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Sample records for rhodium deposits poor

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

    PubMed

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

    2016-07-01

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

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

    PubMed

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

    2016-07-01

    The Ni-base superalloy CMSX 4 used in the turbine blades of aircraft engines was coated with rhodium layer (0.5-μm thick). Next coated CMSX 4 superalloy was aluminized by the CVD method. The rhodium modified aluminide coating and nonmodified aluminide coating were oxidized at 1100°C at the air atmosphere. The rhodium modified aluminide coating showed about twice better oxidation resistance than the nonmodified one. The spallation equal 62% of the total area was observed on the surface of the nonmodified coating whereas only 36% spallation area was observed on the surface of the rhodium modified aluminide coating after the oxidation test. The oxide layer formed on the surface of the nonmodified coating was composed of nonprotective (Ni,Cr)Al2 O4 and (Ni,Cr)O phases. Aluminium in the coating reacts with oxygen, forming a protective α-Al2 O3 oxide on the surface of the rhodium modified aluminide coating. When the oxide cracks and spalls due to oxidation, additional aluminium from the coating diffuses to the surface to form the oxide. The presence of protective Al2 O3 oxide on the surface of the rhodium modified aluminide coating slows coating degradation. Therefore, rhodium modified aluminide coating has better oxidation resistance than the nonmodified one. PMID:27018853

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

    PubMed

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

    2016-03-01

    The CMSX 4 superalloy was coated with rhodium 0.5-μm thick layer and next aluminized by the CVD method. The coating consisted of two layers: the additive and the interdiffusion one. The outward diffusion of nickel from the substrate turned out to be a coating growth dominating factor. The additive layer consists of the β-NiAl phase, whereas the interdiffusion layer consists of the β-NiAl phase with precipitates of σ and μ phases. Rhodium has dissolved in the coating up to the same level in the matrix and in the precipitates. The oxidation test proved that the rhodium modified aluminide coating showed about twice better oxidation resistance than the nonmodified one. PMID:26892917

  4. Transition metal oxides deposited on rhodium and platinum: Surface chemistry and catalysis

    SciTech Connect

    Boffa, A B

    1994-07-01

    The surface chemistry and catalytic reactivity of transition metal oxides deposited on Rh and Pt substrates has been examined in order to establish the role of oxide-metal interactions in influencing catalytic activity. The oxides investigated included titanium oxide (TiOx), vanadium oxide (VOx), iron oxide (FeOx), zirconium oxide (ZrOx), niobium oxide (NbOx), tantalum oxide (TaOx), and tungsten oxide (WOx). The techniques used to characterize the sample included AES, XPS, LEED, TPD, ISS, and STM. After characterization of the surface in UHV, the sample was enclosed in an atmospheric reaction cell to measure the influence of the oxide deposits on the catalytic activity of the pure metal for CO and CO{sub 2} hydrogenation. The oxide deposits were found to strongly enhance the reactivity of the Rh foil. The rates of methane formation were promoted by up to 15 fold with the maximum in rate enhancement occurring at oxide coverages of approximately 0.5 ML. TiOx TaOx, and NbOx were the most effective promoters and were stable in the highest oxidation states during both reactions (compared to VOx, WOx, and FeOx). The trend in promoter effectiveness was attributed to the direct relationship between oxidation state and Lewis acidity. Bonding at the metal oxide/metal interface between the oxygen end of adsorbed CO and the Lewis acidic oxide was postulated to facilitate C-O bond dissociation and subsequent hydrogenation. 192 refs.

  5. Direct deposition of trivalent rhodium hydroxide nanoparticles onto a semiconducting layered calcium niobate for photocatalytic hydrogen evolution.

    PubMed

    Hata, Hideo; Kobayashi, Yoji; Bojan, Vince; Youngblood, W Justin; Mallouk, Thomas E

    2008-03-01

    Well-dispersed Rh(OH)3 nanoparticles were deposited in the interlayer galleries of a Dion-Jacobson type layered perovskite (ACa2Nb3O10: A=H or K). X-ray photoelectron spectra and zeta potential measurements suggest covalent bonding (Rh-O-Nb) between the nanoparticles and the niobate sheets. After calcination of Rh(OH)3/KCa2Nb3O10 at 350 degrees C in air, interlayer Rh(OH)3 nanoparticles were transformed to Rh2O3 and showed higher photocatalytic activity for hydrogen evolution using methanol as a sacrificial electron donor. PMID:18266334

  6. Multiferroic rhodium clusters.

    PubMed

    Ma, Lei; Moro, Ramiro; Bowlan, John; de Heer, Walt A; Kirilyuk, Andrei

    2014-10-10

    Simultaneous magnetic and electric deflection measurements of rhodium clusters (Rh(N), 6 ≤ N ≤ 40) reveal ferromagnetism and ferroelectricity at low temperatures, while neither property exists in the bulk metal. Temperature-independent magnetic moments (up to 1 μ(B) per atom) are observed, and superparamagnetic blocking temperatures up to 20 K. Ferroelectric dipole moments on the order of 1D with transition temperatures up to 30 K are observed. Ferromagnetism and ferroelectricity coexist in rhodium clusters in the measured size range, with size-dependent variations in the transition temperatures that tend to be anticorrelated in the range n = 6-25. Both effects diminish with size and essentially vanish at N = 40. The ferroelectric properties suggest a Jahn-Teller ground state. These experiments represent the first example of multiferroic behavior in pure metal clusters. PMID:25375737

  7. Role of poorly permeable deposits in the formation of economic yield of groundwaters

    SciTech Connect

    Plugina, T.A.

    1986-05-01

    The formation of the economic yield of groundwaters in layered watersaturated systems represented by an alternation of persistent freely and poorly permeable deposits has a quite complex character. In addition to the water in storage in the exploited aquifer, leakage from adjacent aquifers and surface waters through poorly permeable deposits and drawdown of the water in storage in the latter participate in the formation of the groundwater flow. These factors play a dominant role in the formation of the economic yield. At one of the groundwater reservoirs in the Dnepr-Donetsk artesian basin, the role of the 100-m stratum of Bathonian-Callovian clays in the formation of the economic yield of groundwaters was estimated. The studies presented in this paper were based on pumping tests during which observations were carried out not only in the aquifers but also in the poorly permeable deposits. Refinement of the hydrogeological parameters and analysis of their effect on the formation of groundwater flows were carried out on a digital model. The initial parameters of the model were determined from the data of the experimental groundwater flow studies, thermometry, and compression tests of the clays.

  8. Could Poor Fens BE More Sensitive than Bogs to Elevated N Deposition in the Oil Sands Region of Northern Alberta?

    NASA Astrophysics Data System (ADS)

    Wieder, R. K.; Vile, M. A.; Scott, K. D.

    2015-12-01

    Bogs and fens cover 29% of the 140,000 km2 Oil Sands Administrative Area (OSAA) in northern Alberta, a region characterized by quite low background N deposition (1-2 kg/ha/yr). However, development of the oil sands resource has led to increasing emission of nitrogen oxides, which are then returned to regional ecosystems as elevated atmospheric N deposition. Given the nutrient deficient nature of bogs and poor fens, elevated N deposition from oil sands development could potentially affect peatland ecosystem structure and function. To evaluate the ecosystem-level effects of N deposition, since 2011, we have experimentally applied N to a bog and a poor fen near Mariana Lakes, Alberta, located far enough from the OSAA to be unaffected by oil sands emissions. Treatments include simulated rainfall equivalent to N deposition of 0, 5, 10, 15, 20, and 25 kg/ha/yr, plus control plots receiving no added water (3 replicate plots per site per N treatment). Concentrations of NH4+-N, NO3- N, and DON at the top of the peatland water table did not increase with increasing N deposition, averaging 0.61, 0.09, and 1.07 mg/L, respectively, in the bog, and 0.53, 0.10, and 0.81 mg/L, respectively, in the poor fen. Ericaceous shrub abundance increased with increasing N deposition in both the bog and the poor fen, although plot-scale greenness (hand-held spectral measurement of the Normalized Difference Red Edge (NDRE) index) increased with N deposition in the poor fen, but not in the bog. Segmented regression indicated that in the poor fen, at N deposition above 14-16 kg/ha/yr, total microbial, bacterial, and fungal biomass in the top 5 cm of peat increased with N deposition, with no effect at lower N deposition. No effect of N deposition on microbial, bacterial, or fungal biomass was observed at 5-10 cm in the poor fen, or at either 0-5 or 5-10 cm in the bog. In the poor fen, microbial, bacterial, and fungal biomass increased with NDRE, but the effect was not significant in the bog

  9. EVIDENCE FOR CO DISSOCIATION ON RHODIUM SURFACES

    SciTech Connect

    Castner, D.G.; Dubois, L.H.; Sexton, B.A.; Somorjai, G.A.

    1980-06-01

    Carbon monoxide adsorbs molecularly on rhodium surfaces at 300K, but if the rhodium samples are heated in the presence of carbon monoxide, there is evidence for carbon-oxygen bond breaking at step and/or defect sites. The effects of step and defect site density, subsurface oxygen concentration, and oxygen dissolution into the rhodium lattice on CO dissociation are discussed.

  10. Effects of irradiation and annealing on deep levels in rhodium-doped p-GaAs grown by metal-organic chemical-vapor deposition

    NASA Astrophysics Data System (ADS)

    Naz, Nazir A.; Qurashi, Umar S.; Iqbal, M. Zafar

    2011-06-01

    This paper reports a detailed study of the effects of irradiation and thermal annealing on deep levels in Rh-doped p-type GaAs grown by low-pressure metal-organic chemical-vapor deposition, using deep level transient spectroscopy (DLTS) technique. It is found upon irradiation with alpha particles that, in addition to the radiation-induced defect peaks, all the Rh-related peaks observed in majority, as well as minority-carrier emission DLTS scans show an increase in their respective concentrations. The usually observed α-induced defects Hα1, Hα2, and Hα3 are found to have lower introduction rates in Rh-doped samples, as compared to reference samples (not doped with Rh). Alpha-irradiation has been found to decompose the two minority carrier emitting bands (one at low temperature ˜150 K and the other at ˜380 K) observed prior to irradiation into distinct peaks corresponding to deep levels Rh1 and Rh2 and EL2 and Rh3, respectively. A similar effect is also observed for the majority-carrier emitting band composed of hole emission from deep levels RhA and RhB, which separate out well upon irradiation. Further, from the double-correlation DLTS measurements, the emission rates of carriers from the radiation-enhanced peaks corresponding to deep levels Rh1, Rh2, Rh3, and RhC were found to be dependent on junction electric field. For RhC, the field dependence data have been analyzed in terms of the Poole-Frenkel model employing a 3-dimensional Coulomb potential with q = 2e (electronic charge). Temperature dependence of the hole capture cross-sections of the levels RhA and RhC was also studied quantitatively. The observed dependence of the hole capture cross-section of RhC on temperature can be interpreted in terms of multiphonon capture model, yielding a capture barrier of 0.2 eV and σ(∞) = 2.3 × 10-14 cm2. The results of irradiation and isochronal thermal annealing study, in combination with the theoretical analysis of the field dependence of hole emission data

  11. Rhodium Nanoparticles for Ultraviolet Plasmonics

    NASA Astrophysics Data System (ADS)

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

    2015-02-01

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

  12. Rhodium nanoparticles for ultraviolet plasmonics.

    PubMed

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

    2015-02-11

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

  13. 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

    NASA Astrophysics Data System (ADS)

    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 < 5.10-7 Pa) have been prepared. The effect of rhodium cluster size and copper or silver addition on catalytic properties of rhodium in the 1,3 butadiène hydrogenation was studied. Results show that the reaction is sensitive to the size of rhodium aggregates and that there is an important difference between the effect of copper and silver on the rhodium properties. Indeed copper forms an alloy with rhodium and provokes a poison effect on the activity of the noble metal, whereas silver exhibits a mask effect on the rhodium particles without forming alloy with it. Des échantillons mono-métalliques au rhodium et bimétalliques rhodium-cuivre et rhodium-argent déposés sur une 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.

  14. Do deposit-feeders compete? Isotopic niche analysis of an invasion in a species-poor system.

    PubMed

    Karlson, Agnes M L; Gorokhova, Elena; Elmgren, Ragnar

    2015-01-01

    Successful establishment of invasive species is often related to the existence of vacant niches. Competition occurs when invaders use the same limiting resources as members of the recipient community, which will be reflected in some overlap of their trophic niches. The concept of isotopic niche has been used to study trophic niche partitioning among species. Here, we present a two-year field study comparing isotopic niches of the deposit-feeding community in a naturally species-poor system. The isotopic niche analyses showed no overlap between a recent polychaete invader and any of the native species suggesting that it has occupied a vacant niche. Its narrow isotopic niche suggests specialized feeding, however, the high δ(15)N values compared to natives are most likely due to isotope fractionation effects related to nitrogen recycling and a mismatch between biological stoichiometry of the polychaete and the sediment nitrogen content. Notably, highly overlapping isotopic niches were inferred for the native species, which is surprising in a food-limited system. Therefore, our results demonstrate that invaders may broaden the community trophic diversity and enhance resource utilization, but also raise questions about the congruence between trophic and isotopic niche concepts and call for careful examination of assumptions underlying isotopic niche interpretation. PMID:25988260

  15. Do deposit-feeders compete? Isotopic niche analysis of an invasion in a species-poor system

    PubMed Central

    Karlson, Agnes M. L.; Gorokhova, Elena; Elmgren, Ragnar

    2015-01-01

    Successful establishment of invasive species is often related to the existence of vacant niches. Competition occurs when invaders use the same limiting resources as members of the recipient community, which will be reflected in some overlap of their trophic niches. The concept of isotopic niche has been used to study trophic niche partitioning among species. Here, we present a two-year field study comparing isotopic niches of the deposit-feeding community in a naturally species-poor system. The isotopic niche analyses showed no overlap between a recent polychaete invader and any of the native species suggesting that it has occupied a vacant niche. Its narrow isotopic niche suggests specialized feeding, however, the high δ15N values compared to natives are most likely due to isotope fractionation effects related to nitrogen recycling and a mismatch between biological stoichiometry of the polychaete and the sediment nitrogen content. Notably, highly overlapping isotopic niches were inferred for the native species, which is surprising in a food-limited system. Therefore, our results demonstrate that invaders may broaden the community trophic diversity and enhance resource utilization, but also raise questions about the congruence between trophic and isotopic niche concepts and call for careful examination of assumptions underlying isotopic niche interpretation. PMID:25988260

  16. Rhodium(i), rhodium(iii) and iridium(iii) carbaporphyrins.

    PubMed

    Adiraju, Venkata A K; Ferrence, Gregory M; Lash, Timothy D

    2016-09-21

    Treatment of a benzocarbaporphyrin with [Rh(CO)2Cl]2 in refluxing dichloromethane gave a rhodium(i) dicarbonyl complex, and further reaction in refluxing pyridine afforded an organometallic rhodium(iii) derivative. The carbaporphyrin also reacted with [Ir(COD)Cl]2 and pyridine in refluxing p-xylene to generate a related iridium(iii) compound. These novel metalated porphyrinoids retained strongly diatropic characteristics and were fully characterized by XRD. PMID:27529466

  17. Superconductivity in zirconium-rhodium alloys

    NASA Technical Reports Server (NTRS)

    Zegler, S. T.

    1969-01-01

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

  18. Time-resolved, in situ DRIFTS/EDE/MS studies on alumina-supported rhodium catalysts: effects of ceriation and zirconiation on rhodium-CO interactions.

    PubMed

    Kroner, Anna B; Newton, Mark A; Tromp, Moniek; Roscioni, Otello M; Russell, Andrea E; Dent, Andrew J; Prestipino, Carmelo; Evans, John

    2014-10-01

    The effects of ceria and zirconia on the structure-function properties of supported rhodium catalysts (1.6 and 4 wt % Rh/γ-Al2O3) during CO exposure are described. Ceria and zirconia are introduced through two preparation methods: 1) ceria is deposited on γ-Al2O3 from [Ce(acac)3] and rhodium metal is subsequently added, and 2) through the controlled surface modification (CSM) technique, which involves the decomposition of [M(acac)x] (M=Ce, x=3; M=Zr, x=4) on Rh/γ-Al2O3. The structure-function correlations of ceria and/or zirconia-doped rhodium catalysts are investigated by diffuse reflectance infrared Fourier-transform spectroscopy/energy-dispersive extended X-ray absorption spectroscopy/mass spectrometry (DRIFTS/EDE/MS) under time-resolved, in situ conditions. CeOx and ZrO2 facilitate the protection of Rh particles against extensive oxidation in air and CO. Larger Rh core particles of ceriated and zirconiated Rh catalysts prepared by CSM are observed and compared with Rh/γ-Al2O3 samples, whereas supported Rh particles are easily disrupted by CO forming mononuclear Rh geminal dicarbonyl species. DRIFTS results indicate that, through the interaction of CO with ceriated Rh particles, a significantly larger amount of linear CO species form; this suggests the predominance of a metallic Rh phase. PMID:25044889

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

    PubMed Central

    Najjar, Renato; de Oliveira, Elizabeth; Zyngier, Szulim Ber

    1997-01-01

    The distribution of rhodium in Balb/c mice following intraperitoneal (ip) administration of a solution of adduct of rhodium propionate and sodium isonicotinate has been investigated. The metal concentration was determined in blood and in the following organ tissues: brain, heart, lung, liver, spleen, kidney, testes, and uterus/ovary, and the rhodium concentration was obtained by Inductively Coupled Argon Atomic Emission Spectroscopy (ICP-AES). The metal was detected in all organ tissues examined, mainly in spleen, liver, uterus/ovary and heart. Nine days after the injection, traces of rhodium were found in the liver and kidneys and, twenty days after the injection, only in the liver. PMID:18475764

  20. Monodisperse Platinum and Rhodium Nanoparticles as Model Heterogeneous Catalysts

    SciTech Connect

    Grass, Michael Edward

    2008-09-01

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

  1. Cyclopentadiene-mediated hydride transfer from rhodium complexes.

    PubMed

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

    2016-07-12

    Attempts to generate a proposed rhodium hydride catalytic intermediate instead resulted in isolation of (Cp*H)Rh(bpy)Cl (1), a pentamethylcyclopentadiene complex, formed by C-H bond-forming reductive elimination from the fleeting rhodium hydride. The hydride transfer ability of diene 1 was explored through thermochemistry and hydride transfer reactions, including the reduction of NAD(+). PMID:26949917

  2. Poor correlation between the removal or deposition of pollen grains and frequency of pollinator contact with sex organs.

    PubMed

    Sakamoto, Ryota L; Morinaga, Shin-Ichi

    2013-09-01

    Pollinators deposit pollen grains on stigmas and remove pollen grains from anthers. The mechanics of these transfers can now be quantified with the use of high-speed video. We videoed hawkmoths, carpenter bees, and swallowtail butterflies pollinating Clerodendrum trichotomum. The number of grains deposited on stigmas did not vary significantly with the number of times pollinators contacted stigmas. In contrast, pollen removal from the anthers increased significantly with the number of contacts to anthers. Pollen removal varied among the three types of pollinators. Also, the three types carried pollen on different parts of their bodies. In hawkmoths and carpenter bees, a large number of contacted body part with anthers differed significantly from the body part that attached a large number of pollen grains. Our results indicate that a large number of contacts by pollinators does not increase either the male or female reproductive success of plants compared to a small number of contacts during a visit. PMID:23928839

  3. Poor correlation between the removal or deposition of pollen grains and frequency of pollinator contact with sex organs

    NASA Astrophysics Data System (ADS)

    Sakamoto, Ryota L.; Morinaga, Shin-Ichi

    2013-09-01

    Pollinators deposit pollen grains on stigmas and remove pollen grains from anthers. The mechanics of these transfers can now be quantified with the use of high-speed video. We videoed hawkmoths, carpenter bees, and swallowtail butterflies pollinating Clerodendrum trichotomum. The number of grains deposited on stigmas did not vary significantly with the number of times pollinators contacted stigmas. In contrast, pollen removal from the anthers increased significantly with the number of contacts to anthers. Pollen removal varied among the three types of pollinators. Also, the three types carried pollen on different parts of their bodies. In hawkmoths and carpenter bees, a large number of contacted body part with anthers differed significantly from the body part that attached a large number of pollen grains. Our results indicate that a large number of contacts by pollinators does not increase either the male or female reproductive success of plants compared to a small number of contacts during a visit.

  4. Rhodium oxides in unusual oxidation states

    NASA Astrophysics Data System (ADS)

    Reisner, Barbara Alice

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

  5. Vapor deposition of thin films

    DOEpatents

    Smith, David C.; Pattillo, Stevan G.; Laia, Jr., Joseph R.; Sattelberger, Alfred P.

    1992-01-01

    A highly pure thin metal film having a nanocrystalline structure and a process of preparing such highly pure thin metal films of, e.g., rhodium, iridium, molybdenum, tungsten, rhenium, platinum, or palladium by plasma assisted chemical vapor deposition of, e.g., rhodium(allyl).sub.3, iridium(allyl).sub.3, molybdenum(allyl).sub.4, tungsten(allyl).sub.4, rhenium(allyl).sub.4, platinum(allyl).sub.2, or palladium(allyl).sub.2 are disclosed. Additionally, a general process of reducing the carbon content of a metallic film prepared from one or more organometallic precursor compounds by plasma assisted chemical vapor deposition is disclosed.

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

    PubMed

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

    2016-01-01

    Natural enzymes use molecular recognition to perform exquisitely selective transformations on nucleic acids, proteins, and natural products. Rhodium(II) catalysts mimic this selectivity, using molecular recognition to allow selective modification of proteins with a variety of functionalized diazo reagents. The rhodium catalysts and the diazo reactivity have been successfully applied to a variety of protein folds, the chemistry succeeds in complex environments such as cell lysate, and a simple protein blot method accurately assesses modification efficiency. The studies with rhodium catalysts provide a new tool to study and probe protein-binding events, as well as a new synthetic approach to protein conjugates for medical, biochemical, or materials applications. PMID:27586326

  7. Structural properties of small rhodium clusters

    NASA Astrophysics Data System (ADS)

    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.

  8. Structural properties of small rhodium clusters

    SciTech Connect

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

    2015-04-24

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

  9. Polyethylene-bound rhodium(I) hydrogenation catalysts

    SciTech Connect

    Bergbreiter, D.E.; Chandran, R.

    1987-01-07

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

  10. Low gravity containerless processing of immiscible gold rhodium alloys

    NASA Technical Reports Server (NTRS)

    Andrews, J. Barry

    1986-01-01

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

  11. Experimental and theoretical deposition rates from salt-seeded combustion gases of a Mach 0.3 burner rig

    NASA Technical Reports Server (NTRS)

    Santoro, G. J.; Kohl, F. J.; Stearns, C. A.; Gokoglu, S. A.; Rosner, D. E.

    1984-01-01

    Deposition rates on platinum-rhodium cylindrical collectors rotating in the cross streams of the combustion gases of a salt-seeded Mach 0.3 burner rig were determined. The collectors were internally air cooled so that their surface temperatures could be widely varied while they were exposed to constant combustion gas temperatures. The deposition rates were compared with those predicted by the chemically frozen boundary layer (CFBL) computer program, which is based on multicomponent vapor transport through the boundary layer. Excellent agreement was obtained between theory and experiment for the NaCl-seeded case, but the agreement lessened as the seed was changed to synthetic sea salt, NaNO3, and K2SO4, respectively, and was particularly poor in the case of Na2SO4. However, when inertial impaction was assumed to be the deposition mechanism for the Na2SO4 case, the predicted rates agreed well with the experimental rates. The former were calculated from a mean particle diameter that was derived from the measured intial droplet size distribution of the solution spray. Critical experiments showed that liquid phase deposits were blown off the smooth surface of the platinum-rhodium collectors by the aerodynamic shear forces of the high-velocity combustion gases but that rough or porous surfaces retained their liquid deposits.

  12. Size control of rhodium particles of silica-supported catalysts using water-in-oil microemulsion

    NASA Astrophysics Data System (ADS)

    Kishida, Masahiro; Hanaoka, Toshiaki; Kim, Won Young; Nagata, Hideo; Wakabayashi, Katsuhiko

    1997-11-01

    Effects of components of water-in-oil microemulsions on rhodium particle sizes of silica-supported rhodium catalysts were investigated in the catalyst preparation method using microemulsion. In the case of the microemulsion of polyoxyethylene(23)dodecyl ether/ n-alcohols/RhCl 3 aq., the rhodium particle size increased from 3.4 to 5.0 nm as the specific permittivity of the organic solvent increased. The chain length of hydrophilic group of polyoxyethylene- p-nonylphenyl ether ( n = 5 to 15) employed as surfactants had an effect on the rhodium particle size where the rhodium size ranged between 2.0 and 3.6 nm. The rhodium particle size was 1.5 nm in the case of sodium bis(2-ethylhexyl) sulfocuccinate and this value was found to be the smallest. These results could be interpreted in terms of the adsorption of the surfactant on rhodium-hydrazine particle surface.

  13. Monodisperse colloidal metal particle from nonaqueous solutions: catalytic behavior in hydrogenation of but-1-ene of platinum, palladium, and rhodium particles supported on pumice

    SciTech Connect

    Boutonnet, M.; Kizling, J.; Mintsa-Eya, V.; Choplin, A.; Touroude, R.; Maire, G.; Stenius, P.

    1987-01-01

    Metal catalysts have been prepared by depositing monodisperse particles of platinum (2-3 nm), rhodium (2-3 nm), or palladium (5 nm) prepared in reversed micellar solutions on pumice. The particles are well dispersed on the support whereas particles deposited from aqueous or alcoholic solution give large aggregates. The catalytic properties of these different catalysts in the deuteration, isomerization, and hydrogen-deuterium exchange of but-1-ene have been compared. The activities calculated per metal surface atom are similar. However, platinum prepared from microemulsions show unusually high selectivity in the isomerization reaction, and for such particles dehydrogenated species are active in the exchange reaction. The specificity of rhodium and palladium catalysts is independent of the mode of preparation. The reaction mechanisms are discussed.

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

    SciTech Connect

    Parker, A.M.; Thoennessen, M.

    2012-07-15

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

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

    PubMed

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

    2014-12-01

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

  16. Electronic and magnetic properties of small rhodium clusters

    SciTech Connect

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

    2015-04-24

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

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

    PubMed Central

    Selander, Nicklas; Worrell, Brady T.

    2013-01-01

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

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

    PubMed

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

    2014-04-16

    Metal nanoparticles are commonly supported on metal oxides, but their utility as catalysts is limited by coarsening at high temperatures. Rhodium oxide and rhodium metal nanoparticles on niobate and tantalate supports are anomalously stable. To understand this, the nanoparticle-support interaction was studied by isothermal titration calorimetry (ITC), environmental transmission electron microscopy (ETEM), and synchrotron X-ray absorption and scattering techniques. Nanosheets derived from the layered oxides KCa2Nb3O10, K4Nb6O17, and RbTaO3 were compared as supports to nanosheets of Na-TSM, a synthetic fluoromica (Na0.66Mg2.68(Si3.98Al0.02)O10.02F1.96), and α-Zr(HPO4)2·H2O. High surface area SiO2 and γ-Al2O3 supports were also used for comparison in the ITC experiments. A Born-Haber cycle analysis of ITC data revealed an exothermic interaction between Rh(OH)3 nanoparticles and the layered niobate and tantalate supports, with ΔH values in the range -32 kJ·mol(-1) Rh to -37 kJ·mol(-1) Rh. In contrast, the interaction enthalpy was positive with SiO2 and γ-Al2O3 supports. The strong interfacial bonding in the former case led to "reverse" ripening of micrometer-size Rh(OH)3, which dispersed as 0.5 to 2 nm particles on the niobate and tantalate supports. In contrast, particles grown on Na-TSM and α-Zr(HPO4)2·H2O nanosheets were larger and had a broad size distribution. ETEM, X-ray absorption spectroscopy, and pair distribution function analyses were used to study the growth of supported nanoparticles under oxidizing and reducing conditions, as well as the transformation from Rh(OH)3 to Rh nanoparticles. Interfacial covalent bonding, possibly strengthened by d-electron acid/base interactions, appear to stabilize Rh(OH)3, Rh2O3, and Rh nanoparticles on niobate and tantalate supports. PMID:24654835

  19. Osazone anion radical complex of rhodium(III).

    PubMed

    Patra, Sarat Chandra; Biswas, Manas Kumar; Maity, Amarendra Nath; Ghosh, Prasanta

    2011-02-21

    One electron paramagnetic parent osazone complex of rhodium of type trans-Rh(L(NHPh)H(2))(PPh(3))(2)Cl(2) (1), defined as an osazone anion radical complex of rhodium(III), trans-Rh(III)(L(NHPh)H(2)(•-))(PPh(3))(2)Cl(2), 1((t-RhL•)), with a minor contribution (∼2%) of rhodium(II) electromer, trans-Rh(II)(L(NHPh)H(2))(PPh(3))(2)Cl(2), 1((t-Rh•L)), and their nonradical congener, trans-[Rh(III)(L(NHPh)H(2))(PPh(3))(2)Cl(2)]I(3) ([t-1](+)I(3)(-)), have been isolated and are substantiated by spectra, bond parameters, and DFT calculations on equivalent soft complexes [Rh(L(NHPh)H(2))(PMe(3))(2)Cl(2)] (3) and [Rh(L(NHPh)H(2))(PMe(3))(2)Cl(2)](+) (3(+)). 1 is not stable in solution and decomposes to [t-1](+) and a new rhodium(I) osazone complex, [Rh(I)(L(NHPh)H(2))(PPh(3))Cl] (2). 1 absorbs strongly at 351 nm due to MLCT and LLCT, while [t-1](+) and 2 absorb moderately in the range of 300-450 nm, respectively, due to LMCT and MLCT elucidated by TD-DFT calculations on 3((t-RhL•)), [t-3](+), and Rh(I)(L(NHPh)H(2))(PMe(3))Cl (4). EPR spectra of solids at 295 and 77 K, and dichloromethane-toluene frozen glass at 77 K of 1 are similar with g = 1.991, while g = 2.002 for the solid at 25 K. The EPR signal of 1 in dichloromethane solution is weaker (g = 1.992). In cyclic voltammetry, 1 displays two irreversible one electron transfer waves at +0.13 and -1.22 V, with respect to Fc(+)/Fc coupling, due to oxidation of 1((t-RhL•)) to [t-1](+) at the anode and reduction of rhodium(III) to rhodium(II), i.e., [t-1](+) to electromeric 1((t-Rh•L)) at the cathode. PMID:21261283

  20. Plasmonics in the UV range with Rhodium nanocubes

    NASA Astrophysics Data System (ADS)

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

    2016-04-01

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

  1. Preparation and reactivity of macrocyclic rhodium(III) alkyl complexes

    SciTech Connect

    Carraher, Jack M.; Ellern, Arkady; Bakac, Andreja

    2013-09-21

    Macrocyclic rhodium(II) complexes LRh(H2O)(2+) (L = L-1 = cyclam and L-2 = meso-Me-6-cyclam) react with alkyl hydroperoxides RC(CH3)(2)OOH to generate the corresponding rhodium(III) alkyls L(H2O)RhR2+ (R = CH3, C2H5, PhCH2). Methyl and benzyl complexes can also be prepared by bimolecular group transfer from alkyl cobaloximes (dmgH)(2)(H2O) CoR and (dmgBF(2))(2)(H2O) CoR (R = CH3, PhCH2) to LRh(H2O)(2+). The new complexes were characterized by solution NMR and by crystal structure analysis. They exhibit great stability in aqueous solution at room temperature, but undergo efficient Rh-C bond cleavage upon photolysis. (C) 2013 Elsevier B.V. All rights reserved.

  2. Arylation of rhodium(II) azavinyl carbenes with boronic acids.

    PubMed

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

    2012-09-12

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

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

    PubMed Central

    2011-01-01

    Background Rhodium (II) citrate (Rh2(H2cit)4) has significant antitumor, cytotoxic, and cytostatic activity on Ehrlich ascite tumor. Although toxic to normal cells, its lower toxicity when compared to carboxylate analogues of rhodium (II) indicates Rh2(H2cit)4 as a promising agent for chemotherapy. Nevertheless, few studies have been performed to explore this potential. Superparamagnetic particles of iron oxide (SPIOs) represent an attractive platform as carriers in drug delivery systems (DDS) because they can present greater specificity to tumor cells than normal cells. Thus, the association between Rh2(H2cit)4 and SPIOs can represent a strategy to enhance the former's therapeutic action. In this work, we report the cytotoxicity of free rhodium (II) citrate (Rh2(H2cit)4) and rhodium (II) citrate-loaded maghemite nanoparticles or magnetoliposomes, used as drug delivery systems, on both normal and carcinoma breast cell cultures. Results Treatment with free Rh2(H2cit)4 induced cytotoxicity that was dependent on dose, time, and cell line. The IC50 values showed that this effect was more intense on breast normal cells (MCF-10A) than on breast carcinoma cells (MCF-7 and 4T1). However, the treatment with 50 μM Rh2(H2cit)4-loaded maghemite nanoparticles (Magh-Rh2(H2cit)4) and Rh2(H2cit)4-loaded magnetoliposomes (Lip-Magh-Rh2(H2cit)4) induced a higher cytotoxicity on MCF-7 and 4T1 than on MCF-10A (p < 0.05). These treatments enhanced cytotoxicity up to 4.6 times. These cytotoxic effects, induced by free Rh2(H2cit)4, were evidenced by morphological alterations such as nuclear fragmentation, membrane blebbing and phosphatidylserine exposure, reduction of actin filaments, mitochondrial condensation and an increase in number of vacuoles, suggesting that Rh2(H2cit)4 induces cell death by apoptosis. Conclusions The treatment with rhodium (II) citrate-loaded maghemite nanoparticles and magnetoliposomes induced more specific cytotoxicity on breast carcinoma cells than on breast

  4. Time-Resolved, In Situ DRIFTS/EDE/MS Studies on Alumina-Supported Rhodium Catalysts: Effects of Ceriation and Zirconiation on Rhodium–CO Interactions**

    PubMed Central

    Kroner, Anna B; Newton, Mark A; Tromp, Moniek; Roscioni, Otello M; Russell, Andrea E; Dent, Andrew J; Prestipino, Carmelo; Evans, John

    2014-01-01

    The effects of ceria and zirconia on the structure–function properties of supported rhodium catalysts (1.6 and 4 wt % Rh/γ-Al2O3) during CO exposure are described. Ceria and zirconia are introduced through two preparation methods: 1) ceria is deposited on γ-Al2O3 from [Ce(acac)3] and rhodium metal is subsequently added, and 2) through the controlled surface modification (CSM) technique, which involves the decomposition of [M(acac)x] (M=Ce, x=3; M=Zr, x=4) on Rh/γ-Al2O3. The structure–function correlations of ceria and/or zirconia-doped rhodium catalysts are investigated by diffuse reflectance infrared Fourier-transform spectroscopy/energy-dispersive extended X-ray absorption spectroscopy/mass spectrometry (DRIFTS/EDE/MS) under time-resolved, in situ conditions. CeOx and ZrO2 facilitate the protection of Rh particles against extensive oxidation in air and CO. Larger Rh core particles of ceriated and zirconiated Rh catalysts prepared by CSM are observed and compared with Rh/γ-Al2O3 samples, whereas supported Rh particles are easily disrupted by CO forming mononuclear Rh geminal dicarbonyl species. DRIFTS results indicate that, through the interaction of CO with ceriated Rh particles, a significantly larger amount of linear CO species form; this suggests the predominance of a metallic Rh phase. PMID:25044889

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

    PubMed

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

    2016-01-01

    Short-lived ruthenium and rhodium isotopes were produced from a (252)Cf spontaneous fission (SF) source. Their volatile carbonyl complexes were formed in gas-phase reactions in situ with the carbon-monoxide containing gas. A gas-jet system was employed to transport the volatile carbonyls from the recoil chamber to the chemical separation apparatus. The gas-phase chemical behaviors of these carbonyl complexes were studied using an online low temperature isothermal chromatography (IC) technique. Long IC columns made up of FEP Teflon were used to obtain the chemical information of the high-volatile Ru and Rh carbonyls. By excluding the influence of precursor effects, short-lived isotopes of (109-110)Ru and (111-112)Rh were used to represent the chemical behaviours of Ru and Rh carbonyls. Relative chemical yields of about 75% and 20% were measured for Ru(CO)5 and Rh(CO)4, respectively, relative to the yields of KCl aerosols transported in Ar gas. The adsorption enthalpies of ruthenium and rhodium carbonyl complexes on a Teflon surface were determined to be around ΔHads = -33(+1)(-2) kJ mol(-1) and -36(+2)(-1) kJ mol(-1), respectively, by fitting the breakthrough curves of the corresponding carbonyl complexes with a Monte Carlo simulation program. Different from Mo and Tc carbonyls, a small amount of oxygen gas was found to be not effective for the chemical yields of ruthenium and rhodium carbonyl complexes. The general chemical behaviors of short-lived carbonyl complexes of group VI-IX elements were discussed, which can be used in the future study on the gas-phase chemistry of superheavy elements - Bh, Hs, and Mt carbonyls. PMID:26573993

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

    NASA Technical Reports Server (NTRS)

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

    1973-01-01

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

  7. Oxygen Reduction Mechanism of Monometallic Rhodium Hydride Complexes.

    PubMed

    Halbach, Robert L; Teets, Thomas S; Nocera, Daniel G

    2015-08-01

    The reduction of O2 to H2O mediated by a series of electronically varied rhodium hydride complexes of the form cis,trans-Rh(III)Cl2H(CNAd)(P(4-X-C6H4)3)2 (2) (CNAd = 1-adamantylisocyanide; X = F (2a), Cl (2b), Me (2c), OMe (2d)) was examined through synthetic and kinetic studies. Rhodium(III) hydride 2 reacts with O2 to afford H2O with concomitant generation of trans-Rh(III)Cl3(CNAd)(P(4-X-C6H4)3)2 (3). Kinetic studies of the reaction of the hydride complex 2 with O2 in the presence of HCl revealed a two-term rate law consistent with an HX reductive elimination (HXRE) mechanism, where O2 binds to a rhodium(I) metal center and generates an η(2)-peroxo complex intermediate, trans-Rh(III)Cl(CNAd)(η(2)-O2)(P(4-X-C6H4)3)2 (4), and a hydrogen-atom abstraction (HAA) mechanism, which entails the direct reaction of O2 with the hydride. Experimental data reveal that the rate of reduction of O2 to H2O is enhanced by electron-withdrawing phosphine ligands. Complex 4 was independently prepared by the addition of O2 to trans-Rh(I)Cl(CNAd)(P(4-X-C6H4)3)2 (1). The reactivity of 4 toward HCl reveals that such peroxo complexes are plausible intermediates in the reduction of O2 to H2O. These results show that the given series of electronically varied rhodium(III) hydride complexes facilitate the reduction of O2 to H2O according to a two-term rate law comprising HXRE and HAA pathways and that the relative rates of these two pathways, which can occur simultaneously and competitively, can be systematically modulated by variation of the electronic properties of the ancillary ligand set. PMID:26168057

  8. Atomic-absorption determination of rhodium in chromite concentrates

    USGS Publications Warehouse

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

    1969-01-01

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

  9. Molecular recognition in protein modification with rhodium metallopeptides

    PubMed Central

    Ball, Zachary T.

    2015-01-01

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

  10. Determination of rhodium: Since the origins until today Atomic absorption spectrometry.

    PubMed

    Bosch Ojeda, C; Sánchez Rojas, F

    2006-02-28

    Rhodium is present at about 0.001ppm in the earths crust. Rhodium metal is known for its stability in corrosive environments, physical beauty and unique physical and chemical properties. Recent interest in the medical and industrial significance of platinum and to a lesser extent palladium and rhodium has been accompanied by an increasing interest in their determination at low levels. Platinum group elements (PGEs: Pt, Pd, Rh, Ru, Ir and Os) play a decisive role in the performance of catalytic converters, world-wide applied in vehicles and in some household utensils, to reduce the emission of gaseous pollutants, such as carbon monoxide, nitrogen oxides and hydrocarbons. Since then, approximately 73% of the world production of rhodium is consumed in the production of autocatalyst. However, the hot exhaust gases flowing through the converter cause abrasion of these units, leading to the emission of these elements to the environment. The concentration level of rhodium (also platinum and palladium) is still very low in the nature; accordingly, their determination in environmental samples specially appears to be a challenging task for analytical chemists. In recent years, the development of analytical methods for the determination of rhodium has increased. The aim of the present review is to evaluate the utility of atomic absorption spectrometry, applied for the quantification of rhodium in different materials, such as environmental, biological, metallurgical and geological samples. PMID:18970480

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

    PubMed

    Wang, He; Tang, Guodong; Li, Xingwei

    2015-10-26

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

  12. Separation preconcentration method for platinum and rhodium from environmental samples using a chelating resin.

    PubMed

    Bosch Ojeda, C; Sánchez Rojas, F; Cano Pavón, J M

    2006-01-01

    A method of determining trace levels of platinum and rhodium in different samples was investigated. The method involves separation and preconcentration of the platinum and rhodium from the matrix by flow injection (FI) on-line coupled with electrothermal atomic absorption spectrometry (ETAAS) with Zeeman effect background correction. Platinum and rhodium were adsorbed on a microcolumn packed with 1,5-bis(di-2-pyridyl)methylene thiocarbohydrazide immobilized on silica gel (DPTH-gel). The sorbed metals were directly eluted with nitric acid into the graphite furnace and determined by AAS.

  13. Asymmetric dual catalysis via fragmentation of a single rhodium precursor complex.

    PubMed

    Song, Liangliang; Gong, Lei; Meggers, Eric

    2016-06-01

    A strategy for dual transition metal catalysis and organocatalysis is reported via the in situ disintegration of a single rhodium complex. The hereby generated chiral Lewis acid and l-β-phenylalanine synergistically catalyze the Michael addition of α,α-disubstituted aldehydes to α,β-unsaturated 2-acyl imidazoles under the formation of vicinal quaternary/tertiary stereocenters. Conveniently, the chiral-at-metal rhodium catalyst can be synthesized in just two steps starting from rhodium trichloride without the need for any chromatography. PMID:27231188

  14. Cross-conjugated hexaphyrins and their bis-rhodium complexes.

    PubMed

    Naoda, Koji; Sung, Young Mo; Lim, Jong Min; Kim, Dongho; Osuka, Atsuhiro

    2014-06-16

    A cross-conjugated hexaphyrin that carries two meso-oxacyclohexadienylidenyl (OCH) groups 9 was synthesized from the condensation of 5,10-bis(pentafluorophenyl)tripyrrane with 3,5-di-tert-butyl-4-hydroxybenzaldehyde. The reduction of 9 with NaBH4 afforded the Möbius aromatic [28]hexaphyrin 10. Bis-rhodium complex 11, prepared from the reaction of 10 with [{RhCl(CO)2}2], displays strong Hückel antiaromatic character because of the 28 π electrons that occupy the conjugated circuit on the enforced planar structure. The oxidation of 11 with 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) yielded complexes 12 and 13 depending upon the reaction conditions. Both 12 and 13 are planar owing to bis-rhodium metalation. Although complex 12 bears two meso-OCH groups at the long sides and is quinonoidal and nonaromatic in nature, complex 13 bears 3,5-di-tert-butyl-4-hydroxyphenyl and OCH groups and exhibits a moderate diatropic ring current despite its cross-conjugated electronic circuit. The diatropic ring current increases upon increasing the solvent polarity, most likely due to an increased contribution of an aromatic zwitterionic resonance hybrid. PMID:24805261

  15. Preparation and reactivity of macrocyclic rhodium(III) alkyl complexes

    SciTech Connect

    Carraher, Jack M.; Ellern, Arkady; Bakac, Andreja

    2013-09-21

    We found that the macrocyclic rhodium(II) complexes LRh(H2O)2+ (L = L1 = cyclam and L2 = meso-Me-6-cyclam) react with alkyl hydroperoxides RC(CH3)2OOH to generate the corresponding rhodium(III) alkyls L(H2O)RhR2+ (R = CH3, C2H5, PhCH2). Methyl and benzyl complexes can also be prepared by bimolecular group transfer from alkyl cobaloximes (dmgH)2(H2O) CoR and (dmgBF2)2(H2O) CoR (R = CH3, PhCH2) to LRh(H2O)2+. Moreover, the new complexes were characterized by solution NMR and by crystal structure analysis. They exhibit great stability in aqueous solution at room temperature, but undergo efficient Rh-C bond cleavage upon photolysis.

  16. Poorly controlled gout: who is doing poorly?

    PubMed Central

    Chia, Faith Li-Ann

    2016-01-01

    Gout, an inflammatory arthritis caused by the deposition of monosodium urate crystals, is commonly seen in primary care and specialist clinics. In recent years, there has been a resurgence of interest in gout due to advances in therapies and the understanding of pathophysiology, with new guidelines being published by international bodies. However, there is still a gap between the goals of treatment and actual day-to-day practice. Barriers that result in poorly controlled gout include patient factors such as lack of understanding of the disease, stigma and nonadherence to treatment, as well as physician factors such as knowledge gaps, inadequate use of allopurinol and lack of ownership of the disease. The medical profession needs to do more to bridge the gap through physician and patient education, identification of treatment targets with appropriate use of drugs, and dissemination of guidelines. PMID:27549096

  17. Poorly controlled gout: who is doing poorly?

    PubMed

    Chia, Faith Li-Ann

    2016-08-01

    Gout, an inflammatory arthritis caused by the deposition of monosodium urate crystals, is commonly seen in primary care and specialist clinics. In recent years, there has been a resurgence of interest in gout due to advances in therapies and the understanding of pathophysiology, with new guidelines being published by international bodies. However, there is still a gap between the goals of treatment and actual day-to-day practice. Barriers that result in poorly controlled gout include patient factors such as lack of understanding of the disease, stigma and nonadherence to treatment, as well as physician factors such as knowledge gaps, inadequate use of allopurinol and lack of ownership of the disease. The medical profession needs to do more to bridge the gap through physician and patient education, identification of treatment targets with appropriate use of drugs, and dissemination of guidelines. PMID:27549096

  18. Rhodium complex immobilized on graphene oxide as an efficient and recyclable catalyst for hydrogenation of cyclohexene.

    PubMed

    Zhao, Qingshan; Chen, Dafa; Li, Yang; Zhang, Guoliang; Zhang, Fengbao; Fan, Xiaobin

    2013-02-01

    Rhodium complexes can be homogeneously immobilized on functionalized graphene oxide through coordination interaction. The obtained catalyst can be readily recycled and shows enhanced activity in the catalytic hydrogenation of cyclohexene. PMID:23238302

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

    PubMed Central

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

    2014-01-01

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

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

    PubMed

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

    2016-07-11

    Efficient rhodium(III) catalysts were developed for asymmetric hydrogenation of simple olefins. A new series of chloride-bridged dinuclear rhodium(III) complexes 1 were synthesized from the rhodium(I) precursor [RhCl(cod)]2 , chiral diphosphine ligands, and hydrochloric acid. Complexes from the series acted as efficient catalysts for asymmetric hydrogenation of (E)-prop-1-ene-1,2-diyldibenzene and its derivatives without any directing groups, in sharp contrast to widely used rhodium(I) catalytic systems that require a directing group for high enantioselectivity. The catalytic system was applied to asymmetric hydrogenation of allylic alcohols, alkenylboranes, and unsaturated cyclic sulfones. Control experiments support the superiority of dinuclear rhodium(III) complexes 1 over typical rhodium(I) catalytic systems. PMID:27088539

  1. Capsule-controlled selectivity of a rhodium hydroformylation catalyst

    NASA Astrophysics Data System (ADS)

    Bocokić, Vladica; Kalkan, Ayfer; Lutz, Martin; Spek, Anthony L.; Gryko, Daniel T.; Reek, Joost N. H.

    2013-10-01

    Chemical processes proceed much faster and more selectively in the presence of appropriate catalysts, and as such the field of catalysis is of key importance for the chemical industry, especially in light of sustainable chemistry. Enzymes, the natural catalysts, are generally orders of magnitude more selective than synthetic catalysts and a major difference is that they take advantage of well-defined cavities around the active site to steer the selectivity of a reaction via the second coordination sphere. Here we demonstrate that such a strategy also applies for a rhodium catalyst; when used in the hydroformylation of internal alkenes, the selectivity of the product formed is steered solely by changing the cavity surrounding the metal complex. Detailed studies reveal that the origin of the capsule-controlled selectivity is the capsule reorganization energy, that is, the high energy required to accommodate the hydride migration transition state, which leads to the minor product.

  2. THE IMMIGRANT POOR AND THE RESIDUAL POOR.

    ERIC Educational Resources Information Center

    SEGALMAN, RALPH

    AN ANALYSIS OF THE LIVES OF THE POOR IN AMERICA WILL SHOW DIFFERENCES BETWEEN THE IMMIGRANT (AND REFUGEE) POOR AND THE RESIDUAL POOR (NEGROES, PUERTO RICANS, LATIN AMERICANS, INDIANS, AND OTHERS). THE IMMIGRANT POOR WERE ACCULTURATED AND ABSORBED INTO THE MAINSTREAM OF AMERICAN LIFE WITHIN THREE GENERATIONS, WHEREAS THE RESIDUAL POOR HAVE BEEN…

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

    SciTech Connect

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

    2012-06-15

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

  4. Rhodium mediated bond activation: from synthesis to catalysis

    SciTech Connect

    Ho, Hung-An

    2012-01-01

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

  5. Branching Out: Rhodium-Catalyzed Allylation with Alkynes and Allenes.

    PubMed

    Koschker, Philipp; Breit, Bernhard

    2016-08-16

    We present a new and efficient strategy for the atom-economic transformation of both alkynes and allenes to allylic functionalized structures via a Rh-catalyzed isomerization/addition reaction which has been developed in our working group. Our methodology thus grants access to an important structural class valued in modern organic chemistry for both its versatility for further functionalization and the potential for asymmetric synthesis with the construction of a new stereogenic center. This new methodology, inspired by mechanistic investigations by Werner in the late 1980s and based on preliminary work by Yamamoto and Trost, offers an attractive alternative to other established methods for allylic functionalization such as allylic substitution or allylic oxidation. The main advantage of our methodology consists of the inherent atom economy in comparison to allylic oxidation or substitution, which both produce stoichiometric amounts of waste and, in case of the substitution reaction, require prefunctionalization of the starting material. Starting out with the discovery of a highly branched-selective coupling reaction of carboxylic acids with terminal alkynes using a Rh(I)/DPEphos complex as the catalyst system, over the past 5 years we were able to continuously expand upon this chemistry, introducing various (pro)nucleophiles for the selective C-O, C-S, C-N, and C-C functionalization of both alkynes and the double-bond isomeric allenes by choosing the appropriate rhodium/bidentate phosphine catalyst. Thus, valuable compounds such as branched allylic ethers, sulfones, amines, or γ,δ-unsaturated ketones were successfully synthesized in high yields and with a broad substrate scope. Beyond the branched selectivity inherent to rhodium, many of the presented methodologies display additional degrees of selectivity in regard to regio-, diastereo-, and enantioselective transformations, with one example even proceeding via a dynamic kinetic resolution. Many advances

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

    NASA Astrophysics Data System (ADS)

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

    2016-02-01

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

  7. Short communication: kilovoltage measurement with rhodium target and filters on mammography X-ray machines.

    PubMed

    Underwood, A C; Law, J; Goodman, D A; Robinson, A; Rust, A

    1996-08-01

    X-ray machines used for mammography have, until recently, almost exclusively employed molybdenum (Mo) as anode material and filtration. In the UK, the RMI model 232 kVp meter is used extensively for the measurement of kilovoltage on such equipment. This unit is provided with switchable internal calibration only for molybdenum and molybdenum, or tungsten and aluminium, as anode and filtration, respectively. However, rhodium (Rh) has recently been introduced for filtration with either a molybdenum or rhodium anode in mammography equipment but, as yet, calibration facilities are not available for rhodium spectra. In this work, appropriate corrections for readings obtained with the RMI 232 kVp meter are derived for use with rhodium as filtration material with either molybdenum or rhodium anode material. An intercomparison between measurements made with four RMI model 232 kVp meters and nine IGE DMR X-ray sets was undertaken. The reproducibility of the instruments was confirmed and measurements of tube potential made on each of the X-ray sets pooled. Measurements were made from a nominal 25-35 kVp using Mo/Mo, Mo/Rh and Rh/Rh target/filter combinations. Corrections for readings obtained with Mo/Rh and Rh/Rh were produced by comparison with readings obtained with Mo/Mo, assuming stability of tube potential between anodes. The results are compared with data recently produced by the manufacturer of the meter. PMID:8949681

  8. Collisional activation of N2O decomposition and CO oxidation reactions on isolated rhodium clusters.

    PubMed

    Parry, Imogen S; Kartouzian, Aras; Hamilton, Suzanne M; Balaj, O Petru; Beyer, Martin K; Mackenzie, Stuart R

    2013-09-12

    The reactions of nitrous oxide decorated rhodium clusters, RhnN2O(+) (n = 5, 6), have been studied by Fourier transform ion cyclotron resonance mass spectrometry. Collision induced dissociation with Ar is shown to lead to one of two processes; desorption of the intact N2O moiety (indicating molecular adsorption in the parent cluster) or N2O decomposition liberating molecular nitrogen with the latter becoming increasingly dominant at higher collision energies. Consistent with the results of earlier studies, which employed infrared excitation [Hermes, A. C.; et al. J. Phys. Chem. Lett. 2011, 2, 3053], Rh5ON2O(+) is observed to behave qualitatively differently to Rh5N2O(+) with decomposition of the nitrous oxide dominating the chemistry of the former. In other experiments, the reactivity of RhnN2O(+) clusters with CO has been studied. Chemisorption of (13)CO is calculated to deposit ca. 2 eV into the parent cluster, initiating a range of chemical processes on the cluster surface, which are fit to a simple reaction mechanism. Clear differences are again observed in the reaction branching ratios for Rh5N2O(+) and Rh6N2O(+) parent cluster ions. For the n = 5 cluster, the combined N2O reduction/CO oxidation is the most significant reaction channel, while the n = 6 cluster preferentially is oxidized to Rh6O(+) with loss of N2 and CO. Even larger differences are observed in the reactions of the N2O decorated cluster oxides, RhnON2O(+), for which more reaction possibilities arise. The results of all studies are discussed in relation to infrared driven processes on the same parent cluster species [Hamilton, S. M.; et al. J. Am. Chem. Soc. 2010, 132, 1448; J. Phys. Chem. A, 2011, 115, 2489].

