. 2004, 126, 9776) reported to date for the dehydrogenation of dimethylamine-borane. The new catalyst system consists of rhodium(0) nanoclusters stabilized by C(5)H(11)COO(-) anions and Me(2)H(2)N(+) cations and can reproducibly be formed from the reduction of rhodium(II) hexanoate during dehydrogenation of dimethylamine-borane at room temperature. Rhodium(0) nanoclusters in an average particle size of 1.9 +/- 0.6 nm Rh(0)(approximately 190) nanoclusters) provide 1040 turnovers over 26 h with a record initial turnover frequency (TOF) of 60 h(-1) (the average TOF value is 40 h(-1)) in the dehydrogenation of dimethylamine-borane, yielding 100% of the cyclic product (Me(2)NBH(2))(2) at room temperature. The work reported here also includes the full experimental details of the following major components: (i) Characterization of dimethylammonium hexanoate stabilized rhodium(0) nanoclusters by using TEM, STEM, EDX, XRD, UV-vis, XPS, FTIR, (1)H, (13)C, and (11)B NMR spectroscopy, and elemental analysis. (ii) Collection of a wealth of previously unavailable kinetic data to determine the rate law and activation parameters for catalytic dehydrogenation of dimethylamine-borane. (iii) Monitoring of the formation kinetics of the rhodium(0) nanoclusters by a fast dimethylamine-borane dehydrogenation catalytic reporter reaction (Watzky, M. A.; Finke, R. G. J. Am. Chem. Soc. 1997, 119, 10382) at various [Me(2)NH.BH(3)]/[Rh] ratios and temperatures. Significantly, sigmoidal kinetics of catalyst formation was found to be well fit to the two-step, slow nucleation and then autocatalytic surface growth mechanism, A --> B (rate constant k(1)) and A + B --> 2B (rate constant k(2)), in which A is [Rh(C(5)H(11)CO(2))(2)](2) and B is the growing, catalytically active rhodium(0) nanoclusters. (iv) Mercury

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

    Science.gov (United States)

    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.

  1. Thermo-analytical investigations on the superoxides AO{sub 2} (A = K, Rb, Cs), revealing facile access to sesquioxides A{sub 4}O{sub 6}

    Energy Technology Data Exchange (ETDEWEB)

    Merz, Patrick; Schmidt, Marcus; Felser, Claudia [Max-Planck-Institut fuer Chemische Physik fester Stoffe, Dresden (Germany); Jansen, Martin [Max-Planck-Institut fuer Chemische Physik fester Stoffe, Dresden (Germany); Max-Planck-Institut fuer Festkoerperforschung, Stuttgart (Germany)

    2017-04-18

    Rb{sub 4}O{sub 6} and Cs{sub 4}O{sub 6} represent open shell p electron systems, featuring charge, spin, orbital and structural degrees of freedom, which makes them unique candidates for studying the ordering processes related, otherwise exclusively encountered in transition metal based materials. Probing the physical responses has been restrained by the intricacy of synthesizing appropriate amounts of phase pure samples. Tracing the thermal decomposition of respective superoxides has revealed that at least the rubidium and cesium sesquioxides exist in thermodynamic equilibrium, appropriate p-T conditions given. These insights have paved the way to highly efficient and convenient access to Rb{sub 4}O{sub 6} and Cs{sub 4}O{sub 6}. (copyright 2017 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  2. Plasmonics in the UV range with Rhodium nanocubes

    Science.gov (United States)

    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.

  3. Scalar Relativistic Study of the Structure of Rhodium Acetate

    Directory of Open Access Journals (Sweden)

    Emily E. Edwards

    2004-01-01

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

  4. The Isomerization of Allylrhodium Intermediates in the Rhodium-Catalyzed Nucleophilic Allylation of Cyclic Imines**

    Science.gov (United States)

    Hepburn, Hamish B; Lam, Hon Wai

    2014-01-01

    Allylrhodium species generated from potassium allyltrifluoroborates can undergo isomerization by 1,4-rhodium(I) migration to give more complex isomers, which then react with cyclic imines to provide products with up to three new stereochemical elements. High enantioselectivities are obtained using chiral diene–rhodium complexes. PMID:25205604

  5. Rhodium-catalysed arylative annulation of 1,4-enynes with arylboronic acids.

    Science.gov (United States)

    Matsuda, Takanori; Watanuki, Shoichi

    2015-01-21

    The rhodium(I)-catalysed arylative annulation of 1,4-enynes with arylboronic acids was investigated. The reaction was found to proceed via an addition-1,4-rhodium migration-addition sequence, affording the corresponding 1,1-disubstituted 3-(arylmethylene)indanes.

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

    Directory of Open Access Journals (Sweden)

    Maria Michela Dell’Anna

    2010-05-01

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

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

    DEFF Research Database (Denmark)

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

    2010-01-01

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

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

    Science.gov (United States)

    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.

  9. H{sub 2} production from CH{sub 4} decomposition: Regeneration capability and performance of nickel and rhodium oxide catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Rivas, M.E.; Fierro, J.L.G. [Instituto de Catalisis y Petroleoquimica, CSIC, Marie Curie n 2, Cantoblanco, 28049 Madrid (Spain); Hori, C.E. [Faculdade de Engenharia Quimica, Universidade Federal de Uberlandia, Av. Joao Naves de Avila 2121, Campus Santa Monica, Bloco 1K, 38400-902 Uberlandia, MG (Brazil); Goldwasser, M.R. [Centro de Catalisis Petroleo y Petroquimica, Escuela de Quimica, Facultad de Ciencias, Universidad Central de Venezuela, Apartado 47102, Los Chaguaramos, Caracas (Venezuela); Griboval-Constant, A. [Unite de Catalyse et Chimie du Solide, UMR CNRS 8181, U.S.T.L., Batiment C3, 59655, Villeneuve D' Ascq, Cedex (France)

    2008-09-15

    Nickel-lanthanum (LaNiO{sub 3}) and nickel-rhodium-lanthanum (LaNi{sub 0.95}Rh{sub 0.05}O{sub 3}) perovskite-type oxide precursors were synthesized by different methodologies (co-precipitation, sol-gel and impregnation). They were reduced in an H{sub 2} atmosphere to produce nickel and rhodium nanoparticles on the La{sub 2}O{sub 3} substrate. All samples were tested in the catalytic decomposition of CH{sub 4}. Methane decomposed into carbon and H{sub 2} at reaction temperatures as low as 450 C - no other reaction products were observed. Conversions were in the range of 14-28%, and LaNi{sub 0.95}Rh{sub 0.05}O{sub 3} synthesized by co-precipitation was the most active catalyst. All catalysts maintained sustained activity even after massive carbon deposition indicating that these deposits are of the nanotube-type, as confirmed by transmission electron microscopy (TEM). The reaction seems to occur in a way that a nickel or rhodium crystal face is always clean enough to expose sufficient active sites to make the catalytic process continue. The samples were subjected to a reduction-oxidation-reduction cycle and in situ analyses confirmed the stability of the perovskite structure. All diffraction patterns showed a phase change around 400 C, due to reduction of LaNiO{sub 3} to an intermediate La{sub 2}Ni{sub 2}O{sub 5} structure. When the reduction temperatures reach 600 C, this structure collapses through the formation of Ni{sup 0} crystallites deposited on the La{sub 2}O{sub 3}. Under oxidative conditions, the perovskite system is recomposed with nickel re-entering the LaNiO{sub 3} framework structure accounting for the regenerative capability of these solids. (author)

  10. 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.

    Science.gov (United States)

    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.

  11. Improving the Quality of Thermocouple Wire Made of Platinum-rhodium Alloys

    Institute of Scientific and Technical Information of China (English)

    HORIKOV P.A.; MAMONOV S.N.; EFIMOV V.N.; RADKIN A.N.; DROZDOV D.E.

    2012-01-01

    For the manufacture of S-type thermocouple the so-called thermocouple wire of platinum and platinum-rhodium alloy is used.One of the main technical requirements for the quality of the wire,according to State Standard of Russia (GOST 10821),is the uniformity of its largest thermoelectric force (Thermo-emf) in the length different sections.It was found that a determining impact on the uniformity of the wire thermo-emf is the distribution of rhodium along the length of the wire.The impact of platinum- rhodium melt crystallization conditions on the inhomogeneity of wire manufactured from it.It was suggested that the chemical inhomogeneity of the wire is related to the liquation phase of platinum-rhodium alloy.

  12. Hydroaminomethylation of 1-Dodecene Catalyzed by Water-soluble Rhodium Complex

    Institute of Scientific and Technical Information of China (English)

    Ying Yong WANG; Mei Ming LUO; Yao Zhong LI; Hua CHEN; Xian Jun LI

    2004-01-01

    The hydroaminomethylation of 1-dodecene catalyzed by water soluble rhodium complex RhCl(CO)(TPPTS)2 in the presence of surfactant CTAB was investigated. High reactivity and selectivity for tertiary amine were achieved under relatively mild conditions.

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

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    2015-01-05

    AFRL-OSR-VA-TR-2015-0023 (NII) - Local Electric Field Effects on Rhodium-Porphyrin and NHC- Gold Catalysts MATTHEW KANAN LELAND STANFORD JUNIOR UNIV...Effects on Rhodium-Porphyrin and NHC- Gold Catalysts Principal Investigator: Matthew W. Kanan Project Publications: 1. “An Electric Field–Induced Change...electrostatic effects on catalytic reactions, a novel reaction vessel called the “parallel plate cell” was designed and fabricated. The cell is composed

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

    Directory of Open Access Journals (Sweden)

    Teruyuki Kondo

    2010-06-01

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

  16. Rhodium-Catalyzed Acyloxy Migration of Propargylic Esters in Cycloadditions, Inspiration from Recent “Gold Rush”

    Science.gov (United States)

    Shu, Xing-Zhong; Shu, Dongxu; Schienebeck, Casi M.

    2012-01-01

    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. PMID:22895533

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2012-07-01

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

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

    Science.gov (United States)

    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.

  19. Crystal structure of monoclinic samarium and cubic europium sesquioxides and bound coherent neutron scattering lengths of the isotopes {sup 154}Sm and {sup 153}Eu

    Energy Technology Data Exchange (ETDEWEB)

    Kohlmann, Holger [Leipzig Univ. (Germany). Inst. of Inorganic Chemistry; Hein, Christina; Kautenburger, Ralf [Saarland Univ., Saarbruecken (Germany). Inorganic Solid State Chemistry; Hansen, Thomas C.; Ritter, Clemens [Institut Laue-Langevin, Grenoble (France); Doyle, Stephen [Karlsruhe Institute of Technology, Eggenstein-Leopoldshafen (Germany). Inst. for Synchrotron Radiation (ISS)

    2016-11-01

    The crystal structures of monoclinic samarium and cubic europium sesquioxide, Sm{sub 2}O{sub 3} and Eu{sub 2}O{sub 3}, were reinvestigated by powder diffraction methods (laboratory X-ray, synchrotron, neutron). Rietveld analysis yields more precise structural parameters than previously known, especially for oxygen atoms. Interatomic distances d(Sm-O) in Sm{sub 2}O{sub 3} range from 226.3(4) to 275.9(2) pm [average 241.6(3) pm] for the monoclinic B type Sm{sub 2}O{sub 3} [space group C2/m, a = 1418.04(3) pm, b = 362.660(7) pm, c = 885.48(2) pm, β = 100.028(1) ], d(Eu-O) in Eu{sub 2}O{sub 3} from 229.9(2) to 238.8(2) pm for the cubic bixbyite (C) type [space group Ia anti 3, a = 1086.87(1) pm]. Neutron diffraction at 50 K and 2 K did not show any sign for magnetic ordering in Sm{sub 2}O{sub 3}. Isotopically enriched {sup 154}Sm{sub 2}O{sub 3} and {sup 153}Eu{sub 2}O{sub 3} were used for the neutron diffraction work because of the enormous absorption cross section of the natural isotopic mixtures for thermal neutrons. The isotopic purity was determined by inductively coupled plasma - mass spectrometry to be 98.9% for {sup 154}Sm and 99.8% for {sup 153}Eu. Advanced analysis of the neutron diffraction data suggest that the bound coherent scattering lengths of {sup 154}Sm and {sup 153}Eu need to be revised. We tentatively propose b{sub c}({sup 154}Sm) = 8.97(6) fm and b{sub c}({sup 153}Eu) = 8.85(3) fm for a neutron wavelength of 186.6 pm to be better values for these isotopes, showing up to 8% deviation from accepted literature values. It is shown that inaccurate scattering lengths may result in severe problems in crystal structure refinements causing erroneous structural details such as occupation parameters, which might be critically linked to physical properties like superconductivity in multinary oxides.

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

    Energy Technology Data Exchange (ETDEWEB)

    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.

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

    Science.gov (United States)

    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.

  2. Preparation of association compound between rhodium(II) citrate and β-cyclodextrin

    OpenAIRE

    Burgos, Ana E; Coco K. Y. A. Okio; Sinisterra, Rubén D.

    2012-01-01

    Inclusion compound of rhodium(II) citrate with β-cyclodextrin in a 1:1 molar ratio was prepared using freeze-drying method. X-ray diffactometry, thermal analysis (TG/DTG/DSC), infrared and ¹H-NMR with ¹H spin lattice relaxation (¹H T1) measurements and 13C techniques were used to characterize the system prepared. The results indicated the formation of inclusion or association compounds between rhodium(II) citrate and β-cyclodextrin.

  3. Preparation of association compound between rhodium(II citrate and β-cyclodextrin

    Directory of Open Access Journals (Sweden)

    Ana E. Burgos

    2012-01-01

    Full Text Available Inclusion compound of rhodium(II citrate with β-cyclodextrin in a 1:1 molar ratio was prepared using freeze-drying method. X-ray diffactometry, thermal analysis (TG/DTG/DSC, infrared and ¹H-NMR with ¹H spin lattice relaxation (¹H T1 measurements and 13C techniques were used to characterize the system prepared. The results indicated the formation of inclusion or association compounds between rhodium(II citrate and β-cyclodextrin.

  4. SYNTHESIS AND CATALYTIC HYDROSILYLATION PROPERTY OF POLYSILOXANE-SUPPORTED MERCAPTOSELENAETHER PLATINUM OR RHODIUM COMPLEX

    Institute of Scientific and Technical Information of China (English)

    1998-01-01

    Silica-bound mercaptoselenaether-containing silsesquioxane and its platinum or rhodium complex were synthesized from γ-(2,3-epithiopropyl) propyltrimethoxysilane via ring-opening reaction with bis(2-hydroxyethyl) selenide, followed by hydrolysis and immobilization on fumed silica, and then reacting with potassium chloroplatinite or rhodium chloride in acetone under nitrogen atmosphere. It was found that two noble metal complexes can catalyze the hydrosilylation of olefins with triethoxysilane effectively. The influences of temperature, the amount of complex used, the nature of olefin on catalytic activity were investigated.

  5. SYNTHESIS AND CATALYTIC BEHAVIOR OF POLYSILOXANE-SUPPORTED FULLERENE PLATINUM OR RHODIUM COMPLEXES

    Institute of Scientific and Technical Information of China (English)

    Peng-fei Fang; Yuan-yin Chen; Shu-ling Gong; Lei Guo; Qiu-sheng Lu; Ling Zhu

    1999-01-01

    Two polysiloxanes with pendant fullerene moieties and their platinum or rhodium complexes have been prepared from C60 via amination with ω-decenylamine, followed by hydrosilylation with triethoxysilane and immobilization on fumed silica or by hydrosilylation with methyldichlorosilane and polycondensation with polydimethylsiloxanol, and then by reacting them with potassium chloroplatinite or rhodium chloride in acetone respectively under argon atmosphere. It was found that the four noble metal complexes are effective catalysts for the hydrosilylation of olefins with triethoxysilane. The regioselectivity of platinum complexes for styrene increases remarkably by introducing C60 moiety. Factors influencing catalytic activity and the mechanism have been investigated.

  6. Improvement on stability of square planar rhodium (Ⅰ) complexes for carbonylation of methanol to acetic acid

    Institute of Scientific and Technical Information of China (English)

    蒋华; 潘平来; 袁国卿; 陈新滋

    1999-01-01

    A series of square planar cis-dicarbonyl polymer coordinated rhodium complexes with uncoordinated donors near the central rhodium atoms for carbonylation of methanol to acetic acid are reported. Data of IR, XPS and thermal analysis show that these complexes are very stable. The intramolecular substitution reaction is proposed for their high stability. These complexes show excellent catalytic activity, selectivity and less erosion to the equipment for the methanol carbonylation to acetic acid. The distillation process may be used instead of flash vaporization in the manufacture of acetic acid, which reduces the investment on the equipment.

  7. Electrochemical study of {beta}-diketonatobis(triphenylphosphite)rhodium(I) complexes

    Energy Technology Data Exchange (ETDEWEB)

    Erasmus, Johannes J.C. [Department of Chemistry, PO Box 339, University of the Free State, Bloemfontein 9300 (South Africa); Conradie, Jeanet, E-mail: conradj@ufs.ac.z [Department of Chemistry, PO Box 339, University of the Free State, Bloemfontein 9300 (South Africa)

    2011-10-30

    Highlights: > Rh(I) is electrochemically irreversible oxidized to Rh(III) in [Rh(RCOCHCOR')(P(OPh){sub 3}){sub 2}]. > Oxidation potentials E{sub pa}(Rh) and kinetic oxidative addition rate constants relate linearly. > Hammett {sigma} values, group electronegativities and the Lever ligand parameter relate to E{sub pa}(Rh). - Abstract: The electrochemical behaviour of the series of ten [Rh(RCOCHCOR')(P(OPh){sub 3}){sub 2}] complexes with R, R' = CF{sub 3}, CF{sub 3} (1), CF{sub 3}, CH{sub 3} (2), CF{sub 3}, Ph (C{sub 6}H{sub 5}) (3), CF{sub 3}, Fc (ferrocenyl = (C{sub 5}H{sub 5})Fe(C{sub 5}H{sub 4})) (4), CH{sub 3}, Ph (5), CH{sub 3}, CH{sub 3} (6), Ph, Ph (7), Fc, CH{sub 3} (8), Fc, Ph (9) and Fc, Fc (10) were studied in acetonitrile containing 0.100 mol dm{sup -3} tetra-n-butylammonium hexafluorophosphate as supporting electrolyte utilizing a glassy carbon working electrode. Results are consistent with Rh(I) being first oxidized in an electrochemically irreversible two-electron transfer process at peak anodic potentials ranging E{sub pa}(Rh) = 0.124-0.881 V vs. Fc/Fc{sup +}. For the ferrocene-containing complexes (4), and (8)-(10) the rhodium oxidation was followed by the electrochemically reversible oxidation of the ferrocenyl group in a one-electron transfer process at a slightly more positive potential. Relationships were established between the electrochemical quantity E{sub pa}(Rh) and kinetic parameter log k{sub 2} as well the sum of experimental group electronegativities (Gordy Scale) of the R and R' groups ({chi}{sub R} + {chi}{sub R'}), the Hammett {sigma} values ({sigma}{sub R} + {sigma}{sub R'}) and the Lever ligand parameter E{sub L} for the [Rh(RCOCHCOR')(P(OPh){sub 3}){sub 2}] complexes: E{sub pa}(Rh) (vs. Fc/Fc{sup +}/V) = 0.31 ({chi}{sub R} + {chi}{sub R'})-1.09 = 0.56 ({sigma}{sub R} + {sigma}{sub R'}) + 0.28 = S{sub M} ({Sigma}E{sub L}) + (I{sub M} - 0.66 V) = -0.23 log k{sub 2} - 0.03 (k{sub 2

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

    Science.gov (United States)

    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.

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

    Energy Technology Data Exchange (ETDEWEB)

    Favre, F.

    2000-10-26

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

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

    Directory of Open Access Journals (Sweden)

    Albert Khazan

    2008-07-01

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

  11. Monodentate phosphoramidites : A breakthrough in rhodium-catalysed asymmetric hydrogenation of olefins

    NARCIS (Netherlands)

    Berg, Michel van den; Minnaard, Adriaan J.; Haak, Robert M.; Leeman, Michel; Schudde, Ebe P.; Meetsma, Auke; de Vries, Andre H.M.; Maljaars, C. Elizabeth P.; Willans, Charlotte E.; Hyett, David; Boogers, Jeroen A.F.; Henderickx, Hubertus; Feringa, Ben L.

    2003-01-01

    Monodentate phosphoramidites based on BINOL or substituted BINOL are excellent ligands for the rhodium-catalysed asymmetric hydrogenation of olefins. Very high enantioselectivities were obtained with MonoPhos (7a) the simplest member of this class, a ligand that is prepared in a single step from BIN

  12. Synergistic effects of hydrogen plasma exposure, pulsed laser heating and temperature on rhodium surfaces

    NARCIS (Netherlands)

    Marot, L.; De Temmerman, G.; Doerner, R. P.; Umstadter, K.; Wagner, R. S.; Mathys, D.; Duggelin, M.; Meyer, E.

    2013-01-01

    The combined effect of hydrogen plasma exposure and surface heating, either continuous or by short laser pulses (5 ns), on the surface morphology of rhodium layers has been studied. Investigations were performed by reflectivity measurements, scanning electron microscopy (SEM), X-ray

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

    Science.gov (United States)

    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.

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

    NARCIS (Netherlands)

    Rong, Mark K.; Van Duin, Koen; Van Dijk, Tom; De Pater, Jeroen J.M.; Deelman, Berth Jan; Nieger, Martin; Ehlers, A. W.; Slootweg, J. Chris; Lammertsma, Koop

    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

  15. Regio- and Diasteroselectivity of Rhodium-catalyzed Ring Opening Reaction of Oxabenzonorbornadienes with Heteroatom Nucleophiles

    Institute of Scientific and Technical Information of China (English)

    2003-01-01

    A new rhodium catalyzed ring opening reaction of oxabenzonorbornadienes and its derivatives was described. This reaction forms a new carbon-nitrogen bond via an intermolecular allylic displacement of the bridgehead oxygen with a piperazine's derivatives, which proceeds with very high regioselectivity.

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

    DEFF Research Database (Denmark)

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

    2000-01-01

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

  17. Diastereoselective Hydrogenation and Kinetic Resolution of Imines Using Rhodium/Diphosphine Catalyzed Hydrogenation.

    NARCIS (Netherlands)

    Lensink, Cornelis; Vries, Johannes G. de

    1993-01-01

    Kinetic resolution of racemic α-methylbenzyl amine can be achieved with 98% ee. of the remaining amine at 70% conversion using the Rhodium/2S,4S-BDPP catalyzed asymmetric hydrogenation of imines. The same catalyst will hydrogenate optically pure α-methylbenzyl amines with a diastereoselectivity of u

  18. A nordehydroabietyl amide-containing chiral diene for rhodium-catalysed asymmetric arylation to nitroolefins.

    Science.gov (United States)

    Li, Ruikun; Wen, Zhongqing; Wu, Na

    2016-11-29

    A highly enantioselective rhodium catalysed asymmetric arylation (RCAA) of nitroolefins with arylboronic acids is presented using a newly developed, C1-symmetric, non-covalent interacted, phellandrene derived, nordehydroabietyl amide-containing chiral diene under mild conditions. Stereoelectronic effects were studied, suggesting an activation of the bound substrate through the secondary amide as a hydrogen-bond donor.

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

    NARCIS (Netherlands)

    Belser, T; Stöhr, Meike; Pfaltz, A

    2005-01-01

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

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

    Science.gov (United States)

    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.

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

    NARCIS (Netherlands)

    Bijkerk, Lucas

    1937-01-01

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

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

    Science.gov (United States)

    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

  3. A new class of rhodium complexes containing free donor atoms and their intramolecular substitution reaction

    Institute of Scientific and Technical Information of China (English)

    JIANG, Hua; YUAN, Guo-Qing; ZHANG, Shu-Feng; PAN, Ping-Lai; DIAO, Kai-Sheng

    2000-01-01

    A new class of rhodium complexes with high catalytic activity as well as excellent stability, which was used as catalyst for carlbonylation of methanol to acetic acid, is reported. It con tains free donor (namely un-coordinated donor) atoms which enable to improve its stability by intramolecular substitution rearction. Its synthesis, characteristic and catalytic reaction were discussed here.

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

    Science.gov (United States)

    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.

  5. Cooperative dehydrogenation of N-heterocycles using a carbon nanotube-rhodium nanohybrid.

    Science.gov (United States)

    Jawale, Dhanaji V; Gravel, Edmond; Shah, Nimesh; Dauvois, Vincent; Li, Haiyan; Namboothiri, Irishi N N; Doris, Eric

    2015-05-04

    Rhodium nanoparticles were anchored on carbon nanotubes and the resulting nanohybrid was studied as co-catalyst, along with tert-butylcatechol, for the dehydrogenation of various N-heterocycles. The co-catalytic system operates in high yields, under the mildest conditions reported so far, and can be applied to a wide variety of secondary amine-containing scaffolds.

  6. Asymmetric Catalytic Hydrogenation Using Rhodium Diphosphinites Derived From D-glucose and D-mannitol

    Institute of Scientific and Technical Information of China (English)

    2000-01-01

    Three diphosphinites were synthesized for preparing rhodium-diphosphinite complexes. The complexes were used for asymmetric catalytic hydrogenation of amino acid precursor a -acetamidocinnamic acid and its methyl ester. With all complexes, D-amino acid is the most abundant product.

  7. Highly enantioselective rhodium-catalyzed conjugate addition of arylboronic acids to enones at room temperature

    NARCIS (Netherlands)

    Martina, SLX; Minnaard, AJ; Hessen, B; Feringa, BL; Martina, Sébastien L.X.; Feringa, Bernard

    2005-01-01

    The rhodium-phosphoramidite-catalyzed asymmetric conjugate addition of arylboronic acids to enones proceeds at room temperature using [Rh(OH)(cod)](2) or [RhCl(cod)](2)/KOH as stable and readily available catalyst precursors. (c) 2005 Published by Elsevier Ltd.

  8. Rhodium-doped barium titanate perovskite as a stable p-type semiconductor photocatalyst for hydrogen evolution under visible light.

    Science.gov (United States)

    Maeda, Kazuhiko

    2014-02-12

    Rhodium-doped barium titanate (BaTiO3:Rh) powder was prepared by the polymerized complex (PC) method, and the photocatalytic activity for H2 evolution from water was examined. BaTiO3 is a wide-gap n-type semiconductor having a band gap of 3.0 eV. Doping Rh species into the lattice of BaTiO3 resulted in the formation of new absorption bands in visible light region. Upon visible light (λ > 420 nm), BaTiO3:Rh modified with nanoparticulate Pt as a water reduction promoter was capable of producing H2 from water containing an electron donor such as methanol and iodide. The best material prepared by the PC method exhibited higher activity than that made by a conventional solid-state reaction method. Visible-light-driven Z-scheme water splitting was also accomplished using Pt/BaTiO3:Rh as a building block for H2 evolution in combination with PtOx-loaded WO3 as an O2 evolution photocatalyst in the presence of an IO3(-)/I(-) shuttle redox mediator. Photoelectrochemical analysis indicated that a porous BaTiO3:Rh electrode exhibited cathodic photoresponse due to water reduction in a neutral aqueous Na2SO4 solution upon visible light.

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

    Science.gov (United States)

    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.

  10. Effect of deuterium ion beam irradiation onto the mirror-like pulsed laser deposited thin films of rhodium

    Energy Technology Data Exchange (ETDEWEB)

    Mostako, A.T.T., E-mail: abu@iitg.ernet.in [Laser and Photonics Lab, Department of Physics, Indian Institute of Technology Guwahati, Guwahati 781039 (India); Khare, Alika [Laser and Photonics Lab, Department of Physics, Indian Institute of Technology Guwahati, Guwahati 781039 (India); Rao, C.V.S.; Vala, Sudhirsinh; Makwana, R.J.; Basu, T.K. [Neutronics Lab, Institute for Plasma Research, Bhat, Gandhinagar 382428 (India)

    2015-01-01

    Highlights: • Rh mirror like thin films are fabricated by PLD technique for FM application. • Rh thin film FMs are irradiated with 10, 20, and 30 keV D ion beam. • Effect of D ion beam irradiation on Rh FM’s reflectivity is investigated. - Abstract: The effect of deuterium ion beam irradiation on the reflectivity of mirror-like pulsed laser deposited (PLD) thin film of rhodium is reported. The deposition parameters; target-substrate distance and background helium gas pressure were optimized to obtain the good quality rhodium films, of higher thickness, oriented preferentially in (1 1 1) plane. The rhodium thin films deposited at optimum PLD parameters were exposed to 10, 20, and 30 keV deuterium ion beam. The changes in surface morphology and UV–Visible–FIR reflectivity of mirror-like rhodium thin films, as a function of energy of deuterium ion beam, after exposure are reported.

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

    Science.gov (United States)

    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).

  12. Stripping voltammetric determination of palladium, platinum and rhodium in freshwater and sediment samples from South African water resources

    CSIR Research Space (South Africa)

    Van der Horst, C

    2012-08-01

    Full Text Available of platinum (Pt2+), palladium (Pd2+) or rhodium (Rh2+) by means of adsorptive cathodic stripping voltammetry. Optimised experimental conditions included composition of the supporting electrolyte, complexing agent concentration, deposition potential, deposition...

  13. 铂铑合金在硅酸盐熔体中铂和铑损失的研究%Study on the Loss of Platinum and Rhodium in Silicate Melts of Platinum-Rhodium Alloy

    Institute of Scientific and Technical Information of China (English)

    金英杰; 李树屏; 杨志先

    2015-01-01

    Study of the loss of platinum and rhodium in silicate melts of platinum-rhodium alloy. At a certain temperature, platinum and rhodium were lose, and the loss of rhodium was 3.6~5 times of the amount of platium. And qualitative analysis the change of the section rhodium content of PtRh20 in long term use. As a result, the rhodium content was falled 30% to 50%.%研究了铂铑制品中铂和铑在硅酸恿熔体中的损失。发现了在一定温度下,铂和铑在硅酸恿熔体的作用下均会损失,其中铑损失量是铂损失量的3.6~5倍。并定性研究了PtRh20制品在长期使用后厚度方向上铑含量的变化,发现在使用18个月后PtRh20制品铑含量降低了30%~50%。

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

    Science.gov (United States)

    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. Dissolution Behavior of Rhodium in the Na2O-SiO2 and CaO-SiO2 Slags

    Science.gov (United States)

    Wiraseranee, Chompunoot; Okabe, Toru H.; Morita, Kazuki

    2013-06-01

    To understand the behavior of rhodium during its recovery process, the dissolution behaviors of rhodium in Na2O-SiO2 and in CaO-SiO2 slags at temperatures ranging from 1423 K to 1623 K (from 1150 °C to 1350 °C) and from 1773 K to 1873 K (from 1500 °C to 1600 °C), respectively, in an oxidizing atmosphere were investigated. The solubility of rhodium in the slags was found to increase with increasing oxygen partial pressure, temperature, and the basic oxide content. The correlation between the solubility of rhodium and the oxygen partial pressure suggested that rhodium dissolved into the slags as RhO1.5. The dissolution of rhodium was slightly endothermic: the enthalpy change of the dissolution of solid rhodium was determined to be 50 ± 10 kJ/mol for the 50(mass pct)Na2O-50SiO2; and 188 ± 94 kJ/mol for the 56(mass pct)CaO-44SiO2 slag systems. The increase in the solubility of rhodium with the basic oxide content indicated that rhodium exhibits acidic behavior in slags. The correlation between the solubility of rhodium and the sulfide capacity of the slags suggested that the ionic species of rhodium in slags is the rhodate ion, RhO{2/-}. The rhodate capacity of the slags was defined, and its application to estimate the possible rhodium content in various slag systems was proposed.

  16. Rhodium-catalyzed double [2 + 2 + 2] cycloaddition of 1,4-bis(diphenylphosphinoyl)buta-1,3-diyne with tethered diynes: a modular, highly versatile single-pot synthesis of NU-BIPHEP biaryl diphosphines.

    Science.gov (United States)

    Doherty, Simon; Knight, Julian G; Smyth, Catherine H; Harrington, Ross W; Clegg, William

    2007-11-08

    Rhodium-catalyzed double [2 + 2 + 2] cycloaddition of 1,4-bis(diphenylphosphinoyl)buta-1,3-diyne with tethered diynes provides a straightforward, single-pot procedure for the synthesis of a new class of tropos biaryl diphosphine, NU-BIPHEP. This methodology represents a significant improvement on existing multistep procedures. Enantiopure Lewis acid platinum complexes of these diphosphines are highly efficient catalysts for carbonyl-ene and Diels-Alder reactions, and ruthenium diphosphine-diamine complexes catalyze the asymmetric reduction of ketones to give ee's that rival those obtained with their BINAP counterpart.

  17. Ruthenium, osmium and rhodium complexes of polypyridyl ligands: Metal-promoted activities, stereochemical aspects and electrochemical properties

    Indian Academy of Sciences (India)

    Parimal Paul

    2002-08-01

    This article presents a brief overview of the reactions of 2,4,6-tris(2-pyridyl)-1,3,5-triazine (tptz) in presence of rhodium(III), ruthenium(II) and osmium(II) under various experimental conditions. Under certain experimental conditions tptz exhibits metal-assisted hydrolysis/hydroxylation at the triazine ring. However, synthetic methods have also been developed to prepare complexes with intact tptz. Molecular structures of some of the complexes, especially stereoisomers of the hydroxylated products, are established by single crystal X-ray studies. A critical analysis of all data suggests that the electron-withdrawing effect of the metal ion (L→M donation) is the predominant factor, rather than angular strain, that is responsible for metal-promoted reactivities. Electrochemical properties of all of these complexes have been investigated, Rh(III) complexes are excellent catalysts for electrocatalytic reduction of CO2, and dinuclear Ru(II) and Os(II) complexes exhibit strong electronic communication between the metal centres.

  18. Factors affecting the electrochemical regeneration of NADH by (2,2'-bipyridyl) (pentamethylcyclopentadienyl)-rhodium complexes: impact on their immobilization onto electrode surfaces.

    Science.gov (United States)

    Walcarius, Alain; Nasraoui, Rihab; Wang, Zhijie; Qu, Fengli; Urbanova, Veronika; Etienne, Mathieu; Göllü, Mehmet; Demir, Ayhan S; Gajdzik, Janine; Hempelmann, Rolf

    2011-08-01

    Complexes of the (2,2'-bipyridyl) (pentamethylcyclopentadienyl)-rhodium family ([Cp*Rh(bpy)Cl](+), which is actually hydrolyzed in the form of [Cp*Rh(bpy)H(2)O](2+) in aqueous medium) are suitable solution-phase mediators likely to regenerate nicotinamide cofactors associated to dehydrogenases involved in many biocatalytic applications. Their practical application as bioelectrocatalysts, e.g., in fine chemicals synthesis or biosensors, remains however restricted to their durable immobilization in an active form onto solid electrode surfaces. This paper reports some new observations on the electrocatalytic properties of this mediator towards NAD(+) reduction, notably the critical effect of pH and cofactor-to-mediator concentration ratio, and investigates the behavior of a series of ([Cp*Rh(bpy)Cl](+)) derivatives bearing various substituents on the bipyridine ligand in view of their subsequent integration in electrochemical bioreactors. It will be shown that such compounds containing S- or N- moieties (i.e., often used as precursors to functionalize electrode surfaces) lead to inactivation of the electrocatalyst because their interaction with the Rh center prevents the formation of the active rhodium hydride complex. It was thus necessary to find another strategy of immobilization, and we found that adsorption of [Cp*Rh(bpy)Cl](+) by π-stacking on single-walled carbon nanotubes is an effective mean to reach this goal, leading to efficient and stable catalytic responses for NAD(+) reduction. Preliminary electroenzymatic experiments in the presence of d-sorbitol dehydrogenase further point out the interest of this approach for bioelectrocatalysis purposes and provide the proof-of-concept for this immobilization strategy.

  19. Nanostructured rhodium films for advanced mirrors produced by Pulsed Laser Deposition

    Energy Technology Data Exchange (ETDEWEB)

    Uccello, A., E-mail: andrea.uccello@mail.polimi.it [Dipartimento di Energia, Politecnico di Milano, Milan (Italy); Dellasega, D., E-mail: david.dellasega@polimi.it [Dipartimento di Energia, Politecnico di Milano, Milan (Italy); Istituto di Fisica del Plasma, Consiglio Nazionale delle Ricerche, EURATOM-ENEA-CNR Association, Milan (Italy); Perissinotto, S., E-mail: stefano.perissinotto@iit.it [Center for Nano Science and Technology - Polimi, Istituto Italiano di Tecnologia, Milan (Italy); Lecis, N., E-mail: nora.lecis@polimi.it [Dipartimento di Meccanica, Politecnico di Milano, Milan (Italy); Passoni, M., E-mail: matteo.passoni@polimi.it [Dipartimento di Energia, Politecnico di Milano, Milan (Italy); Istituto di Fisica del Plasma, Consiglio Nazionale delle Ricerche, EURATOM-ENEA-CNR Association, Milan (Italy)

    2013-01-15

    In this paper advantages in the production by Pulsed Laser Deposition (PLD) of nanostructured, nanoengineered rhodium films to be used in tokamak First Mirrors (FMs) are shown. The peculiar PLD capability to tailor film structure at the nanoscale gives the possibility to deposit low roughness Rh films with a wide variety of structures and morphologies. By a proper movimentation of the substrate and using high fluence (10-19 J/cm{sup 2}) infrared laser pulses, it has been possible to deposit planar and homogeneous Rh films effectively suppressing surface defects on areas of the order of 10 cm{sup 2} with a satisfactory specular reflectivity. Multilayer deposition has been exploited to produce coatings with high adhesion and good mechanical properties. Finally, an estimation of the requirements to produce by PLD rhodium films suitable for the requests of ITER is provided.

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

    Science.gov (United States)

    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.

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

    Directory of Open Access Journals (Sweden)

    Espósito Breno P.

    2000-01-01

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

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

    Science.gov (United States)

    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.

  3. Modular construction of a porous organometallic network based on rhodium olefin complexation.

    Science.gov (United States)

    Stoeck, Ulrich; Nickerl, Georg; Burkhardt, Ulrich; Senkovska, Irena; Kaskel, Stefan

    2012-10-24

    We describe the rational design and synthesis of the first member of a new class of microporous materials. It is built from rhodium and a polyolefinic ligand featuring a rigid tetraphenylsilane backbone via metal olefin complexation, creating a truly organometallic network. The resulting framework, denoted as DUT-37 (Dresden University of Technology no. 37) exhibits considerable porosity and unprecedented stability under ambient conditions. Furthermore, it is catalytically active in transfer hydrogenation.

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

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    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. Fabrication and buckling behavior of polycrystalline palladium, cobalt, and rhodium nanostructures

    Energy Technology Data Exchange (ETDEWEB)

    Jahed, Zeinab [Department of Chemical Engineering, University of Waterloo, 200 University Avenue West, Waterloo, ON N2L 3G1 (Canada); Department of Mechanical and Mechatronics Engineering, University of Waterloo, 200 University Avenue West, Waterloo, ON N2L 3G1 (Canada); Jin, Sumin [Department of Chemical Engineering, University of Waterloo, 200 University Avenue West, Waterloo, ON N2L 3G1 (Canada); Waterloo Institute for Nanotechnology, University of Waterloo, 200 University Avenue West, Waterloo, ON N2L 3G1 (Canada); Burek, Michael J. [Waterloo Institute for Nanotechnology, University of Waterloo, 200 University Avenue West, Waterloo, ON N2L 3G1 (Canada); Tsui, Ting Y., E-mail: tttsui@uwaterloo.ca [Department of Chemical Engineering, University of Waterloo, 200 University Avenue West, Waterloo, ON N2L 3G1 (Canada); Department of Mechanical and Mechatronics Engineering, University of Waterloo, 200 University Avenue West, Waterloo, ON N2L 3G1 (Canada); Waterloo Institute for Nanotechnology, University of Waterloo, 200 University Avenue West, Waterloo, ON N2L 3G1 (Canada)

    2012-04-30

    Highlights: Black-Right-Pointing-Pointer Pd, Co, and Rh nano-pillars with diameter of {approx}130 nm were fabricated by using novel electron beam lithography and electroplating techniques. Black-Right-Pointing-Pointer Uniaxial compression load and displacement responses of the nanopillars were characterized. Black-Right-Pointing-Pointer Pd nano-pillars have the highest fracture toughness followed by Co and Rh pillars. Black-Right-Pointing-Pointer Tangent moduli of the three materials were extracted from the experimental results. - Abstract: Novel fabrication techniques were developed to manufacture polycrystalline palladium, cobalt, and rhodium nanopillars with diameters of approximately 130 nm. These nanostructures have length-to-radius ratios in the range of 4 and 20. Using uniaxial nano-compression techniques, the buckling behaviors of the produced nanopillars were characterized and critical buckling loads were extracted. The tangent moduli, which were extracted from plots of critical buckling load as a function of effective specimen cross-sectional area, of palladium, cobalt, and rhodium nanopillars are 90 {+-} 6 GPa, 175 {+-} 9 GPa, and 375 {+-} 23 GPa, respectively. As expected, these calculated values are slightly smaller than the bulk polycrystalline elastic moduli for all three materials. Post compression scanning electron microscope images revealed ductile behavior for palladium nanostructures, while cobalt and rhodium specimens failed by fracture.

  7. Rhodium-catalyzed [5 + 2 + 1] cycloaddition of ene-vinylcyclopropanes and CO: reaction design, development, application in natural product synthesis, and inspiration for developing new reactions for synthesis of eight-membered carbocycles.

    Science.gov (United States)

    Wang, Yi; Yu, Zhi-Xiang

    2015-08-18

    Practical syntheses of natural products and their analogues with eight-membered carbocyclic skeletons are important for medicinal and biological investigations. However, methods and strategies to construct the eight-membered carbocycles are limited. Therefore, developing new methods to synthesize the eight-membered carbocycles is highly desired. In this Account, we describe our development of three rhodium-catalyzed cycloadditions for the construction of the eight-membered carbocycles, which have great potential in addressing the challenges in the synthesis of medium-sized ring systems. The first reaction described in this Account is our computationally designed rhodium-catalyzed two-component [5 + 2 + 1] cycloaddition of ene-vinylcyclopropanes (ene-VCPs) and CO for the diastereoselective construction of bi- and tricyclic cyclooctenones. The design of this reaction is based on the hypothesis that the C(sp(3))-C(sp(3)) reductive elimination of the eight-membered rhodacycle intermediate generated from the rhodium-catalyzed cyclopropane cleavage and alkene insertion, giving Wender's [5 + 2] cycloadduct, is not easy. Under CO atmosphere, CO insertion may occur rapidly, converting the eight-membered rhodacycle into a nine-membered rhodacycle, which then undergoes an easy C(sp(2))-C(sp(3)) reductive elimination process and furnishes the [5 + 2 + 1] product. This hypothesis was supported by our preliminary DFT studies and also served as inspiration for the development of two [7 + 1] cycloadditions: the [7 + 1] cycloaddition of buta-1,3-dienylcyclopropanes (BDCPs) and CO for the construction of cyclooctadienones, and the benzo/[7 + 1] cycloaddition of cyclopropyl-benzocyclobutenes (CP-BCBs) and CO to synthesize the benzocyclooctenones. The efficiency of these rhodium-catalyzed cycloadditions can be revealed by the application in natural product synthesis. Two eight-membered ring-containing natural products, (±)-asterisca-3(15),6-diene and (+)-asteriscanolide, have been

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

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    Kassem, Mohammed A; Amin, Alaa S

    2015-02-01

    A new method to estimate rhodium in different samples at trace levels had been developed. Rhodium was complexed with 5-(4'-nitro-2',6'-dichlorophenylazo)-6-hydroxypyrimidine-2,4-dione (NDPHPD) as a complexing agent in an aqueous medium and concentrated by using Triton X-114 as a surfactant. The investigated rhodium complex was preconcentrated with cloud point extraction process using the nonionic surfactant Triton X-114 to extract rhodium complex from aqueous solutions at pH 4.75. After the phase separation at 50°C, the surfactant-rich phase was heated again at 100°C to remove water after decantation and the remaining phase was dissolved using 0.5mL of acetonitrile. Under optimum conditions, the calibration curve was linear for the concentration range of 0.5-75ngmL(-1) and the detection limit was 0.15ngmL(-1) of the original solution. The enhancement factor of 500 was achieved for 250mL 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.

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

    Science.gov (United States)

    Kassem, Mohammed A.; Amin, Alaa S.

    2015-02-01

    A new method to estimate rhodium in different samples at trace levels had been developed. Rhodium was complexed with 5-(4‧-nitro-2‧,6‧-dichlorophenylazo)-6-hydroxypyrimidine-2,4-dione (NDPHPD) as a complexing agent in an aqueous medium and concentrated by using Triton X-114 as a surfactant. The investigated rhodium complex was preconcentrated with cloud point extraction process using the nonionic surfactant Triton X-114 to extract rhodium complex from aqueous solutions at pH 4.75. After the phase separation at 50 °C, the surfactant-rich phase was heated again at 100 °C to remove water after decantation and the remaining phase was dissolved using 0.5 mL of acetonitrile. Under optimum conditions, the calibration curve was linear for the concentration range of 0.5-75 ng mL-1 and the detection limit was 0.15 ng mL-1 of the original solution. The enhancement factor of 500 was achieved for 250 mL samples containing the analyte and relative standard deviations were ⩽1.50%. The method was found to be highly selective, fairly sensitive, simple, rapid and economical and safely applied for rhodium determination in different complex materials such as synthetic mixture of alloys and environmental water samples.

  11. Effect of rhodium modification on structures of sulfiede Rh-Mo-K/Al2O3 catalysts studied by XAFS

    Institute of Scientific and Technical Information of China (English)

    1999-01-01

    Local structures of the molybdenum sulfide species in the sultided Rh-Mo-K/Al2O3 catalysts with various rhodium loadings have been investigated by XAFS.From the fitting results.the Mo-Mo coordination number for the sample free of rhodium(ca.3.7) is similar to that for the crystalline MoS2,indicating that the supported sulfided molybdenum species mainly present as large pateches of MoS2-like slabs.For the rhodium-modified samples,however,the amplitudes of the Mo-S and Mo-Mo coordination shells are sharply reduced,revealing a high dispersion of the MoS2-like species in the catalysts,The scheme of the microstructures of the sulfided molybdenum species stabilized on the alumina support is discussed based upon the analysis of the EXAFS data.

  12. Effect of Al2O3, MgO, and CuOx on the dissolution behavior of rhodium in the Na2O-SiO2 slags

    Directory of Open Access Journals (Sweden)

    Wiraseranee C.

    2013-01-01

    Full Text Available Aiming to optimize rhodium recovery in the high temperature recycling process by minimizing rhodium loss into slags in an oxidizing atmosphere by controlling slag composition, the effects of representative slag components, such as Al2O3, MgO, and CuOx, on the dissolution behavior of rhodium into the Na2O-SiO2 slags was investigated. The solubility of rhodium was measured by equilibrating the sodium silicate based slags with pure solid rhodium at 1473 K in air. Considering that rhodium dissolved into slags as RhO1.5, the effect of the oxide addition on the activity coefficient of RhO1.5 in slags was determined. The dissolution of rhodium in slags was suppressed by the addition of Al2O3 and MgO, where Al2O3 behaved as an acidic oxide and MgO behaved as a diluent of slag basicity at a fixed Na2O/SiO2 ratio of 0.97. The content of copper in solid rhodium equilibrated with the CuOx bearing slags slightly increased with increasing content of CuOx, and CuOx was found to slightly enhance the dissolution of rhodium. Rhodate capacity of all slag systems increased with increasing optical basicity, suggesting that the correlation between rhodate capacity and the optical basicity enables the estimation of the content of rhodium in slags of which thermodynamic properties of rhodium are not clarified.

