Sample records for platinum metals group

  1. Platinum Group Metals New Material

    Institute of Scientific and Technical Information of China (English)

    XIE Ming; ZHANG Jiankang; WANG Saibei; HU Jieqiong; LIU Manmen; CHEN Yongtai; ZHANG Jiming; YANG Youcai; YANG Yunfeng; ZHANG Guoquan


    Platinum group metals (PGM) include six elements,namely Pt,Pd,Rh,Ir,Os and Ru.PGM and their alloys are the important fundamental materials for modern industry and national defense construction,they have special physical and chemical properties,widely used in metallurgy,chemical,electric,electronic,information,energy,environmental protection,aviation,aerospace,navigation and other high technology industry.Platinum group metals and their alloys,which have good plasticity and processability,can be processed to electrical contact materials,resistance materials,solder,electronic paste,temperature-measurement materials,elastic materials,magnetic materials and high temperature structural materials.

  2. Exhaust system having a gold-platinum group metal catalyst

    Energy Technology Data Exchange (ETDEWEB)

    Ragle, Christie Susan [Havana, IL; Silver, Ronald G [Peoria, IL; Zemskova, Svetlana Mikhailovna [Edelstein, IL; Eckstein, Colleen J [Metamora, IL


    A method of providing an exhaust treatment device is disclosed. The method includes applying a catalyst including gold and a platinum group metal to a particulate filter. The concentration of the gold and the platinum group metal is sufficient to enable oxidation of carbon monoxide and nitric oxide.

  3. Development of radioactive platinum group metal catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Chung, H.S.; Kim, Y.S.; Kim, Y.E. [and others


    The fission product nuclides generated during the irradiation of reactor fuel include many useful elements, among them platinum group metals such as ruthenium, rhodium and palladium which are of great industrial importance, occur rarely in nature and are highly valuable. In this research, the authors reviewed various PGM recovery methods. Recovery of palladium from seven-component simulated waste solutions was conducted by selective precipitation method. The recovery yield was more than 99.5% and the purity of the product was more than 99%. Wet-proof catalyst was prepared with the recovered palladium. The specific surface area of the catalyst support was more than 400m{sup 2}/g.The content of palladium impregnated on the support was 1 to 10 wt. %. Hydrogen isotope exchange efficiency of more than 93% to equilibrium with small amount of the catalyst was obtained. It was turned out possible to consider using such palladium or other very low active PGM materials in applications where its activity is unimportant as in nuclear industries. (author). 86 refs., 44 tabs., 88 figs.

  4. Development of radioactive platinum group metal catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Chung, H.S.; Kim, Y.S.; Kim, Y.E. [and others


    The fission product nuclides generated during the irradiation of reactor fuel include many useful elements, among them platinum group metals such as ruthenium, rhodium and palladium which are of great industrial importance, occur rarely in nature and are highly valuable. In this research, the authors reviewed various PGM recovery methods. Recovery of palladium from seven-component simulated waste solutions was conducted by selective precipitation method. The recovery yield was more than 99.5% and the purity of the product was more than 99%. Wet-proof catalyst was prepared with the recovered palladium. The specific surface area of the catalyst support was more than 400m{sup 2}/g.The content of palladium impregnated on the support was 1 to 10 wt. %. Hydrogen isotope exchange efficiency of more than 93% to equilibrium with small amount of the catalyst was obtained. It was turned out possible to consider using such palladium or other very low active PGM materials in applications where its activity is unimportant as in nuclear industries. (author). 86 refs., 44 tabs., 88 figs.

  5. Platinum group metal nitrides and carbides: synthesis, properties and simulation

    Energy Technology Data Exchange (ETDEWEB)

    Ivanovskii, Alexander L [Institute of Solid State Chemistry, Urals Branch of the Russian Academy of Sciences, Ekaterinburg (Russian Federation)


    Experimental and theoretical data on new compounds, nitrides and carbides of the platinum group 4d and 5d metals (ruthenium, rhodium, palladium, osmium, iridium, platinum), published over the past five years are summarized. The extreme mechanical properties of platinoid nitrides and carbides, i.e., their high strength and low compressibility, are noted. The prospects of further studies and the scope of application of these compounds are discussed.

  6. Mineral resource of the month: platinum group metals (United States)

    Loferski, Patricia J.


    The article focuses on platinum group metals (PGMs) and their properties. According to the author, PGMs, which include iridium, osmium, palladium, platinum, rhodium, and ruthenium, are among the rarest mineral commodities in the Earth's crust. PGMs are primarily used as catalytic converters that clean harmful exhaust from vehicle engines. They are also used in the chemical industry as catalysts in the production of nitric acid and in the petroleum refining industry.

  7. Recent strikes in South Africa’s platinum-group metal mines: effects upon world platinum-group metal supplies (United States)

    Yager, Thomas R.; Soto-Viruet, Yadira; Barry, James J.


    The recent labor disputes over wages and working conditions that have affected South Africa’s three leading platinum-group metal (PGM) producers have affected an industry already plagued by market pressures and labor unrest and raised the specter of constraints in the world’s supply of these metals. Although low demand for these metals in 2011 and 2012 helped to offset production losses of recent years, and particularly those losses caused by the strikes in 2012, a prolonged resumption of strikes could cause severe shortages of iridium, platinum, rhodium, ruthenium, and, to a lesser extent, palladium.

  8. Effect of Platinum Group Metal Doping in Magnesium Diboride Wires

    DEFF Research Database (Denmark)

    Grivel, Jean-Claude; Alexiou, Aikaterini; Namazkar, Shahla


    The effect of some platinum group metals(PGM = Rh, Pd, and Pt) on the microstructure and critical current density of Cu/Nb-sheathed MgB2 wires has been studied using Mg1-x PGMxB2 powders with low doping levels. It was found that Pt and Pd do not enter the MgB2 lattice and have only limited....... The results are discussed in comparison with previous investigations using other transition metals for doping on the Mg site....

  9. Modeling platinum group metal complexes in aqueous solution. (United States)

    Lienke, A; Klatt, G; Robinson, D J; Koch, K R; Naidoo, K J


    We construct force fields suited for the study of three platinum group metals (PGM) as chloranions in aqueous solution from quantum chemical computations and report experimental data. Density functional theory (DFT) using the local density approximation (LDA), as well as extended basis sets that incorporate relativistic corrections for the transition metal atoms, has been used to obtain equilibrium geometries, harmonic vibrational frequencies, and atomic charges for the complexes. We found that DFT calculations of [PtCl(6)](2-).3H(2)O, [PdCl(4)](2-).2H(2)O, and [RhCl(6)](3-).3H(2)O water clusters compared well with molecular mechanics (MM) calculations using the specific force field developed here. The force field performed equally well in condensed phase simulations. A 500 ps molecular dynamics (MD) simulation of [PtCl(6)](2-) in water was used to study the structure of the solvation shell around the anion. The resulting data were compared to an experimental radial distribution function derived from X-ray diffraction experiments. We found the calculated pair correlation functions (PCF) for hexachloroplatinate to be in good agreement with experiment and were able to use the simulation results to identify and resolve two water-anion peaks in the experimental spectrum.

  10. Pyrometallurgical Recovery of Platinum Group Metals from Spent Catalysts (United States)

    Peng, Zhiwei; Li, Zhizhong; Lin, Xiaolong; Tang, Huimin; Ye, Lei; Ma, Yutian; Rao, Mingjun; Zhang, Yuanbo; Li, Guanghui; Jiang, Tao


    As an important secondary resource with abundant platinum group metals (PGMs), spent catalysts demand recycling for both economic and environmental benefits. This article reviews the main pyrometallurgical processes for PGM recovery from spent catalysts. Existing processes, including smelting, vaporization, and sintering processes, are discussed based in part on a review of the physiochemical characteristics of PGMs in spent catalysts. The smelting technology, which produces a PGM-containing alloy, is significantly influenced by the addition of various collectors, such as lead, copper, iron, matte, or printed circuit board (PCB), considering their chemical affinities for PGMs. The vaporization process can recover PGMs in vapor form at low temperatures (250-700°C), but it suffers high corrosion and potential environmental and health risks as a result of involvement of the hazardous gases, mainly Cl2 and CO. The sintering process serves as a reforming means for recycling of the spent catalysts by in situ reduction of their oxidized PGMs components. Among these processes, the smelting process seems more promising although its overall performance can be further improved by seeking a suitable target-oriented collector and flux, together with proper pretreatment and process intensification using an external field.

  11. Platinum group metal recovery and catalyst manufacturing process

    Energy Technology Data Exchange (ETDEWEB)

    Chung, H. S.; Kim, Y. S.; Yoo, J. H.; Lee, H. S.; Ahn, D. H.; Kim, K. R.; Lee, S. H.; Paek, S. W.; Kang, H. S.


    The fission product nuclides generated during the irradiation of reactor fuel include many useful elements, among them platinum group metal such as ruthenium, rhodium and palladium which are of great industrial importance, occur rarely in nature and are highly valuable. In this research, the authors reviewed various PGM recovery methods. Recovery of palladium from seven-component simulated waste solution was conducted by selective precipitation method. The recovery yield was more than 99.5% and the purity of the product was more than 99%. Wet-proof catalyst was prepared with the recovered palladium. The specific surface area of the catalyst support was more than 400 m{sup 2}/g. The content of palladium impregnated on the support was 10 wt.%. Hydrogen isotope exchange efficiency of 93 % to equilibrium with small amount of the catalyst was obtained. It was turned out possible to consider using such palladium or other very low active PGM materials in applications where its actively is unimportant as in nuclear industries. (author). 63 refs., 38 tabs., 36 figs.

  12. X-ray characterization of platinum group metal catalysts (United States)

    Peterson, Eric J.

    Platinum group metals (PGMs) are used extensively as catalysts, employed in several sectors of the world energy economy. Fuel cells employing PGM catalysts show promise as power sources in the proposed hydrogen economy, using alcohols as hydrogen storage media. Currently, the most economically important application for PGMs is for the mitigation of emissions from internal combustion engines via catalytic converters. In all applications, efficient use of these expensive metals to fabricate robust catalysts is of the utmost importance. Understanding the catalyst structure/property relationship is the key to the improvement of existing catalysts and the discovery of new catalysts. For example, catalyst particle size can have profound effects on catalyst activity, as in the case of gold nanoparticles. Catalyst particle size control and stability is also important for the efficient use of PGM metals and catalyst deactivation prevention. The challenge is to identify and characterize structural features and determine if and how these features may relate to catalytic properties. The ultimate goal is to simultaneously measure catalyst structural characteristics and catalytic properties under operando conditions, unambiguously establishing the structure/property link. X-ray diffraction (XRD) and X-ray absorption spectroscopy (XAS) are important techniques used for the characterization of PGM catalysts. Microstructural information such as crystallite size, as small as ~ 1 nm, and microstrain can be obtained from Bragg diffraction peak shapes in X-ray diffraction patterns, and long range crystal structure information is found in the intensities and positions of these peaks. In contrast, X-ray absorption spectroscopy provides information about the chemical state and local structure of selected atoms. From the average nearest neighbor coordination numbers, crystallite sizes can also be inferred, with particularly high sensitivity in the sub-nm size range. Electron microscopy

  13. The platinum group metals in Younger Dryas Horizons are terrestrial (United States)

    Wu, Y.; Wikes, E.; Kennett, J.; West, A.; Sharma, M.


    The Younger Dryas (YD) event, which began 12,900 years ago, was a period of abrupt and rapid cooling in the Northern Hemisphere whose primary cause remains unclear. The prevalent postulated mechanism is a temporary shutdown of the thermohaline circulation following the breakup of an ice dam in North America. Firestone et al. (2007) proposed that the cooling was triggered by multiple cometary airbursts and/or impacts that engendered enormous environmental changes and disrupted the thermohaline circulation. The evidence in support for this hypothesis is a black layer in North America and in Europe marking the YD boundary containing charcoal, soot, carbon spherules and glass-like carbon suggesting extensive and intense forest fires. This layer is also enriched in magnetic grains high in iridium, magnetic microspherules, fullerenes containing extraterrestrial He-3, and nanodiamonds. Whereas the nanodiamonds could be produced in an impact or arrive with the impactor, the cometary burst/impact hypothesis remains highly controversial as the YD horizon lacks important impact markers such as craters, breccias, tektites and shocked minerals. Firestone et al. (2007) contend that bulk of Ir found at the YD boundary is associated with magnetic grains. The key issue is whether this Ir is meteorite derived. We used Ir and Os concentrations and Os isotopes to investigate the provenance of the platinum group metals in the YD horizon. The bulk sediment samples from a number of North American YD sites (Blackwater Draw, Murray Springs, Gainey, Sheriden Cave, and Myrtle Beach) and a site in Europe (Lommel) do not show any traces of meteorite derived Os and Ir. The [Os] = 2 to 45 pg/g in these sediments and the 187Os/188Os ratios are similar to the upper continental crustal values (~1.3), much higher than those in meteorites (0.13). Higher [Os] is observed in Blackwater Draw (= 194 pg/g). However, the Os/Ir ratio in Blackwater Draw is 5 (not 1 as expected for a meteorite) and 187Os/188

  14. Friction behavior of members of the platinum metals group with gold (United States)

    Buckley, D. H.


    The adhesion and friction behavior of the platinum metals group was examined with clean surfaces and surfaces selectively contaminated with oxygen, vinyl chloride (C2H3Cl), and methyl mercaptan (CH3SH). A pin or disk specimen configuration was used with the pin being a single crystal of gold of the (111) orientation and with the platinum metal disks also being single crystals of the (111) or (0001) orientation. Loads applied ranged from 1 to 10 g and a sliding velocity of 0.7 mm/min was employed. Results indicate adhesion and transfer of gold to all of the platinum metals. Despite this observation friction differences existed among the metals in the group. These differences are related to surface chemical activity. Adsorption of various friction reducing species was selective. With some adsorbates present strong adhesive forces between metals were still observed.

  15. Reviews of Metallurgical Technology to Recovery Platinum Group Metals from Secondary Resource in China

    Institute of Scientific and Technical Information of China (English)

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


    China is extremely poor in mineral resources of Platinum Group Metals (PGMs),productive output of PGMs from mineral resource is 2.5 tons per year.At the same time,China is the biggest PGMs consumption country in the world,the mineral resource of PGMs is critical shortage,it shows the importance of recycling the secondary resource of PGMs.Sino-Platinum Metals Resource (Yimen) Co., the leader in recycling of PGMs from secondary resource,and has made outstanding contributions to China PGMs secondary resources recycling.This article elucidates the current situation of secondary resources recovery and development of metallurgical technology for PGMs.

  16. Platinum Group Metal Recycling Technology Development - Final Report

    Energy Technology Data Exchange (ETDEWEB)

    Lawrence Shore


    BASF Catalysts LLC, formerly Engelhard Corporation, has completed a project to recover Pt from PEM fuel cell membrane electrode assemblies. The project, which began in 2003, has met the project objective of an environmentally-friendly, cost-effective method for recovery of platinum without release of hydrogen fluoride. This has been achieved using a combination of milling, dispersion and acid leaching. 99% recovery of Pt was achieved, and this high yield can be scaled up using one vessel for a single leach and rinse. Leaching was been successfully achieved using a 10% solids level, double the original target. At this solids content, the reagent and utility costs represent ~0.35% of the Pt value of a lot, using very conservative assumptions. The main cost of the process is capital depreciation, followed by labor.

  17. Peruvian perovskite Between Transition-metal to PGM/PlatinumGroupMetal Catalytic Fusion (United States)

    Maksoed, Wh-


    Strongly correlated electronic materials made of simple building blocks, such as a transition-metal ion in an octahedral oxygen cage forming a perovskite structure- Dagotto & Tokura for examples are the high-temperature superconductivity & the CMR/Colossal Magnetoresistance . Helium-4 denotes from LC Case,ScD: "Catalytic Fusion of Deuterium into Helium-4"- 1998 dealt with gaseous D2- "contacted with a supported metallic catalyst at superatmospheric pressure". The catalyst is a platinum-group metal, at about 0.5% - 1% by weight, on activated C. Accompanies Stephen J Geier, 2010 quotes "transition metal complexes", the Energy thus produced is enormous, and because the deuterium is very cheap in the form of heavy water (less than US 1/g), the fuel cost is very low (<<1 %/KwH). "The oceans contain enough deuterium to satisfy the Earth's energy needs for many millions of year" to keep "maria"/Latin name of seas &Deuteronomy to be eternally preserves. Heartfelt Gratitudes to HE. Mr. Prof. Ir. HANDOJO.

  18. Platinum metals in the environment

    Energy Technology Data Exchange (ETDEWEB)

    Zereini, Fathi [Frankfurt Univ. (Germany). Dept. of Environmental Analytical Chemistry; Wiseman, Clare L.S. (ed.) [Toronto Univ. (Canada). School of the Environment


    This book contains the five chapters with the following topics: 1. SOURCES OF PGE EMISSIONS ELEMENTS: Sources of Platinum Group Elements (PGE) in the Environment; Impact of Platinum Group Element Emissions from Mining and Production Activities. 2. ANALYTICAL METHODS FOR THE DETERMINATION OF PGE IN BIOLOGICAL AND ENVIRONMENTAL MATRICES: Appraisal of Biosorption for Recovery, Separation and Determination of Platinum, Palladium and Rhodium in Environmental Samples; On the Underestimated Factors Influencing the Accuracy of Determination of Pt and Pd by Electrothermal Atomic Absorption Spectrometry in Road Dust Samples; Application of Solid Sorbents for Enrichment and Separation of Platinum Metal Ions; Voltammetric Analysis of Platinum in Environmental Matrices; Speciation Analysis of Chloroplatinates; Analysis of Platinum Group Elements in Environmental Samples: A Review. 3. OCCURRENCE, CHEMICAL BEHAVIOR AND FATE OF PGE IN THE ENVIRONMENT: Brazilian PGE Research Data Survey on Urban and Roadside Soils; Platinum, Palladium and Rhodium in a Bavarian Roadside Soil; Increase of Platinum Group Element Concentrations in Soils and Airborne Dust During the Period of Vehicular Exhaust Catalysts Introduction; Platinum-Group Elements in Urban Fluvial Bed Sediments-Hawaii; Long-Term Monitoring of Palladium and Platinum Contents in Road Dust of the City of Munich, Germany; Characterization of PGEs and Other Elements in Road Dusts and Airborne Particles in Houston, Texas; Accumulation and Distribution of Pt and Pd in Roadside Dust, Soil and Vegetation in Bulgaria; Increase of the Environmental Pt Concentration in the Metropolitan Area of Mexico City Associated to the Use of Automobile Catalytic Converters; Solubility of Emitted Platinum Group Elements (Pt, Pd and Rh) in Airborne Particulate Matter (PM10) in the Presence of Organic Complexing Agents; The Influence of Anionic Species (Cl{sup -}, NO{sub 3}{sup -}, SO{sub 4}{sup 2-}) on the Transformation and Solubility of Platinum in

  19. Hydrothermal synthesis of platinum-group-metal nanoparticles by using HEPES as a reductant and stabilizer. (United States)

    So, Man-Ho; Ho, Chi-Ming; Chen, Rong; Che, Chi-Ming


    Platinum-group-metal (Ru, Os, Rh, Ir, Pd and Pt) nanoparticles are synthesized in an aqueous buffer solution of 4-(2-hydroxyethyl)-1-piperazineethanesulfonic acid (HEPES) (200 mM, pH 7.4) under hydrothermal conditions (180 degrees C). Monodispersed (monodispersity: 11-15%) metal nanoparticles were obtained with an average particle size of less than 5 nm (Ru: 1.8+/-0.2, Os: 1.6+/-0.2, Rh: 4.5+/-0.5, Ir: 2.0+/-0.3, Pd: 3.8+/-0.4, Pt: 1.9+/-0.2 nm). The size, monodispersity, and stability of the as-obtained metal nanoparticles were affected by the HEPES concentration, pH of the HEPES buffer solution, and reaction temperature. HEPES with two tertiary amines (piperazine groups) and terminal hydroxyl groups can act as a reductant and stabilizer. The HEPES molecules can bind to the surface of metal nanoparticles to prevent metal nanoparticles from aggregation. These platinum-group-metal nanoparticles could be deposited onto the surface of graphite, which catalyzed the aerobic oxidation of alcohols to aldehydes.


    Directory of Open Access Journals (Sweden)

    V. V. Primachenko


    Full Text Available As the result of the studies at PJSC « UKRNIIO them. A.S.Berezhnogo» the technology and commercial production of crucibles from stabilized zirconia for the smelting of platinum group metals are develop

  1. Leaching platinum-group metals in a sulfuric acid/chloride solution (United States)

    Mahmoud, M. H. H.


    A leaching process was established based on the ability of platinum-group metals to form stable chloro-complexes in acidic chloride solutions. Industrial catalyst losses were examined for the recovery of platinum, palladium, and rhodium by leaching with a mixture of sulfuric acid and sodium chloride to avoid using aqua regia or autoclave conditions. Extraction of platinum and rhodium in 60% H2SO4 at 135°C steadily increased with increasing NaCl concentrations reaching 95% and 85%, respectively, at 0.1 M NaCl after two hours. By comparison, palladium was dissolved more quickly but also reached 85% under the same conditions. Extraction of each metal increased with temperatures up to 125°C but plateaued at higher temperatures. Similar behavior was observed with increasing H2SO4 concentrations up to 60%. More than 99% extraction of each metal was obtained after ten hours using 0.1 M NaCl and 60% H2SO4 at 125°C.

  2. Global exploration and production capacity for platinum-group metals from 1995 through 2015 (United States)

    Wilburn, David R.