  9. Molecular beam optical Stark study of rhodium mononitride.

    PubMed

    Ma, Tongmei; Gengler, Jamie; Wang, Zhong; Wang, Hailing; Steimle, Timothy C

    2007-06-28

    The optical Stark effect in the Q(1) and R(0) lines of the [15.1]1-X (1)Sigma+ (1,0) band of rhodium mononitride (RhN) were recorded and analyzed to determine the permanent electric dipole moments mu for the X (1)Sigma+(upsilon=0) and [15.1]1(upsilon=1) states to be 2.43(5) and 1.75(1) D, respectively. The determined dipole moments are compared to predicted values obtained from density functional theory [Stevens et al., Chem. Phys. Lett. 421, 281 (2006)] and an all-electron ab initio calculation [Shim et al., J. Mol. Struct. THEOCHEM 393, 127 (1997)]. A simple single configuration molecular orbital correlation diagram is used to rationalize the relative values of mu for the 4d mononitrides and RhO. An electronic configuration for the [15.1]1 state is proposed based on the interpretation of the (103)Rh and (14)N magnetic hyperfine interactions.

  10. Complexes of ruthenium and rhodium with aliphatic amines in the catalysis of hydrogenation of unsaturated hydrocarbons

    SciTech Connect

    Turisbekova, K.K.; Shuikina, L.P.; Parenago, O.P.; Frolov, V.F.

    1989-02-01

    The authors synthesized new catalysts highly active in the hydrogenations of unsaturated hydrocarbons, based on complexes of ruthenium and rhodium with higher aliphatic amines, which are soluble in aromatic solvents. The complexes acquired catalytic activity in hydrogenation as a result of their treatment with diisobutyl aluminum hydride. Olefins (1-hexene, cyclopentene, cyclohexene) or dienes (isoprene) were used as the unsaturated compounds. For the ruthenium based catalysts, the highest activity was observed during the hydrogenation of 1-hexene. For the rhodium-based catalysts, the activity in the hydrogenation of olefins and dienes was approximately the same. In the case of the rhodium complex catalysts, the hydrogenation of 1-hexene was accompanied by a side-reaction consisting in isomerization into olefins with inner double bonds.

  11. Chiral Phosphate in Rhodium-Catalyzed Asymmetric [2+2+2] Cycloaddition: Ligand, Counterion, or Both?

    PubMed

    Barbazanges, Marion; Caytan, Elsa; Lesage, Denis; Aubert, Corinne; Fensterbank, Louis; Gandon, Vincent; Ollivier, Cyril

    2016-06-13

    Investigations based on NMR spectroscopy, mass spectrometry, and DFT calculations shed light on the metallic species generated in the rhodium-catalyzed asymmetric [2+2+2] cycloaddition reaction between diynes and isocyanates with the chiral phosphate TRIP. The catalytic mixture comprising [{Rh(cod)Cl}2 ], 1,4-diphenylphosphinobutane (dppb), and Ag(S)-TRIP actually gives rise to two species, both having an effect on the stereoselectivity. One is a rhodium(I) complex in which TRIP is a weakly coordinating counterion, whereas the other is a bimetallic Rh/Ag complex in which TRIP is a strongly coordinating X-type ligand. PMID:27167983

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

    SciTech Connect

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

    2010-12-07

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

  13. Geometric effects on the mechanical strengths of strong nanocrystalline rhodium sub-micron structures

    NASA Astrophysics Data System (ADS)

    Tsui, Ting Y.; Jahed, Zeinab; Evans, R. D.; Burek, Michael J.

    2015-06-01

    Sub-micron scale nanocrystalline rhodium pillars were fabricated by electron beam lithography and electroplating techniques. The fabricated specimens included solid core pillars and columnar structure with more complex cross-sectional geometries, including x-shaped and annulus shaped. Among these specimens, two groups of sub-micron scale annulus structures with sidewall thicknesses of 250 and 205 nm were fabricated. All of the structures have outer diameters of ~1 μm and consist of average grain size smaller than 22 nm. Uniaxial compression results reveal these rhodium pillars are very strong with true flow stresses exceeding 5 GPa and are not sensitive to the sample cross-sectional geometries.

  14. Rhodium-Catalyzed Geminal Oxyfluorination and Oxytrifluoro-Methylation of Diazocarbonyl Compounds.

    PubMed

    Yuan, Weiming; Eriksson, Lars; Szabó, Kálmán J

    2016-07-11

    A new reaction for the rhodium-catalyzed geminal-difunctionalization-based fluorination is presented. The substrates are aromatic and aliphatic diazocarbonyl compounds. As the fluorine source a stable and easily accessible benziodoxole reagent was used. A variety of alcohol, phenol, and carboxylic acid reagents were employed to introduce the second functionality. The reaction was extended to trifluoromethylation using a benziodoxolon reagent. The fluorination and trifluoromethylation reactions probably proceed by a rhodium-containing onium ylide type intermediate, which is trapped by either the F or CF3 electrophiles. PMID:27219856

  15. Investigation of the active sites of rhodium sulfide for hydrogen evolution/oxidation using carbon monoxide as a probe.

    PubMed

    Singh, Nirala; Upham, David C; Liu, Ru-Fen; Burk, Jonathan; Economou, Nick; Buratto, Steven; Metiu, Horia; McFarland, Eric W

    2014-05-20

    Carbon monoxide (CO) was observed to decrease the activity for hydrogen evolution, hydrogen oxidation, and H2-D2 exchange on rhodium sulfide, platinum, and rhodium metal. The temperature at which the CO was desorbed from the catalyst surface (detected by recovery in the H2-D2 exchange activity of the catalyst) was used as a descriptor for the CO binding energy to the active site. The differences in the CO desorption temperature between the different catalysts showed that the rhodium sulfide active site is not metallic rhodium. Using density functional theory, the binding energy of CO to the Rh sites in rhodium sulfide is found comparable to the binding energy on Pt. Coupled with experiment this supports the proposition that rhodium rather than sulfur atoms in the rhodium sulfide are the active site for the hydrogen reaction. This would indicate the active sites for hydrogen evolution/oxidation as well as oxygen reduction (determined by other groups using X-ray absorption spectroscopy) may be the same.

  16. Synthesis of Chiral β-Amino Nitroalkanes via Rhodium-Catalyzed Asymmetric Hydrogenation.

    PubMed

    Li, Pan; Zhou, Ming; Zhao, Qingyang; Wu, Weilong; Hu, Xinquan; Dong, Xiu-Qin; Zhang, Xumu

    2016-01-01

    The asymmetric hydrogenation of β-amino nitroolefins has been successfully achieved by rhodium/bis(phosphine)-thiourea L1 with excellent enantioselectivities and yields (up to 96% ee, 96% yield, >99% conversion, TON up to 1000) under mild conditions. Chiral β-amino nitroalkane products and their derivatives are versatile intermediates in organic synthesis. PMID:26652759

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

    SciTech Connect

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

    2012-03-14

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

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

    PubMed

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

    2015-08-01

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

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

    PubMed

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

    2015-08-01

    A stereodivergent approach to the central thiolane subunit of Nuphar sesquiterpene thioalkaloids has been developed. This approach features a rhodium-catalyzed Stevens-type rearrangement in conjunction with an enzyme resolution reaction. Further elaboration into a polycyclic ring system via alcohol oxidation and ring-closing metathesis is also described. PMID:26147579

  20. High-temperature, long-term drift of platinum-rhodium thermocouples

    NASA Technical Reports Server (NTRS)

    Szaniszlo, A. J.

    1970-01-01

    Contamination of thermocouples is minimized by use of pure alumina insulators and a controlled low-impurity-level high-vacuum environment. Average thermal electromotive force change for platinum-rhodium thermocouples was -2.8 deg K after 3700 hours exposure to a mean temperature of 1530 deg K.

  1. Synthesis of C60H2 by rhodium-catalyzed hydrogenation of C60

    NASA Technical Reports Server (NTRS)

    Becker, L.; Evans, T. P.; Bada, J. L.; Miller, S. L. (Principal Investigator)

    1993-01-01

    Reduction of C60 with rhodium(0) on alumina and hydrogen in deuterated benzene (C6D6) at ambient temperature and pressure yields a mixture of hydrogenated compounds; C60H2 has been characterized as the major product in 14% yield based on 1H NMR.

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

    PubMed

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

    2016-01-01

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

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

    SciTech Connect

    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.

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

    PubMed

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

    2015-12-18

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

  5. Poor Americans: How the Poor White Live.

    ERIC Educational Resources Information Center

    Pilisuk, Marc; Pilisuk, Phyllis

    Contents of this book include the following essays which originally appeared in "Transaction" magazine: (1) "Poor Americans: an introduction," Marc Pilisuk and Phyllis Pilisuk; (2) "How the white poor live," Marc Pilisuk and Phyllis Pilisuk; (3) "The culture of poverty," Oscar Lewis; (4) "Life in Appalachia--the case of Hugh McCaslin," Robert…

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

    PubMed

    Raoufmoghaddam, Saeed; Drent, Eite; Bouwman, Elisabeth

    2013-09-01

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

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

    PubMed

    Schulz, J; Roucoux, A; Patin, H

    2000-02-18

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

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

    PubMed

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

    2016-04-25

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

  9. Promoting Effect of CeO2 in the Electrocatalytic Activity of Rhodium for Ethanol Electro-Oxidation

    SciTech Connect

    He, Q.; Mukerjee, S; Shyam, B; Ramaker, D; Parres-Esclapex, D; Illan-Gomez, M; Bueno-Lopez, A

    2009-01-01

    The promoting effect of ceria in the electrocatalytic activity of rhodium for ethanol electro-oxidation in alkali media has been studied. Rh/C, CeO2/C and RhCeO2/C catalysts were synthesized and characterized by TEM, XRD, XPS, TG-MS, H2-TPR and XAS. The electrocatalytic activity was studied by Cyclic Voltammetry (CV) and chronoamperometry. The onset potential of oxidation on RhCeO2/C was shifted negatively as compared to that on Rh/C, despite ceria itself does not show any electrocatalytic activity. The promoting effect of ceria has been attributed to the improved rhodium dispersion, and differences in the oxidation state of rhodium between Rh/C and RhCeO2/C were not found. The carbon support reduces rhodium species to Rh0, and also partially reduces ceria, during the samples preparation, and the surface of the carbon support is oxidised.

  10. Preparation of alumina-supported ceria. II. Measurement of ceria surface area after impregnation with platinum or rhodium

    SciTech Connect

    Rogemond, E.; Frety, R.; Perrichon, V.; Primet, M. |

    1997-07-01

    The surface area of cerium oxide was evaluated in an aluminium oxide supported catalyst. The catalyst were impregnated with rhodium chlorides and platinum chlorides. The adsorption of carbon dioxide is discussed.

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

    SciTech Connect

    Sobolevskiy, Anatoly; Rossin, Joseph A.; Knapke, Michael J.

    2011-07-12

    A process for the catalytic reduction of nitrogen oxides (NOx) in a gas stream (29) in the presence of H.sub.2 is provided. The process comprises contacting the gas stream with a catalyst system (38) comprising zirconia-silica washcoat particles (41), a pre-sulfated zirconia binder (44), and a catalyst combination (40) comprising palladium and at least one of rhodium, ruthenium, or a mixture of ruthenium and rhodium.

  12. New SSMS Techniques for the Determination of Rhodium and Other Platinum- Group Elements in Carbonaceous Chondrites

    NASA Astrophysics Data System (ADS)

    Jochum, K. P.; Seufert, H. M.

    1995-09-01

    We have developed new spark source mass spectrometric (SSMS) techniques for simultaneous analysis of platinum-group elements (PGE) together with other trace elements in stony meteorites. We have measured elemental abundances of Rh, Ru, Os, Ir, Pt, Au in carbonaceous chondrites of different types including the two CI chondrites Orgueil and Ivuna. These data are relevant for the determination of solar-system abundances. Whereas the solar-system abundances of most PGE are well known, this is not the case for Rh, and no literature data exist for carbonaceous chondrites, mainly because of analytical difficulties. The SSMS techniques include new calibration procedures and the use of a recently developed multi-ion counting (MIC) system [1]. The mono-isotopic element Rh and the other PGE were determined by using internal standard elements (e.g., Nd, U) that were measured by isotope dilution in the same sample electrode material. The data were calibrated with certified standard solutions of PGE which were doped on trace-element poor rock samples. Ion abundances were measured using both the conventional photoplate detection and the ion-counting techniques. The new MIC technique that uses up to 20 small channeltrons for ion counting measurements has the advantage of improved precision, detection limits and analysis time compared to photoplate detection. Tab. 1 shows the Rh analyses for the meteorites Orgueil, Ivuna, Murchison, Allende and Karoonda obtained by conventional photoplate detection. These are the first Rh results for carbonaceous chondrites. The data for the two CI chondrites Orgueil and Ivuna are identical and agree within 4 % with the CI estimate of Anders and Grevesse [2] which was derived indirectly from analyses for H-chondrites. The PGE Os, Ir, Pt, Au and W, Re, Th, U concentrations were determined by both detection systems. Data obtained with the MIC system are more precise (about 4% for concentrations in the ppb range) compared to the photoplate detection

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

    NASA Astrophysics Data System (ADS)

    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.

  14. Sterilizing the Poor

    ERIC Educational Resources Information Center

    Rothman, Sheila M.

    1977-01-01

    Suggests that freedom for the middle classes may mean vulnerability for the poor. The enthusiasm for sterilization may be so intense as to deprive the poor of their right not to be sterilized. (Author/AM)

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

    PubMed

    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.

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

    PubMed

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

    2015-01-01

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

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

    PubMed

    Ma, Jiajia; Harms, Klaus; Meggers, Eric

    2016-08-01

    A rhodium-based chiral Lewis acid catalyst combined with [Ru(bpy)3](PF6)2 as a photoredox sensitizer allows for the visible-light-activated redox coupling of α-silylamines with 2-acyl imidazoles to afford, after desilylation, 1,2-amino-alcohols in yields of 69-88% and with high enantioselectivity (54-99% ee). The reaction is proposed to proceed via an electron exchange between the α-silylamine (electron donor) and the rhodium-chelated 2-acyl imidazole (electron acceptor), followed by a stereocontrolled radical-radical reaction. Substrate scope and control experiments reveal that the trimethylsilyl group plays a crucial role in this reductive umpolung of the carbonyl group. PMID:27462824

  18. Asymmetric Hydroformylation of Heterocyclic Olefins Mediated by Supramolecularly Regulated Rhodium-Bisphosphite Complexes.

    PubMed

    Rovira, Laura; Vaquero, Mónica; Vidal-Ferran, Anton

    2015-10-16

    Rhodium complexes derived from conformationally transformable α,ω-bisphosphite ligands combined with a suitable alkali metal BArF salt as a regulation agent (RA) provide high regio- and enantioselectivities in the asymmetric hydroformylation (AHF) of three heterocyclic olefins. The outcome of the AHF could be exquisitely regulated by choosing the appropriate RA with an increase in the ee, the reversal of the regioselectivity, or the complete suppression of one byproduct. PMID:26355601

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

    SciTech Connect

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

    2005-01-01

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

  20. Rhodium-catalyzed anti-Markovnikov addition of secondary amines to arylacetylenes at room temperature.

    PubMed

    Sakai, Kazunori; Kochi, Takuya; Kakiuchi, Fumitoshi

    2011-08-01

    An efficient method for synthesis of E-enamines by the anti-Markovnikov addition of secondary amines to terminal alkynes is described. The reaction of a variety of aryl- and heteroarylacetylenes proceeded at room temperature using a combination of a 8-quinolinolato rhodium complex and P(p-MeOC(6)H(4))(3) as a catalyst. The products were obtained as enamines by simple bulb-to-bulb distillation. PMID:21699251

  1. Pyridazine N-Oxides as Precursors of Metallocarbenes: Rhodium-Catalyzed Transannulation with Pyrroles.

    PubMed

    Kanchupalli, Vinaykumar; Joseph, Desna; Katukojvala, Sreenivas

    2015-12-01

    Pyridazine N-oxides are used for the first time as precursors of metallocarbenes. These nitrogen-rich heterocycles led to the discovery of a novel acceptor and donor-acceptor enalcarbenoids. The synthetic utility of these metallocarbenes was demonstrated in the rhodium-catalyzed denitrogenative transannulation of pyridazine N-oxides with pyrroles to the valuable alkyl, 7-aryl, and 7-styryl indoles. The transannulation strategy was applied to the synthesis of a potent anticancer agent.

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

    DOE PAGESBeta

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

    2015-08-17

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

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

    PubMed

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

    2015-09-28

    An electrophilic, coordinatively unsaturated rhodium complex supported by borate-linked oxazoline, oxazoline-coordinated silylene, and N-heterocyclic carbene donors [{κ(3)-N,Si,C-PhB(Ox(Me2))(Ox(Me2)SiHPh)Im(Mes)}Rh(H)CO][HB(C6F5)3] (, Ox(Me2) = 4,4-dimethyl-2-oxazoline; Im(Mes) = 1-mesitylimidazole) is synthesized from the neutral rhodium silyl {PhB(Ox(Me2))2Im(Mes)}RhH(SiH2Ph)CO () and B(C6F5)3. The unusual oxazoline-coordinated silylene structure in is proposed to form by rearrangement of an unobserved isomeric cationic rhodium silylene species [{PhB(Ox(Me2))2Im(Mes)}RhH(SiHPh)CO][HB(C6F5)3] generated by H abstraction. Complex catalyzes reductions of organic carbonyl compounds with silanes to give hydrosilylation products or deoxygenation products. The pathway to these reactions is primarily influenced by the degree of substitution of the organosilane. Reactions with primary silanes give deoxygenation of esters to ethers, amides to amines, and ketones and aldehydes to hydrocarbons, whereas tertiary silanes react to give 1,2-hydrosilylation of the carbonyl functionality. In contrast, the strong Lewis acid B(C6F5)3 catalyzes the complete deoxygenation of carbonyl compounds to hydrocarbons with PhSiH3 as the reducing agent. PMID:26278517

  4. Rich Donors, Poor Countries

    ERIC Educational Resources Information Center

    Thomas, M. A.

    2012-01-01

    The shifting ideological winds of foreign aid donors have driven their policy towards governments in poor countries. Donors supported state-led development policies in poor countries from the 1940s to the 1970s; market and private-sector driven reforms during the 1980s and 1990s; and returned their attention to the state with an emphasis on…

  5. Inference in `poor` languages

    SciTech Connect

    Petrov, S.

    1996-10-01

    Languages with a solvable implication problem but without complete and consistent systems of inference rules (`poor` languages) are considered. The problem of existence of finite complete and consistent inference rule system for a ``poor`` language is stated independently of the language or rules syntax. Several properties of the problem arc proved. An application of results to the language of join dependencies is given.

  6. Adducts of nitrogenous ligands with rhodium(II) tetracarboxylates and tetraformamidinate: NMR spectroscopy and density functional theory calculations.

    PubMed

    Cmoch, Piotr; Głaszczka, Rafał; Jaźwiński, Jarosław; Kamieński, Bohdan; Senkara, Elżbieta

    2014-03-01

    Complexation of tetrakis(μ2-N,N'-diphenylformamidinato-N,N')-di-rhodium(II) with ligands containing nitrile, isonitrile, amine, hydroxyl, sulfhydryl, isocyanate, and isothiocyanate functional groups has been studied in liquid and solid phases using (1)H, (13)C and (15)N NMR, (13)C and (15)N cross polarisation-magic angle spinning NMR, and absorption spectroscopy in the visible range. The complexation was monitored using various NMR physicochemical parameters, such as chemical shifts, longitudinal relaxation times T1 , and NOE enhancements. Rhodium(II) tetraformamidinate selectively bonded only unbranched amine (propan-1-amine), pentanenitrile, and (1-isocyanoethyl)benzene. No complexation occurred in the case of ligands having hydroxyl, sulfhydryl, isocyanate, and isothiocyanate functional groups, and more expanded amine molecules such as butan-2-amine and 1-azabicyclo[2.2.2]octane. Such features were opposite to those observed in rhodium(II) tetracarboxylates, forming adducts with all kind of ligands. Special attention was focused on the analysis of Δδ parameters, defined as a chemical shift difference between signal in adduct and corresponding signal in free ligand. In the case of (1)H NMR, Δδ values were either negative in adducts of rhodium(II) tetraformamidinate or positive in adducts of rhodium(II) tetracarboxylates. Experimental findings were supported by density functional theory molecular modelling and gauge independent atomic orbitals chemical shift calculations. The calculation of chemical shifts combined with scaling procedure allowed to reproduce qualitatively Δδ parameters.

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

    NASA Astrophysics Data System (ADS)

    Kassem, Mohammed A.; Amin, Alaa S.

    2015-02-01

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

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

    PubMed

    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.

  9. Spectroscopic and electron microscopic investigation of iron oxides formed in a highly alkaline medium in the presence of rhodium ions

    NASA Astrophysics Data System (ADS)

    Krehula, Stjepko; Musić, Svetozar

    2010-07-01

    The effect of the presence of rhodium ions on the formation of iron oxides in a highly alkaline precipitation system was investigated using X-ray powder diffraction (XRD), 57Fe Mössbauer and FT-IR spectroscopies, field emission scanning electron microscopy (FE-SEM) and energy dispersive X-ray spectroscopy (EDS). Acicular α-FeOOH particles precipitated in a highly alkaline medium with the addition of tetramethylammonium hydroxide (TMAH) were used as reference material. Characterization of α-FeOOH samples formed in the presence of rhodium ions showed a somewhat smaller mean crystallite size, increased unit-cell dimensions, a reduced average hyperfine magnetic field and a slight shift in the position of IR absorption bands in comparison with the reference α-FeOOH sample. By additional heating of the precipitation system, α-FeOOH precipitated in the presence of rhodium ions transformed to α-Fe 2O 3 crystals in the form of hexagonal bipyramids via a dissolution-recrystallization process. Metallic rhodium nanoparticles were formed simultaneously by the reduction of Rh 3+ ions in the presence of the products of TMAH thermal decomposition (trimethylamine and methanol). These rhodium nanoparticles acted as a catalyst for the reductive dissolution of α-Fe 2O 3 particles and the formation of Fe 3O 4 crystals in the form of octahedrons.

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

    NASA Astrophysics Data System (ADS)

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

    1992-12-01

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

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

    PubMed Central

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

    2016-01-01

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

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

    PubMed

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

    2016-01-01

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

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

    PubMed

    van der Horst, C; Silwana, B; Iwuoha, E; Somerset, V

    2012-01-01

    Stripping voltammetry as technique has proved to be very useful in the analysis of heavy and other metal ions due to its excellent detection limits and its sensitivity in the presence of different metal species or interfering ions. Recent assessments of aquatic samples have shown increased levels of platinum group metals (PGMs) in aquatic ecosystems, caused by automobile exhaust emissions and mining activities. The development of an analytical sensor for the detection and characterisation of PGMs were investigated, since there is an ongoing need to find new sensing materials with suitable recognition elements that can respond selectively and reversibly to specific metal ions in environmental samples. The work reported shows the successful application of another mercury-free sensor electrode for the determination of platinum group metals in environmental samples. The work reported in this study entails the use of a glassy carbon electrode modified with a bismuth film for the determination of platinum (Pt(2+)), palladium (Pd(2+)) or rhodium (Rh(2+)) by means of adsorptive cathodic stripping voltammetry. Optimised experimental conditions included composition of the supporting electrolyte, complexing agent concentration, deposition potential, deposition time and instrumental voltammetry parameters for Pt(2+), Pd(2+) and Rh(2+) determination. Adsorptive differential pulse stripping voltammetric measurements for PGMs were performed in the presence of dimethylglyoxime (DMG) as complexing agent. The glassy carbon bismuth film electrode (GC/BiFE) employed in this study exhibit good and reproducible sensor characteristics. Application of GC/BiFE sensor exhibited well-defined peaks and highly linear behaviour for the stripping analysis of the PGMs in the concentration range between 0 and 3.5 μg/L. The detection limit of Pd, Pt and Rh was found to be 0.12 μg/L, 0.04 μg/L and 0.23 μg/L, respectively for the deposition times of 90 s (Pd) and 150 s (for both Pt and Rh). Good

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

    PubMed

    van der Horst, C; Silwana, B; Iwuoha, E; Somerset, V

    2012-01-01

    Stripping voltammetry as technique has proved to be very useful in the analysis of heavy and other metal ions due to its excellent detection limits and its sensitivity in the presence of different metal species or interfering ions. Recent assessments of aquatic samples have shown increased levels of platinum group metals (PGMs) in aquatic ecosystems, caused by automobile exhaust emissions and mining activities. The development of an analytical sensor for the detection and characterisation of PGMs were investigated, since there is an ongoing need to find new sensing materials with suitable recognition elements that can respond selectively and reversibly to specific metal ions in environmental samples. The work reported shows the successful application of another mercury-free sensor electrode for the determination of platinum group metals in environmental samples. The work reported in this study entails the use of a glassy carbon electrode modified with a bismuth film for the determination of platinum (Pt(2+)), palladium (Pd(2+)) or rhodium (Rh(2+)) by means of adsorptive cathodic stripping voltammetry. Optimised experimental conditions included composition of the supporting electrolyte, complexing agent concentration, deposition potential, deposition time and instrumental voltammetry parameters for Pt(2+), Pd(2+) and Rh(2+) determination. Adsorptive differential pulse stripping voltammetric measurements for PGMs were performed in the presence of dimethylglyoxime (DMG) as complexing agent. The glassy carbon bismuth film electrode (GC/BiFE) employed in this study exhibit good and reproducible sensor characteristics. Application of GC/BiFE sensor exhibited well-defined peaks and highly linear behaviour for the stripping analysis of the PGMs in the concentration range between 0 and 3.5 μg/L. The detection limit of Pd, Pt and Rh was found to be 0.12 μg/L, 0.04 μg/L and 0.23 μg/L, respectively for the deposition times of 90 s (Pd) and 150 s (for both Pt and Rh). Good

  15. Base-Free Conditions for Rhodium-Catalyzed Asymmetric Arylation To Produce Stereochemically Labile α-Aryl Ketones.

    PubMed

    Dou, Xiaowei; Lu, Yixin; Hayashi, Tamio

    2016-06-01

    The asymmetric arylation of 2,2-dialkyl cyclopent-4-ene-1,3-diones with aryl boronic acids was found to be efficiently catalyzed by a chiral diene-rhodium μ-chloro dimer, [{RhCl((R)-diene*)}2 ], in the absence of bases in toluene/H2 O to give 2,2-dialkyl 4-aryl cyclopentane-1,3-diones in high yields with high enantioselectivity. Such compounds can not be obtained with high enantiomeric purity under the standard basic conditions used for rhodium-catalyzed asymmetric arylation because the α-aryl ketone products undergo racemization under the basic conditions. PMID:27100902

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

    SciTech Connect

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

    2015-08-17

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

  17. Intrinsic Selectivity and Structure Sensitivity of Rhodium Catalysts for C(2+) Oxygenate Production.

    PubMed

    Yang, Nuoya; Medford, Andrew J; Liu, Xinyan; Studt, Felix; Bligaard, Thomas; Bent, Stacey F; Nørskov, Jens K

    2016-03-23

    Synthesis gas (CO + H2) conversion is a promising route to converting coal, natural gas, or biomass into synthetic liquid fuels. Rhodium has long been studied as it is the only elemental catalyst that has demonstrated selectivity to ethanol and other C2+ oxygenates. However, the fundamentals of syngas conversion over rhodium are still debated. In this work a microkinetic model is developed for conversion of CO and H2 into methane, ethanol, and acetaldehyde on the Rh (211) and (111) surfaces, chosen to describe steps and close-packed facets on catalyst particles. The model is based on DFT calculations using the BEEF-vdW functional. The mean-field kinetic model includes lateral adsorbate-adsorbate interactions, and the BEEF-vdW error estimation ensemble is used to propagate error from the DFT calculations to the predicted rates. The model shows the Rh(211) surface to be ∼6 orders of magnitude more active than the Rh(111) surface, but highly selective toward methane, while the Rh(111) surface is intrinsically selective toward acetaldehyde. A variety of Rh/SiO2 catalysts are synthesized, tested for catalytic oxygenate production, and characterized using TEM. The experimental results indicate that the Rh(111) surface is intrinsically selective toward acetaldehyde, and a strong inverse correlation between catalytic activity and oxygenate selectivity is observed. Furthermore, iron impurities are shown to play a key role in modulating the selectivity of Rh/SiO2 catalysts toward ethanol. The experimental observations are consistent with the structure-sensitivity predicted from theory. This work provides an improved atomic-scale understanding and new insight into the mechanism, active site, and intrinsic selectivity of syngas conversion over rhodium catalysts and may also guide rational design of alloy catalysts made from more abundant elements. PMID:26958997

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

    PubMed

    Zielinski, Witold; Kukawka, Rafal; Maciejewski, Hieronim; Smiglak, Marcin

    2016-01-01

    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. PMID:27563869

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

    NASA Technical Reports Server (NTRS)

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

    1991-01-01

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

  20. Stereoselective 1,3-Insertions of Rhodium(II) Azavinyl Carbenes

    PubMed Central

    Chuprakov, Stepan; Worrell, Brady T.; Selander, Nicklas; Sit, Rakesh K.; Fokin, Valery V.

    2014-01-01

    Rhodium(II) azavinyl carbenes, conveniently generated from 1-sulfonyl-1,2,3-triazoles, undergo a facile, mild and convergent formal 1,3-insertion into N–H and O–H bonds of primary and secondary amides, various alcohols, and carboxylic acids to afford a wide range of vicinally bis-functionalized Z-olefins with perfect regio- and stereoselectively. Utilizing the distinctive functionality installed through these reactions, a number of subsequent rearrangements and cyclizations expand the repertoire of valuable organic building blocks constructed by reactions of transition metal carbene complexes, including α-allenyl ketones and amino-substituted heterocycles. PMID:24295389

  1. Poor school performance.

    PubMed

    Karande, Sunil; Kulkarni, Madhuri

    2005-11-01

    Education is one of the most important aspects of human resource development. Poor school performance not only results in the child having a low self-esteem, but also causes significant stress to the parents. There are many reasons for children to under perform at school, such as, medical problems, below average intelligence, specific learning disability, attention deficit hyperactivity disorder, emotional problems, poor socio-cultural home environment, psychiatric disorders and even environmental causes. The information provided by the parents, classroom teacher and school counselor about the child's academic difficulties guides the pediatrician to form an initial diagnosis. However, a multidisciplinary evaluation by an ophthalmologist, otolaryngologist, counselor, clinical psychologist, special educator, and child psychiatrist is usually necessary before making the final diagnosis. It is important to find the reason(s) for a child's poor school performance and come up with a treatment plan early so that the child can perform up to full potential. PMID:16391452

  2. Morphosyntax in Poor Comprehenders

    ERIC Educational Resources Information Center

    Adlof, Suzanne M.; Catts, Hugh W.

    2015-01-01

    Children described as "poor comprehenders" (PCs) have reading comprehension difficulties in spite of adequate word reading abilities. PCs are known to display weakness with semantics and higher-level aspects of oral language, but less is known about their grammatical skills, especially with regard to morphosyntax. The purpose of this…

  3. A facile one-step synthesis of polymer supported rhodium nanoparticles in organic medium and their catalytic performance in the dehydrogenation of ammonia-borane.

    PubMed

    Karahan, Senem; Zahmakıran, Mehmet; Özkar, Saim

    2012-01-28

    A new type of supported rhodium nanoparticles were reproducibly prepared from N(2)H(4)BH(3) reduction of [Rh(μ-Cl)(1,5-cod)](2) without using any solid support and pre-treatment technique. Their characterization shows the formation of well dispersed rhodium(0) nanoparticles within the framework of a polyaminoborane based polymeric support. These new rhodium(0) nanoparticles were found to be the most active supported catalyst in the catalytic dehydrogenation of ammonia-borane in water at room temperature. PMID:22158916

  4. Mesoporous Silica Nanoparticle-Stabilized and Manganese-Modified Rhodium Nanoparticles as Catalysts for Highly Selective Synthesis of Ethanol and Acetaldehyde from Syngas

    SciTech Connect

    Huang, Yulin; Deng, Weihua; Guo, Enruo; Chung, Po-Wen; Chen, Senniang; Trewyn, Brian; Brown, Robert; Lin, Victor

    2012-03-30

    Well-defined and monodispersed rhodium nanoparticles as small as approximately 2 nm were encapsulated in situ and stabilized in a mesoporous silica nanoparticle (MSN) framework during the synthesis of the mesoporous material. Although both the activity and selectivity of MSN-encapsulated rhodium nanoparticles in CO hydrogenation could be improved by the addition of manganese oxide as expected, the carbon selectivity for C2 oxygenates (including ethanol and acetaldehyde) was unprecedentedly high at 74.5 % with a very small amount of methanol produced if rhodium nanoparticles were modified by manganese oxide with very close interaction.

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

    NASA Astrophysics Data System (ADS)

    Vasilchenko, Danila B.; Venediktov, Anatoliy B.; Korenev, Sergey V.; Filatov, Evgeniy Yu.; Baidina, Iraida A.; Nadolinnyi, Vladimir A.

    2012-10-01

    Interaction of trans-[Rh(i-Nic)4Cl2]3- anions (i-Nic- - isonicotinate anion) with Cuaq2+ and Coaq2+ cations in water has afforded complex salts Co3[Rh(i-Nic)4Cl2]2·17H2O (1) and Cu3[Rh(i-Nic)4Cl2]2·14H2O (2). Oligonuclear character of 1 and 2 has been established. A coordination polymer Cu5[Rh(i-Nic)4Cl2]2(i-Nic)2(OH)2·2H2O (3) has been crystallized by hydrothermal treatment of 2 at 160 °C, and its structure was determined by X-ray structural analysis. EPR data for the complexes has been collected and interpreted. Thermal decomposition of the salts was studied by c-DTA. Bimetallic alloys rhodium-copper and rhodium-cobalt have been obtained as final products of thermal decomposition.

  6. Application of flow injection on-line electrothermal atomic absorption spectrometry to the determination of rhodium.

    PubMed

    Sanchez Rojas, Fuensanta; Bosch Ojeda, Catalina; Cano Pavón, José Manuel

    2005-06-01

    A fully automated procedure for the determination of rhodium has been developed using flow injection (FI) on-line microcolumn preconcentration coupled with electrothermal atomic absorption spectrometry (ETAAS). The proposed FI manifold and its operation make possible the introduction of the total eluate volume into the graphite atomizer, avoiding the necessity for optimisation of subsampling the eluate. Rhodium is adsorbed on a microcolumn packed with 1,5-bis(di-2-pyridyl)methylene thiocarbohydrazide immobilized on silica gel (DPTH-gel). Under the optimum conditions, using a 60 s preconcentration time, a sample flow rate of 3.5 mL min(-1) and an injection volume of eluent of 50 microL, a linear calibration graph was obtained from 1 to at least 40 ng mL(-1) and the detection limit was 1 ng mL(-1). The proposed method has been successfully applied to the analysis of samples. Its performance was investigated against certified reference catalyst sample SRM-2557 and by recovery measurements on spiked samples (soil, foods and beverages).

  7. Characterization of acetylacetonato carbonyl diphenyl-2-pyridylphosphine rhodium(I): Comparison with other carbonyl complexes

    NASA Astrophysics Data System (ADS)

    Purcell, Walter; Conradie, Jeanet; Chiweshe, Trevor T.; Venter, Johan A.; Visser, Hendrik G.; Coetzee, Michael P.

    2013-04-01

    Different rhodium(I)/(III) diphenyl-2-pyridylphosphine complexes were isolated and successfully characterized. The [Rh(acac)(CO)(DPP)] (DPP = diphenyl-2-pyridylphosphine) complex crystallizes in the P1¯ space group with four molecules per unit cell. The results clearly show that the differences between the two independent molecules are mainly centered around the orientation of the pyridyl ring within the two square planer molecules. The results also indicate that the phosphine ligands act as monodentate ligands in both molecules, with Rh-P and Rh-CO bond distances of 2.243(1); 2.235(1) and 1.791(4); 1.776(4) Å respectively. A comparison of the ν(CO) stretching frequencies of a relatively large number of rhodium complexes indicated little overlap between the ν(CO) of different types of complexes (e.g. Rh(I) vs Rh(III)) and relatively small standard deviations within each type of complex. DFT calculations were used to determine the preferred pyridyl ring orientation. These calculations indicated that at least 12 areas of minimum energy, which exists as broad, low energy wells, are theoretically suitable for DPP group orientation within this kind of structure.

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

    NASA Astrophysics Data System (ADS)

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

    2016-03-01

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

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

    PubMed

    Piou, Tiffany; Rovis, Tomislav

    2015-11-01

    Alkenes are the most ubiquitous prochiral functional groups--those that can be converted from achiral to chiral in a single step--that are accessible to synthetic chemists. For this reason, difunctionalization reactions of alkenes (whereby two functional groups are added to the same double bond) are particularly important, as they can be used to produce highly complex molecular architectures. Stereoselective oxidation reactions, including dihydroxylation, aminohydroxylation and halogenation, are well established methods for functionalizing alkenes. However, the intermolecular incorporation of both carbon- and nitrogen-based functionalities stereoselectively across an alkene has not been reported. Here we describe the rhodium-catalysed carboamination of alkenes at the same (syn) face of a double bond, initiated by a carbon-hydrogen activation event that uses enoxyphthalimides as the source of both the carbon and the nitrogen functionalities. The reaction methodology allows for the intermolecular, stereospecific formation of one carbon-carbon and one carbon-nitrogen bond across an alkene, which is, to our knowledge, unprecedented. The reaction design involves the in situ generation of a bidentate directing group and the use of a new cyclopentadienyl ligand to control the reactivity of rhodium. The results provide a new way of synthesizing functionalized alkenes, and should lead to the convergent and stereoselective assembly of amine-containing acyclic molecules.

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

    PubMed Central

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

    2016-01-01

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

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

    PubMed

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

    2012-10-01

    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.

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

    NASA Astrophysics Data System (ADS)

    Jyothi, Rajesh Kumar; Lee, Jin-Young

    2016-06-01

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

  13. Simultaneous determination of palladium, platinum and rhodium in crude platinum samples by activation analysis and high-resolution gamma spectrometry.

    PubMed

    Turkstra, J; de Wet, W J

    1969-08-01

    Instrumental neutron-activation analysis using a Ge(Li) detector has been investigated for the simultaneous determination of platinum, palladium and rhodium in crude platinum samples contained in lead cupels. This technique proved feasible and appears promising for extension to the determination of most of the noble metals.

  14. RHODIUM CATALYZED CONJUGATED ADDITION OF UNSATURATED CARBONYL COMPOUNDS BY TRIPHENYLBISMUTH IN AQUEOUS MEDIA AND UNDER AN AIR ATMOSPHERE. (R822668)

    EPA Science Inventory

    Abstract

    In the presence of a rhodium catalyst, small alpha, Greek,small beta, Greek-unsaturated est...

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

    PubMed Central

    Jyothi, Rajesh Kumar; Lee, Jin-Young

    2016-01-01

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

  16. Rhodium(II)-catalyzed alkyne amination of homopropargylic sulfamate esters: stereoselective synthesis of functionalized norcaradienes by arene cyclopropanation.

    PubMed

    Brawn, Ryan A; Zhu, Kaicheng; Panek, James S

    2014-01-01

    A rhodium(II) catalyzed nitrene-alkyne cycloaddition of stereochemically well-defined homopropargylic ethers is followed by arene cyclopropanation to afford unique tetracyclic norcaradiene products bearing a cyclic sulfamate. Products from the arene cyclopropanation (Buchner reaction) can be converted to fused cycloheptatrienes via a ring enlarging electrocyclization after nucleophilic ring opening of the cyclic sulfamate ester.

  17. [Poor prognosis childhood cancers].

    PubMed

    Valteau-Couanet, Dominique; Minard, Véronique

    2007-05-31

    Poor prognosis childhood cancers are mainly metastatic diseases represented by stage IV neuroblastomas developed in children more than one year and metastatic Ewing tumours. These both diseases are chemosensitive but not curable with conventional chemotherapy. In these indications, high-dose chemotherapy with autologous peripheral blood stem cells transplantation is delivered in patients achieving a good partial remission with conventional treatment. The toxicity of these procedures is high but manageable; these approaches have improved the prognosis of these patients.

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

    SciTech Connect

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

    1998-03-01

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

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

    SciTech Connect

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

    2009-09-02

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

  20. Synthesis of α-amino ketones from terminal alkynes via rhodium-catalyzed denitrogenative hydration of N-sulfonyl-1,2,3-triazoles.

    PubMed

    Miura, Tomoya; Biyajima, Tsuneaki; Fujii, Tetsuji; Murakami, Masahiro

    2012-01-11

    N-Sulfonyl-1,2,3-triazoles react with water in the presence of a rhodium catalyst to produce α-amino ketones in high yield. An intermediary α-imino rhodium(II) carbenoid undergoes insertion into the O-H bond of water. This transformation formally achieves 1,2-aminohydroxylation of terminal alkynes in a regioselective fashion when combined with the copper(I)-catalyzed 1,3-dipolar cycloaddition with N-sulfonyl azides. PMID:22129424

  1. Poor ovarian reserve.

    PubMed

    Jirge, Padma Rekha

    2016-01-01

    Poor ovarian reserve (POR) is an important limiting factor for the success of any treatment modality for infertility. It indicates a reduction in quantity and quality of oocytes in women of reproductive age group. It may be age related as seen in advanced years of reproductive life or may occur in young women due to diverse etiological factors. Evaluating ovarian reserve and individualizing the therapeutic strategies are very important for optimizing the success rate. Majority or women with POR need to undergo in vitro fertilization to achieve pregnancy. However, pregnancy rate remains low despite a plethora of interventions and is associated with high pregnancy loss. Early detection and active management are essential to minimize the need for egg donation in these women. PMID:27382229

  2. Poor ovarian reserve

    PubMed Central

    Jirge, Padma Rekha

    2016-01-01

    Poor ovarian reserve (POR) is an important limiting factor for the success of any treatment modality for infertility. It indicates a reduction in quantity and quality of oocytes in women of reproductive age group. It may be age related as seen in advanced years of reproductive life or may occur in young women due to diverse etiological factors. Evaluating ovarian reserve and individualizing the therapeutic strategies are very important for optimizing the success rate. Majority or women with POR need to undergo in vitro fertilization to achieve pregnancy. However, pregnancy rate remains low despite a plethora of interventions and is associated with high pregnancy loss. Early detection and active management are essential to minimize the need for egg donation in these women. PMID:27382229

  3. Highly enantioselective reductive cyclization of acetylenic aldehydes via rhodium catalyzed asymmetric hydrogenation.

    PubMed

    Rhee, Jong Uk; Krische, Michael J

    2006-08-23

    Catalytic hydrogenation of acetylenic aldehydes 1a-12a using chirally modified cationic rhodium catalysts enables highly enantioselective reductive cyclization to afford cyclic allylic alcohols 1b-12b. Using an achiral hydrogenation catalyst, the chiral racemic acetylenic aldehydes 13a-15a engage in highly syn-diastereoselective reductive cyclizations to afford cyclic allylic alcohols 13b-15b. Ozonolysis of cyclization products 7b and 9b allows access to optically enriched alpha-hydroxy ketones 7c and 9c. Reductive cyclization of enyne 7a under a deuterium atmosphere provides the monodeuterated product deuterio-7b, consistent with a catalytic mechanism involving alkyne-carbonyl oxidative coupling followed by hydrogenolytic cleavage of the resulting oxametallacycle. These hydrogen-mediated transformations represent the first examples of the enantioselective reductive cyclization of acetylenic aldehydes. PMID:16910650

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

    SciTech Connect

    Ualikhanova, A.; Temirbulatova, A.E.

    1992-01-10

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

  5. Classically exact overlayer dynamics: Diffusion of rhodium clusters on Rh(100)

    SciTech Connect

    Voter, A.F.

    1986-11-15

    A new method is presented for describing the classical dynamics (e.g., diffusion, desorption) of adsorbed overlayers of atoms or molecules, starting from arbitrary interatomic potentials. Provided that a certain dynamical criterion is met, the method yields classically exact results, but with many orders of magnitude less computation than direct molecular dynamics. The approach provides, for what we believe to be the first time, a connection between stochastic lattice-gas dynamical methods and the interatomic potential function. As a sample application, the diffusion constants are computed for two-dimensional rhodium clusters of up to 75 atoms on the Rh(100) surface at T = 2000 K. For clusters larger than n = 15 atoms, the diffusion constant scales as n/sup -1.76//sup +- //sup 0.06/, and the dominant mechanism for the diffusion is found to be atoms running along the edges of the cluster blocks.

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

    PubMed Central

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

    2014-01-01

    Summary Deprotonation of indazolium salts at low temperatures gives N-heterocyclic carbenes of indazoles (indazol-3-ylidenes) which can be trapped as rhodium complexes (X-ray analysis). In the absence of Rh, the indazol-3-ylidenes spontaneously dimerize under ring cleavage of one of the N,N-bonds and ring closure to an indazole–indole spiro compound which possesses an exocyclic imine group. The E/Z isomers of the imines can be separated by column chromatography when methanol is used as eluent. We present results of a single crystal X-ray analysis of one of the E-isomers, which equilibrate in solution as well as in the solid state. Heating of the indazole–indole spiro compounds results in the formation of quinazolines by a ring-cleavage/ring-closure sequence (X-ray analysis). Results of DFT calculations are presented. PMID:24778738

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

    SciTech Connect

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

    2010-10-01

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

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

    SciTech Connect

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

    2010-12-21

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

  9. Methoxy-Directed Aryl-to-Aryl 1,3-Rhodium Migration

    PubMed Central

    Zhang, Jing; Liu, Jun-Feng; Ugrinov, Angel; Pillai, Anthony F. X.; Sun, Zhong-Ming; Zhao, Pinjing

    2015-01-01

    Through-space metal/hydrogen shift is an important strategy for transition metal-catalyzed C-H bond activation. Here we describe the synthesis and characterization of a Rh(I) 2,6-dimethoxybenzoate complex that underwent stoichiometric rearrangement via a highly unusual 1,3- rhodium migration. This aryl-to-aryl 1,3-Rh/H shift was also demonstrated in a Rh(I)-catalyzed decarboxylative conjugate addition to form a C-C bond at a meta position instead of the ipso-carboxyl position. A deuterium-labeling study under the conditions of Rh(I)-catalyzed protodecarboxylation revealed the involvement of an ortho-methoxy group in a multi-step pathway of consecutive sp3 and sp2 C-H bond activations. PMID:24171626

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

    SciTech Connect

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

    2010-09-15

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

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

    SciTech Connect

    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.

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

    NASA Astrophysics Data System (ADS)

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

    2016-10-01

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

  13. Rhodium Nanoparticle-mesoporous Silicon Nanowire Nanohybrids for Hydrogen Peroxide Detection with High Selectivity

    PubMed Central

    Song, Zhiqian; Chang, Hucheng; Zhu, Weiqin; Xu, Chenlong; Feng, Xinjian

    2015-01-01

    Developing nanostructured electrocatalysts, with low overpotential, high selectivity and activity has fundamental and technical importance in many fields. We report here rhodium nanoparticle and mesoporous silicon nanowire (RhNP@mSiNW) hybrids for hydrogen peroxide (H2O2) detection with high electrocatalytic activity and selectivity. By employing electrodes that loaded with RhNP@mSiNW nanohybrids, interference caused from both many electroactive substances and dissolved oxygen were eliminated by electrochemical assaying at an optimal potential of +75 mV. Furthermore, the electrodes exhibited a high detection sensitivity of 0.53 μA/mM and fast response (< 5 s). This high-performance nanohybrid electrocatalyst has great potential for future practical application in various oxidase-base biosensors. PMID:25588953

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

    SciTech Connect

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

    2011-10-01

    Pacific Northwest National Laboratory has been conducting research to investigate the feasibility of producing mixed alcohols from biomass-derived synthesis gas (syngas). In recent years, this research has primarily involved the further development of catalysts containing rhodium and manganese based on the results of earlier catalyst screening tests. Research during FY 2011 continued to examine the performance of RhMn catalysts on alternative supports including selected zeolite, silica, and carbon supports. Catalyst optimization continued using both the Davisil 645 and Merck Grade 7734 silica supports. Research also was initiated in FY 2011, using the both Davisil 645 silica and Hyperion CS-02C-063 carbon supports, to evaluate the potential for further improving catalyst performance, through the addition of one or two additional metals as promoters to the catalysts containing Rh, Mn, and Ir.

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

    SciTech Connect

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

    2012-11-01

    Pacific Northwest National Laboratory has been conducting research to investigate the feasibility of producing mixed alcohols from biomass-derived synthesis gas (syngas). In recent years, this research has primarily involved the further development of catalysts containing rhodium and manganese based on the results of earlier catalyst screening tests. Testing continued in FY 2012 to further improve the Ir-promoted RhMn catalysts on both silica and carbon supports for producing mixed oxygenates from synthesis gas. This testing re-examined selected alternative silica and carbon supports to follow up on some uncertainties in the results with previous test results. Additional tests were conducted to further optimize the total and relative concentrations of Rh, Mn, and Ir, and to examine selected promoters and promoter combinations based on earlier results. To establish optimum operating conditions, the effects of the process pressure and the feed gas composition also were evaluated.

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

    PubMed Central

    Polan, Vojtěch; Soukup, Jan; Vytřas, Karel

    2010-01-01

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

  17. Selective rhodium-catalyzed reduction of tertiary amides in amino acid esters and peptides.

    PubMed

    Das, Shoubhik; Li, Yuehui; Bornschein, Christoph; Pisiewicz, Sabine; Kiersch, Konstanze; Michalik, Dirk; Gallou, Fabrice; Junge, Kathrin; Beller, Matthias

    2015-10-12

    Efficient reduction of the tertiary amide bond in amino acid derivatives and peptides is described. Functional group selectivity has been achieved by applying a commercially available rhodium precursor and bis(diphenylphosphino)propane (dppp) ligand together with phenyl silane as a reductant. This methodology allows for specific reductive derivatization of biologically interesting peptides and offers straightforward access to a variety of novel peptide derivatives for chemical biology studies and potential pharmaceutical applications. The catalytic system tolerates a variety of functional groups including secondary amides, ester, nitrile, thiomethyl, and hydroxy groups. This convenient hydrosilylation reaction proceeds at ambient conditions and is operationally safe because no air-sensitive reagents or highly reactive metal hydrides are needed. PMID:26189442

  18. Selective rhodium-catalyzed reduction of tertiary amides in amino acid esters and peptides.

    PubMed

    Das, Shoubhik; Li, Yuehui; Bornschein, Christoph; Pisiewicz, Sabine; Kiersch, Konstanze; Michalik, Dirk; Gallou, Fabrice; Junge, Kathrin; Beller, Matthias

    2015-10-12

    Efficient reduction of the tertiary amide bond in amino acid derivatives and peptides is described. Functional group selectivity has been achieved by applying a commercially available rhodium precursor and bis(diphenylphosphino)propane (dppp) ligand together with phenyl silane as a reductant. This methodology allows for specific reductive derivatization of biologically interesting peptides and offers straightforward access to a variety of novel peptide derivatives for chemical biology studies and potential pharmaceutical applications. The catalytic system tolerates a variety of functional groups including secondary amides, ester, nitrile, thiomethyl, and hydroxy groups. This convenient hydrosilylation reaction proceeds at ambient conditions and is operationally safe because no air-sensitive reagents or highly reactive metal hydrides are needed.

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

    PubMed

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

    2012-12-01

    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.

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

    USGS Publications Warehouse

    Hapfty, J.; Riley, L.B.

    1968-01-01

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

  1. The activity of platinum, iridium and rhodium drug complexes against Leishmania donovani.

    PubMed

    Croft, S L; Neal, R A; Craciunescu, D G; Certad-Fombona, G

    1992-03-01

    The activities of twenty seven Platinum, Rhodium and Iridium drug complexes were determined against Leishmania donovani amastigotes in mouse peritoneal macrophages in vitro. Eight compounds showed antileishmanial activity of which only three, Rh(III)-mepacrine, Ir(III) pyrrolidine dithiocarbamate and Ir(III) diethyl dithiocarbamate had ED50 values of less than 1 microM. The two Iridium complexes produced, respectively, a 50% and 39% suppression of L. donovani amastigotes in the liver of BALB/c mice following the subcutaneous administration of 200 mg/kg for 5 consecutive days. Ultrastructural studies suggest that the amastigote kinetoplast-mitochondrion complex is the primary site of action of the Ir and Rh complexes. PMID:1598504

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

    PubMed

    Schatzschneider, Ulrich; Barton, Jacqueline K

    2004-07-21

    A conjugate of a DNA mismatch-specific rhodium intercalator, containing the bulky chrysenediimine ligand, and an aniline mustard has been prepared, and targeting of mismatches in DNA by this conjugate has been examined. The preferential alkylation of mismatched over fully matched DNA is found by a mobility shift assay at concentrations where untethered organic mustards show little reaction. The binding site of the Rh intercalator was determined by DNA photocleavage, and the position of covalent modification was established on the basis of the enhanced depurination associated with N-alkylation. The site-selective alkylation at mismatched DNA renders these conjugates useful tools for the covalent tagging of DNA base pair mismatches and new chemotherapeutic design.