  13. MCM-41-Supported Bidentate Phosphine Rhodium Complex: An Efficient and Recyclable Heterogeneous Catalyst for the Hydrosilylation of Olefins%MCM-41-Supported Bidentate Phosphine Rhodium Complex: An Efficient and Recyclable Heterogeneous Catalyst for the Hydrosilylation of Olefins

    Institute of Scientific and Technical Information of China (English)

    胡荣华; 郝文燕; 蔡明中

    2011-01-01

    MCM-41-supported bidentate phosphine rhodium complex (MCM-41-2P-RhC13) was conveniently synthesized from commercially available and cheap γ-aminopropyltriethoxysilane via immobilization on MCM-41, followed by reacting with diphenylphosphinomethanol and rhodium chloride. It was found that the title complex is a highly efficient catalyst for the hydrosilylation of olefins with triethoxysilane and can be recovered and recycled by a simple filtration of the reaction solution and used for at least 10 consecutive trials without any decreases in activity.

  14. Thermal diffusion of {sup 57}Co into rhodium matrix as a second step in preparing Moessbauer sources

    Energy Technology Data Exchange (ETDEWEB)

    Cieszykowska, Izabela; ZoLtowska, MaLgorzata [Institute of Atomic Energy Polatom, Radioisotope Centre, 05-400 Otwock-Swierk (Poland); Zachariasz, Piotr [Institute of Atomic Energy Polatom, Moessbauer Spectroscopy Lab, 05-400 Otwock-Swierk (Poland); Piasecki, Andrzej; Janiak, Tomasz [Institute of Atomic Energy Polatom, Radioisotope Centre, 05-400 Otwock-Swierk (Poland); Mielcarski, MieczysLaw, E-mail: m.mielcarski@polatom.pl [Institute of Atomic Energy Polatom, Radioisotope Centre, 05-400 Otwock-Swierk (Poland)

    2011-09-15

    Thermal diffusion of {sup 57}Co into rhodium matrix was studied. The diffusion degree was evaluated by Moessbauer spectroscopy with the use of {alpha}-Fe absorber. The influence of different annealing conditions was investigated. For a set of sources examined, smooth and rounded Lorentzian lines were observed. The main spectra parameters are fairly acceptable with respect to the typical obtainable values for {alpha}-Fe absorbers in Moessbauer spectroscopy. The results obtained confirm that the deposited {sup 57}Co diffused almost completely into rhodium matrix without substantial loss of the activity deposited.

  15. The mechanism for the rhodium-catalyzed decarbonylation of aldehydes: A combined experimental and theoretical study

    DEFF Research Database (Denmark)

    Fristrup, Peter; Kreis, Michael; Palmelund, Anders

    2008-01-01

    The mechanism for the rhodium-catalyzed decarbonylation of aldehydes was investigated by experimental techniques (Hammett studies and kinetic isotope effects) and extended by a computational study (DFT calculations). For both benzaldehyde and phenyl acetaldehyde derivatives, linear Hammett plots...... were obtained with positive slopes of +0.79 and +0.43, respectively, which indicate a buildup of negative charge in the selectivity-determining step. The kinetic isotope effects were similar for these substrates (1.73 and 1.77 for benzaldehyde and phenyl acetaldehyde, respectively), indicating...

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

    Science.gov (United States)

    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.

  17. Trans-Selective Rhodium Catalysed Conjugate Addition of Organoboron Reagents to Dihydropyranones

    Directory of Open Access Journals (Sweden)

    Hannah J. Edwards

    2015-04-01

    Full Text Available The selective synthesis of 2,6-trans-tetrahydropyran derivatives employing the rhodium catalysed addition of organoboron reagents to dihydropyranone templates, derived from a zinc-catalysed hetero-Diels-Alder reaction, is reported. The addition of both arylboronic acids and potassium alkenyltrifluoroborates have been accomplished in high yields using commercially-available [Rh(cod(OH]2 catalyst. The selective formation of the 2,6-trans-tetrahydropyran stereoisomer is consistent with a mechanism involving alkene association and carbometalation on the less hindered face of the dihydropyranone.

  18. Asymmetric Hydroformylation of Olefins Catalyzed by a Chiral Diphosphite-Rhodium Complex

    Institute of Scientific and Technical Information of China (English)

    YAN, Ming(鄢明); LI, Xing-Shu(黎星术); CHAN, Albert Sun-Chi(陈新滋)

    2004-01-01

    A C2-symmetrical aryl diphosphite derived from chiral binaphthol was prepared and its rhodium complex was used as catalysts in the asymmetric hydroformylation of olefins. High catalytic activity and good regioselectivity were observed. Up to 31.2% ee and 38.1% ee were achieved for the hydroformylation of 4-fluoro-styrene and vinyl acetate respectively. The influences of ligand-to-metal ratio, reaction temperature and the pressure of syn-gas on the enantioselectivity and regioselectivity were also studied.

  19. POLYMER—SUPPORTED RHODIUM CATALYSTS FOR CARBONYLATION OF METHYL ACETATE TO ACETIC ANHYDRIDE

    Institute of Scientific and Technical Information of China (English)

    CHENDean; HUANGShizhuan; 等

    1993-01-01

    Two kinds of rhodium catalysts supported on cross-linked styrene-divinylbenzene copolymers containing bipyridine or o-phenylene diamine have been prepared and found to display high activity for methyl acetate carbonylation to form acetic anhydride,the activities are even higher than their homogeneous counterparts. XPS analysis was used to characterize the synthetic catalysts.The apparent activation parameters were determined to be Eα=73.3KJ/mol,ΔH≠=66.3KJ/mol,ΔS≠=-28.6eu.These parameters are very close to those in methanol carbonylation and imply to have analogous mechanism in both cases.

  20. Composição química de alguns solos do estado de são paulo: III - Sesquióxidos, sílica e certas relações moleculares Chemical composition of some são paulo soils: III. Sesquioxides, silica and molecular valvues

    Directory of Open Access Journals (Sweden)

    F. da Costa Verdade

    1961-01-01

    Full Text Available A análise integral de alguns solos do Estado de São Paulo com origens petrográficas definidas, permitiu estabelecer a composição dos solos oriundos de diversas formações geológicas. A terra-roxa é o extremo de solos enriquecidos com sesquióxidos e de pouca sílica, enquanto os arenitos da Série de São Bento estão no extremo oposto, com altas porcentagens em sílica e baixa quantidade em sesquióxidos. Em alguns casos encontrou-se uma migração diferencial entre os sesquióxidos dentro do perfil, mas nas terras-roxas tal fenômeno não foi constatado. Para os solos derivados de diábase verifica-se maior lavagem de sódio que do potássio e dêste que do cálcio. O magnésio foi o mais retido dentre tôdas as bases. Na terra-roxa verifica-se grande perda de sílica, na meteorização, mas o regolito apresenta a mesma relação molecular, entre os sesquióxidos encontrado na rocha. No solo de granito o fenômeno ésimilar compequenas variações, destacando-se a de que a alumina parece ser retida mais firmemente que os óxidos de ferro.The chemical composition of our soils with established origins shows that the highest content of sesquioxides and the lowest of silica is found in soils derived form diabase. The soils from SERIE DE SÃO BENTO sandstones have the lowest content in sesquioxides and the highest in silica (sand. Several molecular and leaching values are presented. The soils from diabase show no differential migration or elimination from profile between aluminum and fron oxides. In some soils this fenomenon was found. The losses of silica and bases are produced in weathering of rocks ami the residual material is poor in bases for next losses In the diabase decomposition the losses decrease from Na, K, Ca to Mg. Comparing soils form i lie Amazon Valley with those of São Paulo, the most contrasting feature is normal occurence of ground-water laterite, sesquioxide sheet and pisolitics in the tonner. occurence. This

  1. The Studies of Rhodium-catalyzed Ring Opening Reaction of N-Boc azabenzonorbornadiene with Heteroatom Nucleophiles

    Institute of Scientific and Technical Information of China (English)

    Er Chang LIU; Ding Qiao YANG; Ying Feng HAN; Jian Xia DONG

    2006-01-01

    A rhodium-catalyzed ring opening reaction of N-Boc-azabenzonorbornadiene with heteroatom nucleophiles was described. Piperidine and piperazine's derivatives were nucleophiles in this reaction. The yields of the products 2a-f are good and the regioselectivity are excellent.

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

    Science.gov (United States)

    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).

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

    Science.gov (United States)

    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.

  4. Rhodium-catalyzed addition of arylboronic acids to isatins : An entry to diversity in 3-aryl-3-hydroxyoxindoles

    NARCIS (Netherlands)

    Toullec, Patrick Y.; Jagt, Richard B. C.; de Vries, Johannes G.; Feringa, Ben L.; Minnaard, Adriaan J.

    2006-01-01

    A general method for the catalytic 1,2-addition of aryl and alkenyl boronic acids to isatins is described using a rhodium(I)/triphenylphosphite catalyst. The application of this transformation allows the synthesis of a variety of 3-aryl-3-hydroxyoxindole building blocks in high yields. An enantiosel

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

    Science.gov (United States)

    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.

  6. The Rôle of the Element Rhodium in the Hyperbolic Law of the Periodic Table of Elements

    Directory of Open Access Journals (Sweden)

    Khazan A.

    2008-07-01

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

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

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    Rajaratnam, Rajathees; Martin, Elisabeth K; Dörr, Markus; Harms, Klaus; Casini, Angela; Meggers, Eric

    2015-08-17

    Controlling the relative and absolute configuration of octahedral metal complexes constitutes a key challenge that needs to be overcome in order to fully exploit the structural properties of octahedral metal complexes for applications in the fields of catalysis, materials sciences, and life sciences. Herein, we describe the application of a proline-based chiral tridentate ligand to decisively control the coordination mode of an octahedral rhodium(III) complex. We demonstrate the mirror-like relationship of synthesized enantiomers and differences between diastereomers. Further, we demonstrate, using the established pyridocarbazole pharmacophore ligand as part of the organometallic complexes, the importance of the relative and absolute stereochemistry at the metal toward chiral environments like protein kinases. Protein kinase profiling and inhibition data confirm that the proline-based enantiopure rhodium(III) complexes, despite having all of the same constitution, differ strongly in their selectivity properties despite their unmistakably mutual origin. Moreover, two exemplary compounds have been shown to induce different toxic effects in an ex vivo rat liver model.

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

    Science.gov (United States)

    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.

  10. IRC analysis of methanol carbonylation reaction catalyzed by rhodium complex

    Institute of Scientific and Technical Information of China (English)

    HAO Maorong; FENG Wenlin; JI Yongqiang; LEI Ming

    2004-01-01

    In the reaction cycle for methanol carbonylation catalyzed by Rh complex, the structure geometries of the reactant, intermediates, transition states and product of each elemental reaction have been studied by using the energy gradient method at HF/LANL2DZ level, and the changes of their potential profiles have also been calculated. Through IRC analyses of the transition states for each elemental reaction, it is confirmed that the various structure geometries obtained are stationary points on the cycle reaction pathway of methanol carbonylation catalyzed by Rh complex, and the changes are given in energies and structure geometries of the reactant molecules along the reaction pathway of lowest energy. It has been proposed that the geometrical conversions of intermediates play an important role during the cycle reaction. Through analyses of structure geometries, it has been suggested that, in addition to cis- and trans- structure exchange linkage of catalysis reactive species, the two pathways, cis- and trans-cata- lyzed cycle reactions, can also be linked through geometrical conversion of intermediates, of which the activation energy is 49.79 kJ/mol. Moreover, the reductive elimination elemental reaction may be neither cis-cycle nor trans- one, showing that the cycle reaction can be achieved through various pathways. However different the pathway, the oxidative addition elemental reaction of CH3I is the rate-controlling step.

  11. 1H MAS NMR characterization of hydrogen over silica-supported rhodium catalyst

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    Hydrogen species in both SiO2 and Rh/SiO2 catalysts pretreated indifferent atmospheres (H2, O2, helium or air) at different temperatures (773 or 973 K) were investigated by means of 1H MAS NMR. In SiO2 and O2-pretreated catalysts, a series of downfield signals at ~7.0, 3.8-4.0, 2.0 and 1.5-1.0 were detected. The first two signals can be attributed to strongly adsorbed and physisorbed water and the others to terminal silanol (SiOH) and SiOH under the screening of oxygen vacancies in SiO2 lattice, respectively. Besides the above signals, both upfield signal at ~-110 and downfield signals at 3.0 and 0.0 were also detected in H2-pretreated catalyst, respectively. The upfield signal at ~-110 originated from the dissociative adsorption of H2 over rhodium and was found to consist of both the contributions of reversible and irreversible hydrogen. There also probably existed another dissociatively adsorbed hydrogen over rhodium, which was known to be b hydrogen and in a unique form of "delocalized hydrogen". It was presumed that the b hydrogen had an upfield shift of ca. -20- -50, though its 1H NMR signals, which, having been masked by the spinning sidebands of Si-OH, failed to be directly detected out. The downfield signal at 3.0 was assigned to spillover hydrogen weakly bound by the bridge oxygen of SiO2. Another downfield signal at 0.0 was assigned to hydrogen held in the oxygen vacancies of SiO2 (Si-H species), suffering from the screening of trapped electrons. Both the spillover hydrogen and the Si-H resulted from the migration of the reversible hydrogen and the b hydrogen from rhodium to SiO2 in the close vicinity. It was proved that the above migration of hydrogen was preferred to occur at higher temperature than at lower temperature.

  12. Lanthanum oxide promoted rhodium/titania and rhodium-platinum/titania catalysts for alcohol formation from synthesis gas

    Energy Technology Data Exchange (ETDEWEB)

    Bond, G.C.; Richards, D.G.

    1986-12-15

    TiO/sub 2/-supported Rh and Rh-Pt catalysts have been studied for the selective formation of oxygenates from synthesis gas. The addition of La/sub 2/O/sub 3/ as a promoter significantly increased the C/sub 2/H/sub 5/OH selectivities and formation rates. Pt addition increased the overall activity and in combination with La/sub 2/O/sub 3/ led to higher alcohol selectivities of 25% compared with 6% for an unpromoted Rh catalyst. A pronounced induction period was observed for CH/sub 3/OH and C/sub 2/H/sub 5/OH formation, attributed to changes in the nature of the catalytically active sites. A simple theoretical model is used to illustrate the parallel trends in C/sub 2/H/sub 5/OH and hydrocarbon formation after the induction period. Temperature-programmed reduction showed that the La/sub 2/O/sub 3/ increased the stability of Rh oxide. The main role of La/sub 2/O/sub 3/ appears to be promotion of the formation of the C/sub 2/H/sub 5/OH precursor, while Pt increased the rate of hydrogenation. 26 refs., 8 figs., 3 tabs.

  13. Kinetics of benzene hydrogenation on supported platinum, palladium, rhodium and ruthenium catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Nakano, K.; Fueda, Y.; Kusunoiki, K.; Uchino, T.

    1982-10-01

    Although benzene hydrogenation has been widely utilized as a test reaction for the investigation of catalytic activity, the reaction mechanism has not been well elucidated. As to the Langmuir-Hinshelwood rate equations, there have been many reports for the reaction on nickel catalysts, but few papers have been published on platinum metal catalysts, especially on rhodium and ruthenium catalysts. In this communication, reaction rates were measured for benzene hydrogenation over commercially available Pt-, Pd-, Rh- and Ru-Al/sub 2/O/sub 3/ catalysts and the rate equation was derived. The thermodynamic consistency of the rate equation was then tested in the light of the rules established by Boudart et al. and Vannice et al.

  14. Complexation of diphenyl(phenylacetenyl)phosphine to rhodium(III) tetraphenyl porphyrins

    DEFF Research Database (Denmark)

    Stulz, Eugen; Scott, Sonya M; Bond, Andrew D

    2003-01-01

    ). The methylide on rhodium in 3 is not displaced, leading selectively to the mono-phosphine complex (DPAP)(Me)Rh(TPP) (5). The first and second association constants, as determined by isothermal titration calorimetry and UV-vis titrations, are in the range 10(4)-10(7) M(-1) (in CH(2)Cl(2)). Using LDI-TOF mass....... The largest values of DeltaG degrees are found for 6. The thermodynamic and UV-vis data reveal that the methylide and the phosphine ligand have an almost identical electronic trans-influence on the sixth ligand....... spectrometry, the mono-phosphine complexes can be detected but not the bis-phosphine complexes. The electronic spectrum of 4 is similar to those previously reported with other tertiary phosphine ligands, whereas (DPAP)(I)Rh(TPP) (6) displays a low energy B-band absorption and a high energy Q-band absorption...

  15. Half-sandwich 1,3-Di-t-butylcyclopentadienylRhodium Complexes Containing Sulfido Ligands

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    Treatment of 1,3-di-t-butylcyclopentadiene with rhodium trichloride in EtOHleads to the formation of binuclear half-sandwich complex [CptRhCl (μt-Cl)]2 (1) (Cpt = η5-tBu2CsH3) which reacts with trimethylphosphine to give CptRh(PMe3)C12(2) in high yield. 2reacts with ammonium polysulfide, (NH4)2Sx to give cyclooligosulfido half-sandwichcomplexes CptRh(PMe3)(Sn)(n=4(4a),6(4b)). Desulfurization of 4b by excess PPh3 resultsin cyclotetrasulfido product 4a, while 4a takes up sulfur from polysulfide to convertcyclohexasulfido product 4b. The reaction of 2 with Et4NI gives diiodide complex 3 which isdetermined by single crystal X-ray crystallographic analysis.

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

    Energy Technology Data Exchange (ETDEWEB)

    Cernota, Paul D.

    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 ({radical}7x{radical}7) unit cells. One of these is composed of trimers of CO and has three CO molecules in each unit cell. The other structure has an additional CO molecule, making a total of four. This extra CO sits on a top site.

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

    Science.gov (United States)

    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.

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

    Energy Technology Data Exchange (ETDEWEB)

    Cernota, Paul Davis [Univ. of California, Berkeley, CA (United States)

    1999-08-01

    Scanning Tunneling Microscopy studies were carried out on ordered overlayers on the (111) surface of rhodium. These adsorbates include carbon monoxide (CO), cyclohexane, cyclohexene, 1,4-cyclohexadiene, para-xylene, and meta-xylene. Coadsorbate systems included: CO with ethylidyne, CO with para- and meta-xylene, and para-xylene with meta-xylene. In the case of CO, the structure of the low coverage (2x2) overlayer has been observed. The symmetry of the unit cell in this layer suggests that the CO is adsorbed in the 3-fold hollow sites. There were also two higher coverage surface structures with (√7x√7) unit cells. One of these is composed of trimers of CO and has three CO molecules in each unit cell. The other structure has an additional CO molecule, making a total of four. This extra CO sits on a top site.

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

    Energy Technology Data Exchange (ETDEWEB)

    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.

  20. Ionic Liquids as Solvents for Rhodium and Platinum Catalysts Used in Hydrosilylation Reaction

    Directory of Open Access Journals (Sweden)

    Witold Zielinski

    2016-08-01

    Full Text Available A group of imidazolium and pyridinium based ionic liquids has been synthetized, and their ability to dissolve and activate the catalysts used in hydrosilylation reaction of 1-octane and 1,1,1,3,5,5,5-heptamethyltrisiloxane was investigated. An organometallic catalyst as well as inorganic complexes of platinum and rhodium dissolved in ionic liquids were used, forming liquid solutions not miscible with the substrates or with the products of the reaction. The results show that application of such a simple biphasic catalytic system enables reuse of ionic liquid phase with catalysts in multiple reaction cycles reducing the costs and decreasing the amount of catalyst needed per mole of product.

  1. Mapping of the radiation field of a mammography equipment using molybdenum and rhodium filters

    Energy Technology Data Exchange (ETDEWEB)

    Barreira, Jacqueline S.; Campos, Daniela; Vivolo, Vitor, E-mail: jacsales@usp.br [Instituto de Pesquisas Energeticas e Nucleares (IPEN/CNEN-SP), Sao Paulo, SP (Brazil)

    2014-07-01

    The use of X rays for diagnostic radiology is very common and important to Medicine, including mammographic diagnosis focusing decreasing of the doses applied to the patients and preserving high quality of the diagnostic image. A quality control program of the irradiation systems it is very necessary. The Instruments Calibration Laboratory (LCI) of IPEN perform calibration in dosemeters used in radiation dosimetry (in diagnostic radiology) for many years. The objective of that paper is determining the point of greatest intensity of the beam issued by the mammography equipment. Exposures were made with filters Rhodium and Molybdenum. That mapping is important before applied a routine quality control program of the mammography equipment and the calibration of instruments in the diagnosis. (author)

  2. Half-sandwich ruthenium, rhodium and iridium complexes of triazolopyridine ligand: Synthesis and structural studies

    Indian Academy of Sciences (India)

    NARASINGA RAO PALEPU; RAO MOHAN KOLLIPARA

    2017-02-01

    Triazolopyridine ligand, {3-(2-pyridyl)-[1,2,3]triazolo[1,5-a]-pyridine}, L was synthesized by reaction of p-toulenesulphonyl hydrazine and dipyridyl ketone in the presence of acetic acid. Half-sandwich ruthenium, rhodium and iridium complexes [1–4] have been synthesized by reaction of [{(arene)MCl₂}₂] (arene= p-cymene/benzene/Cp* and M = Ru/Rh/Ir) with ligand L in methanol. The reaction in 1:2 (M:L) ratio has yielded all mononuclear cationic complexes such as [(arene)MLκ²N∩N Cl]PF₆, where {(arene)M} = (p-cym)Ru(1), (benz)Ru (2), Cp*Rh (3) and Cp*Ir (4). All the complexes were characterized by spectral studies and the solid state structures of complexes, 1 and 3 were unambiguously determined by crystallographic studies.

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

    Science.gov (United States)

    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. Ligand-induced fate of embryonic species in the shape-controlled synthesis of rhodium nanoparticles.

    Science.gov (United States)

    Biacchi, Adam J; Schaak, Raymond E

    2015-02-24

    The shapes of noble metal nanoparticles directly impact their properties and applications, including in catalysis and plasmonics, and it is therefore important to understand how multiple distinct morphologies can be controllably synthesized. Solution routes offer powerful capabilities for shape-controlled nanoparticle synthesis, but the earliest stages of the reaction are difficult to interrogate experimentally and much remains unknown about how metal nanoparticle morphologies emerge and evolve. Here, we use a well-established polyol process to synthesize uniform rhodium nanoparticle cubes, icosahedra, and triangular plates using bromide, trifluoroacetate, and chloride ligands, respectively. In all of these systems, we identified rhodium clusters with diameters of 1-2 nm that form early in the reactions. The colloidally stable metal cluster intermediates served as a stock solution of embryonic species that could be transformed predictably into each type of nanoparticle morphology. The anionic ligands that were added to the embryonic species determined their eventual fate, e.g., the morphologies into which they would ultimately evolve. Extensive high-resolution transmission electron microscopy experiments revealed that the growth pathway-monomer addition, coalescence, or a combination of the two-was different for each of the morphologies, and was likely controlled by the interactions of each specific anionic adsorbate with the embryonic species. Similar phenomena were observed for related palladium and platinum nanoparticle systems. These studies provide important insights into how noble metal nanoparticles nucleate, the pathways by which they grow into several distinct morphologies, and the imperative role of the anonic ligand in controlling which route predominates in a particular system.

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

    Science.gov (United States)

    Kaltenbach, Angela; Noordmann, Janine; Görlitz, Volker; Pape, Carola; Richter, Silke; Kipphardt, Heinrich; Kopp, Gernot; Jährling, Reinhard; Rienitz, Olaf; Güttler, Bernd

    2015-04-01

    Gravimetrically prepared mono-elemental reference solutions having a well-known mass fraction of approximately 1 g/kg (or a mass concentration of 1 g/L) define the very basis of virtually all measurements in inorganic analysis. Serving as the starting materials of all standard/calibration solutions, they link virtually all measurements of inorganic analytes (regardless of the method applied) to the purity of the solid materials (high-purity metals or salts) they were prepared from. In case these solid materials are characterized comprehensively with respect to their purity, this link also establishes direct metrological traceability to The International System of Units (SI). This, in turn, ensures the comparability of all results on the highest level achievable. Several national metrology institutes (NMIs) and designated institutes (DIs) have been working for nearly two decades in close cooperation with commercial producers on making an increasing number of traceable reference solutions available. Besides the comprehensive characterization of the solid starting materials, dissolving them both loss-free and completely under strict gravimetric control is a challenging problem in the case of several elements like molybdenum and rhodium. Within the framework of the European Metrology Research Programme (EMRP), in the Joint Research Project (JRP) called SIB09 Primary standards for challenging elements, reference solutions of molybdenum and rhodium were prepared directly from the respective metals with a relative expanded uncertainty associated with the mass fraction of U rel(w) < 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.

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

    Science.gov (United States)

    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.

  7. Synthesis and Characterization of Rhodium Doped on TiO2/HCP for Enhanced Photocatalytic Performance on Pentachlorophenol

    Directory of Open Access Journals (Sweden)

    Saheed Olalekan Sanni

    2014-01-01

    Full Text Available Visible-light-responsive material based on Rhodium doped on titanium dispersed on dealuminated clinoptilolite (TiO2/HCP was synthesized via a combination of the sol-gel method and photoreductive deposition technique. The photocatalyst surface characterization, structural and optical properties were investigated by X-ray diffraction (XRD, scanning electron microscopy (SEM, energy-dispersive X-ray analysis (EDAX, Fourier transform infrared spectroscopy (FTIR, thermal gravimetric analysis (TGA, and UV-visible spectra (UV-VIS. Doping TiO2/HCP with Rh imparts a red shifting of the absorption band into the visible light region according to UV-VIS. The prepared composite materials were evaluated for their photocatalytic activities on pentachlorophenol (PCP degradation under sunlight irradiation. The Rhodium doped TiO2/HCP exhibited enhanced photocatalytic activity and can be considered as a potential photocatalyst in wastewater treatment.

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

    Directory of Open Access Journals (Sweden)

    Khazan A.

    2011-01-01

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

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

    Directory of Open Access Journals (Sweden)

    Khazan A.

    2011-01-01

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

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

    Science.gov (United States)

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

    2014-12-08

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

  11. Synthesis and Characterization of Rhodium Doped on TiO2/HCP for Enhanced Photocatalytic Performance on Pentachlorophenol

    OpenAIRE

    Saheed Olalekan Sanni; Omoruyi Gold Idemudia

    2014-01-01

    Visible-light-responsive material based on Rhodium doped on titanium dispersed on dealuminated clinoptilolite (TiO2/HCP) was synthesized via a combination of the sol-gel method and photoreductive deposition technique. The photocatalyst surface characterization, structural and optical properties were investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM), energy-dispersive X-ray analysis (EDAX), Fourier transform infrared spectroscopy (FTIR), thermal gravimetric analysis (...

  12. Rhodium-Catalyzed Acyloxy Migration of Propargylic Esters in Cycloadditions, Inspiration from Recent “Gold Rush”

    OpenAIRE

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

    2012-01-01

    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 a...

  13. Half-sandwich rhodium poly-chalcogenide complexes and a carbon insertion into Te-Te bond

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    Treatment of CptRh(PMe3)Cl2(1) (Cpt = 5(- tBu2C5H3) with [Et4N]2Se6 in DMF solution leads to the formation of cyclo-tetraselenido half-sandwich rhodium complexes CptRh(PMe3)(Se4) (2). The elimination of 2 with excess of nBu3P results in cyclo-diselenido rhodium complex CptRh(PMe3)(Se2) (3). 1 reacts with [nBu4N]2Te5 in DMF solution to yield cyclo-ditellurido rhodium complex CptRh (PMe3)(Te2) (4) in which carbon atom from CH2Cl2 can be inserted into Te-Te bond to form CptRh(PMe3)(TeCH2Te) (5). The new complexes 2-5 have been characterized by their IR, EI-MS, and 1H, 13C, 31P, 103Rh NMR spectra as well as elemental analysis.

  14. Simultaneous nondestructive analysis of palladium, rhodium, platinum, and gold nanoparticles using energy dispersive X-ray fluorescence.

    Science.gov (United States)

    Fiedler, Haidi D; Drinkel, Emma E; Orzechovicz, Beatriz; Leopoldino, Elder C; Souza, Franciane D; Almerindo, Gizelle I; Perdona, Cristian; Nome, Faruk

    2013-11-01

    A selective method is proposed for the determination of palladium, gold, and sulfur in catalytic systems, by direct liquid analysis using energy dispersive X-ray fluorescence (EDXRF), under an atmosphere of helium or air. This method allows a nondestructive analysis of palladium, rhodium, platinum, and gold nanoparticulate catalysts stabilized by imidazolium propane sulfonate based zwitterionic surfactants, allowing the samples to be reused for catalytic studies. The signals from palladium, rhodium, platinum, and gold samples in the presence of imidazolium propane sulfonate-based zwitterionic surfactants obtained using EDXRF before (Pd(2+), Rh(2+), Pt(2+), and Au(3+)) and after (Pd(0), Rh(0), Pt(0), and Au(0)) formation of nanoparticles are essentially identical. The results show that the EDXRF method is nondestructive and allows detection and quantification of the main components of platinum, gold, rhodium, and palladium NPs, including the surfactant concentration, with detection and quantification limits in the range of 0.4-3 mg L(-1). The matrices used in such samples present no problems, even allowing the detection and quantification of interfering elements.

  15. Electrocatalytic oxidation of glucose by rhodium porphyrin-functionalized MWCNT electrodes: application to a fully molecular catalyst-based glucose/O2 fuel cell.

    Science.gov (United States)

    Elouarzaki, Kamal; Le Goff, Alan; Holzinger, Michael; Thery, Jessica; Cosnier, Serge

    2012-08-29

    This paper details the electrochemical investigation of a deuteroporphyrin dimethylester (DPDE) rhodium(III) ((DPDE)Rh(III)) complex, immobilized within a MWCNT/Nafion electrode, and its integration into a molecular catalysis-based glucose fuel cell. The domains of present (DPDE)Rh(I), (DPDE)Rh-H, (DPDE)Rh(II), and (DPDE)Rh(III) were characterized by surface electrochemistry performed at a broad pH range. The Pourbaix diagrams (plots of E(1/2) vs pH) support the stability of (DPDE)Rh(II) at intermediate pH and the predominance of the two-electron redox system (DPDE)Rh(I)/(DPDE)Rh(III) at both low and high pH. This two-electron system is especially involved in the electrocatalytic oxidation of alcohols and was applied to the glucose oxidation. The catalytic oxidation mechanism exhibits an oxidative deactivation coupled with a reductive reactivation mechanism, which has previously been observed for redox enzymes but not yet for a metal-based molecular catalyst. The MWCNT/(DPDE)Rh(III) electrode was finally integrated in a novel design of an alkaline glucose/O(2) fuel cell with a MWCNT/phthalocyanin cobalt(II) (CoPc) electrode for the oxygen reduction reaction. This nonenzymatic molecular catalysis-based glucose fuel cell exhibits a power density of P(max) = 0.182 mW cm(-2) at 0.22 V and an open circuit voltage (OCV) of 0.64 V.

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

    Science.gov (United States)

    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.

  17. Organogold reactivity with palladium, nickel, and rhodium: transmetalation, cross-coupling, and dual catalysis.

    Science.gov (United States)

    Hirner, Joshua J; Shi, Yili; Blum, Suzanne A

    2011-08-16

    Using two transition metals to simultaneously catalyze a reaction can offer distinct opportunities for reactivity and selectivity when compared to using single-metal catalyst systems. Creating dual transition metal catalytic systems is complicated, however, by challenges in predicting compatible reactivities and designing turnover pathways for both metals. In this Account, we describe our development of dual-metal catalysis reactions involving gold and a second transition metal. The unique rearrangement intermediates accessible through gold-only catalysis, which exploits the soft Lewis acidity of Au(I), make gold an attractive partner for dual-metal catalysis reactions. Because of the complexity of achieving simultaneous turnover of two catalysts and predicting compatibilities, our approach has been to first gain a fundamental understanding of the reactivity of the two metals with each other, both in stoichiometric and monocatalyzed reactions. To this end, we have investigated the combined reactivity of organogold compounds with palladium, nickel, and rhodium. We narrate the intricacies of turning over two catalysts simultaneously and thereby illuminate the valuable role of fundamental studies in identifying the optimal conditions to promote desirable two-metal reactivity and compatibility. Transmetalation, redox reactivity, and new mechanisms for dual-metal catalytic turnover were probed from this standpoint. We have applied the knowledge gained through these studies to the development of reactions that are dual-catalyzed by gold and palladium, as well as nickel- and rhodium-catalyzed reactions of organogold compounds. More broadly, these new reactions expand the reactivity available to catalytic organogold intermediates via trapping and functionalization reactions with other transition metals. Our investigations reveal strategies useful for designing dual-metal reactions with gold. First, the versatility of gold as a transmetalation partner suggests that many

  18. 贵金属铑电镀液的研究进展%Research progress of precious metal material rhodium plating solution

    Institute of Scientific and Technical Information of China (English)

    牛飞; 白晓军; 向雄志; 汤有正; 张苏嫚

    2011-01-01

    对贵金属铑电镀液的组分、制备、应用方向、镀覆条件及镀铑废液回收等方面研究现状进行了综述,探讨了影响镀液性质的主要因素,并对今后的研究方向提出了建议,以期得到性能更好的铑镀层.%In this paper, the research status of the following aspects on rhodium plating solution were reviewed,such as the application direction, composition formula, bath preparation, plating conditions, rhodium-plated waste recycling and etc.. The factors which influence the features of the bath were discussed, and the recommendations for future research were made to get rhodium plating with even better performance.

  19. MgF2 prism/rhodium/graphene: efficient refractive index sensing structure in optical domain

    Science.gov (United States)

    Mishra, Akhilesh Kumar; Mishra, Satyendra Kumar

    2017-04-01

    A theoretical study of a noble surface plasmon resonance (SPR) based sensing probe has been carried out. The sensing probe consists of a magnesium fluoride (MgF2) prism with its base coated with rarely used noble metal rhodium (Rh) and a bio-compatible layer of graphene. The refractive indices (RIs) of the sensing medium vary from 1.33 to 1.36 refractive index unit (RIU). The thickness of Rh and the number of graphene layers have been optimized for maximum sensitivity in a constraint set by the detection accuracy (DA). For the operating wavelength of 632 nm, the optimized sensing probe Rh (12 nm)/graphene (single layer) demonstrates sensitivity of ~259 degree/RIU with corresponding DA of ~0.32 degree‑1 while for 532 nm of excitation, the optimized sensing probe Rh (12 nm)/graphene (three layer) exhibits sensitivity of ~240 degree/RIU and DA of ~0.27 degree‑1.

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

    Directory of Open Access Journals (Sweden)

    Albert Poater

    2016-01-01

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

  1. Synthesis and characterization of polymer-protected rhodium and palladium sols in mixed media.

    Science.gov (United States)

    Jaine, Jacob E; Mucalo, Michael R

    2012-06-01

    A series of polymer-protected rhodium and palladium sols were generated in mixed (organic/aqueous) dispersion media. Protecting polymers used were PAA, PVP, PVA and an oligosaccharide-based protecting agent, arabinogalactan. This is the first systematic study of colloids generated in mixed solvent dispersion media with these protecting agents. The sols were characterized by TEM, UV/Vis spectrophotometry and Photon Correlation Spectroscopy (PCS). In general, the macroscopic stability of the sols depended on the protecting agent/organic cosolvent combination used, with a nonlinear dependence on cosolvent concentration. Observed sol stabilities correlated well with pre-existing hydrodynamic data for the protective polymers, e.g. radius of gyration data. Average particle size and polydispersity of all sols examined decreased as cosolvent concentration increased, with actual cosolvent concentration, protecting agent and reducing agent used influencing the extent of decrease. Sol particle sizes ranged from 0.8 nm to 6.0 nm with sol turbidities decreasing in parallel with the particle sizes. Hydrodynamic sizes (from PCS) tended to reflect the sols' macroscopic stabilities. FTIR studies using adsorbed CO as a spectroscopic surface probe indicated decreases in the ν(CO)(ads) stretching frequency with an increase in cosolvent concentration due to competitive adsorption of CO with the cosolvent molecules on the metal colloid surfaces. Copyright © 2012 Elsevier Inc. All rights reserved.

  2. Vapour phase hydrogenation of phenol over rhodium on SBA-15 and SBA-16.

    Science.gov (United States)

    Giraldo, Liliana; Bastidas-Barranco, Marlon; Moreno-Piraján, Juan Carlos

    2014-12-10

    In the present work, mesoporous SBA-15 and SBA-16 were synthesised using classical methods, and their physicochemical properties were investigated by X-ray diffraction (XRD), FTIR, TEM and N2 adsorption-desorption. Rhodium (Rh, 1 wt %) was loaded on the mesoporous SBA-15 and SBA-16 by an impregnation method. The Rh surface coverage, dispersion and crystallite size were determined by room temperature H2 chemisorption on reduced samples. The catalytic activity of Rh supported on mesoporous SBA-15 and SBA-16 was evaluated for the first time in the hydrogenation of phenol in vapour phase in a temperature range between 130 and 270 °C at atmospheric pressure. The reaction over Rh/SBA-15 at 180 °C produced cyclohexanone as the major product (about 60%) along with lower amounts of cyclohexanol (about 35%) and cyclohexane (about 15%). The influences of temperature, H2/phenol ratio, contact time and the nature of the solvent on the catalytic performance were systematically investigated. The Rh/SBA-16 system offered lower phenol conversion compared to Rh/SBA-15, but both have a very high selectivity for cyclohexanone (above 60%).

  3. Vapour Phase Hydrogenation of Phenol over Rhodium on SBA-15 and SBA-16

    Directory of Open Access Journals (Sweden)

    Liliana Giraldo

    2014-12-01

    Full Text Available In the present work, mesoporous SBA-15 and SBA-16 were synthesised using classical methods, and their physicochemical properties were investigated by X-ray diffraction (XRD, FTIR, TEM and N2 adsorption–desorption. Rhodium (Rh, 1 wt % was loaded on the mesoporous SBA-15 and SBA-16 by an impregnation method. The Rh surface coverage, dispersion and crystallite size were determined by room temperature H2 chemisorption on reduced samples. The catalytic activity of Rh supported on mesoporous SBA-15 and SBA-16 was evaluated for the first time in the hydrogenation of phenol in vapour phase in a temperature range between 130 and 270 °C at atmospheric pressure. The reaction over Rh/SBA-15 at 180 °C produced cyclohexanone as the major product (about 60% along with lower amounts of cyclohexanol (about 35% and cyclohexane (about 15%. The influences of temperature, H2/phenol ratio, contact time and the nature of the solvent on the catalytic performance were systematically investigated. The Rh/SBA-16 system offered lower phenol conversion compared to Rh/SBA-15, but both have a very high selectivity for cyclohexanone (above 60%.

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

    Science.gov (United States)

    Mafuné, Fumitaka; Tawaraya, Yuki; Kudoh, Satoshi

    2016-02-18

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

  5. Synthesis and Conformational Behavior of Rhodium(I) Metallohosts Derived from Diphenylglycoluril.

    Science.gov (United States)

    Coolen, Hein K. A. C.; van Leeuwen, Piet W. N. M.; Nolte, Roeland J. M.

    1996-07-12

    The design and synthesis of molecules containing both a substrate-binding cavity and a nearby catalytically active metal center is a useful approach to the development of synthetic systems that function according to the principles of enzymes. To this end the receptor molecule 2a, derived from diphenylglycoluril, was functionalized with triaryl phosphite ligands to give the receptor ligand 2d. Exchange reactions of 2d with (diketonate)Rh(CO)(2), (diketone = acetylacetone, dibenzoylmethane, or dipivaloylmethane) led to the formation of the metallohosts 3a-c, respectively. The properties and conformational behavior of these metal complexes were studied by NMR techniques. Reaction of compounds 3 with H(2) in the presence of a small excess of additional triphenyl phosphite yields the rhodium(I) hydride complex 5. The metallohosts are capable of binding dihydroxybenzene guests in their cavities by hydrogen bonding and pi-pi stacking interactions. On binding a substrate the conformational behavior of hosts 3a-c was affected considerably.

  6. Asymmetric Suzuki-Miyaura coupling of heterocycles via Rhodium-catalysed allylic arylation of racemates

    Science.gov (United States)

    Schäfer, Philipp; Palacin, Thomas; Sidera, Mireia; Fletcher, Stephen P.

    2017-06-01

    Using asymmetric catalysis to simultaneously form carbon-carbon bonds and generate single isomer products is strategically important. Suzuki-Miyaura cross-coupling is widely used in the academic and industrial sectors to synthesize drugs, agrochemicals and biologically active and advanced materials. However, widely applicable enantioselective Suzuki-Miyaura variations to provide 3D molecules remain elusive. Here we report a rhodium-catalysed asymmetric Suzuki-Miyaura reaction with important partners including aryls, vinyls, heteroaromatics and heterocycles. The method can be used to couple two heterocyclic species so the highly enantioenriched products have a wide array of cores. We show that pyridine boronic acids are unsuitable, but they can be halogen-modified at the 2-position to undergo reaction, and this halogen can then be removed or used to facilitate further reactions. The method is used to synthesize isoanabasine, preclamol, and niraparib--an anticancer agent in several clinical trials. We anticipate this method will be a useful tool in drug synthesis and discovery.

  7. Iridium, platinum and rhodium baseline concentration in lichens from Tierra del Fuego (South Patagonia, Argentina).

    Science.gov (United States)

    Pino, Anna; Alimonti, Alessandro; Conti, Marcelo Enrique; Bocca, Beatrice

    2010-10-06

    Lichen samples of Usnea barbata were used as possible biomonitors of the atmospheric background level of iridium (Ir), platinum (Pt) and rhodium (Rh) in the remote region of Tierra del Fuego (South Patagonia, Argentina). Lichens were collected in 2006 at 53 sites covering 7 different areas of the region (24 transplanted lichens of the northern region and 29 native lichen samples of the central-southern region). A microwave acidic digestion procedure was used to mineralize the samples and a sector field inductively coupled plasma mass spectrometry method was developed to quantify the elements. The study of the influence of interferences on analyte signals and a quality control procedure were carried out. The analytical protocol was further applied to evaluate Ir, Pt and Rh bioaccumulation in lichens. The detection limits obtained were 0.010 ng g⁻¹, 0.013 ng g⁻¹ and 0.030 ng g⁻¹ for Ir, Pt and Rh, respectively. Recoveries at different fortification levels were between 96.3% and 106% and precision was 3.3% on average. The metals concentration (as dry weight) spanned the following ranges: Ir, Tierra del Fuego. Values detected are more likely influenced by the long-range atmospheric transport of these pollutants and, in comparison with densely populated areas in the world, they can represent the baseline for low impacted areas.

  8. Preparation of association compound between rhodium(II) citrate and {beta}-cyclodextrin; Preparacao do composto de associacao entre citrato de rodio(II) e {beta}-ciclodextrina

    Energy Technology Data Exchange (ETDEWEB)

    Burgos, Ana E.; Okio, Coco K.Y.A., E-mail: aeburgosc@unal.edu.co [Departamento de Quimica, Universidad Nacional de Colombia, Bogota (Colombia); Sinisterra, Ruben D. [Departamento de Quimica, Instituto de Ciencias Exatas, Universidade Federal de Minas Gerais, Belo Horizonte - MG (Brazil)

    2012-07-01

    Inclusion compound of rhodium(II) citrate with{beta}-cyclodextrin in a 1:1 molar ratio was prepared using freeze-drying method. X-ray diffractometry, thermal analysis (TG/DTG/DSC), infrared and {sup 1}H-NMR with {sup 1}H spin lattice relaxation ({sup 1}H T{sub 1}) measurements and {sup 13}C techniques were used to characterize the system prepared. The results indicated the formation of inclusion or association compounds between rhodium(II) citrate and {beta}-cyclodextrin. (author)

  9. Stereochemical features making deoxycholic acid derived tropos biphenylphosphites efficient chiral ligands for rhodium: the asymmetric hydrogenation of dimethylitaconate as a case study.

    Science.gov (United States)

    Iuliano, Anna; Losi, Debora; Facchetti, Sarah

    2007-10-26

    Different deoxycholic acid derived biphenylphosphites, whose tropos nature was ascertained by NMR and CD measurements, were used in the rhodium-catalyzed asymmetric hydrogenation of dimethylitaconate achieving enantiomeric excesses up to 91%. The comparison of these results to those obtained using the corresponding atropoisomeric binaphthyl analogues, together with NMR and CD measurements on the rhodium complexes of some phosphites, allowed us to shed light on the nature of the active catalytic species and on the asymmetric induction process and hence to recognize the most appropriate stereochemical features to reach good levels of enantioselectivity.

  10. Recent Advances in the Synthesis of Heterocycles and Related Substances Based on α-Imino Rhodium Carbene Complexes Derived from N-Sulfonyl-1,2,3-triazoles.

    Science.gov (United States)

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

    2016-12-12

    In recent years, α-imino rhodium carbene complexes derived by ring-opening of N-sulfonyl-1,2,3-triazoles have attracted much attention from organic chemists. Many transformations of these species have been reported that involve, in most cases, nucleophilic attack at the carbene center of the α-imino rhodium carbene, facilitating the synthesis of a wide range of novel and useful compounds, particularly heterocycles. This Minireview mainly focuses on advances in the transformation of N-sulfonyl-1,2,3-triazoles during the past two years.

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

    Science.gov (United States)

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

    2014-12-01

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

  12. Surface Electrochemistry of Chloro(phthalocyaninato)rhodium(III) species, and Oxygen Reduction Electrocatalysis, Formation of a Dimeric Species

    Science.gov (United States)

    1991-08-20

    filings, anhydrous CaSO 4 (Drierite), molecular sieves BDH 3A), and glass wool. Oxygen gas (Linde) was used as received. Buffer solutions were prepared...temperature, whereupon the fused solid was broken down by boiling with ethanol. The ethanol was boiled off, and the solid crude CIRhIIIPc (plus...2CI2 (0.25 g, 0.75 mmoi) were heated in N,N’-dimethylaminoethanol (25 mL) at 165°C for 48 h. The crude reaction mixture wa, pourcd into water

  13. Simultaneous determination of rhodium and ruthenium by high-resolution continuum source graphite furnace atomic absorption spectrometry

    Science.gov (United States)

    Zambrzycka-Szelewa, Elżbieta; Lulewicz, Marta; Godlewska-Żyłkiewicz, Beata

    2017-07-01

    In the present paper a fast, simple and sensitive analytical method for simultaneous determination of rhodium and ruthenium by high-resolution continuum source graphite furnace atomic absorption spectrometry (HR-CS GFAAS) was developed. Among six pairs of absorption atomic lines of Rh and Ru, which are close enough to enable their simultaneous detection, two pairs were selected for further studies. Best results were obtained for measurements of the resonance line of rhodium at 343.489 nm and the adjacent secondary line of ruthenium at 343.674 nm (23% intensity of this line). For evaluated lines, the absorbance values were obtained using three pixels. The pyrolysis and atomization temperatures were 1200 °C and 2600 °C, respectively. Under these conditions the limits of detection achieved for Rh and Ru were found to be 1.0 μg L- 1 and 1.9 μg L- 1, respectively. The characteristic mass was 12.9 pg for Rh and 71.7 pg for Ru. Repeatability of the results expressed as a relative standard deviation was typically below 6%. The trueness of the method was confirmed by analysis of the certified reference material - platinum ore (SARM 76). The recovery of Rh and Ru from the platinum ore was 93.0 ± 4.6% and 90.1 ± 2.5%, respectively. The method was successfully applied to the direct simultaneous determination of trace amounts of rhodium and ruthenium in spiked river water, road runoff, and municipal sewage. Separation of interfering matrix on cation exchange resin was required before analysis of road dust and tunnel dust (CW-7) by HR-CS GFAAS.