    Platinum-group metals (PGMs) are required in a variety of commercial, industrial, and military applications for many existing and emerging technologies, yet the United States is highly dependent on foreign sources of PGMs. Information on global exploration for PGMs since 1995 has been used in this study as a basis for identifying locations where the industry has determined that exploration has provided data sufficient to warrant development of a new mine or expansion of an existing operation or where a significant increase in capacity for PGMs is anticipated by 2015. Discussions include an overview of the industry and the selected sites, factors affecting mineral supply, and circumstances leading to the development of mineral properties with the potential to affect mineral supply. Of the 52 sites or regional operations that were considered in this analysis, 16 sites were producing before 1995, 28 sites commenced production from 1995 through 2010, and 8 sites were expected to begin production from 2011 through 2015 if development plans came to fruition. The United States imports PGMs primarily from Canada, Russia, South Africa, and Zimbabwe to meet increasing demand for these materials in a variety of specialized and high-tech applications. Feed sources of PGMs are changing in South Africa and Russia, which together accounted for about 89 percent of platinum production and 82 percent of palladium production in 2009. A greater amount of South African PGM capacity is likely to come from deeper, higher cost Upper Group Reef seam 2 deposits and deposits in the Eastern Bushveld area. Future Russian PGM capacity is likely to come from ore zones with generally lower PGM content and different platinum-to-palladium ratios than the nickel-rich ore that dominated PGM supply in the 1990s. Because PGM supply from Canada and Russia is derived as a byproduct of copper and nickel mining, the PGM supply from these countries is influenced by economic, environmental, political, and

  3. Global exploration and production capacity for platinum-group metals from 1995 through 2015 (United States)

    Wilburn, David R.


    Platinum-group metals (PGMs) are required in a variety of commercial, industrial, and military applications for many existing and emerging technologies, yet the United States is highly dependent on foreign sources of PGMs. Information on global exploration for PGMs since 1995 has been used in this study as a basis for identifying locations where the industry has determined that exploration has provided data sufficient to warrant development of a new mine or expansion of an existing operation or where a significant increase in capacity for PGMs is anticipated by 2015. Discussions include an overview of the industry and the selected sites, factors affecting mineral supply, and circumstances leading to the development of mineral properties with the potential to affect mineral supply. Of the 52 sites or regional operations that were considered in this analysis, 16 sites were producing before 1995, 28 sites commenced production from 1995 through 2010, and 8 sites were expected to begin production from 2011 through 2015 if development plans came to fruition. The United States imports PGMs primarily from Canada, Russia, South Africa, and Zimbabwe to meet increasing demand for these materials in a variety of specialized and high-tech applications. Feed sources of PGMs are changing in South Africa and Russia, which together accounted for about 89 percent of platinum production and 82 percent of palladium production in 2009. A greater amount of South African PGM capacity is likely to come from deeper, higher cost Upper Group Reef seam 2 deposits and deposits in the Eastern Bushveld area. Future Russian PGM capacity is likely to come from ore zones with generally lower PGM content and different platinum-to-palladium ratios than the nickel-rich ore that dominated PGM supply in the 1990s. Because PGM supply from Canada and Russia is derived as a byproduct of copper and nickel mining, the PGM supply from these countries is influenced by economic, environmental, political, and

  4. Activity targets for nanostructured platinum-group-metal-free catalysts in hydroxide exchange membrane fuel cells (United States)

    Setzler, Brian P.; Zhuang, Zhongbin; Wittkopf, Jarrid A.; Yan, Yushan


    Fuel cells are the zero-emission automotive power source that best preserves the advantages of gasoline automobiles: low upfront cost, long driving range and fast refuelling. To make fuel-cell cars a reality, the US Department of Energy has set a fuel cell system cost target of US$30 kW-1 in the long-term, which equates to US$2,400 per vehicle, excluding several major powertrain components (in comparison, a basic, but complete, internal combustion engine system costs approximately US$3,000). To date, most research for automotive applications has focused on proton exchange membrane fuel cells (PEMFCs), because these systems have demonstrated the highest power density. Recently, however, an alternative technology, hydroxide exchange membrane fuel cells (HEMFCs), has gained significant attention, because of the possibility to use stable platinum-group-metal-free catalysts, with inherent, long-term cost advantages. In this Perspective, we discuss the cost profile of PEMFCs and the advantages offered by HEMFCs. In particular, we discuss catalyst development needs for HEMFCs and set catalyst activity targets to achieve performance parity with state-of-the-art automotive PEMFCs. Meeting these targets requires careful optimization of nanostructures to pack high surface areas into a small volume, while maintaining high area-specific activity and favourable pore-transport properties.

  5. Activity targets for nanostructured platinum-group-metal-free catalysts in hydroxide exchange membrane fuel cells. (United States)

    Setzler, Brian P; Zhuang, Zhongbin; Wittkopf, Jarrid A; Yan, Yushan


    Fuel cells are the zero-emission automotive power source that best preserves the advantages of gasoline automobiles: low upfront cost, long driving range and fast refuelling. To make fuel-cell cars a reality, the US Department of Energy has set a fuel cell system cost target of US$30 kW(-1) in the long-term, which equates to US$2,400 per vehicle, excluding several major powertrain components (in comparison, a basic, but complete, internal combustion engine system costs approximately US$3,000). To date, most research for automotive applications has focused on proton exchange membrane fuel cells (PEMFCs), because these systems have demonstrated the highest power density. Recently, however, an alternative technology, hydroxide exchange membrane fuel cells (HEMFCs), has gained significant attention, because of the possibility to use stable platinum-group-metal-free catalysts, with inherent, long-term cost advantages. In this Perspective, we discuss the cost profile of PEMFCs and the advantages offered by HEMFCs. In particular, we discuss catalyst development needs for HEMFCs and set catalyst activity targets to achieve performance parity with state-of-the-art automotive PEMFCs. Meeting these targets requires careful optimization of nanostructures to pack high surface areas into a small volume, while maintaining high area-specific activity and favourable pore-transport properties.

  6. Competitive platinum-group-metal (PGM) supply from the Eastern Limb, Bushveld Complex: Geological, mining and mineral economic aspects

    CSIR Research Space (South Africa)

    McGill, JE


    Full Text Available -GROUP-METAL (PGM) SUPPLY FROM THE EASTERN LIMB, BUSHVELD COMPLEX: GEOLOGICAL, MINING, AND MINERAL ECONOMIC ASPECTS Dr. Jeannette E. McGill & Prof. Murray W. Hitzman ACKNOWLEDGEMENTS ? COUNCIL FOR SCIENTIFIC AND INDUSTRIAL RESEARCH (CSIR) ? Centre for Mining... Innovation ? Office of Graduate Studies, Fogarty Endowment ? Mr. VISHNU PILLAY (EXECUTIVE HEAD: JV?S ? Anglo Platinum) ? ACADEMIC ADVISORS Prof. Murray Hitzman (Economic Geology); Dr. Hugh Miller (Mining Engineering); Prof. Rodderick Eggert (Mineral...

  7. Thermal Balance of the Magneto-Hydro-Dynamic Pump for Recovery of Platinum Group Metals from Spent Auto Catalysts

    Directory of Open Access Journals (Sweden)

    Gil S.


    Full Text Available Every new car should be equipped with the catalyst, which limits the amount of harmful chemical compounds such as NOx, CH and CO emitted to the air. Auto catalyst consists of the ceramic or metallic carrier, on which is the layer with Platinum Group Metals playing catalytic role. There are many methods using for recovery those valuable metals from spent auto catalyst, however evry of those methods have some limitations. Proces described in the article is the modified method of metal collector, which used magnetohydrodynamic pump. Rotary electromagnetic field generates in the liquid metal rotary current, which as a consequence washing out the PGM metals from the ceramic carriers. Considering the possibilities of commercialization of the described method, the energy balance was made. From that balance the energetic efficiency of the unit was determined and the analysis of the temperature distribution was shown thermographycally.

  8. Platinum-group elements in the Eastern Deccan volcanic province and a comparison with platinum metals of the western Deccan

    Indian Academy of Sciences (India)

    James Crocket; Dalim Paul; Trisha Lala


    This study is the first detailed investigation of the platinum-group elements (PGE) at the eastern margin of the Deccan volcanic province of India. One of the PGE, osmium, is not included largely because of analytical problems. The study is focused on mafic volcanics and dykes from four areas including Amarkantak, Umaria, Shahdol and Chirimiri. The first two localities represent two lava piles of about 170 and 400 m thickness respectively. In Umaria, 16 flows have been demarcated based on petrography and field studies. The Shahdol samples are basal lava formations overlying Gondwana sediments (Carboniferous) and the Chirimiri samples are dykes. In this study, the western Deccan province is defined as the Western Ghats plus Kutch. On average, the PGE are ∼20% higher in Amarkantak than Umaria and the flows are ∼13% higher in PGE than the dykes. A Zr vs. Pd scattergram found a strong positive correlation for these two elements except for one Umaria sample which indicated severe Pd loss. A comparison of west and east parts of the Deccan volcanic province using primitive mantle normalization showed that higher values prevailed in the western province suite in the Ni-Ir-Ru-Pt region. In contrast, eastern province values dominated in the Pd-Au-Cu region at the ‘Cu’ end of the profiles. A strong dominance of Pd in the eastern Deccan was also of interest. A number of factors, for example, percentage partial melting of the source rock and the temperature and pressure of partial melting strongly influence the character of these profiles. The observed PGE profile characteristics probably result in part from a long distance of subsurface transport of Deccan magma from the western to eastern regions.

  9. First determination of the levels of platinum group metals in Manta birostris (manta ray) caught along the Ghanaian coastline. (United States)

    Essumang, D K


    Tissues from Manta birostris caught by fishermen from Dixcove in the western part of Ghana were analyzed for their Platinum, palladium and rhodium concentrations (PGM). The use of chondrichthyan fish has permitted the study of trace levels of Platinum group metals (PGMs) which have travelled very far into the sea. The analysis showed that Ghana's coastline is fairly polluted with these platinum group metals (PGMs). PGM concentration in manta ray recorded a range of (0.15-0.85) microg/g for Pt, (0.033-0.67) microg/g for Pd and (0.007-0.145) microg/g for Rh. Comparing these values to the UK dietary intake of 0.2 microg/day for Pt and Rh and 1.0 microg/day for Pd, its indicates that the values obtained from the analysis for Pt was above the required level. This is the first study to show the accumulation of PGM in chondrichthyan fish, although the sources of this pollution are not clear as manta birostris is migratory and therefore need to be investigated further. The presence of the PGM is very significant, since manta ray meat is consumed in Ghana. This may presents a health risk, due to a possible accumulation of PGMs in humans.

  10. Calculating the melting curves by the thermodynamic data matching method: Platinum-group refractory metals (Ru, Os, and Ir) (United States)

    Kulyamina, E. Yu.; Zitserman, V. Yu.; Fokin, L. R.


    A technique for reconstructing thermal properties, including the melting curve, of refractory metals based on the use of experimental data on caloric properties available up to the melting point and some regularities of the Debye-Grüneisen theory has been proposed. The calculation result is the consistent system of high-temperature thermal data, including the thermal expansion coefficient, solid-phase density, and volume jump upon melting. This technique was tried-out on refractory platinum-group metals based on experimental data on the enthalpy of the metals and confirmed by consistency with a thermodynamic calculation using shock-wave experiments and results obtained by the quantum molecular dynamics method.

  11. Fate of platinum metals in the environment. (United States)

    Pawlak, Justyna; Łodyga-Chruścińska, Elżbieta; Chrustowicz, Jakub


    For many years now automotive exhaust catalysts have been used to reduce the significant amounts of harmful chemical substances generated by car engines, such as carbon monoxide, nitrogen oxides, and aromatic hydrocarbons. Although they considerably decrease environmental contamination with the above-mentioned compounds, it is known that catalysts contribute to the environmental load of platinum metals (essential components of catalysts), which are released with exhaust fumes. Contamination with platinum metals stems mainly from automotive exhaust converters, but other major sources also exist. Since platinum group elements (PGEs): platinum (Pt), palladium (Pd), rhodium (Rh), ruthenium (Ru) and iridium (Ir) seem to spread in the environment and accumulate in living organisms, they may pose a threat to animals and humans. This paper discusses the modes and forms of PGE emission as well as their impact on the environment and living organisms.

  12. Contamination from gold and platinum-group metals mining in the Gulf of Darién, Colombia (United States)

    Vasquez-Bedoya, L.; Palacio Baena, J.


    Gulf of Darién, triangular southernmost extension of the Caribbean Sea, bounded by Panama on the southwest and by Colombia on the southeast and east. The Gulf is made up of 17 municipalities in the department of Choco and Antioquia. The Gulf of Darién is a geostrategic region, rich in biodiversity, known for its natural resources of minerals, oil, lumber as well as its water and fertile land. The Darién also acts as the bridge between South America and Central America and has access to the Pacific Ocean and the Caribbean Sea. The economy in the region is based mainly on agribusinesses, tourism and mining activities, mainly the 'mining of gold and platinum-group metals'. In our study we determined the degree of trace element contamination in estuarine sediment samples originated from mining activities and municipal waste water discharges of effluents on the gulf of Darién. . Surface samples were taken from 17 locations through the entire Gulf. Grain size, Corg, Ag, Al, Ca , Cr, Cu, Fe, Mg, Mn, Na, Ni, Pb and Zn concentrations were analyzed, and enrichment factors (EF) as well as geo-accumulation indices (Igeo) were calculated. Concentrations of Pb, Zn, Ni, Cu and Cr show levels that are consistent with those typically found in urbanized marine environments. EF and Igeo values revealed that the Gulf is extremely contaminated with Ag and moderately contaminated with Cr and Zn. The sources of Cr, Ag, Hg and Zn are associated with the development of mining activities in the Atrato River basin. The observed enrichment of Ag may be explained as a residue of the extraction of gold and platinum-group metals.

  13. Novel non-platinum metal catalyst material

    DEFF Research Database (Denmark)


    The present invention relates to a novel non-platinum metal catalyst material for use in low temperature fuel cells and electrolysers and to fuel cells and electrolysers comprising the novel non-platinum metal catalyst material. The present invention also relates to a novel method for synthesizing...... the novel non-platinum metal catalyst material....

  14. Assessing Economic Modulation of Future Critical Materials Use: The Case of Automotive-Related Platinum Group Metals. (United States)

    Zhang, Jingshu; Everson, Mark P; Wallington, Timothy J; Field, Frank R; Roth, Richard; Kirchain, Randolph E


    Platinum-group metals (PGMs) are technological and economic enablers of many industrial processes. This important role, coupled with their limited geographic availability, has led to PGMs being labeled as "critical materials". Studies of future PGM flows have focused on trends within material flows or macroeconomic indicators. We complement the previous work by introducing a novel technoeconomic model of substitution among PGMs within the automotive sector (the largest user of PGMs) reflecting the rational response of firms to changing prices. The results from the model support previous conclusions that PGM use is likely to grow, in some cases strongly, by 2030 (approximately 45% for Pd and 5% for Pt), driven by the increasing sales of automobiles. The model also indicates that PGM-demand growth will be significantly influenced by the future Pt-to-Pd price ratio, with swings of Pt and Pd demand of as much as 25% if the future price ratio shifts higher or lower even if it stays within the historic range. Fortunately, automotive catalysts are one of the more effectively recycled metals. As such, with proper policy support, recycling can serve to meet some of this growing demand.

  15. Batch leaching tests of motherboards to assess environmental contamination by bromine, platinum group elements and other selected heavy metals. (United States)

    Almeida, César; Grosselli, Melina; González, Patricia; Martínez, Dante; Gil, Raúl


    In this study, a batch leaching test was executed to evaluate the toxicity associated with chemicals contained in motherboards. The leaching solutions used were distilled water, nitric acid, acetic acid and synthetic acid rain solution. A total of 21 elements including Ag, As, Au, Br, Cd, Co, Cr, Cu, Hf, Ir, Mn, Ni, Os, Pb, Pd, Pt, Rd, Rh, Se, U and Zn were analyzed. In this study, the pH values of all the leachates fell within the range of 2.33-4.88. The highest concentrations of metals were obtained from the acid rain solution, whilst the maximum value of bromine was achieved with solution of acetic acid. Appreciable concentrations of platinum group elements were detected with concentrations around 3.45, 1.43, 1.21 and 22.19 µg L(-1) for Ir, Pd, Pt and Rh, respectively. The different leaching of the motherboards revealed the predominant presence of the toxic substances in the leached from the e-waste.

  16. [Synthesis and luminescent spectral characteristics of porphyrin complexes with platinum group metals]. (United States)

    Rumiantseva, V D; Ivanovskaia, N P; Konovalenko, L I; Tsukanov, S V; Mironov, A F; Osin, N S


    The synthesis of natural and synthetic porphyrin complexes with Pt, Pd, Rh, and Ru is reported. Their electronic absorption spectra, phosphorescence spectra, and lifetimes at room temperature both in the presence and in the absence of oxygen were studied. It has been shown that the variation of the nature of the central metal atom and of the substituents in pyrrole and phenyl rings allows the obtaining of metalloporphyrins with various phosphorescence excitation and phosphorescing emission spectra at room temperature. The English version of the paper: Russian Journal of Bioorganic Chemistry, 2008, vol. 34, no. 2; see also

  17. Strategic and tactical determinants for South African platinum-group-metals supply

    CSIR Research Space (South Africa)

    McGill, JE


    Full Text Available for competitive future supply being derived from the eastern limb. 1 Introduction The mineral resources sector displays a careful balancing act between operation specific tactics designed to maximize shareholder returns; and overarching industry...-related strategies employed by various entities including country governments, global interest groups, and multi-national head offices. This balancing act of short-term business tactics juxtaposed along-side long-run strategic intent of the extraction sector...

  18. Probing Interaction Between Platinum Group Metal (PGM) and Non-PGM Support Through Surface Characterization and Device Performance (United States)

    Saha, Shibely

    High cost and limited abundance of Platinum (Pt) have hindered effective commercialization of Proton Exchange Membrane Fuel Cell and Electrolyzer. Efforts have been undertaken to reduce precious group metal (PGM) requirement for these devices without compromising the activity of the catalyst by using transition metal carbides (TMC) as non-PGM support thanks to their similar electronic and geometric structures as Pt. In this work Mo2C was selected as non-PGM support and Pt was used as the PGM of interest. We hypothesize that the hollow nanotube morphology of Mo2C support combined with Pt nano particles deposited on it via atomic layer deposition (ALD) technique would allow increased interaction between them which may increase the activity of Pt and Mo2C as well as maximize the Pt active surface area. Specifically, a rotary ALD equipment was used to grow Pt particles from atomic level to 2--3 nanometers by simply adjusting number of ALD cycles in order to probe the interaction between the deposited Pt nanoparticles and Mo2C nanotube support. Interaction between the Pt and Mo2 C was analyzed via surface characterization and electrochemical characterization. Interaction between Pt and Mo2C arises due to the lattice mismatch between Pt and Mo2C as well as electron migration between them. Lattice spacing analysis using high resolution transmission electron microscopy (HRTEM) images, combined with Pt binding energy shift in XPS results, clearly showed strong bonding between Pt nanoparticles and the Mo2C nanotube support in all the resultant Pt/Mo2C samples. We postulate that this strong interaction is responsible for the significantly enhanced durability observed in our constant potential electrolysis (CPE) and accelerated degradation testing (ADT). Of the three samples from different ALD cycles (15, 50 and 100), Mo2C nanotubes modified by 50 (1.07 wt% Pt loading) and 100 cycles (4.4 wt% Pt) of Pt deposition, showed higher HER and HOR activity per Pt mass than commercial

  19. Problems and Characteristics of Russian Platinum Metals Exporters

    Institute of Scientific and Technical Information of China (English)



    The paper revealed the place and role of Russia in the global market of platinum metals,highlighted features of pricing in the export of Russian platinum group metals,the main problems of pricing in the export contracts related to the instability of markets and imperfect currency and customs legislation of the Russian Federation,proposed innovative ways to solutions to existing problems in the preparation and conclusion of export contracts.

  20. Experimental observations on noble metal nanonuggets and Fe-Ti oxides, and the transport of platinum group elements in silicate melts (United States)

    Anenburg, Michael; Mavrogenes, John A.