  3. Conclusive evidence on the mechanism of the rhodium-mediated decyanative borylation.

    PubMed

    Esteruelas, Miguel A; Oliván, Montserrat; Vélez, Andrea

    2015-09-30

    The stoichiometric reactions proposed in the mechanism of the rhodium-mediated decyanative borylation have been performed and all relevant intermediates isolated and characterized including their X-ray structures. Complex RhCl{xant(P(i)Pr2)2} (1, xant(P(i)Pr2)2 = 9,9-dimethyl-4,5-bis(diisopropylphosphino)xanthene) reacts with bis(pinacolato)diboron (B2pin2), in benzene, to give the rhodium(III) derivative RhHCl(Bpin){xant(P(i)Pr2)2} (4) and PhBpin. The reaction involves the oxidative addition of B2pin2 to 1 to give RhCl(Bpin)2{xant(P(i)Pr2)2}, which eliminates ClBpin generating Rh(Bpin){xant(P(i)Pr2)2} (2). The reaction of the latter with the solvent yields PhBpin and the monohydride RhH{xant(P(i)Pr2)2} (6), which adds the eliminated ClBpin. Complex 4 and its catecholboryl counterpart RhHCl(Bcat){xant(P(i)Pr2)2} (7) have also been obtained by oxidative addition of HBR2 to 1. Complex 2 is the promoter of the decyanative borylation. Thus, benzonitrile and 4-(trifluoromethyl)benzonitrile insert into the Rh-B bond of 2 to form Rh{C(R-C6H4)═NBpin}{xant(P(i)Pr2)2} (R = H (8), p-CF3 (9)), which evolve into the aryl derivatives RhPh{xant(P(i)Pr2)2} (3) and Rh(p-CF3-C6H4){xant(P(i)Pr2)2} (10), as a result of the extrusion of CNBpin. The reactions of 3 and 10 with B2pin2 yield the arylBpin products and regenerate 2.

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

    PubMed

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

    2015-04-01

    Gravimetrically prepared mono-elemental reference solutions having a well-known mass fraction of approximately 1 g/kg (or a mass concentration of 1 g/L) define the very basis of virtually all measurements in inorganic analysis. Serving as the starting materials of all standard/calibration solutions, they link virtually all measurements of inorganic analytes (regardless of the method applied) to the purity of the solid materials (high-purity metals or salts) they were prepared from. In case these solid materials are characterized comprehensively with respect to their purity, this link also establishes direct metrological traceability to The International System of Units (SI). This, in turn, ensures the comparability of all results on the highest level achievable. Several national metrology institutes (NMIs) and designated institutes (DIs) have been working for nearly two decades in close cooperation with commercial producers on making an increasing number of traceable reference solutions available. Besides the comprehensive characterization of the solid starting materials, dissolving them both loss-free and completely under strict gravimetric control is a challenging problem in the case of several elements like molybdenum and rhodium. Within the framework of the European Metrology Research Programme (EMRP), in the Joint Research Project (JRP) called SIB09 Primary standards for challenging elements, reference solutions of molybdenum and rhodium were prepared directly from the respective metals with a relative expanded uncertainty associated with the mass fraction of U rel(w) < 0.05 %. To achieve this, a microwave-assisted digestion procedure for Rh and a hotplate digestion procedure for Mo were developed along with highly accurate and precise inductively coupled plasma optical emission spectrometry (ICP OES) and multicollector inductively coupled plasma mass spectrometry (MC-ICP-MS) methods required to assist with the preparation and as dissemination tools.

  5. Evidence From a Crystal-Poor, Zoned (Rhyolite-Andesite) Pyroclastic Deposit From Volcan Tepetiltic, Western Mexico for Rapid Generation of Silicic Melt by Partial Melting of Granitoid and not by Segregation From a Long-Lived Crystal-Rich Mush

    NASA Astrophysics Data System (ADS)

    Lange, R. A.; Frey, H.; Hall, C.; Delgado-Granados, H.

    2007-12-01

    Volcan Tepetiltic is an intermediate (56-66 wt % SiO2) arc stratovolcano (~42 km3) that is composed primarily of crystal-rich (25-40 vol%), hornblende-absent andesite flows, with an elliptical caldera (5 km x 2.5 km). The Plinian, caldera-forming eruption produced a zoned (60-75 wt % SiO2) pyroclastic deposit (6-9 km3) that is everywhere crystal-poor (0-3 vol%); where crystals are present, hornblende occurs. The caldera wall exposes ~600 m of stratified lava flows. A series of 40Ar/39Ar dates on these caldera-wall flows, along with numerous dates on flank flows, constrain the time scale for the construction of the andesitic, main edifice of V. Tepetiltic. The collection of Ar dates indicates that V. Tepetiltic was formed at ~525 ka, over an interval of ~90 ± 75 kyrs. In other words, within the 2 sigma error on all the Ar dates, the eruption interval for cone construction of V. Tepetiltic may have been as long as 165 kyrs or as short as 15 kyrs. At the 95% confidence interval, cone construction ceased by ~380 ka. Peripheral to the central vent of V. Tepetiltic are a series of basaltic andesite (56-58 wt%) flows, cones, and one shield (total volume is ~9 km3), which all erupted at ~214 ± 64 ka, over an interval that may have been as long as 128 kyrs or as short as 22 kyrs, within 2 sigma error of the Ar dates. The pyroclastic deposit is found both underneath and on top of these basaltic andesite units, which broadly constrains its eruption age and indicates a temporal association with the pulse of basaltic andesite eruptions. The age of the caldera-forming eruption is further constrained by (must be younger than) the age of a small dacite dome on the caldera floor (190 ± 22 ka) and the age of a lithic (113 ± 76 ka) within the pyroclastic deposit. In summary, the best estimate for the eruption age of the pyroclastic deposit is at ~190 ka. Thus, there was a hiatus of ~200 kyrs between the cone- building episode that produced the crystal-rich (25-40 vol

  6. From para-Benziporphyrin to Rhodium(III) 21-Carbaporphyrins: Imprinting Rh⋅⋅⋅η(2)-CC, Rh⋅⋅⋅η(2)-CO, and Rh⋅⋅⋅η(2)-CH Coordination Motifs.

    PubMed

    Idec, Aneta; Szterenberg, Ludmiła; Latos-Grażyński, Lechosław

    2015-08-24

    Rhodium(III) para-benziporphyrin alters the fundamental reactivity of the built-in para-phenylene moiety. Due to additional macrocyclic stabilization, a sequence of intramolecular rearrangements are triggered to afford rhodium(III) 21-carbaporphyrin, which incorporates the rhodacyclopropane motif. The peculiar reversible transformations of the bridging methylene unit provide an example of selective and reversible aliphatic C-H bond elimination. Rhodium(III) 21-carbaporphyrin can be oxygenated to rhodium(III) 21-oxy-21-carbaporphyrin, whereas the metal ion interacts with the C(21)-O(25) fragment in an η(2) fashion. This species demonstrates a remarkable axial affinity toward alkenes.

  7. Asymmetric hydrogenation in the presence of bisdiphenylphosphine complexes of rhodium. 3. Molecular structure of 2R-3-phenyl-2-(N-methyldiphenylphosphinamino)-1-diphenylphosphinoxypropane (1,5-cyclooctadiene)rhodium(I) perchlorate and its effectiveness as an enantioselective catalyst

    SciTech Connect

    Struchkov, Yu.T.; Yanovskii, A.I.; Pavlov, V.A.; Voloboev, A.A.; Klabunovskii, E.I.

    1987-09-10

    The structure of 2R-3-phenyl-2-methyl-diphenylphosphinamino-1-diphenylphosphinoxypropane(1,5-cyclooctadiene)rhodium (I) perchlorate was determined by x-ray crystallographic analysis, and the asymmetric arrangement of the phosphine phenyl groups was established. Examination of the established structure of the complex in comparison with the previously investigated structures of asymmetric hydrogenation catalysts showed the existence of a correlation between the configuration of the phosphorus atoms in the catalytic complexes and the configuration of the hydrogenation product.

  8. Urban poor program launched.

    PubMed

    1991-01-01

    The government of the Philippines has launched a program to deal with the rapidly growing urban poor population. 60 cities (including Metro Manila) are expected to increase their bloated population by 3.8% over 1990 which would be 27.7 million for 1991. Currently there is an exodus of people from the rural areas and by 2000 half the urban population will be squatters and slum dwellers. Basic services like health and nutrition are not expected to be able to handle this type of volume without a loss in the quality of service. The basic strategy of the new program is to recruit private medical practitioners to fortify the health care delivery and nutrition services. Currently the doctor/urban dweller ration is 1:9000. The program will develop a system to pool the efforts of government and private physicians in servicing the target population. Barangay Escopa has been chosen as the pilot city because it typifies the conditions of a highly populated urban area. The projects has 2 objectives: 1) demonstrate the systematic delivery of health and nutrition services by the private sector through the coordination of the government, 2) reduce mortality and morbidity in the community, especially in the 0-6 age group as well as pregnant women and lactating mothers.

  9. Morphosyntax in Poor Comprehenders

    PubMed Central

    Adlof, Suzanne M.; Catts, Hugh W.

    2016-01-01

    Children described as poor comprehenders (PCs) have reading comprehension difficulties in spite of adequate word reading abilities. PCs are known to display weakness with semantics and higher-level aspects of oral language, but less is known about their grammatical skills, especially with regard to morphosyntax. The purpose of this study was to examine morphosyntax in fourth grade PCs and typically developing readers (TDs), using three experimental tasks involving finiteness marking. Participants also completed standardized, norm-referenced assessments of phonological memory, vocabulary, and broader language skills. PCs displayed weakness relative to TDs on all three morphosyntax tasks and on every other assessment of oral language except phonological memory, as indexed by nonword repetition. These findings help to clarify the linguistic profile of PCs, suggesting that their language weaknesses include grammatical weaknesses that cannot be fully explained by semantic factors. Because finiteness markers are usually mastered prior to formal schooling in typical development, we call for future studies to examine whether assessments of morphosyntax could be used for the early identification of children at risk for future reading comprehension difficulty. PMID:27397969

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

    PubMed

    Barry, Nicolas P E; Sadler, Peter J

    2012-04-21

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

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

    NASA Astrophysics Data System (ADS)

    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.

  12. Chiral ammonium-capped rhodium(0) nanocatalysts: synthesis, characterization, and advances in asymmetric hydrogenation in neat water.

    PubMed

    Bilé, Elodie Guyonnet; Cortelazzo-Polisini, Elodie; Denicourt-Nowicki, Audrey; Sassine, Rita; Launay, Franck; Roucoux, Alain

    2012-01-01

    Optically active amphiphilic compounds derived from N-methylephedrine, N-methylprolinol, or cinchona derivatives possessing bromide or chiral lactate counterions were efficiently used as protective agents for rhodium(0) nanoparticles. The full characterization of these surfactants and the obtained nanocatalysts was performed by means of different techniques. These spherical nanoparticles, with sizes between 0.8-2.5 nm depending on the stabilizer, were evaluated in the hydrogenation of model substrates in neat water as a green solvent. The rhodium catalysts showed relevant kinetic properties, but modest enantiomeric excess values of up to 13 % in the hydrogenation of ethyl pyruvate. They were also investigated in the hydrogenation of disubstituted arenes, such as m-methylanisole, providing interesting catalytic activities and a preferential cis selectivity of around 80 %; however, no asymmetric induction was observed.

  13. Asymmetric Hydrogenation of α-Purine Nucleobase-Substituted Acrylates with Rhodium Diphosphine Complexes: Access to Tenofovir Analogues.

    PubMed

    Sun, Huan-Li; Chen, Fei; Xie, Ming-Sheng; Guo, Hai-Ming; Qu, Gui-Rong; He, Yan-Mei; Fan, Qing-Hua

    2016-05-01

    The first asymmetric hydrogenation of α-purine nucleobase-substituted α,β-unsaturated esters, catalyzed by a chiral rhodium (R)-Synphos catalyst, has been developed. A wide range of mono- and disubstituted acrylates were successfully hydrogenated under very mild conditions in high yields with good to excellent enantioselectivities (up to 99% ee). This method provides a convenient approach to the synthesis of a new kind of optically pure acyclic nucleoside and Tenofovir analogues. PMID:27112983

  14. Rhodium-Catalyzed Regioselective Hydroxylation of Cage B-H Bonds of o-Carboranes with O2 or Air.

    PubMed

    Lyu, Hairong; Quan, Yangjian; Xie, Zuowei

    2016-09-19

    A rhodium-catalyzed hydroxylation of a cage B4-H bond in o-carboranes with either O2 or air as the oxygen source is described, and serves as a new methodology for the regioselective generation of a series of 4-OH-o-carboranes in a one-pot process. The use of either O2 or air as both the oxidant and the oxygen source makes this protocol very environmentally friendly and practical. PMID:27599774

  15. Asymmetric Conjugate Alkynylation of Cyclic α,β-Unsaturated Carbonyl Compounds with a Chiral Diene Rhodium Catalyst.

    PubMed

    Dou, Xiaowei; Huang, Yinhua; Hayashi, Tamio

    2016-01-18

    Asymmetric conjugate alkynylation of cyclic α,β-unsaturated carbonyl compounds (ketones, esters, and amides) was realized by use of diphenyl[(triisopropylsilyl)ethynyl]methanol as an alkynylating reagent in the presence of a rhodium catalyst coordinated with a new chiral diene ligand (Fc-bod; bod=bicyclo[2.2.2]octa-2,5-diene, Fc=ferrocenyl) to give high yields of the corresponding β-alkynyl-substituted carbonyl compounds with 95-98% ee. PMID:26636764

  16. Rhodium-catalyzed dynamic kinetic asymmetric transformations of racemic allenes by the [3+2] annulation of aryl ketimines.

    PubMed

    Tran, Duc N; Cramer, Nicolai

    2013-09-27

    Racemization required: Rhodium(I)-catalyzed C-H activation directed by unprotected ketimines initiates selective [3+2] cycloaddition with allenes, providing access to highly substituted indenylamines. The reaction proceeds through the dynamic kinetic asymmetric transformation of racemic allenes. The catalyst controls the enantio- and diastereoselectivity, the regioselectivities of the C-H activation and allene incorporation, as well as the E/Z ratio.

  17. Rhodium-catalyzed carbonylation of cyclopropyl substituted propargyl esters: a tandem 1,3-acyloxy migration [5 + 1] cycloaddition.

    PubMed

    Shu, Dongxu; Li, Xiaoxun; Zhang, Min; Robichaux, Patrick J; Guzei, Ilia A; Tang, Weiping

    2012-08-01

    We have developed two different types of tandem reactions for the synthesis of highly functionalized cyclohexenones from cyclopropyl substituted propargyl esters. Both reactions were initiated by rhodium-catalyzed Saucy-Marbet 1,3-acyloxy migration. The resulting cyclopropyl substituted allenes derived from acyloxy migration then underwent [5 + 1] cycloaddition with CO. The acyloxy group not only eased the access to allene intermediates but also provided a handle for further selective functionalizations.

  18. Rhodium-Catalyzed Carbonylation of Cyclopropyl Substituted Propargyl Esters: A Tandem 1,3-Acyloxy Migration [5+1] Cycloaddition

    PubMed Central

    Shu, Dongxu; Li, Xiaoxun; Zhang, Min; Robichaux, Patrick J.; Guzei, Ilia A.

    2012-01-01

    We have developed two different types of tandem reactions for the synthesis of highly functionalized cyclohexenones from cyclopropyl substituted propargyl esters. Both reactions were initiated by rhodium-catalyzed Saucy-Marbet 1,3-acyloxy migration. The resulting cyclopropyl substituted allenes derived from acyloxy migration then underwent [5+1] cycloaddition with CO. The acyloxy group not only eased the access to allene intermediates but also provided a handle for further selective functionalizations. PMID:22793991

  19. Carboxylated polymers functionalized by cyclodextrins for the stabilization of highly efficient rhodium(0) nanoparticles in aqueous phase catalytic hydrogenation.

    PubMed

    Noël, Sébastien; Léger, Bastien; Herbois, Rudy; Ponchel, Anne; Tilloy, Sébastien; Wenz, Gerhard; Monflier, Eric

    2012-11-21

    Rhodium(0) nanoparticles stabilized by a polymer containing carboxylate and β-cyclodextrin moieties have high stability and catalytic activity for aqueous hydrogenation reactions of olefins and aromatic substrates. This catalytic system can be recycled and reused without loss of activity. These high catalytic performances can be attributed to conjugated electrostatic interactions (carboxylate groups) and steric interactions (polymer structure and β-cyclodextrin moiety). PMID:23007202

  20. Rhodium-catalyzed annulative coupling of 3-phenylthiophenes with alkynes involving double C-H bond cleavages.

    PubMed

    Iitsuka, Tomonori; Hirano, Koji; Satoh, Tetsuya; Miura, Masahiro

    2014-01-01

    Double CH bond activation took place efficiently upon treatment of 3-phenylthiophenes with alkynes in the presence of a rhodium catalyst and a copper salt oxidant to form the corresponding naphthothiophene derivatives. Dehydrogenative coupling with alkenes was also found to occur on the phenyl moiety rather than the thiophene ring. These reactions provide straightforward synthetic methods for π-conjugated molecules involving a thiophene unit from readily available, simple building blocks. PMID:24288235

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

    PubMed

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

    2014-12-01

    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.

  2. Surface organometallic chemistry: Reaction of tris-allyl rhodium with surfaces of silica, alumina, titania, and magnesia

    SciTech Connect

    Dufour, P.; Houtman, C.; Santini, C.C.

    1992-05-20

    The reaction of Rh({eta}{sup 3}-C{sub 3}H{sub 5}){sub 3}, 1, with silica, alumina, titania, and magnesia has been followed by infrared spectroscopy, isotopic labeling experiments, quantitative analysis of gaseous products, and elemental analysis. Complex 1 reacts rapidly with alumina pretreated to 350{degrees}C and with silica and titania to form a bis-allylic rhodium species grafted to the surface, but no immediate reaction was observed between 1 and alumina pretreated to 200 {degrees}C or magnesia. This reaction likely proceeds via electrophilic cleavage of Rh-C bonds of 1 by a surface OH group. On silica, the results of IR experiments after labeling the surface with {sup 16}O-D and {sup 18}O-H and structural arguments suggest that two 18-electron species are possible on the surface: one for which the rhodium is coordinated both to an oxygen and a hydroxyl group linked to the same silicon atom and another for which the oxygen atom and the OH group are linked to two different silicon atoms. Molecular mechanics modeling of silica, alumina, and titania was used as a complement to the experimental work to test the plausibility of various modes of attachment of the rhodium allyl complex. 40 refs., 17 figs., 4 tabs.

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

    NASA Astrophysics Data System (ADS)

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

    2014-12-01

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

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

    PubMed

    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.

  5. Characterization of model three-way catalysts. 3: Infrared study of the surface composition of platinum-rhodium ceria-alumina catalysts

    SciTech Connect

    Rogemond, E.; Frety, R.; Perrichon, V.; Primet, M.; Chevrier, M.; Gauthier, C.; Mathis, F.

    1999-09-10

    The surface composition of model and commercial bimetallic PtRh catalysts supported on ceria-alumina was tentatively determined by FTIR spectroscopy using the successive adsorption of NO at 473 K and CO at 298 K method which was previously applied to the case of PtRh/Al{sub 2}O{sub 3} catalysts. The study of monometallic model catalysts shows that the adsorption of NO at 473 K on rhodium gives an intense band at 1912 cm{sup {minus}1} which is not modified by the presence of ceria and therefore can be used to quantify the number of surface rhodium atoms. However, the chemisorption properties of platinum toward the subsequent adsorption of CO at 298 K are strongly modified and the quantification of the surface platinum atoms could not be directly measured. However, their number could be indirectly obtained by combining the NO adsorption for rhodium and hydrogen volumetric adsorption for the total number of surface metal atoms, assuming that NO adsorption does not induce an important segregation of rhodium for bimetallic particles. Thus, for the fresh bimetallic model catalyst, the same composition was obtained at the surface and in the bulk. After aging at 1273 K, no rhodium was detected at the surface. This absence of surface rhodium atoms was confirmed by the data obtained from the direct adsorption of CO on platinum at room temperature, which gave the same number of surface atoms as hydrogen chemisorption. Similar results have been obtained with two commercial three-way catalysts. In particular, after aging at 1273 K, rhodium was practically not detected on the surface.

  6. Consequences of Growing Up Poor.

    ERIC Educational Resources Information Center

    Duncan, Greg J., Ed.; Brooks-Gunn, Jeanne, Ed.

    The consequences and correlates of growing up poor as well as the mechanisms through which poverty influences children are explored. This book is organized with a primary focus on research findings and a secondary concern with policy implications. The chapters are: (1) "Poor Families, Poor Outcomes: The Well-Being of Children and Youth" (Jeanne…

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

    PubMed

    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

  8. Rhodium-Catalyzed Dehydrogenative Silylation of Acetophenone Derivatives: Formation of Silyl Enol Ethers versus Silyl Ethers.

    PubMed

    Garcés, Karin; Lalrempuia, Ralte; Polo, Víctor; Fernández-Alvarez, Francisco J; García-Orduña, Pilar; Lahoz, Fernando J; Pérez-Torrente, Jesús J; Oro, Luis A

    2016-10-01

    A series of rhodium-NSiN complexes (NSiN=bis (pyridine-2-yloxy)methylsilyl fac-coordinated) is reported, including the solid-state structures of [Rh(H)(Cl)(NSiN)(PCy3 )] (Cy=cyclohexane) and [Rh(H)(CF3 SO3 )(NSiN)(coe)] (coe=cis-cyclooctene). The [Rh(H)(CF3 SO3 )(NSiN)(coe)]-catalyzed reaction of acetophenone with silanes performed in an open system was studied. Interestingly, in most of the cases the formation of the corresponding silyl enol ether as major reaction product was observed. However, when the catalytic reactions were performed in closed systems, formation of the corresponding silyl ether was favored. Moreover, theoretical calculations on the reaction of [Rh(H)(CF3 SO3 )(NSiN)(coe)] with HSiMe3 and acetophenone showed that formation of the silyl enol ether is kinetically favored, while the silyl ether is the thermodynamic product. The dehydrogenative silylation entails heterolytic cleavage of the Si-H bond by a metal-ligand cooperative mechanism as the rate-determining step. Silyl transfer from a coordinated trimethylsilyltriflate molecule to the acetophenone followed by proton transfer from the activated acetophenone to the hydride ligand results in the formation of H2 and the corresponding silyl enol ether.

  9. Synthesis, Structure, and Conformational Dynamics of Rhodium and Iridium Complexes of Dimethylbis(2-pyridyl)borate†

    PubMed Central

    Pennington-Boggio, Megan K.; Conley, Brian L.; Richmond, Michael G.; Williams, Travis J.

    2014-01-01

    Rhodium(I) and Iridium(I) borate complexes of the structure [Me2B(2-py)2]ML2 (L2 = (tBuNC)2, (CO)2, (C2H4)2, cod, dppe) were prepared and structurally characterized (cod = 1,5-cyclooctadiene; dppe = 1,2-diphenylphosphinoethane). Each contains a boat-configured chelate ring that participates in a boat-to-boat ring flip. Computational evidence shows that the ring flip proceeds through a transition state that is near planarity about the chelate ring. We observe an empirical, quantitative correlation between the barrier of this ring flip and the π acceptor ability of the ancillary ligand groups on the metal. The ring flip barrier correlates weakly to the Tolman and Lever ligand parameterization schemes, apparently because these combine both σ and π effects while we propose that the ring flip barrier is dominated by π bonding. This observation is consistent with metal-ligand π interactions becoming temporarily available only in the near-planar transition state of the chelate ring flip and not the boat-configured ground state. Thus, this is a first-of-class observation of metal-ligand π bonding governing conformational dynamics. PMID:25435645

  10. Unravelling the mechanism of glycerol hydrogenolysis over rhodium catalyst through combined experimental-theoretical investigations.

    PubMed

    Auneau, Florian; Michel, Carine; Delbecq, Françoise; Pinel, Catherine; Sautet, Philippe

    2011-12-01

    We report herein a detailed and accurate study of the mechanism of rhodium-catalysed conversion of glycerol into 1,2-propanediol and lactic acid. The first step of the reaction is particularly debated, as it can be either dehydration or dehydrogenation. It is expected that these elementary reactions can be influenced by pH variations and by the nature of the gas phase. These parameters were consequently investigated experimentally. On the other hand, there was a lack of knowledge about the behaviour of glycerol at the surface of the metallic catalyst. A theoretical approach on a model Rh(111) surface was thus implemented in the framework of density functional theory (DFT) to describe the above-mentioned elementary reactions and to calculate the corresponding transition states. The combination of experiment and theory shows that the dehydrogenation into glyceraldehyde is the first step for the glycerol transformation on the Rh/C catalyst in basic media under He or H(2) atmosphere. PMID:22069214

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

    PubMed

    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%).

  12. Rhodium-Catalyzed Dehydrogenative Silylation of Acetophenone Derivatives: Formation of Silyl Enol Ethers versus Silyl Ethers.

    PubMed

    Garcés, Karin; Lalrempuia, Ralte; Polo, Víctor; Fernández-Alvarez, Francisco J; García-Orduña, Pilar; Lahoz, Fernando J; Pérez-Torrente, Jesús J; Oro, Luis A

    2016-10-01

    A series of rhodium-NSiN complexes (NSiN=bis (pyridine-2-yloxy)methylsilyl fac-coordinated) is reported, including the solid-state structures of [Rh(H)(Cl)(NSiN)(PCy3 )] (Cy=cyclohexane) and [Rh(H)(CF3 SO3 )(NSiN)(coe)] (coe=cis-cyclooctene). The [Rh(H)(CF3 SO3 )(NSiN)(coe)]-catalyzed reaction of acetophenone with silanes performed in an open system was studied. Interestingly, in most of the cases the formation of the corresponding silyl enol ether as major reaction product was observed. However, when the catalytic reactions were performed in closed systems, formation of the corresponding silyl ether was favored. Moreover, theoretical calculations on the reaction of [Rh(H)(CF3 SO3 )(NSiN)(coe)] with HSiMe3 and acetophenone showed that formation of the silyl enol ether is kinetically favored, while the silyl ether is the thermodynamic product. The dehydrogenative silylation entails heterolytic cleavage of the Si-H bond by a metal-ligand cooperative mechanism as the rate-determining step. Silyl transfer from a coordinated trimethylsilyltriflate molecule to the acetophenone followed by proton transfer from the activated acetophenone to the hydride ligand results in the formation of H2 and the corresponding silyl enol ether. PMID:27553810

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

    PubMed

    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.

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

    PubMed Central

    2016-01-01

    Summary 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 C S and C 2 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. PMID:26877814

  15. Study of the reference standard facility of rhodium-iron resistance thermometer

    NASA Astrophysics Data System (ADS)

    Yin, L.; Lin, P.; Qi, X.

    2014-03-01

    A 704 type 4He cryostat is designed and the "National (China) Temperature Working Standard Group of the ITS-90 at 1.2-24 K" have been composed. A 703 type 3He cryostat have been established and the working temperature of the "National Temperature Working Standard Group of the ITS-90 at 1.2-24 K" is extended to 0.65 K, which is the lowest limit temperature of ITS-90. The 5 rhodium-iron resistance thermometers (RIRTs) which compose the Working Standard Group have been transformed to the International Temperature Scale of 1990 (ITS-90). A set of indexing data is fitted and calculated as the indexing table of the standard facility of RIRT. 42 basis temperature points have been measured at 0.67-26.37 K. The results show that the temperature control level could reach 0.5 mK/30 min. The difference between the temperature value of the 5 RIRTs and the average is less than 1.1 mK, and the comparison measurements uncertainty is 0.95 mK.

  16. Properties of Binuclear Rhodium(II) Complexes and Their Antibacterial Activity

    PubMed Central

    Pruchnik, Florian P.; Bień, Małgorzata; Lachowicz, Tadeusz

    1996-01-01

    Binuclear rhodium(II) complexes [Rh2Cl2(μ-OOCR)2(N-N)2], [Rh2(μ-OOCR)2(N-N)2(H2O)2](RCOO)2 and [Rh2Cl2(μ-OOCCH3)(terpy)2](H3O)Cl2.9H2O (R = H, Me, Bun, ph, PhCHOH; N-N = 2,2′-bipyridine (bpy), 1,10-phenanthroline (phen), 2,9-dimethyl-1,10-phenanthroline (dmp) and 6,7-dimethyl-2,3- di(2-pyridyl)quinoxaline (dmpq); terpy 2,2′:6′,2′′-terpyridine) have been synthesized and their structure and properties have been studied by electronic, IR and 1H NMR spectroscopy. Antibacterial activity of these complexes against Staphylococcus aureus and Escherichia coli has been investigated. The most active antibacterial agents against S. aureus were [Rh2(OOCPh)2(phen)2(H2O)2]2+, [Rh2(OOCPh)2(dmpq)2(H2O)2]2+, [Rh2(OOCBu)2(phen)2(H2O)2]2+ and [Rh2-(OOCBu)2(bpy)2(H2O)2]2+ which were considerably more active than the appropriate nitrogen ligands. The complexes show rather low activity against E. coli. PMID:18475754

  17. The Etiology of Poor Neighborhoods.

    ERIC Educational Resources Information Center

    Greenberg, Stanley B.

    The inner city aggregations of blacks, Appalachian whites, and Mexicans are not simply the focal points for short-term instability or remedial governmental programs: they are the first native American urban poor. The poor neighborhoods of America's inner city are a result of three great population movements. One originated in the Atlantic Coastal…

  18. Rhodium-catalyzed (5+1) annulations between 2-alkenylphenols and allenes: a practical entry to 2,2-disubstituted 2H-chromenes.

    PubMed

    Casanova, Noelia; Seoane, Andrés; Mascareñas, José L; Gulías, Moisés

    2015-02-16

    Readily available alkenylphenols react with allenes under rhodium catalysis to provide valuable 2,2-disubstituted 2H-chromenes. The whole process, which involves the cleavage of one C-H bond of the alkenyl moiety and the participation of the allene as a one-carbon cycloaddition partner, can be considered a simple, versatile, and atom-economical (5+1) heteroannulation. The reaction tolerates a broad range of substituents both in the alkenylphenol and in the allene, and most probably proceeds through a mechanism involving a rhodium-catalyzed C-C coupling followed by two sequential pericyclic processes.

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

    PubMed

    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. PMID:25345587

  20. Complexation of heteroaromatic N-oxides with rhodium(II) tetracarboxylates in solution: DFT and NMR investigations

    NASA Astrophysics Data System (ADS)

    Głaszczka, Rafał; Jaźwiński, Jarosław

    2014-03-01

    Complexation of rhodium(II) tetraacetate and rhodium(II) tetrakistrifluoroacetate with a set of heteroaromatic N-oxides containing additional functional groups was investigated by means of density functional theory (DFT) calculations, and 1H, 13C and 15N nuclear magnetic resonance (NMR) spectroscopy in CDCl3 solutions. Chemical shifts for five N-oxides and their 1:1 adducts with rhodium tetraacetate were computed at the B3PW91/[6-311++G(2d,p), Stuttgart ECP)//B3LYP/[6-31G(2d), LANL2DZ] theory level applying IEF PCM (CHCl3) solvation model and taking into account various complexation modes and conformational variety. Calculated values were used for the estimation of complexation shifts Δδ (Δδ = δadduct - δligand). The largest negative complexation shift were estimated for heteroatoms bonded to Rh, from -37 to -70 ppm (N), from -100 to -160 ppm (O in NO group), from -13 to -23 ppm (O in OCH3 group), and from -12 to -22 ppm (Cl). For the remaining heteroatoms in adducts, the corresponding Δδ values ranged from -22 to +8.2 ppm (N), from +3 to +58 ppm (O) and from +6 to +51 ppm (Cl). The Δδ(1H) usually did not exceed 1 ppm, whereas Δδ(13C) varied from ca. -1 to +7 ppm. Some trends useful for the determination of the complexation site were extracted from calculated data sets. Theoretical findings were applied to analyse experimental NMR data.

  1. Reactions of rhodium and ruthenium atoms with nitrous oxide: a combined matrix infrared spectroscopic and theoretical study.

    PubMed

    Jiang, Ling; Xu, Qiang

    2009-05-14

    Reactions of laser-ablated Rh and Ru atoms with N(2)O molecules in excess argon have been investigated using matrix-isolation infrared spectroscopy. Rhodium and ruthenium nitrous oxide complexes, M(NNO)(x) (M = Rh, Ru; x = 1, 2), have been observed and identified on the basis of isotopic shifts, mixed isotopic splitting patterns, and CCl(4)-doping experiments. Density functional theory calculations have been performed on the products. The overall agreement between the experimental and calculated vibrational frequencies, relative absorption intensities, and isotopic shifts supports the identification of these species from the matrix infrared spectra. Furthermore, a plausible reaction mechanism for the formation of the products has been proposed.

  2. Rhodium-Catalyzed Cyclization of 2-Ethynylanilines in the Presence of Isocyanates: Approach toward Indole-3-carboxamides.

    PubMed

    Mizukami, Akiho; Ise, Yumi; Kimachi, Tetsutaro; Inamoto, Kiyofumi

    2016-02-19

    Catalytic synthesis of indole-3-carboxamides from 2-ethynylanilines and isocyanates was achieved in the presence of a rhodium catalyst through a tandem-type, cyclization-addition sequence. This tandem-type process can be performed under mild reaction conditions, affording 2,3-disubstituted indoles in a one-pot manner generally in good to excellent yields. The broad substrate scope and good functional group compatibility make the method highly efficient and widely applicable, providing a facile and entirely novel route toward variously substituted indole-3-carboxamides.

  3. Enantioselective Alkynylation of 2-Trifluoroacetyl Imidazoles Catalyzed by Bis-Cyclometalated Rhodium(III) Complexes Containing Pinene-Derived Ligands.

    PubMed

    Zheng, Yu; Harms, Klaus; Zhang, Lilu; Meggers, Eric

    2016-08-16

    Chiral rhodium(III) complexes containing two cyclometalating 2-phenyl-5,6-(S,S)-pinenopyridine ligands and two additional acetonitriles are introduced as excellent catalysts for the highly enantioselective alkynylation of 2-trifluoroacetyl imidazoles. Whereas the ligand-based chirality permits the straightforward synthesis of the complexes in a diastereomerically and enantiomerically pure fashion, the metal-centered chirality is responsible for the asymmetric induction over the course of the catalysis. For comparison, the analogous iridium congeners provide only low enantioselectivity, and previously reported benzoxazole- and benzothiazole-based catalysts do not show any catalytic activity for this reaction under standard reaction conditions. PMID:27312941

  4. Rhodium-Catalyzed Stereoselective Intramolecular [5 + 2] Cy-cloaddition of 3-Acyloxy-1,4-enyne and Alkene

    PubMed Central

    Shu, Xing-zhong; Schienebeck, Casi M.; Li, Xiaoxun; Zhou, Xin; Song, Wangze; Chen, Lianqing; Guzei, Ilia A.; Tang, Weiping

    2015-01-01

    The first rhodium-catalyzed intramolecular [5 + 2] cycloaddition of 3-acyloxy-1,4-enyne and alkene was developed. The cycloaddition is highly diastereoselective in most cases. Various cis-fused bicyclo[5.3.0]decadienes were prepared stereoselectively. The chirality in the propargylic ester starting materials could be transferred to the bicyclic products with high efficiency. Electron-deficient phosphine ligand greatly facilitated the cycloaddition. Up to three new stereogenic centers could be generated. The resulting diene in the products could be hydrolyzed to enones, which allowed the introduction of more functional groups to the seven-membered ring. PMID:26440751

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

    SciTech Connect

    Quinlan, M.A. |

    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.

  6. Isotopic exchange between 2,2-dimethylbutane and deuterium on rhodium/silica gel catalysts

    SciTech Connect

    Takehara, D.K.; Butt, J.B.; Burwell, R.L. Jr. )

    1992-02-01

    Isotropic exchange between 2.2-dimethylbutane and deuterium has been investigated at 75 C on 10 rhodium on wide-pore silica gel catalysts with H(chemisorbed)/Rh(D{sub h}) ranging from 11 to 108% and subjected to a variety of pretreatment conditions. Some catalysts were prepared by ion exchange with Rh(NH{sub 3}){sub 5}(H{sub 2}O){sup 3-} and some by impregnation to incipient wetness with Rh{sub 4}(CO){sub 12} or Rh{sub 6}(CO){sub 16}. The turnover frequency (N{sub t}) is affected both by D{sub h} and by the conditions of pretreatment. The extreme variation was a factor of 330. Exchange into the ethyl group was about 10 times faster than into the t-butyl group. In general, the catalysts of largest D{sub h} gave the largest N{sub t} and the smallest degree of multiple exchange in the ethyl group. The pretreatment, H{sub 2}, 450 C gave the largest N{sub t}. Mere removal of H* from catalysts so treated by He, 300 C had little effect, but He, 450 C led to a substantial decrease in N{sub t} except for 11-Rh/SiO{sub 2}. The various coupled values of N{sub t} and selectivity resulting from variations in D{sub h} and pretreatment require a minimum of eight different sites. N{sub t}'s and selectivities in the hydrogenolysis of methylcyclopropane on these same catalysts parallel those in the exchange of neohexane.

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

    NASA Astrophysics Data System (ADS)

    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

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

    PubMed

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

    2010-10-01

    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, <0.010-1.011 ng g⁻¹; Pt, 0.016-2.734 ng g⁻¹; and Rh, 0.063-1.298 ng g⁻¹. Data on 7 areas were similar suggesting that no specific source, for example traffic or anthropogenic activity, influenced directly the metal concentrations in 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.

  9. The poor man's cell block

    PubMed Central

    Darlington, Ann

    2010-01-01

    The authors describe a simple method for making formalin or isopropyl alcohol vapour fixed cell blocks from fine needle aspiration cytology specimens that we refer to as ‘The Poor Man's Cell Block.’ PMID:20671053

  10. Economic Rationality of the Poor

    ERIC Educational Resources Information Center

    Newton, Jan M.

    1977-01-01

    Utilizing ethnographic data on several rural families, the economic rationality of the rural poor is demonstrated to be implicit in their behavior. Identification is also made of some of the constraints within which these consumer decisions are made. (JC)

  11. Complexation of oxygen ligands with dimeric rhodium(II) tetrakistrifluoroacetate in chloroform: 1H, 13C NMR and DFT studies

    NASA Astrophysics Data System (ADS)

    Głaszczka, Rafał; Jaźwiński, Jarosław

    2013-03-01

    The complexation of dimeric rhodium(II) tetrakistrifluoroacetylate with 25 ligands containing oxygen atoms: alcohols, ethers, ketones, aldehydes, carboxylic acids and esters in chloroform solution have been investigated by 1H and 13C NMR spectroscopy and Density Functional Theory (DFT) methods. Investigated ligands form 1:1 adducts in our experimental conditions, with stability constants in the order of several hundred mol-1. The exchange of ligands in solution is fast on the NMR spectroscopic timescale. The decrease of longitudinal relaxation times T1 in ligands in the presence of rhodium salt has been tested as the means of determination of the complexation site in ligands. The influence of complexation on chemical shifts in ligands was evaluated by a parameter complexation shift Δδ (Δδ = δadd - δlig). These parameters were positive (>0 ppm) and did not exceed 1 ppm for 1H NMR; and varied from ca. -5 to +15 ppm in the case of 13C NMR. The calculation by DFT methods using the B3LYP functional (structure optimization, electronic energy) and B3PW91 functional (shielding), and combinations of the (6-31G(2d), 6-311G++(2d,p), and LANL2DZ basis sets, followed by scaling procedures reproduced satisfactorily 1H and 13C chemical shifts and, with some limitations, allowed to estimate Δδ parameters.

  12. Cationic mono and dicarbonyl pincer complexes of rhodium and iridium to assess the donor properties of PCcarbeneP ligands.

    PubMed

    Smith, Joel D; Logan, Jessamyn R; Doyle, Lauren E; Burford, Richard J; Sugawara, Shun; Ohnita, Chiho; Yamamoto, Yohsuke; Piers, Warren E; Spasyuk, Denis M; Borau-Garcia, Javier

    2016-08-01

    The donor properties of five different PCcarbeneP ligands are assessed by evaluation of the CO stretching frequencies in iridium(i) and rhodium(i) carbonyl cations. The ligands feature dialkyl phosphine units (R = (i)Pr or (t)Bu) linked to the central benzylic carbon by either an ortho-phenylene bridge, or a 2,3-benzo[b]thiophene linker; in the former, substituent patterns on the phenyl linker are varied. The carbonyl complexes are synthesized from the (PCcarbeneP)M-Cl starting materials via abstraction of the chlorides in the presence of CO gas. In addition to the expected mono carbonyl cations, products with two carbonyl ligands are produced, and for the rhodium example, a novel product in which the second carbonyl ligand adds reversibly across the Rh[double bond, length as m-dash]C bond to give an η(2) ketene moiety was characterized. The IR data for the complexes shows the 2,3-benzo[b]thiophene linked system to be the poorest overall donor, while the phenyl bridged ligands incorporating electron donating dialkyl amino groups para to the anchoring carbene are very strongly donating pincer arrays. PMID:27465584

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

    SciTech Connect

    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.

  14. Reversed reactivity of anilines with alkynes in the rhodium-catalysed C–H activation/carbonylation tandem

    PubMed Central

    Midya, Siba P.; Sahoo, Manoj K.; Landge, Vinod G.; Rajamohanan, P. R.; Balaraman, Ekambaram

    2015-01-01

    Development of multicatalytic approach consisting of two or more mechanistically distinct catalytic steps using a single-site catalyst for rapid and straightforward access of structurally complex molecules under eco-benign conditions has significance in contemporary science. We have developed herein a rhodium-catalysed C–H activation strategy which uses an unprotected anilines and an electron-deficient alkynes to C–C bonded products as a potential intermediate in contrast to the archetypical C–N bonded products with high levels of regioselectivity. This is followed by carbonylation of C–H bond activated intermediate and subsequent annulation into quinolines has been described. This rhodium-catalysed auto-tandem reaction operates under mild, environmentally benign conditions using water as the solvent and CO surrogates as the carbonyl source with the concomitant generation of hydrogen gas. The strategy may facilitate the development of new synthetic protocols for the efficient and sustainable production of chemicals in an atom-economic way from simple, abundant starting materials. PMID:26486182

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

    PubMed

    Lee, Jin-Young; Rajesh Kumar, J; Kim, Joon-Soo; Park, Hyung-Kyu; Yoon, Ho-Sung

    2009-08-30

    Liquid-liquid extraction/separation of platinum(IV) and rhodium(III) from acidic chloride solutions was carried out using tri-iso-octylamine (Alamine 308) as an extractant diluted in kerosene. The percentage extraction of platinum(IV) and rhodium(III) increased with increase in acid concentration up to 8 mol L(-1). However, at 10 mol L(-1) HCl concentration, the extraction behavior was reversed, indicating the solvation type mechanism during extraction. The quantitative extraction of approximately 98% platinum(IV) and 36% rhodium(III) was achieved with 0.01 mol L(-1) Alamine 308. The highest separation factor (S.F.=184.7) of platinum(IV) and rhodium(III) was achieved with 0.01 mol L(-1) Alamine 308 at 1.0 mol L(-1) of hydrochloric acid concentration. Alkaline metal salts like sodium chloride, sodium nitrate, sodium thiocyanate, lithium chloride, lithium nitrate, potassium chloride and potassium thiocyanate used for the salting-out effect. LiCl proved as best salt for the extraction of platinum(IV). Temperature effect demonstrates that the extraction process is exothermic. Hydrochloric acid and thiourea mixture proved to be better stripping reagents when compared with other mineral acids and bases. PMID:19285802

  16. Rhodium-catalyzed asymmetric addition of arylboronic acids to cyclic N-sulfonyl ketimines towards the synthesis of α,α-diaryl-α-amino acid derivatives.

    PubMed

    Takechi, Ryosuke; Nishimura, Takahiro

    2015-05-01

    Rhodium/chiral diene complex-catalyzed asymmetric addition of arylboronic acids to cyclic ketimines having an ester group proceeded to give the corresponding α-amino acid derivatives in high yields with high enantioselectivity. The cyclic amino acid derivative was transformed into a linear α,α-diaryl-substituted α-N-methylamino acid ester.

  17. Poor smokers, poor quitters, and cigarette tax regressivity.

    PubMed

    Remler, Dahlia K

    2004-02-01

    The traditional view that excise taxes are regressive has been challenged. I document the history of the term regressive tax, show that traditional definitions have always found cigarette taxes to be regressive, and illustrate the implications of the greater price responsiveness observed among the poor. I explain the different definitions of tax burden: accounting, welfare-based willingness to pay, and welfare-based time inconsistent. Progressivity (equity across income groups) is sensitive to the way in which tax burden is assessed. Analysis of horizontal equity (fairness within a given income group) shows that cigarette taxes heavily burden poor smokers who do not quit, no matter how tax burden is assessed.

  18. Are Poor Chinese Text Comprehenders Also Poor in Written Composition?

    ERIC Educational Resources Information Center

    Guan, Connie Qun; Ye, Feifei; Meng, Wanjin; Leong, Che Kan

    2013-01-01

    We studied the performance in three genres of Chinese written composition (narration, exposition, and argumentation) of 158 grade 4, 5, and 6 poor Chinese text comprehenders compared with 156 good Chinese text comprehenders. We examined text comprehension and written composition relationship. Verbal working memory (verbal span working memory and…

  19. The management of poor performance

    PubMed Central

    Mayberry, John F

    2007-01-01

    Identification of poor performance is in an integral part of government policy. The suggested approach for the identification of such problems, advocated by the General Medical Council, is that of appraisal. However, traditionally, there has been a reluctance to deal with poor performers, as all doctors have made mistakes and are usually only too ready to forgive and be non‐critical of colleagues. The problems are widespread, and 6% of the senior hospital workforce in any 5‐year period may have problems. PMID:17308213

  20. Synthesis, structural characterization, and ligand replacement reactions of gem-dithiolato-bridged rhodium and iridium complexes.

    PubMed

    Rivas, Angel B; Gascón, José M; Lahoz, Fernando J; Balana, Ana I; Pardey, Alvaro J; Oro, Luis A; Pérez-Torrente, Jesús J

    2008-07-01

    The reaction of gem-dithiol compounds R 2C(SH) 2 (R = Bn (benzyl), (i) Pr; R 2 = -(CH 2) 4-) with dinuclear rhodium or iridium complexes containing basic ligands such as [M(mu-OH)(cod)] 2 and [M(mu-OMe)(cod)] 2, or the mononuclear [M(acac)(cod)] (M = Rh, Ir, cod = 1,5-cyclooctadiene) in the presence of a external base, afforded the dinuclear complexes [M 2(mu-S 2CR 2)(cod) 2] ( 1- 4). The monodeprotonation of 1,1-dimercaptocyclopentane gave the mononuclear complex [Rh(HS 2Cptn)(cod)] ( 5) that is a precursor for the dinuclear compound [Rh 2(mu-S 2Cptn)(cod) 2] ( 6). Carbonylation of the diolefin compounds gave the complexes [Rh 2(mu-S 2CR 2)(CO) 4] ( 7- 9), which reacted with P-donor ligands to stereoselectively produce the trans isomer of the disubstituted complexes [Rh 2(mu-S 2CR 2)(CO) 2(PR' 3) 2] (R' = Ph, Cy (cyclohexyl)) ( 10- 13) and [Rh 2(mu-S 2CBn 2)(CO) 2{P(OR') 3} 2] (R' = Me, Ph) ( 14- 15). The substitution process in [Rh 2(mu-S 2CBn 2)(CO) 4] ( 7) by P(OMe) 3 has been studied by spectroscopic means and the full series of substituted complexes [Rh 2(mu-S 2CBn 2)(CO) 4- n {P(OR) 3} n ] ( n = 1, 4) has been identified in solution. The cis complex [Rh 2(mu-S 2CBn 2)(CO) 2(mu-dppb)] ( 16) was obtained by reaction of 7 with the diphosphine dppb (1,4-bis(diphenylphosphino)butane). The molecular structures of the diolefinic dinuclear complexes [Rh 2(mu-S 2CR 2)(cod) 2] (R = Bn ( 1), (i) Pr ( 2); R 2 = -(CH 2) 4- ( 6)) and that of the cis complex 16 have been studied by X-ray diffraction. PMID:18507456

  1. Poor Memory: A Case Report.

    ERIC Educational Resources Information Center

    Meltzer, Malcolm L.

    1983-01-01

    Presents a case study of a person who had a cardiac arrest with some right-sided brain damage. Describes the effects of poor memory on cognition, personality, and interpersonal relationships based on personal observations during memory impairment. Highlights the course of rehabilitation over a two-year period. (PAS)

  2. Are poor Chinese text comprehenders also poor in written composition?

    PubMed

    Guan, Connie Qun; Ye, Feifei; Meng, Wanjin; Leong, Che Kan

    2013-10-01

    We studied the performance in three genres of Chinese written composition (narration, exposition, and argumentation) of 158 grade 4, 5, and 6 poor Chinese text comprehenders compared with 156 good Chinese text comprehenders. We examined text comprehension and written composition relationship. Verbal working memory (verbal span working memory and operation span working memory) and different levels of linguistic tasks-morphological sensitivity (morphological compounding and morphological chain), sentence processing (syntax construction and syntax integrity), and text comprehension (narrative and expository texts)-were used to predict separately narrative, expository, and argumentation written compositions in these students. Grade for grade, the good text comprehenders outperformed the poor text comprehenders in all tasks, except for morphological chain. Hierarchical multiple regression analyses showed differential contribution of the tasks to different genres of writing. In particular, text comprehension made unique contribution to argumentation writing in the poor text comprehenders. Future studies should ask students to read and write parallel passages in the same genre for better comparison and incorporate both instructional and motivational variables. PMID:23666849

  3. Are poor Chinese text comprehenders also poor in written composition?

    PubMed

    Guan, Connie Qun; Ye, Feifei; Meng, Wanjin; Leong, Che Kan

    2013-10-01

    We studied the performance in three genres of Chinese written composition (narration, exposition, and argumentation) of 158 grade 4, 5, and 6 poor Chinese text comprehenders compared with 156 good Chinese text comprehenders. We examined text comprehension and written composition relationship. Verbal working memory (verbal span working memory and operation span working memory) and different levels of linguistic tasks-morphological sensitivity (morphological compounding and morphological chain), sentence processing (syntax construction and syntax integrity), and text comprehension (narrative and expository texts)-were used to predict separately narrative, expository, and argumentation written compositions in these students. Grade for grade, the good text comprehenders outperformed the poor text comprehenders in all tasks, except for morphological chain. Hierarchical multiple regression analyses showed differential contribution of the tasks to different genres of writing. In particular, text comprehension made unique contribution to argumentation writing in the poor text comprehenders. Future studies should ask students to read and write parallel passages in the same genre for better comparison and incorporate both instructional and motivational variables.

  4. 16 CFR 23.7 - Misuse of the words “platinum,” “iridium,” “palladium,” “ruthenium,” “rhodium,” and “osmium.”

    Code of Federal Regulations, 2012 CFR

    2012-01-01

    ... § 23.7 Misuse of the words “platinum,” “iridium,” “palladium,” “ruthenium,” “rhodium,” and “osmium.” (a...,” and “osmium,” or any abbreviation to mark or describe all or part of an industry product if such... Platinum, Iridium, Palladium, Ruthenium, Rhodium, and Osmium. (b) The following are examples of markings...

  5. 16 CFR 23.7 - Misuse of the words “platinum,” “iridium,” “palladium,” “ruthenium,” “rhodium,” and “osmium.”

    Code of Federal Regulations, 2011 CFR

    2011-01-01

    ... § 23.7 Misuse of the words “platinum,” “iridium,” “palladium,” “ruthenium,” “rhodium,” and “osmium.” (a...,” and “osmium,” or any abbreviation to mark or describe all or part of an industry product if such... Platinum, Iridium, Palladium, Ruthenium, Rhodium, and Osmium. (b) The following are examples of markings...

  6. 16 CFR 23.7 - Misuse of the words “platinum,” “iridium,” “palladium,” “ruthenium,” “rhodium,” and “osmium.”

    Code of Federal Regulations, 2014 CFR

    2014-01-01

    ... § 23.7 Misuse of the words “platinum,” “iridium,” “palladium,” “ruthenium,” “rhodium,” and “osmium.” (a...,” and “osmium,” or any abbreviation to mark or describe all or part of an industry product if such... Platinum, Iridium, Palladium, Ruthenium, Rhodium, and Osmium. (b) The following are examples of markings...

  7. 16 CFR 23.7 - Misuse of the words “platinum,” “iridium,” “palladium,” “ruthenium,” “rhodium,” and “osmium.”

    Code of Federal Regulations, 2010 CFR

    2010-01-01

    ... § 23.7 Misuse of the words “platinum,” “iridium,” “palladium,” “ruthenium,” “rhodium,” and “osmium.” (a...,” and “osmium,” or any abbreviation to mark or describe all or part of an industry product if such... Platinum, Iridium, Palladium, Ruthenium, Rhodium, and Osmium. (b) The following are examples of markings...

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

    Code of Federal Regulations, 2013 CFR

    2013-01-01

    ... § 23.7 Misuse of the words “platinum,” “iridium,” “palladium,” “ruthenium,” “rhodium,” and “osmium.” (a...,” and “osmium,” or any abbreviation to mark or describe all or part of an industry product if such... Platinum, Iridium, Palladium, Ruthenium, Rhodium, and Osmium. (b) The following are examples of markings...