  14. Intramolecular substitutions of square planar rhodium(Ⅰ) catioriic complexes of ds-dicarbonyl nitrogen coordinated tridentate

    Institute of Scientific and Technical Information of China (English)

    袁国卿; 柳忠阳; 朱长城; 潘平来; 刘世宏

    1997-01-01

    Four kinds of square planar cis-dicarbonyl-N,N-bis(2-pyridylethyl)-p-substituted-phenylamino rhodium(Ⅰ) are reported.The changes of their structures were analyzed by XPS,IR and NMR spectroscopy The results show that the weak N→Rh coordinated bond can replace very soon the strong Rh-Cπ back donation bond to form tris-nitrogen coordinated complexes due to the steric effect when the temperature is over 50℃,This reaction is reversible.The bis-nitrogen coordinated structure of the complex recovered when put under the atmosphere of CO

  15. Effective Chirality Transfer in [3+2] Reaction between Allenyl-Rhodium and Enal: Mechanistic Study Based on DFT Calculations.

    Science.gov (United States)

    Qi, Xiaotian; Liu, Song; Zhang, Tao; Long, Rong; Huang, Jun; Gong, Jianxian; Yang, Zhen; Lan, Yu

    2016-09-16

    Theoretical calculation was performed to study the chirality transfer in a newly reported intramolecular [3+2] cycloaddition of enal and alleno rhodium species, generated in situ from an enynol precursor. [3.3.0] bicyclic system which contains two bridgehead quaternary carbons that can be achieved, the chirality of which are controlled by those of the starting material, and the product stereoselectivity is only determined by the α-position of the acetylene moiety. Density functional theory calculations predicted that only the cis [3.3.0] bicyclic product could be generated, regardless of either erythro or threo substrate, which was also confirmed by experimental observations.

  16. Synthesis and Liquid Crystal Behaviors of 2,4-Dioxo-3-pentyl 4-decyloxy Cinnamate Rhodium (I) Complexes

    Institute of Scientific and Technical Information of China (English)

    韩杰; 张良辅; 万文

    2003-01-01

    The title complexes have been synthesized by the reaction of [RhCI(CO)2]2 or [RhCI(COD)]2 (COD = 1,5-cyclooctadiene)with the organic ligand 2,4-dioxo-3-pentyl 4-decyloxy cinnamate 2. The complex 3 based on dicarbonylrhodium(I) shows nematic phase, while the complex 4 containing rhodium(I) bound to a COD ligand is a nonmesogen. The relationship between molecular structures and liquid crystal behavior has also been discussed by means of computer-aided molecular modeling.

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

    Energy Technology Data Exchange (ETDEWEB)

    Uccello, A., E-mail: andrea.uccello@mail.polimi.it [Dipartimento di Energia, Politecnico di Milano, Milan (Italy); Maffini, A., E-mail: alessandro.maffini@mail.polimi.it [Dipartimento di Energia, Politecnico di Milano, Milan (Italy); Dellasega, D., E-mail: david.dellasega@polimi.it [Dipartimento di Energia, Politecnico di Milano, Milan (Italy); Istituto di Fisica del Plasma, Consiglio Nazionale delle Ricerche, EURATOM-ENEA-CNR Association, Milan (Italy); Passoni, M., E-mail: matteo.passoni@polimi.it [Dipartimento di Energia, Politecnico di Milano, Milan (Italy); Istituto di Fisica del Plasma, Consiglio Nazionale delle Ricerche, EURATOM-ENEA-CNR Association, Milan (Italy)

    2013-10-15

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

  18. Thermodynamic properties of rhodium at high temperature and pressure by using mean field potential approach

    Science.gov (United States)

    Kumar, Priyank; Bhatt, Nisarg K.; Vyas, Pulastya R.; Gohel, Vinod B.

    2016-10-01

    The thermophysical properties of rhodium are studied up to melting temperature by incorporating anharmonic effects due to lattice ions and thermally excited electrons. In order to account anharmonic effects due to lattice vibrations, we have employed mean field potential (MFP) approach and for thermally excited electrons Mermin functional. The local form of the pseudopotential with only one effective adjustable parameter rc is used to construct MFP and hence vibrational free energy due to ions - Fion. We have studied equation of state at 300 K and further, to access the applicability of present conjunction scheme, we have also estimated shock-Hugoniot and temperature along principle Hugoniot. We have carried out the study of temperature variation of several thermophysical properties like thermal expansion (βP), enthalpy (EH), specific heats at constant pressure and volume (CP and CV), specific heats due to lattice ions and thermally excited electrons ( and , isothermal and adiabatic bulk moduli (BT and Bs) and thermodynamic Gruneisen parameter (γth) in order to examine the inclusion of anharmonic effects in the present study. The computed results are compared with available experimental results measured by using different methods and previously obtained theoretical results using different theoretical philosophy. Our computed results are in good agreement with experimental findings and for some physical quantities better or comparable with other theoretical results. We conclude that local form of the pseudopotential used accounts s-p-d hybridization properly and found to be transferable at extreme environment without changing the values of the parameter. Thus, even the behavior of transition metals having complexity in electronic structure can be well understood with local pseudopotential without any modification in the potential at extreme environment. Looking to the success of present scheme (MFP + pseudopotential) we would like to extend it further for the

  19. Structural sensitivity studies of ethylene hydrogenation on platinum and rhodium surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Quinlan, M.A. [California Univ., Berkeley, CA (United States). Dept. of Chemistry]|[Lawrence Berkeley National Lab., CA (United States)

    1996-01-01

    The catalytic hydrogenation of ethylene and hydrogen on the well characterized surfaces of the noble metals platinum and rhodium has been studied for the purposes of determining the relative activity of these two substrates as well as the degree of structure sensitivity. The Pt(111) and the Rh(755) single crystal surfaces,as well as Pt and Rh foils, were employed as substrates to study the effect of surface step structure on reactivity. In addition, vibrational spectroscopy studies were performed for ethylene adsorption on the stepped Rh(755) surface. The catalytic reaction were obtained using a combined ultrahigh vacuum chamber coupled with an atmospheric pressure reaction chamber that functioned as a batch reactor. Samples could be prepared using standard surface science techniques and characterized for surface composition and geometry using Auger Electron Spectroscopy and Low Energy Electron Diffraction. A comparison of the reactivity of Rh(111) with the results from this study on Rh(755) allows a direct determination of the effect of step structure on ethylene hydrogenation activity. Structure sensitivity is expected to exhibit orders of magnitude differences in rate as surface orientation is varied. In this case, no significant differences were found, confirming the structure insensitivity of this reaction over this metal. The turnover frequency of the Rh(111) surface, 5 {times} 10{sup 1} s{sup {minus}1}, is in relatively good agreement with the turnover frequency of 9 {times} 10{sup 1} s{sup {minus}1} measured for the Rh(755) surface. Rate measurements made on the Pt(111) surface and the Pt foil are in excellent agreement, both measuring 3 {times} 10{sup 2} s{sup minus}1. Likewise, it is concluded that no strong structure sensitivity for the platinum surfaces exists. High Resolution Electron Energy Loss Spectroscopy studies of adsorbed ethylene on the Rh(755) surface compare favorably with the ethylidyne spectra obtained on the Rh(111) and Rh(100) surfaces.

  20. Synthesis of solution-phase phosphoramidite and phosphite ligand libraries and their in situ screening in the rhodium-catalyzed asymmetric addition of arylboronic acids

    NARCIS (Netherlands)

    Jagt, Richard B. C.; Toullec, Patrick Y.; Schudde, Ebe P.; de Vries, Johannes G.; Feringa, Ben L.; Minnaard, Adriaan J.

    2007-01-01

    Herein, we report the automated parallel synthesis of solution-phase libraries of phosphoramidite ligands for the development of enantioselective catalysts. The ligand libraries are screened in situ in the asymmetric rhodium-catalyzed addition of arylboronic acids to aldehydes and imines. It is show

  1. Synthesis of Multifunctionalized 2-Carbonylpyrrole by Rhodium-Catalyzed Transannulation of 1-Sulfonyl-1,2,3-triazole with β-Diketone.

    Science.gov (United States)

    Cheng, Wanli; Tang, Yanhua; Xu, Ze-Feng; Li, Chuan-Ying

    2016-12-02

    A facile rhodium-catalyzed transannulation of 1-sulfonyl-1,2,3-triazoles with β-diketones was realized, and a series of multisubstituted 2-carbonylpyrroles were synthesized efficiently (up to 94% yield). The protocol features several advantages, such as readily available materials, mild reaction conditions, a concise operating procedure, a broad reaction scope, and excellent regioselectivity when benzoylacetone derivatives were used.

  2. Rhodium-catalyzed selective[2+2+2]cyclizations of 1,6-diynes with monoynes leading to isoindolines and isobenzofurans

    Institute of Scientific and Technical Information of China (English)

    2010-01-01

    A highly efficient and selective[2+2+2]cyclization of diynes and monoalkynes was catalyzed by rhodium under room temperature in water/THF mixed solvent,affording isoindolines and isobenzofurans in good to excellent yields.The center atoms (N,O) in the diynes showed a significant effect for the cyclization.

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

    DEFF Research Database (Denmark)

    Riisager, Anders; Hanson, Brian E.

    2002-01-01

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

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

    Energy Technology Data Exchange (ETDEWEB)

    Ditroi, F., E-mail: ditroi@atomki.hu [Institute of Nuclear Research of the Hungarian Academy of Sciences (ATOMKI), Debrecen (Hungary); Tarkanyi, F.; Takacs, S. [Institute of Nuclear Research of the Hungarian Academy of Sciences (ATOMKI), Debrecen (Hungary); Hermanne, A. [Cyclotron Laboratory, Vrije Universiteit Brussel (VUB), Brussels (Belgium); Yamazaki, H.; Baba, M.; Mohammadi, A. [Cyclotron Radioisotope Center (CYRIC) Tohoku University, Sendai (Japan); Ignatyuk, A.V. [Institute of Physics and Power Engineering (IPPE), Obninsk (Russian Federation)

    2011-09-15

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

  5. Long-Term Testing of Rhodium-Based Catalysts for Mixed Alcohol Synthesis – 2013 Progress Report

    Energy Technology Data Exchange (ETDEWEB)

    Gerber, Mark A.; Gray, Michel J.; Thompson, Becky L.

    2013-09-23

    The U.S. Department of Energy’s Pacific Northwest National Laboratory has been conducting research since 2005 to develop a catalyst for the conversion of synthesis gas (carbon monoxide and hydrogen) into mixed alcohols for use in liquid transportation fuels. Initially, research involved screening possible catalysts based on a review of the literature, because at that time, there were no commercial catalysts available. The screening effort resulted in a decision to focus on catalysts containing rhodium and manganese. Subsequent research identified iridium as a key promoter for this catalyst system. Since then, research has continued to improve rhodium/manganese/iridium-based catalysts, optimizing the relative and total concentrations of the three metals, examining baseline catalysts on alternative supports, and examining effects of additional promoters. Testing was continued in FY 2013 to evaluate the performance and long-term stability of the best catalysts tested to date. Three tests were conducted. A long-term test of over 2300 hr duration at a single set of operating conditions was conducted with the best carbon-supported catalyst. A second test of about 650 hr duration at a single set of operating conditions was performed for comparison using the same catalyst formulation on an alternative carbon support. A third test of about 680 hr duration at a single set of operating conditions was performed using the best silica-supported catalyst tested to date.

  6. In situ evaluation of the reflectivity of molybdenum and rhodium coatings in an ITER-like mixed environment

    Energy Technology Data Exchange (ETDEWEB)

    Eren, Baran, E-mail: baran.eren@unibas.ch [Department of Physics, University of Basel, Klingelbergstrasse 82, CH-4056 Basel (Switzerland); Marot, Laurent; Wisse, Marco [Department of Physics, University of Basel, Klingelbergstrasse 82, CH-4056 Basel (Switzerland); Mathys, Daniel [Centre of Microscopy, University of Basel, Klingelbergstrasse 50/70, CH-4056 Basel (Switzerland); Joanny, Maryline; Travère, Jean-Marcel [CEA, IRFM, F-13108 Saint-Paul-lez-Durance (France); Steiner, Roland; Meyer, Ernst [Department of Physics, University of Basel, Klingelbergstrasse 82, CH-4056 Basel (Switzerland)

    2013-07-15

    Molybdenum and rhodium are foreseen to be utilized in ITER for the light reflecting, plasma facing components called first mirrors (FMs). In this work, the plasma and impurity conditions which FMs are expected to be subjected to were simulated experimentally, while monitoring their reflectivity. Experiments include deuterium plasma exposure with tungsten–carbon and tungsten–aluminum impurities, where aluminum was employed as a proxy for beryllium. The surface composition and morphology of the mirrors were characterized with XPS and SEM. When carbon was present in the plasma, the molybdenum surface became carbidized, while this effect was not observed for rhodium. Aluminum impurities were deposited as oxides, whereas tungsten was either oxidized or carbidized depending on the presence of carbon in the plasma. SEM results show the deposits to be amorphous. The mirrors in erosion conditions showed no critical decrease in the reflectivity, whereas the degradation was severe in net deposition conditions involving carbon. Cleaning techniques have to be developed for mirrors in deposition conditions, which should be part of ITER’s routine operation.

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

    KAUST Repository

    Doherty, Mark D.

    2013-04-15

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

  8. 16 CFR 23.7 - Misuse of the words “platinum,” “iridium,” “palladium,” “ruthenium,” “rhodium,” and “osmium.”

    Science.gov (United States)

    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... marking or description misrepresents the product's true composition. The Platinum Group Metals (PGM)...

  9. Effet de la concentration du cuivre ou de l'argent sur les propriétés des agrégats de rhodium déposés sur silice amorphe dans l'hydrogénation du 1,3 butadiène

    Science.gov (United States)

    Ksibi, Z.; Ghorbel1, A.; Bellamy, B.

    1999-02-01

    Some samples with rhodium, rhodium-copper and rhodium-silver deposited on amorphous silica by vapor deposition of the metallic phase under high-vacuum (P silice amorphe par vapodéposition d'une phase métallique dans des conditions ultra-vide (P < 5.10-7 Pa) ont été préparés. L'effet de la taille des agrégats de rhodium ainsi que celui de l'addition du cuivre ou de l'argent sur les propriétés catalytiques du rhodium dans l'hydrogénation du 1,3 butadiène ont été étudiés. Les résultats montrent que la réaction étudiée est sensible à la taille des agrégats de rhodium et nous notons une différence importante entre l'effet du cuivre et de l'argent sur les propriétés du rhodium. En effet le cuivre forme un alliage avec le rhodium et provoque un effet poison d?où une modification de l'activité du métal noble, alors que l'argent exerce un effet de masque sur les particules de rhodium sans toutefois former d'alliage avec ce dernier.

  10. Insights Into Finding a Mismatch Through the Structure of a Mispaired DNA Bound By a Rhodium Intercalator

    Energy Technology Data Exchange (ETDEWEB)

    Pierre, V.C.; Kaiser, J.T.; Barton, J.K.; /Caltech

    2007-07-12

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

  11. Mechanism, reactivity, and regioselectivity in rhodium-catalyzed asymmetric ring-opening reactions of oxabicyclic alkenes: a DFT Investigation

    Science.gov (United States)

    Qi, Zheng-Hang; Zhang, Yi; Gao, Yun; Zhang, Ye; Wang, Xing-Wang; Wang, Yong

    2017-01-01

    The origin of the enantio- and regioselectivity of ring-opening reaction of oxabicyclic alkenes catalyzed by rhodium/Josiphos has been examined using M06-2X density functional theory(DFT). DFT calculations predict a 98% ee for the enantioselectivity and only the 1,2-trans product as one regio- and diastereomer, in excellent agreement with experimental results. The solvent tetrahydrofuran(THF) plays a key role in assisting nucleophilic attack. Orbital composition analysis of the LUMO and the NPA atomic charge calculations were conducted to probe the origins of the regioselectivity. The orbital composition analysis reveals two potential electrophilic sites of the Rh–π-allyl intermediate M3 and the NPA atomic charges demonstrate that Cα carries more positive charges than Cγ, which suggests that Cα is the electrophilic site. PMID:28074930

  12. Stereodivergent and Protecting-Group-Free Synthesis of the Helicascolide Family: A Rhodium-Catalyzed Atom-Economical Lactonization Strategy.

    Science.gov (United States)

    Haydl, Alexander M; Berthold, Dino; Spreider, Pierre A; Breit, Bernhard

    2016-05-04

    Natural products of polyketide origin, in particular small-sized lactones often possess a very broad range of impressive biological activities. An efficient way to demonstrate the concise access to six-membered lactones was emphasized as part of a stereodivergent and protecting-group-free synthesis of all three representatives of the helicascolide family. This strategy features an atom-economical and highly diastereoselective rhodium-catalyzed "head-to-tail" lactonization by an intramolecular addition of ω-allenyl-substituted carboxylic acids to terminal allenes, including the selective construction of a new stereocenter in the newly formed core structures. The excellent selectivities with which the helicascolide precursors were obtained are remarkable, thus resulting in an expeditious and highly efficient natural product synthesis.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2014-12-08

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

  14. Stepwise construction of discrete parallelogram- and prism-shaped organometallic architectures based on half-sandwich rhodium fragments.

    Science.gov (United States)

    Gao, Wen-Xi; Lin, Yue-Jian; Jin, Guo-Xin

    2017-08-08

    Herein we describe how to take advantage of a multifunctional ligand to conveniently control the shapes and sizes of different types of discrete organometallic assemblies. Using a versatile ligand 2-(pyridin-2-yl)-1H-imidazole-4,5-dicarboxylate (HL(2-)), which features three kinds of chelating sites, together with half-sandwich rhodium fragments, a series of discrete organometallic complexes with tetranuclear parallelogram and hexanuclear trigonal prism shapes were achieved. The isomerization of the hexanuclear assemblies was confirmed by single-crystal X-ray diffraction analysis. The results also reiterate that pyridyl-substituted imidazole-4,5-dicarboxylate ligands can be used as multifunctional organic scaffolds in the construction of elegant architectures.

  15. Preliminary Exploration of the Reactor Configuration for Hydroformylation of 1—Dodecene Catalyzed by Water Soluble Rhodium Complex

    Institute of Scientific and Technical Information of China (English)

    MAOZaisha; BIXinyan; 等

    2002-01-01

    Hydroformylation of 1-dodecene was studied in a biphasic system using water-soluble rhodium complex [RhCl(CO)(TPPTS)2] as catalyst in the presence of cetyl trimethyl ammonium bromide as surfactant to enhance the reaction rate. Efforts were devoted to improve the performance of hydroformylation by exploring reactor the reaction configuration which enhanced the mixing, dispersion and interphase mass transfer. Experiments were carried out in a 0.5L autoclave at the total pressure of 1.1MPa and temperature from 363K to 373K. Several surface aeration configurations were tested, and higher hydroformylation rate with higher normal/branched aldehyde ratio produced were achieved. The experience suggest that improved reactor configuration by taking reaction engineering, measures is beneficial to better process economy in alkene hydroformylation.

  16. A New Synthetic Method of Rhodium Iodide%三碘化铑的新合成方法

    Institute of Scientific and Technical Information of China (English)

    刘桂华; 匡飞平; 潘再富; 余尧; 侯文明; 沈善问; 高金翠; 杨军; 彭玉玲; 杨善晓

    2012-01-01

    A new method has been introduced to synthesize rhodium iodide, an important homogenous catalyst for earbonylation of methanol, to overcome shortcomings of the present methods. These shortcomings include low yield, poor quality and unacceptability with respect to industrial manufacturing. The new method involves the direct reaction of RhC13 with HI. The yield is up to 98.5% and Cl-ean be minimized to 50 ppm by optimizing synthetic operations, superior to the reported data.%三氯化铑与氢碘酸直接合成碘化铑,在最佳反应条件下,合成的收率达到98.5%,产品晶形均一,氯离子含量小于50 mg/kg。

  17. Mechanism, reactivity, and regioselectivity in rhodium-catalyzed asymmetric ring-opening reactions of oxabicyclic alkenes: a DFT Investigation

    Science.gov (United States)

    Qi, Zheng-Hang; Zhang, Yi; Gao, Yun; Zhang, Ye; Wang, Xing-Wang; Wang, Yong

    2017-01-01

    The origin of the enantio- and regioselectivity of ring-opening reaction of oxabicyclic alkenes catalyzed by rhodium/Josiphos has been examined using M06-2X density functional theory(DFT). DFT calculations predict a 98% ee for the enantioselectivity and only the 1,2-trans product as one regio- and diastereomer, in excellent agreement with experimental results. The solvent tetrahydrofuran(THF) plays a key role in assisting nucleophilic attack. Orbital composition analysis of the LUMO and the NPA atomic charge calculations were conducted to probe the origins of the regioselectivity. The orbital composition analysis reveals two potential electrophilic sites of the Rh-π-allyl intermediate M3 and the NPA atomic charges demonstrate that Cα carries more positive charges than Cγ, which suggests that Cα is the electrophilic site.

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

    Science.gov (United States)

    Weidmann, Alyson G; Barton, Jacqueline K

    2015-10-05

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

  19. Active and Recyclable Catalytic Synthesis of Indoles by Reductive Cyclization of 2-(2-Nitroaryl)acetonitriles in the Presence of Co-Rh Heterobimetallic Nanoparticles with Atmospheric Hydrogen under Mild Conditions.

    Science.gov (United States)

    Choi, Isaac; Chung, Hyunho; Park, Jang Won; Chung, Young Keun

    2016-11-04

    A cobalt-rhodium heterobimetallic nanoparticle-catalyzed reductive cyclization of 2-(2-nitroaryl)acetonitriles to indoles has been achieved. The tandem reaction proceeds without any additives under the mild conditions (1 atm H2 and 25 °C). This procedure could be scaled up to the gram scale. The catalytic system is significantly stable under these reaction conditions and could be reused more than ten times without loss of catalytic activity.

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

    Directory of Open Access Journals (Sweden)

    Sid Kalal Hossein

    2012-09-01

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

  1. Synthesis and Application of Amberlite Xad-4 Functionalized with Alizarin Red-S for Preconcentration and Adsorption of Rhodium (iii

    Directory of Open Access Journals (Sweden)

    Hossein Sid Kalal

    2012-09-01

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

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

    Science.gov (United States)

    Sid Kalal, Hossein; Panahi, Homayon Ahmad; Hoveidi, Hassan; Taghiof, Mohammad; Menderjani, Mahnaz Taheri

    2012-09-18

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

  3. A DFT based investigation into the electronic structure and properties of hydride rich rhodium clusters.

    Science.gov (United States)

    Brayshaw, Simon K; Green, Jennifer C; Hazari, Nilay; Weller, Andrew S

    2007-05-14

    Density functional theory has been used to investigate the structures, bonding and properties of a family of hydride rich late transition metal clusters of the type [Rh(6)(PH(3))(6)H(12)](x) (x = 0, +1, +2, +3 or +4), [Rh(6)(PH(3))(6)H(16)](x) (x = +1 or +2) and [Rh(6)(PH(3))(6)H(14)](x) (x = 0, +1 or +2). The positions of the hydrogen atoms around the pseudo-octahedral Rh(6) core in the optimized structures of [Rh(6)(PH(3))(6)H(12)](x) (x = 0, +1, +2, +3 or +4) varied depending on the overall charge on the cluster. The number of semi-bridging hydrides increased (semi-bridging hydrides have two different Rh-H bond distances) as the charge on the cluster increased and simultaneously the number of perfectly bridging hydrides (equidistant between two Rh centers) decreased. This distortion maximized the bonding between the hydrides and the metal centers and resulted in the stabilization of orbitals related to the 2T(2g) set in a perfectly octahedral cluster. In contrast, the optimized structures of the 16-hydride clusters [Rh(6)(PH(3))(6)H(12)](x) (x = +1 or +2) were similar and both clusters contained an interstitial hydride, along with one terminal hydride, ten bridging hydrides and two coordinated H(2) molecules which were bound to two rhodium centers in an eta(2):eta(1)-fashion. All the hydrides were on the outside of the Rh(6) core in the lowest energy structures of the 14-hydride clusters [Rh(6)(PH(3))(6)H(14)] and [Rh(6)(PH(3))(6)H(14)](+), which both contained eleven bridging hydrides, one terminal hydride and one coordinated H(2) molecule. Unfortunately, the precise structure of [Rh(6)(PH(3))(6)H(14)](2+) could not be determined as structures both with and without an interstitial hydride were of similar energy. The reaction energetics for the uptake and release of two molecule of H(2) by a cycle consisting of [Rh(6)(PH(3))(6)H(12)](2+), [Rh(6)(PH(3))(6)H(16)](2+), [Rh(6)(PH(3))(6)H(14)](+), [Rh(6)(PH(3))(6)H(12)](+) and [Rh(6)(PH(3))(6)H(14)](2+) were modelled

  4. CATALYTIC INTERACTIONS OF RHODIUM, RUTHENIUM, AND MERCURY DURING SIMULATED DWPF CPC PROCESSING WITH HYDROGEN GENERATION

    Energy Technology Data Exchange (ETDEWEB)

    Koopman, D

    2008-10-09

    Simulations of the Defense Waste Processing Facility (DWPF) Chemical Processing Cell (CPC) vessels were performed as part of the ongoing investigation into catalytic hydrogen generation. Rhodium, ruthenium, and mercury have been identified as the principal elemental factors affecting the peak hydrogen generation rate in the DWPF Sludge Receipt and Adjustment Tank (SRAT) for a given acid addition. The primary goal of this study is to identify any significant interactions between the three factors. Noble metal concentrations were similar to recent sludge batches. Rh ranged from 0.0026-0.013% and Ru ranged from 0.010-0.050% in the dried sludge solids, while initial Hg ranged from 0.5-2.5 wt%. An experimental matrix was developed to ensure that the existence of statistically significant two-way interactions could be determined without confounding of the main effects with the two-way interaction effects. The nominal matrix design consisted of twelve SRAT cycles. Testing included: a three factor (Rh, Ru, and Hg) study at two levels per factor (eight runs), two duplicate midpoint runs, and two additional replicate runs to assess reproducibility away from the midpoint. Midpoint testing can identify potential quadratic effects from the three factors. A single sludge simulant was used for all tests. Acid addition was kept effectively constant except to compensate for variations in the starting mercury concentration. Six Slurry Mix Evaporator (SME) cycles were performed to supplement the SME hydrogen generation database. Some of the preliminary findings from this study include: (1) Rh was linked to the maximum SRAT hydrogen generation rate in the first two hours after acid addition in preliminary statistical modeling. (2) Ru was linked conclusively to the maximum SRAT hydrogen generation rate in the last four hours of reflux in preliminary statistical modeling. (3) Increasing the ratio of Hg/Rh shifted the noble metal controlling the maximum SRAT hydrogen generation rate from

  5. An ion-exchange method for selective separation of palladium, platinum and rhodium from solutions obtained by leaching automotive catalytic converters.

    Science.gov (United States)

    Gaita, R; Al-Bazi, S J

    1995-02-01

    An ion-exchange method has been developed for the separation of palladium, platinum and rhodium from a solution that is highly acidic and contains a considerable amount of lead, aluminum, iron and cerium, obtained by leaching a used honeycomb type automotive catalytic converter. A column of Amberlite IRA-93 anion-exchange resin was found appropriate to recover platinum metals from the pregnant solution. Selective stripping of these metals from the resin was achieved by eluting rhodium first with 6.0M hydrochloric acid, then palladium with a 1% ammonia solution at ambient temperature, and platinum with 5% of the reagent at elevated temperatures. Optimum conditions for leaching these metals from the catalyst were 5.0M hydrochloric acid and 0.4M sodium chlorate at 70 degrees C. This method can be applied to both analytical as well as large scale operations. It is simple, economical, and relatively safe for human exposure and the environment.

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

    Directory of Open Access Journals (Sweden)

    Siping Wei

    2016-08-01

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

  7. Rhodium-catalyzed acyl-transfer reaction between benzyl ketones and thioesters: synthesis of unsymmetric ketones by ketone CO-C bond cleavage and intermolecular rearrangement.

    Science.gov (United States)

    Arisawa, Mieko; Kuwajima, Manabu; Toriyama, Fumihiko; Li, Guangzhe; Yamaguchi, Masahiko

    2012-07-20

    In the presence of catalytic amounts of RhH(CO)(PPh3)3 and 1,2-bis(diphenylphosphino)benzene (dppBz), acyl groups were transferred between benzyl ketones and thioesters/aryl esters. The rhodium complex catalyzed the cleavage of ketone CO-C bonds and intermolecular rearrangement giving unsymmetric ketones. The acyl-transfer reaction also occurred with 1-(p-chlorophenyl)-3-(p-cyanophenyl)propane-2-one giving unsymmetric ketones.

  8. The interaction of hydrazine with an Rh(1 1 1) surface as a model for adsorption to rhodium nanoparticles: A dispersion-corrected DFT study

    Energy Technology Data Exchange (ETDEWEB)

    He, Yan Bin [School of Chemistry and Materials Science, Shanxi Normal University, Linfen 041004 (China); Pharmaceutical Department, Changzhi Medical College, Changzhi 046000 (China); Jia, Jian Feng, E-mail: jiajf@dns.sxnu.edu.cn [School of Chemistry and Materials Science, Shanxi Normal University, Linfen 041004 (China); Wu, Hai Shun, E-mail: wuhs@mail.sxnu.edu.cn [School of Chemistry and Materials Science, Shanxi Normal University, Linfen 041004 (China)

    2015-02-01

    Highlights: • We propose a model suitable for simulating the adsorption of hydrazine on rhodium nanoparticles. • We found that inclusion of dispersion correction results in significant enhancement for the adsorption to the Rh(1 1 1) surface. • Nanoparticles surface with lower-coordinated sites are more reactive than those with almost saturated surface sites. - Abstract: In recent years, metal nanoparticles were found to be excellent catalysts for hydrogen generation from hydrazine for chemical hydrogen storage. In order to gain a better understanding of these catalytic systems, we have simulated the adsorption of hydrazine on rhodium nanoparticles surfaces by density functional theory (DFT) calculations with dispersion correction, DFT-D3 in the method of Grimme. The rhodium nanoparticles were modeled by the Rh(1 1 1) surface, in addition, the adsorptions at corners and edges sites of nanoparticles were considered by using rhodium adatoms on the surfaces. The calculations showed that hydrazine binds most strongly to the edge of nanoparticle with adsorption energy of −2.48 eV, where the hydrazine bridges adatoms of edge with the molecule twisted to avoid a cis structure; similar adsorption energy was found at the corner of nanoparticle, where the hydrazine bridges corner atom and surface atom with gauche configuration. However, we found that inclusion of the dispersion correction results in significant enhancement of molecule–substrate binding, thereby increasing the adsorption energy, especially the adsorption to the Rh(1 1 1) surface. The results demonstrate that the surface structure is a key factor to determine the thermodynamics of adsorption, with low coordinated atoms which providing sites of strong adsorption from the surface.

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

    Directory of Open Access Journals (Sweden)

    Carmen Mejuto

    2015-12-01

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

  10. A Novel Eco-Friendly Vanadium Precipitation Method by Hydrothermal Hydrogen Reduction Technology

    Directory of Open Access Journals (Sweden)

    Guobin Zhang

    2017-09-01

    Full Text Available In view of the serious pollution problems caused by the traditional vanadium precipitation process, the eco-friendly technology of hydrothermal hydrogen reduction was first applied to precipitate phase pure vanadium sesquioxide (V2O3 products from stripped pentavalent vanadium (V (V solution extracted from vanadium-bearing shale. Thermodynamic analysis demonstrate the method of hydrothermal hydrogen reduction is feasible for precipitating V2O3 from V (V solution at a suitable pH range, and the reduction should better be carried out at a lower pH under the pH range in which V2O3 can exist stably. The V2O3 products of 99.92% in purity and a high vanadium precipitation percentage of 99.25% were achieved under a facile reaction condition of initial solution pH of 6, reaction temperature of 523 K, H2 partial pressure of 4 MPa and reaction time of 2 h. Based on the analysis of XRD and FE-SEM with EDS for the precipitation products obtained at serial reaction times, the phase transformation mechanism was summarized to serial reductions with the phase transformation of HxVyOz(2z−x−5y− → NaV2O5 → VO2(H2O0.5 → VOOH → V2O3. Compared with the two-step traditional method of precipitating vanadium with ammonium salt and roast-reduction (react at above 773 K for more than 3 h for preparing V2O3, this method only experiences one-step reduction under a green atmosphere of H2 gas with a lower reaction temperature of 523 K and a shorter reaction time of 2h. Therefore, this method for vanadium precipitation is characterized by being eco-friendly, having a short process and being low-energy consumption, which has great significance for the sustainable development of vanadium industry.

  11. Poverty Reduction

    OpenAIRE

    Ortiz, Isabel

    2007-01-01

    The paper reviews poverty trends and measurements, poverty reduction in historical perspective, the poverty-inequality-growth debate, national poverty reduction strategies, criticisms of the agenda and the need for redistribution, international policies for poverty reduction, and ultimately understanding poverty at a global scale. It belongs to a series of backgrounders developed at Joseph Stiglitz's Initiative for Policy Dialogue.

  12. Rhodium(I) complexes of -keto-stabilised 1,2-bis(diphenylphosphino)alkane mono ylides

    Indian Academy of Sciences (India)

    D Saravanabharathi; T S Venkatakrishnan; M Nethaji; S S Krishnamurthy

    2003-10-01

    Rhodium(I) complexes of the hybrid ylide-phosphine ligands, Ph2P(CH2)nPPh2(CHC(O)C6H5) ( = 1: dppm-yl, or 2: dppe-yl) have been synthesised from [Rh(-Cl)(COD)]2 (COD = 1,5-cyclooctadiene) and characterized by NMR spectroscopic and X-ray structural methods. The dppe-yl behaves as an ambidentate ligand; it functions as a monodentate P-donor ligand with a dangling ylidic carbon in the neutral chloro complex, [(COD)Rh(Cl)(dppe-yl)] (1), whereas replacement of the chloride by a non-coordinating counter anion results in the formation of the complexes, [(COD)Rh(L-L')]+ (L-L' = dppe-yl (2) or dppm-yl (3)) respectively in which the ligands are bonded to the metal via the phosphorus and the ylidic carbon atoms. The 1,5-cyclooctadiene (COD), present in the Rh(I) precursor, remains intact in the products. The structures of 1, 2 and 3 have been confirmed by X-ray crystallography.

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

    Directory of Open Access Journals (Sweden)

    M.S. Fal Desai

    2015-03-01

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

  14. Octahedral rhodium(III) complexes as kinase inhibitors: Control of the relative stereochemistry with acyclic tridentate ligands.

    Science.gov (United States)

    Mollin, Stefan; Riedel, Radostan; Harms, Klaus; Meggers, Eric

    2015-07-01

    Octahedral metal complexes are attractive structural templates for the design of enzyme inhibitors as has been demonstrated, for example, with the development of metallo-pyridocarbazoles as protein kinase inhibitors. The octahedral coordination sphere provides untapped structural opportunities but at the same time poses the drawback of dealing with a large number of stereoisomers. In order to address this challenge of controlling the relative metal-centered configuration, the synthesis of rhodium(III) pyridocarbazole complexes with facially coordinating acyclic tridentate ligands was investigated. A strategy for the rapid synthesis of such complexes is reported, the diastereoselectivities of these reactions were investigated, the structure of several complexes were determined by X-ray crystallography, the high kinetic stability of such complexes in thiol-containing solutions was demonstrated in (1)H-NMR experiments, and the protein kinase inhibition ability of this class of complexes was confirmed. It can be concluded that the use of multidentate ligands is currently maybe the most practical strategy to avoid a large number of possible stereoisomers in the course of exploiting octahedral coordination spheres as structural templates for the design of bioactive molecules.

  15. Heterobimetallic complexes of rhodium dibenzotetramethylaza[14]annulene [(tmtaa)Rh-M]: formation, structures, and bond dissociation energetics.

    Science.gov (United States)

    Imler, Gregory H; Peters, Garvin M; Zdilla, Michael J; Wayland, Bradford B

    2015-01-05

    A rhodium(II) dibenzotetramethylaza[14]annulene dimer ([(tmtaa)Rh]2) undergoes metathesis reactions with [CpCr(CO)3]2, [CpMo(CO)3]2, [CpFe(CO)2]2, [Co(CO)4]2, and [Mn(CO)5]2 to form (tmtaa)Rh-M complexes (M = CrCp(CO)3, MoCp(CO)3, FeCp(CO)2, Co(CO)4, or Mn(CO)5). Molecular structures were determined for (tmtaa)Rh-FeCp(CO)2, (tmtaa)Rh-Co(μ-CO)(CO)3, and (tmtaa)Rh-Mn(CO)5 by X-ray diffraction. Equilibrium constants measured for the metathesis reactions permit the estimation of several (tmtaa)Rh-M bond dissociation enthalpies (Rh-Cr = 19 kcal mol(-1), Rh-Mo = 25 kcal mol(-1), and Rh-Fe = 27 kcal mol(-1)). Reactivities of the bimetallic complexes with synthesis gas to form (tmtaa)Rh-C(O)H and M-H are surveyed.

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

    Directory of Open Access Journals (Sweden)

    Joseph S. Merola

    2015-02-01

    Full Text Available The crystal structures of two solvates of fac-trichloridotris(trimethylphosphane-κPrhodium(III are reported, i.e. one with water in the crystal lattice, fac-[RhCl3(Me3P3]·H2O, and one with methanol in the crystal lattice, fac-[RhCl3(Me3P3]·0.5CH3OH. These rhodium compounds exhibit distorted octahedral coordination spheres at the metal and are isotypic with the analogous iridium compounds previously reported by us [Merola et al. (2013. Polyhedron, 54, 67–73]. Comparison is made between the rhodium and iridium compounds, highlighting their isostructural relationships.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2015-06-15

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

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2011-01-30

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

  19. Rhodium-Catalyzed Regioselective Domino Azlactone-Alkyne Coupling/Aza-Cope Rearrangement: Facile Access to 2-Allyl-3-oxazolin-5-ones and Trisubstituted Pyridines.

    Science.gov (United States)

    Kuang, Jinqiang; Parveen, Shaista; Breit, Bernhard

    2017-07-10

    Rhodium-catalyzed regioselective addition of azlactones to internal alkynes combined with aza-Cope rearrangement provides efficient atom economic access to 2-allyl-3-oxazolin-5-one derivatives. Extension to a triple domino process, in which the above process is combined with in situ azlactone formation starting from amino acids renders this process even more attractive. Subsequent thermolysis of the 2-allyl-3-oxazolines enabled the de novo synthesis of trisubstituted pyridines. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Rhodium as permanent modifier for atomization of lead from biological fluids using tungsten filament electrothermal atomic absorption spectrometry

    Science.gov (United States)

    Zhou, Ying; Parsons, Patrick J.; Aldous, Kenneth M.; Brockman, Paul; Slavin, Walter

    2002-04-01

    Rhodium (Rh) was investigated as a permanent modifier for the atomization of Pb from biological fluids in W-filament atomic absorption spectrometry (AAS). Heating the W-filament with a Rh solution provided a protective coating for subsequent determinations of Pb in blood and urine matrices. The W-filament AAS instrumentation used was based on a prototype design that utilized self-reversal background correction scheme and peak area measurements. We found that Rh not only stabilized Pb during the pyrolysis step, but also facilitated the removal of carbonaceous residues during the cleaning step, requiring much less power than with phosphate modifier. Thus, the filament lifetime was greatly extended to over 300 firings. Periodic reconditioning with Rh was necessary every 30 firings or so. Conditioning the filament with Rh also permitted direct calibration using simple aqueous Pb standards. The method detection limit for blood Pb was approximately 1.5 μg dl -1, similar to that reported previously. Potential interferences from concomitants such as Na, K, Ca and Mg were evaluated. Accuracy was verified using lead reference materials from the National Institute of Standards and Technology and the New York State Department of Health. Blood lead results below 40 μg dl -1 were within ±1 μg dl -1 of certified values, and within ±10% above 40 μg dl -1; within-run precision was ±10% or better. Additional validation was reported using proficiency test materials and human blood specimens. All blood lead results were within the acceptable limits established by regulatory authorities in the US. When measuring Pb in urine, sensitivity was reduced and matrix-matched calibration became necessary. The method of detection limit was 27 μg l -1 for urine Pb. Urine lead results were also validated using an acceptable range comparable to that established for blood lead by US regulatory agencies.

  1. Rhodium particles supported by thin vanadia films as model systems for catalysis: An electron microscopy study

    Energy Technology Data Exchange (ETDEWEB)

    Penner, S. [Institut fuer Physikalische Chemie, Universitaet Innsbruck, Innrain 52a, A-6020 Innsbruck (Austria); Wang, D. [Fritz-Haber-Institut der Max-Planck-Gesellschaft, Faradayweg, 4-6, D-14195 Berlin (Germany); Schloegl, R. [Fritz-Haber-Institut der Max-Planck-Gesellschaft, Faradayweg, 4-6, D-14195 Berlin (Germany); Hayek, K. [Institut fuer Physikalische Chemie, Universitaet Innsbruck, Innrain 52a, A-6020 Innsbruck (Austria)]. E-mail: konrad.hayek@uibk.ac.at

    2005-07-22

    Well-shaped Rh particles grown epitaxially on NaCl surfaces were coated with a 25 nm layer of crystalline vanadium oxide by reactive deposition in 10{sup -4} mbar oxygen. The Rh/VO{sub x} film was subjected to consecutive heat treatments in 1 bar oxygen and in 1 bar hydrogen up to 673 K. The structural and morphological changes were monitored by (high-resolution) transmission electron microscopy, selected area electron diffraction and electron energy-loss spectroscopy and compared to the alterations of a bare vanadium oxide film treated under equal conditions. The stoichiometry and structure of the VO{sub x} support depend on the temperature of the NaCl template and on the deposition rate. Low deposition rates and high substrate temperatures favour the generation of a pure V{sub 2}O{sub 3} phase, with both V{sub 2}O{sub 3} and the Rh particles in epitaxial relation to NaCl (001). A treatment in 1 bar O{sub 2} between 300 and 573 K converts the supporting oxide into mixed V{sub 2}O{sub 3}, VO{sub 2} and V{sub 2}O{sub 5} phases. Oxidation at 673 K induces a complete reconstruction into a single V{sub 2}O{sub 5} phase, while an oxygen treatment at 723 K transforms also the Rh particles into ({beta})Rh{sub 2}O{sub 3}. Reduction of the bare V{sub 2}O{sub 5} film in 1 bar hydrogen yields cubic VO at 673 K, but reduction of the Rh/V{sub 2}O{sub 5} film leads to VO formation already at 473 K. Finally, a reduction of vanadia-supported Rh particles at and above 573 K results in the formation of Rh/V alloy structures.

  2. Hydroformylation of olefins and reductive carbonylation of aryl halides with syngas formed ex situ from dehydrogenative decarbonylation of hexane-1,6-diol

    DEFF Research Database (Denmark)

    Christensen, Stig Holden; Olsen, Esben Paul Krogh; Rosenbaum, Jascha;

    2014-01-01

    A variety of primary alcohols have been investigated as convenient substrates for the ex situ delivery of carbon monoxide and molecular hydrogen in a two-chamber reactor. The gaseous mixture is liberated in one chamber by an iridium-catalysed dehydrogenative decarbonylation of the alcohol...... and then consumed in the other chamber in either a rhodium-catalysed hydroformylation of olefins or a palladium-catalysed reductive carbonylation of aryl halides. Hexane-1,6-diol was found to be the optimum alcohol for both reactions where moderate to excellent yields were obtained of the product aldehydes...

  3. Determination of Rhodium in Catalysts and in Waste Water by Fire Assay- ICP Measurement%铅试金富集-ICP-AES测定催化剂及含铑废水中的铑

    Institute of Scientific and Technical Information of China (English)

    陈小兰; 朱嘉斌; 刘天平; 周志平; 王芳

    2012-01-01

    Rhodium in catalysts and waste water was concentrated firstly by lead fire assay, using palladium as protective agent for the cupellation to produce palladium -rhodium alloy. Then the alloy was dissolved and ICP - AES was used to measure rhodium. The results show that the enrichment by lead fire was very effective. Palladium matrix didn' t interfere with the measurement. The method is time - saving and accurate. The relative standard deviation is 97%. The method can be applied to the determination of rhodium in the range of 0. x% ~0. 000x% .%用铅试金富集催化剂及含铑废水的铑并用钯作灰吹保护,得到钯、铑合粒.合粒经溶解后,用ICP - AES测定其中的铑.该法的富集效果好,钯基体对测定没有干扰,测定快速、准确,相对标准偏差小于1%(n=7),回收率大于97%.本法可用于含铑0.x% ~0.000x%的测定.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2014-09-16

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

  5. Equilibrium thermodynamics to form a rhodium formyl complex from reactions of CO and H2: metal σ donor activation of CO.

    Science.gov (United States)

    Imler, Gregory H; Zdilla, Michael J; Wayland, Bradford B

    2014-04-23

    A rhodium(II) dibenzotetramethylaza[14]annulene dimer ([(tmtaa)Rh]2) (1) reacts with CO and H2 in toluene and pyridine to form equilibrium distributions with hydride and formyl complexes ((tmtaa)Rh-H (2); (tmtaa)Rh-C(O)H (3)). The rhodium formyl complex ((tmtaa)Rh-C(O)H) was isolated under a CO/H2 atmosphere, and the molecular structure was determined by X-ray diffraction. Equilibrium constants were evaluated for reactions of (tmtaa)Rh-H with CO to produce formyl complexes in toluene (K2(298 K)(tol) = 10.8 (1.0) × 10(3)) and pyridine (K2(298 K)(py) = 2.2 (0.2) × 10(3)). Reactions of 1 and 2 in toluene and pyridine are discussed in the context of alternative radical and ionic pathways. The five-coordinate 18-electron Rh(I) complex ([(py)(tmtaa)Rh(I)](-)) is proposed to function as a nucleophile toward CO to give a two-electron activated bent Rh-CO unit. Results from DFT calculations on the (tmtaa)Rh system correlate well with experimental observations. Reactions of 1 with CO and H2 suggest metal catalyst design features to reduce the activation barriers for homogeneous CO hydrogenation.

  6. Realistic energy surfaces for real-world systems: an IMOMO CCSD(T):DFT scheme for rhodium-catalyzed hydroformylation with the 6-DPPon ligand.

    Science.gov (United States)

    Gellrich, Urs; Himmel, Daniel; Meuwly, Markus; Breit, Bernhard

    2013-11-25

    The hydroformylation of terminal alkenes is one of the most important homogeneously catalyzed processes in industry, and the atomistic understanding of this reaction has attracted enormous interest in the past. Herein, the whole catalytic cycle for rhodium-catalyzed hydroformylation with the 6-diphenylphosphinopyridine-(2H)-1-one (6-DPPon) ligand 1 was studied. This catalytic transformation is challenging to describe computationally, since two requirements must be met: 1) changes in the hydrogen-bond network must be modeled accurately and 2) bond-formation/bond-breaking processes in the coordination sphere of the rhodium center must be calculated accurately. Depending on the functionals used (BP86, B3LYP), the results were found to differ strongly. Therefore, the complete cycle was calculated by using highly accurate CCSD(T) computations for a PH3 model ligand. By applying an integrated molecular orbital plus molecular orbital (IMOMO) method consisting of CCSD(T) as high level and DFT as low-level method, excellent agreement between the two functionals was achieved. To further test the reliability of the calculations, the energetic-span model was used to compare experimentally derived and computed activation barriers. The accuracy of the new IMOMO method apparently makes it possible to predict the catalytic potential of real-world systems.

  7. Ligandless cloud point extraction of trace amounts of palladium and rhodium in road dust samples using Span 80 prior to their determination by flame atomic absorption spectrometry

    Directory of Open Access Journals (Sweden)

    Mahmoud Roushani

    2014-01-01

    Full Text Available In this study, a procedure is developed for cloud point extraction of Pd(II and Rh(III ions in aqueous solution using Span 80 (non-ionic surfactant prior to their determination by flame atomic absorption spectroscopy. This method is based on the extraction of Pd(II and Rh(III ions at a pH of 10 using Span 80 with no chelating agent. We investigated the effect of various parameters on the recovery of the analyte ions, including pH, equilibration temperature and time, concentration of Span 80, and ionic strength. Under the best experimental conditions, the limits of detection based on 3Sb for Pd(II and Rh(III ions were 1.3 and 1.2 ng mL-1, respectively. Seven replicate determinations of a mixture of 0.5 µg mL-1 palladium and rhodium ions gave a mean absorbance of 0.058 and 0.053 with relative standard deviations of 1.8 and 1.6%, respectively. The developed method was successfully applied to the extraction and determination of the palladium and rhodium ions in road dust and standard samples and satisfactory results were obtained.