    Platinum group element (PGE) nanonuggets are a nuisance in experimental studies designed to measure solubility or partitioning of noble metals in silicate melts. Instead of treating nanonuggets as experimental artifacts, we studied their behaviour motivated by recent discoveries of PGE nanonuggets in a variety of natural settings. We used an experimental setup consisting of AgPd, Pt or AuPd capsules and Fe(-Ti) oxide-saturated hydrous peralkaline silicate melts to maximise nanonugget production. TABS (Te, As, Bi, Sb, Sn) commonly occur in PGM (platinum group minerals), prompting addition of Bi to our experiments to investigate its properties as well. Three-dimensional optical examination by 100× objective and immersion oil reveals variable colour which correlates with nanonugget size and shape due to plasmon resonance effects. We observe two textural types: (1) intermediate-sized nanonuggets dispersed in the glass and adhering to oxides, and (2) abundant fine nanonuggets dispersed in the glass with coarse euhedral crystals in contact with oxides. Slow cooling removes dispersed nanonuggets and greatly coarsens existing oxide-associated metal crystals. Nanonugget-free halos are commonly observed around oxide grains. All metal phases are composed of major (Ag, Pd) and trace (Pt, Ir, Au) capsule material. Our results show reduction processes, imposed by growing oxides, causing local metal saturation in the oxide rich zones with preferential nucleation on smaller oxide grains. The redox gradient then blocks additional metals from diffusing into oxide rich zones, forming halos. As the entire experimental charge is reduced throughout the run, nanonuggets form in the distal glass. Bismuth contents of metal phases do not depend on Bi2O3 amounts dissolved in the melt. Further PGM crystallisation consumes nanonuggets as feedstock. We conclude that the appearance of metallic PGE phases happens in two stages: first as nanonuggets and then as larger PGM. Once formed

  1. H{sub 2}/air alkaline membrane fuel cell performance and durability, using novel ionomer and non-platinum group metal cathode catalyst

    Energy Technology Data Exchange (ETDEWEB)

    Piana, Michele; Boccia, Massimiliano; Filpi, Antonio; Flammia, Elisa; Miller, Hamish A.; Orsini, Marco; Salusti, Francesca; Santiccioli, Serena [Acta S.p.A., Fuel cell Technology, via di Lavoria 56/G, I-56042 Crespina (PI) (Italy); Ciardelli, Francesco; Pucci, Andrea [Department of Chemistry and Industrial Chemistry, University of Pisa, Via, Risorgimento 35, I-56126 Pisa (Italy)


    The development of H{sub 2}/air alkaline membrane fuel cells (AMFCs) enables the use of non-platinum group metal (PGM) catalysts which are intrinsically stable and have an activity similar to platinum in alkaline media for the oxygen reduction reaction (ORR). As opposed to PEMFCs, the research and development of these types of catalysts for AMFC has had little attention and even less has been given to the development of alkaline membranes and ionomers. Acta S.p.A. has developed recently new non-PGM ORR catalysts with activity higher than Pt in alkaline media. More importantly, a new anionic ionomer derived from cheap starting materials with optimum performance has been produced. In this paper we demonstrate the use of this new ionomer in H{sub 2}/air AMFCs showing the first polarization and durability data, with current densities higher than those recently reported in the literature. Furthermore, we report the effect of CO{sub 2} on AMFC performance, showing the possibility of use of such alkaline devices not only in outer-space applications, but also with atmospheric air for large scale devices. (author)

  2. Levels of Platinum Group Metals in Selected Species (Sarotherodon melanotheron, Chonophorus lateristriga, Macrobrachium vollenhovenii and Crassostrea tulipa in Some Estuaries and Lagoons Along the Coast of Ghana

    Directory of Open Access Journals (Sweden)

    D. K. Essumang


    Full Text Available The use of some biota as bioindicators of heavy metal pollution has been demonstrated as particularly adequate due to their capacity of bioconcentration. This study evaluated the levels of platinum group metals (PGMs in some selected species along the coastal belt of Ghana, using the neutron activation analysis (NAA method. The result was processed to evaluate pollution indices in order to map the distribution of the metals in those species in the lagoons and estuaries along the costal belt of Ghana. The analysis showed significant levels of all PGMs in blackchin tilapia (Sarotherodon melanotheron Cichlidae, brown goby (Chonophorus lateristriga Gobiidae, shrimp (Macrobrachium vollenhovenii Palaemonidae, and mangrove oysters (Crassostrea tulipa Ostreidae in the lagoons and river Pra estuary. However, the oysters showed an elevated mean concentration of 0.13 μ/g (dry weight Pd. From the pollution indices, most of the sampling sites registered mean contamination factor (CF values between 1.20 and 3.00 for Pt, Pd, and Rh. The pollution load index (PLI conducted also gave an average pollution index between 0.79 and 2.37, indicating progressive contamination levels. The results revealed that anthropogenic sources, industrial and hospital effluent, etc., together with vehicular emissions, could be the contributing factors to the deposition of PGMs along the Ghanaian coast.

  3. Study on separation of platinum group metals from high level liquid waste using macroporous (MOTDGA-TOA)/SiO{sub 2}-P silica-based absorbent

    Energy Technology Data Exchange (ETDEWEB)

    Ito, Tatsuya [Department of Quantum Science and Energy Engineering, Graduate School of Engineering, Tohoku University, Aoba 6-6, Aramaki, Aoba-ku, Sendai, Miyagi 980-8579 (Japan); Japan Atomic Energy Agency, Tokai-mura Naka-gun, Ibarak319-1195 (Japan); Kim, Seong-Yun; Xu, Yuanlai; Hitomi, Keitaro [Cyclotron and Radioisotope Center, Tohoku University, Aoba 6-3, Aramaki, Aoba-ku, Sendai, Miyagi 980-8578 (Japan); Ishii, Keizo [Department of Quantum Science and Energy Engineering, Graduate School of Engineering, Tohoku University, Aoba 6-6, Aramaki, Aoba-ku, Sendai, Miyagi 980-8579 (Japan); Nagaishi, Ryuji; Kimura, Takaumi [Japan Atomic Energy Agency, Tokai-mura Naka-gun, Ibarak319-1195 (Japan)


    The recovery of platinum group metals (PGMs) from high level liquid waste (HLLW) by macroporous silica-based adsorbent, (MOTDGA-TOA)/SiO{sub 2}-P has been developed by impregnating two extractants of N,N'-dimethyl-N,N'-di-n-octyl-thio-diglycolamide (MOTDGA) and tri-n-octylamine (TOA) into a silica/polymer composite support (SiO{sub 2}-P). The adsorption of Ru(III), Rh(III) and Pd(II) have been investigated in simulated HLLW by batch method. The adsorbent has shown good uptake property for Pd(II). In addition, the combined use of MOTDGA and TOA improved the adsorption of Ru(III) and Rh(III) better than the individual use of them. The usability of adsorbent in radiation fields was further confirmed by irradiation experiments. The adsorbent remained to have the uptake capability for PGMs over the absorbed dose of 100 kGy, corresponding with one really adsorbed by the adsorbent, and showed good retention capability for Pd(II) even at the absorbed dose of 800 kGy. The chromatographic separation of metal ions was demonstrated with the adsorbent packed column, there is no influence of Re(VII) (instead of Tc) on the excellent separation behavior of Pd(II). (authors)

  4. Evaluating the abnormal ossification in tibiotarsi of developing chick embryos exposed to 1.0ppm doses of platinum group metals by spectroscopic techniques. (United States)

    Stahler, Adam C; Monahan, Jennifer L; Dagher, Jessica M; Baker, Joshua D; Markopoulos, Marjorie M; Iragena, Diane B; NeJame, Britney M; Slaughter, Robert; Felker, Daniel; Burggraf, Larry W; Isaac, Leon A C; Grossie, David; Gagnon, Zofia E; Sizemore, Ioana E Pavel


    Platinum group metals (PGMs), i.e., palladium (Pd), platinum (Pt) and rhodium (Rh), are found at pollutant levels in the environment and are known to accumulate in plant and animal tissues. However, little is known about PGM toxicity. Our previous studies showed that chick embryos exposed to PGM concentrations of 1mL of 5.0ppm (LD50) and higher exhibited severe skeletal deformities. This work hypothesized that 1.0ppm doses of PGMs will negatively impact the mineralization process in tibiotarsi. One milliliter of 1.0ppm of Pd(II), Pt(IV), Rh(III) aqueous salt solutions and a PGM-mixture were injected into the air sac on the 7th and 14th day of incubation. Control groups with no-injection and vehicle injections were included. On the 20th day, embryos were sacrificed to analyze the PGM effects on tibiotarsi using four spectroscopic techniques. 1) Micro-Raman imaging: Hyperspectral Raman data were collected on paraffin embedded cross-sections of tibiotarsi, and processed using in-house-written MATLAB codes. Micro-Raman univariate images that were created from the ν1(PO4(3-)) integrated areas revealed anomalous mineral inclusions within the bone marrow for the PGM-mixture treatment. The age of the mineral crystals (ν(CO3(2-))/ν1(PO4(3-))) was statistically lower for all treatments when compared to controls (p≤0.05). 2) FAAS: The percent calcium content of the chemically digested tibiotarsi in the Pd and Pt groups changed by ~45% with respect to the no-injection control (16.1±0.2%). 3) Micro-XRF imaging: Abnormal calcium and phosphorus inclusions were found within the inner longitudinal sections of tibiotarsi for the PGM-mixture treatment. A clear increase in the mineral content was observed for the outer sections of the Pd treatment. 4) ICP-OES: PGM concentrations in tibiotarsi were undetectable (<5ppb). The spectroscopic techniques gave corroborating results, confirmed the hypothesis, and explained the observed pathological (skeletal developmental abnormalities

  5. Platinum group metal-free electrocatalysts: Effects of synthesis on structure and performance in proton-exchange membrane fuel cell cathodes (United States)

    Workman, Michael J.; Dzara, Michael; Ngo, Chilan; Pylypenko, Svitlana; Serov, Alexey; McKinney, Sam; Gordon, Jonathan; Atanassov, Plamen; Artyushkova, Kateryna


    Development of platinum group metal free catalysts for the oxygen reduction reaction (ORR) in proton exchange membrane fuel cells (PEMFCs) requires understanding of the interactions between surface chemistry and performance, both of which are strongly dependent on synthesis conditions. To elucidate these complex relationships, a set of Fe-N-C catalysts derived from the same set of precursor materials is fabricated by varying several key synthetic parameters under controlled conditions. The results of physicochemical characterization are presented and compared with the results of rotating disk electrode (RDE) analysis and fuel cell testing. We find that electrochemical performance is strongly correlated with three key properties related to catalyst composition: concentrations of 1) atomically dispersed Fe species, 2) species in which N is bound to Fe, and 3) surface oxides. Not only are these factors related to performance, these types of chemical species are shown to correlate with each other. This study provides evidence supporting the role of iron coordinated with nitrogen as an active species for the ORR, and offers synthetic pathways to increase the density of atomically dispersed iron species and surface oxides for optimum performance.

  6. Catalytic transformations of fatty acids derivatives for food, oleochemicals and fuels over carbon supported platinum group metals

    Energy Technology Data Exchange (ETDEWEB)

    Simakova, I.


    prominent in linoleic acid deoxygenation giving only 3 % conversion of fatty acids in 330 min. The deactivation originated from the formation of C17 aromatic compounds and fatty acid dimers via Diels-Alder reaction. Thus hydrogenation of unsaturated fatty acids can be considered as preliminary chemical modification step in the green diesel production. In this work particular care was taken to strengthen the nano level understanding of the Pd role, in particular metal size effect, in the catalytic hydrogenation and deoxygenation. Pd/C catalysts were synthesized with the same Pd loading and systematically varied metal dispersion via the controllable formation of Pd particles over carbon support surface. The effect of metal dispersion on hydrogenation rate and trans/cis ratio was revealed. An optimum metal dispersion giving the highest decarboxylation reaction rate was observed. In addition to the particle size effect, the impact of mass transfer was elucidated and detail discussions on temperature programmed desorption of CO from the fresh and spent samples was provided. Hydrogenation of vegetable feedstocks was performed in batch and continuous modes, using powdered and granulated Pd/C catalysts correspondingly. One of the main focuses of the work was put on the scale-up of the hydrogenation process. There are several challenges attributed to the scale-up of a chemical process which have to be recognized before progressing to an industrial application. In terms of the high production volumes the logical step is to investigate the performance of hydrogenation as a continuous process. A laboratory study in a continuous fixed bed reactor was performed, giving crucial information about the catalyst long-term stability and catalyst deactivation. Furthermore, the impact of using free fatty acids or triglycerides feedstocks as well as the effect of catalyst particle size and Pd loading were investigated in continuous mode. Finally, the production capacities for different operation

  7. Thermodynamic ground states of platinum metal nitrides

    Energy Technology Data Exchange (ETDEWEB)

    Aberg, D; Sadigh, B; Crowhurst, J; Goncharov, A


    We have systematically studied the thermodynamic stabilities of various phases of the nitrides of the platinum metal elements using density functional theory. We show that for the nitrides of Rh, Pd, Ir and Pt two new crystal structures, in which the metal ions occupy simple tetragonal lattice sites, have lower formation enthalpies at ambient conditions than any previously proposed structures. The region of stability can extend up to 17 GPa for PtN{sub 2}. Furthermore, we show that according to calculations using the local density approximation, these new compounds are also thermodynamically stable at ambient pressure and thus may be the ground state phases for these materials. We further discuss the fact that the local density and generalized gradient approximations predict different values of the absolute formation enthalpies as well different relative stabilities between simple tetragonal and the pyrite or marcasite structures.

  8. Ages and sources of components of Zn-Pb, Cu, precious metal, and platinum group element deposits in the goodsprings district, clark county, Nevada (United States)

    Vikre, P.; Browne, Q.J.; Fleck, R.; Hofstra, A.; Wooden, J.


    The Goodsprings district, Clark County, Nevada, includes zinc-dominant carbonate replacement deposits of probable late Paleozoic age, and lead-dominant carbonate replacement deposits, copper ?? precious metal-platinum group element (PGE) deposits, and gold ?? silver deposits that are spatially associated with Late Triassic porphyritic intrusions. The district encompasses ??500 km2 although the distribution of all deposits has been laterally condensed by late Mesozoic crustal contraction. Zinc, Pb, and Cu production from about 90 deposits was ??160,000 metric tons (t) (Zn > Pb >> Cu), 2.1 million ounces (Moz) Ag, 0.09 Moz Au, and small amounts of PGEs-Co, V, Hg, Sb, Ni, Mo, Mn, Ir, and U-were also recovered. Zinc-dominant carbonate replacement deposits (Zn > Pb; Ag ?? Cu) resemble Mississippi Valley Type (MVT) Zn-Pb deposits in that they occur in karst and fault breccias in Mississippian limestone where the southern margin of the regional late Paleozoic foreland basin adjoins Proterozoic crystalline rocks of the craton. They consist of calcite, dolomite, sphalerite, and galena with variably positive S isotope compositions (??34S values range from 2.5-13%), and highly radiogenic Pb isotope compositions (206Pb/204Pb >19), typical of MVT deposits above crystalline Precambrian basement. These deposits may have formed when southward flow of saline fluids, derived from basinal and older sedimentary rocks, encountered thinner strata and pinch-outs against the craton, forcing fluid mixing and mineral precipitation in karst and fault breccias. Lead-dominant carbonate replacement deposits (Pb > Zn, Ag ?? Cu ?? Au) occur among other deposit types, often near porphyritic intrusions. They generally contain higher concentrations of precious metals than zinc-dominant deposits and relatively abundant iron oxides after pyrite. They share characteristics with copper ?? precious metal- PGE and gold ?? silver deposits including fine-grained quartz replacement of carbonate minerals in

  9. Chemistry of Platinum and Palladium Metal Complexes in Homogeneous and Heterogeneous Catalysis: A Mini Review

    Directory of Open Access Journals (Sweden)

    Mehrban Ashiq


    Full Text Available Transition metal complexes of platinum and palladium are most widely used in catalysis. Many synthetic reactions have been carried out with such complexes (used as a catalyst which have specifically polymer ligands, through hydrosilylation, acetoxylation, hydrogenation, hydro-formylation, oligo-merisation and polymerization. Almost many platinum and palladium catalysts are heterogeneous in nature i.e. the reaction taking place on a solid surface. Now from few years homogeneous catalysts which are completely soluble in the liquid phase reactant, has acknowledged too much attention, yet having small industrial applications, mainly due to the striving of platinum and palladium complexes separation from the catalytic products. More recently a transitional type of platinum and palladium catalysts have been synthesized through attachment of the activated transition metal complexes on the surface of polymer support particularly insoluble which has been establish to offer encouraging new collection of catalysts for effective research on synthesis. Many of such complexes will be based on the palladium and platinum metals group. The major objective of this review is to inaugurate the relationship among the reactivity’s of homogeneous platinum and palladium complexes and heterogeneous complexes of these metals (those bonded to the surface of metals.

  10. Platinum-group elements: so many excellent properties (United States)

    Zientek, Michael L.; Loferski, Patricia J.


    The platinum-group elements (PGE) include platinum, palladium, rhodium, ruthenium, iridium, and osmium. These metals have similar physical and chemical properties and occur together in nature. The properties of PGE, such as high melting points, corrosion resistance, and catalytic qualities, make them indispensable to many industrial applications. PGE are strategic and critical materials for many nations because they are essential for important industrial applications but are mined in a limited number of places and have no adequate substitutes. Exploration and mining companies have found approximately 104,000 metric tons of PGE (with minor gold) in mineral deposits around the world that could be developed. For PGE, almost all known production and resources are associated with three geologic features: the Bushveld Complex, a layered mafic-to-ultramafic intrusion in South Africa; the Great Dyke, a layered mafic-to-ultramafic intrusion in Zimbabwe; and sill-like intrusions associated with flood basalts in the Noril’sk-Talnakh area, Russia. To help predict where PGE supplies might be located, USGS scientists study how and where PGE resources are concentrated in the Earth's crust and use that knowledge to assess the likelihood that undiscovered PGE deposits may exist. Techniques used for assessing mineral resources were developed by the USGS to support the stewardship of Federal lands and evaluate mineral resource availability in a global context. The USGS also compiles statistics and information on the worldwide supply, demand, and flow of PGE. These data are all used to inform U.S. national policymakers.

  11. Platinum metals in magmatic sulfide ores (United States)

    Naldrett, A.J.; Duke, J.M.


    Platinum-group elements (PGE) are mined predominantly from deposits that have formed by the segregation of molten iron-nickel-copper sulfides from silicate magmas. The absolute concentrations of PGE in sulfides from different deposits vary over a range of five orders of magnitude, whereas those of other chalcophile elements vary by factors of only 2 to 100. However, the relative proportions of the different PGE in a given deposit are systematically related to the nature of the parent magma. The absolute and relative concentrations of PGE in magmatic sulfides are explained in terms of the degree of partial melting of mantle peridotite required to produce the parent magma and the processes of batch equilibration and fractional segregation of sulfides. The Republic of South Africa and the U.S.S.R. together possess more than 97 percent of the world PGE reserves, but significant undeveloped resources occur in North America. The Stillwater complex in Montana is perhaps the most important example. Copyright ?? 1980 AAAS.

  12. Palladium and platinum organochalcogenolates and their transformation into metal chalcogenides

    Indian Academy of Sciences (India)

    S Dey; S Narayan; A Singhal; V K Jain


    Platinum group metal chalcogenides find extensive applications in catalysis and in the electronic industry. To develop an efficient low temperature clean preparation of these materials, molecular routes have been explored. Thus the chemistry of mononuclear organochalcogenolates of the type [M(ER 1/4)2(PR3)2], binuclear benzylselenolates, [M2Cl2(∼-SeBz)2(PR3)2], allylpalladium complexes [Pd2(μ-ER)2(3-C4H7)2] and palladium/platinum sulphido/selenido-bridged complexes, [M2(μ-E)2L4] (M = Pd or Pt; E = S, Se or Te; L = tertiary phosphine ligand) has been investigated. All the complexes have been characterized by elemental analysis, NMR (1 H, 31P, 77Se, 195Pt) spectroscopy and in some cases by X-ray diffraction. The thermal behaviour of these complexes has been studied by TGA. The pyrolysis of allylpalladium complexes in refluxing xylene yields Pd4E as established by analysis and XRD patterns.

  13. Enhancement of Platinum Cathode Catalysis by Addition of Transition Metals (United States)

    Duong, Hung Tuan


    The sluggish kinetics of oxygen reduction reaction (ORR) contributes significantly to the loss of cathode overpotential in fuel cells, thus requiring high loadings of platinum (Pt), which is an expensive metal with limited supply. However, Pt and Pt-based alloys are still the best available electrocatalysts for ORR thus far. The research presented…

  14. 阳离子树脂净化铂族金属溶液的研究%Purification of Platinum Group Metals Solution by Cation Exchange

    Institute of Scientific and Technical Information of China (English)

    毕向光; 余建民; 杨金富; 贺洪亮; 李权


    研究了阳离子交换树脂净化含大量贱金属的铂族金属溶液的工艺条件,结果表明,在pH=1~1.5时001×7阳离子交换树脂吸附贱金属的次序为:Ni>Cu>Co>Fe;Fe、Ni、Co、Cu的穿透容量分别为(g/kg):0.13,1.25,0.42,0.87;饱和容量分别为(g/kg):0.32,6.65,2.33,4.72,合计为14.02 g/kg;贱金属的分离效率主要取决于贵贱金属浓度及交换柱的数量;吸附在树脂上的贱金属极易被6 mol/L HCl洗脱,所有贱金属的最大洗脱均发生在洗脱液体积与床体积之比为1.0/1.7处,当洗脱液体积为床体积的2.0倍时贱金属被完全洗脱。实验结果为离子交换分离贱金属净化铂族金属溶液的工业化应用提供了强有力的理论依据。%The platimum group metals ( PGMs) solution containing a large amount of base metals purified with cation exchange resin had been investigated. The results showed that the adsorption of base metals by 001 × 7 cation ion exchange resin at pH=1~1.5 was in the order of Ni>Cu>Co>Fe. From the tests, the breakthrough capacities ( g/kg) of Fe, Ni, Co and Cu were 0.13, 1.25, 0.42 and 0.87, respectively, while the saturated capacities ( g/kg) were 0.32, 6.65, 2.33 and 4.72, respectively and 14.02 g/kg in total. It is shown that the separation efficiency of the base metals depends largely on the concentrations of the precious and base metals, as well as the number of exchange columns. The base metals absorbed on the resin could be easily eluted by adding HCl solution at the amount of 6 mol/L, with the elution reaching the maximum as the eluent volume and bed volume at the ratio of 1.0/1.7 and completely finished as the eluent volume being 2. 0 times the bed volume. The experimental results can definitely provide a theoretical basis favorably for the industrial application of PGMs solution purified by cation exchange resin.

  15. Selective laser extraction of the Pt group metals

    Energy Technology Data Exchange (ETDEWEB)

    Fadeeva, S.; Krynetsky, B.; Prokhorov, A.; Zhidkov, A. [General Physics Institute, Russian Academy of Science, Moscow (Russian Federation)


    The interest to the platinum-group metals extraction from solutions, especially industry waste, is stimulated by their extraordinary chemical inert. The traditional chemical methods of the extraction are uneffective. Have been investigated process of the extraction of metal Pt-group from acid solutions. Discussed processes reduction of noble metals by resonance laser action.

  16. Accumulation of platinum group elements by the marine gastropod Littorina littorea

    Energy Technology Data Exchange (ETDEWEB)

    Mulholland, Rachel [School of Geography, Earth and Environmental Sciences, University of Plymouth, Drake Circus, Plymouth PL4 8AA (United Kingdom); Turner, Andrew, E-mail: [School of Geography, Earth and Environmental Sciences, University of Plymouth, Drake Circus, Plymouth PL4 8AA (United Kingdom)


    The accumulation and trophic transfer of the platinum group elements (PGE): Rh, Pd and Pt; have been studied in short-term (5 day) exposures conducted in aquaria containing the marine macroalga, Ulva lactuca, and/or the grazing mollusc, Littorina littorea. Metals added to sea water (to concentrations of 20 {mu}g L{sup -1}) were taken up by U. lactuca in the order Rh, Pt > Pd and by L. littorea in the order Pd {>=} Pt {>=} Rh, with greatest metal accumulation in the latter generally occurring in the visceral complex and kidney. When fed contaminated alga, accumulation of Rh and Pd by L. littorea, relative to total available metal, increased by an order of magnitude, while accumulation of Pt was not readily detected. We conclude that the diet is the most important vector for accumulation of Rh and Pd, while accumulation of Pt appears to proceed mainly from the aqueous phase. - Research highlights: > Platinum group elements are accumulated by, Littorina littorea. > The aqueous phase and diet are important vehicles for Rh and Pd accumulation by the snail. > Grazing molluscs may serve as biomonitors of coastal PGE contamination. - Platinum group elements are accumulated by the marine snail, Littorina littorea, from both the aqueous phase and the diet.