  9. Health solutions for the poor.

    PubMed

    Castro, J L; Fujiwara, P I; Bhambal, P; Emaille-Léotard, N; Harries, A D

    2014-03-21

    The International Union Against Tuberculosis and Lung Disease (The Union) is the oldest international non-governmental organisation involved in the fight against tuberculosis. In 2008, the Institute of The Union was challenged to think boldly about the future and to develop a diverse work portfolio covering a wide spectrum of lung health and other disease-related problems. The vision adopted by The Union at that time was 'Health solutions for the poor'. More recently, there has been lengthy debate about the need for the Union to concentrate just on its core mandate of tuberculosis and lung health and for the Union's vision to reflect this narrower spectrum of activity as 'Lung health solutions for the poor'. In this viewpoint article we outline our reasons for believing that this narrower vision is incompatible with The Union's mission statement, and we argue that making such a change would be a mistake.

  10. Genotoxicity of poorly soluble particles.

    PubMed

    Schins, Roel P F; Knaapen, Ad M

    2007-01-01

    Poorly soluble particles such as TiO2, carbon black, and diesel exhaust particles have been evaluated for their genotoxicity using both in vitro and in vivo assays, since inhalation of these compounds by rats at high concentrations has been found to lead to tumor formation. Two principle modes of genotoxic action can be considered for particles, referred to as primary and secondary genotoxicity. Primary genotoxicity is defined as genetic damage elicited by particles in the absence of pulmonary inflammation, whereas secondary genotoxicity implies a pathway of genetic damage resulting from the oxidative DNA attack by reactive oxygen/nitrogen species (ROS/RNS), generated during particle-elicited inflammation. Conceptually, primary genotoxicity might operate via various mechanisms, such as the actions of ROS (e.g., as generated from reactive particle surfaces), or DNA-adduct formation by reactive metabolites of particle-associated organic compounds (e.g., polycyclic aromatic hydrocarbons). Currently available literature data, however, merely indicate that the tumorigenesis of poorly soluble particles involves a mechanism of secondary genotoxicity. However, further research is urgently required, since (1) causality between pulmonary inflammation and genotoxicity has not yet been established, and (2) effects of inflammation on fundamental DNA damage responses that orchestrate mutagenesis and carcinogenic outcome,that is, cell cycle arrest, DNA repair, proliferation, and apoptosis, are currently poorly understood. PMID:17886067

  11. A Monofunctional Platinum Complex Coordinated to a Rhodium Metalloinsertor Selectively Binds Mismatched DNA in the Minor Groove

    PubMed Central

    Weidmann, Alyson G.; Barton, Jacqueline K.

    2015-01-01

    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 non-classically 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 triggers cell death via an apoptotic pathway, rather than the necrotic pathway induced by rhodium metalloinsertors. PMID:26397309

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

    SciTech Connect

    Xu, Songchen; Manna, Kuntal; Ellern, Arkady; Sadow, Aaron D

    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

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

    PubMed

    Weidmann, Alyson G; Barton, Jacqueline K

    2015-10-01

    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.

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

    PubMed Central

    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

  15. Combined homogeneous and heterogeneous catalysts. Rhodium and platinum isocyanide complexes tethered on silica-supported metal heterogeneous catalysts: Arene and cyclohexanone hydrogenation

    SciTech Connect

    Gao, H.; Angelici, R.J. |

    1999-03-15

    Rhodium and platinum isocyanide complexes RhCl(CO)[CN(CH{sub 2}){sub 3}Si(OC{sub 2}H{sub 5}){sub 3}]{sub 2} (Rh-CNR{sub 2}), RhCl[CN(CH{sub 2}){sub 3}Si(OC{sub 2}H{sub 5}){sub 3}]{sub 3} (Rh-CNR{sub 3}), and PtCl{sub 2}[CN(CH{sub 2}){sub 3}Si(OC{sub 2}H{sub 5}){sub 3}]{sub 2} (Pt-CNR{sub 2}) were tethered to the silica-supported metal heterogeneous catalysts M-SiO{sub 2} (M = Pd, Pt, Ru) to give the TCSM (tethered complex on supported metal) catalysts Rh-CNR{sub 2}/Pd-SiO{sub 2}, Rh-CNR{sub 3}/M-SiO{sub 2} (M = Pd, Pt, Ru), and Pt-CNR{sub 2}/Pd-SiO{sub 2}. These TCSM catalysts were used to catalyze the hydrogenation of arenes (Rh-CNR{sub 2}/Pd-SiO{sub 2} and Rh-CNR{sub 3}/M-SiO{sub 2}) and cyclohexanone (Pt-CNR{sub 2}/Pd-SiO{sub 2}) under the mild conditions of 40 C and 1 atm. They exhibit activities that are higher than those of the separate homogeneous rhodium (or platinum) isocyanide complex, the separate silica-supported metal heterogeneous catalyst, or the rhodium (or platinum) complex catalyst tethered on just SiO{sub 2}. The activities of the TCSM catalysts are strongly affected by the nature and loading of the supported metal in the catalyst. Among the three silica-supported metal M-SiO{sub 2} (M = Pd, Pt, Ru) catalysts, the rhodium complex Rh-CNR{sub 3} tethered on Pd-SiO{sub 2} exhibits the highest activity for the hydrogenation of toluene (TOF = 5.5 mol H{sub 2}/(mol Rh min) and TO = 2,420 mol H{sub 2}/mol Rh during 8.5 h). The Rh-CNR{sub 3}/Pd-SiO{sub 2} catalyst with 10 wt % Pd is more active than its counterparts with higher or lower palladium loadings. IR (DRIFT) spectral studies of the TCSM catalysts before and after being used for toluene hydrogenation show that the isocyanide ligands remain coordinated to the rhodium (or platinum) center even after extended use. Atomic emission spectroscopic analysis of hydrogenation solutions shows that there is no rhodium (or platinum) leaching into the solutions.

  16. Real-time sub-Ångstrom imaging of reversible and irreversible conformations in rhodium catalysts and graphene

    NASA Astrophysics Data System (ADS)

    Kisielowski, Christian; Wang, Lin-Wang; Specht, Petra; Calderon, Hector A.; Barton, Bastian; Jiang, Bin; Kang, Joo H.; Cieslinski, Robert

    2013-07-01

    The dynamic responses of a rhodium catalyst and a graphene sheet are investigated upon random excitation with 80 kV electrons. An extraordinary electron microscope stability and resolution allow studying temporary atom displacements from their equilibrium lattice sites into metastable sites across projected distances as short as 60 pm. In the rhodium catalyst, directed and reversible atom displacements emerge from excitations into metastable interstitial sites and surface states that can be explained by single atom trajectories. Calculated energy barriers of 0.13 eV and 1.05 eV allow capturing single atom trapping events at video rates that are stabilized by the Rh [110] surface corrugation. Molecular dynamics simulations reveal that randomly delivered electrons can also reversibly enhance the sp3 and the sp1 characters of the sp2-bonded carbon atoms in graphene. The underlying collective atom motion can dynamically stabilize characteristic atom displacements that are unpredictable by single atom trajectories. We detect three specific displacements and use two of them to propose a path for the irreversible phase transformation of a graphene nanoribbon into carbene. Collectively stabilized atom displacements greatly exceed the thermal vibration amplitudes described by Debye-Waller factors and their measured dose rate dependence is attributed to tunable phonon contributions to the internal energy of the systems. Our experiments suggest operating electron microscopes with beam currents as small as zepto-amperes/nm2 in a weak-excitation approach to improve on sample integrity and allow for time-resolved studies of conformational object changes that probe for functional behavior of catalytic surfaces or molecules.

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

    PubMed Central

    2012-01-01

    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%). PMID:23369526

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

    SciTech Connect

    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

  19. Coordination and organometallic chemistry of relevance to the rhodium-based catalyst for ethylene hydroamination.

    PubMed

    Béthegnies, Aurélien; Kirkina, Vladislava A; Filippov, Oleg A; Daran, Jean-Claude; Belkova, Natalia V; Shubina, Elena; Polic, Rinaldo

    2011-12-19

    at the full QM level including solvation effects. The calculations confirm that the bridge splitting reaction is slightly less favorable for the iodido derivative. Overall, the study confirms the active role of rhodium(I) species in ethylene hydroamination catalyzed by RhCl(3)·3H(2)O/PPh(3)/nBu(4)PI and suggest that the catalyst resting state is [RhCl(PPh(3))(2)](2) or its C(2)H(4) adduct, RhCl(PPh(3))(2)(C(2)H(4)), under high ethylene pressure. PMID:22082087

  20. Why are the many poor?

    PubMed

    Townsend, P

    1986-01-01

    In this article the author restates the same arguments put forward in the first Fabian Tract of 1884 entitled Why Are the Many Poor? Today, mass poverty is still the central problem facing the British nation and all nations. The only long-term remedy is to restrict the power and wealth of the rich, to dismantle the present structures of social privilege, and to build social institutions based on fair allocation of wealth and on social equality. The public debate of one hundred years ago on the connections between poverty and wealth is revived in this article.

  1. Seven poor clusters of galaxies

    NASA Astrophysics Data System (ADS)

    Beers, T. C.; Geller, M. J.; Huchra, J. P.; Latham, D. W.; Davis, R. J.

    1984-08-01

    The authors have measured 83 new redshifts for galaxies in the region of seven of the poor clusters of galaxies identified by Morgan, Kayser, and White and Albert, White, and Morgan. For three systems (MKW 1s, AWM 1, and AWM 7) complete redshift samples were obtained for galaxies brighter than mB(0) = 15.7 within 1° of the D or cD galaxy. The authors estimate masses for the clusters by applying both the virial theorem and the projected mass method. For the two clusters with the highest X-ray luminosities, the line-of-sight velocity dispersions are ≡700 km s-1, and mass-to-light ratios M/LB(0) ⪆ 400 M_sun;/L_sun;. For the five other clusters the velocity dispersions are ⪉370 km s-1, and four of the five have mass-to-light ratios ⪉250 M_sun;/L_sun;. The D or cD galaxy in each poor cluster is at the kinematic center of the system.

  2. Bottom-Up Construction of a CO2-Based Cycle for the Photocarbonylation of Benzene, Promoted by a Rhodium(I) Pincer Complex.

    PubMed

    Anaby, Aviel; Feller, Moran; Ben-David, Yehoshoa; Leitus, Gregory; Diskin-Posner, Yael; Shimon, Linda J W; Milstein, David

    2016-08-10

    The use of carbon dioxide for synthetic applications presents a major goal in modern homogeneous catalysis. Rhodium-hydride PNP pincer complex 1 is shown to add CO2 in two disparate pathways: one is the expected insertion of CO2 into the metal-hydride bond, and the other leads to reductive cleavage of CO2, involving metal-ligand cooperation. The resultant rhodium-carbonyl complex was found to be photoactive, enabling the activation of benzene and formation of a new benzoyl complex. Organometallic intermediate species were observed and characterized by NMR spectroscopy and X-ray crystallography. Based on the series of individual transformations, a sequence for the photocarbonylation of benzene using CO2 as the feedstock was constructed and demonstrated for the production of benzaldehyde from benzene. PMID:27400288

  3. Direct detection of key intermediates in rhodium(I)-catalyzed [2+2+2] cycloadditions of alkynes by ESI-MS.

    PubMed

    Parera, Magda; Dachs, Anna; Solà, Miquel; Pla-Quintana, Anna; Roglans, Anna

    2012-10-01

    The mechanism of the Rh-catalysed [2+2+2] cycloaddition reaction of diynes with monoynes has been examined using ESI-MS and ESI-CID-MS analysis. The catalytic system used consisted of the combination of a cationic rhodium(I) complex with bisphosphine ligands, which generates highly active complexes that can be detected by ESI(+) experiments. ESI-MS on-line monitoring has allowed the detection for the first time of all of the intermediates in the catalytic cycle, supporting the mechanistic proposal based mainly on theoretical calculations. For all ESI-MS experiments, the structural assignments of ions are supported by tandem mass spectrometry analyses. Computer model studies based on density functional theory (DFT) support the structural proposal made for the monoyne insertion intermediate. The collective studies provide new insight into the reactivity of cationic rhodacyclopentadienes, which should facilitate the design of related rhodium-catalysed C-C couplings.

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

    PubMed

    Leniak, Arkadiusz; Kamieński, Bohdan; Jaźwiński, Jarosław

    2015-05-01

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

  5. Isomerisation and controlled condensation in an aqueous medium of allyl alcohol catalysed by new water-soluble rhodium complexes with 1,3,5-triaza-7-phosphaadamantane (PTA).

    PubMed

    Smoleński, Piotr; Kirillova, Marina V; Guedes da Silva, M Fátima C; Pombeiro, Armando J L

    2013-08-14

    New aqua-soluble rhodium(I) [Rh(CO)(PTA)4]Cl (1) (PTA = 1,3,5-triaza-7-phosphaadamantane) and rhodium(III) [RhCl2(PTA)4]Cl (2) complexes have been synthesized via the reaction of [{Rh(CO)2(μ-Cl)}2] or RhCl3·3H2O, respectively, with stoichiometric amounts of PTA in ethanol. Compound 1 is also obtained upon reduction of 2 in an H2/CO atmosphere. They have been characterized by IR, (1)H and (31)P{H} NMR spectroscopies, elemental and single crystal X-ray diffraction analyses. While compound 1 shows distorted square-pyramid geometry (τ5 = 0.09) with a P3C-type basal plane, compound 2 is octahedral with the chloro ligands in the cis position. The hydride rhodium(I) complex [RhH(PTA)4] (3) is formed upon the addition of NaBH4 to an aqueous solution of 1 or 2. Compounds 1-3 (in the case of 2 upon reduction by H2) act as homogeneous catalysts, or catalyst precursors, in the isomerisation and condensation of allyl alcohol at room temperature and in an aqueous medium. The product selectivity is easily controlled by changing the concentration of the base in the reaction mixture, thus resulting in the exclusive formation of either 3-hydroxy-2-methylpentanal (HP) or 2-methyl-2-pentenal (MP) in quantitative yields. PMID:23793921

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

    PubMed Central

    Mejuto, Carmen; Royo, Beatriz

    2015-01-01

    Summary 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(CO)2] 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. PMID:26734104

  7. Podiform chromite deposits--database and grade and tonnage models

    USGS Publications Warehouse

    Mosier, Dan L.; Singer, Donald A.; Moring, Barry C.; Galloway, John P.

    2012-01-01

    Chromite ((Mg, Fe++)(Cr, Al, Fe+++)2O4) is the only source for the metallic element chromium, which is used in the metallurgical, chemical, and refractory industries. Podiform chromite deposits are small magmatic chromite bodies formed in the ultramafic section of an ophiolite complex in the oceanic crust. These deposits have been found in midoceanic ridge, off-ridge, and suprasubduction tectonic settings. Most podiform chromite deposits are found in dunite or peridotite near the contact of the cumulate and tectonite zones in ophiolites. We have identified 1,124 individual podiform chromite deposits, based on a 100-meter spatial rule, and have compiled them in a database. Of these, 619 deposits have been used to create three new grade and tonnage models for podiform chromite deposits. The major podiform chromite model has a median tonnage of 11,000 metric tons and a mean grade of 45 percent Cr2O3. The minor podiform chromite model has a median tonnage of 100 metric tons and a mean grade of 43 percent Cr2O3. The banded podiform chromite model has a median tonnage of 650 metric tons and a mean grade of 42 percent Cr2O3. Observed frequency distributions are also given for grades of rhodium, iridium, ruthenium, palladium, and platinum. In resource assessment applications, both major and minor podiform chromite models may be used for any ophiolite complex regardless of its tectonic setting or ophiolite zone. Expected sizes of undiscovered podiform chromite deposits, with respect to degree of deformation or ore-forming process, may determine which model is appropriate. The banded podiform chromite model may be applicable for ophiolites in both suprasubduction and midoceanic ridge settings.

  8. Serving the world's poor, profitably.

    PubMed

    Prahalad, C K; Hammond, Allen

    2002-09-01

    By stimulating commerce and development at the bottom of the economic pyramid, multi-nationals could radically improve the lives of billions of people and help create a more stable, less dangerous world. Achieving this goal does not require MNCs to spearhead global social-development initiatives for charitable purposes. They need only act in their own self-interest. How? The authors lay out the business case for entering the world's poorest markets. Fully 65% of the world's population earns less than $2,000 per year--that's 4 billion people. But despite the vastness of this market, it remains largely untapped. The reluctance to invest is easy to understand, but it is, by and large, based on outdated assumptions of the developing world. While individual incomes may be low, the aggregate buying power of poor communities is actually quite large, representing a substantial market in many countries for what some might consider luxury goods like satellite television and phone services. Prices, and margins, are often much higher in poor neighborhoods than in their middle-class counterparts. And new technologies are already steadily reducing the effects of corruption, illiteracy, inadequate infrastructure, and other such barriers. Because these markets are in the earliest stages of economic development, revenue growth for multi-nationals entering them can be extremely rapid. MNCs can also lower costs, not only through low-cost labor but by transferring operating efficiencies and innovations developed to serve their existing operations. Certainly, succeeding in such markets requires MNCs to think creatively. The biggest change, though, has to come from executives: Unless business leaders confront their own preconceptions--particularly about the value of high-volume, low-margin businesses--companies are unlikely to master the challenges or reap the rewards of these developing markets.

  9. Toward ab initio extremely metal poor stars

    NASA Astrophysics Data System (ADS)

    Ritter, Jeremy S.; Safranek-Shrader, Chalence; Milosavljević, Miloš; Bromm, Volker

    2016-09-01

    Extremely metal poor stars have been the focus of much recent attention owing to the expectation that their chemical abundances can shed light on the metal and dust yields of the earliest supernovae. We present our most realistic simulation to date of the astrophysical pathway to the first metal enriched stars. We simulate the radiative and supernova hydrodynamic feedback of a 60 M⊙ Population III star starting from cosmological initial conditions realizing Gaussian density fluctuations. We follow the gravitational hydrodynamics of the supernova remnant at high spatial resolution through its freely-expanding, adiabatic, and radiative phases, until gas, now metal-enriched, has resumed runaway gravitational collapse. Our findings are surprising: while the Population III progenitor exploded with a low energy of 1051 erg and injected an ample metal mass of 6 M⊙, the first cloud to collapse after the supernova explosion is a dense surviving primordial cloud on which the supernova blast wave deposited metals only superficially, in a thin, unresolved layer. The first metal-enriched stars can form at a very low metallicity, of only 2 - 5 × 10-4 Z⊙, and can inherit the parent cloud's highly elliptical, radially extended orbit in the dark matter gravitational potential.

  10. Surface Finish after Laser Metal Deposition

    NASA Astrophysics Data System (ADS)

    Rombouts, M.; Maes, G.; Hendrix, W.; Delarbre, E.; Motmans, F.

    Laser metal deposition (LMD) is an additive manufacturing technology for the fabrication of metal parts through layerwise deposition and laser induced melting of metal powder. The poor surface finish presents a major limitation in LMD. This study focuses on the effects of surface inclination angle and strategies to improve the surface finish of LMD components. A substantial improvement in surface quality of both the side and top surfaces has been obtained by laser remelting after powder deposition.

  11. Deposited films with improved microstructures

    DOEpatents

    Patten, James W.; Moss, Ronald W.; McClanahan, Edwin D.

    1984-01-01

    Methods for improving microstructures of line-of-sight deposited films are described. Columnar growth defects ordinarily produced by geometrical shadowing during deposition of such films are eliminated without resorting to post-deposition thermal or mechanical treatments. The native, as-deposited coating qualities, including homogeneity, fine grain size, and high coating-to-substrate adherence, can thus be retained. The preferred method includes the steps of emitting material from a source toward a substrate to deposit a coating non-uniformly on the substrate surface, removing a portion of the coating uniformly over the surface, again depositing material onto the surface, but from a different direction, and repeating the foregoing steps. The quality of line-of-sight deposited films such as those produced by sputtering, progressively deteriorates as the angle of incidence between the flux and the surface becomes increasingly acute. Depositing non-uniformly, so that the coating becomes progressively thinner as quality deteriorates, followed by uniformly removing some of the coating, such as by resputtering, eliminates the poor quality portions, leaving only high quality portions of the coating. Subsequently sputtering from a different direction applies a high quality coating to other regions of the surface. Such steps can be performed either simultaneously or sequentially to apply coatings of a uniformly high quality, closed microstructure to three-dimensional or large planar surfaces.

  12. Synthesis, x-ray, and low-temperature neutron diffraction study of a rhodium (V) complex: dihydridobis(triethylsilyl)-pentamethylcyclopentadienylrhodium

    SciTech Connect

    Fernandez, M.J.; Bailey, P.M.; Bentz, P.O.; Ricci, J.S.; Koetzle, T.F.; Maitlis, P.M.

    1984-09-19

    Reaction of (C/sub 5/ qentamethyl Rh)/sub 2/Cl/sub 4/) (1) with triethylsilane leads to the novel rhodium(V) complex (eta/sup 5/-C/sub 5/Me/sub 5/Rh(H)/sub 2/(SiE-triethyl/sub 3/)/sub 2/) (2) characterized by NMR spectra (/sup 1/H, /sup 13/C, /sup 29/Si, and /sup 103/Rh), X-ray diffraction, and neutron diffraction at 20 K. The complex shows a four-legged piano stool geometry with the pentamethylcyclopentadienyl eta/sub 5/-bonded to the rhodium (average Rh-C, 2.283 (9) A) on top and the two triethylsilyl ligands trans in the basal plane (Rh-Si, 2.379 (2) A). The neutron diffraction analysis located the two hydrides, which are trans to each other and cis to the triethylsilyls in the basal plane. The mean Rh-H distance is 1.581 (3) A, and the H-Rh-H angle is 94.8 (2)/sup 0/. Complex 2 is rather stable, but it reacts under forcing conditions with neutral ligands (triphenylphosphine, CO, or maleic anhydride) to give (C/sub 5/Me/sub 5/Rh(PPh/sub 3/)H(SiEt/sub 3/)), (C/sub 5/Me/sub 5/Rh(CO)/sub 2/), or (C/sub 5/M3/5Rh(maleic anhydride)/sup 2/). It reacts more easily with electrophiles such as HBF/sub 4/ to give (C/sub 5/Me/sub 5/Rh)/sub 4/H/sub 4/)/sup 2 +/, with HCl to give 1, with AgBF/sub 4/ in MeCN to give (C/sub 5/Me/sub 5/Rh(MeCN)/sub 3/)/sup 2 +/, and with I/sub 2/ to give ((C/sub 5/Me/sub 5/Rh)/sub 2/I/sub 4/). The predominant mode of reaction involves reductive elimination of Et/sub 3/Si-H, which can be strongly promoted by an electrophile. 43 references, 3 figures, 3 tables.

  13. Molecular models of site-isolated cobalt, rhodium, and iridium catalysts supported on zeolites: Ligand bond dissociation energies

    DOE PAGESBeta

    Chen, Mingyang; Serna, Pedro; Lu, Jing; Gates, Bruce C.; Dixon, David A.

    2015-09-28

    The chemistry of zeolite-supported site-isolated cobalt, rhodium, and iridium complexes that are essentially molecular was investigated with density functional theory (DFT) and the results compared with experimentally determined spectra characterizing rhodium and iridium species formed by the reactions of Rh(C2H4)2(acac) and Ir(C2H4)2(acac) (acac = acetylacetonate) with acidic zeolites such as dealuminated HY zeolite. The experimental results characterize ligand exchange reactions and catalytic reactions of adsorbed ligands, including olefin hydrogenation and dimerization. Two molecular models were used to characterize various binding sites of the metal complexes in the zeolites, and the agreement between experimental and calculated infrared frequencies and metal-ligand distancesmore » determined by extended X-ray absorption fine structure spectroscopy was generally very good. The calculated structures and energies indicate a metal-support-oxygen (M(I)-O) coordination number of two for most of the supported complexes and a value of three when the ligands include the radicals C2H5 or H. The results characterizing various isomers of the supported metal complexes incorporating hydrocarbon ligands indicate that some carbene and carbyne ligands could form. Ligand bond dissociation energies (LDEs) are reported to explain the observed reactivity trends. The experimental observations of a stronger M-CO bond than M-(C2H4) bond for both Ir and Rh match the calculated LDEs, which show that the single-ligand LDEs of the mono and dual-ligand complexes for CO are similar to 12 and similar to 15 kcal/mol higher in energy (when the metal is Rh) and similar to 17 and similar to 20 kcal/mol higher (when the metal is Ir) than the single-ligand LDEs of the mono and dual ligand complexes for C2H4, respectively. The results provide a foundation for the prediction of the catalytic properties of numerous supported metal complexes, as summarized in detail here.« less

  14. Molecular models of site-isolated cobalt, rhodium, and iridium catalysts supported on zeolites: Ligand bond dissociation energies

    SciTech Connect

    Chen, Mingyang; Serna, Pedro; Lu, Jing; Gates, Bruce C.; Dixon, David A.

    2015-09-28

    The chemistry of zeolite-supported site-isolated cobalt, rhodium, and iridium complexes that are essentially molecular was investigated with density functional theory (DFT) and the results compared with experimentally determined spectra characterizing rhodium and iridium species formed by the reactions of Rh(C2H4)2(acac) and Ir(C2H4)2(acac) (acac = acetylacetonate) with acidic zeolites such as dealuminated HY zeolite. The experimental results characterize ligand exchange reactions and catalytic reactions of adsorbed ligands, including olefin hydrogenation and dimerization. Two molecular models were used to characterize various binding sites of the metal complexes in the zeolites, and the agreement between experimental and calculated infrared frequencies and metal-ligand distances determined by extended X-ray absorption fine structure spectroscopy was generally very good. The calculated structures and energies indicate a metal-support-oxygen (M(I)-O) coordination number of two for most of the supported complexes and a value of three when the ligands include the radicals C2H5 or H. The results characterizing various isomers of the supported metal complexes incorporating hydrocarbon ligands indicate that some carbene and carbyne ligands could form. Ligand bond dissociation energies (LDEs) are reported to explain the observed reactivity trends. The experimental observations of a stronger M-CO bond than M-(C2H4) bond for both Ir and Rh match the calculated LDEs, which show that the single-ligand LDEs of the mono and dual-ligand complexes for CO are similar to 12 and similar to 15 kcal/mol higher in energy (when the metal is Rh) and similar to 17 and similar to 20 kcal/mol higher (when the metal is Ir) than the single-ligand LDEs of the mono and dual ligand complexes for C2H4, respectively. The results provide a foundation for the prediction

  15. Understanding of catalyst deactivation caused by sulfur poisoning and carbon deposition in steam reforming of liquid hydrocarbon fuels

    NASA Astrophysics Data System (ADS)

    Xie, Chao

    2011-12-01

    The present work was conducted to develop a better understanding on the catalyst deactivation in steam reforming of sulfur-containing liquid hydrocarbon fuels for hydrogen production. Steam reforming of Norpar13 (a liquid hydrocarbon fuel from Exxon Mobile) without and with sulfur was performed on various metal catalysts (Rh, Ru, Pt, Pd, and Ni) supported on different materials (Al2O3, CeO2, SiO2, MgO, and CeO2- Al2O3). A number of characterization techniques were applied to study the physicochemical properties of these catalysts before and after the reactions. Especially, X-ray absorption near edge structure (XANES) spectroscopy was intensively used to investigate the nature of sulfur and carbon species in the used catalysts to reveal the catalyst deactivation mechanism. Among the tested noble metal catalysts (Rh, Ru, Pt, and Pd), Rh catalyst is the most sulfur tolerant. Al2O3 and CeO2 are much better than SiO2 and MgO as the supports for the Rh catalyst to reform sulfur-containing hydrocarbons. The good sulfur tolerance of Rh/Al2O3 can be attributed to the acidic nature of the Al2O3 support and its small Rh crystallites (1-3 nm) as these characteristics facilitate the formation of electron-deficient Rh particles with high sulfur tolerance. The good catalytic performance of Rh/CeO2 in the presence of sulfur can be ascribed to the promotion effect of CeO2 on carbon gasification, which significantly reduced the carbon deposition on the Rh/CeO2catalyst. Steam reforming of Norpar13 in the absence and presence of sulfur was further carried out over CeO2-Al2O3 supported monometallic Ni and Rh and bimetallic Rh-Ni catalysts at 550 and 800 °C. Both monometallic catalysts rapidly deactivated at 550 °C, iv and showed poor sulfur tolerance. Although ineffective for the Ni catalyst, increasing the temperature to 800 °C dramatically improved the sulfur tolerance of the Rh catalyst. Sulfur K-edge XANES revealed that metal sulfide and organic sulfide are the dominant sulfur

  16. The mechanism of the rhodium(I)-catalyzed [2 + 2 + 1] carbocyclization reaction of dienes and CO: a computational study.

    PubMed

    Pitcock, William H; Lord, Richard L; Baik, Mu-Hyun

    2008-04-30

    The rhodium(I) catalyzed [2 + 2 + 1] carbocyclization of tethered diene-enes to afford substituted hexahydropentalenones with high levels of diastereoselectivity was modeled using density functional theory. Previously, this transformation was observed to be facile, whereas the analogous bis-ene substrate could not be cyclized under any reasonable conditions. To establish a conceptual understanding of the carbocyclization mechanism and to identify the functional role of the diene fragment we analyzed the simulated reaction mechanisms using the two parent systems. We discovered a thus far unrecognized, but intuitively plausible, role of the CO ligand for controlling the electron density at the metal center, which affects the feasibility of oxidative addition and reductive elimination steps that are key components of the mechanism. Our calculations suggest that the diene moiety is unique and required because of its ability to undergo a eta(2)-->eta(4) reorganization allowing for the thermoneutral expulsion of one CO ligand, which in turn generates an electron-rich, coordinatively saturated Rh(I) center that can efficiently promote the oxidative addition with a low barrier. A number of functionalization strategies were considered explicitly to derive a rational plan for optimizing the catalysis and to expose the roles of the different components of the reactant-catalyst complex. PMID:18380438

  17. Well-defined coinage metal transfer agents for the synthesis of NHC-based nickel, rhodium and palladium macrocycles.

    PubMed

    Andrew, Rhiann E; Storey, Caroline M; Chaplin, Adrian B

    2016-06-01

    With a view to use as carbene transfer agents, well-defined silver(i) and copper(i) complexes of a macrocyclic NHC-based pincer ligand, bearing a central lutidine donor and a dodecamethylene spacer [CNC-(CH2)12, 1], have been prepared. Although the silver adduct is characterised by X-ray diffraction as a dinuclear species anti-[Ag(μ-1)]2(2+), variable temperature measurements indicate dynamic structural interchange in solution involving fragmentation into mononuclear [Ag(1)](+) on the NMR time scale. In contrast, a mononuclear structure is evident in both solution and the solid-state for the analogous copper adduct partnered with the weakly coordinating [BAr(F)4](-) counter anion. A related copper derivative, bearing instead the more coordinating cuprous bromide dianion [Cu2Br4](2-), is notable for the adoption of an interesting tetranuclear assembly in the solid-state, featuring two cuprophilic interactions and two bridging NHC donors, but is not retained on dissolution. Coinage metal precursors [M(1)]n[BAr(F)4]n (M = Ag, n = 2; M = Cu, n = 1) both act as carbene transfer agents to afford palladium, rhodium and nickel complexes of 1 and the effectiveness of these precursors has been evaluated under equivalent reaction conditions. PMID:27157720

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

    SciTech Connect

    Onishi, Takashi; Koyama, Shin-ichi; Mimura, Hitoshi

    2013-07-01

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

  19. Well-defined coinage metal transfer agents for the synthesis of NHC-based nickel, rhodium and palladium macrocycles.

    PubMed

    Andrew, Rhiann E; Storey, Caroline M; Chaplin, Adrian B

    2016-06-01

    With a view to use as carbene transfer agents, well-defined silver(i) and copper(i) complexes of a macrocyclic NHC-based pincer ligand, bearing a central lutidine donor and a dodecamethylene spacer [CNC-(CH2)12, 1], have been prepared. Although the silver adduct is characterised by X-ray diffraction as a dinuclear species anti-[Ag(μ-1)]2(2+), variable temperature measurements indicate dynamic structural interchange in solution involving fragmentation into mononuclear [Ag(1)](+) on the NMR time scale. In contrast, a mononuclear structure is evident in both solution and the solid-state for the analogous copper adduct partnered with the weakly coordinating [BAr(F)4](-) counter anion. A related copper derivative, bearing instead the more coordinating cuprous bromide dianion [Cu2Br4](2-), is notable for the adoption of an interesting tetranuclear assembly in the solid-state, featuring two cuprophilic interactions and two bridging NHC donors, but is not retained on dissolution. Coinage metal precursors [M(1)]n[BAr(F)4]n (M = Ag, n = 2; M = Cu, n = 1) both act as carbene transfer agents to afford palladium, rhodium and nickel complexes of 1 and the effectiveness of these precursors has been evaluated under equivalent reaction conditions.

  20. Poor Outcomes in Hepatic Amyloidosis: A Report of 2 Cases

    PubMed Central

    Kertowidjojo, Elizabeth; Zhang, Yue; Patel, Pruthvi

    2016-01-01

    Hepatic amyloidosis is a rare disease entity that results from insoluble amyloid protein deposition in the liver. The disease often presents with vague, nonspecific clinical features. Currently, there is little literature describing treatment outcomes for biopsy-proven hepatic amyloidosis and current treatment guidelines recommend that patients enroll in a clinical trial due to insufficient evidence to suggest an optimal treatment regimen. Here, we present two cases of hepatic amyloidosis at an academic medical center and describe their presentation, treatment, and outcomes. These cases highlight the poor outcomes and difficult management of hepatic amyloidosis. Further understanding and investigation of this rare disease are warranted. PMID:27774327

  1. Determination of rhodium by resonance light-scattering technique coupled with solid phase extraction using Rh(III) ion-imprinted polymers as sorbent.

    PubMed

    Yang, Bing; Zhang, Ting; Tan, Wenxiang; Liu, Peng; Ding, Zhongtao; Cao, Qiue

    2013-02-15

    A resonance light-scattering method (RLS) for the determination of Rh(III) was initially developed, based on the reaction among Rh(III), WO4(2-) and ethylrhodamine B. The method possesses high sensitivity, but lacks selectivity. Therefore, a Rh(III) ion-imprinted polymer (IIP), prepared by precipitation polymerization using 2-(allylthio)nicotinic acid (ANA) as functional monomer, was used as sorbent to construct a ion-imprint based solid-phase extraction (IIP-SPE) method for separation of rhodium from complicated matrices prior to its determination by RLS. The experimental parameters affecting the extraction efficiency and selectivity of IIP-SPE were studied carefully. Under the optimal conditions, the IIP-SPE column with the enrichment factor (EF) of 10 could be used at least 20 times without decreasing its extraction recovery (above 90%) significantly. The calibration graph for the determination of rhodium by RLS coupled with IIP-SPE procedure was linear in the range of 0.06-1.5 ng mL(-1) with the detection limit of 0.024 ng mL(-1). There is no metal ions tested at the concentration below 10 ng mL(-1) interfered in the determination of 0.8 ng mL(-1) Rh(III). The proposed IIP-SPE-RLS method was successfully applied to the extraction and measurement of trace rhodium in catalyst, water and geochemical samples with the relative standard deviation (RSD) of less than 4.0% (n=4).

  2. Grazing incidence reflection coefficients of rhodium, osmium, platinum, and gold from 50 to 300 A

    NASA Technical Reports Server (NTRS)

    Hettrick, M. C.; Edelstein, J.; Flint, S. A.

    1985-01-01

    Reflectance measurements were made of several metals illuminated from various angles with light at 14 wavelengths in the interval 46.5-283 A. The metals, Rh, Os, Pt and Au were deposited as 125 A films on a binding substrate through electron beam epitaxy. Measurements were made with a grazing incidence monochromator and a reflectometer. The data generally showed lowered reflectance with increasing angles of illumination and shorter wavelengths. The reflectance peak, however, was located at wavelengths of 100-160 A, particularly at large grazing incidences. The wavelengths correspond with the 5p to epsilon-d transition in all of the elements. Rh displayed the highest overall reflectance, and both Rh and Os were more efficient than Au or Pt.

  3. A facile approach for shape selective synthesis of rhodium nanostructures and conductivity studies

    SciTech Connect

    Sathe, Bhaskar R.

    2012-12-15

    Shape selective synthesis of Rh nanostructures has been demonstrated with the help of a single step chemical vapor deposition, where different shapes like cubes at 500 Degree-Sign C, pyramids and hexagons at 500 Degree-Sign C, 700 Degree-Sign C and 900 Degree-Sign C respectively have been obtained as a function of temperature. Scanning electron microscopy (SEM), X-ray diffraction (XRD), thermogravimetric analysis (TGA), X-ray photoelectron spectroscopy (XPS) and four probe conductivity measurements were used to study the morphology, crystallinity and phase purity of the structures. The conductivity values for as synthesised nanostructures have been obtained in the range of 2-7 kS/cm{sup 2}. On the basis of the experimental results, from TGA and XPS studies possible mechanistic pathway for the evolution of Rh nanostructures was discussed.

  4. Structural and electronic study of neutral, positive, and negative small rhodium clusters [Rh(n), Rh(n)(+), Rh(n)(-) ; n = 10-13].

    PubMed

    Mora, M A; Mora-Ramirez, M A

    2014-07-01

    We have carried out a systematic study for the determination of the structure and the fundamental state of neutral and ionic small rhodium clusters [Rhn, Rhn(+), Rhn(-); n = 10-13] using ab initio Hartree-Fock methods with a LANL2DZ basis set. A range of spin multiplicities is investigated for each cluster. We present the bond lengths, angles, and geometric configuration adopted by the clusters in its minimum energy conformation showing the differences when the clusters have different number of unpaired electrons. Also we report the vertical ionization potential and the adiabatic one calculated by the Koopmans' theorem.

  5. Structural and electronic study of neutral, positive, and negative small rhodium clusters [Rh(n), Rh(n)(+), Rh(n)(-) ; n = 10-13].

    PubMed

    Mora, M A; Mora-Ramirez, M A

    2014-07-01

    We have carried out a systematic study for the determination of the structure and the fundamental state of neutral and ionic small rhodium clusters [Rhn, Rhn(+), Rhn(-); n = 10-13] using ab initio Hartree-Fock methods with a LANL2DZ basis set. A range of spin multiplicities is investigated for each cluster. We present the bond lengths, angles, and geometric configuration adopted by the clusters in its minimum energy conformation showing the differences when the clusters have different number of unpaired electrons. Also we report the vertical ionization potential and the adiabatic one calculated by the Koopmans' theorem. PMID:24944092

  6. Some Effects of Exposure to Exhaust-gas Streams on Emittance and Thermoelectric Power of Bare-wire Platinum Rhodium - Platinum Thermocouples

    NASA Technical Reports Server (NTRS)

    Glawe, George E; Shepard, Charles E

    1954-01-01

    Thermocouples were exposed to exhaust gases from the combustion of propane, 72-octane gasoline, and JP-4 fuel. Exposure increased the emissivity of the thermocouple wire, which increased its radiation error. Two methods are presented for determining the emittance of the wires. The emissivity of a clean platinum rhodium-platinum thermocouple was approximately 0.2 in the temperature range investigated, while the emittance of an exposed thermocouple coated with exhaust residue was about 0.5. The exposure caused negligible change in the thermoelectric power of the thermocouples.

  7. Preparation of arylzinc reagents and their use in the rhodium-catalyzed asymmetric 1,4-addition for the synthesis of 2-aryl-4-piperidones.

    PubMed

    Shintani, Ryo; Hayashi, Tamio

    2007-01-01

    A protocol for the catalytic asymmetric synthesis of 2-aryl-4-piperidones with high enantiomeric excess (ee) (typically > or = 99% ee) has been described here. The preparation of arylzinc reagents, which are used as nucleophiles in catalysis, is also included. The whole protocol can be completed in 10-20 h, starting from the preparation of the arylzinc reagents, depending on the reaction time of the rhodium-catalyzed process. A detailed protocol is described using the preparation of 4-fluorophenylzinc chloride and its addition to benzyl 3,4-dihydro-4-oxo-1(2H)-pyridinecarboxylate in the presence of [RhCl((R)-binap)]2 as an example.

  8. Ruthenium, rhodium, osmium, and iridium complexes of osazones (osazones = bis-arylhydrazones of glyoxal): radical versus nonradical states.

    PubMed

    Patra, Sarat Chandra; Weyhermüller, Thomas; Ghosh, Prasanta

    2014-03-01

    Phenyl osazone (L(NHPh)H2), phenyl osazone anion radical (L(NHPh)H2(•-)), benzoyl osazone (L(NHCOPh)H2), benzoyl osazone anion radical (L(NHCOPh)H2(•-)), benzoyl osazone monoanion (L(NCOPh)HMe(-)), and anilido osazone (L(NHCONHPh)HMe) complexes of ruthenium, osmium, rhodium, and iridium of the types trans-[Os(L(NHPh)H2)(PPh3)2Br2] (3), trans-[Ir(L(NHPh)H2(•-))(PPh3)2Cl2] (4), trans-[Ru(L(NHCOPh)H2)(PPh3)2Cl2] (5), trans-[Os(L(NHCOPh)H2)(PPh3)2Br2] (6), trans- [Rh(L(NHCOPh)H2(•-))(PPh3)2Cl2] (7), trans-[Rh(L(NHCOPh)HMe(-))(PPh3)2Cl]PF6 ([8]PF6), and trans-[Ru(L(NHCONHPh)HMe)(PPh3)2Cl]Cl ([9]Cl) have been isolated and compared (osazones = bis-arylhydrazones of glyoxal). The complexes have been characterized by elemental analyses and IR, mass, and (1)H NMR spectra; in addition, single-crystal X-ray structure determinations of 5, 6, [8]PF6, and [9]Cl have been carried out. EPR spectra of 4 and 7 reveal that in the solid state they are osazone anion radical complexes (4, gav = 1.989; 7, 2.028 (Δg = 0.103)), while in solution the contribution of the M(II) ions is greater (4, gav = 2.052 (Δg = 0.189); 7, gav = 2.102 (Δg = 0.238)). Mulliken spin densities on L(NHPh)H2 and L(NHCOPh)H2 obtained from unrestricted density functional theory (DFT) calculations on trans-[Ir(L(NHPh)H2)(PMe3)2Cl2] (4(Me)) and trans-[Rh(L(NHCOPh)H2)(PMe3)2Cl2] (7(Me)) in the gas phase with doublet spin states authenticated the existence of L(NHPh)H2(•-) and L(NHCOPh)H2(•-) anion radicals in 4 and 7 coordinated to iridium(III) and rhodium(III) ions. DFT calculations on trans-[Os(L(NHPh)H2)(PMe3)2Br2] (3(Me)), trans-[Os(L(NHCOPh)H2)(PMe3)2Br2] (6(Me)), and trans-[Ru(L(NHCONHPh)HMe(-))(PMe3)2Cl] [9(Me)](+) with singlet spin states established that the closed-shell singlet state (CSS) solutions of 3, 5, 6, and [9]Cl are stable. The lower value of M(III)/M(II) reduction potentials and lower energy absorption bands corroborate the higher extent of mixing of d orbitals with the π* orbital

  9. A comparative study of AumRhn (4 ≤ m + n ≤ 6) clusters in the gas phase versus those deposited on (100) MgO.

    PubMed

    Buendía, Fernando; Vargas, Jorge A; Beltrán, Marcela R; Davis, Jack B A; Johnston, Roy L

    2016-08-10

    A comparative theoretical study has been performed of the gas phase and deposited AumRhn (4 ≤ m + n ≤ 6) clusters. The combined use of a genetic algorithm and Density Functional Theory (DFT) calculations allows us to explore the potential energy surface and, therefore, find efficiently and automatically the global minimum configuration for each composition. Our results show interesting effects on the geometries of the clusters on deposition. This occurs because the rhodium atoms (electronically) prefer to be in contact with the MgO surface, sometimes promoting planar clusters to become three-dimensional when deposited, and three-dimensional clusters in the gas phase to become two-dimensional. Together with the change in geometries, the magnetic moment is reduced from the gas phase, as the electrons rearrange themselves when the cluster interacts with the substrate. PMID:27444254

  10. Poor Rural Children Attract Close Study

    ERIC Educational Resources Information Center

    Viadero, Debra

    2008-01-01

    Growing up poor in isolated rural areas and small towns is qualitatively different from growing up poor in the city. Yet most of what experts know about the effects of poverty on children's development comes from studies conducted in big cities. Now, an ambitious project run by universities in Pennsylvania and North Carolina is putting what some…

  11. The Crisis of the Near Poor

    ERIC Educational Resources Information Center

    Newman, Katherine S.; Tan Chen, Victor

    2007-01-01

    This article focuses on the "missing class," the near poor whose incomes place them above the poverty line, but well below the middle class. Near-poor families with two parents and two children subsist on $20,000 to $40,000 a year, which disqualifies them for virtually all public subsidies, but is a far cry from what they need to be…

  12. Extent of Malnourishment among the Rural Poor.

    ERIC Educational Resources Information Center

    Shotland, Jeffrey

    1989-01-01

    Uses national survey data to demonstrate that, compared to the rural or U.S. non-poor, the rural poor consumed less of eight of nine key nutrients; and disparities were greatest for vitamins A and C, iron, and calcium, and for the youngest (two-five years) age group studied. (SV)

  13. Cognitive Profiles of Korean Poor Readers

    ERIC Educational Resources Information Center

    Cho, Jeung-Ryeul; Ji, Yu-Kyong

    2011-01-01

    This study compared the performance of 30 poor readers in the third grade with those of 30 average readers of the same age and 30 younger readers matched with the same reading level on phonological, visuo-perceptual, orthographic, and naming speed tasks. Individual data revealed heterogeneous profiles for the poor readers: six (20%) exhibited…

  14. Cognitive and Behavioral Distancing from the Poor.

    ERIC Educational Resources Information Center

    Lott, Bernice

    2002-01-01

    Suggests that distancing is the dominant response to poor people by those who are not poor and that distancing, separation, exclusion, and devaluing operationally define discrimination. Examines U.S. classism in the context of theoretical propositions about the moral exclusion of stigmatized others. Describes cognitive, institutional, and…

  15. Ammonia Borane Dehydrogenation Promoted by a Pincer-Square-Planar Rhodium(I) Monohydride: A Stepwise Hydrogen Transfer from the Substrate to the Catalyst.

    PubMed

    Esteruelas, Miguel A; Nolis, Pau; Oliván, Montserrat; Oñate, Enrique; Vallribera, Adelina; Vélez, Andrea

    2016-07-18

    The pincer d(8)-monohydride complex RhH{xant(P(i)Pr2)2} (xant(P(i)Pr2)2 = 9,9-dimethyl-4,5-bis(diisopropylphosphino)xanthene) promotes the release of 1 equiv of hydrogen from H3BNH3 and H3BNHMe2 with TOF50% values of 3150 and 1725 h(-1), to afford [BH2NH2]n and [BH2NMe2]2 and the tandem ammonia borane dehydrogenation-cyclohexene hydrogenation. DFT calculations on the ammonia borane dehydrogenation suggest that the process takes place by means of cis-κ(2)-PP-species, through four stages including: (i) Shimoi-type coordination of ammonia borane, (ii) homolytic addition of the coordinated H-B bond to afford a five-coordinate dihydride-boryl-rhodium(III) intermediate, (iii) reductive intramolecular proton transfer from the NH3 group to one of the hydride ligands, and (iv) release of H2 from the resulting square-planar hydride dihydrogen rhodium(I) intermediate.

  16. Ammonia Borane Dehydrogenation Promoted by a Pincer-Square-Planar Rhodium(I) Monohydride: A Stepwise Hydrogen Transfer from the Substrate to the Catalyst.

    PubMed

    Esteruelas, Miguel A; Nolis, Pau; Oliván, Montserrat; Oñate, Enrique; Vallribera, Adelina; Vélez, Andrea

    2016-07-18

    The pincer d(8)-monohydride complex RhH{xant(P(i)Pr2)2} (xant(P(i)Pr2)2 = 9,9-dimethyl-4,5-bis(diisopropylphosphino)xanthene) promotes the release of 1 equiv of hydrogen from H3BNH3 and H3BNHMe2 with TOF50% values of 3150 and 1725 h(-1), to afford [BH2NH2]n and [BH2NMe2]2 and the tandem ammonia borane dehydrogenation-cyclohexene hydrogenation. DFT calculations on the ammonia borane dehydrogenation suggest that the process takes place by means of cis-κ(2)-PP-species, through four stages including: (i) Shimoi-type coordination of ammonia borane, (ii) homolytic addition of the coordinated H-B bond to afford a five-coordinate dihydride-boryl-rhodium(III) intermediate, (iii) reductive intramolecular proton transfer from the NH3 group to one of the hydride ligands, and (iv) release of H2 from the resulting square-planar hydride dihydrogen rhodium(I) intermediate. PMID:27367792

  17. On the Reaction Mechanism of the Rhodium-Catalyzed Arylation of Fullerene (C60) with Organoboron Compounds in the Presence of Water.

    PubMed

    Martínez, Juan Pablo; Solà, Miquel; Poater, Albert

    2015-12-01

    Density functional theory (DFT) calculations were carried out to study the reaction mechanism of the Suzuki-Miyaura rhodium-catalyzed hydroarylation of fullerene (C60) by phenylboronic acid in the presence of water. As found experimentally, our results confirm that addition of the phenyl group and the hydrogen atom in C60 occurs at the [6,6] bond. The rate-determining step corresponds to the simultaneous transfer of a hydrogen atom from a water molecule to C60 and the recovery of the active species. The use of 2-phenyl-1,3,2-dioxaborinane and the 4,4,5,5-tetramethyl-2-phenyl-1,3,2,-dioxaborolane instead of phenylboronic acid as organoborate agents does not lead to great modifications of the energy profile. The possible higher steric hindrance of 4,4,5,5-tetramethyl-2-phenyl-1,3,2,-dioxaborolane should not inhibit its use in the hydroarylation of C60. Overall, we show how organoboron species arylate C60 in rhodium-based catalysis assisted by water as a source of protons. PMID:27308203

  18. Introduction of luminescent rhenium(I), ruthenium(II), iridium(III) and rhodium(III) systems into rhodamine-tethered ligands for the construction of bichromophoric chemosensors.

    PubMed

    Wang, Chunyan; Lam, Ho-Chuen; Zhu, Nianyong; Wong, Keith Man-Chung

    2015-09-14

    Several classes of luminescent transition metal complexes, including rhenium(I) tricarbonyl diimine, ruthenium(II) diimine, cyclometallated iridium(III) and rhodium(III) diimine, as well as ruthenium(II) and iridium(III) terpyridine systems, tethered with rhodamine moieties, have been synthesized and characterized. The X-ray crystal structure of one cyclometallated rhodium(III) diimine (11) with a rhodamine pendant was determined. Most of the complexes were found to exhibit emission in fluid solution at room temperature. Depending on the nature of the transition metal system, the emission origin was mainly assigned to be derived from the triplet excited state of the metal-to-ligand charge transfer ((3)MLCT) or the intraligand ((3)IL) transition. The cation-binding properties of these complexes toward various cations were investigated by electronic absorption and emission spectroscopy. Some of them were found to exhibit new low-energy absorption and emission bands, attributed to the ring opening of the rhodamine moiety, with high selectivity and/or high sensitivity for various cations, in agreement with sensing and spectroscopic behaviours of the rhodamine derivative. Depending on the nature of the transition metal centres, the chelating ligands as well as the linker to the rhodamine derivative, different sensing properties in terms of selectivity, sensitivity and binding stability, could be obtained.

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

    PubMed Central

    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

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

    PubMed

    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).