  8. Creation of Ge-Nx-Cy Configures in Carbon Nanotubes: Origin of Enhanced Electrocatalytic Performance for Oxygen Reduction Reaction.

    Science.gov (United States)

    She, Xilin; Li, Qianqian; Ma, Na; Sun, Jin; Jing, Dengwei; Chen, Chengmeng; Yang, Lijun; Yang, Dongjiang

    2016-04-27

    High-performance nitrogen and germanium codoped carbon nanotubes (N-Ge-CNTs) were synthesized as oxygen reduction reaction (ORR) catalysts by one-step sintering of carboxyethyl germanium sesquioxide and multiwalled CNTs in NH3 atmosphere. The ORR electrocatalytic activity evaluation was performed by using limited current density, selective reaction pathway, onset potential, H2O2 yields, and kinetic current density. In comparison with Ge or N solely doped CNTs, the codoped samples display more excellent ORR catalytic performance. It was observed that the codoped GeN3C, GeN4, and GeN4 + NC3 microstructures in N-Ge-CNTs are crucial to improving ORR catalytic performance, such as ideal 4 electron pathway (3.95) and positive onset potential (-0.08 V). The high ORR performance is attributed to the synergistic effect of N and Ge doping, which is capable of activating the π electrons of sp(2) hybridized orbital around carbon nantotubes. The ORR catalytic synergistic effect has also been verified by calculating the work function on the basis of density functional theory (DFT).

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

    KAUST Repository

    Bonnefille, Eric

    2012-06-19

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

  10. The organometallic fluorine chemistry of palladium and rhodium: studies toward aromatic fluorination.

    Science.gov (United States)

    Grushin, Vladimir V

    2010-01-19

    Although springing from two established fields, organometallic chemistry and fluorine chemistry, organometallic fluorine chemistry is still in its early stages. However, developments in this area are expected to provide new tools for the synthesis of selectively fluorinated organic compounds that have been in high demand. Selectively fluorinated organic molecules currently account for up to 40% of all agrochemicals and 20% of all pharmaceuticals on the market. Our research efforts have been focused on the development of new organometallic and catalytic methods for the selective introduction of fluorine and the CF(3) group into the aromatic ring. Monofluorinated and trifluoromethylated aromatic compounds are still made by the old technologies that employ stoichiometric quantities of hazardous and costly materials. In this Account, we describe our studies toward the development of safe, catalytic alternatives to these methods. We have synthesized, characterized, and studied the reactivity of the first aryl palladium(II) fluoride complexes. We have demonstrated for the first time that a Pd-F bond can be formed in a soluble and isolable molecular complex: this bond is more stable than previously thought. Toward the goal of fluoroarene formation via Ar-F reductive elimination, we have studied a number of sigma-aryl Pd(II) fluorides stabilized by various P, N, and S ligands. It has been established that numerous conventional tertiary phosphine ligands, most popular in Pd catalysis, are unlikely to be useful for the desired C-F bond formation at the metal center because of the competing, kinetically preferred P-F bond-forming reaction. A metallophosphorane mechanism has been demonstrated for the P-F bond-forming processes at Rh(I) and Pd(II), which rules out the possibility of controlling these reactions by varying the amount of phosphine in the system, a most common and often highly efficient technique in homogeneous catalysis. The novel F/Ph rearrangement of the fluoro

  11. Resistivity, Specific Heat, and Susceptibility of the Intermediate Valence System Cerium ((RHODIUM(X)PALLADIUM(1 -X))(3))

    Science.gov (United States)

    Scoboria, Clarence Preston, III

    In the mixed valent system Ce(Rh(,x)Pd(,1-x))(,3), the dependence of resistivity, magnetic susceptibility, and specific heat on the rhodium concentration x has been experimentally studied. Ce(Rh(,x)Pd(,1-x))(,3) is tetravalent from x = .216 to 1.00, and mixed valent from x = .216 to x = 0. Based on Vegard's rule and lattice constant data, n(,f) is considered to vary linearly with x, ranging from n(,f) = 0 at x = .216 to n(,f) (TURNEQ) .55 at x = 0. The resistivity was measured from 1.5K to 300K for x from 0 to 1. In the tetravalent range the temperature dependence was independent of x. In the mixed valent region (rho) at all temperatures increased rapidly with n(,f). (rho) (T = 0) was found to be proportional to n(,f)('2) in the mixed valent range. Application of pressures up to seven kilobars were found to produce very little change in resistivity in the mixed valent range. The specific heat was measured from 2K to 15K in the mixed valent range and for CeRh(,3). C/T versus T('2) plots were well-fitted by a straight line at low temperature except for a bump at 6K, which is not understood. The mixed valence component of the electronic specific heat coefficient (gamma) is found to be proportional to n(,f)('2). Magnetic susceptibility was measured from 2K to 300K in the mixed valent range. For each x, (chi) (T) was approximately independent of temperature below (TURN) 150K, except for an impurity tail below 40K. (chi)(,0) (the plateau value) was found to be approximately proportional to n(,f) in the mixed valent range. All three quantities (rho), (gamma), and (chi) are compared to the theories of Yosida and Sakurai, and Newns and Hewson. The best fits indicate that the f level density of states is well represented by a lorentzian which can accommodate six electrons.

  12. Preparation and Electrocatalytic Application of Composites Containing Gold Nanoparticles Protected with Rhodium-Substituted Polyoxometalates.

    Science.gov (United States)

    Wiaderek, Kamila M; Cox, James A

    2011-04-01

    Substitution of a metal center of phosphomolybdate, PMo(12)O(40) (3-) (PMo(12)), or its tungsten analogue with dirhodium(II) and subsequent stabilization of gold nanoparticles, AuNPs, with Rh(2)PMo(11) is demonstrated. The AuNP-Rh(2)PMo(11) mediates oxidations but adsorbs too weakly for direct modification of electrode materials. Stability in quiescent solution was achieved by modifying glassy carbon (GC) with 3-aminopropyltriethoxysilane (APTES) and then electrostatically assembling AuNP-Rh(2)PMo(11). At GC|APTES|AuNP-Rh(2)PMo(11), cyclic voltammetry showed the expected set of three reversible peak-pairs for PMo(11) in the range -0.2 to 0.6 vs (Ag/AgCl)/V and the reversible Rh(II,III) couple at 1.0 vs (Ag/AgCl)/V. The presence of AuNPs increased the current for the reduction of bromate by a factor of 2.5 relative to that at GC|Rh(2)PMo(11), and the electrocatalytic oxidation of methionine displayed characteristics of synergism between the AuNP and Rh(II). To stabilize AuNP-Rh(2)PMo(11) on a surface in a flow system, GC was modified by electrochemically assisted deposition of a sol-gel with templated 10-nm pores prior to immobilizing the catalyst in the pores. The resulting electrode permitted determination of bromate by flow-injection amperometry with a detection limit of 4.0 × 10(-8) mol dm(-3).

  13. Investigation of aging processes of graphite tubes modified with iridium and rhodium used for atomic spectrometry

    Science.gov (United States)

    Bulska, Ewa; Piaścik, Marek; Katskov, Dmitri; Darangwa, Nicholas; Grotti, Marco

    2007-11-01

    UV spectrometry (187-380 nm) with charge coupled device (CCD) detection was used to study the evolution of absorption spectra during the vaporization of various species in the pyrocoated graphite furnace, with electrodeposited Ir and Rh as modifiers. In order to mimic a typical matrix composition, various salts of aluminum, manganese, copper, magnesium, sodium, and lead were used in microgram amounts. Changes in spectra and vapor release rate, along with aging of the tubes in the repetitive temperature cycles, were observed. Compared to the unmodified pyrocoated tubes, the presence of Ir or Rh causes a significant reduction in the vaporization efficiency, especially for microgram amounts of copper and aluminum introduced as nitrates, and manganese introduced as a sulfate. The vaporization efficiency, for magnesium and sodium as chlorides, and for lead as a sulfate, remained unchanged. Interestingly, the aging of the tubes was accompanied by partial restoration of the spectral characteristics for unmodified tubes. For example, with unmodified pyrocoated tubes, the vaporization spectrum, appearing as a consequence of the decomposition of aluminum nitrate, consisted of Al2O bands overlapped by Al atomic lines. In the freshly modified tubes, intensities of those lines and bands were substantially reduced, and in this case, the dominance of AlO molecules was observed. The efficiency of vaporization of aluminum species increased in the aged modified tubes. The scanning electron microscopy (SEM) images of the modified surfaces for the new and aged tubes indicated that aging of the tubes is accompanied by the destruction of the pyrocoating, formation of pyrographite shells around the areas where the modifier was electrodeposited, and finally, complete substitution of the metal on the graphite surface by pyrographite debris.

  14. Preparation and Electrocatalytic Application of Composites Containing Gold Nanoparticles Protected with Rhodium-Substituted Polyoxometalates

    Science.gov (United States)

    Wiaderek, Kamila M.; Cox, James A.

    2010-01-01

    Substitution of a metal center of phosphomolybdate, PMo12O403- (PMo12), or its tungsten analogue with dirhodium(II) and subsequent stabilization of gold nanoparticles, AuNPs, with Rh2PMo11 is demonstrated. The AuNP-Rh2PMo11 mediates oxidations but adsorbs too weakly for direct modification of electrode materials. Stability in quiescent solution was achieved by modifying glassy carbon (GC) with 3-aminopropyltriethoxysilane (APTES) and then electrostatically assembling AuNP-Rh2PMo11. At GC|APTES|AuNP-Rh2PMo11, cyclic voltammetry showed the expected set of three reversible peak-pairs for PMo11 in the range -0.2 to 0.6 vs (Ag/AgCl)/V and the reversible RhII,III couple at 1.0 vs (Ag/AgCl)/V. The presence of AuNPs increased the current for the reduction of bromate by a factor of 2.5 relative to that at GC|Rh2PMo11, and the electrocatalytic oxidation of methionine displayed characteristics of synergism between the AuNP and RhII. To stabilize AuNP-Rh2PMo11 on a surface in a flow system, GC was modified by electrochemically assisted deposition of a sol-gel with templated 10-nm pores prior to immobilizing the catalyst in the pores. The resulting electrode permitted determination of bromate by flow-injection amperometry with a detection limit of 4.0 × 10-8 mol dm-3. PMID:21499522

  15. Study on separation and enrichment of rhodium in silver-containing materials by lead fire assay%铅试金分离富集含银物料中铑的研究

    Institute of Scientific and Technical Information of China (English)

    林海山; 唐维学; 戴凤英; 刘天平

    2013-01-01

    报道了一个改进的铅试金分离富集-ICP-AES测定含银物料中铑的方法.用钯粉或钯银粉混合物作灰吹保护剂,分别研究了钯与银的质量比、合粒中钯银与铑的质量比对分离富集合银物料中铑的影响.结果表明:当钯量:银量≥2:1时,铑在灰吹过程的损失可忽略;当钯银量:铑量≥40∶1时合粒中铑在常压下可以完全溶解;当银量:钯量≥1∶10时,合粒可以用HNO3(1+3)快速溶解.研究了钯量对电感耦合等离子体发射光谱法测定铑的影响.方法回收率98.2% ~ 100.5%,对实际样品进行分析,测定值与推荐值一致,相对标准偏差小于4.0%(n=5).%An improvement was made on the separation and enrichment of rhodium by lead fire assay with ICP-AES method. Using palladium powder or a mixture of palladium silver as protective reagent for cupellation, the effects of various testing factors, such as the mass ratio of palladium to silver and the mass ratio of palladium-silver to rhodium, have been studied in detail when rhodium was enriched. The results indicated that loss of rhodium could be ignored for cupellation process at Rh; Pd ≥ 2; 1, rhodium of kernel could be completely dissolved at atmospheric pressure and Pd-Ag:Rh≥40:1, kernel of precious metals could be dissolved with HNO3 (1 +3) at Ag:Pd≥l:10. The effects of palladium on the determination of rhodium with inductively coupled plasma atomic emission spectrometry had been studied. The recoveries of silver in samples ranged from 98. 2% to 100. 5%. Found values were consistent with recommended values, and the relative standard derivations (RSDs) were less than 4. 0 % ( n =5) in the real samples.

  16. The comparison between the dose mode and the standard mode in molybdenum-rhodium target X-ray mammography%钼铑双靶乳腺X线摄影剂量优先模式与标准模式对照研究

    Institute of Scientific and Technical Information of China (English)

    王海阔; 周剑; 张妍; 杨蓉; 房丽蕊

    2015-01-01

    Objective To investigate the value of the dose mode (giving priority to dose reduction)of molybdenum-rhodium tar-get X-ray photography in mammary gland low-dose examination.Methods Fourty patients with breast cancer were recruited,and their bilateral mammographic images were respectively acquired by the standard modes and the dose modes in both CC and MLO po-sition using molybdenum-rhodium target X-ray machine.The total of 1 60 mammograms were obtained and analyzed in order to as-sess the images quality.The values of average glandular dose (AGD)and entrance skin exposure (ESE)on each patient were detec-ted and recorded respectively.Results The higher quality of images were guaranteed in both the standard modes and the dose modes.There was no significant difference in two mammographic modes (χ2 =0.427,P >0.05).Compared with the standard mode, X-ray exposure such as AGD and ESE values were reduced by 28.63% and 28.28% in CC position,and 26.33% and 29.43% in MLO position respectively for the dose mode.The paired t-test results showed that the differences of radiation exposure in AGD and ESE between the dose mode and the standard mode were all statistically significant (P0.05)。与标准模式相比,剂量优先模式摄影 CC 位 AGD 值降低约28.63%,ESE 值降低约28.28%,两者间具有显著性差异(t AGD =12.928,P <0.05,t ESE =8.850,P <0.05);MLO 位 AGD 值降低约26.33%,ESE 值降低约29.43%,两者间具有显著性差异(t AGD =11.006,P <0.05,t ESE =8.400,P <0.05)。结论在获取同等乳腺图像质量的情况下,钼铑双靶乳腺 X 射线摄影检查中剂量优先模式较标准模式能够有效降低受检者的辐射剂量。

  17. Synthesis of iridium and rhodium complexes with new chiral phosphine-NHC ligands based on 1,1'-binaphthyl framework and their application in asymmetric hydrogenation.

    Science.gov (United States)

    Gu, Peng; Zhang, Jun; Xu, Qin; Shi, Min

    2013-10-07

    The first series of chiral phosphine-imidazole carbene ligands based on a 1,1'-binaphthyl framework were synthesized from (R)-2-amine-2'-(diphenylphosphino)-1,1'-binaphthyl (1) in a four-step pathway. After deprotonation of these phosphine-imidazolium salts with LiO(t)Bu, and subsequent complexation with [Ir(COD)Cl]2 and anion exchange with NaBArF, phosphine-carbene chelated iridium complexes (R)-6a and (R)-6b were obtained. Their structures have been characterized by NMR and X-ray diffraction analysis. The NHC-phosphine rhodium complex (R)-6c has been also obtained by a similar synthetic method. These iridium complexes have been applied to catalyze the asymmetric hydrogenation of alkenes to give the corresponding products in moderate to excellent conversion (up to 99%) and moderate enantioselectivities under mild conditions (up to 61% ee).

  18. Theoretical study of the adsorption of rhodium on a TiO{sub 2}(1 1 0)-1 Multiplication-Sign 1 surface

    Energy Technology Data Exchange (ETDEWEB)

    Mutombo, P., E-mail: mutombo@fzu.cz [Institute of Physics of Academy of Sciences of the Czech Republic, Cukrovarnicka 10, 16253 Praha 6 (Czech Republic); Balazs, N. [Reaction Kinetics Laboratory, Institute of Nanochemistry and Catalysis, CRC of the Hungarian Academy of Sciences, University of Szeged, P.O. Box 168, H-6701 Szeged (Hungary); Majzik, Z. [Institute of Physics of Academy of Sciences of the Czech Republic, Cukrovarnicka 10, 16253 Praha 6 (Czech Republic); Reaction Kinetics Laboratory, Institute of Nanochemistry and Catalysis, CRC of the Hungarian Academy of Sciences, University of Szeged, P.O. Box 168, H-6701 Szeged (Hungary); Berko, A. [Reaction Kinetics Laboratory, Institute of Nanochemistry and Catalysis, CRC of the Hungarian Academy of Sciences, University of Szeged, P.O. Box 168, H-6701 Szeged (Hungary); Chab, V. [Institute of Physics of Academy of Sciences of the Czech Republic, Cukrovarnicka 10, 16253 Praha 6 (Czech Republic)

    2012-03-01

    Density functional theory (DFT) calculations were used to study the adsorption of rhodium on a TiO{sub 2}(1 1 0)-1 Multiplication-Sign 1 surface as a function of coverage. It was found that Rh atom prefers the hollow site between a bridging oxygen atom, a threefold oxygen atom and a fivefold coordinated Ti atom, regardless of the coverage used. DFT calculations also suggest that Rh-Rh interaction is attractive along the [0 0 1] direction, implying that the Rh 1D nanostructure should grow preferentially along this direction. Simulated Rh dimer clusters resemble strongly Pd dimers resolved in STM experiments suggesting that both metals occupy the same adsorption site at the TiO{sub 2}(1 1 0) surface.

  19. The role of fluctuations in bistability and oscillations during the H{sub 2} + O{sub 2} reaction on nanosized rhodium crystals

    Energy Technology Data Exchange (ETDEWEB)

    Grosfils, P.; Gaspard, P. [Center for Nonlinear Phenomena and Complex Systems (CENOLI), Université libre de Bruxelles (ULB), Campus Plaine Code Postal 231, B-1050 Brussels (Belgium); Visart de Bocarmé, T. [Center for Nonlinear Phenomena and Complex Systems (CENOLI) and Chemical Physics of Materials—Catalysis and Tribology, Université libre de Bruxelles (ULB), Campus Plaine Code Postal 243, B-1050 Brussels (Belgium)

    2015-08-14

    A combined experimental and theoretical study is presented of fluctuations observed by field ion microscopy in the catalytic reaction of water production on a rhodium tip. A stochastic approach is developed to provide a comprehensive understanding of the different phenomena observed in the experiment, including burst noise manifesting itself in a bistability regime, noisy oscillations, and nanopatterns with a cross-like oxidized zone separating the surface into four quadrants centered on the (111) facets. The study is based on a stochastic model numerically simulating the processes of adsorption, desorption, reaction, and transport. The surface diffusion of hydrogen is described as a percolation process dominated by large clusters corresponding to the four quadrants. The model reproduces the observed phenomena in the ranges of temperature, pressures, and electric field of the experiment.

  20. Rhodium-Catalyzed C-C Bond Formation via Heteroatom-Directed C-H Bond Activation

    Energy Technology Data Exchange (ETDEWEB)

    Colby, Denise; Bergman, Robert; Ellman, Jonathan

    2010-05-13

    Once considered the 'holy grail' of organometallic chemistry, synthetically useful reactions employing C-H bond activation have increasingly been developed and applied to natural product and drug synthesis over the past decade. The ubiquity and relative low cost of hydrocarbons makes C-H bond functionalization an attractive alternative to classical C-C bond forming reactions such as cross-coupling, which require organohalides and organometallic reagents. In addition to providing an atom economical alternative to standard cross - coupling strategies, C-H bond functionalization also reduces the production of toxic by-products, thereby contributing to the growing field of reactions with decreased environmental impact. In the area of C-C bond forming reactions that proceed via a C-H activation mechanism, rhodium catalysts stand out for their functional group tolerance and wide range of synthetic utility. Over the course of the last decade, many Rh-catalyzed methods for heteroatom-directed C-H bond functionalization have been reported and will be the focus of this review. Material appearing in the literature prior to 2001 has been reviewed previously and will only be introduced as background when necessary. The synthesis of complex molecules from relatively simple precursors has long been a goal for many organic chemists. The ability to selectively functionalize a molecule with minimal pre-activation can streamline syntheses and expand the opportunities to explore the utility of complex molecules in areas ranging from the pharmaceutical industry to materials science. Indeed, the issue of selectivity is paramount in the development of all C-H bond functionalization methods. Several groups have developed elegant approaches towards achieving selectivity in molecules that possess many sterically and electronically similar C-H bonds. Many of these approaches are discussed in detail in the accompanying articles in this special issue of Chemical Reviews. One approach

  1. Computational Exploration of Rh(III)/Rh(V) and Rh(III)/Rh(I) Catalysis in Rhodium(III)-Catalyzed C-H Activation Reactions of N-Phenoxyacetamides with Alkynes.

    Science.gov (United States)

    Yang, Yun-Fang; Houk, K N; Wu, Yun-Dong

    2016-06-01

    The selective rhodium-catalyzed functionalization of arenes is greatly facilitated by oxidizing directing groups that act both as directing groups and internal oxidants. We report density functional theory (B3LYP and M06) investigations on the mechanism of rhodium(III)-catalyzed redox coupling reaction of N-phenoxyacetamides with alkynes. The results elucidated the role of the internal oxidizing directing group, and the role of Rh(III)/Rh(I) and Rh(III)/Rh(V) catalysis of C-H functionalizations. A novel Rh(III)-Rh(V)-Rh(III) cycle successfully rationalizes recent experimental observations by Liu and Lu et al. ( Liu , G. Angew. Chem. Int. Ed. 2013 , 52 , 6033 ) on the reactions of N-phenoxyacetamides with alkynes in different solvents. Natural Bond Orbital (NBO) analysis confirms the identity of Rh(V) intermediate in the catalytic cycle.

  2. Rh(III)-Catalyzed Cascade Annulation/C-H Activation of o-Ethynylanilines with Diazo Compounds: One-Pot Synthesis of Benzo[a]carbazoles via 1,4-Rhodium Migration.

    Science.gov (United States)

    Guo, Songjin; Yuan, Kai; Gu, Meng; Lin, Aijun; Yao, Hequan

    2016-10-05

    A Rh(III)-catalyzed cascade annulation/C-H activation of o-ethynylanilines with diazo compounds has been developed. This concise method allows for the rapid formation of a number of benzo[a]carbazoles in high yields, exhibiting good functional group tolerance and scalability. The key to the success of this approach involves one C-N bond and two C-C bond formation, and an aryl-to-aryl 1,4-rhodium migration.

  3. Rhodium-catalyzed intermolecular [3+3] cycloaddition of vinyl aziridines with C,N-cyclic azomethine imines: stereospecific synthesis of chiral fused tricyclic 1,2,4-hexahydrotriazines.

    Science.gov (United States)

    Zhu, Chao-Ze; Feng, Jian-Jun; Zhang, Junliang

    2017-04-25

    An atom-economic route to ring-fused 1,2,4-hexahydrotriazines relying upon a new synthetic application of vinylaziridines in a rhodium-catalyzed intermolecular [3+3] cycloaddition of C,N-cyclic azomethine imines has been reported. Highly efficient chirality transfer in the present transformation was also observed, providing a new method for the synthesis of sp(3)-carbon-rich 1,2,4-hexahydrotriazines in an enantioselective manner.

  4. Rhodium (II) cycle alkanecarboxylate: synthesis, spectroscopic and thermo analytic studies and evaluation of the antitumor potential; Cicloalcanocarboxilatos de rodio(II). Sintese, estudos espectroscopicos, termoanaliticos e avaliacao do potencial antitumor

    Energy Technology Data Exchange (ETDEWEB)

    Souza, Aparecido Ribeiro de

    1995-07-01

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

  5. Determination of Ultra-trace Rhodium in Water Samples by Graphite Furnace Atomic Absorption Spectrometry after Cloud Point Extraction Using 2-(5-Iodo-2-Pyridylazo)-5-Dimethylaminoaniline as a Chelating Agent.

    Science.gov (United States)

    Han, Quan; Huo, Yanyan; Wu, Jiangyan; He, Yaping; Yang, Xiaohui; Yang, Longhu

    2017-03-24

    A highly sensitive method based on cloud point extraction (CPE) separation/preconcentration and graphite furnace atomic absorption spectrometry (GFAAS) detection has been developed for the determination of ultra-trace amounts of rhodium in water samples. A new reagent, 2-(5-iodo-2-pyridylazo)-5-dimethylaminoaniline (5-I-PADMA), was used as the chelating agent and the nonionic surfactant TritonX-114 was chosen as extractant. In a HAc-NaAc buffer solution at pH 5.5, Rh(III) reacts with 5-I-PADMA to form a stable chelate by heating in a boiling water bath for 10 min. Subsequently, the chelate is extracted into the surfactant phase and separated from bulk water. The factors affecting CPE were investigated. Under the optimized conditions, the calibration graph was linear in the range of 0.1-6.0 ng/mL, the detection limit was 0.023 ng/mL for rhodium and relative standard deviation was 3.67% (c = 1.0 ng/mL, n = 11).The method has been applied to the determination of trace rhodium in water samples with satisfactory results.

  6. Electromeric rhodium radical complexes

    NARCIS (Netherlands)

    Puschmann, F.F.; Harmer, J.; Stein, D.; Rüegger, H.; de Bruin, B.; Grützmacher, H.

    2010-01-01

    Radical changes: One single P-Rh-P angle determines whether the odd electron in the paramagnetic complex [Rh(trop2PPh)(PPh3)] is delocalized over the whole molecule (see picture, blue) or is localized on the P—Rh unit (red). The two energetically almost degenerate electromers exist in a fast equilib

  7. Exceptional Reductions

    CERN Document Server

    Marrani, Alessio; Riccioni, Fabio

    2011-01-01

    Starting from basic identities of the group E8, we perform progressive reductions, namely decompositions with respect to the maximal and symmetric embeddings of E7xSU(2) and then of E6xU(1). This procedure provides a systematic approach to the basic identities involving invariant primitive tensor structures of various irreprs. of finite-dimensional exceptional Lie groups. We derive novel identities for E7 and E6, highlighting the E8 origin of some well known ones. In order to elucidate the connections of this formalism to four-dimensional Maxwell-Einstein supergravity theories based on symmetric scalar manifolds (and related to irreducible Euclidean Jordan algebras, the unique exception being the triality-symmetric N = 2 stu model), we then derive a fundamental identity involving the unique rank-4 symmetric invariant tensor of the 0-brane charge symplectic irrepr. of U-duality groups, with potential applications in the quantization of the charge orbits of supergravity theories, as well as in the study of mult...

  8. Selective synthesis and characterization of single-site HY zeolite-supported rhodium complexes and their use as catalysts for ethylene hydrogenation and dimerization

    Science.gov (United States)

    Khivantsev, Konstantin

    Single-site Rh(CO)2, Rh(C2H4)2 and Rh(NO)2 complexes anchored on various dealuminated HY zeolites can be used as precursors for the selective surface mediated synthesis of well-defined site-isolated Rh(CO)(H)x complexes. DFT calculations and D 2 isotope exchange experiments provide strong evidence for the formation of a family of site isolated mononuclear rhodium carbonyl hydride complexes (including the first examples of RhH complexes with undissociated H2 ligands): Rh(CO)(H2), Rh(CO)(H)2, and Rh(CO)(H). The fraction of each individual complex formed varies significantly with the Si/Al ratio of the zeolite and the nature of the precursor used. HY zeolite-supported mononuclear Rh(CO)2 complexes are very active in ethylene hydrogenation and ethylene dimerization under ambient conditions. There is strong evidence for the cooperation mechanism between mononuclear rhodium complexes and Bronsted acid sites of the zeolite support in C-C bond formation process, as well as ethane formation. Finally, it is shown that the dimerization pathway selectivity can be progressively tuned (and completely switched off) by modifying the number of Bronsted acid sites on the zeolite surface. HY zeolite-supported mononuclear Rh(NO)2 complexes can be selectively formed upon exposure of Rh(CO)2/HY to the gas phase NO/He. They are structurally similar to Rh(CO)2/HY with Rh(I) retaining square planar geometry and nitrosyl ligands adopting a linear configuration. Rh(NO)2/HY30 is active in ethylene hydrogenation and ethylene dimerization under ambient conditions. This is the first unprecedented example of a supported transition-metal nitrosyl complex capable of performing a catalytic reaction. Moreover, this is the first example of a site-isolated Rh complex with ligands other than ethylene or carbonyl, which can catalyze both ethylene hydrogenation and dimerization. Unlike its dicarbonyl counterpart, dinitrosyl rhodium complex has a uniquely different reactivity towards ethylene and hydrogen

  9. Toward new organometallic architectures: synthesis of carbene-centered rhodium and palladium bisphosphine complexes. stability and reactivity of [PC(BIm)PRh(L)][PF6] pincers.

    Science.gov (United States)

    Plikhta, Andriy; Pöthig, Alexander; Herdtweck, Eberhardt; Rieger, Bernhard

    2015-10-05

    In this article, we report the synthesis of a tridentate carbene-centered bisphosphine ligand precursor and its complexes. The developed four-step synthetic strategy of a new PC(BIm)P pincer ligand represents the derivatization of benzimidazole in the first and third positions by (diphenylphosphoryl)methylene synthone, followed by phosphine deprotection and subsequent insertion of a noncoordinating anion. The obtained ligand precursor undergoes complexation, with PdCl2 and [μ-OCH3Rh(COD)]2 smoothly forming the target organometallics [PC(BIm)PPdCl][PF6] and [PC(BIm)PRh(L)][PF6] under mild hydrogenation conditions. A more detailed study of the rhodium complexes [PC(BIm)PRh(L)][PF6] reveals significant thermal stability of the PC(BIm)PRh moiety in the solid state as well as in solution. The chemical behavior of 1,3-bis(diphenylphosphinomethylene)benzimidazol-2-ylrhodium acetonitrile hexafluorophosphate has been screened under decarbonylation, hydrogenation, and hydroboration reaction conditions. Thus, the PC(BIm)PRh(I) complex is a sufficiently stable compound, with the potential to be applied in catalysis.

  10. Iridium(III) and Rhodium(III) compounds of dipyridyl-N-alkylimine and dipyridyl-NH-ketimine: Spectral characterization and crystal structure

    Indian Academy of Sciences (India)

    KEISHAM S SINGH; PENG WANG; NITEEN A NARKHEDE; YURIJ MOZHARIVSKYJ

    2017-03-01

    Pentamethylcyclopentadienyl iridium(III) and rhodium(III) complexes of formulation [(η⁵- C₅Me₅)M{(C₅H₄N) ₂C=NR)}Cl]PF₆ were prepared by the reaction of [MCl2(η⁵-C₅Me₅)] ₂ (M = Ir or Rh) with dipyridyl-N-alkylimine ligands, (C₅H₄N) ₂C=NR (R = Me or Et) in the presence of NH₄PF₆ at room temperature. The reaction also produced an unexpected dipyridyl-NH-ketimine organometallic compound [(η⁵-C₅Me₅)M {(C₅H₄N) ₂C=NH}Cl]PF6 as minor product when the reaction was performed under refluxing acetonitrile. The NH-ketimine compounds were formed via N-C single bond cleavage of imine ligand resulting in coordination of the transformed ligand, (C5₅H₄N) ₂C=NH to the metal centre. Complexes were obtained as their hexafluorophosphate salts and characterized based on IR, NMR and ESI-MS spectroscopic data. Authenticity of NH-ketimine organometallic compound was established by single crystal X-ray analysis of a representative compound, which crystallized in orthorhombic space group Pbcn and has a pseudo-octahedral geometry around the metal ion.

  11. Rhodium nanoparticle-modified screen-printed graphite electrodes for the determination of hydrogen peroxide in tea extracts in the presence of oxygen.

    Science.gov (United States)

    Gatselou, Vasiliki A; Giokas, Dimothenis L; Vlessidis, Athanasios G; Prodromidis, Mamas I

    2015-03-01

    In this work we describe the fabrication of nanostructured electrocatalytic surfaces based on polyethyleneimine (PEI)-supported rhodium nanoparticles (Rh-NP) over graphite screen-printed electrodes (SPEs) for the determination of hydrogen peroxide in the presence of oxygen. Rh-NP, electrostatically stabilized by citrate anions, were immobilized over graphite SPEs, through coulombic attraction on a thin film of positively charged PEI. The functionalized sensors, polarized at 0.0 V vs. Ag/AgCl/3 M KCl, exhibited a linear response to H2O2 over the concentration range from 5 to 600 μmol L(-1) H2O2 in the presence of oxygen. The 3σ limit of detection was 2 μmol L(-1) H2O2, while the reproducibility of the method at the concentration level of 10 μmol L(-1) H2O2 (n=10) and between different sensors (n=4) was lower than 3 and 5%, respectively. Most importantly, the sensors showed an excellent working and storage stability at ambient conditions and they were successfully applied to the determination of H2O2 produced by autooxidation of polylphenols in tea extracts with ageing. Recovery rates ranged between 97 and 104% suggesting that the as-prepared electrodes can be used for the development of small-scale, low-cost chemical sensors for use in on-site applications. Copyright © 2014 Elsevier B.V. All rights reserved.

  12. Interception and characterization of catalyst species in rhodium bis(diazaphospholane)-catalyzed hydroformylation of octene, vinyl acetate, allyl cyanide, and 1-phenyl-1,3-butadiene.

    Science.gov (United States)

    Nelsen, Eleanor R; Brezny, Anna C; Landis, Clark R

    2015-11-11

    In the absence of H2, reaction of [Rh(H) (CO)2(BDP)] [BDP = bis(diazaphospholane)] with hydroformylation substrates vinyl acetate, allyl cyanide, 1-octene, and trans-1-phenyl-1,3-butadiene at low temperatures and pressures with passive mixing enables detailed NMR spectroscopic characterization of rhodium acyl and, in some cases, alkyl complexes of these substrates. For trans-1-phenyl-1,3-butadiene, the stable alkyl complex is an η(3)-allyl complex. Five-coordinate acyl dicarbonyl complexes appear to be thermodynamically preferred over the four-coordinate acyl monocarbonyls at low temperatures and one atmosphere of CO. Under noncatalytic (i.e., no H2 present) reaction conditions, NMR spectroscopy reveals the kinetic and thermodynamic selectivity of linear and branched acyl dicarbonyl formation. Over the range of substrates investigated, the kinetic regioselectivity observed at low temperatures under noncatalytic conditions roughly predicts the regioselectivity observed for catalytic transformations at higher temperatures and pressures. Thus, kinetic distributions of off-cycle acyl dicarbonyls constitute reasonable models for catalytic selectivity. The Wisconsin high-pressure NMR reactor (WiHP-NMRR) enables single-turnover experiments with active mixing; such experiments constitute a powerful strategy for elucidating the inherent selectivity of acyl formation and acyl hydrogenolysis in hydroformylation reactions.

  13. Determination of trace rhodium by potassium bromate-safranine O inhibition kinetic spectrophotometry%溴酸钾-番红花红O阻抑动力学光度法测定痕量铑

    Institute of Scientific and Technical Information of China (English)

    张金宝

    2012-01-01

    在1.0 mol/L的硫酸介质和95℃热水浴中,痕量铑(Ⅲ)对KBrO3氧化番红花红O变色反应有很强的抑制作用,据此,建立了阻抑动力学光度法测定痕量铑(Ⅲ)的新方法并测定了有关动力学参数.在选定的试验条件下,方法的线性范围是0.2~0.8 ng/mL,检出限为1.93×10-11 g/mL,表观活化能为118.2 kJ/mol,阻抑反应对硫酸和铑都为一级反应.方法用于测定催化剂中铑,测定结果与SnCl2光度法的测定结果一致,相对标准偏差(RSD)为2.7%和2.9%.%In 1. 0 mol/L sulfuric acid medium and hot water bath at 95 °C , trace rhodium (Ⅲ) had strong inhibition action on the fading reaction of safranine O oxidized by KBrO3. Based on this, a new determination method of trace rhodium (Ⅲ) by inhibition kinetic spectrophotometry was established. Moreover, the related kinetic parameters were measured. Under the selected experimental conditions, the linear range of method was 0. 2 - 0. 8 ng/Ml, the detection limit was 1. 93×10-11 g/Ml, and the apparent activation energy was 118. 2 Kj/mol. The inhibition reaction was first order reaction for both sulfuric acid and rhodium. The proposed method was applied to the determination of rhodium in catalyst. The found results were consistent with those obtained by SnCl2 photometry. The relative standard deviations CRSD) were 2. 7% and 2. 9%.

  14. Lymphedema Risk Reduction Practices

    Science.gov (United States)

    ... now! Position Paper: Lymphedema Risk Reduction Practices Category: Position Papers Tags: Risks Archives Treatment risk reduction garments surgery obesity infection blood pressure trauma morbid obesity body weight ...

  15. Nickel, palladium and rhodium induced IFN-gamma and IL-10 production as assessed by in vitro ELISpot-analysis in contact dermatitis patients

    Directory of Open Access Journals (Sweden)

    Ensoli Fabrizio

    2008-05-01

    Full Text Available Abstract Background Recent attempts to diminish nickel use in most industrial products have led to an increasing utilization of alternative metal compounds for destinations such as the alloys used in orthopaedics, jewellery and dentistry. The present study was undertaken with the aim to evaluate the potential for an allergic response to nickel, palladium and rhodium on the basis of antigen-specific induction of inflammatory/regulatory cytokines, and to characterize, according to the cytokine profiles, the nature of simultaneous positive patch tests elicited in vivo. Peripheral blood mononuclear cells (PBMC from 40 patients with different patch test results were kept in short term cultures in the presence of optimized concentrations of NiSO4 × 6H2O, PdCl2 and Rh(CH3COO2. The production of IFN-γ and IL-10 elicited by metal compounds were analyzed by the ELISpot assay. Results We found a specific IFN-γ response by PBMC upon in vitro stimulation with nickel or palladium in well recognized allergic individuals. All controls with a negative patch test to a metal salt showed an in vitro IL-10 response and not IFN-γ production when challenged with the same compound. Interestingly, all subjects with positive patch test to both nickel and palladium (group 3 showed an in vitro response characterized by the release of IFN-γ after nickel stimulation and production of IL-10 in response to palladium. Conclusion These results strongly suggest that the different cytokine profiles elicited in vitro reflect different immune responses which may lead to the control of the allergic responses or to symptomatic allergic contact dermatitis. The development of sensitive and specific in vitro assays based on the determination of the cytokine profiles in response to contact allergens may have important diagnostic and prognostic implications and may prove extremely useful in complementing the diagnostic limits of traditional patch testing.

  16. Synthesis, structure, DNA/protein binding, and cytotoxic activity of a rhodium(III) complex with 2,6-bis(2-benzimidazolyl)pyridine.

    Science.gov (United States)

    Esteghamat-Panah, Roya; Hadadzadeh, Hassan; Farrokhpour, Hossein; Simpson, Jim; Abdolmaleki, Amir; Abyar, Fatemeh

    2017-02-15

    A new mononuclear rhodium(III) complex, [Rh(bzimpy)Cl3] (bzimpy = 2,6-bis(2-benzimidazolyl)pyridine), was synthesized and characterized by elemental analysis and spectroscopic methods. The molecular structure of the complex was confirmed by single-crystal X-ray crystallography. The interaction of the complex with fish sperm DNA (FS-DNA) was investigated by UV spectroscopy, emission titration, and viscosity measurement in order to evaluate the possible DNA-binding mode and to calculate the corresponding DNA-binding constant. The results reveal that the Rh(III) complex interacts with DNA through groove binding mode with a binding affinity on the order of 10(4). In addition, the binding of the Rh(III) complex to bovine serum albumin (BSA) was monitored by UV-Vis and fluorescence emission spectroscopy at different temperatures. The mechanism of the complex interaction was found to be static quenching. The thermodynamic parameters (ΔH, ΔS, and ΔG) obtained from the fluorescence spectroscopy data show that van der Waals interactions and hydrogen bonds play a major role in the binding of the Rh(III) complex to BSA. For the comparison of the DNA- and BSA-binding affinities of the free bzimpy ligand with its Rh(III) complex, the absorbance titration and fluorescence quenching experiments of the free bzimpy ligand with DNA and BSA were carried out. Competitive experiments using eosin Y and ibuprofen as site markers indicated that the complex was mainly located in the hydrophobic cavity of site I of the protein. These experimental results were confirmed by the results of molecular docking. Finally, the in vitro cytotoxicity properties of the Rh(III) complex against the MCF-7, K562, and HT-29 cell lines were evaluated and compared with those of the free ligand (bzimpy). It was found that the complexation process improved the anticancer activity significantly.

  17. Experimental and Theoretical Studies on Rhodium-Catalyzed Coupling of Benzamides with 2,2-Difluorovinyl Tosylate: Diverse Synthesis of Fluorinated Heterocycles.

    Science.gov (United States)

    Wu, Jia-Qiang; Zhang, Shang-Shi; Gao, Hui; Qi, Zisong; Zhou, Chu-Jun; Ji, Wei-Wei; Liu, Yao; Chen, Yunyun; Li, Qingjiang; Li, Xingwei; Wang, Honggen

    2017-03-08

    Fluorinated heterocycles play an important role in pharmaceutical and agrochemical industries. Herein, we report on the synthesis of four types of fluorinated heterocycles via rhodium(III)-catalyzed C-H activation of arenes/alkenes and versatile coupling with 2,2-difluorovinyl tosylate. With N-OMe benzamide being a directing group (DG), the reaction delivered a monofluorinated alkene with the retention of the tosylate functionality. Subsequent one-pot acid treatment allowed the efficient synthesis of 4-fluoroisoquinolin-1(2H)-ones and 5-fluoropyridin-2(1H)-ones. When N-OPiv benzamides were used, however, [4 + 2] cyclization occurred to provide gem-difluorinated dihydroisoquinolin-1(2H)-ones. Synthetic applications have been demonstrated and the ready availability of both the arene and the coupling partner highlighted the synthetic potentials of these protocols. Mechanistically, these two processes share a common process involving N-H deprotonation, C-H activation, and olefin insertion to form a 7-membered rhodacycle. Thereafter, different reaction pathways featuring β-F elimination and C-N bond formation are followed on the basis of density functional theory (DFT) studies. These two pathways are DG-dependent and led to the open chain and cyclization products, respectively. The mechanistic rationale was supported by detailed DFT studies. In particular, the origins of the intriguing selectivity in the competing β-F elimination versus C-N bond formation were elucidated. It was found that β-F elimination is a facile event and proceeds via a syn-coplanar transition state with a low energy barrier. The C-N bond formation proceeds via a facile migratory insertion of the Rh-C(alkyl) into the Rh(V) amido species. In both reactions, the migratory insertion of the alkene is turnover-limiting, which stays in good agreement with the experimental studies.

  18. Preparation and characterization of sulfated TiO2 with rhodium modification used in esterification reaction and decomposition of methyl orange☆

    Institute of Scientific and Technical Information of China (English)

    Yu Niu; Fuying Li; Kai Yang; Ting Qiu; Renzhang Wang; Cheng Lin

    2016-01-01

    A unique Rh/TiO2 solid acid catalyst modified with H2SO4 was synthesized and evaluated in the esterification reaction of propylene glycol methyl ether and decomposition of methyl orange (MO) in aqueous phase under halogen lamp irradiation. For this purpose, rhodium (Rh) nanoparticles were loaded on SO42−/TiO2 via the photo-deposition method. It was found that SO42−/Rh–TiO2 exhibited stronger catalytic activity than SO42−/TiO2. The new catalysts were characterized by X-ray powder diffraction (XRD), Brunauer–Emmett–Teller (BET), Transmission electron microscopy (TEM) and high-resolution (HRTEM), X-ray photoelectron spec-troscopy (XPS) and Fourier Transform infrared spectroscopy (FTIR). Results from XRD and BET show that SO42−/Rh–TiO2 has higher specific surface area and smaller pore size than SO42−/TiO2. The distribution of loaded Rh was found to be uniform with a particle size of 2–4 nm. Data from XPS reveal that Rh primarily exists as Rh0 and Rh3+in Rh–TiO2 and SO42−/Rh–TiO2. These valence forms of Rh likely contribute to the en-hanced catalytic activity. Furthermore, FT-IR spectra of the catalysts show an abundance of surface hydroxyl groups, which help the formation of hydroxyl radicals and the enhancement of surface acid density. The results show that more acid sites are formed on the sulfated Rh–TiO2, and these acidic sites are largely responsible for improving the catalytic performance. This superior SO42−/Rh–TiO2 catalyst has potential applications in reactions requiring efficient acid catalysts, including esterification reactions and waste water treatment.

  19. Rhodium-Catalyzed/Copper-Mediated Tandem C(sp(2))-H Alkynylation and Annulation: Synthesis of 11-Acylated Imidazo[1,2-a:3,4-a']dipyridin-5-ium-4-olates from 2H-[1,2'-Bipyridin]-2-ones and Propargyl Alcohols.

    Science.gov (United States)

    Li, Ting; Wang, Zhiqiang; Xu, Kun; Liu, Wenmin; Zhang, Xu; Mao, Wutao; Guo, Yongming; Ge, Xiaolin; Pan, Fei

    2016-03-01

    A rhodium-catalyzed/copper-mediated tandem C(sp(2))-H alkynylation and intramolecular annulation of 2H-[1,2'-bipyridin]-2-ones with propargyl alcohols for the synthesis of 11-acylated imidazo[1,2-a:3,4-a']dipyridin-5-ium-4-olates is described.

  20. Synthesis, Structure, and Isomerization of Alkoxycarbonyl(chloro)(cyano)rhodium(III) Complexes, mer-[RhCl(CO2R)(CN)(PMe3)3] (R = Me, Et, nPr, iPr, nBu, and Bn), through C–C Bond Cleavage of Cyanoformates

    National Research Council Canada - National Science Library

    Okuda, Yasuhiro; Okamoto, Takeru; Yamamoto, Arisa; Li, Jing; Nakajima, Kiyohiko; Nishihara, Yasushi

    2014-01-01

    Alkoxycarbonyl(chloro)(cyano)rhodium(III) complexes mer-[RhCl(CO2R)(CN)(PMe3)3] (1: R = Me; 2: R = Et; 3: R = nPr; 4: R = iPr; 5: R = nBu; 6: R = Bn) are prepared via oxidative addition of the corresponding cyanoformates...

  1. Vowel Reduction in Japanese

    Institute of Scientific and Technical Information of China (English)

    Shirai; Setsuko

    2009-01-01

    This paper reports the result that vowel reduction occurs in Japanese and vowel reduction is the part of the language universality.Compared with English,the effect of the vowel reduction in Japanese is relatively weak might because of the absence of stress in Japanese.Since spectral vowel reduction occurs in Japanese,various types of researches would be possible.

  2. Hydroformylation of butyl acrylate catalyzed by water-soluble rhodium carbonyl complexes%水溶性铑羰基配合物催化丙烯酸丁酯的氢甲酰化反应

    Institute of Scientific and Technical Information of China (English)

    黄雪原; 李贤均

    2004-01-01

    The hydroformylation of butyl acrylate was carried out in biphasic system water/toluene in the presence of rhodium carbonyl complexes with the water-soluble ligands to produce the effects of the temperature, ligand-to-rhodium ratio, hydrogen and carbon monoxide partial pressures on the activity and selectivity of the reaction. The performance of monophosphine ligand(TPPTS) was compared with that of diphosphine ligand(BDPXS).%在两相催化体系水/甲苯中,考察了反应温度、配体与催化剂摩尔比率、氢气/一氧化碳压力比对铑羰基配合物与水溶性膦配体催化丙烯酸丁酯的氢甲酰化反应的催化活性和选择性的影响,并比较了单膦配体(TPPTS)和双膦配体(BDPXS)的催化性能.