    Institute of Scientific and Technical Information of China (English)


    Several PVP-stabilized colloidal platinum metals nanoparticles have been synthesized and characterized by FTIR and TEM.Comparing with the pure PVP,carbonyl groups of PVP in the mixture of PVP and the metal precursors or in the PVP-stabilized metal nanoparticles have obvious peak shifts in FTIR spectra.The peak shifts reveal the interaction between PVP and the metal species.The interaction between PVP and metal precursors has effect on the formation of the colloidal metal nanoparticles.Strength of the interaction between PVP and metal nanoparticles has direct influence on the stability and the size of the PVP-stabilized metal nanoparticles.Therein,species of the metal precursors and amount of the stabilizer are main factors on the strength of the interaction.

  18. 76 FR 67793 - Notification of Expanded Pricing Grid for Precious Metals Products Containing Platinum and Gold... (United States)


    ... United States Mint Notification of Expanded Pricing Grid for Precious Metals Products Containing Platinum..., 2009, outlining the new pricing methodology for numismatic products containing platinum and gold. Since that time, the price of platinum and gold has increased considerably, and is approaching the...

  19. Multi-elemental characterization of tunnel and road dusts in Houston, Texas using dynamic reaction cell-quadrupole-inductively coupled plasma-mass spectrometry: Evidence for the release of platinum group and anthropogenic metals from motor vehicles

    Energy Technology Data Exchange (ETDEWEB)

    Spada, Nicholas; Bozlaker, Ayse [Department of Civil and Environmental Engineering, University of Houston, Houston, TX 77204-4003 (United States); Chellam, Shankararaman, E-mail: [Department of Civil and Environmental Engineering, University of Houston, Houston, TX 77204-4003 (United States); Department of Chemical and Biomolecular Engineering, University of Houston, Houston, TX 77204-4004 (United States)


    Highlights: Black-Right-Pointing-Pointer Analytical method for PGEs, main group, transition and rare earth metals developed. Black-Right-Pointing-Pointer Comprehensive characterization of road and tunnel dust samples was accomplished. Black-Right-Pointing-Pointer PGEs in dusts arise from autocatalyst attrition. Black-Right-Pointing-Pointer Mobile sources also contributed to Cu, Zn, Ga, As, Mo, Cd, Sn, Sb, Ba, W and Pb. Black-Right-Pointing-Pointer All other elements, including rare earths arose from crustal sources. - Abstract: Platinum group elements (PGEs) including Rh, Pd, and Pt are important tracers for vehicular emissions, though their measurement is often challenging and difficult to replicate in environmental campaigns. These challenges arise from sample preparation steps required for PGE quantitation, which often cause severe isobaric interferences and spectral overlaps from polyatomic species of other anthropogenically emitted metals. Consequently, most previous road dust studies have either only quantified PGEs or included a small number of anthropogenic elements. Therefore a novel analytical method was developed to simultaneously measure PGEs, lanthanoids, transition and main group elements to comprehensively characterize the elemental composition of urban road and tunnel dusts. Dust samples collected from the vicinity of high-traffic roadways and a busy underwater tunnel restricted to single-axle (predominantly gasoline-driven) vehicles in Houston, TX were analyzed for 45 metals with the newly developed method using dynamic reaction cell-quadrupole-inductively coupled plasma-mass spectrometry (DRC-q-ICP-MS). Average Rh, Pd and Pt concentrations were 152 {+-} 52, 770 {+-} 208 and 529 {+-} 130 ng g{sup -1} respectively in tunnel dusts while they varied between 6 and 8 ng g{sup -1}, 10 and 88 ng g{sup -1} and 35 and 131 ng g{sup -1} in surface road dusts. Elemental ratios and enrichment factors demonstrated that PGEs in dusts originated from autocatalyst

  20. Assessment of metallic mineral resources in the Humboldt River Basin, Northern Nevada, with a section on Platinum-Group-Element (PGE) Potential of the Humboldt Mafic Complex (United States)

    Wallace, Alan R.; Ludington, Steve; Mihalasky, Mark J.; Peters, Stephen G.; Theodore, Ted G.; Ponce, David A.; John, David A.; and Berger, Byron R.; Zientek, Michael L.; Sidder, Gary B.; Zierenberg, Robert A.


    The Humboldt River Basin is an arid to semiarid, internally drained basin that covers approximately 43,000 km2 in northern Nevada. The basin contains a wide variety of metallic and nonmetallic mineral deposits and occurrences, and, at various times, the area has been one of the Nation's leading or important producers of gold, silver, copper, mercury, and tungsten. Nevada currently (2003) is the third largest producer of gold in the world and the largest producer of silver in the United States. Current exploration for additional mineral deposits focuses on many areas in northern Nevada, including the Humboldt River Basin.


    Institute of Scientific and Technical Information of China (English)

    JIANGLingen; HUANGYan


    In this paper the separation of base metals Fe,Co,Ni and Cu from the platinum metals on a cation exchanger column was studies.The convenient separation conditions are 0.5mol·dm-3 NaCl,pH=2. The recovery efficiency of Rh is 98%.

  2. Synthesis and structural study of platinum group metal complexes containing pyrimidine bridged pyrazolyl-pyridine ligand and 5 and 6 - cyclic hydrocarbons

    Indian Academy of Sciences (India)

    Thirumala Prasad Kota; Mohan Rao Kollipara


    The mononuclear compounds [(6-arene)Ru(bppm)Cl]PF6{bppm = 4,6-bis3-(2-pyridyl)-1Hpyrazol-1-yl}pyrimidine; arene = C6H6, [1]; -$^i$PrC6H4Me, [2]; C6Me6, [3]}, [CpRu(bppm)(PPh3)]PF6{Cp = 5-C5H5, [4]; 5-C5Me5, [5]; 5-C9H7, [6]} and [Cp∗M(bppm)Cl]PF6 {M = Rh [7]; Ir [8]} have been synthesized from the reaction of 4,6-bis{3-(2-pyridyl)-1H-pyrazol-1-yl}pyrimidine (bppm) and the corresponding precursor metal complexes [(6-arene)Ru(-Cl)Cl]2, [CpRu(PPh3)2Cl] and [Cp∗M(-Cl)Cl]2, respectively, in the presence of NH4PF6. They were characterized by the following techniques viz. IR, NMR, mass spectrometry and UV-visible spectroscopy. The molecular structures of [2] and [7] have been established by single crystal X-ray structure analyses.

  3. Determination of Platinum Metals in Carbonaceous Mineral Raw Materials by Stripping Voltammetry


    Kolpakova, Nina Alexandrovna; Oskina, Yuliya Aleksandrovna; Dyachenko, Elena Nikolaevna; Pshenichkin, Anatoliy Yakovlevich


    The paper considers the possibility of determining platinum metals in mineral raw materials by stripping voltammetry on a graphite electrode modified by metals. Stripping voltammetry method is characterized by low determination limit, wide intervals of determined content and high sensitivity. As a result of the research the conditions for the determination of gold, platinum and palladium by stripping voltammetry have been selected. The comparison of the results of gold, palladium and platinum...

  4. Recent Development in Simultaneous Multi-Element Determination of the Platinum Group Elements and Gold in Geological and Environmental Samples

    Institute of Scientific and Technical Information of China (English)

    任曼; 邓海琳


    In recent years, the modern methods of multi-element analysis of precious metals have attracted wide attention in scientific research and industry. The application and development in the decomposition of samples, separation and enrichment, and modern instrumental analysis of the platinum-group elements (PGEs) and gold in geological and environmental samples have been reviewed. Finally, the tendency of analysis of precious metals is also prospected.

  5. Potentiometric titration of gold, platinum, and some other precious metals

    Energy Technology Data Exchange (ETDEWEB)

    Selig, W.S.


    Gold, platinum, and several other platinum metals can be determined by titration with cetylpyridinium chloride (CPC). CPC forms a precipitate with AuCl{sub 4}{sup {minus}} and PtCl{sub 6}{sup 2{minus}}. Differentiation of AuCl{sub 4{minus}} and PtCl{sub 6}{sup 2{minus}} with this titrant is not possible; however, their sum can be determined. Titration with tetraphenylarsonium chloride at pH 1 is selective for tetrachloroaurate, which thus can be determined in the presence of hexachloroplatinate. Hexachloroosmate(IV), tetrachloroplatinite(II), tetrachloropalladate(II), hexachloropalladate(IV), and hexachloroiridate(IV) can also be determined potentiometrically vs. CPC. The indicating electrode is prepared by coating a spectroscopic graphite rod with a solution of poly(vinyl chloride) (PVC) and dioctylphthalate (DOP) in tetrahydrofuran (THF). Gold in gold cyanide plating baths and in potassium aurocyanide can be determined by potentiometric titration vs standard silver nitrate, using a silver ion-selective indicating electrode. The monovalent gold need not be converted to the trivalent state with aqua regia, resulting in a considerable saving of time and effort. Free cyanide and aurocyanide can be titrated sequentially by this method. Chloride does not interfere and can, in fact, also be sequentially determined. 17 refs., 2 figs., 3 tabs.

  6. Accumulation of platinum group elements by the marine gastropod Littorina littorea. (United States)

    Mulholland, Rachel; Turner, Andrew


    The accumulation and trophic transfer of the platinum group elements (PGE): Rh, Pd and Pt; have been studied in short-term (5 day) exposures conducted in aquaria containing the marine macroalga, Ulva lactuca, and/or the grazing mollusc, Littorina littorea. Metals added to sea water (to concentrations of 20 μg L⁻¹) were taken up by U. lactuca in the order Rh, Pt > Pd and by L. littorea in the order Pd ≥ Pt ≥ Rh, with greatest metal accumulation in the latter generally occurring in the visceral complex and kidney. When fed contaminated alga, accumulation of Rh and Pd by L. littorea, relative to total available metal, increased by an order of magnitude, while accumulation of Pt was not readily detected. We conclude that the diet is the most important vector for accumulation of Rh and Pd, while accumulation of Pt appears to proceed mainly from the aqueous phase.

  7. Metal Oxide-Supported Platinum Overlayers as Proton-Exchange Membrane Fuel Cell Cathodes

    DEFF Research Database (Denmark)

    Tripkovic, Vladimir; Abild-Pedersen, Frank; Studt, Felix


    We investigated the activity and stability of n=(1, 2, 3) platinum layers supported on a number of rutile metal oxides (MO2; M=Ti, Sn, Ta, Nb, Hf and Zr). A suitable oxide support can alleviate the problem of carbon corrosion and platinum dissolution in Pt/C catalysts. Moreover, it can increase t...

  8. Production of Nanopowders of Platinum Metals Using the Chemical Reduction Method

    Institute of Scientific and Technical Information of China (English)



    The literary data on the application of various methods for the production of nanopowders of platinum metals and alloys have been summarized,and the selection of the method of chemical reduction from salt solutions has been substantiated as the simplest and most affordable.The optimum conditions for the production of nanoparticles of metal palladium and platinum/cobalt alloy,using the effect of boranes with various structures,have been selected.

  9. Advances in the synthesis mulitmetallic systems: hydroxyl group protection in aryldiamine platinum species

    NARCIS (Netherlands)

    Koten, G. van; Davies, P.J.; Grove, D.M.


    A multimetallic system containing three platinum atoms has been synthesized through use of an (aryldiamine)platinum complex with a protected hydroxyl group which, after deprotection, is coupled with the trisubstituted aryl molecule 1,3,5-tris(chlorocarbonyl)benzene that provides the core moiety. The

  10. Comparison between Base Metals and Platinum Group Metals in Nitrogen, M Codoped TiO2 (M = Fe, Cu, Pd, Os for Photocatalytic Removal of an Organic Dye in Water

    Directory of Open Access Journals (Sweden)

    Alex T. Kuvarega


    Full Text Available The photocatalytic performance of a number of nonmetal and metal codoped TiO2 for the degradation of eosin yellow under simulated solar radiation was investigated. The synthesised materials were characterised by FTIR, Raman spectroscopy, XRD, DRUV-Vis, SEM, and TEM. The N, metal codoped TiO2 containing 0.5 wt.% of the metal consisted mainly of the anatase phase, with a particle size range of 15–28 nm. The particles were largely spherical and shifted the absorption edge well into the visible region. Band gap reduction was more pronounced for the N, PGM codoped TiO2 compared to N, base metal codoped samples. Codoping led to an enhancement in the photocatalytic activity of the materials for the degradation of eosin yellow. N, Pd codoped TiO2 was the most effective photocatalyst (99.9% dye removal while N, Cu codoped TiO2 showed the least activity (25.5% removal. The mechanism for the photocatalytic enhancement was proposed on the basis of formation of an electron deficient Schottky barrier at the semiconductor-metal interface, which acts as an electron sink and thus retards electron-hole recombination. It was shown that the ability of the photocatalyst to degrade the dye depends on the nature and type of the metal dopant in the codoped TiO2 system.

  11. Electronic metal-support interaction enhanced oxygen reduction activity and stability of boron carbide supported platinum (United States)

    Jackson, Colleen; Smith, Graham T.; Inwood, David W.; Leach, Andrew S.; Whalley, Penny S.; Callisti, Mauro; Polcar, Tomas; Russell, Andrea E.; Levecque, Pieter; Kramer, Denis


    Catalysing the reduction of oxygen in acidic media is a standing challenge. Although activity of platinum, the most active metal, can be substantially improved by alloying, alloy stability remains a concern. Here we report that platinum nanoparticles supported on graphite-rich boron carbide show a 50-100% increase in activity in acidic media and improved cycle stability compared to commercial carbon supported platinum nanoparticles. Transmission electron microscopy and x-ray absorption fine structure analysis confirm similar platinum nanoparticle shapes, sizes, lattice parameters, and cluster packing on both supports, while x-ray photoelectron and absorption spectroscopy demonstrate a change in electronic structure. This shows that purely electronic metal-support interactions can significantly improve oxygen reduction activity without inducing shape, alloying or strain effects and without compromising stability. Optimizing the electronic interaction between the catalyst and support is, therefore, a promising approach for advanced electrocatalysts where optimizing the catalytic nanoparticles themselves is constrained by other concerns.

  12. Factors Governing concentration of platinum group elements in layered complexes

    DEFF Research Database (Denmark)

    Makovicky, E.; Rose-Hansen, J.; Karup-Møller, Sven


    This report covers the synthetic research results obtained by the Danish group on: (1) The phase system Fe-Ir-S at 1100o, 1000o and 800oC, (2) Metal-rich portions of the phase system Pt-Ir-Fe-S: Pt-Fe-Ir alloys and associated sulfides at 1000oC and 1100oC, (3) The Fe (Cu)-Pt-Rh-S system: alloys a...

  13. 5 and 6 - cyclic -perimeter hydrocarbon platinum group metal complexes of 3-(2-pyridyl)pyrazole derived ligands with a pendant nitrile group: Syntheses, spectral and structural studies

    Indian Academy of Sciences (India)

    Gloria Sairem; Venkateswara Rao Anna; Peng Wang; Bbulal Das; Mohan Rao Kollipara


    Reaction of two equivalents 4-{(3-(pyridine-2-yl) 1H-pyrazole-1-yl}methyl benzonitrile (L1) and 3-{(3-(pyridine-2-yl)1H-pyrazole-1-yl}methyl benzonitrile (L2) with one equivalent of [(6-arene)Ru(- Cl)Cl]2 and [Cp∗M(-Cl)Cl]2 in methanol yielded mononuclear complexes of the formulae [(6-arene)Ru(L1/L2)Cl]BF4{arene =C6H6 (1, 6); C10H14 (2, 7); C6Me6 (3, 8)} and [Cp∗M(L1/L2)Cl]PF6/BF4 {Cp∗= 5-C5Me5, M=Rh (4, 8); Ir (5, 10)}. These complexes are characterized by IR, 1H NMR and identities of the structure are established by single crystal XRD studies of some of the representative complexes. It is confirmed from the spectral studies that the nitrile group is not taking part in complexation; instead it remains as a free pendant group only.

  14. Request for Correction 11001 Toxicological Review of Halogenated Platinum Salts and Platinum Compounds (United States)

    Request for Correction by the International Platinum Group Metals Association seeking the correction of information disseminated in the draft EPA document Toxicological Review of Halogenated Platinum Salts and Platinum Compounds: In Support of Summary Information on the Integrated Risk Information System (IRIS).

  15. Platinum redispersion on metal oxides in low temperature fuel cells

    DEFF Research Database (Denmark)

    Tripkovic, Vladimir; Cerri, Isotta; Nagami, Tetsuo


    in detail; however, due to different operating conditions it is not straightforward to link the chemical and the electrochemical environment. The largest differences reflect in (1) the oxidation state of the surface (the oxygen species coverage), (2) temperature and (3) the possibility of platinum...

  16. Do Scarce Precious Metals Equate to Safe Harbor Investments? The Case of Platinum and Palladium

    Directory of Open Access Journals (Sweden)

    John Francis T. Diaz


    Full Text Available This research establishes the predictability and safe harbor properties of two scarce precious metals, namely, platinum and palladium. Utilizing their spot prices, the study concludes intermediate memory in the return structures of both precious metals, which implies the instability of platinum and palladium returns’ persistency in the long run. However, both the ARFIMA-FIGARCH and the ARFIMA-FIAPARCH models confirm long-memory properties in the volatility of the two spot prices. The leverage effects phenomenon is not also present based on the ARFIMA-APARCH and ARFIMA-FIAPARCH models, which may possibly conclude the resilience of both precious metals against increased volatility. However, further tests proved that only platinum has a symmetric volatility response to shocks with the presence of negative gamma parameter, which proves that only platinum can be considered a safe harbor investment, because negative and positive shocks have equal effects on their returns and volatilities. Comparing the four models utilized in this study, the combined ARFIMA-FIAPARCH models are the best fitting model to characterize both precious metals’ spot prices.

  17. Grouped exposed metal heaters

    Energy Technology Data Exchange (ETDEWEB)

    Vinegar, Harold J [Bellaire, TX; Coit, William George [Bellaire, TX; Griffin, Peter Terry [Brixham, GB; Hamilton, Paul Taylor [Houston, TX; Hsu, Chia-Fu [Granada Hills, CA; Mason, Stanley Leroy [Allen, TX; Samuel, Allan James [Kular Lumpar, ML; Watkins, Ronnie Wade [Cypress, TX


    A system for treating a hydrocarbon containing formation is described. The system includes two or more groups of elongated heaters. The group includes two or more heaters placed in two or more openings in the formation. The heaters in the group are electrically coupled below the surface of the formation. The openings include at least partially uncased wellbores in a hydrocarbon layer of the formation. The groups are electrically configured such that current flow through the formation between at least two groups is inhibited. The heaters are configured to provide heat to the formation.

  18. Grouped exposed metal heaters

    Energy Technology Data Exchange (ETDEWEB)

    Vinegar, Harold J. (Bellaire, TX); Coit, William George (Bellaire, TX); Griffin, Peter Terry (Brixham, GB); Hamilton, Paul Taylor (Houston, TX); Hsu, Chia-Fu (Granada Hills, CA); Mason, Stanley Leroy (Allen, TX); Samuel, Allan James (Kular Lumpar, MY); Watkins, Ronnie Wade (Cypress, TX)


    A system for treating a hydrocarbon containing formation is described. The system includes two or more groups of elongated heaters. The group includes two or more heaters placed in two or more openings in the formation. The heaters in the group are electrically coupled below the surface of the formation. The openings include at least partially uncased wellbores in a hydrocarbon layer of the formation. The groups are electrically configured such that current flow through the formation between at least two groups is inhibited. The heaters are configured to provide heat to the formation.

  19. Platinum impact assessment


    Yip, Joyce Pui Yan


    This paper presents a comprehensive strategic analysis of Company X's strategies to mitigate its risks from volatile platinum prices, since Platinum is a critical component of fuel cells. It is recommended that Company X consider leasing platinum to lower cash flow requirements to meet its platinum demand over the next 5 years. A shorter platinum leasing period will reduce Company X's platinum market risk. OEMs can set up metal accounts with catalyst suppliers to eliminate Company X from plat...

  20. Platinum group element mineralization of the Svetly Bor and Veresovy Bor clinopyroxenite-dunite massifs, Middle Urals, Russia (United States)

    Stepanov, S. Yu.; Malitch, K. N.; Kozlov, A. V.; Badanina, I. Yu; Antonov, A. V.


    The new data for the geology and mineralogy of the platinum group element (PGE) mineralization related to the chromite-platinum ore zones within the dunite of the Svetly Bor and Veresovy Bor massifs in the Middle Urals are discussed. The geological setting of the chromite-platinum ore zones, their platinum content, compositional and morphological features of the platinum group minerals (PGM) are compared to those within the Nizhny Tagil massif, the world standard of the zonal complexes in the Platinum Ural belt. The chromite-platinum orebodies are spatially related to the contacts between differently granular dunites. Majority of PGM are formed by Pt-Fe alloys that are close in terms of stoichiometry to isoferroplatinum (Pt3Fe), and associated with Os-Ir alloys, Ru-Os and Ir-Rh sulfides, and Ir-Rh thiospinels of the cuproiridsite-cuprorhodsite-ferrorhodsite solid solution. The tetraferroplatinum (PtFe)-tulameenite (PtFe0.5Cu0.5) solid solution and Pt-Cu alloys belong to the later PGM assemblage. The established features of the chromite-platinum ore zones testify to the highly probable identification of the PGE mineralization within the dunite of the Svetly Bor and Vesesovy Bor massifs and could be used in prospecting and exploration for platinum.