  1. Essentially Molecular Metal Complexes Anchored to Zeolite: Synthesis and Characterization of Rhodium Complexes and Ruthenium Complexes Prepared from Rh(acac)(2-C2H4)2 and cis-Ru(acac)2( -C2H4)2

    SciTech Connect

    Ogino, I.; Gates, B

    2010-01-01

    Mononuclear complexes of rhodium and of ruthenium, Rh(acac)({eta}{sup 2}-C{sub 2}H{sub 4}){sub 2} and cis-Ru(acac)2({eta}{sup 2}-C{sub 2}H{sub 4}){sub 2} (acac = C{sub 5}H{sub 7}O{sub 2}{sup -}), were used as precursors to synthesize metal complexes bonded to zeolite {beta}. Infrared (IR) and extended X-ray absorption fine structure (EXAFS) spectra show that the species formed from Rh(acac)({eta}{sup 2}-C{sub 2}H{sub 4}){sub 2} was Rh({eta}{sup 2}-C{sub 2}H{sub 4}){sub 2}{sup +}, which was bonded to the zeolite at aluminum sites via two Rh-O bonds. Reaction of this supported rhodium complex with CO gave the supported rhodium gem-dicarbonyl Rh(CO){sub 2}{sup +}, which was characterized by two {nu}{sub CO} bands in the IR spectrum, at 2048 and 2115 cm{sup -1}, that were sharp (fwhm of 2115-cm{sup -1} band = 5 cm{sup -1}), indicating a high degree of uniformity of the supported species. Nearly the same result was observed (Liang, A. et al. J. Am. Chem. Soc. 2009, 131, 8460) for the isostructural rhodium complex supported on dealuminated HY zeolite, which was characterized by frequencies of the {nu}{sub CO} bands that were 4 and 2 cm{sup -1}, respectively, greater than those characterizing the zeolite {beta}-supported complex. This comparison indicates that the Rh atoms in Rh({eta}{sup 2}-C{sub 2}H{sub 4}){sub 2}{sup +} anchored on zeolite {beta} were slightly more electron-rich than those on zeolite Y. This inference is supported by EXAFS results showing shorter Rh-C bonds in the zeolite {beta}-supported rhodium ethene complex than in the zeolite Y-supported rhodium ethene complex. In contrast to these supported rhodium complexes, the zeolite {beta}-supported ruthenium samples were shown by IR and EXAFS spectroscopies to consist of mixtures of mononuclear ruthenium complexes with various numbers of acac ligands; when CO reacted with the supported ruthenium complexes, the resultant ruthenium carbonyls were characterized by {nu}{sub CO} spectra characteristic of both

  2. Effect of support on iron promoted rhodium nanocatalysts for ethanol synthesis from CO hydrogenation

    NASA Astrophysics Data System (ADS)

    Carrillo Sanchez, Pamela Carolina

    Depleting fossil fuel sources coupled with the deleterious effects of petroleum-based fuel combustion have led to the development of sustainable ways for energy production. One alternative is the production of biofuels like ethanol. Ethanol's biggest advantages are its high energy density, biodegradability and carbon neutrality. A potential scalable process is the conversion of synthetic gas (syngas: CO, CO2, H 2) produced from gasification of biomass with the use of Rh-based catalysts. The work presented in this thesis aimed to study the effect of the introduction of 1, 5, and 10 wt % CeO2 into a TiO2 support on Fe promoted-Rh catalysts for ethanol production from CO hydrogenation. The mixed-oxide CeO2-TiO2 support was synthesized by a sol-gel method where Rh and Fe nanoparticles were deposited by wet incipient impregnation. Reactivity studies were carried under CO hydrogenation conditions with the use of gas chromatography. Characterization of the bare support and the catalyst that showed the best ethanol selectivity were performed by in-situ X-ray diffraction synchrotron experiments. Ethanol selectivity increases with ceria content with a shift on product distribution and CO conversion rates compared to Rh supported on single TiO2 and CeO2. This could be explained by a synergetic effect between CeO2 and TiO2 and to the to the formation of amorphous and mobile species of CeOx that can act as dispersing agents for the Rh particles increasing catalytic sites for CO insertion and for the stabilization of HCOx species. XRD characterization analysis of 10%CeO2-90%TiO2 identified three crystallographic phases: anatase, TiO2(B), and cerianite. The unpromoted 2%Rh/10%CeO2-90%TiO2 in-situ XRD analysis showed an absence of Rh0 under CO hydrogenation conditions. Conversely, the addition of Fe to the different mixed-oxide compositions showed comparable ethanol selectivity at the expense of methane formation. Therefore, the introduction of ceria into the titania support on

  3. Tackling poor parenting: a public health issue.

    PubMed

    Poole, Judith

    2003-01-01

    The adverse consequences associated with poor parenting persist down the generations and are a problem for society as well as individuals. The author cites evidence suggesting that in many cases poor parenting is associated with socioeconomic deprivation, including health inequalities. She argues that most parents (especially mothers, as the main child carers) are motivated to do their best for their children but that many families struggle against poverty. Poor parenting skills may be a product of poverty and social exclusion rather than the fault of individual parents. A public health approach, based on partnership with parents to meet their expressed needs in appropriate ways, could offer a constructive way forward.

  4. Energy and minorities, women, and the poor

    SciTech Connect

    Perry, H.L.; Perry, E.B.

    1980-01-01

    A comprehensive, up-to-date (1975 to 1980) bibliography of articles, books and other publications is presented dealing with the subject of energy and minorities, women and the poor. Included are academic, popular, and government publications as well as publications by private groups and organizations. It is intended for political scientists, sociologists, economists, home economists, energy planners, energy managers and others interested in the interface of minorities, women, and the poor with energy. Following a brief introduction, there is a general listing. Also included are references dealing with energy and black Americans, native Americans (Indians), the poor, and women. (MJJ)

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

    NASA Astrophysics Data System (ADS)

    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.

  6. Constraining the Evolution of Poor Clusters

    NASA Astrophysics Data System (ADS)

    Broming, Emma J.; Fuse, C. R.

    2012-01-01

    There currently exists no method by which to quantify the evolutionary state of poor clusters (PCs). Research by Broming & Fuse (2010) demonstrated that the evolution of Hickson compact groups (HCGs) are constrained by the correlation between the X-ray luminosities of point sources and diffuse gas. The current investigation adopts an analogous approach to understanding PCs. Plionis et al. (2009) proposed a theory to define the evolution of poor clusters. The theory asserts that cannibalism of galaxies causes a cluster to become more spherical, develop increased velocity dispersion and increased X-ray temperature and gas luminosity. Data used to quantify the evolution of the poor clusters were compiled across multiple wavelengths. The sample includes 162 objects from the WBL catalogue (White et al. 1999), 30 poor clusters in the Chandra X-ray Observatory archive, and 15 Abell poor clusters observed with BAX (Sadat et al. 2004). Preliminary results indicate that the cluster velocity dispersion and X-ray gas and point source luminosities can be used to highlight a weak correlation. An evolutionary trend was observed for multiple correlations detailed herein. The current study is a continuation of the work by Broming & Fuse examining point sources and their properties to determine the evolutionary stage of compact groups, poor clusters, and their proposed remnants, isolated ellipticals and fossil groups. Preliminary data suggests that compact groups and their high-mass counterpart, poor clusters, evolve along tracks identified in the X-ray gas - X-ray point source relation. While compact groups likely evolve into isolated elliptical galaxies, fossil groups display properties that suggest they are the remains of fully coalesced poor clusters.

  7. How School Taught Me I Was Poor

    ERIC Educational Resources Information Center

    Sapp, Jeff

    2009-01-01

    In this article, the author recounts how school taught him that he was poor. For him, third grade was the year in which he learned in school that he was poor. The author's story reminds everyone that all children do not experience school in the same way. Their social class (in the case described in this article), as well as their race, gender,…

  8. Relationship between electrochemical potentials and substitution reaction rates of ferrocene-containing β-diketonato rhodium(I) complexes; cytotoxicity of [Rh(FcCOCHCOPh)(cod)].

    PubMed

    Conradie, Jeanet; Swarts, Jannie C

    2011-06-14

    A series of ferrocene-containing rhodium complexes of the type [Rh(FcCOCHCOR)(cod)] (cod = 1,5-cyclooctadiene) with R = CF(3), 1, (E(pa)(Rh) = 269; E(o)'(Fc) = 329 mV vs. Fc/Fc(+)), CCl(3), 2, (E(pa) = 256; E(o)' = 312 mV), CH(3), 3, (E(pa) = 177; E(o)' = 232 mV), Ph = C(6)H(5), 4, (E(pa) = 184; E(o)' = 237 mV), and Fc = ferrocenyl = (C(5)H(5))Fe(C(5)H(4)), 5, (E(pa) = 135; E(o)'(Fc1) = 203; E(o)'(Fc2) = 312 mV), have been studied electrochemically in CH(3)CN. Results indicated that the rhodium(I) centre is irreversibly oxidised to Rh(III) in a two-electron transfer process before the ferrocenyl fragment is reversibly oxidized in a one-electron transfer process. The peak anodic (oxidation) potential, E(pa), (in V vs. Fc/Fc(+)) of the rhodium core in 1-5 relates to k(2), the second-order rate constant for the substitution of (FcCOCHCOR)(-) with 1,10-phenanthroline in [Rh(FcCOCHCOR)(cod)] to form [Rh(phen)(cod)](+) in methanol at 25 °C with the equation lnk(2) = 39.5 E(pa)(Rh) - 3.69, while the formal oxidation potential of the ferrocenyl groups in 1-5 relates to k(2) by lnk(2) = 40.8 E(o)'(Fc)-6.34. Complex 4 (IC(50) = 28.2 μmol dm(-3)) was twice as cytotoxic as the free FcCOCH(2)COPh ligand having IC(50) = 54.2 μmol dm(-3), but approximately one order of magnitude less toxic to human HeLa neoplastic cells than cisplatin (IC(50) = 2.3 μmol dm(-3)). PMID:21423964

  9. Why so many children are poor.

    PubMed

    Betson, D M; Michael, R T

    1997-01-01

    According to the official U.S. measure of poverty, in 1995 the child poverty rate in this country was nearly 21%, compared with an adult poverty rate of 11%. This article explores why, according to the official measure, there are so many poor children. Working from the premise that children are poor because they live with poor adults, the reasons for adult poverty are reviewed. Both economic forces and demographic trends have contributed to growing inequality of earnings among workers. That inequality coupled with stagnating real earnings has increased poverty. In addition, education, age, and race affect an individual's earning capacity; the article examines the likelihood that an individual will earn enough to keep his or her family out of poverty, given the individual's educational attainment, age, and race. The reasons for the large difference between the child and adult poverty rates are explored, using a decomposition of the poverty population to show how demographic characteristics such as higher fertility rates among poor families and the higher prevalence of single-parent families among the poor lead to substantially higher poverty rates for children than for adults. Finally, the article examines the validity of the official poverty measure and reviews how an alternative measure proposed by a National Research Council panel would address the official measure's shortcomings. If the panel's proposed measure were adopted, it would change the statistical face of poor children. It would, for example, show an increase in the proportion of poor children who live in families with two parents and a corresponding decrease in the proportion in families with only one parent, and it would show an increase in the proportion of children who live in families with at least one full-time employed adult and a corresponding decrease in the proportion in families with no adult employed full time. PMID:9299835

  10. Photometric Properties of Galaxies in Poor Clusters

    NASA Astrophysics Data System (ADS)

    Sharma, M.; Prabhu, T.

    We study several statistical properties of galaxies in four poor clusters of galaxies using optical photometry. We select these poor clusters as luminous, extended X-ray sources identified with poor galaxy systems in the EMSS catalogue of clusters of galaxies. The clusters are at moderate redshifts (0.08poor clusters, but steeper than the field LF in the R-band. In terms of the statistical properties of their member galaxies, poor clusters appear to be lower-mass extensions of their rich counterparts.

  11. Regio- and enantiospecific rhodium-catalyzed allylic etherification reactions using copper(I) alkoxides: influence of the copper halide salt on selectivity.

    PubMed

    Evans, P Andrew; Leahy, David K

    2002-07-10

    The transition metal-catalyzed allylic etherification represents a fundamentally important cross-coupling reaction for the construction of allylic ethers. We have developed a new regio- and enantiospecific rhodium-catalyzed allylic etherification of acyclic unsymmetrical allylic alcohol derivatives using copper(I) alkoxides derived from primary, secondary and tertiary alcohols. This study demonstrates that the choice of copper(I) halide salt is crucial for obtaining excellent regio- and enantiospecificity, providing another example of the effect of halide ions in asymmetric transition metal-catalyzed reactions. Finally, the ability to alter the reactivity of the alkali metal alkoxides in this manner may provide a useful method for related metal-catalyzed cross-coupling reactions involving heteroatoms.

  12. Synthesis and crystal structure of the rhodium(I) cyclooctadiene complex with bis(3-tert-butylimidazol-2-ylidene)borate ligand

    SciTech Connect

    Chen, F.; Shao, K.-J.; Xiao, Y.-C.; Pu, X.-J.; Zhu, B.; Jiang, M.-J.

    2015-12-15

    The rhodium(I) cyclooctadiene complex with the bis(3-tert-butylimidazol-2-ylidene)borate ligand [H{sub 2}B(Im{sup t}Bu){sup 2}]Rh(COD) C{sup 22}H{sup 36}BN{sup 4}Rh, has been prepared, and its crystal structure is determined by X-ray diffraction. Complex exhibits slightly distorted square planar configurations around the metal center, which is coordinated by the bidentate H{sup 2}B(Im{sup t}Bu){sub 2} and one cyclooctadiene group. The Rh–C{sub carbene} bond lengths are 2.043(4) and 2.074(4) Å, and the bond angle C–Rh1–C is 82.59°. The dihedral angle between two imidazol-2-ylidene rings is 67.30°.

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

    SciTech Connect

    Grosfils, P.; Gaspard, P.; Visart de Bocarmé, T.

    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.

  14. Synthesis and crystal structure of the rhodium(I) cyclooctadiene complex with bis(3- tert-butylimidazol-2-ylidene)borate ligand

    NASA Astrophysics Data System (ADS)

    Chen, F.; Shao, K.-J.; Xiao, Y.-C.; Pu, X.-J.; Zhu, B.; Jiang, M.-J.

    2015-12-01

    The rhodium(I) cyclooctadiene complex with the bis(3- tert-butylimidazol-2-ylidene)borate ligand [H2B( Im t Bu)2]Rh(COD) C22H36BN4Rh, has been prepared, and its crystal structure is determined by X-ray diffraction. Complex exhibits slightly distorted square planar configurations around the metal center, which is coordinated by the bidentate H2B( Im t Bu)2 and one cyclooctadiene group. The Rh-Ccarbene bond lengths are 2.043(4) and 2.074(4) Å, and the bond angle C-Rh1-C is 82.59°. The dihedral angle between two imidazol-2-ylidene rings is 67.30°.

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

    PubMed

    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. PMID:21700510

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

    PubMed

    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.

  17. Metallogenic evolution of uranium deposits in the Middle East and North Africa deposits

    NASA Astrophysics Data System (ADS)

    Howari, Fares; Goodell, Philip; Salman, Abdulaty

    2016-02-01

    This paper is briefly involved in classification and distributions of the Middle East and North Africa (MENA) uranium deposits. The study of these mineral systems can significantly contribute to our further understanding of the metallogeny of known and poorly explored deposits. This provides contribution to, and further enhancement of, current classifications and metallogenic models of uranium systems, allowing researchers to emphasize on unknown or poorly studied mineral systems found in MENA. The present study identified eight metallogenic types of uranium associated with: 1) the Archean rocks and intra-cratonic basins, 2) the Pan-African granites and rhyolites which are characterized by igneous activity, 3) Phanerozoic (Paleozoic) clastics, these deposits are the sedimentological response to Pan African magmatism, 4) Mesozoic (basal) clastics type e.g. Nubia sandstones which are characterized by uranium minerals, 5) regional sedimentary phosphate deposits which are categorized as geosynclinal, or continental margin deposits, on the shelf of the Tethys Ocean, 6) Cenozoic Intracratonic Felsic Magmatism of the Tibesti and Hoggar, and the sandstone U deposits of adjoining Niger. These are similar to the Pan-African magmatism metallogenic, 7) Calcretes, and 8) Resistate minerals which are often enriched in rare earth elements, sometimes including uranium. They are thus sometimes considered as U resources but poorly explored in the MENA region. These metallogenic types are described and discussed in the current paper.

  18. Sediment-Hosted Copper Deposits of the World: Deposit Models and Database

    USGS Publications Warehouse

    Cox, Dennis P.; Lindsey, David A.; Singer, Donald A.; Diggles, Michael F.

    2003-01-01

    Introduction This publication contains four descriptive models and four grade-tonnage models for sediment hosted copper deposits. Descriptive models are useful in exploration planning and resource assessment because they enable the user to identify deposits in the field and to identify areas on geologic and geophysical maps where deposits could occur. Grade and tonnage models are used in resource assessment to predict the likelihood of different combinations of grades and tonnages that could occur in undiscovered deposits in a specific area. They are also useful in exploration in deciding what deposit types meet the economic objectives of the exploration company. The models in this report supersede the sediment-hosted copper models in USGS Bulletin 1693 (Cox, 1986, and Mosier and others, 1986) and are subdivided into a general type and three subtypes. The general model is useful in classifying deposits whose features are obscured by metamorphism or are otherwise poorly described, and for assessing regions in which the geologic environments are poorly understood. The three subtypes are based on differences in deposit form and environments of deposition. These differences are described under subtypes in the general model. Deposit models are based on the descriptions of geologic environments and physical characteristics, and on metal grades and tonnages of many individual deposits. Data used in this study are presented in a database representing 785 deposits in nine continents. This database was derived partly from data published by Kirkham and others (1994) and from new information in recent publications. To facilitate the construction of grade and tonnage models, the information, presented by Kirkham in disaggregated form, was brought together to provide a single grade and a single tonnage for each deposit. Throughout the report individual deposits are defined as being more than 2,000 meters from the nearest adjacent deposit. The deposit models are presented here as

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

    SciTech Connect

    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 that has

  20. Rhodium self-powered neutron detector as a suitable on-line thermal neutron flux monitor in BNCT treatments

    SciTech Connect

    Miller, Marcelo E.; Sztejnberg, Manuel L.; Gonzalez, Sara J.; Thorp, Silvia I.; Longhino, Juan M.; Estryk, Guillermo

    2011-12-15

    Purpose: A rhodium self-powered neutron detector (Rh SPND) has been specifically developed by the Comision Nacional de Energia Atomica (CNEA) of Argentina to measure locally and in real time thermal neutron fluxes in patients treated with boron neutron capture therapy (BNCT). In this work, the thermal and epithermal neutron response of the Rh SPND was evaluated by studying the detector response to two different reactor spectra. In addition, during clinical trials of the BNCT Project of the CNEA, on-line neutron flux measurements using the specially designed detector were assessed. Methods: The first calibration of the detector was done with the well-thermalized neutron spectrum of the CNEA RA-3 reactor thermal column. For this purpose, the reactor spectrum was approximated by a Maxwell-Boltzmann distribution in the thermal energy range. The second calibration was done at different positions along the central axis of a water-filled cylindrical phantom, placed in the mixed thermal-epithermal neutron beam of CNEA RA-6 reactor. In this latter case, the RA-6 neutron spectrum had been well characterized by both calculation and measurement, and it presented some marked differences with the ideal spectrum considered for SPND calibrations at RA-3. In addition, the RA-6 neutron spectrum varied with depth in the water phantom and thus the percentage of the epithermal contribution to the total neutron flux changed at each measurement location. Local (one point-position) and global (several points-positions) and thermal and mixed-field thermal neutron sensitivities were determined from these measurements. Thermal neutron flux was also measured during BNCT clinical trials within the irradiation fields incident on the patients. In order to achieve this, the detector was placed on patient's skin at dosimetric reference points for each one of the fields. System stability was adequate for this kind of measurement. Results: Local mixed-field thermal neutron sensitivities and global

  1. Ruthenium, osmium and rhodium complexes of 1,4-diaryl 1,4-diazabutadiene: radical versus non-radical states.

    PubMed

    Chandra Patra, Sarat; Saha Roy, Amit; Manivannan, Vadivelu; Weyhermüller, Thomas; Ghosh, Prasanta

    2014-09-28

    Ruthenium, osmium and rhodium complexes of 1,4-di(3-nitrophenyl)-1,4-diazabutadiene (LDAB) of types trans-[RuII(LDAB)(PPh3)2Cl2] (1), trans-[OsII(LDAB)(PPh3)2Br2] (2) and trans-[Rh(LDAB)(PPh3)2Cl2] (3) are isolated and characterized by elemental analyses, IR, mass and 1H NMR spectra including the single crystal X-ray structure determination of 1·2toluene. The α-diimine fragment of the LDAB ligand in 1·2toluene is deformed, showing a relatively longer -C=N- bond, 1.320 Å, and a shorter =CH–CH= bond, 1.395 Å. Density functional theory (DFT) calculations on trans-[Ru(LDAB)(PMe3)2Cl2] (1Me) and trans-[Os(LDAB)(PMe3)2Br2] (2Me) with singlet spin states authenticated that the closed shell singlet state (CSS) solutions of 1 and 2 are stable and no perturbation occurs because of the diradical open shell singlet (OSS) state. The EPR spectra of 3 and the Mulliken spin density distribution obtained from the DFT calculation on trans-[Rh(LDAB)(PMe3)2Cl2] (3Me) imply that the ground electronic state of 3 can be defined by the [RhIII(LDAB˙−)(PPh3)2Cl2] (3RhL˙) ↔ [RhII(LDAB)(PPh3)2Cl2] (3Rh˙L) resonating states. In solid, the contribution of 3RhL˙ is higher and the gav is 2.018 with Δg = 0.10, whereas in frozen glasses the contribution of 3Rh˙L is higher and the gav is 2.026 with Δg (frozen glasses) = 0.13. The g parameters of the electrogenerated [1]+ (g1 = 2.456, g2 = 2.128 and g3 = 1.624, Δg = 0.824), [2]+ (g1 = 2.599, g2 = 2.041 and g3 = 1.965, Δg = 0.634), [1]− (g1 = 2.138, g2 = 2.109, g3 = 1.978 and Δg = 0.160) and [2]− (g1 = 2.168, g2 = 2.097, g3 = 1.987 and Δg = 0.181) ions and the spin density distributions obtained from the DFT calculations on [1Me]+, [2Me]+, [1Me]− and [2Me]− reveal that the reversible anodic peaks of 1 and 2 at 0.11 and 0.34 V, referenced versus Fc+/Fc couple, are due to the M(III)/M(II) redox couple, while the reversible cathodic waves at −1.27 V and −0.82 V of 1 and 2 are caused by the LDAB/LDAB˙− redox couple

  2. Residential Mobility among the Rural Poor.

    ERIC Educational Resources Information Center

    Fitchen, Janet M.

    1994-01-01

    The frequency of short-distance residential moves in poor rural New York counties was much greater than nationally, driven by scarce affordable housing and changes in personal and household situations. Higher frequency movement was associated with younger age, fewer children, and weaker social support networks. Discusses impacts of high mobility…

  3. Photometric Properties of Poor Cluster Galaxies

    NASA Astrophysics Data System (ADS)

    Sharma, M.; Prabhu, T. P.

    2002-12-01

    We study several statistical properties of galaxies in four poor clusters of galaxies using multi-color optical photometry obtained at the Vainu Bappu Telescope, India. The clusters, selected from the EMSS Catalog, are at moderate redshifts (0.08 < z < 0.25), of equivalent Abell richness R=0, and appear to be dynamically young. The early-type galaxy populations are clearly evolved, as traced by the tightness of the color-magnitude relations and the accordance of the latter with those of the Virgo cluster. The blue galaxy fractions are similar to those of R=0 clusters and higher than those of richer clusters at similar redshifts. The composite luminosity functions (LFs) in B, V, and R bands are flat at the faint end, similar to the V-band LF derived by Yamagata & Maehara for other (MKW/AWM) poor clusters but steeper than the R-band field LF derived by Lin et al. In terms of the statistical properties of their member galaxies, poor clusters appear to be lower-mass extensions of their rich counterparts. The brightest galaxies of three of these poor clusters appear to be luminous ellipticals with no incontrovertible signatures of a halo. It is likely that they were formed from multiple mergers early in the history of the clusters.

  4. University Students with Poor Reading Comprehension

    ERIC Educational Resources Information Center

    Georgiou, George K.; Das, J. P.

    2015-01-01

    The present study aimed to examine the nature of the working memory and general cognitive ability deficits experienced by university students with a specific reading comprehension deficit. A total of 32 university students with poor reading comprehension but average word-reading skills and 60 age-word-matched controls with no comprehension…

  5. Planning Behaviour in Good and Poor Readers

    ERIC Educational Resources Information Center

    Mahapatra, Shamita

    2016-01-01

    A group of 50 good readers and a group of 50 poor readers of Grade 5 matched for age and intelligence and selected on the basis of their proficiency in reading comprehension were tested for their competence in word reading and the process of planning at three different levels, namely, perceptual, memory and conceptual in order to study the…

  6. The Communication Environment of the Urban Poor.

    ERIC Educational Resources Information Center

    Dervin, Brenda; Greenberg, Bradley, S.

    The purpose of this document is to review the growing body of literature focusing on poverty and communication, assess it, and posit directions for future work. In all, some 4000 different studies are examined to develop an overview of the communication environment of the urban poor. No more than 200 had some relevance to poverty-communication;…

  7. Getting to Know L2 Poor Comprehenders

    ERIC Educational Resources Information Center

    Zoghi, Masoud; Mustapha, Ramlee; Maasum, Tengku Nor Rizan BT Tengku Mohamad

    2011-01-01

    Among the plethora of studies conducted thus far to explore the factors affecting EFL reading effectiveness, scant attention seems to be paid to the why of poor reading comprehension of most EFL learners. In this regard, the present article capitalized on qualitative research on a small scale, for the purpose of addressing the not-so-often debated…

  8. EEG Power Spectra of Adolescent Poor Readers.

    ERIC Educational Resources Information Center

    Ackerman, Peggy T.; McPherson, W. Brian; Oglesby, D. Michael; Dykman, Roscoe A.

    1998-01-01

    Electroencephalographic power spectra were studied in two poor-reading adolescent groups (n=38), dysphonetic and phonetic. Significant Group x Hemisphere effects were found in the alpha and beta bands, with the phonetic group showing right greater than left asymmetry. Results suggest more circumscribed and mature processing in the phonetically…

  9. The Other Poor: Rural Poverty and Education.

    ERIC Educational Resources Information Center

    Books, Sue

    1997-01-01

    This paper argues that rural poverty remains relatively invisible because, although shameful, it is profitable, and the rural poor pose little threat to their suburban neighbors. This is illustrated via interrogation concerning a rural poultry plant fire. The paper examines implications of this case for foundations scholars and educational…

  10. COMPREHENSIVE HEALTH SERVICES FOR THE RURAL POOR.

    ERIC Educational Resources Information Center

    LOGSDON, DONALD N.

    SEVERAL WRITERS HAVE DEPICTED AGRICULTURAL MIGRANTS AS BEING ONE OF THE MOST DEPRIVED GROUPS IN OUR COUNTRY. HOWEVER, THE NON-MIGRANT AGRICULTURAL WORKERS, WHO FAR OUTNUMBER THE MIGRANTS, ALSO LIVE IN EXTREMELY POOR CIRCUMSTANCES AND ARE VIRTUALLY UNNOTICED BECAUSE THEY DO NOT DRAW ATTENTION THROUGH MIGRATION. BOTH OF THESE GROUPS ARE IN DIRE NEED…

  11. Poor, Rural Neighborhoods and Early School Achievement.

    ERIC Educational Resources Information Center

    Bickel, Robert; Smith, Cynthia; Eagle, Teresa Hardman

    A study sought to identify the existence of neighborhood effects on school achievement that are independent of social class and family background among students from poor, rural neighborhoods. Ethnographic material yielded a concept of rural West Virginia neighborhoods in which residents expect their encounters to be friendly, informal, almost…

  12. Adult Literacy and the Poor Farming People.

    ERIC Educational Resources Information Center

    Mathur, J. C.

    1978-01-01

    In discussing Rafe-uz-Zaman's essay on adult literacy and national development (see v9, n1 of this journal), the author cites examples to support his thesis that mass literacy campaigns in predominately agricultural countries can be successful only if there is simultaneous undertaking of economic development programs focused on the rural poor. (MF)

  13. From Many Lands. Voices of the Poor.

    ERIC Educational Resources Information Center

    Narayan, Deepa, Ed.; Petesch, Patti, Ed.

    This book, the last volume in a three-part series, draws on a large-scale worldwide poverty study to present the views, experiences, and aspirations of poor people in 14 selected countries. In each country, interviews and discussion groups were held in 8-15 rural and urban communities that reflected the most prevalent poverty groups and the…

  14. Promoting Upward Mobility for the Working Poor.

    ERIC Educational Resources Information Center

    Rupured, Michael

    2000-01-01

    The working poor are typically defined by researchers as individuals who work at least part of the year and earn less than a given percentage of the federal poverty level. This definition tends to understate the problem. In 1997, 15.8 million employed parents had incomes below 200 percent of the federal poverty level. The federal Earned Income Tax…

  15. Correcting Poor Posture without Awareness or Willpower

    ERIC Educational Resources Information Center

    Wernik, Uri

    2012-01-01

    In this article, a new technique for correcting poor posture is presented. Rather than intentionally increasing awareness or mobilizing willpower to correct posture, this approach offers a game using randomly drawn cards with easy daily assignments. A case using the technique is presented to emphasize the subjective experience of living with poor…

  16. Health and economic expansion in poor lands.

    PubMed

    Malenbaum, W

    1973-01-01

    Economic progress in poor lands remains a major goal as current efforts continue to yield limited advance for the nations where most of the world's people continue to live in poverty. The income gap between poor lands and the rich world continue to grow. Effective solutions require new approaches in three areas of science: the process of economic development, the dynamics of population growth, and the function of the health of man. Neither history or theory provides economic progress a basis for policy or programs in any of these areas. The motivation and attitudes of man are essential elements in the process of population and production change, an emphasis which contrasts with the more conventional concern with a nation's material and physical resources in the process of economic and demographic advance. Health programs thus offer a major contribution to the process of economic and population development. Improved health in poor areas is a joint product of inputs from other professions as much as from the medical and public health sciences proper. In fact, improved health in developing lands may itself derive for the most part from expanding production relative to population. The basic contribution of the health sciences in poor lands is the involvement of health interventions with attitude changes essential to economic progress and to the rates of growth of production and population. Analysis of the interdependence of health, demographic and economic progress is suggested for India, Appalachia and South Africa and reported for Ethiopia, guatemala and St. Lucia.

  17. Resilient Parenting: Overcoming Poor Parental Bonding

    ERIC Educational Resources Information Center

    Travis, Wendy J.; Combs-Orme, Terri

    2007-01-01

    This study identified groups of mothers with varying patterns of adaptive functioning and bonds with their own parents. These patterns were related to mothers' parenting of their own children to understand how some mothers avoid repeating the cycle of poor parenting. Data from 210 new mothers were analyzed before hospital discharge about bonding…

  18. Katharine Drexel: Learning to Love the Poor

    ERIC Educational Resources Information Center

    Murray, Cecilia

    2006-01-01

    Although born into privilege, Katharine Drexel was blessed with parents, siblings, friends, and spiritual guides who kept her rooted in a deep, Eucharistic faith. Responding to the needs of the poor was a responsibility of the rich, and Katharine learned this value at the hands of her parents at an early age. With the good counsel of popes and…

  19. Deposition head for laser

    DOEpatents

    Lewis, Gary K.; Less, Richard M.

    1999-01-01

    A deposition head for use as a part of apparatus for forming articles from materials in particulate form in which the materials are melted by a laser beam and deposited at points along a tool path to form an article of the desired shape and dimensions. The deposition head delivers the laser beam and powder to a deposition zone, which is formed at the tip of the deposition head. A controller comprised of a digital computer directs movement of the deposition zone along the tool path and provides control signals to adjust apparatus functions, such as the speed at which the deposition head moves along the tool path.

  20. The environments of poor clusters of galaxies

    NASA Astrophysics Data System (ADS)

    Bliton, Mark Alan

    Poor clusters of galaxies are fundamental cosmological structures, but have received relatively little attention compared to rich, Abell clusters. In order to fully understand galaxy clustering, we must examine galaxy associations of all masses and richness levels. We have therefore undertaken an X-ray, optical, and radio investigation of the environments of poor clusters, in order to understand how their galaxies, radio sources, and intracluster media influence and interact with one another. To examine the global properties of poor clusters as observed in these three wavelength regimes, we have utilized three major sky surveys: the ROSAT All-Sky Survey, the Digitized Sky Survey, and the NRAO VLA Sky Survey. For the purposes of this study, we construct a complete, volume-limited sample of 306 poor clusters in the redshift range 0.01--0.03. We compute the X-ray luminosity function (XLF) of poor clusters and compare to XLFs of nearby, rich, Abell clusters. We also compute the bivariate radio luminosity function (BRLF), which is the fraction of radio-loud galaxies of a given optical magnitude. Higher richness clusters produce increased AGN activity in M* galaxies. We find that only clusters with an elliptical as their dominant galaxy possess an ICM. This implies that the presence of a dominant elliptical at the center of a poor cluster is more closely linked to the presence of an ICM than the overall morphological mix of the cluster galaxies. We also find a strong anti-correlation between richness and the fraction of starburst radio galaxies in poor clusters. There may be two factors which contribute to this anti-correlation. For richer clusters, the ICM density may be sufficiently strong that it can strip gas from starforming galaxies, thereby reducing the level of star formation in richer systems. Conversely, the poorest clusters contain higher galaxy compactness, which results in smaller nearest-neighbor distances between galaxies. These smaller galaxy separations

  1. Deposit model for volcanogenic uranium deposits

    USGS Publications Warehouse

    Breit, George N.; Hall, Susan M.

    2011-01-01

    The International Atomic Energy Agency's tabulation of volcanogenic uranium deposits lists 100 deposits in 20 countries, with major deposits in Russia, Mongolia, and China. Collectively these deposits are estimated to contain uranium resources of approximately 500,000 tons of uranium, which amounts to 6 percent of the known global resources. Prior to the 1990s, these deposits were considered to be small (less than 10,000 tons of uranium) with relatively low to moderate grades (0.05 to 0.2 weight percent of uranium). Recent availability of information on volcanogenic uranium deposits in Asia highlighted the large resource potential of this deposit type. For example, the Streltsovskoye district in eastern Russia produced more than 100,000 tons of uranium as of 2005; with equivalent resources remaining. Known volcanogenic uranium deposits within the United States are located in Idaho, Nevada, Oregon, and Utah. These deposits produced an estimated total of 800 tons of uranium during mining from the 1950s through the 1970s and have known resources of 30,000 tons of uranium. The most recent estimate of speculative resources proposed an endowment of 200,000 tons of uranium.

  2. Longitudinal stability and predictors of poor oral comprehenders and poor decoders.

    PubMed

    Elwér, Sa; Keenan, Janice M; Olson, Richard K; Byrne, Brian; Samuelsson, Stefan

    2013-07-01

    Two groups of fourth-grade children were selected from a population sample (N=926) to be either poor oral comprehenders (poor oral comprehension but normal word decoding) or poor decoders (poor decoding but normal oral comprehension). By examining both groups in the same study with varied cognitive and literacy predictors, and examining them both retrospectively and prospectively, we could assess how distinctive and stable the predictors of each deficit are. Predictors were assessed retrospectively at preschool and at the end of kindergarten, Grade 1, and Grade 2. Group effects were significant at all test occasions, including those for preschool vocabulary (worse in poor oral comprehenders) and rapid automatized naming (RAN) (worse in poor decoders). Preschool RAN and vocabulary prospectively predicted Grade 4 group membership (77-79% correct classification) within the selected samples. Reselection in preschool of "at-risk" poor decoder and poor oral comprehender subgroups based on these variables led to significant but relatively weak prediction of subtype membership at Grade 4. Implications of the predictive stability of our results for identification and intervention of these important subgroups are discussed. PMID:23528975

  3. Differences in Nutrient Adequacy among Poor and Non-Poor Children.

    ERIC Educational Resources Information Center

    Cook, John T.; Martin, Katie S.

    This study compared the proportion of 1- to 5-year-olds in poor and non-poor households whose intakes of key nutrients were inadequate. Data were obtained from the 1986 United States Department of Agriculture Nationwide Food Consumption Survey and Continuing Survey of Food Intakes by Individuals. An intake below 70 percent of the Recommended Daily…

  4. Redox-neutral rhodium-catalyzed C-H functionalization of arylamine N-oxides with diazo compounds: primary C(sp(3))-H/C(sp(2))-H activation and oxygen-atom transfer.

    PubMed

    Zhou, Bing; Chen, Zhaoqiang; Yang, Yaxi; Ai, Wen; Tang, Huanyu; Wu, Yunxiang; Zhu, Weiliang; Li, Yuanchao

    2015-10-01

    An unprecedented rhodium(III)-catalyzed regioselective redox-neutral annulation reaction of 1-naphthylamine N-oxides with diazo compounds was developed to afford various biologically important 1H-benzo[g]indolines. This coupling reaction proceeds under mild reaction conditions and does not require external oxidants. The only by-products are dinitrogen and water. More significantly, this reaction represents the first example of dual functiaonalization of unactivated a primary C(sp(3) )H bond and C(sp(2) )H bond with diazocarbonyl compounds. DFT calculations revealed that an intermediate iminium is most likely involved in the catalytic cycle. Moreover, a rhodium(III)-catalyzed coupling of readily available tertiary aniline N-oxides with α-diazomalonates was also developed under external oxidant-free conditions to access various aminomandelic acid derivatives by an O-atom-transfer reaction.

  5. Medical risk: implicating poor pregnant women.

    PubMed

    Handwerker, L

    1994-03-01

    Since 1987 the United States courts have increasingly relied on medical testimony to prosecute women labeled 'high risk' for failure to comply with medical advice when their fetuses or babies die. Drawing on fieldwork in a public prenatal clinic in Northern California, it is argued that risk does not represent scientific certainty. While the assessment and management of risk is not standardized or consistently applied in the clinic, health care providers and the legal system make decisions as if risk is unambiguous 'fact'. Consequently, labeling poor pregnant women 'high risk', implicitly and explicitly makes them accountable if they are unable to change their behavior as prescribed by health professionals. Through an examination of the dilemmas facing poor pregnant women seeking prenatal care, this paper suggests how attempts to prosecute women may discourage rather than encourage them to seek care. Overall, there is a need for understanding the complexities of risk and its usages in medical and legal settings.

  6. [Poor school performance: an updated review].

    PubMed

    Siqueira, Cláudia Machado; Gurgel-Giannetti, Juliana

    2011-01-01

    This study aims to develop a comprehensive review on the issue of poor school performance for professionals in both health and education areas. It discusses current aspects of education, learning and the main conditions involved in underachievement. It also presents updated data on key aspects of neurobiology, epidemiology, etiology, clinical presentation, comorbidities and diagnosis, early intervention and treatment of the major pathologies comprised. It is a comprehensive, non-systematic literature review on learning, school performance, learning disorders (dyslexia, dyscalculia and dysgraphia), attention deficit / hyperactivity disorder (ADHD) and developmental coordination disorder (DCD). Poor school performance is a frequent problem faced by our children, causing serious emotional, social and economic issues. An updated view of the subject facilitates clinical reasoning, accurate diagnosis and appropriate treatment. PMID:21390464

  7. Poor response to treatment: beyond medication

    PubMed Central

    Carvajal, César

    2004-01-01

    In psychiatry, one of the main factors contributing to poor response to pharmacological treatment is adherence. Noncompliance with maintenance treatments for chronic illnesses such as schizophrenia and affective disorders can exceed 50%, Poor adherence can be due to drug-related factors (tolerance, complexity of prescription, side effects, or cost), patient-related variables (illness symptoms, comorbidity, insight capacity, belief system, or sociocultural environment), and physician-related factors (communication or psychoeducational style). Psychosocial treatments must be used in conjunction with medication during the maintenance phase to improve adherence to treatment and to achieve - through the management of psychological variables - better social, work, and family functioning. This article reviews the concepts of adherence and noncompliance, and their impact on maintenance treatments, as well as the effect of dealing with psychosocial factors in psychiatric treatment. PMID:22034452

  8. An automatic collector to monitor insoluble atmospheric deposition: application for mineral dust deposition

    NASA Astrophysics Data System (ADS)

    Laurent, B.; Losno, R.; Chevaillier, S.; Vincent, J.; Roullet, P.; Bon Nguyen, E.; Ouboulmane, N.; Triquet, S.; Fornier, M.; Raimbault, P.; Bergametti, G.

    2015-07-01

    Deposition is one of the key terms of the mineral dust cycle. However, dust deposition remains poorly constrained in transport models simulating the atmospheric dust cycle. This is mainly due to the limited number of relevant deposition measurements. This paper aims to present an automatic collector (CARAGA), specially developed to sample the total (dry and wet) atmospheric deposition of insoluble dust in remote areas. The autonomy of the CARAGA can range from 25 days to almost 1 year depending on the programmed sampling frequency (from 1 day to 2 weeks respectively). This collector is used to sample atmospheric deposition of Saharan dust on the Frioul islands in the Gulf of Lions in the Western Mediterranean. To quantify the mineral dust mass in deposition samples, a weighing and ignition protocol is applied. Almost 2 years of continuous deposition measurements performed on a weekly sampling basis on Frioul Island are presented and discussed with air mass trajectories and satellite observations of dust. Insoluble mineral deposition measured on Frioul Island was 2.45 g m-2 for February to December 2011 and 3.16 g m-2 for January to October 2012. Nine major mineral deposition events, measured during periods with significant MODIS aerosol optical depths, were associated with air masses coming from the southern Mediterranean Basin and North Africa.

  9. Physical deposit measures and commercial potential: The case of titanium-bearing heavy-mineral deposits

    USGS Publications Warehouse

    Attanasi, E.D.; DeYoung, J.H., Jr.

    1988-01-01

    Physical measures of mineral deposit characteristics, such as grade and tonnage, long have been used in both subjective and analytic models to predict favorability of areas for the occurrence of mineral deposits of particular types. After a deposit has been identified, however, the explorationist must decide whether to continue data collection, begin an economic feasibility study, or abandon the prospect. The decision maker can estimate the probability that a deposit will be commercial by examining physical measures. The amount of sampling data required before such a probability estimate can be considered reliable can be determined. A logit probability model estimated from onshore titanium-bearing heavy-mineral deposit data identifies and quantifies the relative influence of a deposit's physical measures on the chances of the deposit becoming commercial. A principal conclusion that can be drawn from the analysis is that, along with a measure of deposit size, the characteristics most important in predicting commercial potential are grades of the constituent minerals. Total heavy-mineral-bearing sand grade or even total titanium grade (without data on constituent mineral grades) are poor predictors of the deposit's commercial potential. ?? 1988 International Association for Mathematical Geology.

  10. Soil-like deposits observed by Sojourner, the Pathfinder rover

    USGS Publications Warehouse

    Moore, Henry J.; Bickler, Donald B.; Crisp, Joy A.; Eisen, Howard J.; Gensler, Jeffrey A.; Haldemann, Albert F.C.; Matijevic, Jacob R.; Reid, Lisa K.; Pavlics, Ferenc

    1999-01-01

    Most of the soil-like materials at the Pathfinder landing site behave like moderately dense soils on Earth with friction angles near 34°-39° and are called cloddy deposits. Cloddy deposits appear to be poorly sorted with dust-sized to granule-sized mineral or rock grains; they may contain pebbles, small rock fragments, and clods. Thin deposits of porous, compressible drifts with friction angles near 26°-28° are also present. Drifts are fine grained. Cohesions of both types of deposits are small. There may be indurated soil-like deposits and/or coated or crusted rocks. Cloddy deposits may be fluvial sediments of the Ares-Tiu floods, but other origins, such as ejecta from nearby impact craters, should be considered. Drifts are probably dusts that settled from the Martian atmosphere. Remote-sensing signatures of the deposits inferred from rover observations are consistent with those observed from orbit and Earth.

  11. The interaction of carbon monoxide with rhodium on potassium-modified CeO2(111)

    NASA Astrophysics Data System (ADS)

    Mullins, David R.

    2016-10-01

    The adsorption and reactions of CO adsorbed on Rh particles deposited on K-covered CeO2(111) were studied by temperature programmed desorption and photoelectron spectroscopy. K deposited on CeO2(111) forms a KOX over-layer by extracting O from the ceria and partially reducing some of the Ce4 + to Ce3 +. CO does not adsorb on the KOX/ CeO2 - X(111) surface in the absence of Rh particles. CO adsorbed on Rh/K/CeO2(111) adsorbs molecularly on the Rh at 200 K. As the surface is heated the CO spills-over and reacts with the KOX to form carbonate. The carbonate decomposes at elevated temperature to produce CO and CO2. The carbonate stabilizes the KOX so that K desorbs at a higher temperature than it would in the absence of CO. When the Rh and K deposition are reversed so that K is deposited on both the Rh and the CeO2(111), CO adsorbs as CO2- at 200 K. The CO2- decomposes below 350 K to produce gas phase CO and adsorbed CO32 - and CO. The CO is stabilized by the K on the Rh and desorbs above 540 K. The carbonate decomposes into gas phase CO and CO2.

  12. The Interaction of Carbon Monoxide with Rhodium on Potassium-Modified CeO2(111)

    DOE PAGESBeta

    Mullins, David R.

    2016-02-03

    The adsorption and reactions of CO adsorbed on Rh particles deposited on K-covered CeO2(111) were studied by temperature programmed desorption and photoelectron spectroscopy. K deposited on CeO2(111) forms a KOX over-layer by extracting O from the ceria and partially reducing some of the Ce4+ to Ce3+. CO does not adsorb on the KOX / CeO2-X(111) surface in the absence of Rh particles. CO adsorbed on Rh / K / CeO2(111) adsorbs molecularly on the Rh at 200 K. As the surface is heated the CO spills-over and reacts with the KOX to form carbonate. The carbonate decomposes at elevated temperaturemore » to produce CO and CO2. The carbonate stabilizes the KOX so that K desorbs at a higher temperature than it would in the absence of CO. When the Rh and K deposition are reversed so that K is deposited on both the Rh and the CeO2(111), CO adsorbs as CO2- at 200 K. The CO2- decomposes below 350 K to produce gas phase CO and adsorbed CO32- and CO. The CO is stabilized by the K on the Rh and desorbs above 540 K. The carbonate decomposes into gas phase CO and CO2.« less

  13. Cascadia Tsunami Deposit Database

    USGS Publications Warehouse

    Peters, Robert; Jaffe, Bruce; Gelfenbaum, Guy; Peterson, Curt

    2003-01-01

    The Cascadia Tsunami Deposit Database contains data on the location and sedimentological properties of tsunami deposits found along the Cascadia margin. Data have been compiled from 52 studies, documenting 59 sites from northern California to Vancouver Island, British Columbia that contain known or potential tsunami deposits. Bibliographical references are provided for all sites included in the database. Cascadia tsunami deposits are usually seen as anomalous sand layers in coastal marsh or lake sediments. The studies cited in the database use numerous criteria based on sedimentary characteristics to distinguish tsunami deposits from sand layers deposited by other processes, such as river flooding and storm surges. Several studies cited in the database contain evidence for more than one tsunami at a site. Data categories include age, thickness, layering, grainsize, and other sedimentological characteristics of Cascadia tsunami deposits. The database documents the variability observed in tsunami deposits found along the Cascadia margin.

  14. Glacial atmospheric phosphorus deposition

    NASA Astrophysics Data System (ADS)

    Kjær, Helle Astrid; Dallmayr, Remi; Gabrieli, Jacopo; Goto-Azuma, Kumiko; Hirabayashi, Motohiro; Svensson, Anders; Vallelonga, Paul

    2016-04-01

    Phosphorus in the atmosphere is poorly studied and thus not much is known about atmospheric phosphorus and phosphate transport and deposition changes over time, though it is well known that phosphorus can be a source of long-range nutrient transport, e.g. Saharan dust transported to the tropical forests of Brazil. In glacial times it has been speculated that transport of phosphorus from exposed shelves would increase the ocean productivity by wash out. However whether the exposed shelf would also increase the atmospheric load to more remote places has not been investigated. Polar ice cores offer a unique opportunity to study the atmospheric transport of aerosols on various timescales, from glacial-interglacial periods to recent anthropogenic influences. We have for the first time determined the atmospheric transport of phosphorus to the Arctic by means of ice core analysis. Both total and dissolved reactive phosphorus were measured to investigate current and past atmospheric transport of phosphorus to the Arctic. Results show that glacial cold stadials had increased atmospheric total phosphorus mass loads of 70 times higher than in the past century, while DRP was only increased by a factor of 14. In the recent period we find evidence of a phosphorus increase over the past 50 yrs in ice cores close to human occupation likely correlated to forest fires. References: Kjær, Helle Astrid, et al. "Continuous flow analysis method for determination of dissolved reactive phosphorus in ice cores." Environmental science & technology 47.21 (2013): 12325-12332. Kjær, Helle Astrid, et al. "Greenland ice cores constrain glacial atmospheric fluxes of phosphorus." Journal of Geophysical Research: Atmospheres120.20 (2015).

  15. Asthma Care in Resource-Poor Settings

    PubMed Central

    2011-01-01

    Asthma prevalence in low-to middle-income countries is at least the same or higher than in rich countries, but with increased severity. Lack of control in these settings is due to various factors such as low accessibility to effective medications, multiple and uncoordinated weak infrastructures of medical services for the management of chronic diseases such as asthma, poor compliance with prescribed therapy, lack of asthma education, and social and cultural factors. There is an urgent requirement for the implementation of better ways to treat asthma in underserved populations, enhancing the access to preventive medications and educational approaches with modern technological methods. PMID:23282401

  16. Poor mental health status and aggression are associated with poor driving behavior among male traffic offenders

    PubMed Central

    Abdoli, Nasrin; Farnia, Vahid; Delavar, Ali; Esmaeili, Alirez; Dortaj, Fariborz; Farrokhi, Noorali; Karami, Majid; Shakeri, Jalal; Holsboer-Trachsler, Edith; Brand, Serge

    2015-01-01

    Background In Iran, traffic accidents and deaths from traffic accidents are among the highest in the world, and generally driver behavior rather than either technical failures or environmental conditions are responsible for traffic accidents. In the present study, we explored the extent to which aggressive traits, health status, and sociodemographic variables explain driving behavior among Iranian male traffic offenders. Method A total of 443 male driving offenders (mean age: M =31.40 years, standard deviation =9.56) from Kermanshah (Iran) took part in the study. Participants completed a questionnaire booklet covering sociodemographic variables, traits of aggression, health status, and driving behavior. Results Poor health status, such as symptoms of depression, anxiety, insomnia, and social dysfunction, and also higher levels of trait aggression explained poor driving behavior. Multiple regressions indicated that poor health status, but not aggression, independently predicted poor driving behavior. Conclusion Results suggest that health status concerns are associated with poor driving behavior. Prevention and intervention might therefore focus on drivers reporting poor mental health status. PMID:26316753

  17. Deposition of Atmospheric Pollutants

    NASA Astrophysics Data System (ADS)

    Malet, L. M.

    Deposition of Atmospheric Pollutants, containing the proceedings of a colloquium held at Oberursel/Taunus, FRG, November 9-11, 1981, is divided into three main parts: dry deposition; wet deposition; and deposition on plants and vegetation.The 20 articles in the volume permit a fair survey of present-day knowledge and will be a useful tool to all working on the topic. Pollution by deposition of either the dry or wet sort is very insidious; its importance only appears in the long range, when its effects are or are almost irreversible. That is why concern was so long in emerging from decision makers.

  18. Magmatic ore deposits in layered intrusions - Descriptive model for reef-type PGE and contact-type Cu-Ni-PGE deposits

    USGS Publications Warehouse

    Zientek, Michael L.

    2012-01-01

    Layered, ultramafic to mafic intrusions are uncommon in the geologic record, but host magmatic ore deposits containing most of the world's economic concentrations of platinum-group elements (PGE) (figs. 1 and 2). These deposits are mined primarily for their platinum, palladium, and rhodium contents (table 1). Magmatic ore deposits are derived from accumulations of crystals of metallic oxides, or immiscible sulfide, or oxide liquids that formed during the cooling and crystallization of magma, typically with mafic to ultramafic compositions. "PGE reefs" are stratabound PGE-enriched lode mineralization in mafic to ultramafic layered intrusions. The term "reef" is derived from Australian and South African literature for this style of mineralization and used to refer to (1) the rock layer that is mineralized and has distinctive texture or mineralogy (Naldrett, 2004), or (2) the PGE-enriched sulfide mineralization that occurs within the rock layer. For example, Viljoen (1999) broadly defined the Merensky Reef as "a mineralized zone within or closely associated with an unconformity surface in the ultramafic cumulate at the base of the Merensky Cyclic Unit." In this report, we will use the term PGE reef to refer to the PGE-enriched mineralization, not the host rock layer. Within a layered igneous intrusion, reef-type mineralization is laterally persistent along strike, extending for the length of the intrusion, typically tens to hundreds of kilometers. However, the mineralized interval is thin, generally centimeters to meters thick, relative to the stratigraphic thickness of layers in an intrusion that vary from hundreds to thousands of meters. PGE-enriched sulfide mineralization is also found near the contacts or margins of layered mafic to ultramafic intrusions (Iljina and Lee, 2005). This contact-type mineralization consists of disseminated to massive concentrations of iron-copper-nickel-PGE-enriched sulfide mineral concentrations in zones that can be tens to hundreds

  19. How poor are women in rural India?

    PubMed

    Rajuladevi, A K

    1992-07-01

    The assessment of poor women in India as dependent and exploited regardless of poverty focused strategies is reflected in this review of relevant literature. The scholarly approaches to the problems of poor women involve redirection and expansion of resources to women (increase bank credit) through policy and institutional changes, and involve improving women's welfare through changes in class and gender hierarchies; both pertain to restructuring power groups. A little ascribed to belief is that the organization of women's numbers will empower women; the constraints are stated. There is also some argument over whether to design women-specific programs or integrate women into existing programs; some examples are given of successes and difficulties. The regionalization of poverty in eastern and central India is discussed. The growth of the poor has been among the landless, wage-dependent households. 9.6% of households (7.5 million) are headed by women. Women work fewer hours and at lower wage scales and have fewer employment opportunities. Lower earnings are coupled with differentials in demand for female and male labor in agriculture and a crowded labor market. There is a concentration of women in less visible, nonmonetary subsistence production and domestic work. Women are undercounted in employment studies. Women predominate in agricultural activity. Women's status is influenced by economic status, caste, and ethnic background. Domestic work increases status for women and households. The poorer households have greater labor force participation, particularly as wage laborers rather than unpaid family workers. Regional factors affecting rural household strategies are factors affecting the economy (topography, rainfall, climate) and the degree of development, plus sociocultural variables (kinship and religious beliefs which affect the social domain of women), and the degree of dependence on hired vs. family labor. There are sharp contrasts in the value and survival

  20. Imbalanced phosphorus and nitrogen deposition in China's forests

    NASA Astrophysics Data System (ADS)

    Du, Enzai; de Vries, Wim; Han, Wenxuan; Liu, Xuejun; Yan, Zhengbing; Jiang, Yuan

    2016-07-01

    Acceleration of anthropogenic emissions in China has substantially increased nitrogen (N) deposition during the last 3 decades and may result in an imbalance of atmospheric N and phosphorus (P) inputs in terrestrial ecosystems. However, the status of P deposition in China is poorly understood. This study synthesized data on total P and total N concentrations in bulk precipitation and throughfall from published literature to assess the characteristics of P deposition, N deposition and N : P deposition ratio in China's forests. Our results show relatively high mean rates of bulk P deposition (0.38 kg P ha-1 yr-1) and total P deposition (0.69 kg P ha-1 yr-1), but they were accompanied by even more elevated N inputs via bulk deposition (16.5 kg N ha-1 yr-1) and total deposition (21.6 kg N ha-1 yr-1), resulting in high N : P ratios in bulk deposition (44.4) and total deposition (32.8). Based on the difference between total deposition and bulk deposition, canopy-captured dry P and N deposition was estimated to be 0.31 kg P ha-1 yr-1 and 5.1 kg N ha-1 yr-1, respectively. We found significantly higher P deposition and lower N : P ratios at sites nearby than those far from semiarid regions. The estimated bulk and total deposition of P and N both showed a significant power-law increase with decreasing distance to the nearest large cities either in the areas nearby or far from semiarid regions. Our results suggest an anthropogenic alternation of regional P and N cycling, which may shift large areas of China's forests towards human-induced P limitation especially in southern China.