  3. Infinitary Combinatory Reduction Systems: Normalising Reduction Strategies

    NARCIS (Netherlands)

    Ketema, Jeroen; Simonsen, Jakob Grue

    2010-01-01

    We study normalising reduction strategies for infinitary Combinatory Reduction Systems (iCRSs). We prove that all fair, outermost-fair, and needed-fair strategies are normalising for orthogonal, fully-extended iCRSs. These facts properly generalise a number of results on normalising strategies in fi

  4. Considerações radiodosimétricas da braquiterapia ocular com iodo-125 e rutênio/ródio-106 Radiodosimetric considerations on ocular brachytherapy with iodine-125 and ruthenium/rhodium-106

    Directory of Open Access Journals (Sweden)

    Arnaldo Prata Mourão

    2009-02-01

    Full Text Available OBJETIVO: Analisar, por meio de um modelo computacional da região ocular, as características da distribuição da dose utilizando placas contendo iodo-125 e rutênio/ródio-106. MATERIAIS E MÉTODOS: Foi utilizado um modelo computacional de voxels da região ocular incluindo os diversos tecidos, com a placa posicionada sobre a esclera. O código Monte Carlo foi utilizado para simular a irradiação. A distribuição da dose é apresentada por curvas de isodoses. RESULTADOS: As simulações computacionais apresentam a distribuição da dose no interior do bulbo e nas estruturas externas. Os resultados permitem comparar a distribuição espacial das doses geradas por partículas beta e por fótons. As simulações mostram que a aplicação de sementes de iodo-125 implica alta dose no cristalino, enquanto o rutênio/ródio-106 produz alta dose na superfície da esclera. CONCLUSÃO: A dose no cristalino depende da espessura do tumor, da posição e do diâmetro da placa, e do radionuclídeo utilizado. No presente estudo, a fonte de rutênio/ródio-106 é recomendada para tumores de dimensões reduzidas. A irradiação com iodo-125 gera doses maiores no cristalino do que a irradiação com rutênio/ródio-106. O valor máximo de dose no cristalino corresponde a 12,75% do valor máximo de dose com iodo-125 e apenas 0,005% para rutênio/ródio-106.OBJECTIVE: To analyze dose distribution utilizing plaques with iodine-125 and ruthenium/rhodium-106 in a computational model of the ocular region. MATERIALS AND METHODS: A voxel-based computational model including the different tissues of the ocular region was utilized with the plaque positioned on the sclera. The Monte Carlo code was utilized for simulating irradiation. The dose distribution is demonstrated by isodoses curves. RESULTS: Computational simulations demonstrate the dose distribution inside the ocular bulb as well as in adjacent outside structures. The results have allowed the authors to compare

  5. Local reduction in physics

    Science.gov (United States)

    Rosaler, Joshua

    2015-05-01

    A conventional wisdom about the progress of physics holds that successive theories wholly encompass the domains of their predecessors through a process that is often called "reduction." While certain influential accounts of inter-theory reduction in physics take reduction to require a single "global" derivation of one theory's laws from those of another, I show that global reductions are not available in all cases where the conventional wisdom requires reduction to hold. However, I argue that a weaker "local" form of reduction, which defines reduction between theories in terms of a more fundamental notion of reduction between models of a single fixed system, is available in such cases and moreover suffices to uphold the conventional wisdom. To illustrate the sort of fixed-system, inter-model reduction that grounds inter-theoretic reduction on this picture, I specialize to a particular class of cases in which both models are dynamical systems. I show that reduction in these cases is underwritten by a mathematical relationship that follows a certain liberalized construal of Nagel/Schaffner reduction, and support this claim with several examples. Moreover, I show that this broadly Nagelian analysis of inter-model reduction encompasses several cases that are sometimes cited as instances of the "physicist's" limit-based notion of reduction.

  6. Reduction in language testing

    DEFF Research Database (Denmark)

    Dimova, Slobodanka; Jensen, Christian

    2013-01-01

    /video recorded speech samples and written reports produced by two experienced raters after testing. Our findings suggest that reduction or reduction-like pronunciation features are found in tested L2 speech, but whenever raters identify and comment on such reductions, they tend to assess reductions negatively......This study represents an initial exploration of raters' comments and actual realisations of form reductions in L2 test speech performances. Performances of three L2 speakers were selected as case studies and illustrations of how reductions are evaluated by the raters. The analysis is based on audio...

  7. I. Interaction of ammonia with single crystal rhodium catalysts. II. Hydrogen and nitrogen adsorption on a W(111) surface: a theoretical molecular orbital approach

    Energy Technology Data Exchange (ETDEWEB)

    Vavere, A.

    1979-01-01

    Rates of ammonia decomposition on (110), (100), and (111) single crystal faces of rhodium were measured at 580 to 725/sup 0/K and 10/sup -3/ to 500 x 10/sup -3/ torr. The decomposition rates were proportional to P/sub NH/sub 3//sup/1/2/ and P/sub NH/sub 3// at low and high hydrogen pressures, respectively. The H/sub 2/ kinetic order varied from 0 (low P/sub H/sub 2//) to -1.0 (high P/sub H/). The rate was independent of N/sub 2/ pressure. NH/sub 3/ decomposes about 1.5 times faster than ND/sub 3/ on the (110) and (111) faces. Rates on the (110) surface are over 10 times as rapid as on the (111). LEED, Auger, and flash desorption experiments indicated that boron was a significant surface poison and that the Rh(110) surface was essentially nitrogen-free. A rate expression is derived from a model involving surface species Rh/sub 2/NH, RhH, and RhN on a nearly bare RH surface. The rate limiting process involves the concurrent dehydrogenation of Rh/sub 2/NH and desorption of N/sub 2/. A decreasing NH/sub 3/ order (< 1/2) at high P/sub NH/sub 3// and low T is due to buildup of surface intermediates. The relative bonding energies of hydrogen and nitrogen chemisorbed at three sites on a W(111) surface were obtained via the extended Hueckel molecular orbital theory. The preferred site for both H and N chemisorption was determined as the TOP position, i.e., a single coordination site on top of a protruding W atom. The W(111) surface was simulated by truncated arrays of seven tungsten atoms. The basis set for the calculations included the tungsten valence orbitals plus the filled 5p orbitals needed for repulsion at small internuclear distances. N adsorption in the three-fold holes available on the W(111) lattices used disrupted the W--W bonds sufficiently to cause the overall bond energy to be less than for the single coordination site. The dissymmetry between the three-fold lattices and the four-fold W d orbitals may also be a contributing factor.

  8. Modern Reduction Methods

    CERN Document Server

    Andersson, Pher G

    2008-01-01

    With its comprehensive overview of modern reduction methods, this book features high quality contributions allowing readers to find reliable solutions quickly and easily. The monograph treats the reduction of carbonyles, alkenes, imines and alkynes, as well as reductive aminations and cross and heck couplings, before finishing off with sections on kinetic resolutions and hydrogenolysis. An indispensable lab companion for every chemist.

  9. I.C. Engine emission reduction by copper oxide catalytic converter

    Science.gov (United States)

    Venkatesan, S. P.; Shubham Uday, Desai; Karan Hemant, Borana; Rajarshi Kushwanth Goud, Kagita; Lakshmana Kumar, G.; Pavan Kumar, K.

    2017-05-01

    The toxic gases emitted from diesel engines are more than petrol engines. Predicting the use of diesel engines, even more in future, this system is developed and can be used to minimize the harmful gases. Toxic gases include NOX, CO, HC and Smoke which are harmful to the atmosphere as well as to the human beings. The main aim of this work is to fabricate system, where the level of intensity of toxic gases is controlled through chemical reaction to more agreeable level. This system acts itself as an exhaust system; hence there is no needs to fit separate the silencer. The whole assembly is fitted in the exhaust pipe from engine. In this work, catalytic converter with copper oxide as a catalyst, by replacing noble catalysts such as platinum, palladium and rhodium is fabricated and fitted in the engine exhaust. With and without catalytic converter, the experimentations are carried out at different loads such as 0%, 25%, 50%, 75%, and 100% of maximum rated load. From the experimental results it is found that the maximum reduction is 32%, 61% and 21% for HC, NOx and CO respectively at 100% of maximum rated load when compared to that of without catalytic converter. This catalytic converter system is cash effective and more economical than the existing catalytic converter.

  10. Synthesis and reactivity of fluoro complexes: Part 2. Rhodium(I) fluoro complexes with alkene and phosphine ligands. Synthesis of the first isolated rhodium(I) bifluoride complexes. Structure of [Rh3(mu3-OH)2(COD)(3)](HF2) by X-ray powder diffraction.

    Science.gov (United States)

    Vicente, José; Gil-Rubio, Juan; Bautista, Delia; Sironi, Angelo; Masciocchi, Norberto

    2004-09-01

    The reaction between [Rh(mu-OH)(COD)](2) (COD = 1,5-cyclooctadiene) and 73% HF in THF gives [Rh(3)(mu(3)-OH)(2)(COD)(3)](HF(2)) (1). Its crystal structure, determined by ab initio X-ray powder diffraction methods (from conventional laboratory data), contains complex trimetallic cations linked together in 1D chains by a mu(3)-OH...F-H-F...HO-mu(3) sequence of strong hydrogen bonds. The complex [Rh(mu-F)(COE)(2)](2) (COE = cyclooctene; 2), prepared by reacting [Rh(mu-OH)(COE)(2)](2) with NEt(3).3HF (3:2), has been characterized. Complex 1 reacts with PR(3) (1:3) to give [RhF(COD)(PR(3))] [R = Ph (3), C(6)H(4)OMe-4 (4), (i)Pr (5), Cy (6)] that can be prepared directly by reacting [Rh(mu-OH)(COD)](2) with 73% HF and PR(3) (1:2:2). The reactions of 1 with PPh(3) or Et(3)P have been studied by NMR spectroscopy at different molar ratios. Complexes [RhF(PEt(3))(3)] (7), [RhF(COD)(PEt(3))] (8), and [RhF(PPh(3))(3)] (9) have been detected. The complex [Rh(F)(NBD)(iPr(3)P)] (NBD = norbornadiene; 10) was prepared by the sequential treatment of [Rh(mu-OMe)(NBD)](2) with 1 equiv of NEt(3).3HF and (i)Pr(3)P. The first isolated bifluoride rhodium(I) complexes [Rh(FHF)(COD)(PR(3))] [R = Ph (11), (i)Pr (12), Cy (13)], obtained by reacting fluoro complexes 3, 5, and 6 with NEt(3).3HF (3:1), have been characterized. The crystal structures of 3 and 11 have been determined.

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

    Science.gov (United States)

    Zhang, Gai; Tian, Min

    2015-04-01

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

  12. 2-(Methylamido)pyridine-Borane: A Tripod κ(3)-N,H,H Ligand in Trigonal Bipyramidal Rhodium(I) and Iridium(I) Complexes with an Asymmetric Coordination of Its BH3 Group.

    Science.gov (United States)

    Brugos, Javier; Cabeza, Javier A; García-Álvarez, Pablo; Kennedy, Alan R; Pérez-Carreño, Enrique; Van der Maelen, Juan F

    2016-09-06

    The complexes [M(κ(3)-N,H,H-mapyBH3)(cod)] (M = Rh, Ir; HmapyBH3 = 2-(methylamino)pyridine-borane; cod = 1,5-cyclooctadiene), which contain a novel anionic tripod ligand coordinated to the metal atom through the amido N atom and through two H atoms of the BH3 group, were prepared by treating the corresponding [M2(μ-Cl)2(cod)2] (M = Rh, Ir) precursor with K[mapyBH3]. X-ray diffraction studies and a theoretical Quantum Theory of Atoms in Molecules analysis of their electron density confirmed that the metal atoms of both complexes are in a very distorted trigonal bipyramidal coordination environment, in which two equatorial sites are asymmetrically spanned by the H-B-H fragment. While both 3c-2e BH-M interactions are more κ(1)-H (terminal σ coordination of the B-H bond) than κ(2)-H,B (agostic-type coordination of the B-H bond), one BH-M interaction is more agostic than the other, and this difference is more marked in the iridium complex than in the rhodium one. This asymmetry is not evident in solution, where the cod ligand and the BH3 group of these molecules participate in two concurrent dynamic processes of low activation energies (variable-temperature NMR and density functional theory studies), namely, a rotation of the cod ligand that interchanges its two alkene fragments (through a square pyramidal transition state) and a rotation of the BH3 group about the B-N bond that equilibrates the three B-H bonds (through a square planar transition state). While the cod rotation has similar activation energy in 2 and 3, the barrier to the BH3 group rotation is higher in the iridium complex than in the rhodium one.

  13. Synthesis, structure, and reactivity of rhodium and iridium complexes of the chelating bis-sulfoxide tBuSOC2H4SOtBu. Selective O-H activation of 2-hydroxy-isopropyl-pyridine.

    Science.gov (United States)

    Schaub, Thomas; Diskin-Posner, Yael; Radius, Udo; Milstein, David

    2008-07-21

    The chloro-bridged rhodium and iridium complexes [M2(BTSE)2Cl2] (M = Rh 1, Ir 2) bearing the chelating bis-sulfoxide tBuSOC2H4SOtBu (BTSE) were prepared by the reaction of [M2(COE)4Cl2] (M = Rh, Ir; COE = cyclooctene) with an excess of a racemic mixture of the ligand. The cationic compounds [M(BTSE)2][PF6] (M = Rh 3, Ir 4), bearing one S- and one O-bonded sulfoxide, were also obtained in good yields. The chloro-bridges in 2 can be cleaved with 2-methyl-6-pyridinemethanol and 2-aminomethyl pyridine, resulting in the iridium(I) complexes [Ir(BTSE)(Py)(Cl)] (Py = 2-methyl-6-pyridinemethanol 5, 2-aminomethyl-pyridine 6). In case of the bulky 2-hydroxy- isopropyl-pyridine, selective OH oxidative addition took place, forming the Ir(III)-hydride [Ir(BTSE)(2-isopropoxy-pyridine)(H)(Cl)] 7, with no competition from the six properly oriented C-H bonds. The cationic rhodium(I) and iridium(I) compounds [M(BTSE)(2-aminomethyl-pyridine)][X] (M = Rh 8, Ir 10), [Rh(BTSE)(2-hydroxy- isopropyl-pyridine)][X] 9(stabilized by intramolecular hydrogen bonding), [Ir(BTSE)(pyridine)2][PF6] 12, [Ir(BTSE)(alpha-picoline)2][PF6] 13, and [Rh(BTSE)(1,10-phenanthroline)][PF6] 14 were prepared either by chloride abstraction from the dimeric precursors or by replacement of the labile oxygen bonded sulfoxide in 3 or 4. Complex 14 exhibits a dimeric structure in the solid state by pi-pi stacking of the phenanthroline ligands.

  14. ON THE SYMPLECTIC REDUCTIONS

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    A symplectic reduction method for symplectic G-spaces is given in this paper without using the existence of momentum mappings.By a method similar to the above one,the arthors give a symplectic reduction method for the Poisson action of Poisson Lie groups on symplectic manifolds,also without using the existence of momentum mappings.The symplectic reduction method for momentum mappings is thus a special case of the above results.

  15. Finding optimal exact reducts

    KAUST Repository

    AbouEisha, Hassan M.

    2014-01-01

    The problem of attribute reduction is an important problem related to feature selection and knowledge discovery. The problem of finding reducts with minimum cardinality is NP-hard. This paper suggests a new algorithm for finding exact reducts with minimum cardinality. This algorithm transforms the initial table to a decision table of a special kind, apply a set of simplification steps to this table, and use a dynamic programming algorithm to finish the construction of an optimal reduct. I present results of computer experiments for a collection of decision tables from UCIML Repository. For many of the experimented tables, the simplification steps solved the problem.

  16. CARBON DIOXIDE REDUCTION SYSTEM.

    Science.gov (United States)

    CARBON DIOXIDE , *SPACE FLIGHT, RESPIRATION, REDUCTION(CHEMISTRY), RESPIRATION, AEROSPACE MEDICINE, ELECTROLYSIS, INSTRUMENTATION, ELECTROLYTES, VOLTAGE, MANNED, YTTRIUM COMPOUNDS, ZIRCONIUM COMPOUNDS, NICKEL.

  17. Strategies for poverty reduction

    OpenAIRE

    Øyen, Else

    2003-01-01

    SIU konferanse Solstrand 6.-7. October 2003 Higher education has a value of its own. When linked to the issue of poverty reduction it is necessary to ask another set of questions, including the crutial one whether higher education in general is the best tool for poverty reduction.

  18. Strategies for poverty reduction

    OpenAIRE

    Øyen, Else

    2003-01-01

    SIU konferanse Solstrand 6.-7. October 2003 Higher education has a value of its own. When linked to the issue of poverty reduction it is necessary to ask another set of questions, including the crutial one whether higher education in general is the best tool for poverty reduction.

  19. Reduct and Attribute Order

    Institute of Scientific and Technical Information of China (English)

    Su-Qing Han; Jue Wang

    2004-01-01

    Based on the principle of discernibility matrix,a kind of reduction algorithm with attribute order has been developed and its solution has been proved to be complete for reduct and unique for a given attribute order.Being called the reduct problem,this algorithm can be regarded as a mapping R = Reduct(S)from the attribute order space θ to the reduct space R for an information system ,where U is the universe and C and D are two sets of condition and decision attributes respectively.This paper focuses on the reverse problem of reduct problem S = Order(R),i.e.,for a given reduct R of an information system,we determine the solution of S = Order(R)in the space θ.First,we need to prove that there is at least one attribute order S such that S = Order(R).Then,some decision rules are proposed,which can be used directly to decide whether the pair of attribute orders has the same reduct.The main method is based on the fact that an attribute order can be transformed into another one by moving the attribute for limited times.Thus,the decision of the pair of attribute orders can be altered to the decision of the sequence of neighboring pairs of attribute orders.Therefore,the basic theorem of neighboring pair of attribute orders is first proved,then,the decision theorem of attribute order is proved accordingly by the second attribute.

  20. Lymphedema Risk Reduction Practices

    Science.gov (United States)

    ... LSAP Perspective (9) 2017 NLN International Conference Position Paper: Lymphedema Risk Reduction Practices Category: Position Papers Tags: ... and water, pat dry, then apply a topical antibacterial. d. Wear non-constricting protective gear over the ...

  1. Reduction Redux of Adinkras

    CERN Document Server

    Gates,, S James; Stiffler, Kory

    2013-01-01

    We show performing general ``0-brane reduction'' along an arbitrary fixed direction in spacetime and applied to the starting point of minimal, off-shell 4D, $\\cal N$ $=$ 1 irreducible supermultiplets, yields adinkras whose adjacency matrices are among some of the special cases proposed by Kuznetsova, Rojas, and Toppan. However, these more general reductions also can lead to `Garden Algebra' structures beyond those described in their work. It is also shown that for light-like directions, reduction to the 0-brane breaks the equality in the number of fermions and bosons for dynamical theories. This implies that light-like reductions should be done instead to the space of 1-branes or equivalently to the worldsheet.

  2. Breast Reduction Surgery

    Science.gov (United States)

    ... breastfeeding: A systematic review. Journal of Plastic, Reconstructive & Aesthetic Surgery. 2010;63:1688. Kerrigan CL, et al. Evidence-based medicine: Reduction mammoplasty. Plastic and Reconstructive Surgery. 2013;132: ...

  3. Work Truck Idling Reduction

    Energy Technology Data Exchange (ETDEWEB)

    None

    2017-03-01

    Hybrid utility trucks, with auxiliary power sources for on-board equipment, significantly reduce unnecessary idling resulting in fuel costs savings, less engine wear, and reduction in noise and emissions.

  4. New Reductive Desulfurization Technology

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    @@ The project for the research of the pulse plasma reductive desulfurization technology undertaken by Huazhong University of Science and Technology recently passed the research achievement appraisal in Wuhan, Hubei province.

  5. Dissimilatory metal reduction.

    Science.gov (United States)

    Lovley, D R

    1993-01-01

    Microorganisms can enzymatically reduce a variety of metals in metabolic processes that are not related to metal assimilation. Some microorganisms can conserve energy to support growth by coupling the oxidation of simple organic acids and alcohols, H2, or aromatic compounds to the reduction of Fe(III) or Mn(IV). This dissimilatory Fe(III) and Mn(IV) reduction influences the organic as well as the inorganic geochemistry of anaerobic aquatic sediments and ground water. Microorganisms that use U(VI) as a terminal electron acceptor play an important role in uranium geochemistry and may be a useful tool for removing uranium from contaminated environments. Se(VI) serves as a terminal electron acceptor to support anaerobic growth of some microorganisms. Reduction of Se(VI) to Se(O) is an important mechanism for the precipitation of selenium from contaminated waters. Enzymatic reduction of Cr(VI) to the less mobile and less toxic Cr(III), and reduction of soluble Hg(II) to volatile Hg(O) may affect the fate of these compounds in the environment and might be used as a remediation strategy. Microorganisms can also enzymatically reduce other metals such as technetium, vanadium, molybdenum, gold, silver, and copper, but reduction of these metals has not been studied extensively.

  6. Reactivity of rhodium(I) complexes bearing nitrogen-containing ligands toward CH3I: synthesis and full characterization of neutral cis-[RhX(CO)2(L)] and acetyl [RhI(μ-I)(COMe)(CO)(L)]2 complexes.

    Science.gov (United States)

    Adcock, Romain J; Nguyen, Duc Hanh; Ladeira, Sonia; Le Berre, Carole; Serp, Philippe; Kalck, Philippe

    2012-08-20

    The neutral rhodium(I) square-planar complexes [RhX(CO)(2)(L)] [X = Cl (3), I (4)] bearing a nitrogen-containing ligand L [diethylamine (a), triethylamine (b), imidazole (c), 1-methylimidazole (d), pyrazole (e), 1-methylpyrazole (f), 3,5-dimethylpyrazole (g)] are straightforwardly obtained from L and [Rh(μ-X)(CO)(2)](2) [X = Cl (1), I (2)] precursors. The synthesis is extended to the diethylsulfide ligand h for 3h and 4h. According to the CO stretching frequency of 3 and 4, the ranking of the electronic density on the rhodium center follows the order b > a ≈ d > c > g > f ≈ h > e. The X-ray molecular structures of 3a, 3d-3f, 4a, and 4d-4f were determined. Results from variable-temperature (1)H and (13)C{(1)H} NMR experiments suggest a fluxional associative ligand exchange for 4c-4h and a supplementary hydrogen-exchange process in 4e and 4g. The oxidative addition reaction of CH(3)I to complexes 4c-4g affords the neutral dimeric iodo-bridged acetylrhodium(III) complexes [RhI(μ-I)(COCH(3))(CO)(L)](2) (6c-6g) in very good isolated yields, whereas 4a gives a mixture of neutral 6a and dianionic [RhI(2)(μ-I)(COCH(3))(CO)][NHMeEt(2)](2) and 4h exclusively provides the analogue dianionic complex with [SMeEt(2)](+) as the counterion. X-ray molecular structures for 6d(2) and 6e reveal that the two apical CO ligands are in mutual cis positions, as are the two apical d and e ligands, whereas isomer 6d(1) is centrosymmetric. Further reactions of 6d and 6e with CO or ligand e gave quantitatively the monomeric complexes [RhI(2)(COCH(3))(CO)(2)(d)] (7d) and [RhI(2)(COCH(3))(CO)(e)(2)] (8e), respectively, as confirmed by their X-ray structures. The initial rate of CH(3)I oxidative addition to 4 as determined by IR monitoring is dependent on the nature of the nitrogen-containing ligand. For 4a and 4h, reaction rates similar to those of the well-known rhodium anionic [RhI(2)(CO)(2)](-) species are observed and are consistent with the formation of this intermediate species

  7. Reduction zero-knowledge

    Institute of Scientific and Technical Information of China (English)

    ZHAO Yunlei; DENG Xiaotie; LEE C. H.; ZHU Hong

    2004-01-01

    The nature of zero-knowledge is re-examined and the evidence for the following belief is shown:the classic simulation based definitions of zero-knowledge(simulation zero-knowledge)may be somewhat too strong to include some "nice" protocols in which the malicious verifier seems to learn nothing but we do not know how to construct a zero-knowledge simulator for it.To overcome this problem a new relaxation of zero-knowledge,reduction zero-knowledge,is introduced.It is shown that reduction zero-knowledge just lies between simulation zero-knowledge and witness indistinguishability.Under the assumption of existence of one-way permutations a 4-round public-coin reduction zero-knowledge proof system for NP is presented and in practice this protocol works in 3 rounds since the first verifier's message can be fixed once and for all.

  8. The cyclic reduction algorithm

    Science.gov (United States)

    Bini, Dario; Meini, Beatrice

    2009-05-01

    Cyclic reduction is an algorithm invented by G.H. Golub and R. W. Hockney in the mid 1960s for solving linear systems related to the finite differences discretization of the Poisson equation over a rectangle. Among the algorithms of Gene Golub, it is one of the most versatile and powerful ever created. Recently, it has been applied to solve different problems from different applicative areas. In this paper we survey the main features of cyclic reduction, relate it to properties of analytic functions, recall its extension to solving more general finite and infinite linear systems, and different kinds of nonlinear matrix equations, including algebraic Riccati equations, with applications to Markov chains, queueing models and transport theory. Some new results concerning the convergence properties of cyclic reduction and its applicability are proved under very weak assumptions. New formulae for overcoming breakdown are provided.

  9. REDUCTIONS WITHOUT REGRET: SUMMARY

    Energy Technology Data Exchange (ETDEWEB)

    Swegle, J.; Tincher, D.

    2013-09-16

    This paper briefly summarizes the series in which we consider the possibilities for losing, or compromising, key capabilities of the U.S. nuclear force in the face of modernization and reductions. The first of the three papers takes an historical perspective, considering capabilities that were eliminated in past force reductions. The second paper is our attempt to define the needed capabilities looking forward in the context of the current framework for force modernization and the current picture of the evolving challenges of deterrence and assurance. The third paper then provides an example for each of our undesirable outcomes: the creation of roach motels, box canyons, and wrong turns.

  10. Time, Chance, and Reduction

    Science.gov (United States)

    Ernst, Gerhard; Hüttemann, Andreas

    2010-01-01

    List of contributors; 1. Introduction Gerhard Ernst and Andreas Hütteman; Part I. The Arrows of Time: 2. Does a low-entropy constraint prevent us from influencing the past? Mathias Frisch; 3. The part hypothesis meets gravity Craig Callender; 4. Quantum gravity and the arrow of time Claus Kiefer; Part II. Probability and Chance: 5. The natural-range conception of probability Jacob Rosenthal; 6. Probability in Boltzmannian statistical mechanics Roman Frigg; 7. Humean mechanics versus a metaphysics of powers Michael Esfeld; Part III. Reduction: 8. The crystallisation of Clausius's phenomenological thermodynamics C. Ulises Moulines; 9. Reduction and renormalization Robert W. Batterman; 10. Irreversibility in stochastic dynamics Jos Uffink; Index.

  11. Bronchoscopic lung volume reduction

    Directory of Open Access Journals (Sweden)

    M. I. Polkey

    2006-12-01

    Full Text Available Surgical lung volume reduction can improve exercise performance and forced expiratory volume in one second in patients with emphysema. However, the procedure is associated with a 5% mortality rate and a nonresponse rate of 25%. Accordingly, interest has focused on alternative ways of reducing lung volume. Two principle approaches are used: collapse of the diseased area using blockers placed endobronchially and the creation of extrapulmonary pathways. Preliminary data from the former approach suggest that it can be successful and that the magnitude of success is related to reduction in dynamic hyperinflation.

  12. Dimensionality Reduction Mappings

    NARCIS (Netherlands)

    Bunte, Kerstin; Biehl, Michael; Hammer, Barbara

    2011-01-01

    A wealth of powerful dimensionality reduction methods has been established which can be used for data visualization and preprocessing. These are accompanied by formal evaluation schemes, which allow a quantitative evaluation along general principles and which even lead to further visualization schem

  13. EURAMET key comparison no. EURAMET.T-K1: realisations of the ITS-90 from 2.6 K to 24.5561 K, using rhodium-iron resistance thermometers

    Science.gov (United States)

    Gaiser, Christof; Fellmuth, Bernd; Steur, Peter; Szmyrka-Grzebyk, Anna; Manuszkiewicz, Henryk; Lipinski, Leszek; Peruzzi, Andrea; Rusby, Richard; Head, David

    2017-01-01

    In the temperature range from 0.65 K to 24.5561 K, the ITS-90 is defined by specified vapour-pressure equations for 3He and 4He and interpolation equations for a constant-volume gas thermometer using 3He or 4He. The definitions are given in sections 3.1 and 3.2 of the ITS-90 text, and methods for realising the scale in this range are outlined in chapters 4 and 5 of the Guide to the Realization of the ITS-90 (formerly Supplementary Information for the ITS-90). Direct realisations of the ITS-90 by these methods require relatively sophisticated apparatus and time-consuming experiments, and consequently they are rarely carried out. The situation is acceptable in practice only because rhodium-iron resistance thermometers (RIRTs) are available that, once calibrated, are able to maintain their calibrations reliably for long periods of time. They are the practical thermometers on which realisations of the ITS-90 are most accurately maintained, disseminated and compared. The key comparison EURAMET.T-K1 is therefore a comparison of calibrated RIRTs. Main text To reach the main text of this paper, click on Final Report. Note that this text is that which appears in Appendix B of the BIPM key comparison database kcdb.bipm.org/. The final report has been peer-reviewed and approved for publication by the CCT, according to the provisions of the CIPM Mutual Recognition Arrangement (CIPM MRA).

  14. Fully Awake Breast Reduction.

    Science.gov (United States)

    Filson, Simon A; Yarhi, Danielle; Ramon, Yitzhak

    2016-11-01

    The authors present 25 cases and an in-depth 4-minute video of fully awake aesthetic breast reduction, which was made possible by thoracic epidural anesthesia. There are obvious and important advantages to this technique. Not only does this allow for intraoperative patient cooperation (i.e., patient self-positioning and opinion for comparison of breasts), meaning a shorter and more efficient intraoperative time, there also is a reduction in postoperative pain, complications, recovery, and discharge times. The authors have also enjoyed great success and no complications with this technique in over 150 awake abdominoplasty/total body lift patients. The authors feel that the elimination of the need for general anesthesia by thoracic epidural sensorial-only anesthesia is a highly effective and efficient technique, with very few disadvantages/complications, providing advantages to both patients and surgeons. Therapeutic, IV.

  15. Injury reduction at Fermilab

    Energy Technology Data Exchange (ETDEWEB)

    Griffing, Bill; /Fermilab

    2005-06-01

    In a recent DOE Program Review, Fermilab's director presented results of the laboratory's effort to reduce the injury rate over the last decade. The results, shown in the figure below, reveal a consistent and dramatic downward trend in OSHA recordable injuries at Fermilab. The High Energy Physics Program Office has asked Fermilab to report in detail on how the laboratory has achieved the reduction. In fact, the reduction in the injury rate reflects a change in safety culture at Fermilab, which has evolved slowly over this period, due to a series of events, both planned and unplanned. This paper attempts to describe those significant events and analyze how each of them has shaped the safety culture that, in turn, has reduced the rate of injury at Fermilab to its current value.

  16. Jet Engine Noise Reduction

    Science.gov (United States)

    2009-04-01

    Technology Solutions, Lockheed Martin Robert S. Carnes , M.D. NRAC Member, Battelle Memorial Institute MajGen Paul A. Fratarangelo, USMC (Ret) NRAC...Development, Acquisition) (VADM Architzel). The Naval Research Advisory Committee members (Bowes, Bowler, Carnes and Fratarangelo) have broad...Lockheed Martin ADP Boeing: Jet Engine Noise Reduction for Tactical Fighter Aircraft Mr. Tom Kaemming, K. Viswanathan, Ph . D. Tactical Jet Noise

  17. Investigation of Catalytic NO{sub x}, reduction with transient techniques, isotopic exchange and FT-IR spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Rahkamaa-Tolonen, K.

    2001-07-01

    Emissions from vehicles are suppressed by catalytic conversion, i.e. total oxidation of carbon monoxide and hydrocarbons and reduction of nitrogen oxides. The on-going demand for lower emissions requires more detailed knowledge about the catalytic reaction mechanisms and kinetics on the level of elementary steps, especially because of the mutual interactions in the complex reaction mixture. The reaction mechanisms for the abatement of nitrogen oxides (NO{sub x}) are of particular interest, since they are environmentally very unfriendly compounds. Transient experimental techniques can be used as a tool to understand the reaction mechanisms and to develop mathematical models allowing simulation and optimisation of the behaviour of three-way catalyst converters. In chemical kinetics, isotope-labelled reactants are frequently employed to follow reaction pathways and to determine reaction mechanisms. The kinetics and mechanisms of the catalytic reduction of nitrogen oxide (NO) by hydrogen as well as self-decomposition of NO and N{sub 2}O were studied over alumina based palladium and rhodium-alumina monoliths. In addition, NO reduction with H{sub 2} and D{sub 2}, isotope exchange of hydrogen atoms in water, ammonia and hydrogen with deuterium, as well as adsorption of ammonia and water on the Pd-monolith were studied with transient experiments. Transient step-response experiments, isotopic jumping techniques, steady- state isotopic-transient analysis, temperature programmed desorption (TPD) and Fourier-transformed infrared spectroscopy (FT-IR) were used as experimental techniques. The catalysts were characterised by carbon monoxide chemisorption, nitrogen physisorption and X-ray photoelectron spectroscopy (XPS). Nitrogen, nitrous oxide, ammonia, and water were detected as reaction products in NO reduction by hydrogen. The transient and FT-IR experiments yielded information about the surface reaction mechanisms. The dissociation of NO on the catalyst surface is the

  18. Investigation of Titanium Sesquioxide Ti2O3: Synthesis and Physical Properties

    KAUST Repository

    Li, Yangyang

    2016-11-08

    Titanium is one of the earth-abundant elements, and its oxides including titanium dioxide (TiO2) and strontium titanium oxide (SrTiO3) are widely used in technologies of electronics, energy conversion, catalysis, sensing, and so on. Generally, the Ti ions in these compounds have a valence of 4+ with the outer shell electron configuration of 3d0. In this thesis, we explore interface and titanite containing Ti3+ ions with 3d1 itinerate electrons, which we believe open new doors towards some new titanite-based technologies. In the first part of this thesis (Chapter 3), we will discuss the nanoscale chemical and valence evolution at a metal/oxide interface: Ti/SrTiO3. In many devices, metal-oxide interfaces are ubiquitous and play important roles in the performance of a wide range of electronic and optoelectronic devices. This motivated us to examine the microscopic structure of the interfaces between strontium titanium oxide and metals. In this work, one unit cell of cubic perovskite Ti2O3 was observed at the Ti/SrTiO3 interface, and oxygen diffusion depth of ~3.2 nm was observed in the sample fabricated at room temperature. Meanwhile, oxygen vacancy domains in the SrTiO3 substrates was observed and characterized by low angle annular dark field (LAADF) imaging and electron energy loss spectra (EELS). In the main part of this thesis, we will focus on the structure and physical properties of Ti2O3, a titanite which has received less attention so far in the research community. Different from TiO2 and SrTiO3, Ti2O3 has a much narrower band-gap (~0.1 eV), and we will discuss some preliminary results of its physical properties and potential applications. In Chapter 4, we will discuss the photothermal application and mid-infrared photodetectors using Ti2O3 nanoparticles based on its ultra-narrow bandgap. Photo-thermal effect via a Ti2O3/membrane structure is further applied to seawater desalination. A high temperature of 70 °C was achieved when this Ti2O3/membrane double layer structure floating on top surface of water subjected to the white light illumination of 7 kW/cm2. Furthermore, room temperature mid-infrared (10 μm) photodetectors based on Ti2O3/graphene hybrid structure was fabricated and studied. The photoresponsivity of this hybrid device, operated from 4.5 to 10 μm, is above ~ 100 A/W, which, to our knowledge, is the highest value for the mid-infrared photodetectors operating in the photocurrent (PC) mode. In chapter 5, structure, optical, transport properties of Ti2O3 epitaxial thin films on sapphire fabricated by pulsed laser deposition (PLD) will be discussed. By tailoring growth conditions, two different: trigonal and orthorhombic, of Ti2O3 were stabilized on Al2O3 substrates. More interestingly, the orthorhombic Ti2O3 has never been reported, and, moreover, superconductivity (~8 K) and high temperature ferromagnetism (up to 700 K) was discovered in this new stabilized phase. More details of the physical properties of Ti2O3 will be discussed in the following chapters of this dissertation.

  19. Reduction of turbomachinery noise

    Science.gov (United States)

    Waitz, Ian A. (Inventor); Brookfield, John M. (Inventor); Sell, Julian (Inventor); Hayden, Belva J. (Inventor); Ingard, K. Uno (Inventor)

    1999-01-01

    In the invention, propagating broad band and tonal acoustic components of noise characteristic of interaction of a turbomachine blade wake, produced by a turbomachine blade as the blade rotates, with a turbomachine component downstream of the rotating blade, are reduced. This is accomplished by injection of fluid into the blade wake through a port in the rotor blade. The mass flow rate of the fluid injected into the blade wake is selected to reduce the momentum deficit of the wake to correspondingly increase the time-mean velocity of the wake and decrease the turbulent velocity fluctuations of the wake. With this fluid injection, reduction of both propagating broad band and tonal acoustic components of noise produced by interaction of the blade wake with a turbomachine component downstream of the rotating blade is achieved. In a further noise reduction technique, boundary layer fluid is suctioned into the turbomachine blade through a suction port on the side of the blade that is characterized as the relatively low-pressure blade side. As with the fluid injection technique, the mass flow rate of the fluid suctioned into the blade is here selected to reduce the momentum deficit of the wake to correspondingly increase the time-mean velocity of the wake and decrease the turbulent velocity fluctuations of the wake; reduction of both propagating broad band and tonal acoustic components of noise produced by interaction of the blade wake with a turbomachine component downstream of the rotating blade is achieved with this suction technique. Blowing and suction techniques are also provided in the invention for reducing noise associated with the wake produced by fluid flow around a stationary blade upstream of a rotating turbomachine.

  20. Infinitary Combinatory Reduction Systems

    DEFF Research Database (Denmark)

    Ketema, Jeroen; Simonsen, Jakob Grue

    2011-01-01

    We define infinitary Combinatory Reduction Systems (iCRSs), thus providing the first notion of infinitary higher-order rewriting. The systems defined are sufficiently general that ordinary infinitary term rewriting and infinitary ¿-calculus are special cases. Furthermore,we generalise a number...... of knownresults fromfirst-order infinitary rewriting and infinitary ¿-calculus to iCRSs. In particular, for fully-extended, left-linear iCRSs we prove the well-known compression property, and for orthogonal iCRSs we prove that (1) if a set of redexes U has a complete development, then all complete developments...

  1. Oxygen Reduction on Platinum

    DEFF Research Database (Denmark)

    Nesselberger, Markus

    This thesis investigates the electro reduction of oxygen on platinum nanoparticles, which serve as catalyst in low temperature fuel cells. Kinetic studies on model catalysts as well as commercially used systems are presented in order to investigate the particle size effect, the particle proximity...... carbon (HSAC) supported Pt nanoparticle (Pt/C) catalysts (of various size between 1 and 5 nm). The difference in SA between the individual Pt/C catalysts (1 to 5 nm) is very small and within the error of the measurements. The factor four of loss in SA when comparing platinum bulk and Pt/C can largely...

  2. Reduction operators of Burgers equation.

    Science.gov (United States)

    Pocheketa, Oleksandr A; Popovych, Roman O

    2013-02-01

    The solution of the problem on reduction operators and nonclassical reductions of the Burgers equation is systematically treated and completed. A new proof of the theorem on the special "no-go" case of regular reduction operators is presented, and the representation of the coefficients of operators in terms of solutions of the initial equation is constructed for this case. All possible nonclassical reductions of the Burgers equation to single ordinary differential equations are exhaustively described. Any Lie reduction of the Burgers equation proves to be equivalent via the Hopf-Cole transformation to a parameterized family of Lie reductions of the linear heat equation.

  3. Microbial reduction of iodate

    Science.gov (United States)

    Councell, T.B.; Landa, E.R.; Lovley, D.R.

    1997-01-01

    The different oxidation species of iodine have markedly different sorption properties. Hence, changes in iodine redox states can greatly affect the mobility of iodine in the environment. Although a major microbial role has been suggested in the past to account for these redox changes, little has been done to elucidate the responsible microorganisms or the mechanisms involved. In the work presented here, direct microbial reduction of iodate was demonstrated with anaerobic cell suspensions of the sulfate reducing bacterium Desulfovibrio desulfuricans which reduced 96% of an initial 100 ??M iodate to iodide at pH 7 in 30 mM NaHCO3 buffer, whereas anaerobic cell suspensions of the dissimilatory Fe(III)-reducing bacterium Shewanella putrefaciens were unable to reduce iodate in 30 mM NaHCO3 buffer (pH 7). Both D. desulfuricans and S. putrefaciens were able to reduce iodate at pH 7 in 10 mM HEPES buffer. Both soluble ferrous iron and sulfide, as well as iron monosulfide (FeS) were shown to abiologically reduce iodate to iodide. These results indicate that ferric iron and/or sulfate reducing bacteria are capable of mediating both direct, enzymatic, as well as abiotic reduction of iodate in natural anaerobic environments. These microbially mediated reactions may be important factors in the fate and transport of 129I in natural systems.

  4. Islam and harm reduction.

    Science.gov (United States)

    Kamarulzaman, A; Saifuddeen, S M

    2010-03-01

    Although drugs are haram and therefore prohibited in Islam, illicit drug use is widespread in many Islamic countries throughout the world. In the last several years increased prevalence of this problem has been observed in many of these countries which has in turn led to increasing injecting drug use driven HIV/AIDS epidemic across the Islamic world. Whilst some countries have recently responded to the threat through the implementation of harm reduction programmes, many others have been slow to respond. In Islam, The Quran and the Prophetic traditions or the Sunnah are the central sources of references for the laws and principles that guide the Muslims' way of life and by which policies and guidelines for responses including that of contemporary social and health problems can be derived. The preservation and protection of the dignity of man, and steering mankind away from harm and destruction are central to the teachings of Islam. When viewed through the Islamic principles of the preservation and protection of the faith, life, intellect, progeny and wealth, harm reduction programmes are permissible and in fact provide a practical solution to a problem that could result in far greater damage to the society at large if left unaddressed.

  5. Sonoassisted microbial reduction of chromium.

    Science.gov (United States)

    Kathiravan, Mathur Nadarajan; Karthick, Ramalingam; Muthu, Naggapan; Muthukumar, Karuppan; Velan, Manickam

    2010-04-01

    This study presents sonoassisted microbial reduction of hexavalent chromium (Cr(VI)) using Bacillus sp. isolated from tannery effluent contaminated site. The experiments were carried out with free cells in the presence and absence of ultrasound. The optimum pH and temperature for the reduction of Cr(VI) by Bacillus sp. were found to be 7.0 and 37 degrees C, respectively. The Cr(VI) reduction was significantly influenced by the electron donors and among the various electron donors studied, glucose offered maximum reduction. The ultrasound-irradiated reduction of Cr(VI) with Bacillus sp. showed efficient Cr(VI) reduction. The percent reduction was found to increase with an increase in biomass concentration and decrease with an increase in initial concentration. The changes in the functional groups of Bacillus sp., before and after chromium reduction were observed with FTIR spectra. Microbial growth was described with Monod and Andrews model and best fit was observed with Andrews model.

  6. Consumer's Guide to Radon Reduction

    Science.gov (United States)

    ... Radon Share Facebook Twitter Google+ Pinterest Contact Us Consumer's Guide to Radon Reduction: How to Fix Your ... See EPA’s About PDF page to learn more. Consumer's Guide to Radon Reduction: How to Fix Your ...

  7. Multiple gas reduction strategy

    Energy Technology Data Exchange (ETDEWEB)

    A. Kurosawa [Institute of Applied Energy, Tokyo (Japan)

    2003-07-01

    Future global warming has a close relationship with the abatement potential of six greenhouse gases (GHGs), including carbon dioxide (CO{sub 2}), methane (CH{sub 4}), nitrous oxide (N{sub 2}O), hydrofluorocarbons (HFCs), perfluorocarbons (PFCs), and sulfur hexafluoride (SF6). Therefore, multiple gas reduction flexibility should be assessed. The emission of each non-CO{sub 2} GHG is calculated endogenously by the sum of the product of the emission factor and the endogenous activity index using an integrated assessment model, GRAPE (Global Relationship Assessment to Protect the Environment). The model consists of five modules dealing with issues on energy, climate, land use, macroeconomics and environmental impacts. The uncertainty in the non-CO{sub 2} GHG emission inventory and emission factors is discussed. 5 refs., 3 figs., 1 tab.

  8. Testing the reduction rule

    CERN Document Server

    Hegerfeldt, G C

    2011-01-01

    The reduction rule, also known as the projection postulate, specifies the state after an ideal measurement. There are two forms, the original rule of von Neumann and a nowadays mostly used modification thereof due to L\\"uders, but sometimes also attributed to von Neumann. However, which form applies depends on the details of the measuring apparatus. Here we therefore consider the following problem: Given an ensemble of systems in an unknown pure or mixed state, an observable $\\hat A$ and an apparatus which performs a measurement of $\\hat A$ on the ensemble, but whose detailed working is unknown ('black box'), how can one test whether the apparatus performs a L\\"uders or von Neumann measurement?

  9. Reducts of Ramsey structures

    CERN Document Server

    Bodirsky, Manuel

    2011-01-01

    One way of studying a relational structure is to investigate functions which are related to that structure and which leave certain aspects of the structure invariant. Examples are the automorphism group, the self-embedding monoid, the endomorphism monoid, or the polymorphism clone of a structure. Such functions can be particularly well understood when the relational structure is countably infinite and has a first-order definition in another relational structure which has a finite language, is totally ordered and homogeneous, and has the Ramsey property. This is because in this situation, Ramsey theory provides the combinatorial tool for analyzing these functions -- in a certain sense, it allows to represent such functions by functions on finite sets. This is a survey of results in model theory and theoretical computer science obtained recently by the authors in this context. In model theory, we approach the problem of classifying the reducts of countably infinite ordered homogeneous Ramsey structures in a fin...

  10. Dose Reduction Techniques

    Energy Technology Data Exchange (ETDEWEB)

    WAGGONER, L.O.

    2000-05-16

    As radiation safety specialists, one of the things we are required to do is evaluate tools, equipment, materials and work practices and decide whether the use of these products or work practices will reduce radiation dose or risk to the environment. There is a tendency for many workers that work with radioactive material to accomplish radiological work the same way they have always done it rather than look for new technology or change their work practices. New technology is being developed all the time that can make radiological work easier and result in less radiation dose to the worker or reduce the possibility that contamination will be spread to the environment. As we discuss the various tools and techniques that reduce radiation dose, keep in mind that the radiological controls should be reasonable. We can not always get the dose to zero, so we must try to accomplish the work efficiently and cost-effectively. There are times we may have to accept there is only so much you can do. The goal is to do the smart things that protect the worker but do not hinder him while the task is being accomplished. In addition, we should not demand that large amounts of money be spent for equipment that has marginal value in order to save a few millirem. We have broken the handout into sections that should simplify the presentation. Time, distance, shielding, and source reduction are methods used to reduce dose and are covered in Part I on work execution. We then look at operational considerations, radiological design parameters, and discuss the characteristics of personnel who deal with ALARA. This handout should give you an overview of what it takes to have an effective dose reduction program.