  1. Noble Metal Catalysts for Mercury Oxidation in Utility Flue Gas: Gold, Palladium and Platinum Formulations

    Energy Technology Data Exchange (ETDEWEB)

    Presto, A.A.; Granite, E.J


    The use of noble metals as catalysts for mercury oxidation in flue gas remains an area of active study. To date, field studies have focused on gold and palladium catalysts installed at pilot scale. In this article, we introduce bench-scale experimental results for gold, palladium and platinum catalysts tested in realistic simulated flue gas. Our initial results reveal some intriguing characteristics of catalytic mercury oxidation and provide insight for future research into this potentially important process.

  2. Characteristics of platinum-group elements in basalts from spreading axis of Mariana Trough

    Institute of Scientific and Technical Information of China (English)

    CAO Zhimin; ZHENG Jianbin; ZHOU Meifu; AN Wei; QI Liang


    Total platinum-group elements (PGEs) abundances in basalts from the spreading axis of Mariana Trough ranged from 0.418 × 10-9 to 1.022 × 10-9, and primitive mantle-normalized PGE patterns are of positive slope showing the relative enrichment of PPGE (platinum, palladium, rhodium) and gold relative to IPGE. Compared with other mantle-originated rocks, these basalts have lower PGE contents and wider ranges of primitive mantle-normalized ratios of palladium content to iridium one, palladium content to platinum one and palladium content to gold one exhibiting relative platinum and iridium depletion. Characteristics of PGE patterns indicated that the studied Mariana Trough basalts originated from low partial melting, and the MORB mantle beneath the spreading center had been contaminated by the arc-island mantle. In the aspect of trace elements, Mariana Trough basalts showed the enrichment of LILE, lead and LREE, indicating that they had been influenced by subduction compositions. All these demonstrated that Mariana Trough basalts are products of partial melting from a mixed mantle ( the contamination of MORB mantle by arc-island mantle).

  3. Meeting report on 8th International Symposium on Platinum and Other Metal Coordination Compounds in Cancer Chemotherapy. (United States)

    Kelland, L R


    The platinum-based drugs, cisplatin and carboplatin, represent major agents in the chemotherapeutic treatment of a variety of types of cancer. Novel, "third-generation" agents aimed at broadening the clinical activity of this class of drug are currently undergoing clinical evaluation. These include oxaliplatin, ZD0473 and BBR3464. Clinical trials and preclinical studies are also being conducted with liposomal (SPI-077 and L-NDDP) and polymeric platinum complexes (linked to HPMA or albumin). Combination studies of cisplatin/carboplatin with other anticancer drugs such as gemcitabine and UCN-01 (7-hydroxystaurosporine) and agents designed to reduce platinum drug toxicities (e.g., BNP-7787, DIMESNA) are ongoing. Preclinically, there is interest in trans platinum complexes, terpyridine platinum(II) complexes and other metal-containing agents (ruthenium and gold).

  4. A comparison of the marginal and internal adaptation of titanium and gold-platinum-palladium metal ceramic crowns. (United States)

    Valderrama, S; Van Roekel, N; Andersson, M; Goodacre, C J; Munoz, C A


    The marginal and internal adaptation of metal ceramic crowns fabricated by electrical discharge machining and conventional metal ceramic alloys were compared. The crowns were cemented using zinc phosphate cement, embedded in epoxy resin, and sectioned in two planes: diagonal and buccolingual. The crowns were then measured at nine sites. The results showed that there were no statistical differences between the external marginal opening of the titanium and the gold-platinum-palladium crowns. The overall marginal discrepancies for the restorations in this study were 61 microns (+/- 34 microns) for the titanium metal ceramic crowns and 47 microns (+/- 17 microns) for the gold-platinum-palladium metal ceramic crowns.

  5. High pressure stability of the monosilicides of cobalt and the platinum group elements

    Energy Technology Data Exchange (ETDEWEB)

    Hernandez, J.A., E-mail: [Laboratoire de géologie de Lyon, CNRS UMR 5276, École Normale Supérieure de Lyon, Université Claude Bernard Lyon 1, 46 Allée d’Italie, 69364 Lyon Cedex 07 (France); Vočadlo, L.; Wood, I.G. [Department of Earth Sciences, University College London, WC1E 6BT (United Kingdom)


    Highlights: • We model the high-pressure phases of cobalt- and platinum-group-monosilicides. • CoSi, RuSi, OsSi transform with pressure from the ε-FeSi to the CsCl structure. • RhSi and IrSi transform with pressure from the MnP structure to the ε-FeSi structure. • PdSi and PtSi transform with pressure from the MnP structure to the CuTi structure. - Abstract: The high pressure stability of CoSi, RuSi, RhSi, PdSi, OsSi, IrSi and PtSi was investigated by static first-principles calculations up to 300 GPa at 0 K. As found experimentally, at atmospheric pressure, CoSi, RuSi and OsSi were found to adopt the cubic ε-FeSi structure (P2{sub 1}3) whereas RhSi, PdSi, IrSi and PtSi were found to adopt the orthorhombic MnP (Pnma) structure. At high pressure, CoSi, RuSi and OsSi show a phase transition to the CsCl structure (Pm3{sup ¯}m) structure at 270 GPa, 7 GPa and 6 GPa respectively. RhSi and IrSi were found to transform to an ε-FeSi structure at 10 GPa and 25 GPa. For PdSi and PtSi, a transformation from the MnP structure to the tetragonal CuTi structure (P4/nmm) occurs at 13 GPa and 20 GPa. The pressure dependence of the electronic density of states reveals that RuSi and OsSi are semiconductors in the ε-FeSi structure and become metallic in the CsCl structure. RhSi and IrSi are metals in the MnP structure and become semimetals in their high pressure ε-FeSi form. CoSi in the ε-FeSi configuration is a semimetal. PdSi and PtSi remain metallic throughout up to 300 GPa.

  6. Antitumor activities and interaction with DNA of oxaliplatin-type platinum complexes with linear or branched alkoxyacetates as leaving groups. (United States)

    Yin, Runting; Gou, Shaohua; Liu, Xia; Lou, Liguang


    Five oxaliplatin-typed platinum complexes containing trans-1R, 2R-diaminocyclohexane chelating platinum cores, characteristic of linear or branched alkoxycarboxylates as leaving groups, were biologically evaluated. These compounds showed higher antitumor activity, lower toxicity in vivo than cisplatin or oxaliplatin. And the results revealed that the antitumor activity and interaction with DNA of these compounds were highly related to the nature of leaving groups. Among these complexes, 5a, cis-(trans-1R, 2R-diaminocyclohexane) bis (2-tert-butoxyacetate) platinum(II), showed the highest antitumor activity and the lowest toxicity.

  7. Characterization of the Sukinda and Nausahi ultramafic complexes, Orissa, India by platinum-group element geochemistry (United States)

    Page, N.J.; Banerji, P.K.; Haffty, J.


    Samples of 20 chromitite, 14 ultramafic and mafic rock, and 9 laterite and soil samples from the Precambrian Sukinda and Nausahi ultramafic complexes, Orissa, India were analyzed for platinum-group elements (PGE). The maximum concentrations are: palladium, 13 parts per billion (ppb); platinum, 120 ppb; rhodium, 21 ppb; iridium, 210 ppb; and ruthenium, 630 ppb. Comparison of chondrite-normalized ratios of PGE for the chromitite samples of lower Proterozoic to Archean age with similar data from Paleozoic and Mesozoic ophiolite complexes strongly implies that these complexes represent Precambrian analogs of ophiolite complexes. This finding is consistent with the geology and petrology of the Indian complexes and suggests that plate-tectonic and ocean basin developement models probably apply to some parts of Precambrian shield areas. ?? 1985.

  8. Clinical utility of platinum chromium bare-metal stents in coronary heart disease

    Directory of Open Access Journals (Sweden)

    Jorge C


    Full Text Available Claudia Jorge,1 Christophe Dubois1,2 1Department of Cardiovascular Medicine, University Hospitals Leuven, 2Department of Cardiovascular Sciences, Katholieke Universiteit Leuven, Leuven, Belgium Abstract: Coronary stents represent a key development for the treatment of obstructive coronary artery disease since the introduction of percutaneous coronary intervention. While drug-eluting stents gained wide acceptance in contemporary percutaneous coronary intervention practice, further developments in bare-metal stents remain crucial for patients who are not candidates for drug-eluting stents, or to improve metallic platforms for drug elution. Initially, stent platforms used biologically inert stainless steel, restricting stent performance due to limitations in flexibility and strut thickness. Later, cobalt chromium stent alloys outperformed steel as the material of choice for stents, allowing latest generation stents to be designed with significantly thinner struts, while maintaining corrosion resistance and radial strength. Most recently, the introduction of the platinum chromium alloy refined stent architecture with thin struts, high radial strength, conformability, and improved radiopacity. This review will provide an overview of the novel platinum chromium bare-metal stent platforms available for coronary intervention. Mechanical properties, clinical utility, and device limitations will be summarized and put into perspective. Keywords: bare metal stent, coronary stent alloys, coronary artery disease

  9. Developmental Validation of the Huaxia Platinum System and application in 3 main ethnic groups of China. (United States)

    Wang, Zheng; Zhou, Di; Jia, Zhenjun; Li, Luyao; Wu, Wei; Li, Chengtao; Hou, Yiping


    STRs, scattered throughout the genome with higher mutation rate, are attractive to genetic application like forensic, anthropological and population genetics studies. STR profiling has now been applied in various aspects of human identification in forensic investigations. This work described the developmental validation of a novel and universal assay, the Huaxia Platinum System, which amplifies all markers in the expanded CODIS core loci and the Chinese National Database in one single PCR system. Developmental validation demonstrated that this novel assay is accurate, sensitive, reproducible and robust. No discordant calls were observed between the Huaxia Platinum System and other STR systems. Full genotypes could be achieved even with 250 pg of human DNA. Additionally, 402 unrelated individuals from 3 main ethnic groups of China (Han, Uygur and Tibetan) were genotyped to investigate the effectiveness of this novel assay. The CMP were 2.3094 × 10(-27), 4.3791 × 10(-28) and 6.9118 × 10(-27), respectively, and the CPE were 0.99999999939059, 0.99999999989653 and 0.99999999976386, respectively. Aforementioned results suggested that the Huaxia Platinum System is polymorphic and informative, which provides efficient tool for national DNA database and facilitate international data sharing.

  10. Heterogeneous platinum-catalyzed hydrogenation of dialkyl(diolefin)platinum(II) complexes: A new route to platinum surface alkyls


    McCarthy, Thomas J.; Shih, Yen-Shiang; Whitesides, George M.


    Platinum metal catalyzes the reduction of dialkyl(diolefin)platinum(II) complexes by dihydrogen to alkanes and platinum(0). The reaction involves adsorption of the platinum(II) complex on the platinum(0) catalyst surface with conversion of the alkyl moieties to platinum surface alkyls; these appear as alkane products. The platinum atom originally present in the soluble organoplatinum species becomes part of the platinum(0) surface.

  11. Domestic Production Issues in Chromium and Platinum-Group Metals (United States)


    Protection Agency. OPA 87-005. Washington: Government Printing Office, May 1987. 16. Foley, Jeffrey Y. and James C. Barker . Chromite Deposits Along...Mining, Metallurgical, and Petroleum Engineers, 1976. 52. Stowe, Clive W. Evolution of Chromium Ore Fields. New York: Van Nostrand Reinhold Company

  12. Platinum group elements geochemistry of ultramafic and associated rocks from Pindar in Madawara Igneous Complex, Bundelkhand massif, central India

    Indian Academy of Sciences (India)

    V Balaram; S P Singh; M Satyanarayanan; K V Anjaiah


    Ultramafic rocks comprising dunite, harburgite, lehzolite, olivine webserite and websterite occur as intrusives in the form of small hillocks at around Pindar into the granite–gneisses of Bundelkhand Gneissic Complex (BnGC). The peridotites are dominated by olivine cumulates where chromite and precious metal-bearing sulphides crystallized along with pyroxenes, subsequent to crystallization of olivine into the interstitial spaces of cumulates during cooling. Ultramafic rocks of Pindar are characterized by high MgO (up to 46.0 wt%) and FeO (up to 5.8 wt%); low SiO2 (40.8 to 48.0 wt%), TiO2 (0.2 to 0.5 wt%), Al2O3 (∼3.2 wt% av.), CaO(∼ 2.7 wt% av.) and Cu (11 to 73 g/g). Cr and Ni values range from 2297 to 3150 g/g and 2434 to 2767 g/g, respectively. Distribution of Ir (up to 20 ng/g), Ru (27 to 90 ng/g), Rh (3 to 14 ng/g), Pt (18 to 72 ng/g), Pd (10 to 27 ng/g) and Au (22 to 57 ng/g) indicate platinum group element (PGE) and associated gold mineralization in these ultramafic rocks. A mineral phase representing sperrylite (PtAs2) was also identified within the sulphides in Scanning electron microscopy with energy dispersive spectrometer (SEM–EDS) studies. The primitive mantle-normalized siderophile elements pattern shows platinum group element PGE (PPGE) enrichment (Rh, Pt, Pd). Discrimination diagrams of Pd/Ir vs. Ni/Cu, Pd/Pt vs. Ni/Cu, Cu/Pd vs. Pd, and Cu vs. Pd for the peridotites of Pindar attribute to affinity towards komatiite magma, derived from high degree of partial melting of prolonged depleted mantle, and the sulphur saturation condition incurred during the crystallization of chromite which was favourable for PGE mineralization.

  13. Experience in the Production of Horizontal Ingots of Platinum Metals and Alloys

    Institute of Scientific and Technical Information of China (English)



    The quality of semi-products of platinum metals and alloys,produced by way of plastic working,essentially depends on or,in many cases,is completely determined by the quality of ingots.Plastic working does not make it possible to eliminate or localize metallurgical defects.In many cases it promotes the occurence thereof.Low-rate casting with directional crystallization can ensure the production of dense ingots free of non-metallic inclusions,shrinkage and gas weakness,with observance of certain temperature/rate modes.After comparative tests of vertical and horizontal molds,preference has been given to horizontal water-cooled molds,allowing to cast all alloys in the conditions of directional crystallization.

  14. Technology Development and Production of Certain Chemical Platinum Metals Compounds at JSC "Krastsvetmet"

    Institute of Scientific and Technical Information of China (English)



    In recent years JSC "Krastsvetmet" has successfully developed the production of chemically pure compounds of precious metals.Currently methods have been developed and facilities have been provided for industrial production of the following platinum metals compounds:- Rhodium (Ⅲ) chloride hydrate,rhodium (Ⅲ) chloride solution,rhodium ( Ⅲ) nitrate solution,rhodium ( Ⅲ)iodide,rhodium ( Ⅲ) sulfate,hydrated rhodium ( Ⅲ) oxide,ammonium hexachlororodiate,rhodium ( Ⅲ)phosphate solution,rhodium electrolytes;Iridium (Ⅳ) chloride hydrate,iridium (Ⅲ) chloride hydrate,ammonium hexachloroiridate (Ⅳ),hexachloriridium acid solution,hexachloriridium crystalline acid;- Ruthenium (Ⅲ) chloride hydrate,ruthenium (Ⅳ) hydroxide chloride,ruthenium (Ⅳ) hydroxide chloride solution,ammonium hexachlororuthenate,ruthenium (Ⅲ) chloride solution,potassium,diaquaoctachloronitrido diruthenate.The quality of the production meets the requirements of Russian and foreign consumers.

  15. Platinum Group Thiophenoxyimine Complexes: Syntheses,Crystallographic and Computational Studies of Structural Properties

    Energy Technology Data Exchange (ETDEWEB)

    Krinsky, Jamin L.; Arnold, John; Bergman, Robert G.


    Monomeric thiosalicylaldiminate complexes of rhodium(I) and iridium(I) were prepared by ligand transfer from the homoleptic zinc(II) species. In the presence of strongly donating ligands, the iridium complexes undergo insertion of the metal into the imine carbon-hydrogen bond. Thiophenoxyketimines were prepared by non-templated reaction of o-mercaptoacetophenone with anilines, and were complexed with rhodium(I), iridium(I), nickel(II) and platinum(II). X-ray crystallographic studies showed that while the thiosalicylaldiminate complexes display planar ligand conformations, those of the thiophenoxyketiminates are strongly distorted. Results of a computational study were consistent with a steric-strain interpretation of the difference in preferred ligand geometries.

  16. Effects of interdigitated platinum finger geometry on spectral response characteristics of germanium metal-semiconductor-metal photodetectors. (United States)

    Yang, Hyun-Duk; Janardhanam, V; Shim, Kyu-Hwan; Choi, Chel-Jong


    We fabricated interdigitated germanium (Ge) metal-semiconductor-metal photodetectors (MSM PDs) with interdigitated platinum (Pt) finger electrodes and investigated the effects of Pt finger width and spacing on their spectral response. An increase in the incident optical power enhances the creation of electron-hole pairs, resulting in a significant increase in photo current. Lowering of the Schottky barrier could be a main cause of the increase in both photo and dark current with increasing applied bias. The manufactured Ge MSM PDs exhibited a considerable spectral response for wavelengths in the range of 1.53-1.56 μm, corresponding to the entire C-band spectrum range. A reduction in the area fraction of the Pt finger electrode in the active region by decreasing and increasing finger width and spacing, respectively, led to an increase in illuminated active area and suppression of dark current, which was responsible for the improvement in responsivity and quantum efficiency of Ge MSM PDs.

  17. Leaves of Phragmites australis as potential atmospheric biomonitors of Platinum Group Elements. (United States)

    Bonanno, Giuseppe; Pavone, Pietro


    The increasing emissions of Platinum Group Elements (PGEs), namely Pt, Pd and Rh, may pose a significant risk to ecosystem processes and human health. A periodic assessment of PGEs distribution in the environment is thus of the utmost importance for the implementation of timely measures of mitigation. Although several studies have quantified PGEs in different life forms such as mammals, birds, fish, crustaceans, algae, mosses and even human beings, data about vascular plants need further surveys. This study aimed to test the suitability of the grass Phragmites australis (common reed) as a biomonitor of PGEs atmospheric pollution. The results showed that Pd and Pt concentrations in leaves are significantly higher in urban areas. In particular, Pd showed the highest range of values in line with current studies that consider palladium as the main element of traffic-related pollution. Overall, the leaves of Phragmites australis reflected the different gradient of PGEs emissions, and may thus be considered as potential biomonitors of atmospheric pollution.

  18. Platinum-group elements and minerals in the lower and middle group chromitites of the western Bushveld Complex, South Africa (United States)

    Junge, Malte; Oberthür, Thomas; Osbahr, Inga; Gutter, Paul


    The chromitites of the Bushveld Complex in South Africa contain vast resources of platinum-group elements (PGE). However, knowledge of the distribution and the mineralogical siting of the PGE in the lower group (LG) and middle group (MG) chromitite seams of the Bushveld Complex is limited. We studied concentrates from the LG-6 and MG-2 chromitites of the western Bushveld Complex by a variety of microanalytical techniques. The dominant PGM are sulfides, namely laurite, cooperite-braggite, and malanite-cuprorhodsite, followed by PGE-sulfarsenides, sperrylite, and Pt-Fe alloys. Laurite is the most abundant PGM (vol%). The matching sets of PGM present in the LG and MG chromitites of both the western and the eastern Bushveld Complex, and in the UG-2 chromitite, show strong similarities which support the assumption of a characteristic and general chromitite-related PGM assemblage. Palladium and Rh contents in pentlandite are low and erratic although maximum contents of 7730 ppm Pd and 6020 ppm Rh were detected. Rare thiospinels of the polydymite-linnaeite-greigite series have PGE contents of 1430 ppm Pt, 5370 ppm Rh, and 1460 ppm Pd. The various PGE occur in different deportment: Platinum is generally present in the form of discrete PGM (sulfides, arsenides, alloys). Palladium is present as a large variety of discrete PGM and also incorporated in pentlandite. Rhodium forms discrete PGM and is occasionally present in pentlandite. The IPGE (Os, Ir, and Ru) are dominantly incorporated in laurite (often as inclusions in chromite) and also occur as sulfarsenides.

  19. Platinum-group mineralization at the margin of the Skaergaard intrusion, East Greenland (United States)

    Andersen, Jens C. Ø.; Rollinson, Gavyn K.; McDonald, Iain; Tegner, Christian; Lesher, Charles E.


    Two occurrences of platinum-group elements (PGEs) along the northern margin of the Skaergaard intrusion include a sulfide-bearing gabbro with slightly less than 1 ppm PGE + Au and a clinopyroxene-actinolite-plagioclase-biotite-ilmenite schist with 16 vol% sulfide and 1.8 ppm PGE + Au. Both have assemblages of pyrrhotite, pentlandite, and chalcopyrite typical for orthomagmatic sulfides. Matching platinum-group mineral assemblages with sperrylite (PtAs2), kotulskite (Pd(Bi,Te)1-2), froodite (PdBi2), michenerite (PdBiTe), and electrum (Au,Ag) suggest a common origin. Petrological and geochemical similarities suggest that the occurrences are related to the Skaergaard intrusion. The Marginal Border Series locally displays Ni depletion consistent with sulfide fractionation, and the PGE fractionation trends of the occurrences are systematically enriched by 10-50 times over the chilled margin. The PGE can be explained by sulfide-silicate immiscibility in the Skaergaard magma with R factors of 110-220. Nickel depletion in olivine suggests that the process occurred within the host cumulate, and the low R factors require little sulfide mobility. The sulfide assemblages are different to the chalcopyrite-bornite-digenite assemblage found in the Skaergaard Layered Series and Platinova Reef. These differences can be explained by the early formation of sulfide melt, while magmatic differentiation or sulfur loss caused the unusual sulfide assemblage within the Layered Series. The PGEs indicate that the sulfides formed from the Skaergaard magma. The sulfides and PGEs could not have formed from the nearby Watkins Fjord wehrlite intrusion, which is nearly barren in sulfide. We suggest that silicate-sulfide immiscibility led to PGE concentration where the Skaergaard magma became contaminated with material from the Archean basement.