  1. Primary Hepatic Carcinoid Tumor with Poor Outcome.

    PubMed

    Parkash, Om; Ayub, Adil; Naeem, Buria; Najam, Sehrish; Ahmed, Zubair; Jafri, Wasim; Hamid, Saeed

    2016-03-01

    Primary Hepatic Carcinoid Tumor (PHCT) represents an extremely rare clinical entity with only a few cases reported to date. These tumors are rarely associated with metastasis and surgical resection is usually curative. Herein, we report two cases of PHCT associated with poor outcomes due to late diagnosis. Both cases presented late with non-specific symptoms. One patient presented after a 2-week history of symptoms and the second case had a longstanding two years symptomatic interval during which he remained undiagnosed and not properly worked up. Both these cases were diagnosed with hepatic carcinoid tumor, which originates from neuroendocrine cells. Case 1 opted for palliative care and expired in one month’s time. Surgical resection was advised to the second case, but he left against medical advice. PMID:26975959

  2. Primary Hepatic Carcinoid Tumor with Poor Outcome.

    PubMed

    Parkash, Om; Ayub, Adil; Naeem, Buria; Najam, Sehrish; Ahmed, Zubair; Jafri, Wasim; Hamid, Saeed

    2016-03-01

    Primary Hepatic Carcinoid Tumor (PHCT) represents an extremely rare clinical entity with only a few cases reported to date. These tumors are rarely associated with metastasis and surgical resection is usually curative. Herein, we report two cases of PHCT associated with poor outcomes due to late diagnosis. Both cases presented late with non-specific symptoms. One patient presented after a 2-week history of symptoms and the second case had a longstanding two years symptomatic interval during which he remained undiagnosed and not properly worked up. Both these cases were diagnosed with hepatic carcinoid tumor, which originates from neuroendocrine cells. Case 1 opted for palliative care and expired in one month’s time. Surgical resection was advised to the second case, but he left against medical advice.

  3. Color constancy enhancement under poor illumination.

    PubMed

    Liu, Jun; Shao, Zhenfeng; Cheng, Qimin

    2011-12-15

    In this Letter, the color constancy and its realization were studied and a novel color constancy image enhancement algorithm under poor illumination was presented. The purpose of this algorithm is to maintain the hue of an image during the processing so that the change of saturation can be minimized. The original image was first multiplied by a scale parameter obtained by the adaptive quadratic function to enhance the luminance, and then the edge details were restored by a shifting parameter. Numerical results of the Simon Fraser University (SFU) image database indicated that the proposed algorithm performed much better in preserving the hue and saturation and avoiding color distortion compared with the existing image enhancement algorithms. PMID:22179895

  4. Employees are paying for poor health habits.

    PubMed

    Cave, D G

    1992-08-01

    Realizing that corporate America may have limited control over how and when medical services are delivered, employers are beginning to attack the demand side of the health-care equation. That is, improving employee health status should result in a lower demand for medical services. However, to realize significant medical-claims savings, employers must encourage the least healthy employees both to enroll in work-site health-promotion programs and to permanently change their health-risk behaviors. One way to accomplish these objectives is to shift more financial risk onto employees by redesigning the company's medical benefit plan. As the 1990s progress and as medical costs continue to spiral upward, we are bound to observe greater employer involvement in employees' life-styles, both at work and at home. The bounds of discrimination and privacy laws will be tested as companies employ more restrictive policies and benefit plan designs to encourage employees to modify current poor-risk behaviors.

  5. Direct multiangle solution for poorly stratified atmospheres.

    PubMed

    Kovalev, Vladimir; Wold, Cyle; Petkov, Alexander; Hao, Wei Min

    2012-09-01

    The direct multiangle solution is considered, which allows improving the scanning lidar-data-inversion accuracy when the requirement of the horizontally stratified atmosphere is poorly met. The signal measured at zenith or close to zenith is used as a core source for extracting optical characteristics of the atmospheric aerosol loading. The multiangle signals are used as auxiliary data to extract the vertical transmittance profile from the zenith signal. Details of the retrieval methodology are considered that eliminate, or at least soften, some specific ambiguities in the multiangle measurements in horizontally heterogeneous atmospheres. Simulated and experimental elastic lidar data are presented that illustrate the essentials of the data-processing technique. Finally, the prospects of the utilization of high-spectral-resolution lidar in the multiangle mode are discussed. PMID:22945162

  6. Airfoil deposition model

    NASA Technical Reports Server (NTRS)

    Kohl, F. J.

    1982-01-01

    The methodology to predict deposit evolution (deposition rate and subsequent flow of liquid deposits) as a function of fuel and air impurity content and relevant aerodynamic parameters for turbine airfoils is developed in this research. The spectrum of deposition conditions encountered in gas turbine operations includes the mechanisms of vapor deposition, small particle deposition with thermophoresis, and larger particle deposition with inertial effects. The focus is on using a simplified version of the comprehensive multicomponent vapor diffusion formalism to make deposition predictions for: (1) simple geometry collectors; and (2) gas turbine blade shapes, including both developing laminar and turbulent boundary layers. For the gas turbine blade the insights developed in previous programs are being combined with heat and mass transfer coefficient calculations using the STAN 5 boundary layer code to predict vapor deposition rates and corresponding liquid layer thicknesses on turbine blades. A computer program is being written which utilizes the local values of the calculated deposition rate and skin friction to calculate the increment in liquid condensate layer growth along a collector surface.

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

    PubMed Central

    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

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

    PubMed

    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.

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

    PubMed

    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. Temporal and spatial studies of autocatalyst-derived platinum, rhodium, and palladium and selected vehicle-derived trace elements in the environment.

    PubMed

    Jarvis, K E; Parry, S J; Piper, J M

    2001-03-15

    The distribution of platinum, rhodium, and palladium (platinum-group elements; PGEs) adjacent to two major U.K. roads shows a rapid decrease (more than 1 order of magnitude) away from the road and reflects patterns shown by other traffic-derived trace elements such as Pb and Zn. However, ratios of Pt:Rh remain relatively constant from 0 to 10 m distance, suggesting that at least some of the PGEs are transported away from the source. A temporal study over a 12-month period, of road dust and surface samples, reveals elevated concentrations above background levels, with maximum values of Pt >500 ng g(-1), Rh 70 ng g(-1), and Pd 70 ng g(-1). Concentrations vary considerably throughout the year and show some tentative correlation with rainfall. Element speciation, an essential control on mobility and hence distribution, was investigated, and the results of solubility experiments show that up to 30% of the Pd present dissolves in acid solutions. This indicates that at least some of the Pd is present in a soluble form and is therefore potentially highly mobile.

  11. Enantioselective Arylation of N-Tosylimines by Phenylboronic Acid Catalysed by a Rhodium/Diene Complex: Reaction Mechanism from Density Functional Theory.

    PubMed

    Sieffert, Nicolas; Boisson, Julien; Py, Sandrine

    2015-06-26

    A DFT study of the reaction mechanism of the rhodium-catalysed enantioselective arylation of (E)-N-propylidene-4-methyl-benzenesulfonamide by phenylboronic acid [Lin et al J. Am. Chem. Soc. 2011, 133, 12394] is reported. The catalyst ([{Rh(OH)(diene)}2]) includes a chiral diene ligand and the reaction is conducted in 1,4-dioxane in the presence of drying agents (4 Å molecular sieves). Because phenylboronic acid is in equilibrium with phenylboroxin and water under the reaction conditions, three catalytic cycles are proposed that differ in the way the transmetallation and the release of the product are brought about, depending on the availability of phenylboronic acid, water and boroxin in the reaction medium. Based on computations, a new mechanism for the title reaction is proposed, in which phenylboronic acid plays the double role of "aryl source" and proton donor. This path does not require the presence of adventitious water molecules, in keeping with a reaction conducted in a dry medium. Comparisons with the generally accepted mechanism for arylation of enones proposed by Hayashi and co-workers (J. Am. Chem. Soc. 2002, 124, 5052) show that the latter mechanism is less favourable and is not expected to operate in the case of the N-tosylimine substrate considered herein. Finally, the possibility that phenylboroxin is the aryl source has also been investigated, but is not found to be competitive. PMID:26032123

  12. Labile behavior of carbonyl ligands in butadienecarbonyl and ethylenecarbonyl complexes of rhodium(I) under the action of 1,5-cyclooctadiene

    SciTech Connect

    Varshavskii, Yu.S.; Cherkasov, T.G.; Bresler, L.S.

    1987-04-01

    The processes resulting in the redistribution of the carbonyl groups between the rhodium(I) complexes in a solution of (Rh(C2H4)COCl)2 (I) in chloroform under the action 1,5-cyclooctadiene (cod) have been studied by the methods of IR, TC NMR, and H NMR spectroscopy. It has been shown that in reaction mixtures containing I + x mole cod/Rh the asymmetric complex (cod)RhCl2Rh(CO)2 (II) with nu(CO) = 2092 and 2022 cm , delta( TC) = 178.7 ppm, and J(CRh) = 75.2 Hz forms when x less than or equal to 0.5. When x > 0.5, the pentacoordinate monocarbonyl complex (cod) CORhCl2RhCO(cod)(III) with nu(CO) = 2050 cm , which is stable in the presence of cod, forms. When x greater than or equal to 3, III is the main product present in the reaction mixtures. In the spectra of such mixtures the TC signal is a singlet with delta( TC) = 178.4 ppm. The butadienecarbonyl complex ((RhCOCl)2C4H6)/sub n/ behaves similarly to I. The reaction involving the replacement of CO ligands by cod in (Rh(CO)2)Cl)2 in a chloroform medium with cod;Rh = 1 passes through a step involving the formation of III; when the reaction is conducted in heptane, the formation of III is not detected.

  13. Iodide-mediated control of rhodium epitaxial growth on well-defined noble metal nanocrystals: synthesis, characterization, and structure-dependent catalytic properties.

    PubMed

    Sneed, Brian T; Kuo, Chun-Hong; Brodsky, Casey N; Tsung, Chia-Kuang

    2012-11-01

    Metal nanocrystals (NCs) comprising rhodium are heterogeneous catalysts for CO oxidation, NO reduction, hydrogenations, electro-oxidations, and hydroformylation reactions. It has been demonstrated that control of structure at the nanoscale can enhance the performance of a heterogeneous metal catalyst, such as Rh, but molecular-level control of NCs comprising this metal is less studied compared to gold, silver, platinum, and palladium. We report an iodide-mediated epitaxial overgrowth of Rh by using the surfaces of well-defined foreign metal crystals as substrates to direct the Rh surface structures. The epigrowth can be accomplished on different sizes, morphologies, and identities of metal substrates. The surface structures of the resulting bimetallic NCs were studied using electron microscopy, and their distinct catalytic behaviors were examined in CO stripping and the electro-oxidation of formic acid. Iodide was found to play a crucial role in the overgrowth mechanism. With the addition of iodide, the Rh epigrowth can even be achieved on gold substrates despite the rather large lattice mismatch of ~7%. Hollow Rh nanostructures have also been generated by selective etching of the core substrates. The new role of iodide in the overgrowth and the high level of control for Rh could hold the key to future nanoscale control of this important metal's architecture for use in heterogeneous catalysis.

  14. Merging rhodium-catalysed C–H activation and hydroamination in a highly selective [4+2] imine/alkyne annulation

    PubMed Central

    Manan, Rajith S.; Zhao, Pinjing

    2016-01-01

    Catalytic C–H activation and hydroamination represent two important strategies for eco-friendly chemical synthesis with high atom efficiency and reduced waste production. Combining both C–H activation and hydroamination in a cascade process, preferably with a single catalyst, would allow rapid access to valuable nitrogen-containing molecules from readily available building blocks. Here we report a single metal catalyst-based approach for N-heterocycle construction by tandem C–H functionalization and alkene hydroamination. A simple catalyst system of cationic rhodium(I) precursor and phosphine ligand promotes redox-neutral [4+2] annulation between N–H aromatic ketimines and internal alkynes to form multi-substituted 3,4-dihydroisoquinolines (DHIQs) in high chemoselectivity over competing annulation processes, exclusive cis-diastereoselectivity, and distinct regioselectivity for alkyne addition. This study demonstrates the potential of tandem C–H activation and alkene hydrofunctionalization as a general strategy for modular and atom-efficient assembly of six-membered heterocycles with multiple chirality centres. PMID:27321650

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

    PubMed

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

    2015-10-01

    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.

  16. Ionized cluster beam deposition

    NASA Astrophysics Data System (ADS)

    Kirkpatrick, A. R.

    1983-11-01

    Ionized Cluster Beam (ICB) deposition, a new technique originated by Takagi of Kyoto University in Japan, offers a number of unique capabilities for thin film metallization as well as for deposition of active semiconductor materials. ICB allows average energy per deposited atom to be controlled and involves impact kinetics which result in high diffusion energies of atoms on the growth surface. To a greater degree than in other techniques, ICB involves quantitative process parameters which can be utilized to strongly control the characteristics of films being deposited. In the ICB deposition process, material to be deposited is vaporized into a vacuum chamber from a confinement crucible at high temperature. Crucible nozzle configuration and operating temperature are such that emerging vapor undergoes supercondensation following adiabatic expansion through the nozzle.

  17. Ionized cluster beam deposition

    NASA Technical Reports Server (NTRS)

    Kirkpatrick, A. R.

    1983-01-01

    Ionized Cluster Beam (ICB) deposition, a new technique originated by Takagi of Kyoto University in Japan, offers a number of unique capabilities for thin film metallization as well as for deposition of active semiconductor materials. ICB allows average energy per deposited atom to be controlled and involves impact kinetics which result in high diffusion energies of atoms on the growth surface. To a greater degree than in other techniques, ICB involves quantitative process parameters which can be utilized to strongly control the characteristics of films being deposited. In the ICB deposition process, material to be deposited is vaporized into a vacuum chamber from a confinement crucible at high temperature. Crucible nozzle configuration and operating temperature are such that emerging vapor undergoes supercondensation following adiabatic expansion through the nozzle.

  18. Poor education linked with teen pregnancies.

    PubMed

    Westall, J

    1997-02-22

    Two reports concerning socioeconomic factors associated with adolescent pregnancy have been released: a study from the NHS Centre for Reviews and Dissemination at the University of York; and a survey from the Alan Guttmacher Institute, a non-profit reproductive health analysis organization in New York. The first report associates truancy, low academic achievement and poor sex education with the high pregnancy rate in Britain among women 15-19 years old. The rate is the highest in western Europe, although the rate of conceptions in Britain among women 16-19 years old has declined since 1990 and is currently 56.8 per 1000. For girls under 16 years old, a group targeted by the British government's Health of the Nation strategy to achieve a conception rate of 4.8 per 1000 by the year 2000, the rate has remained steady for the last 20 years and stands at 8.3 per 1000. The report calls for better school-based sex education and for improved access to confidential contraceptive services for young people. The second report, an international survey, shows that the number of teenage pregnancies worldwide is declining (although 15 million babies, 10% unplanned, are born annually to teenage mothers), and that women with a higher education level tend to delay marriage and childbearing. A figure compares the percentages of women 20-24 years old who gave birth by age 20 for 4 educational levels (less than 7 years, greater than or equal to 7 years, less than 12 years, greater than or equal to 12 years) for Ghana, Kenya, Zimbabwe, Bangladesh, Egypt, Indonesia, the Philippines, Bolivia, Brazil, Columbia, Mexico, France, Japan, and the United States. Teenage pregnancy in both reports was associated with poor social, economic, and health outcomes for mother and child. According to the second report, the risk of maternal death during childbirth is 2-4 times greater for mothers 17 and younger, in comparison to mothers age 20 and older. Dr. Kathleen Kiernan, a senior research fellow at

  19. Kinematics of AWM and MKW Poor Clusters

    NASA Astrophysics Data System (ADS)

    Koranyi, Daniel M.; Geller, Margaret J.

    2002-01-01

    We have measured 1365 redshifts to a limiting magnitude of R~15.5 in 15 AWM/MKW clusters and have collected another 203 from the literature in MKW 4s, MKW 2, and MKW 2s. In AWM 7 we have extended the redshift sample to R~18 in the cluster center. We have identified 704 cluster members in 17 clusters; 201 are newly identified. We summarize the kinematics and distributions of the cluster galaxies and provide an initial discussion of substructure, mass and luminosity segregation, spectral segregation, velocity-dispersion profiles, and the relation of the central galaxy to global cluster properties. We compute optical mass estimates, which we compare with X-ray mass determinations from the literature. The clusters are in a variety of dynamical states, reflected in the three classes of behavior of the velocity-dispersion profile in the core: rising, falling, or flat/ambiguous. The velocity dispersion of the emission-line galaxy population significantly exceeds that of the absorption-line galaxies in almost all of the clusters, and the presence of emission-line galaxies at small projected radii suggests continuing infall of galaxies onto the clusters. The presence of a cD galaxy does not constrain the global cluster properties; these clusters are similar to other poor clusters that contain no cD. We use the similarity of the velocity-dispersion profiles at small radii and the cD-like galaxies' internal velocity dispersions to argue that cD formation is a local phenomenon. Our sample establishes an empirical observational baseline of poor clusters for comparison with simulations of similar systems. Observations reported in this paper were obtained at the Multiple Mirror Telescope Observatory, a facility operated jointly by the University of Arizona and the Smithsonian Institution; at the Whipple Observatory, a facility operated jointly by the Smithsonian Astrophysical Observatory and Harvard University; and at the WIYN Observatory, a joint facility of the University of

  20. Aggregating poor and near-poor elderly under different resource definitions.

    PubMed

    Rendall, M S

    1996-07-01

    The large number of near-poor relative to poor elderly persons in the United States may be recharacterized as a high-prevalence, low-intensity type of poverty. The present study investigates how this characterization is affected by accounting for assets and non-cash transfers in addition to cash income in resources available for current-year consumption. The Foster, Greer, Thorbecke (FGT) poverty index is used to separately and jointly analyze prevalence and intensity of poverty. Estimation is from 1984 Survey of Income and Program Participation data. Adding the annuity value of assets removes many elderly persons from the ranks of the poor and near-poor, while adding non-cash transfers moves many elderly persons from poverty into near-poverty. Their combined effect reinforces a high-prevalence, low-intensity characterization of poverty. Large total poverty reduction effects are missed by income-only resource definition, and large poverty-intensity reduction effects are missed by prevalence-only aggregation.

  1. Discrepantly poor verbal skills in poor readers: a failure of learning or ability?

    PubMed

    Langdon, D W; Rosenblatt, N; Mellanby, J H

    1998-05-01

    Poor verbal skills in poor readers have long been reported in the literature. There have been many attempts to understand the interaction between poor verbal ability and poor verbal achievement. The methodological problems are considerable, including the measurement of verbal ability, which has been confounded by previous learning. A new reasoning test, the VESPAR, has been designed to measure novel problem solving and thus to be less reliant on acquired verbal skills. One hundred and seventy 14-year-olds completed the VESPAR, the Cognitive Abilities Test (CAT) and a single-word reading test. Overall, verbal scores were weaker than spatial scores. A subgroup of 38 pupils with particularly marked discrepancies between verbal and non-verbal CAT was identified. The especially discrepant pupils were matched with other non-discrepant pupils from the year group for either verbal or non-verbal CAT. The discrepant group's reading was at the same level as the matched verbal CAT group. However, the primary verbal ability of the discrepancy group, as measured on the VESPAR, was greater than the matched verbal CAT group. This raises the possibility that CAT- but not VESPAR-discrepant pupils may be at particular risk of under-achievement in the verbal domain.

  2. Hydrogen-poor superluminous stellar explosions.

    PubMed

    Quimby, R M; Kulkarni, S R; Kasliwal, M M; Gal-Yam, A; Arcavi, I; Sullivan, M; Nugent, P; Thomas, R; Howell, D A; Nakar, E; Bildsten, L; Theissen, C; Law, N M; Dekany, R; Rahmer, G; Hale, D; Smith, R; Ofek, E O; Zolkower, J; Velur, V; Walters, R; Henning, J; Bui, K; McKenna, D; Poznanski, D; Cenko, S B; Levitan, D

    2011-06-08

    Supernovae are stellar explosions driven by gravitational or thermonuclear energy that is observed as electromagnetic radiation emitted over weeks or more. In all known supernovae, this radiation comes from internal energy deposited in the outflowing ejecta by one or more of the following processes: radioactive decay of freshly synthesized elements (typically (56)Ni), the explosion shock in the envelope of a supergiant star, and interaction between the debris and slowly moving, hydrogen-rich circumstellar material. Here we report observations of a class of luminous supernovae whose properties cannot be explained by any of these processes. The class includes four new supernovae that we have discovered and two previously unexplained events (SN 2005ap and SCP 06F6) that we can now identify as members of the same class. These supernovae are all about ten times brighter than most type Ia supernova, do not show any trace of hydrogen, emit significant ultraviolet flux for extended periods of time and have late-time decay rates that are inconsistent with radioactivity. Our data require that the observed radiation be emitted by hydrogen-free material distributed over a large radius (∼10(15) centimetres) and expanding at high speeds (>10(4) kilometres per second). These long-lived, ultraviolet-luminous events can be observed out to redshifts z > 4.

  3. Poorly Understood Aspects of Striated Muscle Contraction

    PubMed Central

    Månsson, Alf

    2015-01-01

    Muscle contraction results from cyclic interactions between the contractile proteins myosin and actin, driven by the turnover of adenosine triphosphate (ATP). Despite intense studies, several molecular events in the contraction process are poorly understood, including the relationship between force-generation and phosphate-release in the ATP-turnover. Different aspects of the force-generating transition are reflected in the changes in tension development by muscle cells, myofibrils and single molecules upon changes in temperature, altered phosphate concentration, or length perturbations. It has been notoriously difficult to explain all these events within a given theoretical framework and to unequivocally correlate observed events with the atomic structures of the myosin motor. Other incompletely understood issues include the role of the two heads of myosin II and structural changes in the actin filaments as well as the importance of the three-dimensional order. We here review these issues in relation to controversies regarding basic physiological properties of striated muscle. We also briefly consider actomyosin mutation effects in cardiac and skeletal muscle function and the possibility to treat these defects by drugs. PMID:25961006

  4. Carbon balance of a temperate poor fen

    NASA Astrophysics Data System (ADS)

    Carroll, Paul; Crill, Patrick

    1997-09-01

    The dynamic carbon balance of a southeastern New Hampshire wetland was constructed for the 1994 growing season using a light-dark box sampling method. Net ecosystem exchange (NEE) (n = 414) and ecosystem respiration (n=234) measurements were made at the 1.7 ha Sphagnum spp. dominated poor fen. The NEE rates ranged from -192 to 492 mg C m-2 h-1 and the ecosystem respiration measurements were between -10 and -365 mg C m-2 h-1. The negative values represent a loss of carbon from the wetland system. NEE and respiration data were used to derive photosynthesis rates of the vegetation at the study site. A simple model, using hourly averages of photosynthetically active radiation, and air and soil temperatures to generate hourly rates of photosynthesis and respiration, was constructed to interpolate the carbon cycling rates at this fen through the entire 1994 growing season. Results of the carbon balance model suggest that the wetland lost an estimated 145 g C m-2 for the 9 month modeling period (April through December). The 1994 climate season was warmer (+1.15°C/month)and drier (-12.3 cm) than the 30 year normals for Durham, New Hampshire, the nearest meteorological station. These data suggest that if future climate change brings about warmer temperatures and lower water tables in peatland soils, positive climatic feedback leading to substantial releases of CO2 from boreal and subarctic peatlands is probable.

  5. Domestic phosphate deposits

    USGS Publications Warehouse

    McKelvey, V.E.; Cathcart, J.B.; Altschuler, Z.S.; Swanson, R.W.; Lutz, Katherine

    1953-01-01

    Most of the worlds phosphate deposits can be grouped into six types: 1) igneous apatite deposits; 2) marine phosphorites; 3) residual phosphorites; 4) river pebble deposits; 5) phosphatized rock; and 6) guano. The igneous apatites and marine phosphorites form deposits measurable in millions or billions of tons; the residual deposits are measurable in thousands or millions; and the other types generally only in thousands of tons. Igneous apatite deposits have been mined on a small scale in New York, New Jersey, and Virginia. Marine phosphorites have been mined in Montana, Idaho, Utah, Wyoming, Arkansas, Tennessee, North Carolina, South Carolina, Georgia, and Florida. Residual phosphorites have been mined in Tennessee, Pennsylvania, and Florida. River pebble has been produced in South Carolina and Florida; phosphatized rock in Tennessee and Florida; and guano in New Mexico and Texas. Present production is limited almost entirely to Florida, Tennessee, Montana, Idaho, and Wyoming. Incomplete but recently partly revised estimates indicate the presence of about 5 billion tons of phosphate deposits in the United States that is minable under present economic conditions. Deposits too lean in quality or thickness to compete with those in the western and southeastern fields probably contain tens of billions of tons.

  6. Radionuclide deposition control

    DOEpatents

    Brehm, William F.; McGuire, Joseph C.

    1980-01-01

    The deposition of radionuclides manganese-54, cobalt-58 and cobalt-60 from liquid sodium coolant is controlled by providing surfaces of nickel or high nickel alloys to extract the radionuclides from the liquid sodium, and by providing surfaces of tungsten, molybdenum or tantalum to prevent or retard radionuclide deposition.

  7. Thinning segregated graphene layers on high carbon solubility substrates of rhodium foils by tuning the quenching process.

    PubMed

    Liu, Mengxi; Zhang, Yanfeng; Chen, Yubin; Gao, Yabo; Gao, Teng; Ma, Donglin; Ji, Qingqing; Zhang, Yu; Li, Cong; Liu, Zhongfan

    2012-12-21

    We report the synthesis of large-scale uniform graphene films on high carbon solubility substrates of Rh foils for the first time using an ambient-pressure chemical vapor deposition method. We find that, by increasing the cooling rate in the growth process, the thickness of graphene can be tuned from multilayer to monolayer, resulting from the different segregation amount of carbon atoms from bulk to surface. The growth feature was characterized with scanning electron microscopy, Raman spectra, transmission electron microscopy, and scanning tunneling microscopy. We also find that bilayer or few-layer graphene prefers to stack deviating from the Bernal stacking geometry, with the formation of versatile moiré patterns. On the basis of these results, we put forward a segregation growth mechanism for graphene growth on Rh foils. Of particular importance, we propose that this randomly stacked few-layer graphene can be a model system for exploring some fantastic physical properties such as van Hove singularities.

  8. 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.

    PubMed

    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

  9. Crystal structures of bis-[2-(pyridin-2-yl)phenyl-κ(2) N,C (1)]rhodium(III) complexes containing an aceto-nitrile or monodentate thyminate(1-) ligand.

    PubMed

    Sakate, Mika; Hosoda, Haruka; Suzuki, Takayoshi

    2016-04-01

    The crystal structures of bis-[2-(pyridin-2-yl)phen-yl]rhodium(III) complexes with the metal in an octahedral coordination containing chloride and aceto-nitrile ligands, namely (OC-6-42)-aceto-nitrile-chlorido-bis-[2-(pyridin-2-yl)phenyl-κ(2) N,C (1)]rhodium(III), [RhCl(C11H8N)2(CH3CN)] (1), thyminate(1-) and methanol, namely (OC-6-42)-methanol(5-methyl-2,4-dioxo-1,2,3,4-tetrahydro-pyrimidin-1-ido-κN (1))bis-[2-(pyridin-2-yl)phenyl-κ(2) N,C (1)]rhodium(III), [Rh(C11H8N)2(C5H5N2O2)(CH3OH)]·CH3OH·0.5H2O (2), and thy-min-ate(1-) and ethanol, namely (OC-6-42)-ethanol(5-methyl-2,4-dioxo-1,2,3,4-tetra-hydro-pyrimidin-1-ido-κN (1))bis[2-(pyridin-2-yl)phenyl-κ(2) N,C (1)]rhodium(III), [Rh(C11H8N)2(C5H5N2O2)(C2H5OH)]·C2H5OH (3), are reported. The aceto-nitrile complex, 1, is isostructural with the Ir(III) analog. In complexes 2 and 3, the monodeprotonated thyminate (Hthym(-)) ligand coordinates to the Rh(III) atom through the N atom, and the resulting Rh-N(Hthym) bond lengths are relatively long [2.261 (2) and 2.252 (2) Å for 2 and 3, respectively] as compared to the Rh-N bonds in the related thyminate complexes. In each of the crystals of 2 and 3, the complexes are linked via a pair of inter-molecular N-H⋯O hydrogen bonds between neighbouring Hthym(-) ligands, forming an inversion dimer. A strong intra-molecular O-H⋯O hydrogen bond between the thyminate(1-) and alcohol ligands in mutually cis positions to each other is also observed. PMID:27375885

  10. Crystal structures of bis­[2-(pyridin-2-yl)phenyl-κ2 N,C 1]rhodium(III) complexes containing an aceto­nitrile or monodentate thyminate(1−) ligand

    PubMed Central

    Sakate, Mika; Hosoda, Haruka; Suzuki, Takayoshi

    2016-01-01

    The crystal structures of bis­[2-(pyridin-2-yl)phen­yl]rhodium(III) complexes with the metal in an octahedral coordination containing chloride and aceto­nitrile ligands, namely (OC-6-42)-aceto­nitrile­chlorido­bis­[2-(pyridin-2-yl)phenyl-κ2 N,C 1]rhodium(III), [RhCl(C11H8N)2(CH3CN)] (1), thyminate(1−) and methanol, namely (OC-6-42)-methanol(5-methyl-2,4-dioxo-1,2,3,4-tetrahydro­pyrimidin-1-ido-κN 1)bis­[2-(pyridin-2-yl)phenyl-κ2 N,C 1]rhodium(III), [Rh(C11H8N)2(C5H5N2O2)(CH3OH)]·CH3OH·0.5H2O (2), and thy­min­ate(1−) and ethanol, namely (OC-6-42)-ethanol(5-methyl-2,4-dioxo-1,2,3,4-tetra­hydro­pyrimidin-1-ido-κN 1)bis[2-(pyridin-2-yl)phenyl-κ2 N,C 1]rhodium(III), [Rh(C11H8N)2(C5H5N2O2)(C2H5OH)]·C2H5OH (3), are reported. The aceto­nitrile complex, 1, is isostructural with the IrIII analog. In complexes 2 and 3, the monodeprotonated thyminate (Hthym−) ligand coordinates to the RhIII atom through the N atom, and the resulting Rh—N(Hthym) bond lengths are relatively long [2.261 (2) and 2.252 (2) Å for 2 and 3, respectively] as compared to the Rh—N bonds in the related thyminate complexes. In each of the crystals of 2 and 3, the complexes are linked via a pair of inter­molecular N—H⋯O hydrogen bonds between neighbouring Hthym− ligands, forming an inversion dimer. A strong intra­molecular O—H⋯O hydrogen bond between the thyminate(1−) and alcohol ligands in mutually cis positions to each other is also observed. PMID:27375885

  11. Biomimetic thin film deposition

    SciTech Connect

    Rieke, P.R.; Graff, G.E.; Campbell, A.A.; Bunker, B.C.; Baskaran, S.; Song, L.; Tarasevich, B.J.; Fryxell, G.E.

    1995-09-01

    Biological mineral deposition for the formation of bone, mollusk shell and other hard tissues provides materials scientists with illustrative materials processing strategies. This presentation will review the key features of biomineralization and how these features can be of technical importance. We have adapted existing knowledge of biomineralization to develop a unique method of depositing inorganic thin films and coating. Our approach to thin film deposition is to modify substrate surfaces to imitate the proteins found in nature that are responsible for controlling mineral deposition. These biomimetic surfaces control the nucleation and growth of the mineral from a supersaturated aqueous solution. This has many processing advantages including simple processing equipment, environmentally benign reagents, uniform coating of highly complex shapes, and enhanced adherence of coating. Many different types of metal oxide, hydroxide, sulfide and phosphate materials with useful mechanical, optical, electronic and biomedical properties can be deposited.

  12. Solution deposition assembly

    SciTech Connect

    Roussillon, Yann; Scholz, Jeremy H; Shelton, Addison; Green, Geoff T; Utthachoo, Piyaphant

    2014-01-21

    Methods and devices are provided for improved deposition systems. In one embodiment of the present invention, a deposition system is provided for use with a solution and a substrate. The system comprises of a solution deposition apparatus; at least one heating chamber, at least one assembly for holding a solution over the substrate; and a substrate curling apparatus for curling at least one edge of the substrate to define a zone capable of containing a volume of the solution over the substrate. In another embodiment of the present invention, a deposition system for use with a substrate, the system comprising a solution deposition apparatus; at heating chamber; and at least assembly for holding solution over the substrate to allow for a depth of at least about 0.5 microns to 10 mm.

  13. Stratiform chromite deposit model

    USGS Publications Warehouse

    Schulte, Ruth F.; Taylor, Ryan D.; Piatak, Nadine M.; Seal, Robert R., II

    2010-01-01

    Stratiform chromite deposits are of great economic importance, yet their origin and evolution remain highly debated. Layered igneous intrusions such as the Bushveld, Great Dyke, Kemi, and Stillwater Complexes, provide opportunities for studying magmatic differentiation processes and assimilation within the crust, as well as related ore-deposit formation. Chromite-rich seams within layered intrusions host the majority of the world's chromium reserves and may contain significant platinum-group-element (PGE) mineralization. This model of stratiform chromite deposits is part of an effort by the U.S. Geological Survey's Mineral Resources Program to update existing models and develop new descriptive mineral deposit models to supplement previously published models for use in mineral-resource and mineral-environmental assessments. The model focuses on features that may be common to all stratiform chromite deposits as a way to gain insight into the processes that gave rise to their emplacement and to the significant economic resources contained in them.

  14. Tsunami Deposit Data Base

    NASA Astrophysics Data System (ADS)

    Keating, B. H.; Wanink, M.

    2007-05-01

    A digital database has been established describing tsunami deposits around the world (3 phases; 15 months). The projects involved the review and tabulation of data derived from books, catalogs, journals, preprints, citations and abstracts (currently 1000 references), into a database designed to provide a comprehensive review of the types of tsunami deposits, their geographic distribution and location, sedimentary characteristics, fossil content, age, preservation, run-up, wave height and inundation observations, etc. (34 parameters). The tsunami occurrences can be divided into many subjects, e.g., Volcanogenic (N=375), Seismites (N=49), Co-seismic (N=258), K/T Boundary Impact-triggered debris flows (N=97), Landslides (N=43), etc. Numerous publications compare tsunami deposits to storm deposits (N=38), or analyze the origin of megaboulders (N=22). Tsunami deposits occur throughout geologic time (Pre-Cambrian to present day), and because of plate tectonics, they occur along plate margins (primarily subduction zones) as well as interior to plates. In addition, they occur in epi-continental seas, fjords, etc. Few publications describe depositional processes. Deposits generated by tsunamis occur in multiple environments such as the marine, fresh water, and subaerial. Common characteristics of tsunami deposits include: 1) Deposition of thin sand sheets (can be normal, massive, inversely graded, chaotic or bimodal). 2) Erosional: basal uncomformity, mud balls, rip-up clasts, reworked fossils produced by scouring. 3) Lithology: Stacks of couplets reflecting marine incursions (often sands) into fresh water or subaerial environments (mud, soil, peat). 4) Fossil: Couplets reflects marine fossils, fresh water fossils or a mixed assemblage. 5) Geomorphology: The sand sheets taper landward and can rise in elevation. 6) Deformation: syn-depositional (soft sediments) and intraformational (stiff sediments).

  15. Childhood Absence Epilepsy: Poor Attention Is More Than Seizures

    MedlinePlus

    ... Spencer, MD Steven Karceski, MD Childhood absence epilepsy Poor attention is more than seizures Liu Lin Thio, ... of this article is prohibited. Childhood absence epilepsy: Poor attention is more than seizures Liu Lin Thio ...

  16. A Problem Solving Framework for Managing Poor Readers in Classrooms.

    ERIC Educational Resources Information Center

    Beck, Judith S.

    1988-01-01

    Points out that poor readers may exhibit behavioral, cognitive, and emotional problems. Offers a problem-solving framework for intervention in poor readers' nonacademic problems, and describes several possible types of intervention. (ARH)

  17. DFT calculations of 15N NMR shielding constants, chemical shifts and complexation shifts in complexes of rhodium(II) tetraformate with some nitrogenous organic ligands

    NASA Astrophysics Data System (ADS)

    Leniak, Arkadiusz; Jaźwiński, Jarosław

    2015-03-01

    Benchmark calculations of 15N NMR shielding constants for a set of model complexes of rhodium(II) tetraformate with nine organic ligands using the Density Functional Theory (DFT) methods have been carried out. The calculations were performed by means of several methods: the non-relativistic, relativistic scalar ZORA, and spin-orbit ZORA approaches at the CGA-PBE/QZ4P theory level, and the GIAO NMR method using the B3PW91 functional with the 6-311++G(2d,p) basis set for C, H, N, O atoms and the Stuttgart basis set for the Rh atom. The geometry of compounds was optimised either by the same basis set as for the NMR calculations or applying the B3LYP functional with the 6-31G(2d) basis set for C, H, N, O atoms and LANL2DZ for the Rh atom. Computed 15N NMR shielding constants σ were compatible with experimental 15N chemical shifts δ of complexes exhibiting similar structure and fulfil the linear equation δ = aσ + b. The a and b parameters for all data sets have been estimated by means of linear regression analysis. In contrast to the correlation method giving "scaled" chemical shifts, the conversion of shielding constants to chemical shifts with respect to the reference shielding of CH3NO2 provided very inaccurate "raw" δ values. The application of the former to the calculation of complexation shifts Δδ (Δδ = δcompl - δlig) reproduced experimental values qualitatively or semi-quantitatively. The non-relativistic B3PW91/[6-311++G(2d,p), Stuttgart] theory level reproduced the NMR parameters as good as the more expensive relativistic CGA-PBE//QZ4P ZORA approaches.

  18. Carbonate Deposition on Antarctic Shelves

    NASA Astrophysics Data System (ADS)

    Frank, T. D.; James, N. P.; Malcolm, I.

    2011-12-01

    Limestones associated with glaciomarine deposits occur throughout the geologic record but remain poorly understood. The best-described examples formed during major ice ages of the Neoproterozoic and Late Paleozoic. Quaternary analogs on Antarctic shelves have received comparatively little study. Here, we report on the composition, spatial distribution, and stratigraphic context of carbonate sediments contained in piston cores from the Ross Sea. The goals of this work are to (1) document the nature and distribution of carbonate sediments on the Ross Sea continental shelf and (2) examine temporal relationships to Quaternary glaciation. Results will be used to develop criteria that will improve understanding of analogous deposits in the ancient record. All carbonate-rich intervals in piston cores from the Ross Rea, now housed at the Antarctic Marine Geology Research Facility at Florida State University, were examined and described in detail. Sediment samples were disaggregated and sieved into size fractions before description with paleontological analysis carried out on the coarsest size fraction (>250 microns). Carbonate-rich sediments are concentrated in the northwestern Ross Sea, along the distal margins of Mawson and Pennell Banks. Calcareous facies include a spectrum of lithologies that range from fossiliferous mud, sand, and gravel to skeletal floatstone-rudstone and bafflestone. Floatstone-rudstone and bafflestone is most abundant along western-facing slopes in areas protected from the Antarctic Coastal Current. Sand-prone facies dominate the tops of banks and mud-prone, often spicultic, facies occur in deeper areas. The carbonate factory is characterized by a low-diversity, heterozoan assemblage that is dominated by stylasterine hydrocorals, barnacles, and bryozoans. Molluscs and echinoids are present but not abundant. Planktic and benthic foraminifera are ubiquitous components of the sediment matrix, which is locally very rich in sponge spicules. Biota rarely

  19. Orthographic Processing and Visual Sequential Memory in Unexpectedly Poor Spellers

    ERIC Educational Resources Information Center

    Holmes, Virginia M.; Malone, Aisling M.; Redenbach, Holly

    2008-01-01

    Does unexpectedly poor spelling in adults result from inferior visual sequential memory? In one experiment, unexpectedly poor spellers performed significantly worse than better spellers in the immediate reproduction of sequences of visual symbols, but in a second experiment, the effect was not replicated. Poor spellers were also no worse at the…

  20. Advertising and the Poor. Journalism Monographs Number Seventy-Five.

    ERIC Educational Resources Information Center

    Bowen, Lawrence

    This monograph examines the impact of media advertising on the poor. The first half of the report discusses research on the conceptual styles of the poor, mass communication among the poor, and advertising and the low-income consumer. The second half describes the methodology and results of a study of the advertising evaluation capacity and…

  1. Very Early Language Skills of Fifth-Grade Poor Comprehenders

    ERIC Educational Resources Information Center

    Justice, Laura; Mashburn, Andrew; Petscher, Yaacov

    2013-01-01

    This study tested the theory that future poor comprehenders would show modest but pervasive deficits in both language comprehension and production during early childhood as compared with future poor decoders and typical readers. Using an existing database (NICHD ECCRN), fifth-grade students were identified as having poor comprehension skills…

  2. Laboring for Less: Working but Poor in Rural America.

    ERIC Educational Resources Information Center

    Shapiro, Isaac

    Most of the nonmetropolitan poor live in a household with at least one worker. In 1987, 70% of nonmetro poor family heads who were not ill, disabled, or retired worked for at least part of the year, and 24% worked full time, year-round. The employed proportion of the poor was significantly larger in nonmetro than metro areas. Despite a lengthy…

  3. NITROGEN OUTPUTS OF SMALL MAMMALS FROM FECAL AND URINE DEPOSITION: IMPLICATIONS FOR NITROGEN CYCLING

    EPA Science Inventory

    The contribution of small mammals in nitrogen cycling is poorly understood and could have reverberations back to the producer community by maintaining or even magnifying increased nitrogen availability. Our objective was to model nitrogen outputs (deposition of feces and urine) ...

  4. Surface properties of pulsed laser deposited Ir, Rh, and Ir 0.9Rh 0.1 thin films for use as microelectrode arrays in electroanalytical heavy metal trace sensors

    NASA Astrophysics Data System (ADS)

    Le Drogoff, B.; El Khakani, M. A.; Silva, P. R. M.; Chaker, M.; Ross, G. G.

    1999-11-01

    Pulsed laser deposition (PLD) of iridium, rhodium, and Ir 0.9Rh 0.1 thin films onto a-SiC:H-coated silicon substrates for use in heavy metal sensors has been achieved by ablating iridium and/or rhodium targets with a KrF excimer laser. The deposited films are polycrystalline and exhibited very smooth surfaces with an average roughness value ( Ra) of ˜1 nm. The wettability by mercury of their surface was investigated by means of the contact angle measurement technique, and compared to that of Ag and Pt films. The PLD films (whether Ir, Rh, or Ir 0.9Rh 0.1) were found to present an almost identical Hg-wetting behavior, which is characterized by a high static contact angle of 132±2°. Moreover, in contrast to the cases of Pt or Ag films, where amalgamation with Hg rapidly occurs during the contact angle measurements, no evident interaction of Hg with the surface of the PLD films was observed. Microelectrode arrays of each of the three films (Ir, Rh and Ir 0.9Rh 0.1) were fabricated and used as a conducting base onto which Hg microdrops are electroplated. Reproducible and uniform Hg deposits on the microelectrode arrays were obtained. The electroanalytical performance of these Hg-electroplated microelectrode arrays based sensors was then evaluated by means of Square Wave Anodic Stripping Voltammetry (SWASV), in synthetic solutions containing Zn, Cd and Pb ion traces. Over a concentration range as wide as 0.2-20 ppb, the detected signals are found to exhibit a strong linear correlation with ion concentration. For a preconcentration time of only 5 min, detection limits as low as 0.2 ppb for both Cd and Pb, and 0.5 ppb for Zn were achieved.

  5. Classification of Broken Hill-Type Pb-Zn-Ag Deposits: A Refinement

    NASA Astrophysics Data System (ADS)

    Spry, P. G.; Teale, G. S.; Steadman, J. A.

    2009-05-01

    Broken Hill Hill-type Pb-Zn-Ag (BHT) deposits constitute some of the largest ore deposits in the world. The Broken Hill deposit is the largest accumulation of Pb, Zn, and Ag on Earth and the Cannington deposit is currently the largest silver deposit. Characteristic features of BHT deposits include: 1. high Pb+Zn+Ag values with Pb > Zn; 2. Metamorphism to amphibolite-granulite facies; 3. Paleo-to Mesoprotoerozoic clastic metasedimentary host rocks; 4. Sulfides that are spatially associated with bimodal (felsic and mafic) volcanic rocks, and stratabound gahnite- and garnet-bearing rocks and iron formations, 5. Stacked orebodies with characteristic Pb:Zn:Ag ratios and skarn-like Fe-Mn-Ca-F gangue assemblages, and the presence of Cu, Au, Bi, As, and Sb; and 6. Sulfur-poor assemblages. Broken Hill (Australia) has a prominent footwall feeder zone whereas other BHT deposits have less obvious alteration zones (footwall garnet spotting and stratabound alteration haloes). Deposits previously regarded in the literature as BHT deposits are Broken Hill, Cannington, Oonagalabie, Menninie Dam, and Pegmont (Australia), Broken Hill, Swartberg, Big Syncline, and Gamsberg (South Africa), Zinkgruvan (Sweden), Sullivan, Cottonbelt, and Foster River (Canada), and Boquira (Brazil). Of these deposits, only the Broken Hill (Australia, South Africa), Pinnacles, Cannington, Pegmont, and Swartberg deposits are BHT deposits. Another BHT deposit includes the Green Parrot deposit, Jervois Ranges (Northern Territory). The Foster River, Gamsberg, and Sullivan deposits are considered to be "SEDEX deposits with BHT affinities", and the Oonagalabie, Green Mountain (Colorado), and Zinkgruvan are "VMS deposits with BHT affinities". In the Broken Hill area (Australia), Corruga-type Pb-Zn-Ag deposits occur in calc-silicate rocks and possess some BHT characteristics; the Big Syncline, Cottonbelt, Menninie Dam, and Saxberget deposits are Corruga-type deposits. SEDEX deposits with BHT affinities, VMS

  6. Comparative assessment of synthetic strategies toward active platinum-rhodium-tin electrocatalysts for efficient ethanol electro-oxidation

    NASA Astrophysics Data System (ADS)

    Erini, Nina; Krause, Paul; Gliech, Manuel; Yang, Ruizhi; Huang, Yunhui; Strasser, Peter

    2015-10-01

    The present work explores the effect of autoclave-based autogenous-pressure vs. ambient pressure conditions on the synthesis and properties of carbon-supported Pt-Rh-Sn nanoparticle electrocatalysts. The Pt-Rh-Sn nanoparticles were characterized by X-ray spectroscopy, electron microscopy and mass spectroscopy and deployed as catalysts for the electrocatalytic ethanol oxidation reaction. Pt-Rh-Sn catalysts precipitated with carbon already present showed narrow particle size distribution around 7 nm, while catalysts supported on carbon after particle formation showed broader size distribution ranging from 8 to 16 nm, similar metal loadings between 40 and 48 wt.% and similar atomic ratios of Pt:Rh:Sn of 30:10:60. The highest ethanol oxidation activity at low overpotentials associated with exceptionally early ethanol oxidation onset potential was observed for ambient-pressure catalysts with the active ternary alloy phase formed in presence of the carbon supports. In contrast, catalysts prepared under ambient pressure in a two-step approach, involving alloy particle formation followed by particle separation and subsequent deposition on the carbon support, yielded the highest overall mass activities. Based on the observed synthesis-activity correlations, a comparative assessment is provided of the synthetic techniques at high vs. low pressures, and in presence and absence of carbon support. Plausible hypotheses in terms of particle dispersion and interparticle distance accounting for these observed differences are discussed.

  7. Seedless Polyol Synthesis and CO Oxidation Activity of Monodisperse (111) and (100)-Oriented Rhodium Nanocrystals in Sub-10 nm Sizes

    SciTech Connect

    Zhang, Yawen; Grass, Michael E.; Huang, Wenyu; Somorjai, Gabor A.

    2010-03-15

    Monodisperse sub-10 nm (6.5 nm) sized Rh nanocrystals with (111) and (100) surface structures were synthesized by a seedless polyol reduction in ethylene glycol, with poly(vinylpyrrolidone) as a capping ligand. When using [Rh(Ac){sub 2}]{sub 2} as the metal precursor, (111)-oriented Rh nanopolyhedra containing 76% (111)-twined hexagons (in 2D projection) were obtained; whereas, when employing RhCl{sub 3} as the metal precursor in the presence of alkylammonium bromide, such as tetramethylammonium bromide and trimethyl(tetradecyl)ammonium bromide, (100)-oriented Rh nanocubes were obtained with 85% selectivity. The {l_brace}100{r_brace} faces of the Rh nanocrystals are stabilized by chemically adsorbed Br{sup -} ions from alkylammonium bromides, which led to (100)-oriented nanocubes. Monolayer films of the (111)-oriented Rh nanopolyhedra and (100)-oriented Rh nanocubes were deposited on silicon wafers in a Langmuir-Blodgett trough to make model 2D nanoarray catalysts. These nanocatalysts were active for CO oxidation by O{sub 2}, and the turnover frequency was independent of nanoparticle shape, consistent with that previously observed for Rh(111) and Rh(100) single crystals.

  8. World oil shale deposits

    SciTech Connect

    Hook, C.O.; Russell, P.L.

    1982-01-01

    The article estimates resources in-place and their oil equivalent. The major deposits are described in the U.S., Australia, USSR, Peoples Republic of China, Morocco, Israel, Jordan, Syria, Europe and South America. 2 refs.

  9. Chemical vapor deposition growth

    NASA Technical Reports Server (NTRS)

    Ruth, R. P.; Manasevit, H. M.; Kenty, J. L.; Moudy, L. A.; Simpson, W. I.; Yang, J. J.

    1976-01-01

    A chemical vapor deposition (CVD) reactor system with a vertical deposition chamber was used for the growth of Si films on glass, glass-ceramic, and polycrystalline ceramic substrates. Silicon vapor was produced by pyrolysis of SiH4 in a H2 or He carrier gas. Preliminary deposition experiments with two of the available glasses were not encouraging. Moderately encouraging results, however, were obtained with fired polycrystalline alumina substrates, which were used for Si deposition at temperatures above 1,000 C. The surfaces of both the substrates and the films were characterized by X-ray diffraction, reflection electron diffraction, scanning electron microscopy optical microscopy, and surface profilometric techniques. Several experiments were conducted to establish baseline performance data for the reactor system, including temperature distributions on the sample pedestal, effects of carrier gas flow rate on temperature and film thickness, and Si film growth rate as a function of temperature.

  10. Automatic Payroll Deposit System.

    ERIC Educational Resources Information Center

    Davidson, D. B.

    1979-01-01

    The Automatic Payroll Deposit System in Yakima, Washington's Public School District No. 7, directly transmits each employee's salary amount for each pay period to a bank or other financial institution. (Author/MLF)

  11. Gemstone deposits of Serbia

    NASA Astrophysics Data System (ADS)

    Miladinović, Zoran; Simić, Vladimir; Jelenković, Rade; Ilić, Miloje

    2016-06-01

    Gemstone minerals in Serbia have never been regarded as an interesting and significant resource. Nevertheless, more than 150 deposits and occurrences have been recorded and some of them preliminarily explored in the last 50 years. The majority of deposits and occurrences are located within the Serbo-Macedonian metallogenic province and the most significant metallogenic units at the existing level of knowledge are the Fruska Gora ore district, Cer ore district, Sumadija metallogenic zone, Kopaonik metallogenic zone and Lece-Halkidiki metallogenic zone. The most important genetic type of deposits is hydrothermal, particularly in case of serpentinite/peridotite as host/parent rock. Placer deposits are also economically important. The dominant gemstones are silica minerals: chalcedony (Chrysoprase, carnelian, bluish chalcedony etc.), jasper (picture, landscape, red etc.), common opal (dendritic, green, milky white etc.), silica masses (undivided), and quartz (rock crystal, amethyst etc.). Beside silica minerals significant gemstones in Serbia include also beryl (aquamarine), garnet (almandine and pyrope), tourmaline, fluorite, rhodochrosite, carbonate-silica breccia, carbonate-silica onyx, silicified wood, howlite, serpentinite, marble onyx, and kyanite. This paper aims to present an overview of Serbian gemstone deposits and occurrences and their position based on a simplified gemstone metallogenic map of Serbia, as well as genetic-industrial classification of gemstone deposits and gemstone varieties.

  12. Deposited atmospheric chemicals

    SciTech Connect

    Schell, W.R.

    1986-09-01

    A mountaintop bog in western Pennsylvania serves as a reservoir for materials deposited from the atmosphere. Biological activity in the bog decomposes plant matter, which becomes humified and mineralized at increasing depths. Little or no mixing of elements occurs below the active root zone. Radionuclides produced by natural means and by nuclear weapons have been used to measure the ages of the layers deposited during the growing season of each year. The upper layers of the bog indicate that the deposition of total sulfur is at least 20 times and that of nitrogen is 45 times the value estimated prior to cutting the forest, with a doubling time for each of 25-35 yr. Bromine deposition also doubles every 35 yr. The pattern of mass and element deposition illustrates the changes in land use and industrial effluents that were sources for the material deposited on the bog. The decrease in atmospheric particle removal shows up in the 1960 and later layers. Compared with terrestrial abundances, the relative enrichments over time for chlorine, nitrogen, sulfur, and bromine are more than 100 times those calculated for 1817; lead, calcium, and antimony are 10 to 40 times greater.