  11. 辛酸铑催化剂的消解及其铑含量的测定%The Digestion of Rhodium Octanoate Dimer Catalyst and Determination of Rh

    Institute of Scientific and Technical Information of China (English)

    易秉智; 袁建良

    2013-01-01

    提出了新的辛酸铑催化剂消解方法,重点研究了消解法的条件,比较了几种分解法及其铑含量测定的方法。结果表明:使用聚四氟乙烯消解罐,于160℃,12 mL HNO3-3 mL H2O2消解4 h,能完全消解0.1~0.2 g 样品。所用消解方法操作简便,Rh 不损失。采用硝酸六氨合钴重量法测定26.30%的铑含量,相对标准偏差0.099%。方法测定结果准确、精密。%A new digestion method of octanoate dimer catalyst was introduced, the conditions of digestion methods were emphatically studied. The different digestion processes and dissolution methods were compared. The results showed that 0.1~0.2 g Rh octanoate dimer sample could be digested completely with 12 mL HNO3 and 3 mL H2O2 at 160℃ in a PTFE jar for 4 h. The operation of the digestion method was easy without of the Rh loss. The gravimetry with nitrate cobaltic hexamine was used to determinate the rhodium content of 26.30%, and the RSD was 0.099%. This method is accuracy and precision compared with other methods.

  12. Mono-, di- and tetranuclear rhodium(I) complexes of morpholine and -methylpiperazine functionalized cyclodiphosph(III)azanes, cis-[(tBuN-)2(PNC4H8X)2] (X = O, NMe)

    Indian Academy of Sciences (India)

    Maravanji S Balakrishna; D Suresh; Joel T Mague

    2011-11-01

    The reactions of cyclodiphosphazanes, cis-[(tBuN-)2(PNC4H8O)2] (1, R = NC4H8O; 2, R = NC4H8NMe ) (2) with [{RhCl(COD)}2] and [{RhCl(CO)2}2] are described. The reactions of 1 or 2 with [{RhCl(COD)}2] in 2:1 molar ratio yielded the mononuclear complexes [(COD)RhCl{(-NtBuP)2(NC4H8X)2}] (3, X = O; 4, X = NMe) in good yield. Treatment of one equivalent of [{RhCl(CO)2}2] with four equivalents of 1 or 2 produced the trans-[(CO)RhCl{(-NtBuP)2(NC4H8X)2}2] (5, X = O; 6, X = NMe) complexes as pale yellow solids. On changing the molar ratio of [{RhCl(CO)2}2] and 1 or 2 from 1:4 to 1:1 resulted in the formation of tetranuclear complexes [{(CO)Rh(-Cl)(-NtBuP)(NC4H8X)}4] (7, X = O; 8, X = NMe) under similar reaction conditions. The tetranuclear rhodium(I) complex 8 upon stirring with wet acetonitrile or in the presence of four equivalents of water at room temperature afforded a novel hydroxo bridged zwitterionic dirhodium(I) complex [{(ClRh(CO))2(-OH)(MeNC4H8N)(-NBuP)2(NC4H8NHMe)}] (9). The crystal structures of 5, 6 and 9 were established by single crystal X-ray diffraction studies.

  13. Alcohol harm reduction in Europe

    DEFF Research Database (Denmark)

    Herring, Rachel; Betsy, Thom; Beccaria, Franca

    2010-01-01

    The EMCDDA’s 10th scientific monograph, entitled Harm reduction: evidence, impacts and challenges provides a comprehensive overview of the harm reduction field. Part I of the monograph looks back at the emergence of harm reduction approaches and their diffusion, and explores the concept from diff...

  14. Abstract models of transfinite reductions

    DEFF Research Database (Denmark)

    Bahr, Patrick

    2010-01-01

    We investigate transfinite reductions in abstract reduction systems. To this end, we study two abstract models for transfinite reductions: a metric model generalising the usual metric approach to infinitary term rewriting and a novel partial order model. For both models we distinguish between...

  15. Determination of the thickness of rhodium cover and major elements in gold and platinum jewelry by XRF%X射线荧光光谱法测试金铂饰品中铑覆盖层厚度及主体元素

    Institute of Scientific and Technical Information of China (English)

    龙建; 王丽敏; 黄佩英

    2015-01-01

    X ray fluorescence( XRF) is applied to determine the thickness of rhodium cover and major elements in gold and platinum jewelry without damaging them by comparing standard rhodium cover slice, standard gold alloy slice and standard platinum alloy slice. The test result is verified by comparing the results of classic coulometry, ICP subtraction and fire assay, proving to be very accurate.%采用X射线荧光光谱法,通过对比标准铑覆盖层片、标准金合金片和标准铂合金片,在非破坏性的前提下,同时测定金、铂饰品中的铑镀层厚度及主体元素。采用该方法的测试结果与经典库仑法、ICP差减法和火试金法的测试结果进行了对比验证,该方法测试结果具有较高的准确度。

  16. Heart Failure Readmission Reduction.

    Science.gov (United States)

    Drozda, Joseph P; Smith, Donna A; Freiman, Paul C; Pursley, Janet; VanSlette, Jeffrey A; Smith, Timothy R

    Little is known regarding effectiveness of readmission reduction programs over time. The Heart Failure Management Program (HFMP) of St. John's Physician Group Practice (PGP) Demonstration provided an opportunity to assess outcomes over an extended period. Data from an electronic health record, an inpatient database, a disease registry, and the Social Security Death Master File were analyzed for patients admitted with heart failure (HF) for 5 years before (Period 1) and 5 years after (Period 2) inception of PGP. HF admissions decreased (Period 1, 58.3/month; Period 2, 52.4/month, P = .007). Thirty-day all-cause readmission rate dropped from Period 1 (annual average 18.8% [668/3545]) to year 1 of Period 2 (16.9% [136/804], P = .04) and remained stable thereafter (annual average 16.8% [589/3503]). Thirty-day mortality rate was flat throughout. HFMP was associated with decreased readmissions, primarily related to outpatient case management, while mortality remained stable.

  17. Electrochemical reduction of NOx

    DEFF Research Database (Denmark)

    Traulsen, Marie Lund

    NO and NO2 (collectively referred to as NOx) are air pollutants, and the largest single contributor to NOx pollution is automotive exhaust. This study investigates electrochemical deNOx, a technology which aims to remove NOx from automotive diesel exhaust by electrochemical reduction of NOx to N2...... and O2. The focus in this study is on improving the activity and selectivity of solid oxide electrodes for electrochemical deNOx by addition of NOx storage compounds to the electrodes. Two different composite electrodes, La0.85Sr0.15MnO3-δ-Ce0.9Gd0.1O1.95 (LSM15-CGO10) and La0.85Sr0.15FeO3-δ-Ce0.9Gd0.1O......1.95 (LSF15-CGO10), have been investigated in combination with three different NOx storage compounds: BaO, K2O and MnOx. The main focus in the investigation has been on conversion measurements and electrochemical characterization, the latter by means of electrochemical impedance spectroscopy...

  18. Setting goals for drug policy: harm reduction or use reduction?

    Science.gov (United States)

    Caulkins, J P; Reuter, P

    1997-09-01

    Historically, United States drug policy has focused on use reduction; harm reduction is a prominent alternative. This paper aims to provoke and inform more debate about the relative merits of these two. Since harm is not necessarily proportional to use, use reduction and harm reduction differ. Both terms are somewhat ambiguous; precisely defining them clarifies thinking and policy implications. Measures associated with use reduction goals are poor; those associated with harm reduction are even worse. National goals influence the many decentralized individuals who collectively make drug policy; clearly enunciating goals makes some policy choices transparent and goals serve a variety of purposes besides guiding programmatic decisions. We recommend that the overall objective be to minimize the total harm associated with drug production, distribution, consumption and control. Reducing use should be seen as a principal means of attaining that end.

  19. Removal of CO from CO-contaminated hydrogen gas by carbon-supported rhodium porphyrins using water-soluble electron acceptors

    Science.gov (United States)

    Yamazaki, Shin-ichi; Siroma, Zyun; Asahi, Masafumi; Ioroi, Tsutomu

    2016-10-01

    Carbon-supported Rh porphyrins catalyze the oxidation of carbon monoxide by water-soluble electron acceptors. The rate of this reaction is plotted as a function of the redox potential of the electron acceptor. The rate increases with an increase in the redox potential until it reaches a plateau. This profile can be explained in terms of the electrocatalytic CO oxidation activity of the Rh porphyrin. The removal of CO from CO(2%)/H2 by a solution containing a carbon-supported Rh porphyrin and an electron acceptor is examined. The complete conversion of CO to CO2 is achieved with only a slight amount of Rh porphyrins. Rh porphyrin on carbon black gives higher conversion than that dissolved in solution. This reaction can be used not only to remove CO in anode gas of stationary polymer electrolyte fuel cells but also to regenerate a reductant in indirect CO fuel cell systems.

  20. Deliberating emission reduction options

    Energy Technology Data Exchange (ETDEWEB)

    Dowd, A.M.; Rodriguez, M.; Jeanneret, T. [Commonwealth Scientific and Industrial Research Organisation CSIRO, 37 Graham Rd, Highett VIC 3190 (Australia); De Best-Waldhober, M.; Straver, K.; Mastop, J.; Paukovic, M. [Energy research Centre of the Netherlands ECN, Policy Studies, Amsterdam (Netherlands)

    2012-06-15

    For more than 20 years there has been a concerted international effort toward addressing climate change. International conventions, such as the United Nations Foreign Convention on Climate Change (UNFCCC; ratified in 1994), have been established by committed nations seeking to address global climate change through the reduction of greenhouse gases emitted into the Earth's atmosphere (Global CCS Institute, 2011). Long recognised as the most crucial of the greenhouse gases to impact global warming, the majority of carbon dioxide's anthropogenic global emissions are directly related to fuel combustion of which both Australia and the Netherlands' energy production is significantly reliant. Both these nations will need to consider many opinions and make hard decisions if alternative energy options are to be implemented at the scale that is required to meet international emission targets. The decisions that are required not only need to consider the many options available but also their consequences. Along with politicians, policy developers and industry, the general public also need to be active participants in deciding which energy options, and their subsequent consequences, are acceptable for implementation at the national level. Access to balanced and factual information is essential in establishing informed opinions on the many policy options available. Past research has used several methods to measure public perceptions and opinions yet for complex issues, such as emission reduction, some of these methods have shown to be problematic. For example, semi structured interviews can provide data that is flexible and context rich yet is does also come with the limitations such as it seldom provides a practical assessment that can be utilised from researcher to researcher, across disciplines and public participation techniques. Surveys on the other hand usually address these limitations but surveys that do not encourage comparison of information or ask

  1. Robust methods for data reduction

    CERN Document Server

    Farcomeni, Alessio

    2015-01-01

    Robust Methods for Data Reduction gives a non-technical overview of robust data reduction techniques, encouraging the use of these important and useful methods in practical applications. The main areas covered include principal components analysis, sparse principal component analysis, canonical correlation analysis, factor analysis, clustering, double clustering, and discriminant analysis.The first part of the book illustrates how dimension reduction techniques synthesize available information by reducing the dimensionality of the data. The second part focuses on cluster and discriminant analy

  2. Turbulent drag reduction by polymers

    Energy Technology Data Exchange (ETDEWEB)

    Bonn, Daniel [Van der Waals-Zeeman Instituut, University of Amsterdam, Valckenierstraat 65 1018, XE Amsterdam (Netherlands); Amarouchene, Yacine [CPMOH, Universite Bordeaux 1, 351 Cours de la Liberation, 33405 Talence cedex (France); Wagner, Christian [Institut fuer Experimentalphysik, Universitaet des Saarlandes, Saarbruecken (Germany); Douady, Stephane [Laboratoire de Physique Statistique de l' ENS, 24 rue Lhomond, 75231 Paris cedex 05 (France); Cadot, Olivier [ENSTA, Chemin de la Huniere, 91761 Palaiseau cedex (France)

    2005-04-13

    The reduction of turbulent energy dissipation by addition of polymers is studied experimentally. We first address the question of where the action of the polymers is taking place. Subsequently, we show that there is a direct correlation of drag reduction with the elongational viscosity of the polymers. For this, the reduction of turbulent energy dissipation by addition of the biopolymer DNA is studied. These results open the way for a direct visualization study of the polymer conformation in a turbulent boundary layer.

  3. Routh reduction and Cartan mechanics

    Science.gov (United States)

    Capriotti, S.

    2017-04-01

    In the present work a Cartan mechanics version for Routh reduction is considered, as an intermediate step towards Routh reduction in field theory. Motivation for this generalization comes from a scheme for integrable systems (Fehér and Gábor, 2002), used for understanding the occurrence of Toda field theories in so called Hamiltonian reduction of WZNW field theories (Fehér et al., 1992). As a way to accomplish with this intermediate aim, this article also contains a formulation of the Lagrangian Adler-Kostant-Symes systems discussed in Fehér and Gábor (2002) in terms of Routh reduction.

  4. Casting light on harm reduction

    DEFF Research Database (Denmark)

    Jourdan, Michael

    2009-01-01

    reduction in its more comprehensive forms continuously stir up controversy. In spite of this the notion of complementarity is commonly upheld leaving opposition to harm reduction inexplicable and non-researchable. Methods: Teaching experience in multiple settings in which opposing views have surfaced...

  5. Reduction-Fired Seedpod Bowls.

    Science.gov (United States)

    Beyke, Rod

    2001-01-01

    Focuses on a reduction-firing process with an aim of producing high-quality blackware similar to the black-on-black pottery of Maria Martinez and other American Indian potters. Includes a lesson on creating reduction-fired seedpod bowls, lists of instructional resources and materials, and the objectives and evaluation. (CMK)

  6. Chronic sleep reduction in adolescents

    NARCIS (Netherlands)

    Dewald-Kaufmann, J.F.

    2012-01-01

    Based on the results of this thesis, it can be concluded that sleep problems and chronic sleep reduction have a high impact on adolescents’ daytime functioning. Additionally, this research shows that gradual sleep extension can improve adolescents’ sleep and especially their chronic sleep reduction.

  7. Reduction of chemical reaction models

    Science.gov (United States)

    Frenklach, Michael

    1991-01-01

    An attempt is made to reconcile the different terminologies pertaining to reduction of chemical reaction models. The approaches considered include global modeling, response modeling, detailed reduction, chemical lumping, and statistical lumping. The advantages and drawbacks of each of these methods are pointed out.

  8. Rhodium Catalysts in the Oxidation of CO by O2 and NO: Shape, Composition, and Hot Electron Generation

    Energy Technology Data Exchange (ETDEWEB)

    Renzas, James R. [Univ. of California, Berkeley, CA (United States)

    2010-03-08

    It is well known that the activity, selectivity, and deactivation behavior of heterogeneous catalysts are strongly affected by a wide variety of parameters, including but not limited to nanoparticle size, shape, composition, support, pretreatment conditions, oxidation state, and electronic state. Enormous effort has been expended in an attempt to understand the role of these factors on catalytic behavior, but much still remains to be discovered. In this work, we have focused on deepening the present understanding of the role of nanoparticle shape, nanoparticle composition, and hot electrons on heterogeneous catalysis in the oxidation of carbon monoxide by molecular oxygen and nitric oxide. These reactions were chosen because they are important for environmental applications, such as in the catalytic converter, and because there is a wide range of experimental and theoretical insight from previous single crystal work as well as experimental data on nanoparticles obtained using new state-of-the-art techniques that aid greatly in the interpretation of results on complex nanoparticle systems. In particular, the studies presented in this work involve three types of samples: ~ 6.5 nm Rh nanoparticles of different shapes, ~ 15 nm Rh1-xPdx core-shell bimetallic polyhedra nanoparticles, and Rh ultra-thin film (~ 5 nm) catalytic nanodiodes. The colloidal nanoparticle samples were synthesized using a co-reduction of metal salts in alcohol and supported on silicon wafers using the Langmuir-Blodgett technique. This synthetic strategy enables tremendous control of nanoparticle size, shape, and composition. Nanoparticle shape was controlled through the use of different organic polymer capping layers. Bimetallic core-shell nanoparticles were synthesized by careful choice of metal salt precursors. Rh/TiOx and Rh/GaN catalytic nanodiodes were fabricated using a variety of thin film device fabrication techniques, including reactive DC magnetron

  9. 钼铑双靶X线摄影在乳腺疾病普查中的应用(附1000例分析)%Application of molybdenum and rhodium dual-target X-ray mammograms in breast disease census(an analysis of 1000 cases)

    Institute of Scientific and Technical Information of China (English)

    黄永杰; 刘明; 王虹

    2013-01-01

    目的 分析钼铑双靶X线检查在乳腺疾病诊断中的应用价值.方法 采用乳腺临床触诊等方法对60000例40~ 86岁妇女进行乳腺疾病普查.回顾性分析1000例有临床症状的乳腺疾病患者,全部做乳腺钼铑双靶X线检查.结果 X线诊断为阳性病变者706例,经临床治疗或手术后154例,恶性病变为18例,误诊2例.结论 普及宣传妇女乳腺疾病防治知识,注意各年龄阶段乳腺疾病防治重点,合理认识和正确使用普查方法可提高乳腺癌检出率.X线钼铑双靶摄影对乳腺疾病的诊断具有很大的价值,可作为一种常规的检查手段.%Objective To analyze the application value of molybdenum and rhodium dual-target X-ray examination in diagnosis of breast disease.Methods Breast disease census was conducted for 60,000 women aged 40-86 year old by breast palpation examination.One thousand patients with clinical symptoms of breast disease were retrospectively analyzed,all patients took the examination of molybdenum and rhodium dual-target marnmograms.Results Seven hundred and six positive cases were diagnosed by X-ray,154 patients were in clinical treatment or postoperative,18 cases of malignant breast lesions were pathologically confirmed,2 cases were misdiagnosed.Conclusions Prevention knowledge of women breast disease should be popularized and propagated.Reasonable understanding and proper use of the census method can improve the detection rate of breast cancer.Molybdenum and rhodium dual-target mammogram has a great value in diagnosis of breast disease.It can be used as a routine check means.

  10. Acute IPPS - Readmissions Reduction Program

    Data.gov (United States)

    U.S. Department of Health & Human Services — Section 3025 of the Affordable Care Act added section 1886(q) to the Social Security Act establishing the Hospital Readmissions Reduction Program, which requires CMS...

  11. Model Reduction of Hybrid Systems

    DEFF Research Database (Denmark)

    Shaker, Hamid Reza

    systems are derived in this thesis. The results are used for output feedback control of switched nonlinear systems. Model reduction of piecewise affine systems is also studied in this thesis. The proposed method is based on the reduction of linear subsystems inside the polytopes. The methods which......High-Technological solutions of today are characterized by complex dynamical models. A lot of these models have inherent hybrid/switching structure. Hybrid/switched systems are powerful models for distributed embedded systems design where discrete controls are applied to continuous processes...... of hybrid systems, designing controllers and implementations is very high so that the use of these models is limited in applications where the size of the state space is large. To cope with complexity, model reduction is a powerful technique. This thesis presents methods for model reduction and stability...

  12. Fermion masses from dimensional reduction

    Energy Technology Data Exchange (ETDEWEB)

    Kapetanakis, D. (National Research Centre for the Physical Sciences Democritos, Athens (Greece)); Zoupanos, G. (European Organization for Nuclear Research, Geneva (Switzerland))

    1990-10-11

    We consider the fermion masses in gauge theories obtained from ten dimensions through dimensional reduction on coset spaces. We calculate the general fermion mass matrix and we apply the mass formula in illustrative examples. (orig.).

  13. Approximate reduction of dynamical systems

    CERN Document Server

    Tabuada, Paulo; Julius, Agung; Pappas, George J

    2007-01-01

    The reduction of dynamical systems has a rich history, with many important applications related to stability, control and verification. Reduction of nonlinear systems is typically performed in an exact manner - as is the case with mechanical systems with symmetry--which, unfortunately, limits the type of systems to which it can be applied. The goal of this paper is to consider a more general form of reduction, termed approximate reduction, in order to extend the class of systems that can be reduced. Using notions related to incremental stability, we give conditions on when a dynamical system can be projected to a lower dimensional space while providing hard bounds on the induced errors, i.e., when it is behaviorally similar to a dynamical system on a lower dimensional space. These concepts are illustrated on a series of examples.

  14. Transitive Reduction of Citation Networks

    CERN Document Server

    Clough, James R; Loach, Tamar V; Evans, Tim S

    2013-01-01

    Citation networks form directed acyclic graphs. The transitive reduction of such a DAG removes all edges in the graph that are implied by transitivity, but retains the causal structure of the original network. We investigate how the degree distribution, clustering coefficients and relationship between time of publication and degree (representing citation count) are changed under transitive reduction. We show that models which accurately reproduce the degree distribution of a citation network before transitive reduction may not do so afterwards and hence suggest that these models fail to accurately capture the causal structure of the network. We also investigate how the citation count of individual papers is changed and suggest that information about the types of citations a paper receives can be inferred from the number of citations which are retained after transitive reduction. These methods are tested on citation networks from the hep-th and hep-ph sections of the arXiv repository, and all data has been mad...

  15. Logistics Reduction and Repurposing Project

    Data.gov (United States)

    National Aeronautics and Space Administration — The Advanced Exploration Systems (AES) Logistics Reduction and Repurposing (LRR) project will enable a mission-independent cradle-to-grave-to-cradle...

  16. The relaxation & stress reduction workbook

    National Research Council Canada - National Science Library

    Davis, Martha; Eshelman, Elizabeth Robbins; McKay, Matthew

    2008-01-01

    "The Relaxation & Stress Reduction Workbook broke new ground when it was first published in 1980, detailing easy, step-by-step techniques for calming the body and mind in an increasingly overstimulated world...

  17. Chemical model reduction under uncertainty

    KAUST Repository

    Najm, Habib

    2016-01-05

    We outline a strategy for chemical kinetic model reduction under uncertainty. We present highlights of our existing deterministic model reduction strategy, and describe the extension of the formulation to include parametric uncertainty in the detailed mechanism. We discuss the utility of this construction, as applied to hydrocarbon fuel-air kinetics, and the associated use of uncertainty-aware measures of error between predictions from detailed and simplified models.

  18. 2dfdr: Data reduction software

    Science.gov (United States)

    AAO software Team

    2015-05-01

    2dfdr is an automatic data reduction pipeline dedicated to reducing multi-fibre spectroscopy data, with current implementations for AAOmega (fed by the 2dF, KOALA-IFU, SAMI Multi-IFU or older SPIRAL front-ends), HERMES, 2dF (spectrograph), 6dF, and FMOS. A graphical user interface is provided to control data reduction and allow inspection of the reduced spectra.

  19. 火焰原子吸收光谱法测定尾气净化金属载体催化剂中铂钯铑%Determination of platinum, palladium, rhodium in metal carrier catalyst for exhaust gas purification by flame atomic absorption spectrometry

    Institute of Scientific and Technical Information of China (English)

    施意华; 王晟; 杨仲平; 靳晓珠; 胡圣虹; 邓水平

    2012-01-01

    建立了火焰原子吸收光谱法测定尾气净化金属载体催化剂中Pt、Pd、Rh含量的新方法.研究了试样分解方法、共沉淀条件、测定干扰因素及消除方法.采用盐酸-超声波处理尾气净化金属载体催化剂,过滤,不溶物用过氧化钠分解,盐酸酸化后全部转化为样品溶液.在含2~3 mol/L盐酸的样品溶液.中,加入10 mg氧化碲和10 mL 200 g/L氯化亚锡溶液共沉淀富集样品溶液中的Pt、Pd、Rh,与基体元素Fe、Ni、Al、Cr、Na等完全分离,共沉淀物用王水溶解后,采用火焰原子吸收光谱法测定Pt、Pd、Rh.方法的检出限分别为:Pt 4.72 μg/g,Pd1.13μg/g,Rh 1.06 μg/g.将本方法用于实际样品分析,结果与电感耦合等离子体原子发射光谱法测定值一致,相对标准偏差(RSD,n=11)分别为:3.0%(Pt),1.9%(Pd),4.2%(Rh).%A novel method for the determination of platinum, palladium and rhodium in metal carrier catalyst for exhaust gas purification was established by flame atomic absorption spectrometrometry (FAAS). The sample decomposition method) coprecipitation condition, interference factor and elimination method were studied. The metal carrier catalyst sample for exhaust gas purification was treated by hydrochloric acid-ultrasonic wave, and filtrated. The insoluble substance was decomposed with sodium peroxide and acidized with hydrochloric acid, and then it was mixed with sample solution. 10 mg of tellurium oxide and 10 mL of 200 g/L SnCl2 solution were added to sample solution in the medium of 2-3 mol/L hydrochloric acid for the coprecipitation, enrichment and separation of palladium, platinum and rhodium from matrix elements such as Fe, Ni, Al, Cr and Na. After the coprecipitate was dissolved with aqua regia, the content of palladium, platinum and rhodium was determined by flame a-tomic absorption spectrometry. The detection limits of method for Pt, Pd and Rh are 4. 72,1.13 and 1. 06,respectively. The proposed method was applied to

  20. Preliminary Exploration of the Reactor Configuration for Hydroformylation of 1-Dodecene Catalyzed by Water Soluble Rhodium Complex%水溶性铑络合物催化1-十二碳烯氢甲酰化反应器构型的初步探索

    Institute of Scientific and Technical Information of China (English)

    毛在砂; 毕新艳; 禹耕之; 张永强; 杨超; 王蓉

    2002-01-01

    Hydroformylation of 1-dodecene was studied in a biphasic system using water-soluble rhodium complex [RhCl(CO)(TPPTS)2] as catalyst in the presence of cetyl trimethyl ammonium bromide as surfactant to enhance the reaction rate. Efforts were devoted to improve the performance of hydroformylation by exploring reactor configuration which enhanced the mixing, dispersion and interphase mass transfer. Experiments were carried out in a 0.5 L autoclave at the total pressure of 1.1 MPa and temperature from 363 K to 373 K. Several surface aeration configurations were tested, and higher hydroformylation rate with higher normal/branched aldehyde ratio produced were achieved. The experiences suggest that improved reactor configuration by taking reaction engineering measures is beneficial to better process economy in alkene hydroformylation.

  1. Study on the Ion-associated Complex of Rhodium-tungstate-rhodamine 6G by the Resonance Light-Scattering Technique and Its Application%铑-钨酸盐-罗丹明6G缔合体系的共振光散射技术研究及其应用

    Institute of Scientific and Technical Information of China (English)

    苗兆涛; 龙巍然; 陶晋飞; 张婷; 曹秋娥

    2012-01-01

    The intensive signal of the resonance light - scattering at 579 nm was observed when the ion -associated complex was formed among rhodium(III) , tungstate and rhodamine 6G in the presence of acacia Senegal. And this phenomenon was used to develop a method for the determination of trace amounts of Rh( III). The method was free from the interference of a lot of common ions with the linear range of 0.01 ~0.25 ng/mL and detection limit of 0. 0024 ng/mL. The results for determination of rhodium in real samples obtained by this method were consistent well with those obtained by SnCl2 standard method.%Rh(Ⅲ)与钨酸盐及罗丹明6G在阿拉伯胶存在下能形成离子缔合物,且该离子缔合物在579nm处具有强烈的共振瑞利光散射信号.据此,建立了一种测定痕量Rh(Ⅲ)的共振瑞利散射光谱法,该方法的线性范围为0.01~0.25ng/mL,检出限为0.0024ng/mL,且大量存在的常见离子对Rh(Ⅲ)的测定不干扰.将方法用于测定催化剂及冶金产品中的铑,结果与标准方法(SnCl2法)测得值基本一致.

  2. [Substances considered addictive: prohibition, harm reduction and risk reduction].

    Science.gov (United States)

    Menéndez, Eduardo

    2012-01-01

    Latin America is currently the region with the highest rate of homicides worldwide, and a large part of the killings are linked to so-called organized crime, especially drug trafficking. The trafficking of drugs is a consequence of the illegality of certain substances which - at least presently - is based in and legitimated by biomedical criteria that turns the production, commercialization and often the consumption of certain substances considered addictive into "offenses against health." This text briefly analyzes the two policies formulated and implemented thus far in terms of prohibition and harm reduction, considering the failure of prohibitionism as well as the limitations of harm reduction proposals. The constant and multiple inconsistencies and contradictions of prohibitionism are noted, indicating the necessity of regarding cautiously repeated comments about its "failure." The text proposes the implementation of a policy of risk reduction that includes not only the behavior of individuals and groups, but also the structural dimension, both in economic-political and cultural terms.

  3. State of the direct reduction and reduction smelting processes

    Directory of Open Access Journals (Sweden)

    Markotić A.

    2002-01-01

    Full Text Available For quite a long time efforts have been made to develop processes for producing iron i.e. steel without employing conventional procedures - from ore, coke, blast furnace, iron, electric arc furnace, converter to steel. The insufficient availability and the high price of the coking coals have forced many countries to research and adopt the non-coke-consuming reduction and metal manufacturing processes (non-coke metallurgy, direct reduction, direct processes. This paper represents a survey of the most relevant processes from this domain by the end of 2000, which display a constant increase in the modern process metallurgy.

  4. Unfavourable results following reduction mammoplasty

    Directory of Open Access Journals (Sweden)

    Lakshmi Saleem

    2013-01-01

    Full Text Available Breast reduction is a common cosmetic surgical procedure. It aims not only at bringing down the size of the breast proportionate to the build of the individual, but also to overcome the discomfort caused by massive, ill-shaped and hanging breasts. The operative procedure has evolved from mere reduction of breast mass to enhanced aesthetic appeal with a minimum of scar load. The selection of technique needs to be individualised. Bilateral breast reduction is done most often. Haematoma, seroma, fat necrosis, skin loss, nipple loss and unsightly, painful scars can be the complications of any procedure on the breast. These may result from errors in judgement, wrong surgical plan and imprecise execution of the plan. Though a surfeit of studies are available on breast reduction, very few dwell upon its complications. The following article is a distillation of three decades of experience of the senior author (L.S. in reduction mammoplasty. An effort is made to understand the reasons for unfavourable results. To conclude, most complications can be overcome with proper selection of procedure for the given patient and with gentle tissue handling.

  5. GFAAS Determination of Platinum, Palladium, Rhodium and Iridium in Ores%石墨炉原子吸收光谱法测定矿石中铂、钯、铑、铱

    Institute of Scientific and Technical Information of China (English)

    羊波; 杨新周; 李银科; 叶艳清; 胡秋芬

    2012-01-01

    矿石样品铂、钯、铑和铱经铅试金富集,所得金属合粒用硝酸-盐酸溶解,用石墨炉原子吸收光谱法测定矿石样品中铂、钯、铑和铱的含量。在优化的石墨炉工作条件下测得:铂的质量浓度在20-150μg·L-1、钯在15-120μg·L-1、铑和铱在6-100μg·L-1范围内与其吸光度呈线性关系,检出限(3s/k)依次为4.6,4.0,1.5,1.5μg·L-1。方法用于分析了2种矿石国家标准物质(GBW07341、GBW07342),测定结果与认定值相符。方法的回收率在87.6%~105.5%之间。测定值的日内和日间相对标准偏差(n=7)分别在2.8%~3.6%和3.5%~4.7%之间。%Platinum, palladium, rhodium and iridium in ore samples were enriched by the lead fire assaying method, and the alloy of precious metals obtained was dissolved in HNO3 and HCl. The contents of Pt, Pd, Rh and Ir in the sample solution were determined by GFAAS. It was found that under the optimum working conditions of the graphite furnace, linear relationships between values of absorbance and mass concentration were obtained in the ranges of 20--150 μg·L-1 for Pt, 15--120μg·L-1 for Pd, 6-100 μg·L-1 for Rh and It. Detection limits (3s/ k) found were 4. 6/lg ~ L-1 (Pt), 4. 0μg·L-1(Pd) and 1.5μg·L-1(Rh and It). The proposed method was used in the analysis of 2 ore CRM's (GBW 07341, GBW 07342) and the results obtained were in conformity with the certified values. Values of recovery found by standard addition method were in the range of 87. 6%--105. 5%. Values of intra-day and inter-day RSD's (n=7) found were in the ranges of 2. 8%--3. 6% and 3. 5%--4. 7% respectively.

  6. Kloosterman sheaves for reductive groups

    CERN Document Server

    Heinloth, Jochen; Yun, Zhiwei

    2010-01-01

    Deligne constructed a remarkable local system on $\\bP^1-\\{0,\\infty\\}$ attached to a family of Kloosterman sums. Katz calculated its monodromy and asked whether there are Kloosterman sheaves for general reductive groups and which automorphic forms should be attached to these local systems under the Langlands correspondence. Motivated by work of Gross and Frenkel-Gross we find an explicit family of such automorphic forms and even a simple family of automorphic sheaves in the framework of the geometric Langlands program. We use these automorphic sheaves to construct l-adic Kloosterman sheaves for any reductive group in a uniform way, and describe the local and global monodromy of these Kloosterman sheaves. In particular, they give motivic Galois representations with exceptional monodromy groups G_2,F_4,E_7 and E_8. This also gives an example of the geometric Langlands correspondence with wild ramifications for any reductive group.

  7. Microbial reduction of iron ore

    Science.gov (United States)

    Hoffmann, Michael R.; Arnold, Robert G.; Stephanopoulos, Gregory

    1989-01-01

    A process is provided for reducing iron ore by treatment with microorganisms which comprises forming an aqueous mixture of iron ore, microorganisms operable for reducing the ferric iron of the iron ore to ferrous iron, and a substrate operable as an energy source for the microbial reduction; and maintaining the aqueous mixture for a period of time and under conditions operable to effect the reduction of the ore. Preferably the microorganism is Pseudomonas sp. 200 and the reduction conducted anaerobically with a domestic wastewater as the substrate. An aqueous solution containing soluble ferrous iron can be separated from the reacted mixture, treated with a base to precipitate ferrous hydroxide which can then be recovered as a concentrated slurry.

  8. Model reduction of parametrized systems

    CERN Document Server

    Ohlberger, Mario; Patera, Anthony; Rozza, Gianluigi; Urban, Karsten

    2017-01-01

    The special volume offers a global guide to new concepts and approaches concerning the following topics: reduced basis methods, proper orthogonal decomposition, proper generalized decomposition, approximation theory related to model reduction, learning theory and compressed sensing, stochastic and high-dimensional problems, system-theoretic methods, nonlinear model reduction, reduction of coupled problems/multiphysics, optimization and optimal control, state estimation and control, reduced order models and domain decomposition methods, Krylov-subspace and interpolatory methods, and applications to real industrial and complex problems. The book represents the state of the art in the development of reduced order methods. It contains contributions from internationally respected experts, guaranteeing a wide range of expertise and topics. Further, it reflects an important effor t, carried out over the last 12 years, to build a growing research community in this field. Though not a textbook, some of the chapters ca...

  9. Uranium isotopes fingerprint biotic reduction

    Science.gov (United States)

    Stylo, Malgorzata; Neubert, Nadja; Wang, Yuheng; Monga, Nikhil; Romaniello, Stephen J.; Weyer, Stefan; Bernier-Latmani, Rizlan

    2015-01-01

    Knowledge of paleo-redox conditions in the Earth’s history provides a window into events that shaped the evolution of life on our planet. The role of microbial activity in paleo-redox processes remains unexplored due to the inability to discriminate biotic from abiotic redox transformations in the rock record. The ability to deconvolute these two processes would provide a means to identify environmental niches in which microbial activity was prevalent at a specific time in paleo-history and to correlate specific biogeochemical events with the corresponding microbial metabolism. Here, we demonstrate that the isotopic signature associated with microbial reduction of hexavalent uranium (U), i.e., the accumulation of the heavy isotope in the U(IV) phase, is readily distinguishable from that generated by abiotic uranium reduction in laboratory experiments. Thus, isotope signatures preserved in the geologic record through the reductive precipitation of uranium may provide the sought-after tool to probe for biotic processes. Because uranium is a common element in the Earth’s crust and a wide variety of metabolic groups of microorganisms catalyze the biological reduction of U(VI), this tool is applicable to a multiplicity of geological epochs and terrestrial environments. The findings of this study indicate that biological activity contributed to the formation of many authigenic U deposits, including sandstone U deposits of various ages, as well as modern, Cretaceous, and Archean black shales. Additionally, engineered bioremediation activities also exhibit a biotic signature, suggesting that, although multiple pathways may be involved in the reduction, direct enzymatic reduction contributes substantially to the immobilization of uranium. PMID:25902522

  10. NEC-2020 emission reduction scenarios

    DEFF Research Database (Denmark)

    Slentø, Erik; Nielsen, Ole-Kenneth; Hoffmann, Leif

    The upcoming NEC-2020 EU directive sets up emission ceilings for NOX, SO2, NH3, NMVOC and PM in order to meet the environmental exposure targets of the Thematic Strategy. This report contains an assessment of intermediary emission reduction scenarios for Denmark, computed by the GAINS model 2007......, which serves as the basis for the pending negotiations in EU. The assessment is brought up to date by including a brief evaluation of the new reduction scenarios published in 2008, founding the European Commission NEC-2020 directive proposal....

  11. Complexity reduction of astrochemical networks

    CERN Document Server

    Grassi, T; Gianturco, F A; Baiocchi, P; Merlin, E

    2012-01-01

    We present a new computational scheme aimed at reducing the complexity of the chemical networks in astrophysical models, one which is shown to markedly improve their computational efficiency. It contains a flux-reduction scheme that permits to deal with both large and small systems. This procedure is shown to yield a large speed-up of the corresponding numerical codes and provides good accord with the full network results. We analyse and discuss two examples involving chemistry networks of the interstellar medium and show that the results from the present reduction technique reproduce very well the results from fuller calculations.

  12. Flavin reduction activates Drosophila cryptochrome.

    Science.gov (United States)

    Vaidya, Anand T; Top, Deniz; Manahan, Craig C; Tokuda, Joshua M; Zhang, Sheng; Pollack, Lois; Young, Michael W; Crane, Brian R

    2013-12-17

    Entrainment of circadian rhythms in higher organisms relies on light-sensing proteins that communicate to cellular oscillators composed of delayed transcriptional feedback loops. The principal photoreceptor of the fly circadian clock, Drosophila cryptochrome (dCRY), contains a C-terminal tail (CTT) helix that binds beside a FAD cofactor and is essential for light signaling. Light reduces the dCRY FAD to an anionic semiquinone (ASQ) radical and increases CTT proteolytic susceptibility but does not lead to CTT chemical modification. Additional changes in proteolytic sensitivity and small-angle X-ray scattering define a conformational response of the protein to light that centers at the CTT but also involves regions remote from the flavin center. Reduction of the flavin is kinetically coupled to CTT rearrangement. Chemical reduction to either the ASQ or the fully reduced hydroquinone state produces the same conformational response as does light. The oscillator protein Timeless (TIM) contains a sequence similar to the CTT; the corresponding peptide binds dCRY in light and protects the flavin from oxidation. However, TIM mutants therein still undergo dCRY-mediated degradation. Thus, photoreduction to the ASQ releases the dCRY CTT and promotes binding to at least one region of TIM. Flavin reduction by either light or cellular reductants may be a general mechanism of CRY activation.

  13. Reduction des effectifs ou licenciements

    CERN Multimedia

    Maiani, Luciano

    2002-01-01

    "Vous faites un amalgame entre la reduction en cours des effectifs du CERN (organisation europeenne pour la recherche nucleaire) et les economies que le laboratoire doit realiser dans les cinq ans a venir pour financer le projet de grand collisionneur de hadrons (Le Monde du 4 septembre)" (1/2 page).

  14. GumTree: Data reduction

    Science.gov (United States)

    Rayner, Hugh; Hathaway, Paul; Hauser, Nick; Fei, Yang; Franceschini, Ferdi; Lam, Tony

    2006-11-01

    Access to software tools for interactive data reduction, visualisation and analysis during a neutron scattering experiment enables instrument users to make informed decisions regarding the direction and success of their experiment. ANSTO aims to enhance the experiment experience of its facility's users by integrating these data reduction tools with the instrument control interface for immediate feedback. GumTree is a software framework and application designed to support an Integrated Scientific Experimental Environment, for concurrent access to instrument control, data acquisition, visualisation and analysis software. The Data Reduction and Analysis (DRA) module is a component of the GumTree framework that allows users to perform data reduction, correction and basic analysis within GumTree while an experiment is running. It is highly integrated with GumTree, able to pull experiment data and metadata directly from the instrument control and data acquisition components. The DRA itself uses components common to all instruments at the facility, providing a consistent interface. It features familiar ISAW-based 1D and 2D plotting, an OpenGL-based 3D plotter and peak fitting performed by fityk. This paper covers the benefits of integration, the flexibility of the DRA module, ease of use for the interface and audit trail generation.

  15. Asymmetry Reduction Theory of FDI

    DEFF Research Database (Denmark)

    Li, Xin

    In this paper, I first briefly introduce Moon & Roehl’s (1993, 2001) imbalance theory of FDI, then I identify its three deficiencies that may be responsible for the relative lack of impact of the potentially powerful imbalance logic, and then I propose an asymmetry reduction theory (ARC) of FDI...

  16. Representative mass reduction in sampling

    DEFF Research Database (Denmark)

    Petersen, Lars; Esbensen, Harry Kim; Dahl, Casper Kierulf

    2004-01-01

    We here present a comprehensive survey of current mass reduction principles and hardware available in the current market. We conduct a rigorous comparison study of the performance of 17 field and/or laboratory instruments or methods which are quantitatively characterized (and ranked) for accuracy...

  17. Background reduction in cryogenic detectors

    Energy Technology Data Exchange (ETDEWEB)

    Bauer, Daniel A.; /Fermilab

    2005-04-01

    This paper discusses the background reduction and rejection strategy of the Cryogenic Dark Matter Search (CDMS) experiment. Recent measurements of background levels from CDMS II at Soudan are presented, along with estimates for future improvements in sensitivity expected for a proposed SuperCDMS experiment at SNOLAB.

  18. APPLICATION OF RADON REDUCTION METHODS

    Science.gov (United States)

    The document is intended to aid homeowners and contractors in diagnosing and solving indoor radon problems. It will also be useful to State and Federal regulatory officials and many other persons who provide advice on the selection, design and operation of radon reduction methods...

  19. Sulfate reduction in freshwater peatlands

    Energy Technology Data Exchange (ETDEWEB)

    Oequist, M.

    1996-12-31

    This text consist of two parts: Part A is a literature review on microbial sulfate reduction with emphasis on freshwater peatlands, and part B presents the results from a study of the relative importance of sulfate reduction and methane formation for the anaerobic decomposition in a boreal peatland. The relative importance of sulfate reduction and methane production for the anaerobic decomposition was studied in a small raised bog situated in the boreal zone of southern Sweden. Depth distribution of sulfate reduction- and methane production rates were measured in peat sampled from three sites (A, B, and C) forming an minerotrophic-ombrotrophic gradient. SO{sub 4}{sup 2-} concentrations in the three profiles were of equal magnitude and ranged from 50 to 150 {mu}M. In contrast, rates of sulfate reduction were vastly different: Maximum rates in the three profiles were obtained at a depth of ca. 20 cm below the water table. In A it was 8 {mu}M h{sup -1} while in B and C they were 1 and 0.05 {mu}M h{sup -1}, respectively. Methane production rates, however, were more uniform across the three nutrient regimes. Maximum rates in A (ca. 1.5 {mu}g d{sup -1} g{sup -1}) were found 10 cm below the water table, in B (ca. 1.0 {mu}g d{sup -1} g{sup -1}) in the vicinity of the water table, and in C (0.75 {mu}g d{sup -1} g{sup -1}) 20 cm below the water table. In all profiles both sulfate reduction and methane production rates were negligible above the water table. The areal estimates of methane production for the profiles were 22.4, 9.0 and 6.4 mmol m{sup -2} d{sup -1}, while the estimates for sulfate reduction were 26.4, 2.5, and 0.1 mmol m{sup -2} d{sup -1}, respectively. The calculated turnover times at the sites were 1.2, 14.2, and 198.7 days, respectively. The study shows that sulfate reducing bacteria are important for the anaerobic degradation in the studied peatland, especially in the minerotrophic sites, while methanogenic bacteria dominate in ombrotrophic sites Examination

  20. A novel strontium-rhodium hydride

    Energy Technology Data Exchange (ETDEWEB)

    Bortz, M.; Yvon, K. [Geneva Univ. (Switzerland); Fauth, F. [Paul Scherrer Inst. (PSI), Villigen (Switzerland)

    1997-09-01

    The attempt to determine the structure of `LiSr{sub 2}RhD{sub 6}` that was reported to crystallize in a tetragonal primitive cell with one formula unit by neutron diffraction experiments on powder samples at room temperature and at 1.5 K led to the discovery of a new tetragonal deuteride of refined composition Sr{sub 2}RhD{sub 6}. (author) 2 figs., 3 refs.

  1. Rhodium-catalyzed restructuring of carbon frameworks.

    Science.gov (United States)

    Murakami, Masahiro

    2010-10-01

    Metal-catalyzed reactions involving an elementary step which cleaves a carbon-carbon bond provide unique organic transformations. Restructuring reactions recently developed in our laboratory, through which the carbon framework of a starting substance is restructured into a totally different carbon framework, are discussed, with the possibility of applying such methods to the synthesis of natural products.

  2. Rhodium-Catalyzed Alkene Difunctionalization with Nitrenes.

    Science.gov (United States)

    Ciesielski, Jennifer; Dequirez, Geoffroy; Retailleau, Pascal; Gandon, Vincent; Dauban, Philippe

    2016-06-27

    The Rh(II) -catalyzed oxyamination and diamination of alkenes generate 1,2-amino alcohols and 1,2-diamines, respectively, in good to excellent yields and with complete regiocontrol. In the case of diamination, the intramolecular reaction provides an efficient method for the preparation of pyrrolidines, and the intermolecular reaction produces vicinal amines with orthogonal protecting groups. These alkene difunctionalizations proceed by aziridination followed by nucleophilic ring opening induced by an Rh-bound nitrene generated in situ, details of which were uncovered by both experimental and theoretical studies. In particular, DFT calculations show that the nitrogen atom of the putative [Rh]2 =NR metallanitrene intermediate is electrophilic and support an aziridine activation pathway by N⋅⋅⋅N=[Rh]2 bond formation, in addition to the N⋅⋅⋅[Rh]2 =NR coordination mode. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Discovering Natural Laws by Reduction

    Institute of Scientific and Technical Information of China (English)

    吴轶华

    1989-01-01

    A polynomial algorithm.called Reduction,is presented to discover natural laws by analysing a set of experimental data.instead of a heuristic exploration which,when adopted in BACON,can only lead to rediscovering simple laws.A complex law with multiple variables involved can be discovered by reducing it to a search.This search is so efficient that it does not need any backtracking and is able to cover most of possible laws.A reduction-based discovery system,called DISCOVER 2.0,was developed with a flexible knowledge base and an ability of dealing with imperfect data.The system has been verified to be valid computationally,practically,and theoretically,by discovering a great number o complex laws,and can be also viewed as a leaming engine embodied in any intelligent systems to improve their performance by obtaining a general rule from the accumulated data.

  4. Mechanochemical reduction of copper sulfide

    DEFF Research Database (Denmark)

    Balaz, P.; Takacs, L.; Jiang, Jianzhong

    2002-01-01

    The mechanochemical reduction of copper sulfide with iron was induced in a Fritsch P-6 planetary mill, using WC vial filled with argon and WC balls. Samples milled for specific intervals were analyzed by XRD and Mossbauer spectroscopy. Most of the reaction takes place during the first 10 min...... of milling and only FeS and Cu are found after 60 min. The main chemical process is accompanied by phase transformations of the sulfide phases as a result of milling. Djurleite partially transformed to chalcocite and a tetragonal copper sulfide phase before reduction. The cubic modification of FeS was formed...... first, transforming to hexagonal during the later stages of the process. The formation of off-stoichiometric phases and the release of some elemental sulfur by copper sulfide are also probable....

  5. Random walks on reductive groups

    CERN Document Server

    Benoist, Yves

    2016-01-01

    The classical theory of Random Walks describes the asymptotic behavior of sums of independent identically distributed random real variables. This book explains the generalization of this theory to products of independent identically distributed random matrices with real coefficients. Under the assumption that the action of the matrices is semisimple – or, equivalently, that the Zariski closure of the group generated by these matrices is reductive - and under suitable moment assumptions, it is shown that the norm of the products of such random matrices satisfies a number of classical probabilistic laws. This book includes necessary background on the theory of reductive algebraic groups, probability theory and operator theory, thereby providing a modern introduction to the topic.