  20. Analyses of platinum group elements in mosses as indicators of road traffic emissions in Austria (United States)

    Zechmeister, Harald G.; Hagendorfer, Harald; Hohenwallner, Daniela; Hanus-Illnar, Andrea; Riss, Alarich

    The concentrations of platinum group elements (PGE; platinum, palladium, rhodium) and 17 other elements in mosses growing at 32 sampling sites along 12 roads in Austria were analysed. The study included passive monitoring of naturally growing mosses with an experimental design using mosses samples exposed in a tunnel experiment. PGEs (Pt, Pd, Rh) were analysed by ICP-MS (ELAN DRC II, Perkin Elmer SCIEX) according to EN ISO 17294-2 Tl.29. Mean concentrations of PGEs in five moss species were: Pt 7.07±9.97, Pd 2.8±5.2 und Rh 0.6±0.8 ng g -1 dry weight. This is comparable to data derived from measurements of gasoline autocatalyst emissions or airborne particles (<10 μm). Compared to soils and road dust along highways, concentrations in mosses were lower by a factor of ten, compared to grasses they were comparable or somewhat higher. The ratios between the various PGEs were calculated as follows (mean values): Pt/Pd 7.9±10.2, Pt/Rh 12.6±8.3 and Pd/Rh 3.7±2.2. The number of light duty vehicles (<3.5 t) and the distance from the road were the main influential factors for PGE concentrations. Especially strong correlations could be found between Pt and Sb, Cu, Zn, and Cd (in decreasing order), which are all elements derived mainly from road traffic emissions. Cluster analysis (Partioning Around Medoids Method) separated elements derived mainly from soil dust (Ca, Al). An analysis of spatial deposition patterns of PGEs showed a reciprocal decrease of concentrations with increasing distance from the road, reaching background values at distances between 10 and 200 m, sometimes even more, but outside the spatial range of our investigation.

  1. Mapping the UV Photophysics of Platinum Metal Complexes Bound to Nucleobases (United States)

    Sen, Ananya; Dessent, Caroline


    We report the first UV laser spectroscopic study of isolated gas-phase complexes of Platinum metal complex anions bound to a nucleobase as model systems for exploring at the molecular level the key photophysical processes involved in photodynamic therapy. Spectra of the PtIV CN 6 2 - • Uracil and PtII CN 4 2 - • Uracil complexes were acquired across the 220 -320 nm range using mass-selective photodepletion and photofragment action spectroscopy. The spectra of both complexes reveal prominent UV absorption bands that we assign primarily to excitation of the Uracil π - π * localized chromophore. Distinctive UV photofragments are observed for the complexes, with PtIV CN 6 2 - • Uracil photoexcitation resulting in complex fission, while PtII CN 4 2 - • Uracil photoexcitation initiates a nucleobase proton-transfer reaction across 4.4 -5.2 eV and electron detachment above 5.2 eV. The observed photofragments are consistent with ultrafast decay of a Uracil localized excited state back to the electronic ground state followed by intramolecular vibrational relaxation and ergodic complex fragmentation. In addition, we present recent results to explore how the photophysics of the Platinum complex-nucleobase clusters evolves as a function of nucleobase. Results are presented for PtII CN 4 2 - • Uracil complexed to Cytosine, Thymine and Adenine, reveal distinctive decay dynamics which we attribute to the intrinsic decay dynamics of the nucleobase. JPC. Lett. 2014, 5, 3281 to 3285 and PCCP 2014, 16, 15490 to 15500.

  2. Platinum-coated non-noble metal-noble metal core-shell electrocatalysts

    Energy Technology Data Exchange (ETDEWEB)

    Adzic, Radoslav; Zhang, Junliang; Mo, Yibo; Vukmirovic, Miomir


    Core-shell particles encapsulated by a thin film of a catalytically active metal are described. The particles are preferably nanoparticles comprising a non-noble core with a noble metal shell which preferably do not include Pt. The non-noble metal-noble metal core-shell nanoparticles are encapsulated by a catalytically active metal which is preferably Pt. The core-shell nanoparticles are preferably formed by prolonged elevated-temperature annealing of nanoparticle alloys in an inert environment. This causes the noble metal component to surface segregate and form an atomically thin shell. The Pt overlayer is formed by a process involving the underpotential deposition of a monolayer of a non-noble metal followed by immersion in a solution comprising a Pt salt. A thin Pt layer forms via the galvanic displacement of non-noble surface atoms by more noble Pt atoms in the salt. The overall process is a robust and cost-efficient method for forming Pt-coated non-noble metal-noble metal core-shell nanoparticles.

  3. Platinum-group minerals from the Jinbaoshan Pd-Pt deposit, SW China: evidence for magmatic origin and hydrothermal alteration (United States)

    Wang, Christina Yan; Prichard, Hazel M.; Zhou, Mei-Fu; Fisher, Peter C.


    The Jinbaoshan Pt-Pd deposit in Yunnan, SW China, is hosted in a wehrlite body, which is a member of the Permian (˜260 Ma) Emeishan Large Igneous Province (ELIP). The deposit is reported to contain one million tonnes of Pt-Pd ore grading 0.21% Ni and 0.16% Cu with 3.0 g/t (Pd + Pt). Platinum-group minerals (PGM) mostly are ˜10 μm in diameter, and are commonly Te-, Sn- and As-bearing, including moncheite (PtTe2), atokite (Pd3Sn), kotulskite (PdTe), sperrylite (PtAs2), irarsite (IrAsS), cooperite (PtS), sudburyite (PdSb), and Pt-Fe alloy. Primary rock-forming minerals are olivine and clinopyroxene, with clinopyroxene forming anhedral poikilitic crystals surrounding olivine. Primary chromite occurs either as euhedral grains enclosed within olivine or as an interstitial phase to the olivine. However, the intrusion has undergone extensive hydrothermal alteration. Most olivine grains have been altered to serpentine, and interstitial clinopyroxene is often altered to actinolite/tremolite and locally biotite. Interstitial chromite grains are either partially or totally replaced by secondary magnetite. Base-metal sulfides (BMS), such as pentlandite and chalcopyrite, are usually interstitial to the altered olivine. PGM are located with the BMS and are therefore also interstitial to the serpentinized olivine grains, occurring within altered interstitial clinopyroxene and chromite, or along the edges of these minerals, which predominantly altered to actinolite/tremolite, serpentine and magnetite. Hydrothermal fluids were responsible for the release of the platinum-group elements (PGE) from the BMS to precipitate the PGM at low temperature during pervasive alteration. A sequence of alteration of the PGM has been recognized. Initially moncheite and atokite have been corroded and recrystallized during the formation of actinolite/tremolite, and then, cooperite and moncheite were altered to Pt-Fe alloy where they are in contact with serpentine. Sudburyite occurs in veins

  4. The influence of platinum washing-out time on its recovery from used auto catalytic converters

    Directory of Open Access Journals (Sweden)

    A. Fornalczyk


    Full Text Available The used catalytic converters contain small amounts of precious metals. Recovery of these metals is essential for environmental and economic reasons. This work presents a method of Platinum Group Metals (PGM recovery from auto catalytic converters in which they are washed out by a liquid metal. The magneto-hydro-dynamic pump was used to force circulation of liquid metal under the influence of electromagnetic fields The influence of process time on platinum recovery was also carried out.

  5. Distribution of Platinum group elements in road dust in Beijing metropolitan area, China

    Institute of Scientific and Technical Information of China (English)

    WANG Juan; ZHU Ruo-hua; SHI Yan-zhi


    Dust samples collected from the Beijing metropolitan area (China) were evaluated to determine the distribution and the concentration of platinum group elements (PGEs). The dust particles that were smaller than 100 mesh size fraction (150 μm) were analyzed after aqua regia digestion. Concentrations[RL2] of Pt, Rh, and Pd were found to be between 3.96 and 356.3 ng/g, 2.76 and 97.11 ng/g, and 0.1 and 124.9 ng/g, respectively, in the urban areas of Beijing, whereas for the background samples collected from the suburbs of Beijing, the concentration of Pt, Pd, and Rh were very low and ranged from 0.1 to 0.9 ng/g, 0.5 to 1.4 ng/g, and 0.8 to 2.2 ng/g, respectively. The[RL3] distributions of PGEs in road dust were an accurate reflection of the levels of pollution and were found to match with the local traffic conditions. A strong positive correlation was established among all the elements found in road dust. This suggests that emissions of abraded fragments from vehicle exhausts may be the source of the high concentration of Pt, Rh, and Pd in road dust along the main roads of Beijing.

  6. Anticancer and DNA binding activities of platinum (IV) complexes; importance of leaving group departure rate. (United States)

    Pouryasin, Zahra; Yousefi, Reza; Nabavizadeh, S Masoud; Rashidi, Mehdi; Hamidizadeh, Peyman; Alavianmehr, Mohammad-Mehdi; Moosavi-Movahedi, Ali Akbar


    The two six-coordinate Pt(IV) complexes, containing bidentate nitrogen donor/methyl ligands with general formula [Pt(X)2Me2((t)bu2bpy)], where (t)bu2bpy = 4,4'-ditert-butyl-2,2'-bipyridine and X = Cl (C1) or Br (C2), serving as the leaving groups were synthesized for evaluation of their anticancer activities and DNA binding properties. To examine anticancer activities of the synthetic complexes, 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide assay and ethidium bromide/acridine orange (EB/AO) staining method were performed. The binding properties of these complexes to DNA and purine nucleotides were examined, using different spectroscopic techniques. These complexes demonstrated significant anticancer activities against three cancer cell lines Jurkat, K562, and MCF-7. On the basis of the results of EB/AO staining, C1 and C2 were also capable to induce apoptosis in cancer cells. These complexes comprise halide leaving groups, displaying different departure rates; accordingly, they demonstrated slightly dissimilar anticancer activity and significantly different DNA/purine nucleotide binding properties. The results of DNA interaction studies of these complexes suggest a mixed-binding mode, comprising partial intercalation and groove binding. Overall, the results presented herein indicate that the newly synthesized Pt(IV) complexes are promising class of the potential anticancer agents which can be considered as molecular templates in designing novel platinum anticancer drugs. This study also highlights the importance of leaving group in anticancer activity and DNA binding properties of Pt(IV) complexes.

  7. Platinum-group elements in southern Africa: mineral inventory and an assessment of undiscovered mineral resources: Chapter Q in Global mineral resource assessment (United States)

    Zientek, Michael L.; Causey, J. Douglas; Parks, Heather L.; Miller, Robert J.


    The platinum-group elements, platinum, palladium, rhodium, ruthenium, iridium, and osmium, possess unique physical and chemical characteristics that make them indispensable to modern technology and industry. However, mineral deposits that are the main sources of these elements occur only in three countries in the world, raising concerns about potential disruption in mineral supply. Using information in the public domain, mineral resource and reserve information has been compiled for mafic and ultramafic rocks in South Africa and Zimbabwe that host most of the world’s platinum-group element resources.

  8. Material and Energy Flows Associated with Select Metals in GREET 2. Molybdenum, Platinum, Zinc, Nickel, Silicon

    Energy Technology Data Exchange (ETDEWEB)

    Benavides, Pahola T. [Argonne National Lab. (ANL), Argonne, IL (United States); Dai, Qiang [Argonne National Lab. (ANL), Argonne, IL (United States); Sullivan, John L. [Argonne National Lab. (ANL), Argonne, IL (United States); Kelly, Jarod C. [Argonne National Lab. (ANL), Argonne, IL (United States); Dunn, Jennifer B. [Argonne National Lab. (ANL), Argonne, IL (United States)


    In this work, we analyzed the material and energy consumption from mining to production of molybdenum, platinum, zinc, and nickel. We also analyzed the production of solar- and semiconductor-grade silicon. We described new additions to and expansions of the data in GREET 2. In some cases, we used operating permits and sustainability reports to estimate the material and energy flows for molybdenum, platinum, and nickel, while for zinc and silicon we relied on information provided in the literature.

  9. Anticancer Platinum(IV) Prodrugs Containing Monoaminophosphonate Ester as a Targeting Group Inhibit Matrix Metalloproteinases and Reverse Multidrug Resistance. (United States)

    Huang, Xiaochao; Huang, Rizhen; Gou, Shaohua; Wang, Zhimei; Wang, Hengshan


    A novel class of platinum(IV) complexes comprising a monoaminophosphonate ester moiety, which can not only act as a bone-targeting group but also inhibit matrix metalloproteinases (MMPs), were designed and synthesized. Biological assay of these compounds showed that they had potent antitumor activities against the tested cancer cell lines compared with cisplatin and oxaliplatin and indicated low cytotoxicity to human normal liver cells. Particularly, the platinum(IV) complexes were very sensitive to cisplatin resistant cancer cell lines. The corresponding structure-activity relationships were studied and discussed. Related mechanism study revealed that the typical complex 11 caused cell cycle arrest at S phase and induced apoptosis in Bel-7404 cells via a mitochondrial-dependent apoptosis pathway. Moreover, complex 11 had potent ability to inhibit the tumor growth in the NCI-H460 xenograft model comparable to cisplatin.

  10. [Pollution characteristics of platinum group elements in road rust in Xiamen]. (United States)

    Hong, Zhen-yu; Hong, You-wei; Yin, Li-qian; Chen, Jin-sheng; Chen, Yan-ting; Xu, Ling-ling


    With the potential risks for the environment and human health, the concentration and distribution characteristics of platinum group element(PGEs) in road dust in Xiamen city were investigated. Road dust samples were collected from the traffic trunk road, tunnel, tourism area, and industrial area of Xiamen on October 2012. The samples were digested with aqua regia in a microwave assisted digestion system under high pressure condition, separated and purified with cation exchange resin( Dowex AG50W-X8), and the resulting solutions were analyzed by inductively coupled plasma mass spectrometry (ICP-MS). The results showed that the average concentrations(range) of Pd, Pt and Rh in road dust were 246.82 (58.68-765.52) ng x g(-1), 95.45 (42.14-371.36) ng x g(-1) and 51.76 (21.04-119.72) ng x g(-1), respectively, which were two orders of magnitude higher than the background values. Compared with other cities worldwide, the concentrations of Pd, Pt and Rh in road dust in Xiamen were at higher levels. Theconcentrations of PGEs for different functional areas were listed in the following order: tunnel > urban district > industrial area > tourism area, which indicated that their spatial distributions were mainly affected by the traffic intensity. Correlation analysis results showed that concentration of Pd in the urban traffic artery was significantly correlated with Rh, while Pt was not so correlated with Pd and Rh, suggesting that other sources contributed to PGEs in road dust in addition to the vehicle emission. Although motor vehicle traveling was banned in tourist area, the concentration of PGEs was still at a high level. Some of them might originate from the road dust in surrounding area by atmosphere diffusion.

  11. Complex anthropogenic sources of platinum group elements in aerosols on Cape Cod, USA. (United States)

    Sen, Indra S; Peucker-Ehrenbrink, Bernhard; Geboy, Nicholas


    Platinum group elements (PGE) of anthropogenic origin have been reported in rainwater, snow, roadside soil and vegetation, industrial waste, and urban airborne particles around the world. As recent studies have shown that PGE are bioavailable in the environment and pose health risks at chronic levels, the extent of PGE pollution is of global concern. In this study, we report PGE concentrations and osmium isotope ((187)Os/(188)Os) ratios of airborne particles (particulate matter, PM10) collected in Woods Hole, a small coastal village on Cape Cod, Massachusetts, U.S.A. The sampling site is more than 100 km away from the nearest urban centers (Boston, Providence) and has no large industrial emission center within a 30 km radius. The study reveals that, although PGE concentrations in rural airborne particulate matter are orders of magnitude lower than in urban aerosols, 69% of the total osmium is of anthropogenic origin. Anthropogenic PGE signatures in airborne particles are thus not restricted to large cities with high traffic flows and substantial industries; they can also be found in rural environments. We further conclude that the combination of Pt/Rh concentration ratios and (187)Os/(188)Os composition can be used to trace PGE sources. The Pt/Rh and (187)Os/(188)Os composition of Woods Hole aerosols indicate that the anthropogenic PGE fraction is primarily sourced from ore smelting processes, with possible minor contributions from fossil fuel burning and automobile catalyst-derived materials. Our results further substantiate the use of (187)Os/(188)Os in source apportionment studies on continental scales.

  12. Behind platinum's sparkle. (United States)

    Yam, Vivian W W


    As a rare and precious metal that is also resistant to wear and tarnish, platinum is known to be particularly well-suited to jewellery. Vivian Yam reflects on how, beyond its prestigious image, platinum has also found its way into a variety of fields ranging from the petrochemical to the pharmaceutical industry.

  13. Platinum-group elements. Quantification in collected exhaust fumes and studies of catalyst surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Palacios, M.A.; Gomez, M.M.; Moldovan, M. [Departamento de Quimica Analitica, Facultad de CC Quimicas, Universidad Complutense de Madrid, 28040- Madrid (Spain); Morrison, G.; Rauch, S. [Chalmers University of Technology, Gothenburg (Sweden); McLeod, C.; Ma, R. [University of Sheffield, Sheffield (United Kingdom); Laserna, J.; Lucena, P. [University of Malaga, Malaga (Spain); Caroli, S.; Alimonti, A.; Petrucci, F.; Bocca, B. [Istituto Superiore di Sanita, Rome (Italy); Schramel, P.; Lustig, S.; Zischka, M. [GSF-Forschung, Neuherberg (Germany); Wass, U.; Stenbom, B. [Volvo, Gothenberg (Sweden); Luna, M. [Ford, Madrid (Spain); Saenz, J.C. [Instituto Nacional de Tecnica Aeroespacial, INTA, Madrid (Spain); Santamaria, J.; Torrens, J.M. [Seat, Barcelona (Spain)


    Automotive catalytic converters, in which Pt, Pd and Rh (platinum-group elements; PGEs) are the active components for eliminating several noxious components from exhaust fumes, have become the main source of environmental urban pollution by PGEs. This work reports on the catalyst morphology through changes in catalyst surface by scanning electron microscopy/energy dispersive X-ray spectroscopy (SEM/EDX) and laser-induced breakdown spectrometry (LIBS) from fresh to aged catalytic converters. The distribution of these elements in the fresh catalysts analysed (Pt-Pd-Rh gasoline catalyst) is not uniform and occurs mainly in a longitudinal direction. This heterogeneity seems to be greater for Pt and Pd. PGEs released by the catalysts, fresh and aged 30000 km, were studied in parallel. Whole raw exhaust fumes from four catalysts of three different types were also examined. Two of these were gasoline catalysts (Pt-Pd-Rh and Pd-Rh) and the other two were diesel catalysts (Pt). Samples were collected following the 91441 EUDC driving cycle for light-duty vehicle testing. The results show that at 0 km the samples collected first have the highest content of particulate PGEs and although the general tendency is for the release to decrease with increasing number of samples taken, exceptions are frequent. At 30000 km the released PGEs in gasoline and diesel catalysts decreased significantly. For fresh gasoline catalysts the mean of the total amount released was approximately 100, 250 and 50 ng km{sup -1} for Pt, Pd and Rh, respectively. In diesel catalysts the Pt release varied in the range 400-800 ng km{sup -1}. After ageing the catalysts up to 30000 km, the gasoline catalysts released amounts of Pt between 6 and 8 ng km{sup -1}, Pd between 12 and 16 ng km{sup -1} and Rh between 3 and 12 ng km{sup -1}. In diesel catalysts the Pt release varied in the range 108-150 ng km{sup -1}. The soluble portion of PGEs in the HNO{sub 3} collector solution represented less than 5% of the

  14. Experimental partitioning of Zr, Ti, and Nb between silicate liquid and a complex noble metal alloy and the partitioning of Ti between perovskite and platinum metal (United States)

    Jurewicz, Stephen R.; Jones, John H.


    El Goresy et al.'s observation of Nb, Zr, and Ta in refractory platinum metal nuggets (RPMN's) from Ca-Al-rich inclusions (CAI's) in the Allende meteorite led them to propose that these lithophile elements alloyed in the metallic state with noble metals in the early solar nebula. However, Grossman pointed out that the thermodynamic stability of Zr in the oxide phase is vastly greater than metallic Zr at estimated solar nebula conditions. Jones and Burnett suggested this discrepancy may be explained by the very non-ideal behavior of some lithophile transition elements in noble metal solutions and/or intermetallic compounds. Subsequently, Fegley and Kornacki used thermodynamic data taken from the literature to predict the stability of several of these intermetallic compounds at estimated solar nebula conditions. Palme and Schmitt and Treiman et al. conducted experiments to quantify the partitioning behavior of certain lithophile elements between silicate liquid and Pt-metal. Although their results were somewhat variable, they did suggest that Zr partition coefficients were too small to explain the observed 'percent' levels in some RPMN's. Palme and Schmitt also observed large partition coefficients for Nb and Ta. No intermetallic phases were identified. Following the work of Treiman et al., Jurewicz and Jones performed experiments to examine Zr, Nb, and Ti partitioning near solar nebula conditions. Their results showed that Zr, Nb, and Ti all have an affinity for the platinum metal, with Nb and Ti having a very strong preference for the metal. The intermetallic phases (Zr,Fe)Pt3, (Nb,Fe)Pt3, and (Ti,Fe)Pt3 were identified. Curiously, although both experiments and calculations indicate that Ti should partition strongly into Pt-metal (possibly as TiPt3), no Ti has ever been observed in any RPMN's. Fegley and Kornacki also noticed this discrepancy and hypothesized that the Ti was stabilized in perovskite which is a common phase in Allende CAI's.

  15. Investigation of Catalytic Finite-Size-Effects of Platinum Metal Clusters

    DEFF Research Database (Denmark)

    Li, Lin; Larsen, Ask Hjorth; Romero, Nichols A.


    In this paper, we use density functional theory (DFT) calculations on highly parallel computing resources to study size-dependent changes in the chemical and electronic properties of platinum (Pt) for a number of fixed freestanding clusters ranging from 13 to 1415 atoms, or 0.7–3.5 nm in diameter...