  13. Convective microsphere monolayer deposition

    NASA Astrophysics Data System (ADS)

    Gilchrist, James

    2011-03-01

    There is perhaps no simpler way of modifying surface chemistry and morphology than surface deposition of particles. Micron-sized microspheres were deposited into thin films via rapid convective deposition, similar to the `coffee ring effect' using a similar method to that studied by Prevo and Velev, Langmuir, 2003. By varying deposition rate and blade angle, the optimal operating ranges in which 2D close-packed arrays of microspheres existed were obtained. Self-assembly of colloidal particles through a balance of electrostatic and capillary forces during solvent evaporation was revealed. These interactions were explored through a model comparing the residence time of a particle in the thin film and the characteristic time of capillary-driven crystallization to describe the morphology and microstructure of deposited particles. Co-deposition of binary suspensions of micron and nanoscale particles was tailored to generate higher-quality surface coatings and a simple theory describes the immergence of instabilities that result in formation of stripes. Optical and biomedical applications that utilize the described nanoscale control over surface morphology will also be discussed.

  14. 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.

    PubMed

    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.

  15. Becquerel Crater Deposit

    NASA Technical Reports Server (NTRS)

    2002-01-01

    (Released 28 May 2002) The finely layered deposit in Becquerel crater, seen in the center of this THEMIS image, is slowly being eroded away by the action of windblown sand. Dark sand from a source north of the bright deposit is collecting along its northern edge, forming impressive barchan style dunes. These vaguely boomerang-shaped dunes form with their two points extending in the downwind direction, demonstrating that the winds capable of moving sand grains come from the north. Grains that leave the dunes climb the eroding stair-stepped layers, collecting along the cliff faces before reaching the crest of the deposit. Once there, the sand grains are unimpeded and continue down the south side of the deposit without any significant accumulation until they fall off the steep cliffs of the southern margin. The boat-hull shaped mounds and ridges of bright material called yardangs form in response to the scouring action of the migrating sand. To the west, the deposit has thinned enough that the barchan dunes extend well into the deeply eroded north-south trending canyons. Sand that reaches the south side collects and reforms barchan dunes with the same orientation as those on the north side of the deposit. Note the abrupt transition between the bright material and the dark crater floor on the southern margin. Steep cliffs are present with no indication of rubble from the obvious erosion that produced them. The lack of debris at the base of the cliffs is evidence that the bright material is readily broken up into particles that can be transported away by the wind. The geological processes that are destroying the Becquerel crater deposit appear active today. But it is also possible that they are dormant, awaiting a particular set of climatic conditions that produces the right winds and perhaps even temperatures to allow the erosion to continue.

  16. Long term response of acid-sensitive Vermont Lakes to sulfate deposition

    EPA Science Inventory

    Atmospheric deposition of sulfur can negatively affect the health of lakes and streams, particularly in poorly buffered catchments. In response to the Clean Air Act Amendments, wet deposition of sulfate decreased more than 35% in Vermont between 1990 and 2008. However, most of ...

  17. 76 FR 41392 - Interest on Deposits; Deposit Insurance Coverage

    Federal Register 2010, 2011, 2012, 2013, 2014

    2011-07-14

    ... From the Federal Register Online via the Government Publishing Office FEDERAL DEPOSIT INSURANCE CORPORATION 12 CFR Parts 329 and 330 RIN 3064-AD78 Interest on Deposits; Deposit Insurance Coverage AGENCY: Federal Deposit Insurance Corporation (FDIC). ACTION: Final rule. SUMMARY: The FDIC is issuing a...

  18. 76 FR 21265 - Interest on Deposits; Deposit Insurance Coverage

    Federal Register 2010, 2011, 2012, 2013, 2014

    2011-04-15

    ... From the Federal Register Online via the Government Publishing Office FEDERAL DEPOSIT INSURANCE CORPORATION 12 CFR Parts 329 and 330 RIN 3064-AD78 Interest on Deposits; Deposit Insurance Coverage AGENCY: Federal Deposit Insurance Corporation (FDIC). ACTION: Notice of proposed rulemaking (NPR) and request...

  19. Vacuum arc deposition devices

    NASA Astrophysics Data System (ADS)

    Boxman, R. L.; Zhitomirsky, V. N.

    2006-02-01

    The vacuum arc is a high-current, low-voltage electrical discharge which produces a plasma consisting of vaporized and ionized electrode material. In the most common cathodic arc deposition systems, the arc concentrates at minute cathode spots on the cathode surface and the plasma is emitted as a hypersonic jet, with some degree of contamination by molten droplets [known as macroparticles (MPs)] of the cathode material. In vacuum arc deposition systems, the location and motion of the cathode spots are confined to desired surfaces by an applied magnetic field and shields around undesired surfaces. Substrates are mounted on a holder so that they intercept some portion of the plasma jet. The substrate often provides for negative bias to control the energy of depositing ions and heating or cooling to control the substrate temperature. In some systems, a magnetic field is used to guide the plasma around an obstacle which blocks the MPs. These elements are integrated with a deposition chamber, cooling, vacuum gauges and pumps, and power supplies to produce a vacuum arc deposition system.

  20. Vacuum arc deposition devices

    SciTech Connect

    Boxman, R.L.; Zhitomirsky, V.N.

    2006-02-15

    The vacuum arc is a high-current, low-voltage electrical discharge which produces a plasma consisting of vaporized and ionized electrode material. In the most common cathodic arc deposition systems, the arc concentrates at minute cathode spots on the cathode surface and the plasma is emitted as a hypersonic jet, with some degree of contamination by molten droplets [known as macroparticles (MPs)] of the cathode material. In vacuum arc deposition systems, the location and motion of the cathode spots are confined to desired surfaces by an applied magnetic field and shields around undesired surfaces. Substrates are mounted on a holder so that they intercept some portion of the plasma jet. The substrate often provides for negative bias to control the energy of depositing ions and heating or cooling to control the substrate temperature. In some systems, a magnetic field is used to guide the plasma around an obstacle which blocks the MPs. These elements are integrated with a deposition chamber, cooling, vacuum gauges and pumps, and power supplies to produce a vacuum arc deposition system.

  1. Metallogeny of gold deposits

    SciTech Connect

    Hutchinson, R.W.

    1985-01-01

    The metallogeny of various gold deposits, particularly their broad temporal and spatial relations, and their relations to other metallic ores, is significant to genetic understanding and also useful in exploration. Archean gold deposits co-exist, both regionally and locally, with certain iron formations, massive base metal and nickel sulfide ores, but these occur generally in differing parts of the host stratigraphic sequences. Gold deposits in marine-eugeosynclinal environments are most important and numerous in Archean rocks. They become increasingly rare in successively younger strata where epithermal deposits in subaerial-continental rocks become important. The hydrothermal systems that formed both were apparently similar; one active in submarine tectonic settings, the other in sub-volcanic continental ones. Gold was apparently first introduced extensively into supracrustal rocks by sub-sea floor hydrothermal processes in Archean time, forming gold-enriched exhalites. These were reworked by metamorphic processes forming epithermal veins in many lode districts, and by sedimentary processes in the Witwatersrand. Epithermal gold deposits were generated where these older, auriferous basement source rocks were affected by younger, plutonic-volcanic-hydrothermal activity.

  2. Deposition Rates and Characterization of Arabian Mineral Dust

    NASA Astrophysics Data System (ADS)

    Puthan Purakkal, J.; Stenchikov, G. L.; Engelbrecht, J. P.

    2015-12-01

    Airborne mineral dust directly and indirectly impacts on global climate, continental and marine biochemistry, human and animal health, agriculture, equipment, and visibility. Annual global dust emissions are poorly known with estimates differing by a factor of at least two. Local dust emission and deposition rates are even less quantified. Dust deposition rate is a key parameter, which helps to constrain the modeled dust budget of the atmosphere. However, dust deposition remains poorly known, due to the limited number of reliable measurements. Simulations and satellite observations suggest that coastal dusts contribute substantially to the total deposition flux into the Red Sea. Starting December 2014, deposition samplers, both the "frisbee" type, and passive samplers for individual particle scanning electron microscopy were deployed at King Abdullah University of Science and Technology (KAUST), along the Red Sea in Saudi Arabia. Sampling periods of one month were adopted. The deposition rates range from 3 g m-2 month-1 for fair weather conditions to 23 g m-2 month-1 for high dust events. The X-ray diffraction (XRD) analyses of deposited dust samples show mineralogical compositions different from any of the parent soils, the former consisting mainly of gypsum, calcite, and smaller amounts of albite, montmorillonite, chlorite, quartz and biotite. The deposited dust samples on the other hand contain more gypsum and less quartz than the previously collected soil samples. This presentation discusses the results from XRD, chemical analysis and SEM-based individual particle analysis of the soils and the deposited dust samples. The monthly dust accumulation rates and their seasonal and spatial variability are compared with the regional model predictions. Data from this study provide an observational basis for validating the regional dust mass balance along the Arabian Red Sea coastal plain.

  3. Pulsed laser deposition: Prospects for commercial deposition of epitaxial films

    SciTech Connect

    Muenchausen, R.E.

    1999-03-01

    Pulsed laser deposition (PLD) is a physical vapor deposition (PVD) technique for the deposition of thin films. The vapor source is induced by the flash evaporation that occurs when a laser pulse of sufficient intensity (about 100 MW/cm{sup 2}) is absorbed by a target. In this paper the author briefly defines pulsed laser deposition, current applications, research directed at gaining a better understanding of the pulsed laser deposition process, and suggests some future directions to enable commercial applications.

  4. Comparative solution equilibrium studies on pentamethylcyclopentadienyl rhodium complexes of 2,2'-bipyridine and ethylenediamine and their interaction with human serum albumin.

    PubMed

    Enyedy, Éva A; Mészáros, János P; Dömötör, Orsolya; Hackl, Carmen M; Roller, Alexander; Keppler, Bernhard K; Kandioller, Wolfgang

    2015-11-01

    Complex formation equilibrium processes of the (N,N) donor containing 2,2'-bipyridine (bpy) and ethylenediamine (en) with (η(5)-pentamethylcyclopentadienyl)rhodium(III) were investigated in aqueous solution via pH-potentiometry, (1)H NMR spectroscopy, and UV-vis spectrophotometry in the absence and presence of chloride ions. The structure of [RhCp*(en)Cl]ClO4 (Cp*, pentamethylcyclopentadienyl) was also studied by single-crystal X-ray diffraction. pKa values of 8.56 and 9.58 were determined for [RhCp*(bpy)(H2O)](2+) and [RhCp*(en)(H2O)](2+), respectively resulting in the formation of negligible amount of mixed hydroxido complexes at pH 7.4. Stability and the H2O/Cl(-) co-ligand exchange constants of bpy and en complexes considerably exceed those of the bidentate O-donor deferiprone. The strong affinity of the bpy and en complexes to chloride ions most probably contributes to their low antiproliferative effect. Interactions between human serum albumin (HSA) and [RhCp*(H2O)3](2+), its complexes formed with deferiprone, bpy and en were also monitored by (1)H NMR spectroscopy, ultrafiltration/UV-vis and spectrofluorometry. Numerous binding sites (≥ 8) are available for [RhCp*(H2O)3](2+); and the interaction takes place most probably via covalent bonds through the imidazole nitrogen of His. According to the various fluorescence studies [RhCp*(H2O)3](2+) binds on sites I and II, and coordination of surface side chain donor atoms of the protein is also feasible. The binding of the bpy and en complex is weaker and slower compared to that of [RhCp*(H2O)3](2+), and formation of ternary HSA-RhCp*-ligand adducts was proved. In the case of the deferiprone complex, the RhCp* fragment is cleaved off when HSA is loaded with low equivalents of the compound.

  5. In vitro investigations of platinum, palladium, and rhodium mobility in urban airborne particulate matter (PM10, PM2.5, and PM1) using simulated lung fluids.

    PubMed

    Zereini, Fathi; Wiseman, Clare L S; Püttmann, Wilhelm

    2012-09-18

    Environmental concentrations of platinum group elements (PGE) have been increasing since the introduction of automotive catalytic converters to control harmful emissions. Assessments of the human health risks of exposures to these elements, especially through the inhalation of PGE-associated airborne particulate matter (PM), have been hampered by a lack of data on their bioaccessibility. The purpose of this study is to apply in vitro methods using simulated human lung fluids [artificial lysosomal fluid (ALF) and Gamble's solution] to assess the mobility of the PGE, platinum (Pt), palladium (Pd), and rhodium (Rh) in airborne PM of human health concern. Airborne PM samples (PM(10), PM(2.5), and PM(1)) were collected in Frankfurt am Main, Germany. For comparison, the same extraction experiments were conducted using the standard reference material, Used Auto Catalyst (monolith) (NIST 2557). Pt and Pd concentrations were measured using isotope dilution ICP-Q-MS, while Rh was measured directly with ICP-Q-MS (in collision mode with He), following established matrix separation and enrichment procedures, for both solid (filtered residues) and extracted sample phases. The mobilized fractions measured for PGE in PM(10), PM(2.5), and PM(1) were highly variable, which can be attributed to the heterogenic nature of airborne PM and its composition. Overall, the mobility of PGE in airborne PM samples was notable, with a mean of 51% Rh, 22% Pt, and 29% Pd present in PM(1) being mobilized by ALF after 24 h. For PM(1) exposed to Gamble's solution, a mean of 44% Rh, 18% Pt, and 17% Pd was measured in solution after 24 h. The mobility of PGE associated with airborne PM was also determined to be much higher compared to that measured for the auto catalyst standard reference material. The results suggest that PGE emitted from automotive catalytic converters are likely to undergo chemical transformations during and/or after being emitted in the environment. This study highlights the need

  6. Mechanistic Insights into Carbonyl-Directed Rhodium-Catalyzed Hydroboration: ab Initio Study of a Cyclic γ,δ-Unsaturated Amide.

    PubMed

    Yang, Zhao-Di; Pal, Rhitankar; Hoang, Gia L; Zeng, Xiao Cheng; Takacs, James M

    2014-03-01

    A two-point binding mechanism for the cationic rhodium(I)-catalyzed carbonyl-directed catalytic asymmetric hydroboration of a cyclic γ,δ-unsaturated amide is investigated using density functional theory. Geometry optimizations and harmonic frequency calculations for the model reaction are carried out using the basis set 6-31+G** for C, O, P, B, N, and H and LANL2DZ for Rh atoms. The Gibbs free energy of each species in THF solvent is obtained based on the single-point energy computed using the PCM model at the ECP28MWB/6-311+G(d,p) level plus the thermal correction to Gibbs free energy by deducting translational entropy contribution. The Rh-catalyzed reaction cycle involves the following sequence of events: (1) chelation of the cyclic γ,δ-unsaturated amide via alkene and carbonyl complexation in a model active catalytic species, [Rh(L2)2S2](+), (2) oxidative addition of pinacol borane (pinBH), (3) migratory insertion of the alkene double bond into Rh-H (preferred pathway) or Rh-B bond, (4) isomerization of the resulting intermediate, and finally, (5) reductive elimination to form the B-C or H-C bond with regeneration of the catalyst. Free energy profiles for potential pathways leading to the major γ-borylated product are computed and discussed in detail. The potential pathways considered include (1) pathways proceeding via migratory insertion into the Rh-H bond (pathways I, I-1, and I-2), (2) a potential pathway proceeding via migratory insertion into the Rh-B bond (pathway II), and two potential competing routes to a β-borylated byproduct (pathway III). The results find that the Rh-H migratory insertion pathway I-2, followed in sequence by an unanticipated isomerization via amide rotation and reductive elimination, is the most favorable reaction pathway. A secondary consequence of amide rotation is access to a competing β-hydride elimination pathway. The pathways computed in this study are supported by and help explain related experimental results. PMID

  7. In vitro investigations of platinum, palladium, and rhodium mobility in urban airborne particulate matter (PM10, PM2.5, and PM1) using simulated lung fluids.

    PubMed

    Zereini, Fathi; Wiseman, Clare L S; Püttmann, Wilhelm

    2012-09-18

    Environmental concentrations of platinum group elements (PGE) have been increasing since the introduction of automotive catalytic converters to control harmful emissions. Assessments of the human health risks of exposures to these elements, especially through the inhalation of PGE-associated airborne particulate matter (PM), have been hampered by a lack of data on their bioaccessibility. The purpose of this study is to apply in vitro methods using simulated human lung fluids [artificial lysosomal fluid (ALF) and Gamble's solution] to assess the mobility of the PGE, platinum (Pt), palladium (Pd), and rhodium (Rh) in airborne PM of human health concern. Airborne PM samples (PM(10), PM(2.5), and PM(1)) were collected in Frankfurt am Main, Germany. For comparison, the same extraction experiments were conducted using the standard reference material, Used Auto Catalyst (monolith) (NIST 2557). Pt and Pd concentrations were measured using isotope dilution ICP-Q-MS, while Rh was measured directly with ICP-Q-MS (in collision mode with He), following established matrix separation and enrichment procedures, for both solid (filtered residues) and extracted sample phases. The mobilized fractions measured for PGE in PM(10), PM(2.5), and PM(1) were highly variable, which can be attributed to the heterogenic nature of airborne PM and its composition. Overall, the mobility of PGE in airborne PM samples was notable, with a mean of 51% Rh, 22% Pt, and 29% Pd present in PM(1) being mobilized by ALF after 24 h. For PM(1) exposed to Gamble's solution, a mean of 44% Rh, 18% Pt, and 17% Pd was measured in solution after 24 h. The mobility of PGE associated with airborne PM was also determined to be much higher compared to that measured for the auto catalyst standard reference material. The results suggest that PGE emitted from automotive catalytic converters are likely to undergo chemical transformations during and/or after being emitted in the environment. This study highlights the need

  8. Venus - Landslide Deposits

    NASA Technical Reports Server (NTRS)

    1992-01-01

    The Magellan spacecraft has observed remnant landslide deposits apparently resulting from the collapse of volcanic structures. This image, centered at 45.2 degrees south latitude, 201.4 degrees east longitude, shows a collapse deposit 70 kilometers (43 miles) across. The bright, highly textured deposit near the center of the image probably consists of huge blocks of fractured volcanic rock, many as large as several hundred meters across. A remnant of the volcano itself, about 20 kilometers (12.4 miles) across, is seen at the center of the image. The distorted radar appearance of the volcano is a result of extremely steep slopes on the 'scars' from which the landslide material originated. A field of numerous small volcanic domes can be seen in the northern half of the image. The bright irregular lineaments trending to the north-northwest are ridges caused by regional tectonic deformation of the upper layers of the Venusian crust.

  9. Methods for making deposited films with improved microstructures

    DOEpatents

    Patten, James W.; Moss, Ronald W.; McClanahan, Edwin D.

    1982-01-01

    Methods for improving microstructures of line-of-sight deposited films are described. Columnar growth defects ordinarily produced by geometrical shadowing during deposition of such films are eliminated without resorting to post-deposition thermal or mechanical treatments. The native, as-deposited coating qualities, including homogeneity, fine grain size, and high coating-to-substrate adherence, can thus be retained. The preferred method includes the steps of emitting material from a source toward a substrate to deposit a coating non-uniformly on the substrate surface, removing a portion of the coating uniformly over the surface, again depositing material onto the surface, but from a different direction, and repeating the foregoing steps. The quality of line-of-sight deposited films such as those produced by sputtering, progressively deteriorates as the angle of incidence between the flux and the surface becomes increasingly acute. Depositing non-uniformly, so that the coating becomes progressively thinner as quality deteriorates, followed by uniformly removing some of the coating, such as by resputtering, eliminates the poor quality portions, leaving only high quality portions of the coating. Subsequently sputtering from a different direction applies a high quality coating to other regions of the surface. Such steps can be performed either simultaneously or sequentially to apply coatings of a uniformly high quality, closed microstructure to three-dimensional or larger planar surfaces.

  10. Electroless Deposition Processes and Tools

    NASA Astrophysics Data System (ADS)

    Hu, Z.; Ritzdorf, T.

    Electroless deposition, which was introduced in 1946 by Brenner and Riddell [1], is a type of electrochemical deposition that is gaining interest in semiconductor and related applications. Electroless deposition utilizes complementary electrochemical reactions to cause metal deposition. The oxidation of a reducing agent supplies the electrons needed for reducing metal ions to their metallic state [2]. This encompasses both immersion (displacement) deposition reactions and autocatalytic reactions. One should use electroless deposition in cases where it is desirable to deposit metal on non-conducting surfaces or to deposit metal selectively to certain underlying materials, especially if there is no possibility to have a continuous conductive underlayer. Current applications of interest in the microelectronics industry include copper deposition for seed layer and interconnect metallization, nickel and gold depositions for contact metallurgy in microelectronics packaging and related applications, and cobalt-tungsten alloys as diffusion barrier for copper interconnects.

  11. Laser assisted deposition

    NASA Technical Reports Server (NTRS)

    Dutta, S.

    1983-01-01

    Applications of laser-based processing techniques to solar cell metallization are discussed. Laser-assisted thermal or photolytic maskless deposition from organometallic vapors or solutions may provide a viable alternative to photovoltaic metallization systems currently in use. High power, defocused excimer lasers may be used in conjunction with masks as an alternative to direct laser writing to provide higher throughput. Repeated pulsing with excimer lasers may eliminate the need for secondary plating techniques for metal film buildup. A comparison between the thermal and photochemical deposition processes is made.

  12. Kinematics and dynamics of the MKW/AWM poor clusters

    NASA Technical Reports Server (NTRS)

    Beers, Timothy C.; Kriessler, Jeffrey R.; Bird, Christina M.; Huchra, John P.

    1995-01-01

    We report 472 new redshifts for 416 galaxies in the regions of the 23 poor clusters of galaxies originally identified by Morgan, Kayser, and White (MKW), and Albert, White, and Morgan (AWM). Eighteen of the poor clusters now have 10 or more available redshifts within 1.5/h Mpc of the central galaxy; 11 clusters have at least 20 available redshifts. Based on the 21 clusters for which we have sufficient velocity information, the median velocity scale is 336 km/s, a factor of 2 smaller than found for rich clusters. Several of the poor clusters exhibit complex velocity distributions due to the presence of nearby clumps of galaxies. We check on the velocity of the dominant galaxy in each poor cluster relative to the remaining cluster members. Significantly high relative velocities of the dominant galaxy are found in only 4 of 21 poor clusters, 3 of which we suspect are due to contamination of the parent velocity distribution. Several statistical tests indicate that the D/cD galaxies are at the kinematic centers of the parent poor cluster velocity distributions. Mass-to-light ratios for 13 of the 15 poor clusters for which we have the required data are in the range 50 less than or = M/L(sub B(0)) less than or = 200 solar mass/solar luminosity. The complex nature of the regions surrounding many of the poor clusters suggests that these groupings may represent an early epoch of cluster formation. For example, the poor clusters MKW7 and MKWS are shown to be gravitationally bound and likely to merge to form a richer cluster within the next several Gyrs. Eight of the nine other poor clusters for which simple two-body dynamical models can be carried out are consistent with being bound to other clumps in their vicinity. Additional complex systems with more than two gravitationally bound clumps are observed among the poor clusters.

  13. Kinematics and dynamics of the MKW/AWM poor clusters

    NASA Astrophysics Data System (ADS)

    Beers, Timothy C.; Kriessler, Jeffrey R.; Bird, Christina M.; Huchra, John P.

    1995-03-01

    We report 472 new redshifts for 416 galaxies in the regions of the 23 poor clusters of galaxies originally identified by Morgan, Kayser, and White (MKW), and Albert, White, and Morgan (AWM). Eighteen of the poor clusters now have 10 or more available redshifts within 1.5/h Mpc of the central galaxy; 11 clusters have at least 20 available redshifts. Based on the 21 clusters for which we have sufficient velocity information, the median velocity scale is 336 km/s, a factor of 2 smaller than found for rich clusters. Several of the poor clusters exhibit complex velocity distributions due to the presence of nearby clumps of galaxies. We check on the velocity of the dominant galaxy in each poor cluster relative to the remaining cluster members. Significantly high relative velocities of the dominant galaxy are found in only 4 of 21 poor clusters, 3 of which we suspect are due to contamination of the parent velocity distribution. Several statistical tests indicate that the D/cD galaxies are at the kinematic centers of the parent poor cluster velocity distributions. Mass-to-light ratios for 13 of the 15 poor clusters for which we have the required data are in the range 50 less than or = M/LB(0) less than or = 200 solar mass/solar luminosity. The complex nature of the regions surrounding many of the poor clusters suggests that these groupings may represent an early epoch of cluster formation. For example, the poor clusters MKW7 and MKWS are shown to be gravitationally bound and likely to merge to form a richer cluster within the next several Gyrs. Eight of the nine other poor clusters for which simple two-body dynamical models can be carried out are consistent with being bound to other clumps in their vicinity. Additional complex systems with more than two gravitationally bound clumps are observed among the poor clusters.

  14. Pleiotrophin promotes vascular abnormalization in gliomas and correlates with poor survival in patients with astrocytomas.

    PubMed

    Zhang, Lei; Kundu, Soumi; Feenstra, Tjerk; Li, Xiujuan; Jin, Chuan; Laaniste, Liisi; El Hassan, Tamador Elsir Abu; Ohlin, K Elisabet; Yu, Di; Olofsson, Tommie; Olsson, Anna-Karin; Pontén, Fredrik; Magnusson, Peetra U; Nilsson, Karin Forsberg; Essand, Magnus; Smits, Anja; Dieterich, Lothar C; Dimberg, Anna

    2015-12-01

    Glioblastomas are aggressive astrocytomas characterized by endothelial cell proliferation and abnormal vasculature, which can cause brain edema and increase patient morbidity. We identified the heparin-binding cytokine pleiotrophin as a driver of vascular abnormalization in glioma. Pleiotrophin abundance was greater in high-grade human astrocytomas and correlated with poor survival. Anaplastic lymphoma kinase (ALK), which is a receptor that is activated by pleiotrophin, was present in mural cells associated with abnormal vessels. Orthotopically implanted gliomas formed from GL261 cells that were engineered to produce pleiotrophin showed increased microvessel density and enhanced tumor growth compared with gliomas formed from control GL261 cells. The survival of mice with pleiotrophin-producing gliomas was shorter than that of mice with gliomas that did not produce pleiotrophin. Vessels in pleiotrophin-producing gliomas were poorly perfused and abnormal, a phenotype that was associated with increased deposition of vascular endothelial growth factor (VEGF) in direct proximity to the vasculature. The growth of pleiotrophin-producing GL261 gliomas was inhibited by treatment with the ALK inhibitor crizotinib, the ALK inhibitor ceritinib, or the VEGF receptor inhibitor cediranib, whereas control GL261 tumors did not respond to either inhibitor. Our findings link pleiotrophin abundance in gliomas with survival in humans and mice, and show that pleiotrophin promotes glioma progression through increased VEGF deposition and vascular abnormalization. PMID:26645582

  15. Influence of deposit architecture on intrastratal deformation, slope deposits of the Tres Pasos Formation, Chile

    NASA Astrophysics Data System (ADS)

    Auchter, Neal C.; Romans, Brian W.; Hubbard, Stephen M.

    2016-07-01

    Slope sediments on passive and active margins deform and fail across a broad range of scales ranging from loading and sediment remobilization near the sediment-water interface to submarine landslides and mass movements that incorporate significant volumes of slope deposits. Deformational styles are characterized by updip extension and downdip compressional features that occur above a detachment surface. Conditions for failure and deformation include the presence of weak layer(s) that serve as a detachment surface, competency contrasts that allow for detachment and downslope movement, deformation above a detachment surface, and a triggering mechanism(s) that initiates failure. Slope failure processes and products are well documented at scales resolvable by seismic-reflection surveys and in instances of extensive downslope failure, but the processes and products associated with intermediate-scale slope deformation are poorly understood. Intrastratal deformation is defined as stratigraphically isolated zones of deformation bounded above and below by concordant and undeformed strata. In this study, outcrop examples of intrastratal deformation from the Upper Cretaceous Tres Pasos Formation are used to elucidate the influence of depositional architecture on slope deformation. The facies distribution associated with compensational stacking of lobe deposits is shown to have a first-order control on the location and style of deformation. Detachment planes that form in mudstone deposits associated with lobe fringe and interlobe deposits are spatially limited and deformation is restricted to interbedded sandstone and mudstone associated with off-axial lobe positions. Downslope translation was arrested by stratigraphic buttresses associated with more sandstone-prone axial deposits. Emplacement of a regionally extensive mass transport deposit is interpreted as the triggering mechanism for contemporaneous intrastratal deformation of > 60 m of underlying stratigraphy. A vertical

  16. A comparison of the language skills of ELLs and monolinguals who are poor decoders, poor comprehenders, or normal readers.

    PubMed

    Geva, Esther; Massey-Garrison, Angela

    2013-01-01

    The overall objective of this article is to examine how oral language abilities relate to reading profiles in English language learners (ELLs) and English as a first language (EL1) learners, and the extent of similarities and differences between ELLs and EL1s in three reading subgroups: normal readers, poor decoders, and poor comprehenders. The study included 100 ELLs and 50 EL1s in Grade 5. The effect of language group (ELL/EL1) and reading group on cognitive and linguistic skills was examined. Except for vocabulary, there was no language group effect on any measure. However, within ELL and EL1 alike, significant differences were found between reading groups: Normal readers outperformed the two other groups on all the oral language measures. Distinct cognitive and linguistic profiles were associated with poor decoders and poor comprehenders, regardless of language group. The ELL and EL1 poor decoders outperformed the poor comprehenders on listening comprehension and inferencing. The poor decoders displayed phonological-based weaknesses, whereas the poor comprehenders displayed a more generalized language processing weakness that is nonphonological in nature. Regardless of language status, students with poor decoding or comprehension problems display difficulties with various aspects of language.

  17. Patterns of Risk: The Nutritional Status of the Rural Poor.

    ERIC Educational Resources Information Center

    Shotland, Jeffrey; Loonin, Deanne

    Nutrition and health are underlying influences to education performance. This report is a collection and analysis of data on nutrition and the rural poor in the United States. It presents an empirical assessment of critical nutritional and social-service problems experienced by the rural poor population. The first section of the report uses data…

  18. Metropolitan Influences on Migration into Poor and Nonpoor Neighborhoods*

    PubMed Central

    South, Scott J.; Pais, Jeremy; Crowder, Kyle

    2011-01-01

    Data from the Panel Study of Income Dynamics and three decennial U.S. censuses are used to examine the influence of metropolitan-area characteristics on black and white households' propensity to move into poor versus nonpoor neighborhoods. We find that a nontrivial portion of the variance in the odds of moving to a poor rather to a nonpoor neighborhood exists between metropolitan areas. Net of established individual-level predictors of inter-neighborhood migration, black and white households are more likely to move to a poor or extremely poor tract rather than to a nonpoor tract in metropolitan areas containing many poor neighborhoods and a paucity of recently-built housing in nonpoor areas. Blacks are especially likely to move to a poor tract in metropolitan areas characterized by high levels of racial residential segregation and in which poor tracts have a sizeable concentration of blacks. White households are more likely to move to a poor than to a nonpoor tract in metropolitan areas that have comparatively few African Americans. PMID:21625368

  19. Pathologizing the Language and Culture of Poor Children

    ERIC Educational Resources Information Center

    Dudley-Marling, Curt; Lucas, Krista

    2009-01-01

    There has been a resurgence of deficit discourses that implicate deficiencies in the language and culture of poor students as the cause of their academic failures. An influential study by Betty Hart and Todd Risley concludes that high levels of academic failure among poor children can be linked to the quantity and quality of language interactions…

  20. Distinguishing between Poor/Dysfunctional Parenting and Child Emotional Maltreatment

    ERIC Educational Resources Information Center

    Wolfe, David A.; McIsaac, Caroline

    2011-01-01

    Objective: This paper was intended to distinguish between poor parenting and child emotional maltreatment (CEM), to inform child welfare and public health policymakers of the need for differentiated responses. Methods: Scientific literature was integrated with current practice and assumptions relating to poor/dysfunctional parenting and child…

  1. Benefits of Computer-Presented Speed Training for Poor Readers

    ERIC Educational Resources Information Center

    Irausquin, Rosemarie S.; Drent, Jeanine; Verhoeven, Ludo

    2005-01-01

    The effects of computer-presented automatization exercises in a group of 14 poor readers were assessed in comparison to a matched control group of 14 poor readers that received computer-presented exercises aimed at the use of context for word identification and comprehension. Training took place three sessions a week for 15 minutes per session and…

  2. Unexpectedly Poor Spelling and Phonological-Processing Skill

    ERIC Educational Resources Information Center

    Holmes, Virginia M.; Quinn, Lisa

    2009-01-01

    This study investigated the phonological skills of university students who were unexpectedly poor spellers relative to their word reading accuracy. Compared with good spellers, unexpectedly poor spellers showed no deficits in phonological memory, selection of appropriate graphemes for phonemes in word misspellings and nonword spellings, and…

  3. Prevalence and Nature of Late-Emerging Poor Readers

    ERIC Educational Resources Information Center

    Catts, Hugh W.; Compton, Donald; Tomblin, J. Bruce; Bridges, Mindy Sittner

    2012-01-01

    Some children demonstrate adequate or better reading achievement in early school grades but fall significantly behind their peers in later grades. These children are often referred to as late-emerging poor readers. In this study, we investigated the prevalence and heterogeneity of these poor readers. We also examined the early language and…

  4. Sustainable School Music for Poor, White, Rural Students

    ERIC Educational Resources Information Center

    Bates, Vincent C.

    2011-01-01

    "Poor white trash" is likely the most enduring and degrading in a long line of "stigmatypes"--"stigmatizing boundary terms that simultaneously denote and enact cultural and cognitive divides between in-groups and out-groups"--such as "redneck," "cracker," and "hillbilly." Some people apply these terms in reference to poor or working-class, usually…

  5. The Prevalence of Poor Reading in Dutch Special Elementary Education

    ERIC Educational Resources Information Center

    van Bon, Wim H. J.; Bouwmans, Mieke; Broeders, Ivy N. L. D. C.

    2006-01-01

    The relative frequency of poor readers in Dutch general elementary education (GEE) and special elementary education (SEE) and the characteristics of their reading performance were investigated using a lexical decision procedure. According to the same norms that identified 9% of students as poor readers in GEE, no less than 73% of the students in…

  6. An Image Study on the Rich and Poor Perception

    ERIC Educational Resources Information Center

    Koçak, Recep

    2015-01-01

    The aim of this study is to project people's perceptions about the rich and poor. In this descriptive study, a questionnaire developed by the researcher and caricatures were used to collect data. The questionnaire composed of seven items including questions directed to adjectives related to the participants' perceptions about the rich and poor as…

  7. Mandated empowerment: handing antipoverty policy back to the poor?

    PubMed

    Banerjee, Abhijit V; Duflo, Esther

    2008-01-01

    The current trend in antipoverty policy emphasizes mandated empowerment: the poor are being handed the responsibility for making things better for themselves, largely without being asked whether this is what they want. Beneficiary control is now being built into public service delivery, while microcredit and small business promotion are seen as better ways to help the poor. The clear presumption is that the poor are both able and happy to exercise these new powers. This essay uses two examples to raise questions about these strategies. The first example is about entrepreneurship among the poor. Using data from a number of countries, we argue that there is no evidence that the median poor entrepreneur is trying his best to expand his existing businesses, even if we take into account the many constraints he faces. While many poor people own businesses, this seems to be more a survival strategy than something they want to do. The second example comes from an evaluation of a program in India that aims to involve poor rural parents in improving local public schools. The data suggest that despite being informed that they now have both the right to intervene in the school and access to funds for that purpose, and despite being made aware of how little the children were learning, parents opt to not get involved. Both examples raise concerns about committing ourselves entirely to antipoverty strategies that rely on the poor doing a lot of the work.

  8. The War against the Poor. The Underclass and Antipoverty Policy.

    ERIC Educational Resources Information Center

    Gans, Herbert J.

    For much of its history, America has been waging war against many of its poor people. Chapters 1 through 4 of this book discuss the labeling of the poor as morally inferior, which has increased in the last 15 years, blames them falsely for the ills of the American society and economy, reinforces their mistreatment, increases their misery, and…

  9. Exploring Written Narrative in Children with Poor Reading Comprehension

    ERIC Educational Resources Information Center

    Cragg, Lucy; Nation, Kate

    2006-01-01

    This study investigated written language production in 10-year-old children with impaired reading comprehension. Despite fluent and accurate reading, these children are poor at understanding what they read. Participants completed a spelling test, and were asked to write an extended narrative, prompted by a series of pictures. Poor comprehenders…

  10. Rich Man, Poor Man: Developmental Differences in Attributions and Perceptions

    ERIC Educational Resources Information Center

    Sigelman, Carol K.

    2012-01-01

    In an examination guided by cognitive developmental and attribution theory of how explanations of wealth and poverty and perceptions of rich and poor people change with age and are interrelated, 6-, 10-, and 14-year-olds (N = 88) were asked for their causal attributions and trait judgments concerning a rich man and a poor man. First graders, like…

  11. Poor Kids in a Rich Nation: Eating the Seed Corn.

    ERIC Educational Resources Information Center

    Garrett, Patricia

    This paper examines the problem of having many poor children in the wealthy United States and the need to find answers to this problem. Despite much recent talk about "family values," the dominant U.S. ideology holds that family welfare is a private rather than a public responsibility. Poor children are seen as a special population that diverts…

  12. "Total Deposition (TDEP) Maps"

    EPA Science Inventory

    The presentation provides an update on the use of a hybrid methodology that relies on measured values from national monitoring networks and modeled values from CMAQ to produce of maps of total deposition for use in critical loads and other ecological assessments. Additionally, c...

  13. Heavy metals contamination of soils surrounding waste deposits in Romania

    NASA Astrophysics Data System (ADS)

    Matache, M.; Rozylowicz, L.; Ropota, M.; Patroescu, C.

    2003-05-01

    Soils contamination with heavy metals is one of the most severe aspects of environmental pollution in Romania, independently of the origin sources (domestic or industrial activities) or type of disposal (organised landfill or hazardous deposits)[l-2]. This fact is the consequence of the poor state of the existing waste deposits in Romania and of the significant costs involved by the establishing of a new landfill according with the international regulations. The present study is trying to emphasise the contamination of soils surrounding different categories of waste deposits (sewage sludge ponds, domestic and industrial waste landfills, hillocks, sterile deposits) from various regions of Romania. Some case studies show a special interest being localise in a protected area (Iron Gates Natural Park). In order to quantify the concentration of metals like Cd, Cr, Cu, Pb, Zn, Ni, Mo in soil samples, analysis were performed using Inductively Coupled Plasma - Optical Emission Spectrometry (ICP-OES). Romanian standards were used as reference values[3].

  14. Do Poor Readers Feel Angry, Sad, and Unpopular?

    PubMed Central

    Morgan, Paul L.; Farkas, George; Wu, Qiong

    2015-01-01

    We investigated whether being poorly skilled in reading contributes to children’s self-reported feelings of anger, distractibility, anxiety, sadness, loneliness, and social isolation. Data were analyzed from a longitudinal sub-sample of children (N=2,751) participating in the Early Childhood Longitudinal Study—Kindergarten Cohort. Multi-level logistic regression analyses indicated that poor readers in 3rd grade were more likely to consider themselves as angry, distractible, sad, lonely, and unpopular in 5th grade than those who had not been poor readers in 3rd grade. About 20% of 3rd grade poor readers reported feeling angry and unpopular in 5th grade. Being poorly skilled in mathematics increased children’s risk of feeling sad or lonely, but not of feeling angry, distractible, or unpopular. The results provide additional empirical evidence that reading failure contributes to generalized socio-emotional maladjustment in young children. PMID:26180489

  15. Volcanogenic Massive Sulfide Deposit Density

    USGS Publications Warehouse

    Mosier, Dan L.; Singer, Donald A.; Berger, Vladimir I.

    2007-01-01

    A mineral-deposit density model for volcanogenic massive sulfide deposits was constructed from 38 well-explored control areas from around the world. Control areas contain at least one exposed volcanogenic massive sulfide deposit. The control areas used in this study contain 150 kuroko, 14 Urals, and 25 Cyprus massive sulfide subtypes of volcanogenic massive sulfide deposits. For each control area, extent of permissive rock, number of exposed volcanogenic massive sulfide deposits, map scale, deposit age, and deposit density were determined. The frequency distribution of deposit densities in these 38 control areas provides probabilistic estimates of the number of deposits for tracts that are permissive for volcanogenic massive sulfide deposits-90 percent of the control areas have densities of 100 or more deposits per 100,000 square kilometers, 50 percent of the control areas have densities of 700 or more deposits per 100,000 square kilometers, and 10 percent of the control areas have densities of 3,700 or more deposits per 100,000 square kilometers. Both map scale and the size of the control area are shown to be predictors of deposit density. Probabilistic estimates of the number of volcanogenic massive sulfide deposits can be made by conditioning the estimates on sizes of permissive area. The model constructed for this study provides a powerful tool for estimating the number of undiscovered volcanogenic massive sulfide deposits when conducting resource assessments. The value of these deposit densities is due to the consistency of these models with the grade and tonnage and the descriptive models. Mineral-deposit density models combined with grade and tonnage models allow reasonable estimates of the number, size, and grades of volcanogenic massive sulfide deposits to be made.

  16. Trouvelot Crater Deposit

    NASA Technical Reports Server (NTRS)

    2002-01-01

    [figure removed for brevity, see original site]

    Like many of the craters in the Oxia Palus region of Mars, Trouvelot Crater hosts an eroded, light-toned, sedimentary deposit on its floor. Compared with the much larger example in Becquerel Crater to the NE, the Trouvelot deposit has been so eroded by the scouring action of dark, wind-blown sand that very little of it remains. Tiny outliers of bright material separated from the main mass attest to the once, more really extensive coverage by the deposit. A similar observation can be made for White Rock, the best known example of a bright, crater interior deposit. The origin of the sediments in these deposits remains enigmatic but they are likely the result of fallout from ash or dust carried by the thin martian atmosphere.

    Note: this THEMIS visual image has not been radiometrically nor geometrically calibrated for this preliminary release. An empirical correction has been performed to remove instrumental effects. A linear shift has been applied in the cross-track and down-track direction to approximate spacecraft and planetary motion. Fully calibrated and geometrically projected images will be released through the Planetary Data System in accordance with Project policies at a later time.

    NASA's Jet Propulsion Laboratory manages the 2001 Mars Odyssey mission for NASA's Office of Space Science, Washington, D.C. The Thermal Emission Imaging System (THEMIS) was developed by Arizona State University, Tempe, in collaboration with Raytheon Santa Barbara Remote Sensing. The THEMIS investigation is led by Dr. Philip Christensen at Arizona State University. Lockheed Martin Astronautics, Denver, is the prime contractor for the Odyssey project, and developed and built the orbiter. Mission operations are conducted jointly from Lockheed Martin and from JPL, a division of the California Institute of Technology in Pasadena.

  17. Particle size-density relationships in pyroclastic deposits: using component subpopulations to elucidate depositional conditions

    NASA Astrophysics Data System (ADS)

    Mackaman-Lofland, C. A.; Brand, B. D.; Taddeucci, J.

    2012-12-01

    Pyroclastic Density Currents (PDCs) are ground-hugging currents of hot gas, ash, and rock that travel at velocities up to 150 m/s down the flanks of volcanoes. PDCs are the most dangerous hazard associated with explosive volcanic eruptions, but because of current opacity and the risk inherent to observing PDCs in real time, their processes are poorly understood. Geologists rely on depositional relationships to lend insight into PDC transport and depositional processes. Outcrop exposure is typically incomplete, however, and the extent to which outcrop-scale depositional characteristics are representative of the parent current is still uncertain. The May 18th, 1980 eruption of Mt. St. Helens (MSH) produced multiple PDCs, burying the area north of the crater under 10s of meters of PDC deposits. Deep drainage erosion over the past 30 years has exposed these deposits in three dimensions, allowing a detailed study of deposit structures to be conducted for a variety of locations and depositional regimes with distance from source. We examine the grain size distribution and density characteristics of the discrete component subpopulations that make up the solids fraction of PDC deposits, focusing on changes associated with lateral facies variation, distance from source, and degree of topographic roughness. We analyze the grain size and density relationships of the component subpopulations using sequential fragmentation / transport theory (SFT), and use crystal morphoscopy to determine how different regional transport systems effect feldspar and hornblende crystal shape following the methods of Taddeucci and Palladino ((2002) Particle size-density relationships in pyroclastic deposits: inferences for emplacement processes. Bull Volcanol 64:273-284). Calculations of representative proximal and distal samples indicate juvenile pumice densities of ~1.3g/mL, accidental lithic densities of ~2.7g/mL, and crystal densities of ~2.6g/mL. We observe a general decrease in grain size and

  18. The Grainsize Characteristics of Coignimbrite Deposits

    NASA Astrophysics Data System (ADS)

    Engwell, Samantha; Eychenne, Julia

    2015-04-01

    . The deposits are very fine grained (< 100 microns), have unimodal grain size distributions skewed towards the fines, and are more poorly sorted in medial to distal areas than tephra fall deposits from vent-derived plumes at the same distance. Deposits from a single eruption show constant grain size over hundreds to thousands of kilometres, except for a slight coarsening close to source in some cases. In intermediate size eruptions, co-ignimbrite ash often settles synchronously to vent-derived tephra, leading to bimodal grain size fallout deposits. These observations highlight the propensity of the ash to remain in the atmosphere for extended periods of time, and pose important questions regarding how the ash is deposited, and especially the role of aggregation. The uniformity of co-ignimbrite ash means that, with regards to real-time dispersion modelling during an eruption, few assumptions are required for the initial grain size, however depositional assumptions utilised when modelling vent-derived plume dispersion, may not be able to accurately reproduce co-ignimbrite depositional patterns.

  19. Mycorrhizal weathering of apatite as an important calcium source in base-poor forest ecosystems.

    PubMed

    Blum, Joel D; Klaue, Andrea; Nezat, Carmen A; Driscoll, Charles T; Johnson, Chris E; Siccama, Thomas G; Eagar, Christopher; Fahey, Timothy J; Likens, Gene E

    2002-06-13

    The depletion of calcium in forest ecosystems of the northeastern USA is thought to be a consequence of acidic deposition and to be at present restricting the recovery of forest and aquatic systems now that acidic deposition itself is declining. This depletion of calcium has been inferred from studies showing that sources of calcium in forest ecosystems namely, atmospheric deposition and mineral weathering of silicate rocks such as plagioclase, a calcium-sodium silicate do not match calcium outputs observed in forest streams. It is therefore thought that calcium is being lost from exchangeable and organically bound calcium in forest soils. Here we investigate the sources of calcium in the Hubbard Brook experimental forest, through analysis of calcium and strontium abundances and strontium isotope ratios within various soil, vegetation and hydrological pools. We show that the dissolution of apatite (calcium phosphate) represents a source of calcium that is comparable in size to known inputs from atmospheric sources and silicate weathering. Moreover, apatite-derived calcium was utilized largely by ectomycorrhizal tree species, suggesting that mycorrhizae may weather apatite and absorb the released ions directly, without the ions entering the exchangeable soil pool. Therefore, it seems that apatite weathering can compensate for some of the calcium lost from base-poor ecosystems, and should be considered when estimating soil acidification impacts and calcium cycling.

  20. A Comparison of the Language Skills of ELLs and Monolinguals Who Are Poor Decoders, Poor Comprehenders, or Normal Readers

    ERIC Educational Resources Information Center

    Geva, Esther; Massey-Garrison, Angela

    2013-01-01

    The overall objective of this article is to examine how oral language abilities relate to reading profiles in English language learners (ELLs) and English as a first language (EL1) learners, and the extent of similarities and differences between ELLs and EL1s in three reading subgroups: normal readers, poor decoders, and poor comprehenders. The…

  1. Early Disparities in Mathematics Gains among Poor and Non-Poor Children: Examining the Role of Behavioral Engagement in Learning

    ERIC Educational Resources Information Center

    Robinson, Keith

    2013-01-01

    Multilevel modeling was used to investigate the relationship between poverty status, mathematics achievement gains, and behavioral engagement in learning over kindergarten. Data included information on 11,680 poor, low-income, and non-poor kindergartners from the Early Childhood Longitudinal Study-Kindergarten Cohort of 1998-1999 (ECLS-K). Results…

  2. 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.

    PubMed

    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.

  3. 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

    NASA Astrophysics Data System (ADS)

    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.

  4. Rhodium-catalyzed cascade oxidative annulation leading to substituted naphtho[1,8-bc]pyrans by sequential cleavage of C(sp2)-H/C(sp3)-H and C(sp2)-H/O-H bonds.

    PubMed

    Tan, Xing; Liu, Bingxian; Li, Xiangyu; Li, Bin; Xu, Shansheng; Song, Haibin; Wang, Baiquan

    2012-10-01

    The cascade oxidative annulation reactions of benzoylacetonitrile with internal alkynes proceed efficiently in the presence of a rhodium catalyst and a copper oxidant to give substituted naphtho[1,8-bc]pyrans by sequential cleavage of C(sp(2))-H/C(sp(3))-H and C(sp(2))-H/O-H bonds. These cascade reactions are highly regioselective with unsymmetrical alkynes. Experiments reveal that the first-step reaction proceeds by sequential cleavage of C(sp(2))-H/C(sp(3))-H bonds and annulation with alkynes, leading to 1-naphthols as the intermediate products. Subsequently, 1-naphthols react with alkynes by cleavage of C(sp(2))-H/O-H bonds, affording the 1:2 coupling products. Moreover, some of the naphtho[1,8-bc]pyran products exhibit intense fluorescence in the solid state. PMID:22989331

  5. Reconstructing Tsunami Flow Speed from Sedimentary Deposits

    NASA Astrophysics Data System (ADS)

    Jaffe, B. E.; Gelfenbaum, G. R.

    2014-12-01

    Paleotsunami deposits contain information about the flow that created them that can be used to reconstruct tsunami flow speed and thereby improving assessment of tsunami hazard. We applied an inverse tsunami sediment transport model to sandy deposits near Sendai Airport, Japan, that formed during the 11 March 2011 Tohoku-oki tsunami to test model performance and explore the spatial variations in tsunami flow speed. The inverse model assumes the amount of suspended sediment in the water column is in equilibrium with local flow speed and that sediment transport convergences, primarily from bedload transport, do not contribute significantly to formation of the portion of the deposit we identify as formed by sediment settling out of suspension. We interpret massive or inversely graded intervals as forming from sediment transport convergences and do not model them. Sediment falling out of suspension forms a specific type of normal grading, termed 'suspension' grading, where the entire grain size distribution shifts to finer sizes higher up in a deposit. Suspension grading is often observed in deposits of high-energy flows, including turbidity currents and tsunamis. The inverse model calculates tsunami flow speed from the thickness and bulk grain size of a suspension-graded interval. We identified 24 suspension-graded intervals from 7 trenches located near the Sendai Airport from ~250-1350 m inland from the shoreline. Flow speeds were highest ~500 m from the shoreline, landward of the forested sand dunes where the tsunami encountered lower roughness in a low-lying area as it traveled downslope. Modeled tsunami flow speeds range from 2.2 to 9.0 m/s. Tsunami flow speeds are sensitive to roughness, which is unfortunately poorly constrained. Flow speed calculated by the inverse model was similar to those calculated from video taken from a helicopter about 1-2 km inland. Deposit reconstructions of suspension-graded intervals reproduced observed upward shifts in grain size

  6. A systems view of health care for the poor.

    PubMed Central

    Prasad, N.

    1989-01-01

    A systems view is a synthesis of health policy, medical sociology, public health, and common clinical problems to describe the current crisis in health care for the poor. Medical sociology and public health are particularly relevant to understand the complexity of clinical issues. Although preventive medicine is in desuetude, it is crucial if we are to reduce the future liability of postponed medical care among the poor. Medicaid metamorphosed to Medicare, as half of its outlays are spent on care of the elderly in nursing homes. Health care for the poor will remain a moral challenge to the architects of health policy and the medical profession. PMID:2659807

  7. Poor specific antibody response immunodeficiency (dysgammaglobulinemia) predates systemic lupus erythematosus.

    PubMed

    Al Hamzi, H; Al Shaikh, A; Arnaout, R K

    2013-08-01

    Poor specific antibody response is a well-known primary immunodeficiency that is related to hypogammaglobulinemia or common variable immunodeficiency (CVID). The co-existence of CVID or hypogammaglobulinemia and systemic lupus erythematosus (SLE) has been rarely described. In all reported cases, the diagnosis of SLE antedates CVID. We report a 15-year-old Saudi girl who was diagnosed with poor specific antibody response at age 6 years in the form of poor or no antibody response and dysgammaglobulinemia. She developed SLE with musculoskeletal and hematological manifestations, positive antinuclear antibody and high anti-dsDNA nine years later. She was treated with rituximab with good response.

  8. Laser-induced deposition of nanostructured copper microwires on surfaces of composite materials

    NASA Astrophysics Data System (ADS)

    Tumkin, Ilia I.; Panov, Maxim S.; Shishkova, Ekaterina V.; Bal'makov, Michail D.

    2015-05-01

    Microelectronics industry is growing fast and the rate of new devices' development increases every year. Therefore, methods for simple and high-precision metal coating on dielectrics are needed. Existing methods do not allow performing the high-precision metal deposition without using photomasks, while making photomask for each prototype is long and expensive process. One of the methods of maskless metal deposition is laser-induced chemical liquid-phase deposition (LCLD). In this work we show the effect of substrate surface type on a result of LCLD. Deposited copper structures were characterized by SEM, EDX and impedance spectroscopy. The results show that laser-induced copper deposition is highly affected by the surface being homogeneous or composite material. It was found that the deposits with low resistivity and high quality metal localization mostly appear on the two-phase surfaces. In contrast, deposits on one-phase surfaces exhibited poor topology of copper material.

  9. 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.

    PubMed

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

    2016-09-01

    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. PMID:27518763

  10. 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.