  6. Designing Tone Reservation PAR Reduction

    Directory of Open Access Journals (Sweden)

    Johansson Albin

    2006-01-01

    Full Text Available Tone reservation peak-to-average (PAR ratio reduction is an established area when it comes to bringing down signal peaks in multicarrier (DMT or OFDM systems. When designing such a system, some questions often arise about PAR reduction. Is it worth the effort? How much can it give? How much does it give depending on the parameter choices? With this paper, we attempt to answer these questions without resolving to extensive simulations for every system and every parameter choice. From a specification of the allowed spectrum, for instance prescribed by a standard, including a PSD-mask and a number of tones, we analytically predict achievable PAR levels, and thus implicitly suggest parameter choices. We use the ADSL2 and ADSL2+ systems as design examples.

  7. Wind load reduction for heliostats

    Energy Technology Data Exchange (ETDEWEB)

    Peterka, J.A.; Hosoya, N.; Bienkiewicz, B.; Cermak, J.E.

    1986-05-01

    This report presents the results of wind-tunnel tests supported through the Solar Energy Research Institute (SERI) by the Office of Solar Thermal Technology of the US Department of Energy as part of the SERI research effort on innovative concentrators. As gravity loads on drive mechanisms are reduced through stretched-membrane technology, the wind-load contribution of the required drive capacity increases in percentage. Reduction of wind loads can provide economy in support structure and heliostat drive. Wind-tunnel tests have been directed at finding methods to reduce wind loads on heliostats. The tests investigated primarily the mean forces, moments, and the possibility of measuring fluctuating forces in anticipation of reducing those forces. A significant increase in ability to predict heliostat wind loads and their reduction within a heliostat field was achieved.

  8. Exploring Paradigms of Crime Reduction

    DEFF Research Database (Denmark)

    Soothill, Keith; Christoffersen, Mogens N.; Hussain, Azhar

    2010-01-01

    Using Danish registers for a 1980 birth cohort of 29,944 males with parental information and following up these cases for 25 years, the study considers four paradigms of crime reduction (parental child rearing, structural factors around adolescence, locality and individual resources). Focusing...... have more widespread benefits, but the assumed causal links need to be further explored. The use of population registers, under controlled conditions, provides an important window on criminal careers....

  9. Seismic Disaster Reduction in China

    Institute of Scientific and Technical Information of China (English)

    Ministry of Construction

    2001-01-01

    @@ Great accomplishments have been made in seismic disaster reduction in China's engineering construction and city construction projects during the past decade (1990~2000). A new national map on the division of seismic intensity has been promulgated, and a series of anti-seismic standards and norms have been drafted or revised, which has further improved the country's technical code system on anti-seismic engineering measures.

  10. Sustained Low Temperature NOx Reduction

    Energy Technology Data Exchange (ETDEWEB)

    Zha, Yuhui

    2017-04-05

    Increasing regulatory, environmental, and customer pressure in recent years led to substantial improvements in the fuel efficiency of diesel engines, including the remarkable breakthroughs demonstrated through the Super Truck program supported by the U.S. Department of Energy (DOE). On the other hand, these improvements have translated into a reduction of exhaust gas temperatures, thus further complicating the task of controlling NOx emissions, especially in low power duty cycles. The need for improved NOx conversion over these low temperature duty cycles is also observed as requirements tighten with in-use emissions testing. Sustained NOx reduction at low temperatures, especially in the 150-200oC range, shares some similarities with the more commonly discussed cold-start challenge, however poses a number of additional and distinct technical problems. In this project we set a bold target of achieving and maintaining a 90% NOx conversion at the SCR catalyst inlet temperature of 150oC. The project is intended to push the boundaries of the existing technologies, while staying within the realm of realistic future practical implementation. In order to meet the resulting challenges at the levels of catalyst fundamentals, system components, and system integration, Cummins has partnered with the DOE, Johnson Matthey, and Pacific Northwest National Lab and initiated the Sustained Low-Temperature NOx Reduction program at the beginning of 2015. Through this collaboration, we are exploring catalyst formulations and catalyst architectures with enhanced catalytic activity at 150°C; opportunities to approach the desirable ratio of NO and NO2 in the SCR feed gas; options for robust low-temperature reductant delivery; and the requirements for overall system integration. The program is expected to deliver an on-engine demonstration of the technical solution and an assessment of its commercial potential. In the SAE meeting, we will share the initial performance data on engine to

  11. Model Reduction via Reducibility Matrix

    Institute of Scientific and Technical Information of China (English)

    Musa Abdalla; Othman Alsmadi

    2006-01-01

    In this work, a new model reduction technique is introduced. The proposed technique is derived using the matrix reducibility concept. The eigenvalues of the reduced model are preserved; that is, the reduced model eigenvalues are a subset of the full order model eigenvalues. This preservation of the eigenvalues makes the mathematical model closer to the physical model. Finally, the outcomes of this method are fully illustrated using simulations of two numeric examples.

  12. Dimensional Reduction for Conformal Blocks

    CERN Document Server

    Hogervorst, Matthijs

    2016-01-01

    We consider the dimensional reduction of a CFT, breaking multiplets of the d-dimensional conformal group SO(d+1,1) up into multiplets of SO(d,1). This leads to an expansion of d-dimensional conformal blocks in terms of blocks in d-1 dimensions. In particular, we obtain a formula for 3d conformal blocks as an infinite sum over 2F1 hypergeometric functions with closed-form coefficients.

  13. Insular volume reduction in schizophrenia.

    Science.gov (United States)

    Saze, Teruyasu; Hirao, Kazuyuki; Namiki, Chihiro; Fukuyama, Hidenao; Hayashi, Takuji; Murai, Toshiya

    2007-12-01

    Structural and functional abnormalities of the insular cortex have been reported in patients with schizophrenia. Most studies have shown that the insular volumes in schizophrenia patients are smaller than those of healthy people. As the insular cortex is functio-anatomically divided into anterior and posterior subdivisons, recent research is focused on uncovering a specific subdivisional abnormality of the insula in patients with schizophrenia. A recent ROI-based volumetric MRI study demonstrated specific left anterior insular volume reduction in chronic schizophrenia patients (Makris N, Goldstein J, Kennedy D, Hodge S, Caviness V, Faraone S, Tsuang M, Seidman L (2006) Decreased volume of left and total anterior insular lobule in schizophrenia. Schizophr Res 83:155-171). On the other hand, our VBM-based volumetric study revealed a reduction in right posterior insular volume (Yamada M, Hirao K, Namiki C, Hanakawa T, Fukuyama H, Hayashi T, Murai T (2007) Social cognition and frontal lobe pathology in schizophrenia: a voxel-based morphometric study. NeuroImage 35:292-298). In order to address these controversial results, ROI-based subdivisional volumetry was performed using the MRI images from the same population we analyzed in our previous VBM-study. The sample group comprised 20 schizophrenia patients and 20 matched healthy controls. Patients with schizophrenia showed a global reduction in insular gray matter volumes relative to healthy comparison subjects. In a simple comparison of the volumes of each subdivision between the groups, a statistically significant volume reduction in patients with schizophrenia was demonstrated only in the right posterior insula. This study suggests that insular abnormalities in schizophrenia would include anterior as well as posterior parts. Each subdivisional abnormality may impact on different aspects of the pathophysiology and psychopathology of schizophrenia; these relationships should be the focus of future research.

  14. Performance of lazy combinator graph reduction

    NARCIS (Netherlands)

    Hartel, Pieter H.; Hartel, P.H.

    The performance of program-derived combinator graph reduction is known to be superior to that of graph reduction based on a fixed set of standard combinators. The major advantage of program-derived combinator reduction is that it uses less transient store than standard combinator reduction. We show

  15. 20 CFR 226.71 - Initial reduction.

    Science.gov (United States)

    2010-04-01

    ... EMPLOYEE, SPOUSE, AND DIVORCED SPOUSE ANNUITIES Reduction for Workers' Compensation and Disability Benefits... a disability annuity and workers' compensation or a public disability benefit. The reduction ends... the workers compensation or public disability benefit ends. (b) Amount of reduction. The reduction for...

  16. Model Reduction by Manifold Boundaries

    Science.gov (United States)

    Transtrum, Mark K.; Qiu, Peng

    2015-01-01

    Understanding the collective behavior of complex systems from their basic components is a difficult yet fundamental problem in science. Existing model reduction techniques are either applicable under limited circumstances or produce “black boxes” disconnected from the microscopic physics. We propose a new approach by translating the model reduction problem for an arbitrary statistical model into a geometric problem of constructing a low-dimensional, submanifold approximation to a high-dimensional manifold. When models are overly complex, we use the observation that the model manifold is bounded with a hierarchy of widths and propose using the boundaries as submanifold approximations. We refer to this approach as the manifold boundary approximation method. We apply this method to several models, including a sum of exponentials, a dynamical systems model of protein signaling, and a generalized Ising model. By focusing on parameters rather than physical degrees of freedom, the approach unifies many other model reduction techniques, such as singular limits, equilibrium approximations, and the renormalization group, while expanding the domain of tractable models. The method produces a series of approximations that decrease the complexity of the model and reveal how microscopic parameters are systematically “compressed” into a few macroscopic degrees of freedom, effectively building a bridge between the microscopic and the macroscopic descriptions. PMID:25216014

  17. The reduction of packaging waste

    Energy Technology Data Exchange (ETDEWEB)

    Raney, E.A.; Hogan, J.J.; McCollom, M.L.; Meyer, R.J.

    1994-04-01

    Nationwide, packaging waste comprises approximately one-third of the waste disposed in sanitary landfills. the US Department of Energy (DOE) generated close to 90,000 metric tons of sanitary waste. With roughly one-third of that being packaging waste, approximately 30,000 metric tons are generated per year. The purpose of the Reduction of Packaging Waste project was to investigate opportunities to reduce this packaging waste through source reduction and recycling. The project was divided into three areas: procurement, onsite packaging and distribution, and recycling. Waste minimization opportunities were identified and investigated within each area, several of which were chosen for further study and small-scale testing at the Hanford Site. Test results, were compiled into five ``how-to`` recipes for implementation at other sites. The subject of the recipes are as follows: (1) Vendor Participation Program; (2) Reusable Containers System; (3) Shrink-wrap System -- Plastic and Corrugated Cardboard Waste Reduction; (4) Cardboard Recycling ; and (5) Wood Recycling.

  18. Results Evaluation in Reduction Rhinoplasty

    Directory of Open Access Journals (Sweden)

    Arima, Lisandra Megumi

    2011-01-01

    Full Text Available Introduction: Final results evaluation after rhinoplasty is a not a topic widely studied from the patient's viewpoint. Objective:Evaluate the satisfaction of the patients submitted to reduction rhinoplasty, from the questionnaire Rhinoplasty Outcomes Evaluation (ROE. Method: Longitudinal study, retrospective cut type, of the preoperative and postoperative satisfaction. The sample was composed by 28 patients who were submitted to rhinoplasty and answered the ROE questionnaire. Three variables were obtained: satisfaction note that the patient had with his/her image before the surgery; note of satisfaction with the current appearance; the difference of the average satisfaction notes between postoperative and preoperative approaches. Results: The postoperative note was higher than the preoperative in all patients. We noticed a difference between the average of the postoperative and preoperative of 48.3 (p75 considered to be an excellent outcome (67.9%. Conclusions: The ROE questionnaire is a helpful tool to show the satisfaction of the patient submitted to reduction rhinoplasty. About 92% of the patients submitted to reduction rhinoplasty consider the postoperative result to be good or excellent.

  19. From Outermost Reduction Semantics to Abstract Machine

    DEFF Research Database (Denmark)

    Danvy, Olivier; Johannsen, Jacob

    Reduction semantics is a popular format for small-step operational semantics of deterministic programming languages with computational effects. Each reduction semantics gives rise to a reduction-based normalization function where the reduction sequence is enumerated. Refocusing is a practical way...... of the term to enumerate the reduction sequence, in contrast to the reduction-based normalization function. We have discovered that refocusing does not apply as readily for reduction semantics that use an outermost reduction strategy and have overlapping rules where a contractum can be a proper subpart...... of a redex. In this article, we consider such an outermost reduction semantics with backward-overlapping rules, and we investigate how to apply refocusing to still obtain a reduction-free normalization function in the form of an abstract machine....

  20. The anaerobic degradation of organic matter in Danish coastal sediments: iron reduction, manganese reduction, and sulfate reduction

    DEFF Research Database (Denmark)

    Canfield, Donald Eugene; Thamdrup, B; Hansen, Jens Würgler

    1993-01-01

    important than sulfate reduction. Most of the Mn reduction in these sediments may have been coupled to the oxidation of acid volatile sulfides (AVS), rather than to dissimilatory reduction. High rates of metal oxide reduction at all sites were driven by active recycling of both Fe and Mn, encouraged......We used a combination of porewater and solid phase analysis, as well as a series of sediment incubations, to quantify organic carbon oxidation by dissimilatory Fe reduction, Mn reduction, and sulfate reduction, in sediments from the Skagerrak (located off the northeast coast of Jutland, Denmark......). In the deep portion of the basin, surface Mn enrichments reached 3.5 wt%, and Mn reduction was the only important anaerobic carbon oxidation process in the upper 10 cm of the sediment. In the less Mn-rich sediments from intermediate depths in the basin, Fe reduction ranged from somewhat less, to far more...

  1. 乳腺单纯簇状钙化灶数字化钼铑双靶X线摄影的影像表现及临床价值%IMAGING PERFORMANCE AND CLINICAL VALUE OF ISOLATED CLUSTERED MICROCALCIFICATIONS IN BREST BY DIGITAL MOLYBDENUM AND RHODIUM DOUBLE - TARGETED X - RAY MAMMOGRAPHY

    Institute of Scientific and Technical Information of China (English)

    陈健; 徐海峰; 牛广明

    2011-01-01

    目的:应用数字化钼铑双靶摄影观察乳腺内局灶性单纯簇状微钙化灶的影像表现,探讨其诊断及治疗价值.方法:使用GE Senographe2000D全数字钼铑双靶乳腺摄影机,全自动曝光条件,常规头尾位、侧斜位或加撮侧位对乳腺1.0cm2内单纯簇状钙化灶进行定位诊断后行手术治疗.对部分较小簇状钙化灶术后病灶组织再摄片确定钙化灶切除是否完整.对其中3例微小钙化灶术后摄片同时针刺定位以助病理切片.结果:21例25个钙化灶中,簇状微细钙化19例23个病灶;分支状钙化灶1例1个病灶,粗细不均钙化灶1例1个病灶.经手术、病理证实为浸润型乳腺癌7例9个病灶(占36%),早期浸润型乳癌12例14个病灶(56%);良性病变2例2个病灶(8%).结论:数字化钼铑双靶乳腺摄影可提高早期乳腺癌及微小乳腺癌的检出率.乳腺术前术后摄片可以辅助手术切除病灶、病理取材,提高乳腺疾病的临床诊断治疗水平.%Objective: To observe the imaging findings and clinical value of brest isolated clustered microcalcifications by digital Molybdenum and Rhodium double - targeted mammography. Method; Breast isolated clustered microcalcifications within 1 cm2 found by digital X - ray mammography were operated. Excisional tissue was re - filmed to determine the completeness of resection. For assisting biopsy , microcalcifications in excisional tissue were located by needling after re - filming. Result: There are 23 clustered microcalcifications (in 19 cases) , 1 branching calcification and 1 thickness uneven calcification in 25 clustered calcifications (in 21 cases). Invasive breast cancer were 7 cases 9 leisons (36% ) , early invasive breast cancer were 12 cases 14 leisons (56% ), and 2 cases 2 leisons (8% )are benign after surgical biopsy. Conclusion: Digital Molybdenum and Rhodium double - targeted X -ray mammography can increase the detection rate of early breast cancer and minute breast

  2. Determination of Ruthenium, Rhodium, Palladium, Iridium and Platinum in Copper-Nickel Sulfide Ores by Bismuth-Antimony Fire Assay%铋锑试金测定硫化铜镍矿中钌铑钯铱铂

    Institute of Scientific and Technical Information of China (English)

    李可及; 刘淑君; 邵坤

    2014-01-01

    建立了用于预富集硫化铜镍矿中钌铑钯铱铂5种铂族元素的铋锑试金方法。40.0 g 氧化铋、25.0 g硼酸、10.0 g 碳酸钠、1.00 g 淀粉与10.0 g 待测样品于120 mL 瓷皿中,充分混匀,850℃入炉,20 min 后升至1000℃,保留40 min,出炉后趁热倾倒熔渣,使铋试金于空气中自然冷却。设计两段灰吹流程,铋试金先在镁砂灰皿内灰吹,直至剩余直径约5 mm,而后直接转入盛有20 g 熔融锑粉的坩埚盖中继续灰吹,获得直径约1 mm 的试金合粒。所得合粒经微波消解,冷却后定容至10 mL。铂钯用 ICP-OES 分析;钌铑铱质量数选择99 Ru,103 Rh 和191 Ir,以115 In 和185 Re 为内标,应用 ICP-MS 分析。对标准物质 GBW07196平行测定12次,铂族元素相对标准偏差为7.0%~9.5%。在10 g 取样量条件下,方法对 Ru, Rh, Pd, Ir 和 Pt 的检出限分别为0.027,0.016,0.11,0.10和0.11 ng/ g。应用本方法处理标准物质 GBW07194,GBW07195和 GBW07196均获得了满意的结果。%A bismuth-antimony fire assay method for the preconcentration of ruthenium, rhodium, palladium, iridium and platinum in copper-nickel sulfide ores was developed. 40. 0 g bismuth trioxide, 25. 0 g boric acid, 10. 0 g sodium carbonate and 1. 00 g starch were mixed with 10. 0 g sample in a 120 mL porcelain bowl, which was put in a furnace at 850 ℃. After 20 min the temperature was raised to 1000 ℃ and held for another 40 min, and then the bowl was taken out, with the slag poured, which left the bismuth button to air cooling. A two-step cupellation procedure was developed. During the first step, the bismuth button was cupellated in a magnesia cupel until its diameter reached 5 mm or so, then it was transferred to a crucible cover containing 20 g melting antimony and kept cupellating, at last a bead with a diameter of 1 mm was obtained. The bead was microwave-digested, after cooling down to room temperature, the solvent of which was transferred to a volumetric flask and

  3. Regression Testing Cost Reduction Suite

    Directory of Open Access Journals (Sweden)

    Mohamed Alaa El-Din

    2014-08-01

    Full Text Available The estimated cost of software maintenance exceeds 70 percent of total software costs [1], and large portion of this maintenance expenses is devoted to regression testing. Regression testing is an expensive and frequently executed maintenance activity used to revalidate the modified software. Any reduction in the cost of regression testing would help to reduce the software maintenance cost. Test suites once developed are reused and updated frequently as the software evolves. As a result, some test cases in the test suite may become redundant when the software is modified over time since the requirements covered by them are also covered by other test cases. Due to the resource and time constraints for re-executing large test suites, it is important to develop techniques to minimize available test suites by removing redundant test cases. In general, the test suite minimization problem is NP complete. This paper focuses on proposing an effective approach for reducing the cost of regression testing process. The proposed approach is applied on real-time case study. It was found that the reduction in cost of regression testing for each regression testing cycle is ranging highly improved in the case of programs containing high number of selected statements which in turn maximize the benefits of using it in regression testing of complex software systems. The reduction in the regression test suite size will reduce the effort and time required by the testing teams to execute the regression test suite. Since regression testing is done more frequently in software maintenance phase, the overall software maintenance cost can be reduced considerably by applying the proposed approach.

  4. Climate Change and Poverty Reduction

    Energy Technology Data Exchange (ETDEWEB)

    Anderson, Simon

    2011-08-15

    Climate change will make it increasingly difficult to achieve and sustain development goals. This is largely because climate effects on poverty remain poorly understood, and poverty reduction strategies do not adequately support climate resilience. Ensuring effective development in the face of climate change requires action on six fronts: investing in a stronger climate and poverty evidence base; applying the learning about development effectiveness to how we address adaptation needs; supporting nationally derived, integrated policies and programmes; including the climate-vulnerable poor in developing strategies; and identifying how mitigation strategies can also reduce poverty and enable adaptation.

  5. The CARMA Data Reduction Pipeline

    Science.gov (United States)

    Friedel, D. N.

    2013-10-01

    The Combined Array for Millimeter-wave Astronomy (CARMA) data reduction pipeline (CADRE) has been developed to give investigators a first look at a fully reduced set of their data. It runs automatically on all data produced by the telescope as they arrive in the data archive. CADRE is written in Python and uses Python wrappers for MIRIAD subroutines for direct access to the data. It applies passband, gain and flux calibration to the data sets and produces a set of continuum and spectral line maps in both MIRIAD and FITS format. CADRE has been in production for a year and this poster will discuss the current capabilities and planned improvements.

  6. Memory Reduction via Delayed Simulation

    Directory of Open Access Journals (Sweden)

    Michael Holtmann

    2011-02-01

    Full Text Available We address a central (and classical issue in the theory of infinite games: the reduction of the memory size that is needed to implement winning strategies in regular infinite games (i.e., controllers that ensure correct behavior against actions of the environment, when the specification is a regular omega-language. We propose an approach which attacks this problem before the construction of a strategy, by first reducing the game graph that is obtained from the specification. For the cases of specifications represented by "request-response"-requirements and general "fairness" conditions, we show that an exponential gain in the size of memory is possible.

  7. Geophysics and Seismic Hazard Reduction

    Institute of Scientific and Technical Information of China (English)

    YuGuihua; ZhouYuanze; YuSheng

    2003-01-01

    The earthquake is a natural phenomenon, which often brings serious hazard to the human life and material possession. It is a physical process of releasing interior energy of the earth, which is caused by interior and outer forces in special tectonic environment in the earth, especially within the lithosphere. The earthquake only causes casualty and loss in the place where people inhabit. Seismic hazard reduction is composed of four parts as seismic prediction, hazard prevention and seismic engineering, seismic response and seismic rescuing, and rebuilding.

  8. Noise reduction of spiral ducts.

    Science.gov (United States)

    Lapka, Wojciech; Cempel, Czesław

    2007-01-01

    The paper presents noise reduction (NR) of spiral ducts as a result of computational modeling of acoustic wave propagation. Three-dimensional models were created with the finite element method in COMSOL Multiphysics version 3.3. Nine models of spiral ducts with 1-9 spiral leads were considered. Time-harmonic analysis was used to predict NR, which was shown in spectral and interval frequency bands. Spiral duct performance can be seen as a comparison of NR before and after a change from a circular to a spiral duct.

  9. Model reduction for circuit simulation

    CERN Document Server

    Hinze, Michael; Maten, E Jan W Ter

    2011-01-01

    Simulation based on mathematical models plays a major role in computer aided design of integrated circuits (ICs). Decreasing structure sizes, increasing packing densities and driving frequencies require the use of refined mathematical models, and to take into account secondary, parasitic effects. This leads to very high dimensional problems which nowadays require simulation times too large for the short time-to-market demands in industry. Modern Model Order Reduction (MOR) techniques present a way out of this dilemma in providing surrogate models which keep the main characteristics of the devi

  10. CCD data reductions at ESO

    Science.gov (United States)

    Grosbol, Preben

    The image-processing and data-reduction functions of the IHAP and MIDAS software packages developed at ESO for CCD astronomy are briefly reviewed. IHAP and MIDAS perform the same basic operations on HP 1000 and VAX computers, respectively, and MIDAS is currently being modified to run in the UNIX operating system as well as in VAX VMS. Consideration is given to the special properties of CCD data, the removal of gross errors (due to bad pixels and cosmic-ray events), photometric correction for dark current and sensitivity variations, digital filtering and Fourier transforms, detection and classification algorithms for direct imaging, surface photometry of extended objects, function fitting, and image deconvolution.

  11. XRT -- ROSAT XRT Data Reduction

    Science.gov (United States)

    Davenhall, A. C.; Platon, R. T.

    XRT is a package for reducing data acquired with the ROSAT XRT instruments. The XRT (X-Ray Telescope) was the principal scientific payload of the ROSAT X-ray astronomy satellite. The XRT had two instruments: the PSPC (Position Sensitive Proportional Counter) and the HRI (High Resolution Imager). The XRT package operates on data produced by these instruments and can be used to transform them into calibrated images, spectra, time-series etc. XRT was created by taking the ROSAT XRT-specific functions in the ASTERIX general X-ray astronomy data reduction system and re-packaging them as stand-alone applications.

  12. Cohomological reduction of sigma models

    Energy Technology Data Exchange (ETDEWEB)

    Candu, Constantin; Mitev, Vladimir; Schomerus, Volker [DESY, Hamburg (Germany). Theory Group; Creutzig, Thomas [North Carolina Univ., Chapel Hill, NC (United States). Dept. of Physics and Astronomy

    2010-01-15

    This article studies some features of quantum field theories with internal supersymmetry, focusing mainly on 2-dimensional non-linear sigma models which take values in a coset superspace. It is discussed how BRST operators from the target space super- symmetry algebra can be used to identify subsectors which are often simpler than the original model and may allow for an explicit computation of correlation functions. After an extensive discussion of the general reduction scheme, we present a number of interesting examples, including symmetric superspaces G/G{sup Z{sub 2}} and coset superspaces of the form G/G{sup Z{sub 4}}. (orig.)

  13. From Outermost Reduction Semantics to Abstract Machine

    DEFF Research Database (Denmark)

    Danvy, Olivier; Johannsen, Jacob

    to transform a reduction-based normalization function into a reduction-free one where the reduction sequence is not enumerated. This reduction-free normalization function takes the form of an abstract machine that navigates from one redex site to the next without systematically detouring via the root...... of a redex. In this article, we consider such an outermost reduction semantics with backward-overlapping rules, and we investigate how to apply refocusing to still obtain a reduction-free normalization function in the form of an abstract machine....

  14. Representative mass reduction in sampling

    DEFF Research Database (Denmark)

    Petersen, Lars; Esbensen, Harry Kim; Dahl, Casper Kierulf

    2004-01-01

    We here present a comprehensive survey of current mass reduction principles and hardware available in the current market. We conduct a rigorous comparison study of the performance of 17 field and/or laboratory instruments or methods which are quantitatively characterized (and ranked) for accuracy...... always be representative in the full Theory of Sampling (TOS) sense. This survey also allows empirical verification of the merits of the famous ??Gy?s formula?? for order-of-magnitude estimation of the Fundamental Sampling Error (FSE).......We here present a comprehensive survey of current mass reduction principles and hardware available in the current market. We conduct a rigorous comparison study of the performance of 17 field and/or laboratory instruments or methods which are quantitatively characterized (and ranked) for accuracy...... dividers, the Boerner Divider, the ??spoon method??, alternate/fractional shoveling and grab sampling. Only devices based on riffle splitting principles (static or rotational) passes the ultimate representativity test (with minor, but significant relative differences). Grab sampling, the overwhelmingly...

  15. Biocatalytic reduction of carboxylic acids.

    Science.gov (United States)

    Napora-Wijata, Kamila; Strohmeier, Gernot A; Winkler, Margit

    2014-06-01

    An increasing demand for non-petroleum-based products is envisaged in the near future. Carboxylic acids such as citric acid, succinic acid, fatty acids, and many others are available in abundance from renewable resources and they could serve as economic precursors for bio-based products such as polymers, aldehyde building blocks, and alcohols. However, we are confronted with the problem that carboxylic acid reduction requires a high level of energy for activation due to the carboxylate's thermodynamic stability. Catalytic processes are scarce and often their chemoselectivity is insufficient. This review points at bio-alternatives: currently known enzyme classes and organisms that catalyze the reduction of carboxylic acids are summarized. Two totally distinct biocatalyst lines have evolved to catalyze the same reaction: aldehyde oxidoreductases from anaerobic bacteria and archea, and carboxylate reductases from aerobic sources such as bacteria, fungi, and plants. The majority of these enzymes remain to be identified and isolated from their natural background in order to evaluate their potential as industrial biocatalysts.

  16. Tri-Sasakian consistent reduction

    CERN Document Server

    Cassani, Davide

    2011-01-01

    We establish a universal consistent Kaluza-Klein truncation of M-theory based on seven-dimensional tri-Sasakian structure. The four-dimensional truncated theory is an N=4 gauged supergravity with three vector multiplets and a non-abelian gauge group, containing the compact factor SO(3). Consistency follows from the fact that our truncation takes exactly the same form as a left-invariant reduction on a specific coset manifold, and we show that the same holds for the various universal consistent truncations recently put forward in the literature. We describe how the global symmetry group SL(2,R) x SO(6,3) is embedded in the symmetry group E7(7) of maximally supersymmetric reductions, and make the connection with the approach of Exceptional Generalized Geometry. Vacuum AdS4 solutions spontaneously break the amount of supersymmetry from N=4 to N=3,1 or 0, and the spectrum contains massive modes. We find a subtruncation to minimal N=3 gauged supergravity as well as an N=1 subtruncation to the SO(3)-invariant secto...

  17. Chemical model reduction under uncertainty

    KAUST Repository

    Malpica Galassi, Riccardo

    2017-03-06

    A general strategy for analysis and reduction of uncertain chemical kinetic models is presented, and its utility is illustrated in the context of ignition of hydrocarbon fuel–air mixtures. The strategy is based on a deterministic analysis and reduction method which employs computational singular perturbation analysis to generate simplified kinetic mechanisms, starting from a detailed reference mechanism. We model uncertain quantities in the reference mechanism, namely the Arrhenius rate parameters, as random variables with prescribed uncertainty factors. We propagate this uncertainty to obtain the probability of inclusion of each reaction in the simplified mechanism. We propose probabilistic error measures to compare predictions from the uncertain reference and simplified models, based on the comparison of the uncertain dynamics of the state variables, where the mixture entropy is chosen as progress variable. We employ the construction for the simplification of an uncertain mechanism in an n-butane–air mixture homogeneous ignition case, where a 176-species, 1111-reactions detailed kinetic model for the oxidation of n-butane is used with uncertainty factors assigned to each Arrhenius rate pre-exponential coefficient. This illustration is employed to highlight the utility of the construction, and the performance of a family of simplified models produced depending on chosen thresholds on importance and marginal probabilities of the reactions.

  18. Measurement of thermal lensing in end-pumped Yb-doped yttrium vanadate crystal and sesquioxide laser ceramics

    Science.gov (United States)

    Pestryakov, E. V.; Petrov, V. V.; Trunov, V. I.; Kirpichnikov, A. V.; Merzliakov, M. A.; Laptev, A. V.; Polyakov, K. V.

    2011-02-01

    The results of theoretical and experimental study of thermal lensing in diode-pumped Yb:YVO4 laser crystal, Yb:Y2O3 and Yb:Sc2O3 laser ceramics are presented. Shown, that influence of thermo-lensing effect is necessary to consider for creation of effective high-intensity femtosecond Yb-doped laser systems.

  19. Ab initio LSDA and LSDA+U study of pure and Cd-doped cubic lanthanide sesquioxides

    DEFF Research Database (Denmark)

    Richard, D.; Muñoz, E.L.; Rentería, M.

    2013-01-01

    approximation (LSDA) and the Coulomb-corrected LSDA+U. In the case of the pure systems, our calculations show that LSDA+U gives a better representation of the band structure compared to LSDA. The predicted equilibrium structures and the electric field gradient (EFG) tensor at Ln sites were calculated...... and compared with those obtained by means of hyperfine techniques and with theoretical results obtained in In2O3, Sc2O3, and Lu2O3 reported in the literature. The origin of the EFG at Ln sites and the role played by the 4f electrons on this quantity are discussed. In the case of the Cd-doped systems, the APW......+lo method (also within LSDA and LSDA+U) was applied to treat the electronic structure of the doped system. The role of the Ln 4felectrons on the EFG at Cd impurity sites, and other variables like structural distortions induced by the Cd impurity, were investigated in detail and are discussed and compared...

  20. Heteroepitaxial praseodymium sesquioxide films on Si(1 1 1): A new model catalyst system for praseodymium oxide based catalysts

    Science.gov (United States)

    Schaefer, A.; Schroeder, T.; Lupina, G.; Borchert, Y.; Dabrowski, J.; Wenger, Ch.; Bäumer, M.

    2007-03-01

    The structure, growth and stoichiometry of heteroepitaxial Pr 2O 3 films on Si(1 1 1) were characterized by a combined RHEED, XRD, XPS and UPS study in view of future applications as a surface science model catalyst system. RHEED and XRD confirm the growth of a (0 0 0 1) oriented hexagonal Pr 2O 3 phase on Si(1 1 1), matching the surface symmetry by aligning the oxide in-plane direction along the Si azimuth. After an initial nucleation stage RHEED growth oscillation studies point to a Frank-van der Merwe growth mode up to a thickness of approximately 12 nm. XPS and UPS prove that the initial growth of the Pr 2O 3 layer on Si up to ˜1 nm thickness is characterized by an interface reaction with Si. Nevertheless stoichiometric Pr 2O 3 films of high crystalline quality form on top of these Pr-silicate containing interlayers.

  1. Effects of Ionic Strength and Sesquioxides on Adsorption of Toxin of Bacillus thuringiensis subsp, kurstaki on Soils

    Institute of Scientific and Technical Information of China (English)

    FU Qing-Ling; PENG Ya-Wen; HUANG Tao; HU Hong-Qing; DENG Ya-Li; YU Xia

    2012-01-01

    Chemical reactions and fate of the toxins of Bacillus thuringiensis (Bt) in the soil environment are causing increasing concerns due to the large-scale cultivation of transgenic Bt plants.In this study,the effect of ionic strength (0-1000 mmol kg-1) adjusted by NaCl or CaCl2 on adsorption of Bt toxin by a lateritic red soil,a paddy soil and these soils after chemical removal of organic-bound or free Fe and Al oxides,as well as by pure minerals (goethite,hematite and gibbsite) which are widespread in these soils,were studied.The results indicated that when the supporting electrolyte was NaCl,the adsorption of Bt toxin by the lateritic red soil and paddy soil increased rapidly until the ionic strength reached 250 mmol kg- 1 and then gradually slowed down with the increase of ionic strength; while in case the supporting electrolyte was CaCl2,the adsorption of Bt toxin enhanced significantly at low ionic strength (< 10 mmol kg-1) and then decreased as the ionic strength increased.The adsorption of Bt toxin by the tested minerals and soils after the removal of organic-bound or free Fe and Al oxides also increased with increasing ionic strength controlled by NaC1.Removing organic-bound Fe and Al oxides obviously increased the adsorption of Bt toxin in the tested soils.Differently,removing free Fe and Al oxides increased the Bt adsorption by the paddy soil,but decreased the adsorption by the lateritic red soil.The study indicated that the varieties of ionic strength and the presence of Fe and Al oxides affected the adsorption of Bt toxin by the soils,which would contribute to the further understanding of the fate of Bt toxin in the soil environment and provide references for the ecological risk assessment of transgenic Bt plants.

  2. NOX REMOVAL WITH COMBINED SELECTIVE CATALYTIC REDUCTION AND SELECTIVE NONCATALYTIC REDUCTION: PILOT- SCALE TEST RESULTS

    Science.gov (United States)

    Pilot-scale tests were conducted to develop a combined nitrogen oxide (NOx) reduction technology using both selective catalytic reduction (SCR) and selective noncatalytic reduction (SNCR). A commercially available vanadium-and titatnium-based composite honeycomb catalyst and enh...

  3. Carbon Monoxide Silicate Reduction System Project

    Data.gov (United States)

    National Aeronautics and Space Administration — The Carbon Monoxide Silicate Reduction System (COSRS) is an innovative method that for the first time uses the strong reductant carbon monoxide to both reduce iron...

  4. Reduction mechanism of natural ilmenite with graphite

    Institute of Scientific and Technical Information of China (English)

    WANG Yu-ming; YUAN Zhang-fu; GUO Zhan-cheng; TAN Qiang-qiang; LI Zhao-yi; JIANG Wei-zhong

    2008-01-01

    Reduction of Bama ilmenite concentrate containing 49.78% TiO2 and 27.96% total Fe by graphite was studied using thermogravimetric analysis system under argon gas ambient from 850 to 1 400 ℃. The reduction degree of Bama ilmenite is enhanced with increasing temperature and the molar ratio of carbon to oxygen, and the reaction rate varies with temperature and reduction time simultaneously. The phase transformation, chemical composition, microstructure and morphology of reduced samples were investigated by using X-ray diffractometry, scanning electron microscopy, and energy disperse spectroscopy, respectively. The high content of impurities in Bama ilmenite evidently bates the reduction of ilmenite. Forming the enrichment zone of manganese prevents complete reduction of Fe2+. The reduction products are mostly reduced iron, rutile, reduced rutiles, Ti3O5 and pseudobrookite solid solution. The reduction kinetics was also discussed. The results show that the reduction temperature is a key factor to control reaction rate.

  5. Morphologisation or Reduction by Context?

    DEFF Research Database (Denmark)

    Heegård Petersen, Jan

    2013-01-01

    The article investigates the factors that underlie schwa elision in-te, [d], endings in Standard Copenhagen Danish adjectives and preterite verb forms. The study shows that preterite [d] is much more likely to undergo schwa elision to [d] than adjectival [d]. The data are analysed by use of regre......The article investigates the factors that underlie schwa elision in-te, [d], endings in Standard Copenhagen Danish adjectives and preterite verb forms. The study shows that preterite [d] is much more likely to undergo schwa elision to [d] than adjectival [d]. The data are analysed by use...... that are often mentioned in the literature as causing phonetic reduction. The article discusses whether preterite verb forms can be said to be more grammatical than adjectives, or whether the high frequency schwa elided variant of verbal te is a sign of morphologisation, an allomorph,-t, of the preterite...

  6. PLAINS CO2 REDUCTION PARTNERSHIP

    Energy Technology Data Exchange (ETDEWEB)

    Edward N. Steadman; John A. Harju; Erin M. O' Leary; James A. Sorensen; Daniel J. Daly; Melanie D. Jensen; Thea E. Reikoff

    2004-10-01

    The Plains CO{sub 2} Reduction (PCOR) Partnership continues to make great progress. Task 2 (Technology Deployment) focused on developing information regarding deployment issues to support Task 5 (Modeling and Phase II Action Plans) by providing information to be used to assess CO{sub 2} sequestration opportunities in the PCOR Partnership region. Task 3 (Public Outreach) focused on developing an informational video about CO{sub 2} sequestration. Progress in Task 4 (Sources, Sinks, and Infrastructure) included the continued collection of data regarding CO{sub 2} sources and sinks and data on the performance and costs for CO{sub 2} separation, capture, treatment, and compression for pipeline transportation. Task 5 focused on screening and qualitatively assessing sequestration options. Task 5 activities also continue to be useful in structuring data collection and other activities in Tasks 2, 3, and 5.

  7. The Olympics and harm reduction?

    Directory of Open Access Journals (Sweden)

    Kayser Bengt

    2012-07-01

    Full Text Available Abstract The current anti-doping policy (‘war on doping’ resembles the ‘war on drugs’ in several aspects, including a zero-tolerance approach, ideology encroaching on human rights and public health principles, high cost using public money for repression and control, and attempts to shape internationally harmonized legal frameworks to attain its aim. Furthermore, even if for different reasons, both wars seem not to be able to attain their objectives, and possibly lead to more harm to society than they can prevent. The Olympic buzz is mounting and we can expect multiple headlines in the media on doping and anti-doping stories related to this event. In this article we describe current anti-doping policy, reflect on its multiple unplanned consequences, and end with a discussion, if lessons learned from harm reduction experiences in the illicit drugs field could be applied to anti-doping.

  8. PLAINS CO2 REDUCTION PARTNERSHIP

    Energy Technology Data Exchange (ETDEWEB)

    Edward N. Steadman; John A. Harju; Erin M. O' Leary; James A. Sorensen; Daniel J. Daly; Melanie D. Jensen; Thea E. Reikoff

    2005-01-01

    The Plains CO{sub 2} Reduction (PCOR) Partnership continues to make great progress. Task 2 (Technology Deployment) focused on developing information regarding deployment issues to support Task 5 (Modeling and Phase II Action Plans) by providing information to be used to assess CO{sub 2} sequestration opportunities in the PCOR Partnership region. Task 3 (Public Outreach) focused on developing an informational video about CO{sub 2} sequestration. Progress in Task 4 (Sources, Sinks, and Infrastructure) included the continued collection of data regarding CO{sub 2} sources and sinks and data on the performance and costs for CO{sub 2} separation, capture, treatment, and compression for pipeline transportation. Task 5 focused on screening and qualitatively assessing sequestration options. Task 5 activities also continue to be useful in structuring data collection and other activities in Tasks 2, 3, and 5.

  9. Large Engine Emission Reduction - LEER

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    2006-10-15

    The target of the project LEER is to find the most cost-effective means of today to reduce exhaust gas emissions, particularly NO{sub x} and particulates, of power-plant and ship propulsion diesel engines. The methods are controlling of the combustion and exhaust gas after-treatment. As research methods, theoretical and literature studies as well as engine tests are used. Using the state of the art technology in the whole engine process from combustion control to after treatment is vital for keeping the product competitive in today's engine market. The project consists of two main tasks, Performance and Emission. The Performance task deals with controlling the combustion for optimising the trade-off between fuel consumption and pollutant formation, NO{sub x} in particular. The Emission task concentrates on improving the after treatment technology in particulate reduction, and understanding the particulate formation by gaining information of particulate nature and composition. (orig.)

  10. Wind reduction by aerosol particles

    Science.gov (United States)

    Jacobson, Mark Z.; Kaufman, Yoram J.

    2006-12-01

    Aerosol particles are known to affect radiation, temperatures, stability, clouds, and precipitation, but their effects on spatially-distributed wind speed have not been examined to date. Here, it is found that aerosol particles, directly and through their enhancement of clouds, may reduce near-surface wind speeds below them by up to 8% locally. This reduction may explain a portion of observed ``disappearing winds'' in China, and it decreases the energy available for wind-turbine electricity. In California, slower winds reduce emissions of wind-driven soil dust and sea spray. Slower winds and cooler surface temperatures also reduce moisture advection and evaporation. These factors, along with the second indirect aerosol effect, may reduce California precipitation by 2-5%, contributing to a strain on water supply.

  11. PLAINS CO2 REDUCTION PARTNERSHIP

    Energy Technology Data Exchange (ETDEWEB)

    Edward N. Steadman; John A. Harju; Erin M. O' Leary; James A. Sorensen; Daniel J. Daly; Melanie D. Jensen; Thea E. Reikoff

    2005-01-01

    The Plains CO{sub 2} Reduction (PCOR) Partnership continues to make great progress. Task 2 (Technology Deployment) focused on developing information regarding deployment issues to support Task 5 (Modeling and Phase II Action Plans) by providing information to be used to assess CO{sub 2} sequestration opportunities in the PCOR Partnership region. Task 3 (Public Outreach) focused on developing an informational video about CO{sub 2} sequestration. Progress in Task 4 (Sources, Sinks, and Infrastructure) included the continued collection of data regarding CO{sub 2} sources and sinks and data on the performance and costs for CO{sub 2} separation, capture, treatment, and compression for pipeline transportation. Task 5 focused on screening and qualitatively assessing sequestration options. Task 5 activities also continue to be useful in structuring data collection and other activities in Tasks 2, 3, and 5.

  12. Drag Reduction of Bacterial Cellulose Suspensions

    Directory of Open Access Journals (Sweden)

    Satoshi Ogata

    2011-01-01

    Full Text Available Drag reduction due to bacterial cellulose suspensions with small environmental loading was investigated. Experiments were carried out by measuring the pressure drop in pipe flow. It was found that bacterial cellulose suspensions give rise to drag reduction in the turbulent flow range. We observed a maximum drag reduction ratio of 11% and found that it increased with the concentration of the bacterial cellulose suspension. However, the drag reduction effect decreased in the presence of mechanical shear.

  13. Reductions for Entrepreneurs in Health Insurance Contributions

    Directory of Open Access Journals (Sweden)

    Paweł Lenio

    2014-09-01

    Full Text Available This paper describes the reductions for entrepreneurs in health insurance contributions. Only entrepreneurs from specific social groups can take advantage of said reductions. They apply only to people retired, on pensions or handicapped. The reductions are also dependent on the potential recipient's income and revenue of the company. Handicapped entrepreneurs can benefit from some additional privileges as well. Author analyzes the legal regulations behind these reductions and exposes their shortcomings which cause the benefits to be rarely used.

  14. Reductions for Entrepreneurs in Health Insurance Contributions

    OpenAIRE

    Paweł Lenio

    2014-01-01

    This paper describes the reductions for entrepreneurs in health insurance contributions. Only entrepreneurs from specific social groups can take advantage of said reductions. They apply only to people retired, on pensions or handicapped. The reductions are also dependent on the potential recipient's income and revenue of the company. Handicapped entrepreneurs can benefit from some additional privileges as well. Author analyzes the legal regulations behind these reductions and exposes their sh...

  15. Sulphate reduction experiment: SURE-1

    Energy Technology Data Exchange (ETDEWEB)

    Pedersen, K.; Arlinger, J.; Bengtsson, A.; Edlund, J.; Eriksson, L.; Hallbeck, L.; Johansson, J.; Paeaejaervi, A.; Rabe, L. [Microbial Analytics Sweden AB, Moelnlycke (Sweden)

    2013-11-15

    It was previously concluded that opposing gradients of sulphate and methane, observations of 16S rDNA sequences displaying great similarity to those of anaerobic methane-oxidizing Archaea, and a peak in sulphide concentration in groundwater from a depth of 250-350 m in Olkiluoto, Finland, indicated proper conditions for methane oxidation with sulphate. In the present research (SURE-1), pressure-resistant, gas-tight circulating systems were constructed to enable the investigation of attached and unattached anaerobic microbial populations from a depth of 327 m in Olkiluoto under in situ pressure (2.4 MPa), diversity, dissolved gas, and hydrochemical conditions of groundwater station ONKPVA6. Three parallel flow cell cabinets were configured to allow observation of the influence on microbial metabolic activity of 11 mM methane, 11 mM methane plus 10 mM H{sub 2}, or 2.1 mM O{sub 2} plus 7.9 mM N{sub 2} (i.e., air). The concentrations of these gases and of organic acids and carbon, sulphur chemistry, pH and E{sub h}, ATP, numbers of cultivable microorganisms, and total numbers of cells and bacteriophages were subsequently recorded under batch conditions for 105 d. The system containing H{sub 2} and methane displayed microbial reduction of 0.7 mM sulphate to sulphide, while the system containing only methane produced 0.2 mM reduced sulphate. The system containing added air became inhibited and displayed no signs of microbial activity. Added H{sub 2} and methane induced increasing numbers of lysogenic bacteriophages per cell. It appears possible that a microbial anaerobic methane-oxidizing process coupled to acetate formation and sulphate reduction may be ongoing in aquifers at a depth of 250-350 m in Olkiluoto, but clear evidence of such an AOM process was not obtained. (orig.)

  16. Geometric Reductivity--A Quotient Space Approach

    CERN Document Server

    Sastry, Pramathanath

    2010-01-01

    We give another proof that a reductive algebraic group is geometrically reductive. We show that a quotient of the semi-stable locus (by a linear action of a reductive algebraic group on a projective scheme) exists, and from this Haboush's Theorem (Mumford's Conjecture) follows.

  17. The Wisdom of Class-Size Reduction

    Science.gov (United States)

    Graue, Elizabeth; Hatch, Kelly; Rao, Kalpana; Oen, Denise

    2007-01-01

    In this study, the authors explore the implementation of a statewide class-size reduction program in nine high-poverty schools. Through qualitative methods, they examined how schools used class-size reduction to change staffing patterns and instructional programs. Requiring changes in space allocation, class-size reduction was accomplished through…

  18. Generalized Time-Limited Balanced Reduction Method

    DEFF Research Database (Denmark)

    Shaker, Hamid Reza; Shaker, Fatemeh

    2013-01-01

    In this paper, a new method for model reduction of bilinear systems is presented. The proposed technique is from the family of gramian-based model reduction methods. The method uses time-interval generalized gramians in the reduction procedure rather than the ordinary generalized gramians...