  16. Long range diffusion noise in platinum microwires with metallic adhesion layers

    NARCIS (Netherlands)

    Moktadir, Z.; van Honschoten, J.W.; Elwenspoek, Michael Curt


    Voltage fluctuations of platinum wires hosted by silicon nitride beams were investigated. The authors considered four variants of the wires: three with an adhesion layer and one without an adhesion layer. They found that the presence of an adhesion layer changes the nature of the power spectrum

  17. Osmium-Isotope and Platinum-Group-Element Systematics of Impact-Melt Rocks, Chesapeake Bay Impact Structure, Virginia, USA (United States)

    Lee, Seung Ryeol; Wright Horton, J., Jr.; Walker, Richard J.


    Osmium (Os) isotopes and platinum-group elements (PGEs) are useful for geochemically identifying a meteoritic component within impact structures, because meteorites are typically characterized by low (187)Os/(188)Os ratios and high PGE concentrations. In contrast, most types of crustal target rocks have high radiogenic Os and very low PGE concentrations. We have examined Os isotope and PGE systematics of impact-melt rocks and pre-impact target rocks from a 2004 test hole in the late Eocene Chesapeake Bay impact structure and from nearby coreholes. Our goal is to determine the proportion of the projectile component in the melt rock Additional information is included in the original extended abstract.

  18. Geochemistry and mineralogy of platinum-group elements (PGE in chromites from Centralnoye I, Polar Urals, Russia

    Directory of Open Access Journals (Sweden)

    Jan Pašava


    Full Text Available The Polar Urals region of northern Russia is well known for large chromium (Cr-bearing massifs with major chromite orebodies, including the Centralnoye I deposit in the Ray-Iz ultramafic massif of the Ural ophiolite belt. New data on platinum (Pt-group elements (PGE, geochemistry and mineralogy of the host dunite shows that the deposit has anomalous iridium (Ir values. These values indicate the predominance of ruthenium–osmium–iridium (Ru–Os–Ir-bearing phases among the platinum-group mineral (PGM assemblage that is typical of mantle-hosted chromite ores. Low Pt values in chromites and increased Pt values in host dunites might reflect the presence of cumulus PGM grains. The most abundant PGM found in the chromite is erlichmanite (up to 15 μm. Less common are cuproiridsite (up to 5 μm, irarsite (up to 4–5 μm, and laurite (up to 4 μm. The predominant sulfide is heazlewoodite, in intergrowth with Ni–Fe alloys, sporadically with pentlandite, and rarely with pure nickel. Based on the average PGE values and estimated Cr-ore resources, the Centralnoye I deposit can be considered as an important resource of PGE.

  19. Unprecedented 1D Mixed-metal Polynuclear Cyclometalated Platinum Complexes: Synthesis,Structural Characterization and Spectroscopic Properties

    Institute of Scientific and Technical Information of China (English)

    CAO Qian-Yong; GAN Xin; ZHANG Jun-Feng; CHI Shao-Ming; LI Hui-Fangjie; FU Wen-Fu


    The complexes [Pt2L2(μ-dppm)](ClO4)2.(1) and {[Pt2L2(μ-dppm)Li(CH3CN)2](ClO4)3}n (2),where HL is 6-[4-(diethoxyphosphorylmethyl)phenyl]-2,2'-bipyridinyl and dppm is bis(diphenylphosphino)methane,have been synthesized and characterized.In complex 1 the platinum(Ⅱ) center adopts a distorted square planar coordination geometry.The polymer 2 exhibits a "stairstep" configuration with one-dimensional Pt(Ⅱ)N^N^CPO- Li(Ⅰ)-OPC^N^NPt(Ⅱ) mixed-metal units which are linked through dppm.Both complexes have metal-metal interaction with PtPt distances of 3.325(2) and 3.1432(9) (A),respectively,and display strong metal-metal-to-ligand charge-transfer (MMLCT) triplet state emission.The density-functional-theory calculation was used to interpret the absorption spectra of the complexes.

  20. Oxidizing behavior of some platinum metal fluorides. [Xe complexes with Pt, Pd fluorides; Chlorine-2 oxidation by transition metal hexafluorides

    Energy Technology Data Exchange (ETDEWEB)

    Graham, L.


    The previously known compounds Xe/sub 2/F/sub 3//sup +/PtF/sub 6//sup -/, XeF/sup +/PtF/sub 6//sup -/ and XeF/sub 2/.2PtF/sub 4/(XePt/sub 2/F/sub 10/) were prepared by the interaction of XeF/sub 2/ with PtF/sub 4/. The new compounds XeF/sub 2/.PdF/sub 4/ and XeF/sub 2/.2PdF/sub 4/(XePd/sub 2/F/sub 10/) were produced by interaction of XeF/sub 2/ with either PdF/sub 4/ or Pd/sub 2/F/sub 6/. A weight loss-versus-time curve indicated the presence of 4:1, 3:1 and 2:1 XeF/sub 2//PdF/sub 4/ complexes. The thermal decomposition of XeFPtF/sub 6/ or XePd/sub 2/F/sub 10/ yields highly pure XeF/sub 4/. Thus the interaction of XeF/sub 2/ with platinum fluorides (PtF/sub 4/ or PtF/sub 5/) or palladium fluorides (Pd/sub 2/F/sub 6/ or PdF/sub 4/) provides for the conversion of XeF/sub 2/ to XeF/sub 4/. The compound XePd/sub 2/F/sub 10/ is a close structural relative of XePt/sub 2/F/sub 10/, and spectroscopic evidence suggests that both are salts of XeF/sup +/ and a polymeric (M/sub 2/F/sub 9/)/sub x//sup x-/ ion. A Xe:PtF/sub 6/ material of approximately 1:1 stoichiometry has been prepared and compared with XePdF/sub 6/(XeF/sub 2/.PdF/sub 4/). The interaction of chlorine with the third-series transition metal hexafluorides has been investigated. Gravimetric and tensimetric evidence indicate that the initial product of the Cl/sub 2/ plus IrF/sub 6/ reaction is a solid of composition Cl/sub 2/IrF/sub 6/. Vibrational spectroscopic and other evidence indicates that this solid yields a sequence of products, of which Cl/sub 3//sup +/IrF/sub 6//sup -/, Cl/sub 3//sup +/Ir/sub 2/F/sub 11//sup -/ and Ir/sub 4/F/sub 20/ have been identified, the last being the ultimate solid product of the room temperature decomposition of the adduct. A new chlorine fluoride generated in the room temperature decomposition of Cl/sub 2/IrF/sub 6/ has been tentatively formulated as Cl/sub 3/F from infrared evidence.

  1. Binding of kinetically inert metal ions to RNA: the case of platinum(II). (United States)

    Chapman, Erich G; Hostetter, Alethia A; Osborn, Maire F; Miller, Amanda L; DeRose, Victoria J


    In this chapter several aspects of Pt(II) are highlighted that focus on the properties of Pt(II)-RNA adducts and the possibility that they influence RNA-based processes in cells. Cellular distribution of Pt(II) complexes results in significant platination of RNA, and localization studies find Pt(II) in the nucleus, nucleolus, and a distribution of other sites in cells. Treatment with Pt(II) compounds disrupts RNA-based processes including enzymatic processing, splicing, and translation, and this disruption may be indicative of structural changes to RNA or RNA-protein complexes. Several RNA-Pt(II) adducts have been characterized in vitro by biochemical and other methods. Evidence for Pt(II) binding in non-helical regions and for Pt(II) cross-linking of internal loops has been found. Although platinated sites have been identified, there currently exists very little in the way of detailed structural characterization of RNA-Pt(II) adducts. Some insight into the details of Pt(II) coordination to RNA, especially RNA helices, can be gained from DNA model systems. Many RNA structures, however, contain complex tertiary folds and common, purine-rich structural elements that present suitable Pt(II) nucleophiles in unique arrangements which may hold the potential for novel types of platinum-RNA adducts. Future research aimed at structural characterization of platinum-RNA adducts may provide further insights into platinum-nucleic acid binding motifs, and perhaps provide a rationale for the observed inhibition by Pt(II) complexes of splicing, translation, and enzymatic processing.

  2. Formation of {open_quotes}metal wool{close_quotes} structures and dynamics of catalytic etching of platinum surfaces during ammonia oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Lyubovsky, M.R.; Barelko, V.V. [Institute of Chemical Physics in Chernogolovka, Moscow (Russian Federation)


    Reconstruction of a clean surface of a platinum catalyst and a platinum surface covered with gold during ammonia oxidation was studied by SEM observations. It was found that the process of catalytic etching had two sequential stages in which different crystal structures with different rates of growth formed on the surface. The first stage was the formation of parallel facets, and the second stage was the formation of individual microcrystals with perfect crystal faces. It was also found that the second state had a threshold character, beginning after some delay from the start of the reaction. A structure resembling metal wool and consisting of interlaced platinum filaments was found to form on the surface of gold-covered platinum catalysts. Characteristic features of this structure`s development are reported. The growth of filaments is attributed to the vapor-liquid-solid mechanism of whisker growth. On the basis of the observed platinum whisker formation and behavior during ammonia oxidation, a mechanism of catalyst surface reconstruction that explains observed characteristic features of the process of catalytic etching is proposed. 25 refs., 8 figs.

  3. Kinetics and mechanism for reversible chloride transfer between mercury(II) and square-planar platinum(II) chloro ammine, aqua, and sulfoxide complexes. Stabilities, spectra, and reactivities of transient metal-metal bonded platinum-mercury adducts. (United States)

    Gröning, O; Sargeson, A M; Deeth, R J; Elding, L I


    The Hg2+aq- and HgCl+aq-assisted aquations of [PtCl4]2- (1), [PtCl3(H2O)]- (2), cis-[PtCl2(H2O)2] (3), trans-[PtCl2(H2O)2] (4), [PtCl(H2O)3]+ (5), [PtCl3Me2SO]- (6), trans-[PtCl2(H2O)Me2SO] (7), cis-[PtCl(H2O)2Me2SO]+ (8), trans-[PtCl(H2O)2M32SO]+ (9), trans-[PtCl2(NH3)2] (10), and cis-[PtCl2(NH3)2] (11) have been studied at 25.0 degrees C in a 1.00 M HClO4 medium buffered with chloride, using stopped-flow and conventional spectrophotometry. Saturation kinetics and instantaneous, large UV/vis spectral changes on mixing solutions of platinum complex and mercury are ascribed to formation of transient adducts between Hg2+ and several of the platinum complexes. Depending on the limiting rate constants, these adducts are observed for a few milliseconds to a few minutes. Thermodynamic and kinetics data together with the UV/vis spectral changes and DFT calculations indicate that their structures are characterized by axial coordination of Hg to Pt with remarkably short metal-metal bonds. Stability constants for the Hg2+ adducts with complexes 1-6, 10, and 11 are (2.1 +/- 0.4) x 10(4), (8 +/- 1) x 10(2), 94 +/- 6, 13 +/- 2, 5 +/- 2, 60 +/- 6, 387 +/- 2, and 190 +/- 3 M-1, respectively, whereas adduct formation with the sulfoxide complexes 7-9 is too weak to be observed. For analogous platinum(II) complexes, the stabilities of the Pt-Hg adducts increase in the order sulfoxide < aqua < ammine complex, reflecting a sensitivity to the pi-acid strength of the Pt ligands. Rate constants for chloride transfer from HgCl+ and HgCl2 to complexes 1-11 have been determined. Second-order rate constants for activation by Hg2+ are practically the same as those for activation by HgCl+ for each of the platinum complexes studied, yet resolved contributions for Hg2+ and HgCl+ reveal that the latter does not form dinuclear adducts of any significant stability. The overall experimental evidence is consistent with a mechanism in which the accumulated Pt(II)-Hg2+ adducts are not reactive

  4. Platinum group elements in stream sediments of mining zones: The Hex River (Bushveld Igneous Complex, South Africa) (United States)

    Almécija, Clara; Cobelo-García, Antonio; Wepener, Victor; Prego, Ricardo


    Assessment of the environmental impact of platinum group elements (PGE) and other trace elements from mining activities is essential to prevent potential environmental risks. This study evaluates the concentrations of PGE in stream sediments of the Hex River, which drains the mining area of the Bushveld Igneous Complex (South Africa), at four sampling points. Major, minor and trace elements (Fe, Ca, Al, Mg, Mn, V, Cr, Zn, Cu, As, Co, Ni, Cd, and Pb) were analyzed by FAAS and ETAAS in suspended particulate matter and different sediment fractions (rocks. The highest concentrations were observed closer to the mining area, decreasing with distance and in the cycle, increasing the presence of PGE in the fine fraction of river sediments. We propose that indicators such as airborne particulate matter, and soil and river sediment quality, should be added to the protocols for evaluating the sustainability of mining activities.

  5. Platinum-group elements in rocks from the voikar-syninsky ophiolite complex, Polar Urals, U.S.S.R. (United States)

    Page, N.J.; Aruscavage, P. J.; Haffty, J.


    Analyses of platinum-group elements (PGE) in rocks collected from the Voikar-Syninsky ophiolite in the Polar Urals suggest that the distribution and geochemistry of PGE in this Paleozoic ophiolite are similar to those in Mesozoic ophiolites from elsewhere. Chondrite-normalized PGE patterns for chromitite, the tectonite unit, and ultramafic and mafic cumulate unit have negative slopes. These results are similar to those found for chromitites from other ophiolites; stratiform chromities show positive slopes. If the magmas that form both types of chromitite originate from similar mantle source material with respect to PGE content, the processes involved must be quite different. However, the distinct chondrite-normalized PGE patterns may reflect differing source materials. ?? 1983 Springer-Verlag.

  6. Fibrous Platinum-Group Minerals in “Floating Chromitites” from the Loma Larga Ni-Laterite Deposit, Dominican Republic

    Directory of Open Access Journals (Sweden)

    Thomas Aiglsperger


    Full Text Available This contribution reports on the observation of enigmatic fibrous platinum-group minerals (PGM found within a chromitite body included in limonite (“floating chromitite” from Ni-laterites in the Dominican Republic. Fibrous PGM have a Ru-Os-Ir-Fe dominated composition and are characterized by fibrous textures explained by grain-forming fibers which are significantly longer (1–5 µm than they are wide (~100 nm. Back-scattered electron (BSE images suggest that these nanofibers are platinum-group elements (PGE-bearing and form <5 µm thick layers of bundles which are oriented orthogonal to grains’ surfaces. Trace amounts of Si are most likely associated with PGE-bearing nanofibers. One characteristic fibrous PGM was studied in detail: XRD analyses point to ruthenian hexaferrum. However, the unpolished fibrous PGM shows numerous complex textures on its surface which are suggestive for neoformation processes: (i features suggesting growth of PGE-bearing nanofibers; (ii occurrence of PGM nanoparticles within film material (biofilm? associated with PGE-bearing nanofibers; (iii a Si-rich and crater-like texture hosting PGM nanoparticles and an Ir-rich accumulation of irregular shape; (iv complex PGM nanoparticles with ragged morphologies, resembling sponge spicules and (v oval forms (<1 µm in diameter with included PGM nanoparticles, similar to those observed in experiments with PGE-reducing bacteria. Fibrous PGM found in the limonite may have formed due to supergene (bio-weathering of fibrous Mg-silicates which were incorporated into desulphurized laurite during stages of serpentinization.

  7. Novel platinum(II) complexes of long chain aliphatic diamine ligands with oxalato as the leaving group: Comparative cytotoxic activity relative to chloride precursors

    Energy Technology Data Exchange (ETDEWEB)

    Silva, Heveline; Barra, Carolina V.; Rocha, Fillipe V.; Fontes, Ana Paula S. [Universidade Federal de Juiz de Fora (UFJF), MG (Brazil). Dept. de Quimica; Lopes, Miriam T.P. [Universidade Federal deMinas Gerais (UFMG), Belo Horizonte, MG (Brazil). Dept. de Farmacologia; Frezard, Frederic, E-mail: frezard@icb.ufmg.b [Universidade Federal de Minas Gerais (UFMG), Belo Horizonte, MG (Brazil). Dept. de Fisiologia e Biofisica


    Platinum complexes play an important role in the development of anticancer drugs. Their cytotoxicity can be influenced by the nature of the leaving ligands, due to the hydrolysis reaction that occurs prior to the binding of the platinum complex to DNA. Also, non-leaving groups such as lipophilic diamines may affect cellular uptake. In this work, we describe the synthesis of platinum(II) complexes having oxalato and long chain aliphatic N-alkyl ethylenediamines as ligands. The products were characterized by elemental analyses, infrared spectroscopy and {sup 1}H, {sup 13}C and {sup 195}Pt NMR spectroscopy. Biological activity was assessed against tumor cell lines (A{sub 549}, B16-F1, B16-F10, MDA-MB-231) and non-tumor cell lines (BHK-21 and CHO). The length of the carbon chain affects the cytotoxicity and the oxalato complexes were less cytotoxic than the respective chloride-containing analogues. (author)

  8. Incorporation of transition and platinum group elements (PGE) in Co-rich Mn crusts at Afanasiy-Nikitin Seamount (AFS) in the equatorial S Indian Ocean

    Digital Repository Service at National Institute of Oceanography (India)

    Glasby, G.P.

    table of elements in the ocean. Available from URL: http:// Peucker-Ehrenbrink, B., Bach, W., Hart, S. R., Blusztajn, J. S. and Abbruzzese, T. (2003) Rhenium-osmium isotope systematics and platinum group element...

  9. Platinum-group element abundance and distribution in chromite deposits of the Acoje Block, Zambales Ophiolite Complex, Philippines (United States)

    Bacuta, G.C.; Kay, R.W.; Gibbs, A.K.; Lipin, B.R.


    Platinum-group elements (PGE) occur in ore-grade concentration in some of the chromite deposits related to the ultramafic section of the Acoje Block of the Zambales Ophiolite Complex. The deposits are of three types: Type 1 - associated with cumulate peridotites at the base of the crust; Type 2 - in dunite pods from the top 1 km of mantle harzburgite; and Type 3 - like Type 2, but in deeper levels of the harzburgite. Most of the deposites have chromite compositions that are high in Cr with Cr/(Cr + Al) (expressed as chromium index, Cr#) > 0.6; high-Al (Cr# Pd, thought to be characteristic of PGE-barren deposits) and positive slope (Ir Platinum and Pd occur as alloy inclusions (and possibly as solid solution) in interstitial Ni-Cu sulfides and as tellurobismuthides in serpentine and altered sulfides. Variability of PGE distribution may be explained by alteration, crystal fractionation or partial melting processes. Alteration and metamorphism were ruled out, because PGE contents do not correlate with degree of serpentinization or the abundance and type (hydroxyl versus non-hydroxyl) of silicate inclusions in chromite. Preliminary Os isotopic data do not support crustal contamination as a source of the PGEs in the Acoje deposits. The anomalous PGE concentrations in Type 1 high-Cr chromite deposits are attributed to two stages of enrichment: an early enrichment of their mantle source from previous melting events and a later stage of sulfide segregation accompanying chromite crystallization. High-Al chromite deposits which crystallized from basalts derived from relatively low degrees of melting owe their low PGE content to partitioning of PGEs in sulfides and alloys that remain in the mantle. High-Cr deposits crystallized from melts that were previously enriched with PGEs during early melting events of their mantle source; Pt and Pd ore concentrations (ppm levels) are attained by segregation of magmatic sulfides. The Acoje deposits indicate that ophiolites are a

  10. Homochiral helical metal-organic frameworks of group 1 metals. (United States)

    Reger, Daniel L; Leitner, Andrew; Smith, Mark D; Tran, T Thao; Halasyamani, P Shiv


    The reactions of (S)-2-(1,8-naphthalimido)propanoic acid (HL(ala)) and (S)-2-(1,8-naphthalimido)-3-hydroxypropanoic acid (HL(ser)), protonated forms of ligands that contain a carboxylate donor group, an enantiopure chiral center, and a 1,8-naphthalimide π···π stacking supramolecular tecton and in the case of HL(ser) an alcohol functional group, with the appropriate alkali metal hydroxide followed by a variety of crystallization methods leads to the formation of crystalline K(L(ala))(MeOH) (1), K(L(ala))(H2O) (2), Na(L(ala))(H2O) (3), KL(ser) (4), CsL(ser) (5), and CsL(ala) (6). Each of these new complexes has a solid state structure based on six-coordinate metals linked into homochiral helical rod secondary building unit (SBU) central cores. In addition to the bonding of the carboxylate and solvent (in the case of L(ser) the ligand alcohol) to the metals, both oxygens on the 1,8-naphthalimide act as donor groups. One naphthalimide oxygen bonds to the same helical rod SBU as the carboxylate group of that ligand forming a chelate ring. The other naphthalimide oxygen bonds to adjacent SBUs. In complexes 1-3, this inter-rod link has a square arrangement bonding four other rods forming a three-dimensional enantiopure metal-organic framework (MOF) structure, whereas in 4-6 this link has a linear arrangement bonding two other rods forming a two-dimensional, sheet structure. In the latter case, the third dimension is supported exclusively by interdigitated π···π stacking interactions of the naphthalimide supramolecular tecton, forming enantiopure supramolecular MOF solids. Compounds 1-3 lose the coordinated solvent when heating above 100 °C. For 1, the polycrystalline powder reverts to 1 only by recrystallization from methanol, whereas compounds 2 and 3 undergo gas/solid, single-crystal to single-crystal transformations to form dehydrated compounds 2* and 3*, and rehydration occurs when crystals of these new complexes are left out in air. The reversible single

  11. Platinum Group Organometallics Based on "Pincer" Complexes: Sensors, Switches, and Catalysts In memory of Prof. Dr. Luigi M. Venanzi and his pioneering work in organometallic chemistry, particularly in PCP pincer chemistry. (United States)

    Albrecht, Martin; van Koten, Gerard


    Since the first reports in the late 1970s on transition metal complexes containing pincer-type ligands-named after the particular coordination mode of these ligands-these systems have attracted increasing interest owing to the unusual properties of the metal centers imparted by the pincer ligand. Typically, such a ligand comprises an anionic aryl ring which is ortho,ortho-disubstituted with heteroatom substituents, for example, CH(2)NR(2), CH(2)PR(2) or CH(2)SR, which generally coordinate to the metal center, and therefore support the M-C sigma bond. This commonly results in a terdentate and meridional coordination mode consisting of two metallacycles which share the M-C bond. Detailed studies of the formation and the properties of a large variety of pincers containing platinum group metal complexes have provided direct access to both a fundamental understanding of a variety of reactions in organometallic chemistry and to a range of new applications of these complexes. The discovery of alkane dehydrogenation catalysts, the mechanistic elucidation of fundamental transformations (for example, C-C bond activation), the construction of the first metallodendrimers for sustainable homogeneous catalysis, and the engineering of crystalline switches for materials processing represent only a few of the many highlights which have emanated from these numerous investigations. This review discusses the synthetic methodologies that are currently available for the preparation of platinum group metal complexes containing pincer ligands and especially emphasizes different applications that have been realized in materials science such as the development and engineering of sensors, switches, and catalysts.