    PubMed

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

    2016-09-01

    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.

  11. Spatial Patterns of Atmospherically Deposited Organic Contaminants at High Elevation in the Southern Sierra Nevada Mountains, California

    EPA Science Inventory

    Atmospherically deposited contaminants in the Sierra Nevada mountains of California have been implicated as adversely affecting amphibians and fish, yet the distributions of contaminants within the mountains are poorly known, particularly at high elevation. We tested the hypothe...

  12. Spatial Patterns of Atmospherically Deposited Organic Contaminants at High Elevation in the Southern Sierra Nevada Mountains, California

    EPA Science Inventory

    Atmospherically deposited contaminants in the Sierra Nevada mountains of California have been implicated as a factor adversely affecting biological resources such as amphibians and fish, yet the distributions of contaminants within the mountains are poorly known, particularly at...

  13. Inkjet deposited circuit components

    NASA Astrophysics Data System (ADS)

    Bidoki, S. M.; Nouri, J.; Heidari, A. A.

    2010-05-01

    All-printed electronics as a means of achieving ultra-low-cost electronic circuits has attracted great interest in recent years. Inkjet printing is one of the most promising techniques by which the circuit components can be ultimately drawn (i.e. printed) onto the substrate in one step. Here, the inkjet printing technique was used to chemically deposit silver nanoparticles (10-200 nm) simply by ejection of silver nitrate and reducing solutions onto different substrates such as paper, PET plastic film and textile fabrics. The silver patterns were tested for their functionality to work as circuit components like conductor, resistor, capacitor and inductor. Different levels of conductivity were achieved simply by changing the printing sequence, inks ratio and concentration. The highest level of conductivity achieved by an office thermal inkjet printer (300 dpi) was 5.54 × 105 S m-1 on paper. Inkjet deposited capacitors could exhibit a capacitance of more than 1.5 nF (parallel plate 45 × 45 mm2) and induction coils displayed an inductance of around 400 µH (planar coil 10 cm in diameter). Comparison of electronic performance of inkjet deposited components to the performance of conventionally etched items makes the technique highly promising for fabricating different printed electronic devices.

  14. Intricately Rippled Sand Deposits

    NASA Technical Reports Server (NTRS)

    2006-01-01

    [figure removed for brevity, see original site] Click on the image for Intricately Rippled Sand Deposits (QTVR)

    NASA's Mars Exploration Rover Spirit welcomed the beginning of 2006 on Earth by taking this striking panorama of intricately rippled sand deposits in Gusev Crater on Mars. This is an approximate true-color rendering of the 'El Dorado' ripple field provided by Spirit over the New Year's holiday weekend. The view spans about 160 degrees in azimuth from left to right and consists of images acquired by Spirit's panoramic camera on Spirit's 708th and 710th Martian days, or sols, (Dec. 30, 2005 and Jan. 1, 2006). Spirit used the Pancam's 750-nanometer, 530-nanometer and 430-nanometer filters to capture the colors on Mars. Scientists have eliminated seams between individual frames in the sky portion of the mosaic to better simulate the vista a person standing on Mars would see. Spirit spent several days acquiring images, spectral data, and compositional and mineralogical information about these large sand deposits before continuing downhill toward 'Home Plate.'

  15. Electrophoretic deposition of biomaterials.

    PubMed

    Boccaccini, A R; Keim, S; Ma, R; Li, Y; Zhitomirsky, I

    2010-10-01

    Electrophoretic deposition (EPD) is attracting increasing attention as an effective technique for the processing of biomaterials, specifically bioactive coatings and biomedical nanostructures. The well-known advantages of EPD for the production of a wide range of microstructures and nanostructures as well as unique and complex material combinations are being exploited, starting from well-dispersed suspensions of biomaterials in particulate form (microsized and nanoscale particles, nanotubes, nanoplatelets). EPD of biological entities such as enzymes, bacteria and cells is also being investigated. The review presents a comprehensive summary and discussion of relevant recent work on EPD describing the specific application of the technique in the processing of several biomaterials, focusing on (i) conventional bioactive (inorganic) coatings, e.g. hydroxyapatite or bioactive glass coatings on orthopaedic implants, and (ii) biomedical nanostructures, including biopolymer-ceramic nanocomposites, carbon nanotube coatings, tissue engineering scaffolds, deposition of proteins and other biological entities for sensors and advanced functional coatings. It is the intention to inform the reader on how EPD has become an important tool in advanced biomaterials processing, as a convenient alternative to conventional methods, and to present the potential of the technique to manipulate and control the deposition of a range of nanomaterials of interest in the biomedical and biotechnology fields.

  16. Uranium deposits of Brazil

    SciTech Connect

    1991-09-01

    Brazil is a country of vast natural resources, including numerous uranium deposits. In support of the country`s nuclear power program, Brazil has developed the most active uranium industry in South America. Brazil has one operating reactor (Angra 1, a 626-MWe PWR), and two under construction. The country`s economic challenges have slowed the progress of its nuclear program. At present, the Pocos de Caldas district is the only active uranium production. In 1990, the Cercado open-pit mine produced approximately 45 metric tons (MT) U{sub 3}O{sub 8} (100 thousand pounds). Brazil`s state-owned uranium production and processing company, Uranio do Brasil, announced it has decided to begin shifting its production from the high-cost and nearly depleted deposits at Pocos de Caldas, to lower-cost reserves at Lagoa Real. Production at Lagoa Real is schedules to begin by 1993. In addition to these two districts, Brazil has many other known uranium deposits, and as a whole, it is estimated that Brazil has over 275,000 MT U{sub 3}O{sub 8} (600 million pounds U{sub 3}O{sub 8}) in reserves.

  17. Electrophoretic deposition of biomaterials

    PubMed Central

    Boccaccini, A. R.; Keim, S.; Ma, R.; Li, Y.; Zhitomirsky, I.

    2010-01-01

    Electrophoretic deposition (EPD) is attracting increasing attention as an effective technique for the processing of biomaterials, specifically bioactive coatings and biomedical nanostructures. The well-known advantages of EPD for the production of a wide range of microstructures and nanostructures as well as unique and complex material combinations are being exploited, starting from well-dispersed suspensions of biomaterials in particulate form (microsized and nanoscale particles, nanotubes, nanoplatelets). EPD of biological entities such as enzymes, bacteria and cells is also being investigated. The review presents a comprehensive summary and discussion of relevant recent work on EPD describing the specific application of the technique in the processing of several biomaterials, focusing on (i) conventional bioactive (inorganic) coatings, e.g. hydroxyapatite or bioactive glass coatings on orthopaedic implants, and (ii) biomedical nanostructures, including biopolymer–ceramic nanocomposites, carbon nanotube coatings, tissue engineering scaffolds, deposition of proteins and other biological entities for sensors and advanced functional coatings. It is the intention to inform the reader on how EPD has become an important tool in advanced biomaterials processing, as a convenient alternative to conventional methods, and to present the potential of the technique to manipulate and control the deposition of a range of nanomaterials of interest in the biomedical and biotechnology fields. PMID:20504802

  18. Silicon source for vacuum deposition

    NASA Technical Reports Server (NTRS)

    Racette, G. W.; Rutecki, D. J.

    1979-01-01

    Device using two independent silicon sources for ultra-high-vacuum deposition on large substrates can deposit P and N types of silicon simultaneously. Efficient water cooled copper shield supports and cools structure and isolates two filaments.

  19. Nickel-cobalt laterites: a deposit model: Chapter H in Mineral deposit models for resource assessment

    USGS Publications Warehouse

    Marsh, Erin; Anderson, Eric J.; Gray, Floyd

    2013-01-01

    Nickel-cobalt (Ni-Co) laterite deposits are supergene enrichments of Ni±Co that form from intense chemical and mechanical weathering of ultramafic parent rocks. These regolith deposits typically form within 26 degrees of the equator, although there are a few exceptions. They form in active continental margins and stable cratonic settings. It takes as little as one million years for a laterite profile to develop. Three subtypes of Ni-Co laterite deposits are classified according to the dominant Ni-bearing mineralogy, which include hydrous magnesium (Mg)-silicate, smectite, and oxide. These minerals form in weathering horizons that begin with the unweathered protolith at the base, saprolite next, a smectite transition zone only in profiles where drainage is very poor, followed by limonite, and then capped with ferricrete at the top. The saprolite contains Ni-rich hydrous Mg-silicates, the Ni-rich clays occur in the transition horizon, and Ni-rich goethite occurs in the limonite. Although these subtypes of deposits are the more widely used terms for classification of Ni-Co laterite deposits, most deposits have economic concentrations of Ni in more than one horizon. Because of their complex mineralogy and heterogeneous concentrations, mining of these metallurgically complex deposits can be challenging. Deposits range in size from 2.5 to about 400 million tonnes, with Ni and Co grades of 0.66–2.4 percent (median 1.3) and 0.01–0.15 percent (median 0.08), respectively. Modern techniques of ore delineation and mineralogical identification are being developed to aid in streamlining the Ni-Co laterite mining process, and low-temperature and low-pressure ore processing techniques are being tested that will treat the entire weathered profile. There is evidence that the production of Ni and Co from laterites is more energy intensive than that of sulfide ores, reflecting the environmental impact of producing a Ni-Co laterite deposit. Tailings may include high levels of

  20. Effects of debris flow composition on runout, depositional mechanisms, and deposit morphology in laboratory experiments

    NASA Astrophysics Data System (ADS)

    Haas, Tjalling; Braat, Lisanne; Leuven, Jasper R. F. W.; Lokhorst, Ivar R.; Kleinhans, Maarten G.

    2015-09-01

    Predicting debris flow runout is of major importance for hazard mitigation. Apart from topography and volume, runout distance and area depends on debris flow composition and rheology, but how is poorly understood. We experimentally investigated effects of composition on debris flow runout, depositional mechanisms, and deposit geometry. The small-scale experimental debris flows were largely similar to natural debris flows in terms of flow behavior, deposit morphology, grain size sorting, channel width-depth ratio, and runout. Deposit geometry (lobe thickness and width) in our experimental debris flows is largely determined by composition, while the effects of initial conditions of topography (i.e., outflow plain slope and channel slope and width) and volume are negligible. We find a clear optimum in the relations of runout with coarse-material fraction and clay fraction. Increasing coarse-material concentration leads to larger runout. However, excess coarse material results in a large accumulation of coarse debris at the flow front and enhances diffusivity, increasing frontal friction and decreasing runout. Increasing clay content initially enhances runout, but too much clay leads to very viscous flows, reducing runout. Runout increases with channel slope and width, outflow plain slope, debris flow volume, and water fraction. These results imply that debris flow runout depends at least as much on composition as on topography. This study improves understanding of the effects of debris flow composition on runout and may aid future debris flow hazard assessments.

  1. Los Angeles County Poor Farm, Patient Ward Nos. 210 & ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    Los Angeles County Poor Farm, Patient Ward Nos. 210 & 211 - Type B Plan, 7601 Imperial Highway; bounded by Esperanza Street, Laurel Street, Flores Street, and Descanso Street, Downey, Los Angeles County, CA

  2. Los Angeles County Poor Farm, Patient Wards 201, 202, 203, ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    Los Angeles County Poor Farm, Patient Wards 201, 202, 203, 204, 205, 206, 207, 208 & 209 - Type A Plan, 7601 Imperial Highway; bounded by Esperanza Street, Hawthorn Avenue, Laurel Street, and Descanso Street, Downey, Los Angeles County, CA

  3. Poor Weight Gain in Infants and Children (Beyond the Basics)

    MedlinePlus

    ... month) – Poor quality of suck (whether breast- or bottle-fed), incorrect formula preparation; breastfeeding problems; inadequate number ... to feed him/herself (eg, by holding a bottle or eating finger foods), but may need to ...

  4. Depleting depletion: Polymer swelling in poor solvent mixtures

    NASA Astrophysics Data System (ADS)

    Mukherji, Debashish; Marques, Carlos; Stuehn, Torsten; Kremer, Kurt

    A polymer collapses in a solvent when the solvent particles dislike monomers more than the repulsion between monomers. This leads to an effective attraction between monomers, also referred to as depletion induced attraction. This attraction is the key factor behind standard polymer collapse in poor solvents. Strikingly, even if a polymer exhibits poor solvent condition in two different solvents, it can also swell in mixtures of these two poor solvents. This collapse-swelling-collapse scenario is displayed by poly(methyl methacrylate) (PMMA) in aqueous alcohol. Using molecular dynamics simulations of a thermodynamically consistent generic model and theoretical arguments, we unveil the microscopic origin of this phenomenon. Our analysis suggests that a subtle interplay of the bulk solution properties and the local depletion forces reduces depletion effects, thus dictating polymer swelling in poor solvent mixtures.

  5. Ruprecht 106 - A young metal-poor Galactic globular cluster

    SciTech Connect

    Buonanno, R.; Buscema, G.; Fusi Pecci, F.; Richer, H.B.; Fahlman, G.G. Bologna Universita British Columbia Univ., Vancouver )

    1990-12-01

    The first CCD photometric survey in the Galactic globular cluster Ruprecht 106 has been performed. The results show that Ruprecht 106 is a metal-poor cluster with (Fe/H) about -2 located at about 25 kpc from the Galactic center. A sizable, high centrally concentrated population of blue stragglers was detected. Significant differences in the positions of the turnoffs in the color-magnitude diagram are found compared to those in metal-poor clusters. The cluster appears younger than other typical metal-poor Galactic globulars by about 4-5 Gyr; if true, this object would represent the first direct proof of the existence of a significant age spread among old, very metal-poor clusters. 51 refs.

  6. Many Hispanics, Poor Still Without Health Insurance: Report

    MedlinePlus

    ... fullstory_160507.html Many Hispanics, Poor Still Without Health Insurance: Report Majority live in states that haven't ... 2016 (HealthDay News) -- Despite an overall rise in health insurance coverage among all Americans, Hispanics, low-income earners ...

  7. Poor Sleep May Worsen Thinking Problems in MS Patients

    MedlinePlus

    ... https://medlineplus.gov/news/fullstory_159463.html Poor Sleep May Worsen Thinking Problems in MS Patients Study found link between severity of sleep apnea and performance on attention, memory tests To ...

  8. Exploring the early Universe with extremely metal-poor stars

    NASA Astrophysics Data System (ADS)

    Hansen, Terese T.; Christlieb, Norbert; Hansen, Camilla J.; Beers, Timothy C.

    2016-08-01

    The earliest phases of Galactical chemical evolution and nucleosynthesis can be investigated by studying the old metal-poor stars. It has been recognized that a large fraction of metal-poor stars possess significant over-abundances of carbon relative to iron. Here we present the results of a 23-star homogeneously analyzed sample of metal-poor candidates from the Hamburg/ESO survey. We have derived abundances for a large number of elements ranging from Li to Pb. The sample includes four ultra metal-poor stars ([Fe/H] < -4.0), six CEMP-no stars, five CEMP-s stars, two CEMP-r stars and two CEMP-r/s stars. This broad variety of the sample stars gives us an unique opportunity to explore different abundance patterns at low metallicity.

  9. [Poorly healing periorbital wounds. Therapeutic use of maggots].

    PubMed

    Pitz, S; Renieri, G; Gericke, A

    2012-05-01

    The treatment of poorly healing wounds, although not a typical problem in the periorbital area, has been enriched by the option of biosurgery, the therapeutic application of larvae of the blow fly (Lucilia sericata).

  10. Explaining the Role of Proximate Determinants on Fertility Decline among Poor and Non-Poor in Asian Countries

    PubMed Central

    Majumder, Nabanita; Ram, Faujdar

    2015-01-01

    Objectives We examined the overall contributions of the poor and non-poor in fertility decline across the Asian countries. Further, we analyzed the direct and indirect factors that determine the reproductive behaviour of two distinct population sub-groups. Design Data from several new rounds of DHS surveys are available over the past few years. The DHS provides cross-nationally comparable and useful data on fertility, family planning, maternal and child health along with the other information. Six selected Asian countries namely: Bangladesh, India, Indonesia, Nepal, Philippines, and Vietnam are considered for the purpose of the study. Three rounds of DHS surveys for each country (except Vietnam) are considered in the present study. Methods Economic status is measured by computing a “wealth index”, i.e. a composite indicator constructed by aggregating data on asset ownership and housing characteristics using principal components analysis (PCA). Computed household wealth index has been broken into three equal parts (33.3 percent each) and the lowest and the highest 33.3 percent is considered as poor and non-poor respectively. The Bongaarts model was employed to quantify the contribution of each of the proximate determinants of fertility among poor and non-poor women. Results Fertility reduction across all population subgroups is now an established fact despite the diversity in the level of socio-economic development in Asian countries. It is clear from the analysis that fertility has declined irrespective of economic status at varying degrees within and across the countries which can be attributed to the increasing level of contraceptive use especially among poor women. Over the period of time changing marriage pattern and induced abortion are playing an important role in reducing fertility among poor women. Conclusions Fertility decline among majority of the poor women across the Asian countries is accompanied by high prevalence of contraceptive use followed by

  11. Physical properties of luminous dust-poor quasars

    SciTech Connect

    Jun, Hyunsung David; Im, Myungshin E-mail: mim@astro.snu.ac.kr

    2013-12-20

    We identify and characterize a population of luminous, dust-poor quasars at 0 < z < 5 that is photometrically similar to objects previously found at z > 6. This class of active galactic nuclei is known to show little IR emission from dusty structure, but it is poorly understood in terms of number evolution and dependence on physical quantities. To better understand the properties of these quasars, we compile a rest-frame UV to IR library of 41,000 optically selected type 1 quasars with L {sub bol} > 10{sup 45.7} erg s{sup –1}. After fitting the broadband spectral energy distributions (SEDs) with accretion disk and dust components, we find 0.6% of our sample to be hot dust-poor, with rest-frame 2.3 μm to 0.51 μm flux density ratios of –0.5 dex or less. The dust-poor SEDs are blue in the UV-optical and weak in the mid-IR, such that their accretion disks are less obscured and the hot dust emission traces that of warm dust down to the dust-poor regime. At a given bolometric luminosity, dust-poor quasars are lower in black hole mass and higher in Eddington ratio than general luminous quasars, suggesting that they are in a rapidly growing evolutionary state in which the dust-poor phase appears as a short or rare phenomenon. The dust-poor fraction increases with redshift, and possible implications for their evolution are discussed.

  12. Imaging features of poorly controlled congenital adrenal hyperplasia in adults

    PubMed Central

    Sherlock, M; Healy, N A; Doody, O; Govender, P; Torreggiani, W C

    2015-01-01

    Congenital adrenal hyperplasia (CAH) is a genetic autosomal recessive condition most frequently as a result of a mutation in the 21-hydroxylase enzyme gene. Patients with poorly controlled CAH can manifest characteristic imaging findings as a result of adrenocorticotrophic hormone stimulation or the effects of cortisol precursor excess on various target organs. We present a spectrum of imaging findings encountered in adult patients with poorly treated CAH, with an emphasis on radiological features and their clinical relevance. PMID:26133223

  13. Pulse plating of nickel deposits

    SciTech Connect

    Stimetz, C.J.; Stevenson, M.F.

    1980-02-01

    Pulse plated and conventional nickel deposits have been compared for differences in morphology, mechanical properties, and microstructure. The deposits were obtained from nickel sulfamate, nickel chloride, and Watts nickel plating solutions. No significant differences were found in the direct and pulse current deposits from the sulfamate and chloride solutions; however, significant differences in microstructure, yield strength, and microhardness were observed in deposits from the Watts nickel solution.

  14. Clinicopathological significance of gastric poorly differentiated medullary carcinoma.

    PubMed

    Hirai, Hideaki; Yoshizawa, Tadashi; Morohashi, Satoko; Haga, Toshihiro; Wu, Yunyan; Ota, Rie; Takatsuna, Masafumi; Akasaka, Harue; Hakamada, Kenichi; Kijima, Hiroshi

    2016-01-01

    Poorly differentiated gastric adenocarcinoma of solid type is known to show a clinicopathological diversity, but its morphological characteristics have rarely been investigated. In this study, we defined poorly differentiated medullary carcinoma indicating the following three characteristics: (i) more than 90% of the entire tumor were composed of poorly differentiated adenocarcinoma in a medullary growth, (ii) the tumor exhibited an expansive growth at the tumor margin, and (iii) special types such as an α-fetoprotein-producing carcinoma, neuroendocrine carcinoma, and carcinoma with lymphoid stroma were excluded. Based on the definition, we subclassified the poorly differentiated gastric adenocarcinoma of solid type into the two groups: medullary carcinoma and non-medullary carcinoma, and clinicopathologically analyzed 23 cases of medullary carcinomas and 38 cases of non-medullary carcinomas. The medullary carcinomas less frequently displayed lymphatic invasion, venous invasion, and lymph node metastasis, compared with the non-medullary carcinoma (P < 0.001, P = 0.002, and P < 0.001, respectively). The patients with medullary carcinomas significantly showed better disease-free survival (P = 0.017). This is the first study to demonstrate that poorly differentiated adenocarcinoma of solid type can be subclassified into tumors with low and high malignant potentials. Gastric poorly differentiated medullary carcinoma is considered to be a novel histological type predicting good patients' prognosis. PMID:27108877

  15. Poor Mental Health and Reduced Decline in Smoking Prevalence

    PubMed Central

    Steinberg, Marc L.; Williams, Jill M.; Li, Yunqing

    2015-01-01

    Introduction Although smoking prevalence has been declining for smokers without mental illness, it has been static for those with mental illness. The purpose of this study is to examine differences in smoking rates and trajectories of smoking prevalence in the often-overlooked population of smokers with poor mental health, compared with those with better mental health. Methods Data were obtained from the Behavioral Risk Factor Surveillance System from 2001 to 2010 to examine the relationship between poor mental health and current, daily, and intermittent tobacco use in New Jersey. Data were analyzed in 2014. Results During 2001–2010, current, daily, and intermittent smoking prevalence was higher in participants with poor mental health than those with better mental health. In addition, with the exception of 2 years, prevalence rates remained unchanged in this 10-year period for those with poor mental health while they significantly decreased for those with better mental health. Conclusions The disparity in which smokers with poor mental health are more likely to be current smokers and less likely to be never smokers as compared with those with better mental health has increased over time. These data suggest the need to more closely examine tobacco control and treatment policies in smokers with behavioral health issues. It is possible that tobacco control strategies are not reaching those with poor mental health, or, if they are, their messages are not translating into successful cessation. PMID:26071864

  16. Kinematics and dynamics of the Morgan poor clusters

    NASA Astrophysics Data System (ADS)

    Bird, Christina M.; Beers, Timothy C.; Kriessler, Jeffrey R.; Huchra, John P.

    1995-07-01

    Eighteen of the 23 MKW and AWM poor clusters now have 10 or more measured redshifts within 1.5h-1 Mpc of the central galaxy; 11 clusters have at least 20 measured redshifts. Based on the 21 clusters for which we have sufficient velocity information, the median velocity scale is 336 km s-1, a factor of two smaller than found for rich clusters. Several of the poor clusters exhibit complex velocity distributions due to the presence of nearby clumps of galaxies. We check on the velocity of the dominant galaxy in each poor cluster relative to the remaining cluster members. Significantly high relative velocities of the dominant galaxy are found in only 4 of 21 poor clusters, 3 of which we suspect are due to contamination of the parent velocity distribution. Several statistical tests indicate that the D/cD galaxies are at the kinematic centers of the parent poor cluster velocity distributions. Mass-to-light ratios for the 13 of the 15 poor clusters for which we have the required data are in the range 50<=M/LB(0)<=200 Msolar/Lsolar.

  17. Sedimentary facies of alluvial fan deposits, Death Valley, California

    SciTech Connect

    Middleton, G.V. )

    1992-01-01

    Fans in Death Valley include both diamicts and bedded gravels. Seven facies may be recognized. The diamicts include: (1) matrix-rich, coarse wackestones; (2) thin, matrix-rich, fine wackestones, that may show grading; (3) matrix-poor, coarse packstones, transitional to wackestones. The bedded facies include: (4) weakly bedded, poorly sorted packstones or grainstones, that show patchy imbrication, and cut-and-fill structures; (5) packed, imbricated cobble lenses, generally interbedded in facies 4; (6) distinctly bedded gravels, that are better bedded, finer and better sorted, and show better imbrication than facies 4, but still do not show clear separation of sand and gravel beds; (7) backfill cross-bedded gravels. Sand beds are not seen in fan deposits. Sand is present in eolian deposits, as plane-laminated, back-eddy deposits in Death Valley Wash, and as laminated or rippled sand in the Amargosa River. The most remarkable features of the fan deposits are the very weak segregation of sand and gravel, and the complete absence of any lower flow-regime structures produced by ripples or dunes. During floods, the slope of fan and even large wash surfaces is steep enough to produce upper flow regimes. There are also very few trends in facies abundance down fans: most fans in Death Valley itself are not strongly dominated by debris flow deposits (diamicts). The facies characteristics of a given fan vary little from proximal to distal regions, but may differ strongly from the facies seen in adjacent fans. Ancient deposits that show clear segregation of gravel from cross-bedded sand beds, or strong proximal to distal facies transitions, must have been deposited in environments quite different from Death Valley.

  18. Late Quaternary carbonate deposition at the bottom of the world

    NASA Astrophysics Data System (ADS)

    Frank, Tracy D.; James, Noel P.; Bone, Yvonne; Malcolm, Isabelle; Bobak, Lindsey E.

    2014-05-01

    Carbonate sediments on polar shelves hold great potential for improving understanding of climate and oceanography in regions of the globe that are particularly sensitive to global change. Such deposits have, however, not received much attention from sedimentologists and thus remain poorly understood. This study investigates the distribution, composition, diagenesis, and stratigraphic context of Late Quaternary calcareous sediments recovered in 15 piston cores from the Ross Sea shelf, Antarctica. Results are used to develop a depositional model for carbonate deposition on glaciated, polar shelves. The utility of the deposits as analogs for the ancient record is explored. In the Ross Sea, carbonate-rich lithofacies, consisting of poorly sorted skeletal sand and gravel, are concentrated in the west and along the outer reaches of the continental shelf and upper slope. Analysis of fossil assemblages shows that deposits were produced by numerous low-diversity benthic communities dominated locally by stylasterine hydrocorals, barnacles, or bryozoans. Radiocarbon dating indicates that carbonate sedimentation was episodic, corresponding to times of reduced siliciclastic deposition. Most accumulation occurred during a time of glacial expansion in the lead-up to the Last Glacial Maximum. A more recent interval of carbonate accumulation postdates the early Holocene sea level rise and the establishment of the modern grounding line for the Ross Ice Shelf. When carbonate factories were inactive, fossil debris was subjected to infestation by bioeroders, dissolution, fragmentation, and physical reworking. This study reveals the episodic nature of carbonate deposition in polar settings and a reciprocal relationship with processes that deliver and redistribute siliciclastic debris. Carbonate production is most active during colder periods of the glacial-interglacial cycle, a potential new sedimentological paradigm for polar carbonate systems. Low accumulation rates and long residence

  19. Depositional belts in Nevada during the Famennian

    SciTech Connect

    Coles, K.S. )

    1991-02-01

    Deformed upper Famennian strata near the base of the Roberts Mountains allochthon in Nevada add detail to the paleogeography of the region at the time it was undergoing the transition from the shelf-slope setting of the early Paleozoic to the foreland basin and highland of the Antler orogeny. The uppermost Devonian part of the Pinecone sequence and correlative rocks in central and northeastern Nevada consists of black chert and argillite, commonly with nodular phosphate. Deposition took place in a detritus-starved, oxygen-poor slope or foredeep setting east of the advancing, but still submerged, Roberts Mountains allochthon. The Pinecone is less far-traveled than much of the allochthon as the time interval from deposition to the end of thrust movement and deformation was shorter. The late Famennian saw at least three contrasting belts of deposition in the vicinity of Nevada. First, black shale and micrite of the Leatham member of the Pilot Shale in eastern Nevada and western Utah formed in the deep subtidal/dysaerobic belt described by Sandberg and coworkers. Second, a bathyal belt, in central Nevada to the west of the Pilot, contained black chert and phosphate in a zone of high surface productivity. Also present, but rare, were beds of carbonate detritus with a probable provenance to the east, and olistoliths( ) of quartz sandstone like that known in the approaching Roberts Mountains allochthon to the west. Third, greenstones and chert of the Schoonover sequence, described by E. Miller and co-workers, were being deposited somewhere beyond the allochthon in an oxygenated, oceanic setting.

  20. Deposition of SOCs in forests

    SciTech Connect

    Horstmann, M.; McLachlan, M.S.

    1995-12-31

    The bulk deposition, wet-only deposition, dry-only deposition and ambient air concentrations of PCDD/Fs, PCBs and PAHs were measured in an 80 year old spruce forest, an 80 year old mixed deciduous (beech and oak) forest, and in an adjacent clearing over a period of 1--2 years. The deposition of the less volatile compounds that are primarily particle bound in the atmosphere was similar at both sites. These compounds were deposited primarily through wet deposition, as shown by the measurements in the clearing. In contrast, the deposition of the more volatile compounds was much higher at the forest sites than in the clearing. For instance, the annual deposition of Cl{sub 4}DF was 5 times higher in the spruce forest and 8 times higher in the deciduous forest. The excess deposition in the deciduous forest was almost completely due to the leaf fall in October--December, while about half of the excess deposition in the spruce forest was the result of needle fall. A further, as yet unexplained deposition mechanism accounted for the remainder of the flux in the spruce forest. Other studies have shown that more volatile SOCs are deposited to vegetation primarily through dry gaseous deposition. Hence, while forests have little influence on the deposition of less volatile compounds like the higher chlorinated PCDD/Fs and the 5--6 ring PAHs, dry deposition to leaves/needles and their subsequent falling to the forest floor make forest soils an extremely important sink for more volatile SOC.

  1. Synthesis and sup 31 P NMR spectroscopy of trinuclear, phosphido-bridged iridium and rhodium clusters. Crystal and molecular structures of (M sub 3 (. mu. -PPh sub 2 ) sub 3 (CO) sub n L sub 2 ) (M = Ir or Rh, n = 3, L sub 2 = bis(diphenylphosphino)methane: M = Ir, n = 5, L = t-BuNC)

    SciTech Connect

    Berry, D.E.; Browning, J.; Dehghan, K.; Dixon, K.R.; Meanwell, N.J.; Phillips, A.J. )

    1991-02-06

    Reaction of (Ir{sub 2}(cyclooctene){sub 4}Cl{sub 2}) with CO, NHEt{sub 2}, and PHPh{sub 2} provides a synthetic route to the trinuclear, phosphido-bridged iridium clusters (Ir{sub 3}({mu}-PPh{sub 2}){sub 3}(CO){sub n}L{sub 2}) (n = 3, L = CO or PPh{sub 3}, L{sub 2} = bis(diphenylphosphino)methane (dppm); n = 5, L = t-BuNC). The CO and PPh{sub 3} complexes are analogues of previously known rhodium derivatives, and rhodium analogues of the dppm and t-BuNC complexes are also reported. The crystal structure of both the Ir and Rh complexes was determined and are reported. The molecular structure was also determined. Complete analyses of the {sup 31}P NMR spectra of the prepared complexes are also reported.

  2. Multi-chamber deposition system

    DOEpatents

    Jacobson, Richard L.; Jeffrey, Frank R.; Westerberg, Roger K.

    1989-10-17

    A system for the simultaneous deposition of different coatings onto a thin web within a large volume vacuum chamber is disclosed which chamber is provided with a plurality of deposition chambers in which the different layers are deposited onto the film as its moves from a supply roll to a finished take-up roll of coated web. The deposition chambers provided within the large vacuum chamber are provided with separate seals which minimize back diffusion of any dopant gas from adjacent deposition chambers.

  3. Multi-chamber deposition system

    DOEpatents

    Jacobson, Richard L.; Jeffrey, Frank R.; Westerberg, Roger K.

    1989-06-27

    A system for the simultaneous deposition of different coatings onto a thin web within a large volume vacuum chamber is disclosed which chamber is provided with a plurality of deposition chambers in which the different layers are deposited onto the film as its moves from a supply roll to a finished take-up roll of coated web. The deposition chambers provided within the large vacuum chamber are provided with separate seals which minimize back diffusion of any dopant gas from adjacent deposition chambers.

  4. Database of recent tsunami deposits

    USGS Publications Warehouse

    Peters, Robert; Jaffe, Bruce E.

    2010-01-01

    This report describes a database of sedimentary characteristics of tsunami deposits derived from published accounts of tsunami deposit investigations conducted shortly after the occurrence of a tsunami. The database contains 228 entries, each entry containing data from up to 71 categories. It includes data from 51 publications covering 15 tsunamis distributed between 16 countries. The database encompasses a wide range of depositional settings including tropical islands, beaches, coastal plains, river banks, agricultural fields, and urban environments. It includes data from both local tsunamis and teletsunamis. The data are valuable for interpreting prehistorical, historical, and modern tsunami deposits, and for the development of criteria to identify tsunami deposits in the geologic record.

  5. Critical elements in sediment-hosted deposits (clastic-dominated Zn-Pb-Ag, Mississippi Valley-type Zn-Pb, sedimentary rock-hosted Stratiform Cu, and carbonate-hosted Polymetallic Deposits): A review: Chapter 12

    USGS Publications Warehouse

    Marsh, Erin; Hitzman, Murray W.; Leach, David L.

    2016-01-01

    Some sediment-hosted base metal deposits, specifically the clastic-dominated (CD) Zn-Pb deposits, carbonate-hosted Mississippi Valley-type (MVT) deposits, sedimentary-rock hosted stratiform copper deposits, and carbonate-hosted polymetallic (“Kipushi type”) deposits, are or have been important sources of critical elements including Co, Ga, Ge, and Re. The generally poor data concerning trace element concentrations in these types of sediment-hosted ores suggest that there may be economically important concentrations of critical elements yet to be recognized.

  6. Chemical vapor deposition sciences

    SciTech Connect

    1992-12-31

    Chemical vapor deposition (CVD) is a widely used method for depositing thin films of a variety of materials. Applications of CVD range from the fabrication of microelectronic devices to the deposition of protective coatings. New CVD processes are increasingly complex, with stringent requirements that make it more difficult to commercialize them in a timely fashion. However, a clear understanding of the fundamental science underlying a CVD process, as expressed through computer models, can substantially shorten the time required for reactor and process development. Research scientists at Sandia use a wide range of experimental and theoretical techniques for investigating the science of CVD. Experimental tools include optical probes for gas-phase and surface processes, a range of surface analytic techniques, molecular beam methods for gas/surface kinetics, flow visualization techniques and state-of-the-art crystal growth reactors. The theoretical strategy uses a structured approach to describe the coupled gas-phase and gas-surface chemistry, fluid dynamics, heat and mass transfer of a CVD process. The software used to describe chemical reaction mechanisms is easily adapted to codes that model a variety of reactor geometries. Carefully chosen experiments provide critical information on the chemical species, gas temperatures and flows that are necessary for model development and validation. This brochure provides basic information on Sandia`s capabilities in the physical and chemical sciences of CVD and related materials processing technologies. It contains a brief description of the major scientific and technical capabilities of the CVD staff and facilities, and a brief discussion of the approach that the staff uses to advance the scientific understanding of CVD processes.

  7. [Triglyceride deposit cardiomyovasculopathy].

    PubMed

    Hirano, Ken-Ichi

    2013-09-01

    Cholesterol is a vital causal factor and focus of research into heart diseases, however the involvement of triglycerides remains unclear. We recently reported a patient suffering from severe congestive heart failure and needing cardiac transplantation. Massive accumulation of triglycerides was noted in coronary atherosclerotic lesions as well as in the myocardium. We named this phenotype"triglyceride deposit cardiomyovasculopathy (TGCV)". The patient was identified as homozygous for a genetic mutation in the adipose triglyceride lipase (ATGL), an essential molecule for hydrolysis of intracellular triglycerides. In this paper, we describe clinical characteristics of ATGL deficiency and discuss what we can learn from this disorder.

  8. Rapid tooling by electron-beam vapor deposition

    SciTech Connect

    Meier, T. C., LLNL

    1998-02-25

    Electron-beam physical vapor deposition (EBPVD) of tooling metal, onto a shaped substrate to produce a replica of the substrate surface, offers the potential for significant cost savings over present methods of injection mold manufacturing. These savings are realized by the high deposition rate and the corresponding short manufacturing times provided by the EBPVD process. However, on route to realizing these gains, there are process technical issues which need to be resolved. Mold surfaces typically contain relatively high aspect ratio details that must be replicated to dimensional tolerances within +/- 2 mils. The deposited mold material must also provide high surface hardness and high fracture toughness. Good quality grain structure can be obtained in deposited Al 10-wt% Cu mold material when the substrate and corresponding deposit are at high process temperature. However, the resulting mold is subject to distortion during cooldown due to differential temperatures and shrinkage rates. Thermally controlled cooldown and the use of crushable substrate materials reduce these distortions, but not to the required levels of tolerance. Deposition of the Al-Cu at lower temperature produces columnar, poorly joined grains which result in a brittle and weakened mold material. When Al 10-wt% Cu metal vapor is deposited across high aspect ratio step features on the substrate surface, a grain growth defect can form in the step-shadowed regions of the deposited material, alongside the step feature. The step coverage defect consists of entrained voids which persist at intermediate deposition temperatures and produce a weakened mold. This final 1997 LDRD report investigates causes of this step coverage defect and offers methods for their control and elimination.

  9. Newly Discovered Alpha-poor Stars in the Solar Neighborhood

    NASA Astrophysics Data System (ADS)

    Xing, Q. F.; Zhao, G.

    2015-06-01

    We present an abundance analysis for two newly discovered α-poor stars based on high-resolution spectroscopy. These stars were previously identified in the Large Sky Area Multi-Object Fiber Spectroscopic Telescope (LAMOST) Data Release 1 as candidate α-poor stars. We observed these candidate α-poor stars with the Magellan Inamori Kyocera Echelle (MIKE) spectrograph on the 6.5 m Magellan-Clay Telescope located at Las Campanas Observatory. This high-resolution analysis confirms the low [α/Fe] abundance ratios for these stars compared to those of the majority of Galactic stars with comparable metallicities ([Fe/H] ∼ -0.5). The large deficiencies of α-elements suggest that these stars possess an anomalous chemical enrichment history. To have found such α-poor stars in our sample indicates that large scatters of the α-element abundance ratios may exist near solar metallicity. These results also demonstrate that our method is capable of selecting α-poor stars from low-resolution stellar spectra.

  10. Deposition System Controller

    2005-10-01

    This software is a complete thin film deposition controller. The software takes as its input a script file that dictates enablinig/disabling of sputtering power supplies, pause times, velocities and distances to move a substrate. An emulator has been created and built into the software package that can debug in advance any deposition script and decide if there is an overrun condition, accidental infinite look, and can estimate a time for completion. All necessary process variablesmore » are data logged and recorded for later inspection. This emulator currently interfaces to a Parker-Compumotor SX6 stepper moror indexer, but the software is written in such a way that it is easily modifiable for interface to othe brand and models of motor drivers. Other process I/O variables may be easily added. The software uses any multifunction DAQ card from National Instruments via their free NIDAQ API package, but again, the software is written such that othe brand DAQ cards may be used.« less

  11. Canyon Floor Deposits

    NASA Technical Reports Server (NTRS)

    2005-01-01

    [figure removed for brevity, see original site] Context image for PIA03598 Canyon Floor Deposits

    The layered and wind eroded deposits seen in this VIS image occur on the floor of Chandor Chasma.

    Image information: VIS instrument. Latitude 5.2S, Longitude 283.4E. 17 meter/pixel resolution.

    Note: this THEMIS visual image has not been radiometrically nor geometrically calibrated for this preliminary release. An empirical correction has been performed to remove instrumental effects. A linear shift has been applied in the cross-track and down-track direction to approximate spacecraft and planetary motion. Fully calibrated and geometrically projected images will be released through the Planetary Data System in accordance with Project policies at a later time.

    NASA's Jet Propulsion Laboratory manages the 2001 Mars Odyssey mission for NASA's Office of Space Science, Washington, D.C. The Thermal Emission Imaging System (THEMIS) was developed by Arizona State University, Tempe, in collaboration with Raytheon Santa Barbara Remote Sensing. The THEMIS investigation is led by Dr. Philip Christensen at Arizona State University. Lockheed Martin Astronautics, Denver, is the prime contractor for the Odyssey project, and developed and built the orbiter. Mission operations are conducted jointly from Lockheed Martin and from JPL, a division of the California Institute of Technology in Pasadena.

  12. Sediment Sources, Sedimentation Processes and Post-Depositional Changes of the 2011 Tohoku-Oki Tsunami Deposits on the Sendai Plain, Japan

    NASA Astrophysics Data System (ADS)

    Szczucinski, W.; Chague-Goff, C.; Goto, K.; Sugawara, D.; Jagodzinski, R.; Kokocinski, M.; Cachao, M.; Sternal, B.; Rzeszewski, M.; Goff, J. R.; Jaffe, B. E.

    2012-12-01

    The 11th March 2011 Tohoku-oki tsunami inundated the low-lying Sendai Plain (Japan) more than 5 km inland leaving sand and mud deposits over most of the area. In order to establish the sources of the tsunami deposits and interpret processes of their sedimentation, samples were collected from the deposits, underlying soils and the beach along a shore-perpendicular transect and analysed for grain size, heavy minerals, diatom assemblages and nannoliths. Surveys were undertaken 2, 5 and 7 months after the tsunami to assess the importance of post-depositional changes in tsunami deposits. The last survey took place shortly after a major typhoon. The fining-inland tsunami deposits consisted of poorly to moderately sorted medium to coarse sand within 2 km of the coastline and very poorly to poorly sorted mud farther inland. The tsunami deposits also exhibited vertical changes including fining upward and coupled coarsening-fining upward trends. Heavy minerals comprised on average 35% of the tsunami deposit in the 0.125 - 0.25 mm grain size fraction. Heavy mineral concentrations and assemblages were similar in the tsunami deposits, beach and underlying soils. Diatoms were rare in beach sediments, soils and tsunami deposits within 1 km of the coastline, while they were more abundant farther inland. Diatom assemblages in the soil and tsunami deposits were similar and dominated by species typical of freshwater-brackish habitats, while no typically marine species were encountered. Nannoliths were generally absent in the studied sediments, except for few specimens. Our data indicate that there was probably no or only a very minor component of marine sediments transported onland by the tsunami. The sandy tsunami deposits within ~1 km of the coastline were mostly derived from beach and dune erosion. From 1 to 2 km landward the contribution of these sources decreased, while sources comprising local soil and inland canal sediments increased. Farther inland, mud deposits were mostly

  13. Radioactive deposits in California

    USGS Publications Warehouse

    Walker, George W.; Lovering, Tom G.

    1954-01-01

    Reconnaissance examination by Government geologists of many areas, mine properties, and prospects in California during the period between 1948 and 1953 has confirmed the presence of radioactive materials in place at more than 40 localities. Abnormal radioactivity at these localities is due to concentrations of primary and secondary uranium minerals, to radon gas, radium (?), and to thorium minerals. Of the known occurrences only three were thought to contain uranium oxide (uranitite or pitchblende), 4 contained uranium-bearing columbate, tantalate, or titanate minerals, 12 contained secondary uranium minerals, such as autunite, carnotite, and torbernite, one contained radon gas, 7 contained thorium minerals, and, at the remaining 16 localities, the source of the anomalous radiation was not positively determined. The occurrences in which uranium oxide has been tentatively identified include the Rathgeb mine (Calaveras County), the Yerih group of claims (San Bernardino County), and the Rainbow claim (Madera County). Occurrences of secondary uranium minerals are largely confined to the arid desert regions of south-eastern California including deposits in San Bernardino, Kern, Inyo, and Imperial Counties. Uranium-bearing columbate, tantalate, or titanate minerals have been reported from pegmatite and granitic rock in southeastern and eastern California. Thorium minerals have been found in vein deposits in eastern San Bernardino County and from pegmatites and granitic rocks in various parts of southeastern California; placer concentrations of thorium minerals are known from nearly all areas in the State that are underlain, in part, by plutonic crystalline rocks. The primary uranium minerals occur principally as minute accessory crystals in pegmatite or granitic rock, or with base-metal sulfide minerals in veins. Thorium minerals also occur as accessory crystals in pegmatite or granitic rock, in placer deposits derived from such rock, and, at Mountain Pass, in veins

  14. Deposition Kinetics of Bioinspired Phenolic Coatings on Titanium Surfaces.

    PubMed

    Geißler, Sebastian; Barrantes, Alejandro; Tengvall, Pentti; Messersmith, Phillip B; Tiainen, Hanna

    2016-08-16

    Polyphenols can form functional coatings on a variety of different materials through auto-oxidative surface polymerization in a manner similar to polydopamine coatings. However, the mechanisms behind the coating deposition are poorly understood. We report the coating deposition kinetics of the polyphenol tannic acid (TA) and the simple phenolic compound pyrogallol (PG) on titanium surfaces. The coating deposition was followed in real time over a period of 24 h using a quartz crystal microbalance with dissipation monitoring (QCM-D). TA coatings revealed a multiphasic layer formation: the deposition of an initial rigid layer was followed by the buildup of an increasingly dissipative layer, before mass adsorption stopped after approximately 5 h of coating time. The PG deposition was biphasic, starting with the adsorption of a nonrigid viscoelastic layer which was followed by layer stiffening upon further mass adsorption. Coating evaluation by ellipsometry and AFM confirmed the deposition kinetics determined by QCM-D and revealed maximum coating thicknesses of approximately 50 and 75 nm for TA and PG, respectively. Chemical characterization of the coatings and polymerized polyphenol particles indicated the involvement of both physical and chemical interactions in the auto-oxidation reactions.

  15. Deposition Kinetics of Bioinspired Phenolic Coatings on Titanium Surfaces.

    PubMed

    Geißler, Sebastian; Barrantes, Alejandro; Tengvall, Pentti; Messersmith, Phillip B; Tiainen, Hanna

    2016-08-16

    Polyphenols can form functional coatings on a variety of different materials through auto-oxidative surface polymerization in a manner similar to polydopamine coatings. However, the mechanisms behind the coating deposition are poorly understood. We report the coating deposition kinetics of the polyphenol tannic acid (TA) and the simple phenolic compound pyrogallol (PG) on titanium surfaces. The coating deposition was followed in real time over a period of 24 h using a quartz crystal microbalance with dissipation monitoring (QCM-D). TA coatings revealed a multiphasic layer formation: the deposition of an initial rigid layer was followed by the buildup of an increasingly dissipative layer, before mass adsorption stopped after approximately 5 h of coating time. The PG deposition was biphasic, starting with the adsorption of a nonrigid viscoelastic layer which was followed by layer stiffening upon further mass adsorption. Coating evaluation by ellipsometry and AFM confirmed the deposition kinetics determined by QCM-D and revealed maximum coating thicknesses of approximately 50 and 75 nm for TA and PG, respectively. Chemical characterization of the coatings and polymerized polyphenol particles indicated the involvement of both physical and chemical interactions in the auto-oxidation reactions. PMID:27452793

  16. Fat, oil and grease deposits in sewers: characterisation of deposits and formation mechanisms.

    PubMed

    Williams, J B; Clarkson, C; Mant, C; Drinkwater, A; May, E

    2012-12-01

    Fat, oil and grease deposits (FOG) in sewers are a major problem and can cause sewer overflows, resulting in environmental damage and health risks. Often simplistically portrayed as cooling of fats, recent research has suggested that saponification may be involved in FOG formation. However there are still questions about the mechanisms effecting transformations in sewers and the role and source of metal cations involved in saponification. This study characterises FOG deposits from pumping stations, sewers and sewage works from different water hardness zones across the UK. The sites all had previous problems with FOG and most catchments contained catering and food preparation establishments. The FOG deposits were highly variable with moisture content ranging from 15 to 95% and oil content from 0 to 548 mg/g. Generally the pumping stations had lower moisture content and higher fat content, followed by the sewers then the sewage works. The water in contact with the FOG had high levels of oil (mean of about 800 mg/L) and this may indicate poor kitchen FOG management practices. FOG fatty acid profiles showed a transformation from unsaturated to saturated forms compared to typical cooking oils. This seems to relate to ageing in the sewer network or the mechanism of formation, as samples from pumping stations had higher proportions of C18:1 compared to C16. This may be due to microbial transformations by bacteria such as Clostridium sp. in a similar process to adipocere formation. There was an association between water hardness and increased Ca levels in FOG along with harder deposits and higher melting points. A link between FOG properties and water hardness has not been previously reported for field samples. This may also be due to microbial processes, such as biocalcification. By developing the understanding of these mechanisms it may be possible to more effectively control FOG deposits, especially when combined with promotion of behavioural change.

  17. Fat, oil and grease deposits in sewers: characterisation of deposits and formation mechanisms.

    PubMed

    Williams, J B; Clarkson, C; Mant, C; Drinkwater, A; May, E

    2012-12-01

    Fat, oil and grease deposits (FOG) in sewers are a major problem and can cause sewer overflows, resulting in environmental damage and health risks. Often simplistically portrayed as cooling of fats, recent research has suggested that saponification may be involved in FOG formation. However there are still questions about the mechanisms effecting transformations in sewers and the role and source of metal cations involved in saponification. This study characterises FOG deposits from pumping stations, sewers and sewage works from different water hardness zones across the UK. The sites all had previous problems with FOG and most catchments contained catering and food preparation establishments. The FOG deposits were highly variable with moisture content ranging from 15 to 95% and oil content from 0 to 548 mg/g. Generally the pumping stations had lower moisture content and higher fat content, followed by the sewers then the sewage works. The water in contact with the FOG had high levels of oil (mean of about 800 mg/L) and this may indicate poor kitchen FOG management practices. FOG fatty acid profiles showed a transformation from unsaturated to saturated forms compared to typical cooking oils. This seems to relate to ageing in the sewer network or the mechanism of formation, as samples from pumping stations had higher proportions of C18:1 compared to C16. This may be due to microbial transformations by bacteria such as Clostridium sp. in a similar process to adipocere formation. There was an association between water hardness and increased Ca levels in FOG along with harder deposits and higher melting points. A link between FOG properties and water hardness has not been previously reported for field samples. This may also be due to microbial processes, such as biocalcification. By developing the understanding of these mechanisms it may be possible to more effectively control FOG deposits, especially when combined with promotion of behavioural change. PMID:23039918

  18. The characteristics of coignimbrite deposits and inferences for their formation

    NASA Astrophysics Data System (ADS)

    Engwell, S. L.; Eychenne, J.; Wulf, S.; De'Michieli Vitturi, M.

    2014-12-01

    Coignimbrite deposits form as fine-grained ash (< 250 microns) is lofted into the atmosphere from the top of pyroclastic density currents, producing convective plumes. Such material can be transported over continental sized areas and the fine-grained nature of this ash means that it poses great hazard, in respect to health, infrastructure and air traffic. To date, few coignimbrite deposits have been studied in detail, mainly due to their poor preservation potential, and difficulty distinguishing these deposits from Plinian deposits. As such, there is little in the published record regarding the physical characteristics of coignimbrite deposits. Deposits from Lago Grande di Monticchio, a maar lake 120 km east of the Campanian Volcanic Zone, Italy were analysed for this study. These lake sediments contain more than 340 distinct tephra layers, of which more than 300 are thought to have originated from the Campanian region. The physical characteristics of deposits from eruptions from within the past 50 kyrs are studied with particular emphasis placed on those with a known pyroclastic density current phase. Results show that in most cases, stratigraphy is comparable to proximal stratigraphy, and in the case of the Campanian Ignimbrite (Phlegrean Fields, 39.3 ka) and Monte Epomeo Green Tuff (Ischia, 55 ka) particularly, the coignimbrite contribution is easily identified. These coignimbrite deposits are composed of glass shards, with very small lithic and expanded pumice contents. Grainsize data from these coignimbrite events show remarkably similar characteristics, typically described by a very fine-grained mode (~50 microns), and poor sorting. This fine grain size implicates aggregation as the dominant process by which this ash is deposited. Similar trends are identified in the literature, for different types and scales of eruptions indicating the grainsize of these deposits is controlled by current dynamics rather than primary eruptive conditions at the vent. The

  19. Luminescence dating of Middle Stone Age deposits at Die Kelders.

    PubMed

    Feathers, J K; Bush, D A

    2000-01-01

    Luminescence dating of sediments has not been used extensively for dating Middle Stone Age deposits in South Africa, despite its potential for contributing to a poorly dated record. Such deposits at Die Kelders cave, on the southern South African coast, consist of narrow bands of occupation debris separated by thicker layers of aeolian sands containing much less evidence of occupation. Homogeneous, aeolian sediments are usually considered ideal for luminescence dating. Here we report luminescence analyses of five samples from these sands that demonstrate sufficient bleaching prior to burial to validate dating and that yield ages of about 60-70 ka, in agreement with other evidence from sedimentology, archaeology and electron spin resonance. Lack of significant differences in the ages suggests the deposits accumulated fairly rapidly during the early part of the Last Glaciation. PMID:10627398

  20. Spatial variation in atmospheric nitrogen deposition on low canopy vegetation.

    PubMed

    Verhagen, Rene; van Diggelen, Rudy

    2006-12-01

    Current knowledge about the spatial variation of atmospheric nitrogen deposition on a local scale is limited, especially for vegetation with a low canopy. We measured nitrogen deposition on artificial vegetation at variable distances of local nitrogen emitting sources in three nature reserves in the Netherlands, differing in the intensity of agricultural practices in the surroundings. In the nature reserve located in the most intensive agricultural region nitrogen deposition decreased with increasing distance to the local farms, until at a distance of 1500 m from the local nitrogen emitting sources the background level of 15 kg N ha(-1) yr(-1) was reached. No such trend was observed in the other two reserves. Interception was considerably lower than in woodlands and hence affected areas were larger. The results are discussed in relation to the prospects for the conservation or restoration of endangered vegetation types of nutrient-poor soil conditions.