  19. Generalized Time-Limited Balanced Reduction Method

    DEFF Research Database (Denmark)

    Shaker, Hamid Reza; Shaker, Fatemeh

    2013-01-01

    In this paper, a new method for model reduction of bilinear systems is presented. The proposed technique is from the family of gramian-based model reduction methods. The method uses time-interval generalized gramians in the reduction procedure rather than the ordinary generalized gramians and in ...

  20. Identifying the Rhetoric of Uncertainty Reduction.

    Science.gov (United States)

    Williams, David E.

    Offering a rhetorical perspective of uncertainty reduction, this paper (1) discusses uncertainty reduction theory and dramatism; (2) identifies rhetorical strategies inherent in C. W. Berger and R. J. Calabrese's theory; (3) extends predicted outcome value to influenced outcome value; and (4) argues that the goal of uncertainty reduction and…

  1. Ultrasound-Assisted Distal Radius Fracture Reduction

    Science.gov (United States)

    Socransky, Steve; Skinner, Andrew; Bromley, Mark; Smith, Andrew; Anawati, Alexandre; Middaugh, Jeff; Ross, Peter

    2016-01-01

    Introduction Closed reduction of distal radius fractures (CRDRF) is a commonly performed emergency department (ED) procedure. The use of point-of-care ultrasound (PoCUS) to diagnose fractures and guide reduction has previously been described. The primary objective of this study was to determine if the addition of PoCUS to CRDRF changed the perception of successful initial reduction. This was measured by the rate of further reduction attempts based on PoCUS following the initial clinical determination of achievement of best possible reduction. Methods  We performed a multicenter prospective cohort study, using a convenience sample of adult ED patients presenting with a distal radius fracture to five Canadian EDs. All study physicians underwent standardized PoCUS training for fractures. Standard clinically-guided best possible fracture reduction was initially performed. PoCUS was then used to assess the reduction adequacy. Repeat reduction was performed if deemed indicated. A post-reduction radiograph was then performed. Clinician impression of reduction adequacy was scored on a 5 point Likert scale following the initial clinically-guided reduction and following each PoCUS scan and the post-reduction radiograph. Results  There were 131 patients with 132 distal radius fractures. Twelve cases were excluded prior to analysis. There was no significant difference in the assessment of the initial reduction status by PoCUS as compared to the clinical exam (mean score: 3.8 vs. 3.9; p = 0.370; OR 0.89; 95% CI 0.46 to 1.72; p = 0.87). Significantly fewer cases fell into the uncertain category with PoCUS than with clinical assessment (2 vs 12; p = 0.008). Repeat reduction was performed in 49 patients (41.2%). Repeat reduction led to a significant improvement (p < 0.001) in the PoCUS determined adequacy of reduction (mean score: 4.3 vs 3.1; p < 0.001). In this group, the odds ratio for adequate vs. uncertain or inadequate reduction assessment using PoCUS was 12.5 (95% CI 3

  2. PLAINS CO2 REDUCTION PARTNERSHIP

    Energy Technology Data Exchange (ETDEWEB)

    Edward N. Steadman; John A. Harju; Erin M. O' Leary; James A. Sorensen; Daniel J. Daly; Melanie D. Jensen; Lisa S. Botnen

    2005-07-01

    The Plains CO{sub 2} Reduction (PCOR) Partnership characterization work is nearing completion, and most remaining efforts are related to finalizing work products. Task 2 (Technology Deployment) has developed a Topical Report entitled ''Deployment Issues Related to Geologic CO{sub 2} Sequestration in the PCOR Partnership Region''. Task 3 (Public Outreach) has developed an informational Public Television program entitled ''Nature in the Balance'', about CO{sub 2} sequestration. The program was completed and aired on Prairie Public Television in this quarter. Task 4 (Sources, Sinks, and Infrastructure) efforts are nearing completion, and data regarding CO{sub 2} sources and sinks and data on the performance and costs for CO{sub 2} separation, capture, treatment, and compression for pipeline transportation are being incorporated into a series of topical reports. The expansion of the Decision Support System Geographic Information System database has continued with the development of a ''save bookmark'' feature that allows users to save a map from the system easily. A feature that allows users to develop a report that summarizes CO{sub 2} sequestration parameters was also developed. Task 5 (Modeling and Phase II Action Plans) focused on screening and qualitatively assessing sequestration options and developing economic estimates for important regional CO{sub 2} sequestration strategies.

  3. PLAINS CO2 REDUCTION PARTNERSHIP

    Energy Technology Data Exchange (ETDEWEB)

    Edward N. Steadman; John A. Harju; Erin M. O' Leary; James A. Sorensen; Daniel J. Daly; Melanie D. Jensen; Thea E. Reikoff

    2005-04-01

    The Plains CO{sub 2} Reduction (PCOR) Partnership continues to make great progress. Task 2 (Technology Deployment) focused on developing information regarding deployment issues to support Task 5 (Modeling and Phase II Action Plans) and provided information to be used to assess CO{sub 2} sequestration opportunities in the PCOR Partnership region. Task 2 efforts also included preparation of a draft topical report entitled ''Deployment Issues Related to Geologic CO{sub 2} Sequestration in the PCOR Partnership Region'', which is nearing completion. Task 3 (Public Outreach) focused on developing an informational video about CO{sub 2} sequestration. The video will be completed and aired on Prairie Public Television in the next quarter. Progress in Task 4 (Sources, Sinks, and Infrastructure) included the continued collection of data regarding CO{sub 2} sources and sinks and data on the performance and costs for CO{sub 2} separation, capture, treatment, and compression for pipeline transportation. The addition of the Canadian province of Alberta to the PCOR Partnership region expanded the decision support system (DSS) geographic information system database. Task 5 screened and qualitatively assessed sequestration options. Task 5 activities also continue to be useful in structuring data collection and other activities in Tasks 2, 3, and 5.

  4. 20 CFR 410.540 - Reductions; more than one reduction event.

    Science.gov (United States)

    2010-04-01

    ... 20 Employees' Benefits 2 2010-04-01 2010-04-01 false Reductions; more than one reduction event. 410.540 Section 410.540 Employees' Benefits SOCIAL SECURITY ADMINISTRATION FEDERAL COAL MINE HEALTH...; more than one reduction event. If a reduction for receipt of State benefits (see § 410.520) and a...

  5. Energy and angular distributions of excited rhodium atoms ejected from the rhodium (100) surface

    Energy Technology Data Exchange (ETDEWEB)

    El-Maazawi, M.; Maboudian, R.; Postawa, Z.; Winograd, N. (Department of Chemistry, The Pennsylvania State University, University Park, Pennsylvania 16802 (US))

    1991-05-15

    Multiphoton resonance ionization spectroscopy has been used to determine the polar-angle and the kinetic-energy distribution of Rh atoms desorbed from the ion-bombarded Rh{l brace}100{r brace} surface in the fine-structure components of the {ital a}{sup 4}{ital F}{sub {ital J}} ground-state multiplet ({ital J}=9/2 and 7/2). The overall behavior is found to be very similar to that observed for higher-lying metastable levels. The energy distribution of the metastable level ({sup 4}{ital F}{sub 7/2} with excitation energy of {similar to}0.2 eV) is found to be broader than the ground-state ({sup 4}{ital F}{sub 9/2}) distribution. The energy distribution of the excited ejected atoms is shown to depend mainly on the electron configuration of the excited state. The measured spectra have also been used to investigate the dependence of the excitation probability on the emission velocity. It is shown that the excitation probability depends strongly on this parameter, approaching an exponential dependence on the reciprocal of the normal component of velocity at higher velocities ({gt}5{times}10{sup 5} cm/sec).

  6. Monoclonal antibody disulfide reduction during manufacturing

    Science.gov (United States)

    Hutterer, Katariina M.; Hong, Robert W.; Lull, Jonathon; Zhao, Xiaoyang; Wang, Tian; Pei, Rex; Le, M. Eleanor; Borisov, Oleg; Piper, Rob; Liu, Yaoqing Diana; Petty, Krista; Apostol, Izydor; Flynn, Gregory C.

    2013-01-01

    Manufacturing-induced disulfide reduction has recently been reported for monoclonal human immunoglobulin gamma (IgG) antibodies, a widely used modality in the biopharmaceutical industry. This effect has been tied to components of the intracellular thioredoxin reduction system that are released upon cell breakage. Here, we describe the effect of process parameters and intrinsic molecule properties on the extent of reduction. Material taken from cell cultures at the end of production displayed large variations in the extent of antibody reduction between different products, including no reduction, when subjected to the same reduction-promoting harvest conditions. Additionally, in a reconstituted model in which process variables could be isolated from product properties, we found that antibody reduction was dependent on the cell line (clone) and cell culture process. A bench-scale model using a thioredoxin/thioredoxin reductase regeneration system revealed that reduction susceptibility depended on not only antibody class but also light chain type; the model further demonstrates that the trend in reducibility was identical to DTT reduction sensitivity following the order IgG1λ > IgG1κ > IgG2λ > IgG2κ. Thus, both product attributes and process parameters contribute to the extent of antibody reduction during production. PMID:23751615

  7. Lake Nasser evaporation reduction study

    Directory of Open Access Journals (Sweden)

    Hala M.I. Ebaid

    2010-10-01

    Full Text Available This study aims to evaluate the reduction of evaporation of Lake Nasser’s water caused by disconnecting (fully or partially some of its secondary channels (khors. This evaluation integrates remote sensing, Geographic Information System (GIS techniques, aerodynamic principles, and Landsat7 ETM+ images. Three main procedures were carried out in this study; the first derived the surface temperature from Landsat thermal band; the second derived evaporation depth and approximate evaporation volume for the entire lake, and quantified evaporation loss to the secondary channels’ level over one month (March by applied aerodynamic principles on surface temperature of the raster data; the third procedure applied GIS suitability analysis to determine which of these secondary channels (khors should be disconnected. The results showed evaporation depth ranging from 2.73 mm/day at the middle of the lake to 9.58 mm/day at the edge. The evaporated water-loss value throughout the entire lake was about 0.86 billion m3/month (March. The analysis suggests that it is possible to save an approximate total evaporation volume loss of 19.7 million m3/month (March, and thus 2.4 billion m3/year, by disconnecting two khors with approximate construction heights of 8 m and 15 m. In conclusion, remote sensing and GIS are useful for applications in remote locations where field-based information is not readily available and thus recommended for decision makers remotely planning in water conservation and management.

  8. Development of an expert data reduction assistant

    Science.gov (United States)

    Miller, Glenn E.; Johnston, Mark D.; Hanisch, Robert J.

    1993-01-01

    We propose the development of an expert system tool for the management and reduction of complex datasets. the proposed work is an extension of a successful prototype system for the calibration of CCD (charge coupled device) images developed by Dr. Johnston in 1987. (ref.: Proceedings of the Goddard Conference on Space Applications of Artificial Intelligence). The reduction of complex multi-parameter data sets presents severe challenges to a scientist. Not only must a particular data analysis system be mastered, (e.g. IRAF/SDAS/MIDAS), large amounts of data can require many days of tedious work and supervision by the scientist for even the most straightforward reductions. The proposed Expert Data Reduction Assistant will help the scientist overcome these obstacles by developing a reduction plan based on the data at hand and producing a script for the reduction of the data in a target common language.

  9. Emergence, Reduction and Supervenience: a Varied Landscape

    CERN Document Server

    Butterfield, Jeremy

    2011-01-01

    This is one of two papers about emergence, reduction and supervenience. It expounds these notions and analyses the general relations between them. The companion paper analyses the situation in physics, especially limiting relations between physical theories. I shall take emergence as behaviour that is novel and robust relative to some comparison class. I shall take reduction as deduction using appropriate auxiliary definitions. And I shall take supervenience as a weakening of reduction, viz. to allow infinitely long definitions. The overall claim of this paper will be that emergence is logically independent both of reduction and of supervenience. In particular, one can have emergence with reduction, as well as without it; and emergence without supervenience, as well as with it. Of the subsidiary claims, the four main ones (each shared with some other authors) are: (i): I defend the traditional Nagelian conception of reduction (Section 3); (ii): I deny that the multiple realizability argument causes trouble fo...

  10. Nox reduction in the sintering process

    Institute of Scientific and Technical Information of China (English)

    Yan-guang Chen; Zhan-cheng Guo; Zhi Wang; Gen-sheng Feng

    2009-01-01

    A new process, NOx reduction with recycling flue gas and modifying coke breeze, was proposed. The effects of modified coke breeze and recycled flue gas on NOx reduction were investigated by sinter pot tests. The results show that the NOx reduction rate is over 10wt% in the sintering of modified coke breeze, the effects of the additives on NOx reduction are: CeO2CaOK2CO3.The NOx reduction rate increases with the amount of recycled flue gas, and is 22.35wt% in the sintering with recycling 30vo1% of the flue gas. When 30vo1% of the flue gas is recycled into the sintering of CeO2, CaO, and K2CO3 modified coke breeze, the NOx reduc-tion rates are 36.10wt%, 32.56wt%, and 32.17wt%, respectively.

  11. 50 CFR 600.1011 - Reduction methods and other conditions.

    Science.gov (United States)

    2010-10-01

    ... reduction loan balance that results from all reduction payments that NMFS actually makes and does not...' tender of the reduction payment for the reduction permit, forever revoked. Each reduction permit holder shall, upon NMFS' tender of the reduction payment, surrender the original reduction permit to NMFS....

  12. Model Reduction for Complex Hyperbolic Networks

    OpenAIRE

    Himpe, Christian; Ohlberger, Mario

    2013-01-01

    We recently introduced the joint gramian for combined state and parameter reduction [C. Himpe and M. Ohlberger. Cross-Gramian Based Combined State and Parameter Reduction for Large-Scale Control Systems. arXiv:1302.0634, 2013], which is applied in this work to reduce a parametrized linear time-varying control system modeling a hyperbolic network. The reduction encompasses the dimension of nodes and parameters of the underlying control system. Networks with a hyperbolic structure have many app...

  13. REDUCTIONS WITHOUT REGRET: HISTORICAL PERSPECTIVES

    Energy Technology Data Exchange (ETDEWEB)

    Swegle, J.; Tincher, D.

    2013-09-09

    This is the first of three papers (in addition to an introductory summary) aimed at providing a framework for evaluating future reductions or modifications of the U.S. nuclear force, first by considering previous instances in which nuclear-force capabilities were eliminated; second by looking forward into at least the foreseeable future at the features of global and regional deterrence (recognizing that new weapon systems currently projected will have expected lifetimes stretching beyond our ability to predict the future); and third by providing examples of past or possible undesirable outcomes in the shaping of the future nuclear force, as well as some closing thoughts for the future. This paper examines the circumstances and consequences of the elimination of The INF-range Pershing II ballistic missile and Gryphon Ground-Launched Cruise Missile (GLCM), deployed by NATO under a dual-track strategy to counter Soviet intermediate-range missiles while pursuing negotiations to limit or eliminate all of these missiles. The Short-Range Attack Missile (SRAM), which was actually a family of missiles including SRAM A, SRAM B (never deployed), and SRAM II and SRAM T, these last two cancelled during an over-budget/behind-schedule development phase as part of the Presidential Nuclear Initiatives of 1991 and 1992. The nuclear-armed version of the Tomahawk Land-Attack Cruise Missile (TLAM/N), first limited to shore-based storage by the PNIs, and finally eliminated in deliberations surrounding the 2010 Nuclear Posture Review Report. The Missile-X (MX), or Peacekeeper, a heavy MIRVed ICBM, deployed in fixed silos, rather than in an originally proposed mobile mode. Peacekeeper was likely intended as a bargaining chip to facilitate elimination of Russian heavy missiles. The plan failed when START II did not enter into force, and the missiles were eliminated at the end of their intended service life. The Small ICBM (SICBM), or Midgetman, a road-mobile, single-warhead missile for

  14. Reductive photocatalysis and smart inks.

    Science.gov (United States)

    Mills, Andrew; Wells, Nathan

    2015-05-21

    Semiconductor-sensitised photocatalysis is a well-established and growing area of research, innovation and commercialisation; the latter being mostly limited to the use of TiO2 as the semiconductor. Most of the work on semiconductor photocatalytic systems uses oxygen as the electron acceptor and explores a wide range of electron donors; such systems can be considered to be examples of oxidative photocatalysis, OP. OP underpins most current examples of commercial self-cleaning materials, such as: glass, tiles, concrete, paint and fabrics. OP, and its myriad of applications, have been reviewed extensively over the years both in this journal and elsewhere. However, the ability of TiO2, and other semiconductor sensitisers, to promote reductive photocatalysis, RP, especially of dyes, is significant and, although less well-known, is of growing importance. In such systems, the source of the electrons is some easily oxidised species, such as glycerol. One recent, significant example of a RP process is with respect to photocatalyst activity indicator inks. paiis, which provide a measure of the activity of a photocatalytic film under test via the rate of change of colour of the dye in the ink coating due to irreversible RP. In contrast, by incorporating the semiconductor sensitiser in the ink, rather than outside it, it is possible to create an effective UV dosimeter, based on RP, which can be used as a sun-burn warning indicator. In the above examples the dye is reduced irreversibly, but when the photocatalyst in an ink is used to reversibly photoreduce a dye, a novel, colourimetric oxygen-sensitive indicator ink can be created, which has commercial potential in the food packaging industry. Finally, if no dye is present in the ink, and the semiconductor photocatalyst-loaded ink film coats an easily reduced substrate, such as a metal oxide film, then it can be used to reduce the latter and so, for example, clean up tarnished steel. The above are examples of smart inks, i

  15. First Class Call Stacks: Exploring Head Reduction

    Directory of Open Access Journals (Sweden)

    Philip Johnson-Freyd

    2016-06-01

    Full Text Available Weak-head normalization is inconsistent with functional extensionality in the call-by-name λ-calculus. We explore this problem from a new angle via the conflict between extensionality and effects. Leveraging ideas from work on the λ-calculus with control, we derive and justify alternative operational semantics and a sequence of abstract machines for performing head reduction. Head reduction avoids the problems with weak-head reduction and extensionality, while our operational semantics and associated abstract machines show us how to retain weak-head reduction's ease of implementation.

  16. What is dimensional reduction really telling us?

    CERN Document Server

    Coumbe, Daniel

    2015-01-01

    Numerous approaches to quantum gravity report a reduction in the number of spacetime dimensions at the Planck scale. However, accepting the reality of dimensional reduction also means accepting its consequences, including a variable speed of light. We provide numerical evidence for a variable speed of light in the causal dynamical triangulation (CDT) approach to quantum gravity, showing that it closely matches the superluminality implied by dimensional reduction. We argue that reconciling the appearance of dimensional reduction with a constant speed of light may require modifying our understanding of time, an idea originally proposed in Ref. 1.

  17. Solvothermal reduction of graphene oxide in dimethylformamide

    Science.gov (United States)

    Kim, Sujin; Choi, Kwangrok; Park, Sungjin

    2016-11-01

    The reduction of graphene oxide (G-O) is one of the most promising methods for the large scale production of graphene-based materials. In this paper, we report a simple and non-toxic method to produce reduced graphene oxide (rG-O) by refluxing G-O in N, N-dimethylformamide without the aid of a reducing agent. The rG-O materials with high degrees of reduction are prepared and the levels of reduction are controlled using reflux time. Successful reduction is confirmed by combustion-based elemental analysis and X-ray photoelectron and Fourier transform infrared spectroscopy.

  18. Chromate reduction by rabbit liver aldehyde oxidase

    Energy Technology Data Exchange (ETDEWEB)

    Banks, R.B.; Cooke, R.T. Jr.

    1986-05-29

    Chromate was reduced during the oxidation of 1-methylnicotinamide chlorine by partially purified rabbit liver aldehyde oxidase. In addition to l-methylnicotinamide, several other electron donor substrates for aldehyde oxidase were able to support the enzymatic chromate reduction. The reduction required the presence of both enzyme and the electron donor substrate. The rate of the chromate reduction was retarded by inhibitors or aldehyde oxidase but was not affected by substrates or inhibitors of xanthine oxidase. These results are consistent with the involvement of aldehyde oxidase in the reduction of chromate by rabbit liver cytosolic enzyme preparations.

  19. Dissolution and reduction of magnetite by bacteria

    Science.gov (United States)

    Kostka, J. E.; Nealson, K. H.

    1995-01-01

    Magnetite (Fe3O4) is an iron oxide of mixed oxidation state [Fe(II), Fe(III)] that contributes largely to geomagnetism and plays a significant role in diagenesis in marine and freshwater sediments. Magnetic data are the primary evidence for ocean floor spreading and accurate interpretation of the sedimentary magnetic record depends on an understanding of the conditions under which magnetite is stable. Though chemical reduction of magnetite by dissolved sulfide is well known, biological reduction has not been considered likely based upon thermodynamic considerations. This study shows that marine and freshwater strains of the bacterium Shewanella putrefaciens are capable of the rapid dissolution and reduction of magnetite, converting millimolar amounts to soluble Fe(II)in a few days at room temperature. Conditions under which magnetite reduction is optimal (pH 5-6, 22-37 degrees C) are consistent with an enzymatic process and not with simple chemical reduction. Magnetite reduction requires viable cells and cell contact, and it appears to be coupled to electron transport and growth. In a minimal medium with formate or lactate as the electron donor, more than 10 times the amount of magnetite was reduced over no carbon controls. These data suggest that magnetite reduction is coupled to carbon metabolism in S. putrefaciens. Bacterial reduction rates of magnetite are of the same order of magnitude as those estimated for reduction by sulfide. If such remobilization of magnetite occurs in nature, it could have a major impact on sediment magnetism and diagenesis.

  20. Isothermal reduction of titanomagnetite concentrates containing coal

    Institute of Scientific and Technical Information of China (English)

    Tu Hu; Xue-wei Lü; Chen-guang Bai; Gui-bao Qiu

    2014-01-01

    The isothermal reduction of the Panzhihua titanomagnetite concentrates (PTC) briquette containing coal under argon atmosphere was investigated by thermogravimetry in an electric resistance furnace within the temperature range of 1250-1350°C. The samples reduced in argon at 1350°C for different time were examined by X-ray diffraction (XRD) analysis. Model-fitting and model-free methods were used to evaluate the apparent activation energy of the reduction reaction. It is found that the reduction rate is very fast at the early stage, and then, at a later stage, the reduction rate becomes slow and decreases gradually to the end of the reduction. It is also observed that the reduction of PTC by coal depends greatly on the temperature. At high temperatures, the reduction degree reaches high values faster and the final value achieved is higher than at low temperatures. The final phase composition of the reduced PTC-coal briquette consists in iron and fer-rous-pseudobrookite (FeTi2O5), while Fe2.75Ti0.25O4, Fe2.5Ti0.5O4, Fe2.25Ti0.75O4, ilmenite (FeTiO3) and wustite (FeO) are intermediate products. The reaction rate is controlled by the phase boundary reaction for reduction degree less than 0.2 with an apparent activation energy of about 68 kJ·mol-1 and by three-dimensional diffusion for reduction degree greater than 0.75 with an apparent activation energy of about 134 kJ·mol-1. For the reduction degree in the range of 0.2-0.75, the reaction rate is under mixed control, and the activation energy increases with the increase of the reduction degree.

  1. Achieve inventory reduction and improve customer service?

    Science.gov (United States)

    Moody, M C

    2000-05-01

    Is it really possible to achieve significant reductions in your manufacturing inventories while improving customer service? If you really want to achieve significant inventory reductions, focus on the root causes, and develop countermeasures and a work plan, to execute your countermeasures. Include measurements for recording your progress, and deploy your countermeasures until they are no longer required, or until new ones are needed.

  2. Transfinite reductions in orthogonal term rewriting systems

    NARCIS (Netherlands)

    J.R. Kennaway (Richard); J.W. Klop (Jan Willem); M.R. Sleep (Ronan); F.-J. de Vries (Fer-Jan)

    1991-01-01

    textabstractStrongly convergent reduction is the fundamental notion of reduction in infinitary orthogonal term rewriting systems (OTRSs). For these we prove the Transfinite Parallel Moves Lemma and the Compressing Lemma. Strongness is necessary as shown by counterexamples. Normal forms, which we

  3. Time-Weighted Balanced Stochastic Model Reduction

    DEFF Research Database (Denmark)

    Tahavori, Maryamsadat; Shaker, Hamid Reza

    2011-01-01

    A new relative error model reduction technique for linear time invariant (LTI) systems is proposed in this paper. Both continuous and discrete time systems can be reduced within this framework. The proposed model reduction method is mainly based upon time-weighted balanced truncation and a recent...

  4. Growth and poverty reduction in Tanzania

    DEFF Research Database (Denmark)

    Arndt, Channing; Demery, Lionel; McKay, Andy

    . The household survey data documents a limited reduction in consumption poverty over the period, and what poverty reduction there has been has mostly occurred in Dar es Salaam. Indicators of non-monetary poverty have gradually improved over the past 20 years but significant differences across the country remain....

  5. Growth and poverty reduction in Tanzania

    DEFF Research Database (Denmark)

    Arndt, Channing; Demery, Lionel; McKay, Andy

    . The household survey data documents a limited reduction in consumption poverty over the period, and what poverty reduction there has been has mostly occurred in Dar es Salaam. Indicators of non-monetary poverty have gradually improved over the past 20 years but significant differences across the country remain....

  6. An algorithm for reduct cardinality minimization

    KAUST Repository

    AbouEisha, Hassan M.

    2013-12-01

    This is devoted to the consideration of a new algorithm for reduct cardinality minimization. This algorithm transforms the initial table to a decision table of a special kind, simplify this table, and use a dynamic programming algorithm to finish the construction of an optimal reduct. Results of computer experiments with decision tables from UCI ML Repository are discussed. © 2013 IEEE.

  7. Handling Biological Complexity Using Kron Reduction

    NARCIS (Netherlands)

    Jayawardhana, Bayu; Rao, Shodhan; Sikkema, Ward; Bakker, Barbara; Camlibel, Kanat; Julius, Agung; Pasumarthy, Ramkrishna; Scherpen, Jacquelien

    2015-01-01

    We revisit a model reduction method for detailed-balanced chemical reaction networks based on Kron reduction on the graph of complexes. The resulting reduced model preserves a number of important properties of the original model, such as, the kinetics law and identity of the chemical species. For de

  8. Biological sulphate reduction with synthesis gas.

    NARCIS (Netherlands)

    Houten, van R.T.

    1996-01-01

    The objectives of this thesis are (1) to study the feasibility of using synthesis gas as electron donor and carbon source for biological sulphate reduction and (2) to develop criteria for design and operation of gas- lift bioreactors for sulphate reduction using immobilized biomass.At appeared that

  9. Representations of reductive normal algebraic monoids

    OpenAIRE

    Doty, Stephen

    2014-01-01

    The rational representation theory of a reductive normal algebraic monoid (with one-dimensional center) forms a highest weight category, in the sense of Cline, Parshall, and Scott. This is a fundamental fact about the representation theory of reductive normal algebraic monoids. We survey how this result was obtained, and treat some natural examples coming from classical groups.

  10. Harm Reduction in MSW Substance Abuse Courses

    Science.gov (United States)

    Eversman, Michael H.

    2012-01-01

    Professional social work largely has endorsed the empirically supported paradigm of harm reduction in relation to substance abuse issues. Despite literature detailing similarities between social work and harm reduction, little is known about its presence in MSW substance abuse coursework. A purposive sample of 133 social work faculty from…

  11. Handling Biological Complexity Using Kron Reduction

    NARCIS (Netherlands)

    Jayawardhana, Bayu; Rao, Shodhan; Sikkema, Ward; Bakker, Barbara; Camlibel, Kanat; Julius, Agung; Pasumarthy, Ramkrishna; Scherpen, Jacquelien

    2015-01-01

    We revisit a model reduction method for detailed-balanced chemical reaction networks based on Kron reduction on the graph of complexes. The resulting reduced model preserves a number of important properties of the original model, such as, the kinetics law and identity of the chemical species. For

  12. Reduction of soil erosion on forest roads

    Science.gov (United States)

    Edward R. Burroughs; John G. King

    1989-01-01

    Presents the expected reduction in surface erosion from selected treatments applied to forest road traveledways, cutslopes, fillslopes, and ditches. Estimated erosion reduction is expressed as functions of ground cover, slope gradient, and soil properties whenever possible. A procedure is provided to select rock riprap size for protection of the road ditch.

  13. National Satellite Disaster Reduction Application Service

    Institute of Scientific and Technical Information of China (English)

    2008-01-01

    @@ The groundbreaking ceremony for National Satellite Disaster Reduction Application Service was held on January 22,2008 in Beijing.The establishment of the center will further improve the disaster monitoring system using remote sensing technology and provides a platform for the application of remote sensing technology and satellite constellation in China's disaster reduction and relief services.

  14. SELECTIVE CATALYTIC REDUCTION MERCURY FIELD SAMPLING PROJECT

    Science.gov (United States)

    A lack of data still exists as to the effect of selective catalytic reduction (SCR), selective noncatalytic reduction (SNCR), and flue gas conditioning on the speciation and removal of mercury (Hg) at power plants. This project investigates the impact that SCR, SNCR, and flue gas...

  15. Integrated Countermeasures for Urban Industrial Disaster Reduction

    Institute of Scientific and Technical Information of China (English)

    JIN Lei

    2001-01-01

    The 2nd UN World Conference on Disaster Reduction convened in July 1999 proposed the "Geneva Strategy" which highlighted the need that disaster reduction should be focused on cities and communities in the 21st Cent try. Having long been engaged in research on urban disaster reduction, the author noticed that although great importance has been attached to natural disasters and related accidents in recent years, little attention has been paid to urban industrial accidents that constitute the biggest threat to cities. Urban disaster reduction should be given enough attention whether in developing large and medium-sized cities or promoting the construction of small towns in China. Attention should be paid not only to the research on the mechanism of industrial accidents,but also to industrial construction and disaster reduction planning and layout. This is of strategic importance to sustainable development.

  16. Automated data reduction workflows for astronomy

    CERN Document Server

    Freudling, W; Bramich, D M; Ballester, P; Forchi, V; Garcia-Dablo, C E; Moehler, S; Neeser, M J

    2013-01-01

    Data from complex modern astronomical instruments often consist of a large number of different science and calibration files, and their reduction requires a variety of software tools. The execution chain of the tools represents a complex workflow that needs to be tuned and supervised, often by individual researchers that are not necessarily experts for any specific instrument. The efficiency of data reduction can be improved by using automatic workflows to organise data and execute the sequence of data reduction steps. To realize such efficiency gains, we designed a system that allows intuitive representation, execution and modification of the data reduction workflow, and has facilities for inspection and interaction with the data. The European Southern Observatory (ESO) has developed Reflex, an environment to automate data reduction workflows. Reflex is implemented as a package of customized components for the Kepler workflow engine. Kepler provides the graphical user interface to create an executable flowch...

  17. Dechlorination by combined electrochemical reduction and oxidation

    Institute of Scientific and Technical Information of China (English)

    CONG Yan-qing; WU Zu-cheng; TAN Tian-en

    2005-01-01

    Chlorophenols are typical priority pollutants listed by USEPA (U.S. Environmental Protection Agency). The removal of chlorophenol could be carried out by a combination of electrochemical reduction and oxidation method. Results showed that it was feasible to degrade contaminants containing chlorine atoms by electrochemical reduction to form phenol, which was further degraded on the anode by electrochemical oxidation. Chlorophenol removal rate was more than 90% by the combined electrochemical reduction and oxidation at current of 6 mA and pH 6. The hydrogen atom is a powerful reducing agent that reductively dechlorinates chlorophenols. The instantaneous current efficiency was calculated and the results indicated that cathodic reduction was the main contributor to the degradation of chlorophenol.

  18. [Reduction and positioning of cervical spine injuries].

    Science.gov (United States)

    Blauth, M; Knop, C; Bastian, L; Schmidt, U

    1998-01-01

    Prerequisites for successful reduction of cervical spine injuries are an exact analysis and classification of every lesion. In locked dislocations disc protrusion should be excluded prior to reduction by MRI or CT-scan. For manual reduction and closed manipulation by the trauma surgeon we use a halo-ring which is applied in local anaesthesia and fluoroscopic control. The anatomic position is maintained by a halo-fixator until surgery. Skeletal traction is used mainly for locked dislocations and late malalignements. Traction is provided by a halo-ring and weights up to 20 kg. Repeated clinical and neurological examinations are necessary to rule out overdistraction of the spine or neurologic deterioration. The weight may be reduced after reduction to 2 kg. For intraoperative positioning and reduction of cervical spine injuries we designed a special device which is connected to the halo ring and allows to fix the head and spine in any desired position. It may be used in prone or supine position of the patient. Operative reductions are rarely necessary on the cervical spine. Typical indication are fractures of posterior elements of the spine preventing closed reduction. Reduction manoeuvers depend on the kind of injury and are mainly composed of traction and a reversal of the trauma mechanism. The most severe complication is a neurologic deterioration. Reports in literature about 13 patients having sustained such a fate are showing the following: In most cases disc material dislocated in the spinal canal during reduction could be made responsible for the catastrophic course. Especially at risk are patients with open reduction from a posterior approach.

  19. Exploring the reductive capacity of Pyrococcus furiosus. The reduction of carboxylic acids and pyridine nucleotides

    OpenAIRE

    Ban, van den, A.W.

    2001-01-01

    This Ph.D. project started in 1997 and its main goal was to obtain insight in the reductive capacity of the hyperthermophilic archaeon Pyrococcus furiosus . The research was focused on the biocatalytic reduction of carboxylic acids.Reductions of carboxylic acids are interesting reactions, since the generated products, aldehydes and alcohols, are potentially applicable in the fine-chemical industry. However, the reduction of carboxylic acids to the corresponding aldehydes is a thermodynamicall...

  20. INDUSTRIAL BOILER RETROFIT FOR NOX CONTROL: COMBINED SELECTIVE NONCATALYTIC REDUCTION AND SELECTIVE CATALYTIC REDUCTION

    Science.gov (United States)

    The paper describes retrofitting and testing a 590 kW (2 MBtu/hr), oil-fired, three-pass, fire-tube package boiler with a combined selective noncatalytic reduction (SNCR) and selective catalytic reduction (SCR) system. The system demonstrated 85% nitrogen oxides (NOx) reduction w...

  1. Exploring the reductive capacity of Pyrococcus furiosus. The reduction of carboxylic acids and pyridine nucleotides

    NARCIS (Netherlands)

    Ban, van den E.C.D.

    2001-01-01

    This Ph.D. project started in 1997 and its main goal was to obtain insight in the reductive capacity of the hyperthermophilic archaeon Pyrococcus furiosus . The research was focused on the biocatalytic reduction of carboxylic acids.Reductions of carboxylic acids are interes

  2. Voltage-induced reduction of graphene oxide

    Science.gov (United States)

    Faucett, Austin C.

    Graphene Oxide (GO) is being widely researched as a precursor for the mass production of graphene, and as a versatile material in its own right for flexible electronics, chemical sensors, and energy harvesting applications. Reduction of GO, an electrically insulating material, into reduced graphene oxide (rGO) restores electrical conductivity via removal of oxygen-containing functional groups. Here, a reduction method using an applied electrical bias, known as voltage-induced reduction, is explored. Voltage-induced reduction can be performed under ambient conditions and avoids the use of hazardous chemicals or high temperatures common with standard methods, but little is known about the reduction mechanisms and the quality of rGO produced with this method. This work performs extensive structural and electrical characterization of voltage-reduced GO (V-rGO) and shows that it is competitive with standard methods. Beyond its potential use as a facile and eco-friendly processing approach, V-rGO reduction also offers record high-resolution patterning capabilities. In this work, the spatial resolution limits of voltage-induced reduction, performed using a conductive atomic force microscope probe, are explored. It is shown that arbitrary V-rGO conductive features can be patterned into insulating GO with nanoscale resolution. The localization of voltage-induced reduction to length scales < 10 nm allows studies of reduction reaction kinetics, using electrical current obtained in-situ, with statistical robustness. Methods for patterning V-rGO nanoribbons are then developed. After presenting sub-10nm patterning of V-rGO nanoribbons in GO single sheets and films, the performance of V-rGO nanoribbon field effect transistors (FETs) are demonstrated. Preliminary measurements show an increase in electrical current on/off ratios as compared to large-area rGO FETs, indicating transport gap modulation that is possibly due to quantum confinement effects.

  3. A defense of Hellwig-Kraus reductions

    CERN Document Server

    Mould, R A

    1999-01-01

    Aharonov and Albert analyze a thought experiment which they believe shows that quantum mechanical state reductions occur along temporal hypersurfaces in Minkowski space. They conclude that the covariant state reduction theory of Hellwig and Kraus does not apply. In Part I of this paper we disagree with this interpretation of the A-A experiment, and show the adequacy of the H-K theory. In Part II we examine the belief that H-K reductions produce self contradicting causal loops, and/or give rise to absurd boundary conditions. These objections to the theory are shown to be unfounded.

  4. A conceptual framework for noise reduction

    CERN Document Server

    Benesty, Jacob

    2015-01-01

    Though noise reduction and speech enhancement problems have been studied for at least five decades, advances in our understanding and the development of reliable algorithms are more important than ever, as they support the design of tailored solutions for clearly defined applications. In this work, the authors propose a conceptual framework that can be applied to the many different aspects of noise reduction, offering a uniform approach to monaural and binaural noise reduction problems, in the time domain and in the frequency domain, and involving a single or multiple microphones. Moreover, the derivation of optimal filters is simplified, as are the performance measures used for their evaluation.

  5. Structured building model reduction toward parallel simulation

    Energy Technology Data Exchange (ETDEWEB)

    Dobbs, Justin R. [Cornell University; Hencey, Brondon M. [Cornell University

    2013-08-26

    Building energy model reduction exchanges accuracy for improved simulation speed by reducing the number of dynamical equations. Parallel computing aims to improve simulation times without loss of accuracy but is poorly utilized by contemporary simulators and is inherently limited by inter-processor communication. This paper bridges these disparate techniques to implement efficient parallel building thermal simulation. We begin with a survey of three structured reduction approaches that compares their performance to a leading unstructured method. We then use structured model reduction to find thermal clusters in the building energy model and allocate processing resources. Experimental results demonstrate faster simulation and low error without any interprocessor communication.

  6. Suspension Hydrogen Reduction of Iron Oxide Concentrates

    Energy Technology Data Exchange (ETDEWEB)

    H.Y. Sohn

    2008-03-31

    The objective of the project is to develop a new ironmaking technology based on hydrogen and fine iron oxide concentrates in a suspension reduction process. The ultimate objective of the new technology is to replace the blast furnace and to drastically reduce CO2 emissions in the steel industry. The goals of this phase of development are; the performance of detailed material and energy balances, thermochemical and equilibrium calculations for sulfur and phosphorus impurities, the determination of the complete kinetics of hydrogen reduction and bench-scale testing of the suspension reduction process using a large laboratory flash reactor.

  7. Project identification for methane reduction options

    Energy Technology Data Exchange (ETDEWEB)

    Kerr, T.

    1996-12-31

    This paper discusses efforts directed at reduction in emission of methane to the atmosphere. Methane is a potent greenhouse gas, which on a 20 year timeframe may present a similar problem to carbon dioxide. In addition, methane causes additional problems in the form of smog and its longer atmospheric lifetime. The author discusses strategies for reducing methane emission from several major sources. This includes landfill methane recovery, coalbed methane recovery, livestock methane reduction - in the form of ruminant methane reduction and manure methane recovery. The author presents examples of projects which have implemented these ideas, the economics of the projects, and additional gains which come from the projects.

  8. Suspension Hydrogen Reduction of Iron Oxide Concentrates

    Energy Technology Data Exchange (ETDEWEB)

    H.Y. Sohn

    2008-03-31

    The objective of the project is to develop a new ironmaking technology based on hydrogen and fine iron oxide concentrates in a suspension reduction process. The ultimate objective of the new technology is to replace the blast furnace and to drastically reduce CO2 emissions in the steel industry. The goals of this phase of development are; the performance of detailed material and energy balances, thermochemical and equilibrium calculations for sulfur and phosphorus impurities, the determination of the complete kinetics of hydrogen reduction and bench-scale testing of the suspension reduction process using a large laboratory flash reactor.

  9. Controller reduction by preserving impulse response energy

    Science.gov (United States)

    Craig, Roy R., Jr.; Su, Tzu-Jeng

    1989-01-01

    A model order reduction algorithm based on a Krylov recurrence formulation is developed to reduce order of controllers. The reduced-order controller is obtained by projecting the full-order LQG controller onto a Krylov subspace in which either the controllability or the observability grammian is equal to the identity matrix. The reduced-order controller preserves the impulse response energy of the full-order controller and has a parameter-matching property. Two numerical examples drawn from other controller reduction literature are used to illustrate the efficacy of the proposed reduction algorithm.

  10. Asymmetric Ketone Reduction by Imine Reductases.

    Science.gov (United States)

    Lenz, Maike; Meisner, Jan; Quertinmont, Leann; Lutz, Stefan; Kästner, Johannes; Nestl, Bettina M

    2017-02-01

    The rapidly growing area of asymmetric imine reduction by imine reductases (IREDs) has provided alternative routes to chiral amines. Here we report the expansion of the reaction scope of IREDs by showing the stereoselective reduction of 2,2,2-trifluoroacetophenone. Assisted by an in silico analysis of energy barriers, we evaluated asymmetric hydrogenations of carbonyls and imines while considering the influence of substrate reactivity on the chemoselectivity of this novel class of reductases. We report the asymmetric reduction of C=N as well as C=O bonds catalysed by members of the IRED enzyme family. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Boundary Fluctuations and A Reduction Entropy

    CERN Document Server

    Herzog, Christopher

    2016-01-01

    The boundary Weyl anomalies live on a codimension-1 boundary, $\\partial {\\cal M}$. The entanglement entropy originates from infinite correlations on both sides of a codimension-2 surface, $\\Sigma$. Motivated to have a further understanding of the boundary effects, we introduce a notion of reduction entropy, which, guided by thermodynamics, is a combination of the boundary effective action and the boundary stress tensor defined by allowing the metric on $\\partial {\\cal M}$ to fluctuate. We discuss how a reduction might be performed so that the reduction entropy reproduces the entanglement structure.

  12. Multiloop Integrand Reduction for Dimensionally Regulated Amplitudes

    CERN Document Server

    Mastrolia, P; Ossola, G; Peraro, T

    2013-01-01

    We present the integrand reduction via multivariate polynomial division as a natural technique to encode the unitarity conditions of Feynman amplitudes. We derive a recursive formula for the integrand reduction, valid for arbitrary dimensionally regulated loop integrals with any number of loops and external legs, which can be used to obtain the decomposition of any integrand analytically with a finite number of algebraic operations. The general results are illustrated by applications to two-loop Feynman diagrams in QED and QCD, showing that the proposed reduction algorithm can also be seamlessly applied to integrands with denominators appearing with arbitrary powers.

  13. Development of Direct Reduction Process and Smelting Reduction Processes for the Steel Production

    Directory of Open Access Journals (Sweden)

    Kožuh S.

    2006-01-01

    Full Text Available Although the blast furnace and basic oxygen furnace are going to be primary routes for steel production in future, the steelmaking industry using the electric arc furnace route will continue to grow. The importance of high-quality steel products manufactured by direct reduction of iron ore and/or by smelting reduction processes has been increasing. In the past decade the world steel production by direct reduction rose by 140 per cent, from about 20 to about 49.5 Mt/year. In this paper major industrial processes involving direct reduction and smelting reduction of iron ore are described, and their development is analysed.

  14. Minimal Reductions and Cores of Edge Ideals

    CERN Document Server

    Fouli, Louiza

    2010-01-01

    We study minimal reductions of edge ideals of graphs containing a unique even cycle, and determine restrictions on the coefficients of the generators of these minimal reductions. We focus our attention on two special subclasses of edge ideals; the first is edge ideals of even cycles and the second is edge ideals of even cycles with an arbitrary number of whiskers. We prove that $\\rm{core}(I)=\\mathfrak{m} I$, where $I$ is the edge ideal in the corresponding localized polynomial ring and $\\mathfrak{m}$ is the maximal ideal of this ring. Moreover, we show that the core is obtained as a finite intersection of homogeneous minimal reductions in the case of even cycles. The formula for the core does not hold in general for the edge ideal of any graph and we provide a counterexample. In particular, we show in this example that the core is not obtained as a finite intersection of general minimal reductions.

  15. Bubble Drag Reduction Requires Large Bubbles

    Science.gov (United States)

    Verschoof, Ruben A.; van der Veen, Roeland C. A.; Sun, Chao; Lohse, Detlef

    2016-09-01

    In the maritime industry, the injection of air bubbles into the turbulent boundary layer under the ship hull is seen as one of the most promising techniques to reduce the overall fuel consumption. However, the exact mechanism behind bubble drag reduction is unknown. Here we show that bubble drag reduction in turbulent flow dramatically depends on the bubble size. By adding minute concentrations (6 ppm) of the surfactant Triton X-100 into otherwise completely unchanged strongly turbulent Taylor-Couette flow containing bubbles, we dramatically reduce the drag reduction from more than 40% to about 4%, corresponding to the trivial effect of the bubbles on the density and viscosity of the liquid. The reason for this striking behavior is that the addition of surfactants prevents bubble coalescence, leading to much smaller bubbles. Our result demonstrates that bubble deformability is crucial for bubble drag reduction in turbulent flow and opens the door for an optimization of the process.

  16. British Universities' Responses to Financial Reductions.

    Science.gov (United States)

    Sizer, John

    1987-01-01

    The impact on nine British universities' of substantial financial reductions in 1980-81 and the policy implications for national funding agencies are examined. Implementation of institutional retrenchment plans and the role of high-level administrators are discussed. (MSE)

  17. Drag Reduction by Microvortexes in Transverse Microgrooves

    Directory of Open Access Journals (Sweden)

    Bao Wang

    2014-07-01

    Full Text Available A transverse microgrooved surface was employed here to reduce the surface drag force by creating a slippage in bottom layer in turbulent boundary layer. A detailed simulation and experimental investigation on drag reduction by transverse microgrooves were given. The computational fluid dynamics simulation, using RNG k-ε turbulent model, showed that the vortexes were formed in the grooves and they were a main reason for the drag reduction. On the upside of the vortex, the revolving direction was consistent with the main flow, which decreased the flow shear stress by declining the velocity gradient. The experiments were carried out in a high-speed water tunnel with flow velocity varying from 17 to 19 m/s. The experimental results showed that the drag reduction was about 13%. Therefore, the computational and experimental results were cross-checked and consistent with each other to prove that the presented approach achieved effective drag reduction underwater.

  18. Heat reduction of the MWD telemetry system

    OpenAIRE

    Matviykiv, Taras

    2012-01-01

    In this paper the simplified thermal model of conventional downhole MWD (Measurements While Drilling) telemetry system has been made. The heat reduction methods for the IC (integrated circuits) components of downhole drilling tools have been analyzed.

  19. Three Syntactic Theories for Combinatory Graph Reduction

    DEFF Research Database (Denmark)

    Danvy, Olivier; Zerny, Ian

    2011-01-01

    We present a purely syntactic theory of graph reduction for the canonical combinators S, K, and I, where graph vertices are represented with evaluation contexts and let expressions. We express this syntactic theory as a reduction semantics, which we refocus into the first storeless abstract machine...... for combinatory graph reduction, which we refunctionalize into the first storeless natural semantics for combinatory graph reduction.We then factor out the introduction of let expressions to denote as many graph vertices as possible upfront instead of on demand, resulting in a second syntactic theory, this one...... of term graphs in the sense of Barendregt et al. The corresponding storeless abstract machine and natural semantics follow mutatis mutandis. We then interpret let expressions as operations over a global store (thus shifting, in Strachey's words, from denotable entities to storable entities), resulting...

  20. Marine Debris Research, Prevention, and Reduction Act

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — The Marine Debris Research, Prevention, and Reduction Act legally establishes the National Oceanic and Atmospheric Administration's (NOAA) Marine Debris Program. The...