  12. Inorganic nanocarriers for platinum drug delivery

    Directory of Open Access Journals (Sweden)

    Ping’an Ma


    Full Text Available Nowadays platinum drugs take up almost 50% of all the clinically used anticancer drugs. Besides cisplatin, novel platinum agents including sterically hindered platinum (II drugs, chemically reductive platinum (IV drugs, photosensitive platinum (IV drugs, and multinuclear platinum drugs have been developed recently, with a few entering clinic trials. Rapid development of nanobiotechnology makes targeted delivery of anticancer platinum agents to the tumor site possible, while simultaneously minimizing toxicity and maximizing the drug efficacy. Being versatile drug carriers to deliver platinum drugs, inorganic nanovehicles such as gold nanoparticles, iron oxide nanomaterials, carbon nanotubes, mesoporous nanosilica, metal-organic frameworks (MOFs, have been extensively studied over the past decades. In contrast to conventional polymeric and lipid nanoparticles, inorganic nanoparticles based drug carriers are peculiar as they have shown excellent theranostic effects, revealing themselves an indispensable part of future nanomedicine. Here, we will elaborate recent research advances on fabrication of inorganic nanoparticles for platinum drug delivery.

  13. Platinum nitride with fluorite structure

    Energy Technology Data Exchange (ETDEWEB)

    Yu, Rong; Zhang, Xiao-Feng


    The mechanical stability of platinum nitride has been studied using first-principles calculations. By calculating the single-crystal elastic constants, we show that platinum nitride can be stabilized in the fluorite structure, in which the nitrogen atoms occupy all the tetrahedral interstitial sites of the metal lattice. The stability is attributed to the pseudogap effect from analysis of the electronic structure.

  14. Investigation of the usefulness of NTA, EDTA and DTPA in separation of some platinum metals on cellulose exchangers. (United States)

    Brajter, K; Słonawska, K


    The possibility of using NTA, EDTA and DTPA as complexing agents for separation of some platinum group ions on cellulose ion-exchangers has been investigated. The greatest differences in the affinities of Pd(II) and Pt(IV) toward the cellulose ion-exchangers are obtained in the presence of DPTA, Cellex D (as ion-exchanger) in hydroxide form. The column separation of Pd(II) from Pt(IV), Rh(III) from Pd(II) and of a Rh(III)Pd(II)Pt(IV) mixture can be achieved with DPTA and chloride solutions. The method can be for determination of the components of RhPdPt alloys.

  15. Intrinsic thermoelectric power of group VB metals

    Directory of Open Access Journals (Sweden)

    Gunadhor Singh Okram


    Full Text Available We have reinvestigated the thermopower of group VB metals in polycrystalline forms in the temperature range of 6-300K, taking into account the critical nature of the sample surface and heat treatment especially for niobium. Strikingly small magnitude, negative sign, phonon drag dip and superconductivity not reported previously were observed in surface-cleaned single crystalline Nb. However, while thermopower magnitudes are small, mixed signs were found in the polycrystalline V, Nb and Ta samples. These properties were therefore interpreted as their intrinsic properties and were briefly discussed taking into account of the existing theory by fitting also the data that give the Fermi energies of 10.94 eV, 5.08 eV and 1.86eV, respectively.

  16. Platinum Group Elements (PGE) geochemistry of komatiites and boninites from Dharwar Craton, India: Implications for mantle melting processes (United States)

    Saha, Abhishek; Manikyamba, C.; Santosh, M.; Ganguly, Sohini; Khelen, Arubam C.; Subramanyam, K. S. V.


    High MgO volcanic rocks having elevated concentrations of Ni and Cr are potential hosts for platinum group elements (PGE) owing to their primitive mantle origin and eruption at high temperatures. Though their higher PGE abundance is economically significant in mineral exploration studies, their lower concentrations are also valuable geochemical tools to evaluate petrogenetic processes. In this paper an attempt has been made to evaluate the PGE geochemistry of high MgO volcanic rocks from two greenstone belts of western and eastern Dharwar Craton and to discuss different mantle processes operative at diverse geodynamic settings during the Neoarchean time. The Bababudan greenstone belt of western and Gadwal greenstone belt of eastern Dharwar Cratons are dominantly composed of high MgO volcanic rocks which, based on distinct geochemical characteristics, have been identified as komatiites and boninites respectively. The Bababudan komatiites are essentially composed of olivine and clinopyroxene with rare plagioclase tending towards komatiitic basalts. The Gadwal boninites contain clinopyroxene, recrystallized hornblende with minor orthopyroxene, plagioclase and sulphide minerals. The Bababudan komatiites are Al-undepleted type (Al2O3/TiO2 = 23-59) with distinctly high MgO (27.4-35.8 wt.%), Ni (509-1066 ppm) and Cr (136-3036 ppm) contents. These rocks have low ΣPGE (9-42 ppb) contents with 0.2-2.4 ppb Iridium (Ir), 0.2-1.4 ppb Osmium (Os) and 0.4-4.4 ppb Ruthenium (Ru) among Iridium group PGE (IPGE); and 1.4-16.2 ppb Platinum (Pt), 2.8-19 ppb Palladium (Pd) and 0.2-9.8 ppb Rhodium (Rh) among Platinum group PGE (PPGE). The Gadwal boninites are high-Ca boninites with CaO/Al2O3 ratios varying between 0.8 and 1.0, with 12-24 wt.% MgO, 821-1168 ppm Ni and 2307-2765 ppm Cr. They show higher concentration of total PGE (82-207 ppb) with Pt concentration ranging from 13 to 19 ppb, Pd between 65 and 180 ppb and Rh in the range of 1.4-3 ppb compared to the Bababudan komatiites. Ir

  17. Platinum-Group Minerals and Other Accessory Phases in Chromite Deposits of the Alapaevsk Ophiolite, Central Urals, Russia

    Directory of Open Access Journals (Sweden)

    Federica Zaccarini


    Full Text Available An electron microprobe study has been carried out on platinum-group minerals, accessory phases, and chromite in several chromite deposits of the Alapaevsk ophiolite (Central Urals, Russia namely the Bakanov Kluch, Kurmanovskoe, Lesnoe, 3-d Podyony Rudnik, Bol’shaya Kruglyshka, and Krest deposits. These deposits occur in partially to totally serpentinized peridotites. The microprobe data shows that the chromite composition varies from Cr-rich to Al-rich. Tiny platinum-group minerals (PGM, 1–10 µm in size, have been found in the chromitites. The most abundant PGM is laurite, accompanied by minor cuproiridsite and alloys in the system Os–Ir–Ru. A small grain (about 20 μm was found in the interstitial serpentine of the Bakanov Kluch chromitite, and its calculated stoichiometry corresponds to (Ni,Fe5P. Olivine, occurring in the silicate matrix or included in fresh chromite, has a mantle-compatible composition in terms of major and minor elements. Several inclusions of amphibole, Na-rich phlogopite, and clinopyroxene have been identified. The bimodal Cr–Al composition of chromite probably corresponds to a vertical distribution in the ophiolite sequence, implying formation of Cr-rich chromitites in the deep mantle, and Al-rich chromitites close to the Moho-transition zone, in a supra-subduction setting. The presence of abundant hydrous silicate inclusions, such as amphibole and phlogopite, suggests that the Alapaevsk chromitites crystallized as a result of the interaction between a melt enriched in fluids and peridotites. Laurite and cuproiridsite are considered to be magmatic in origin, i.e., entrapped as solid phases during the crystallization of chromite at high temperatures. The sulfur fugacity was relatively high to allow the precipitation of Ir-bearing sulfides, but below the Os–OsS2 buffer. The alloys in the system Os–Ir–Ru are classified as secondary PGM, i.e., formed at low temperature during the serpentinization process. The

  18. Vapour Treatment Method Against Other Pyro- and Hydrometallurgical Processes Applied to Recover Platinum From Used Auto Catalytic Converters

    Institute of Scientific and Technical Information of China (English)

    Agnieszka FORNALCZYK; Mariola SATERNUS


    Today more and more cars are produced every year.All of them have to be equipped with catalytic converters,the main role of which is to obtain substances harmless to the environment instead of exhausted gases.Catalytic converters contain platinum group metals (PGM) especially platinum,palladium and rhodium.The price of these metals and their increasing demand are the reasons why today it is necessary to recycle used auto catalytic converters.There are many available methods of recovering PGM metals from them,especially platinum.These methods used mainly hydrometallurgical processes; however pyrometallurgical ones become more and more popular.The article presents results of the research mainly concerning pyrometallurgical processes.Two groups of research were carried out.In the first one different metals such as lead,magnesium and copper were used as a metal collector.During the tests,platinum went to those metals forming an alloy.In other research metal vapours were blown through catalytic converter carrier (grinded or whole).In the tests metals such as calcium,magnesium,cadmium and zinc were applied.As a result white or grey powder (metal plus platinum) was obtained.The tables present results of the research.Processing parameters and conclusions are also shown.To compare efficiency of pyrometallurgical and hydrometallurgical methods catalytic converter carrier and samples of copper with platinum obtained from pyrometallurgical method were solved in aqua regia,mixture of aqua regia and fluoric acid.


    Institute of Scientific and Technical Information of China (English)

    CHEN Yuanyin; MENG Lingzhi; YIN Yihua; GENG Chengai


    The title polymer was prepared from 5-diethylamino-3-thia-pentyl glycidyl ether and diethylene glycol bisglycidyl ether via ring-opening copolymerization. It was found that this reaction could be catalyzed by sodium, but not Lewis acid. The obtained polymer can coordinate with platinum compound, and the platinum complex is a new kind of catalyst for the hydrosilylation of olefins with triethoxysilane.

  20. In vitro permeation of platinum and rhodium through Caucasian skin. (United States)

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


    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.

  1. Osmium isotope evidence for a crustal origin of platinum group elements in the Sudbury nickel ore, Ontario, Canada (United States)

    Dickin, A. P.; Richardson, J. M.; Crocket, J. H.; McNutt, R. H.; Peredery, W. V.


    Sulphide ores from the International Nickel Company's (INCO) Creighton Mine, Sudbury, were analysed for osmium isotope ratios by ICP-MS. Rhenium and osmium abundances were determined by isotope dilution using a mixed spike in solid solution in a nickel sulphide matrix. Calculated initial 187Os /188Os ratios at 1.85 Ga (the emplacement age of the Sudbury complex) cluster around 0.60. The occurrence of less radiogenic compositions is attributed to post-emplacement, open-system behaviour of the Re/Os system. The Creighton results strongly overlap the initial ratios of published osmium data from two other Sudbury mines, suggesting a narrow range of isotope ratio in the original ore, within the range of estimated osmium isotope compositions in the country rock at 1.85 Ga, using published and new data. Therefore, the sulphide ores of the Sudbury complex can have an entirely crustal source without a mantle-derived contribution. This conclusion is consistent with published neodymium isotope data for the complex and supports the meteorite impact hypothesis, since this is the most effective means of fusing the large quantity of crustal rocks necessary to generate the complex. The extraction of platinum group elements (PGE) from this silicate melt by a nickel sulphide liquid was probably analogous to the laboratory fire assay procedure.

  2. Reliability assessment of MVP-BURN and JENDL-4.0 related to nuclear transmutation of light platinum group elements (United States)

    Terashima, Atsunori; Nilsson, Mikael; Ozawa, Masaki; Chiba, Satoshi


    The Aprés ORIENT research program, as a concept of advanced nuclear fuel cycle, was initiated in FY2011 aiming at creating stable, highly-valuable elements by nuclear transmutation from ↓ssion products. In order to simulate creation of such elements by (n, γ) reaction succeeded by β- decay in reactors, a continuous-energy Monte Carlo burnup calculation code MVP-BURN was employed. Then, it is one of the most important tasks to con↓rm the reliability of MVP-BURN code and evaluated neutron cross section library. In this study, both an experiment of neutron activation analysis in TRIGA Mark I reactor at University of California, Irvine and the corresponding burnup calculation using MVP-BURN code were performed for validation of the simulation on transmutation of light platinum group elements. Especially, some neutron capture reactions such as 102Ru(n, γ)103Ru, 104Ru(n, γ)105Ru, and 108Pd(n, γ)109Pd were dealt with in this study. From a comparison between the calculation (C) and the experiment (E) about 102Ru(n, γ)103Ru, the deviation (C/E-1) was signi↓cantly large. Then, it is strongly suspected that not MVP-BURN code but the neutron capture cross section of 102Ru belonging to JENDL-4.0 used in this simulation have made the big di↑erence as (C/E-1) >20%.

  3. Reliability assessment of MVP-BURN and JENDL-4.0 related to nuclear transmutation of light platinum group elements

    Directory of Open Access Journals (Sweden)

    Terashima Atsunori


    Full Text Available The Aprés ORIENT research program, as a concept of advanced nuclear fuel cycle, was initiated in FY2011 aiming at creating stable, highly-valuable elements by nuclear transmutation from ↓ssion products. In order to simulate creation of such elements by (n, γ reaction succeeded by β− decay in reactors, a continuous-energy Monte Carlo burnup calculation code MVP-BURN was employed. Then, it is one of the most important tasks to con↓rm the reliability of MVP-BURN code and evaluated neutron cross section library. In this study, both an experiment of neutron activation analysis in TRIGA Mark I reactor at University of California, Irvine and the corresponding burnup calculation using MVP-BURN code were performed for validation of the simulation on transmutation of light platinum group elements. Especially, some neutron capture reactions such as 102Ru(n, γ103Ru, 104Ru(n, γ105Ru, and 108Pd(n, γ109Pd were dealt with in this study. From a comparison between the calculation (C and the experiment (E about 102Ru(n, γ103Ru, the deviation (C/E-1 was signi↓cantly large. Then, it is strongly suspected that not MVP-BURN code but the neutron capture cross section of 102Ru belonging to JENDL-4.0 used in this simulation have made the big di↑erence as (C/E-1 >20%.

  4. Chemical composition of the ore and occurrence state of the elements in Jingbaoshan platinum- palladium deposit

    Institute of Scientific and Technical Information of China (English)

    SONG Huanbin; HE Mingqin; ZHANG Shangzhong; YI Fenghuang


    The Jingbaoshan platinum-palladium deposit is China's largest independent PGM (platinum-group metals) deposit so far discovered. There are eleven kinds of useful components in the ore: Pt, Pd, Os, Ir, Ru, Rh, Au, Ag, Cu, Ni, and Co. The platinum-group elements, gold and silver occur in the form of minerals in ores. twenty-five kinds of precious metal minerals have been found, of which twenty one belong to the platinum-group minerals. The minerals are very small in grain size. Copper occurs mainly as copper sulfide with a small amount of free copper oxide, and the beneficiated copper accounts for 95.21%. Nickel occurs mainly as nickel sulfide, and some nickel silicate and nickel oxide occur in the ore. The beneficiated nickel accounts for 72.03%. Cobalt occurs mainly as cobalt sulfide, and there are some cobalt oxide and other kinds of cobalt. The beneficiated cobalt accounts for 77.58%.

  5. Comparative analysis of high temperature strength of platinum and its binary alloys with low content of alloying element

    Directory of Open Access Journals (Sweden)

    Stanković Draško S.


    Full Text Available The comparative analysis of platinum and its binary alloys (containing alloying elements up to 10 mass% mechanical properties at high temperatures has been carried out. The goal of the analysis was to investigate new application possibilities for products based on platinum and platinum alloys, and to expand the existing database of platinum metals, originating from the RTB group, Serbia. Palladium, rhodium, ruthenium, iridium and gold were used as alloying elements. In order to examine the effect of alloying elements’ low concentrations on the high-temperature platinum durability, creep rate, rupture time, tensile strength and relative elongation at high temperatures, up to 1400 °C, were determined. In addition, changes in the structure of dislocations were tracked. The summary of investigation results led to conclusion that, of all the alloying elements used, the best influence on high-temperature platinum durability has rhodium.

  6. Platinum-group minerals in the LG and MG chromitites of the eastern Bushveld Complex, South Africa (United States)

    Oberthür, Thomas; Junge, Malte; Rudashevsky, Nikolay; de Meyer, Eveline; Gutter, Paul


    The chromitites of the Bushveld Complex in South Africa contain vast resources of platinum-group elements (PGE); however, except for the economic upper group (UG)-2 chromitite seam, information on the distribution of the PGE in the ores and on the mineralogical nature, assemblages, and proportions of platinum-group minerals (PGM) is essentially missing. In the present geochemical and mineralogical study, PGE concentrates originating from the lower group (LG)-6 and middle group (MG)-1/2 chromitites were investigated with the intention to fill this gap of knowledge. Chondrite-normalized PGE patterns of bulk rock and concentrates are characterized by a positive slope from Os to Rh, a slight drop to Pt, and an increase to Pd again. The pronounced similarities of the PGE patterns indicate similar primary processes of PGE concentration in the chromitites, namely "sulfide control" of the PGE mineralization, i.e., co-precipitation of chromite and sulfide. Further, the primary control of PGE concentration in chromitites appears to be dual in character: (i) base-level concentrations of IPGE (up to ˜500 ppb) hosted within chromite and (ii) co-precipitation of chromite and sulfide, the latter containing virtually the entire remaining PGE budget. Sulfides (chalcopyrite, pentlandite, and pyrite; pyrrhotite is largely missing) are scarce within the chromitites and occur mainly interstitial to chromite grains. Pd and Rh contents in pentlandite are low and erratic. Essentially, the whole PGE inventory of the ores occurs in the form of discrete PGM. The PGM are almost always associated with sulfides. The dominant PGM are various Pt-Pd-Rh sulfides (cooperite/braggite [(Pt,Pd)S] and malanite/cuprorhodsite [CuPt2S4]/[CuRh2S4]), laurite [RuS2], the main carrier of the IPGE (Os, Ir, Ru), sulfarsenides [(Rh,Pt,Ir)AsS], sperrylite [PtAs2], Pt-Fe alloys, and a large variety of mainly Pd-rich PGM. The LG and MG chromitites have many characteristics in common and define a general, "typical

  7. Relationship between cellular uptake rate and chemical behavior of diammine/diaminocyclohexane platinum (II) complexes with oxygen-ligating anionic groups. (United States)

    Zou, J; Yang, X D; An, F; Wang, K


    The uptake kinetics of the platinum (II) complexes of the formula Pt(NH3)2X, Pt(dach)X by human erythrocyte in the plasma isotonic buffer was studied. The results showed that across-membrane transport of all the platinum complexes studied follows a first-order kinetic process. The uptake rate constants decrease with the change of oxygen-ligating anionic group in the sequence: sulfato > selenato > anion of squaric acid > oxalato > anion of demethylcantharic acid > malonato and increase with increasing lipophilicity of carrier group. The relationship between uptake rate and reactivity of these complexes was established. The stereochemistry of dach isomers was shown without effect on the reactivity and the sequence.

  8. Determination of platinum group elements by inductively coupled plasma-mass spectrometry combined with nickel sulfide fire assay and tellurium coprecipitation (United States)

    Sun, Yali; Guan, Xiyun; Du, Andao


    A method was developed for the determination of trace platinum group elements (PGEs) by nickel sulfide fire assay inductively coupled plasma-mass spectrometry (ICP-MS). With isotope dilution, the improved technique gives precise Os content data. Through the purification of the reagent nickel oxide, reagent blank was greatly reduced. Results obtained for the standard reference materials (SRM) GPt-1-GPt-7(GBW 07288-07294, China), DZ Σ-2 (GBW 07102, China) and Guilin Cu-Ni Ore are in good agreement with the recommended values for platinum group elements. The detection limits ranged from 0.01 to 0.39 ng/g. The relative standard deviations for Ru, Rh, Pd and Ir were less than 5%, for Os less than 1%, and Pt less than 8% for SRM GPt-6.

  9. Catalytic converters as a source of platinum

    Directory of Open Access Journals (Sweden)

    A. Fornalczyk


    Full Text Available The increase of Platinum Group Metals demand in automotive industry is connected with growing amount of cars equipped with the catalytic converters. The paper presents the review of available technologies during recycling process. The possibility of removing platinum from the used catalytic converters applying pyrometallurgical and hyrdometallurgical methods were also investigated. Metals such as Cu, Pb, Ca, Mg, Cd were used in the pyrometallurgical research (catalytic converter was melted with Cu, Pb and Ca or Mg and Cd vapours were blown through the whole carrier. In hydrometallurgical research catalytic converters was dissolved in aqua regia. Analysis of Pt contents in the carrier before and after the process was performed by means of atomic absorption spectroscopy. Obtained result were discussed.

  10. Synthesis of Platinum Nanotubes and Nanorings via Simultaneous Metal Alloying and Etching

    KAUST Repository

    Huang, Zhiqi


    Metallic nanotubes represent a class of hollow nanostructures with unique catalytic properties. However, the wet-chemical synthesis of metallic nanotubes remains a substantial challenge, especially for those with dimensions below 50 nm. This communication describes a simultaneous alloying-etching strategy for the synthesis of Pt nanotubes with open ends by selective etching Au core from coaxial Au/Pt nanorods. This approach can be extended for the preparation of Pt nanorings when Saturn-like Au core/Pt shell nanoparticles are used. The diameter and wall thickness of both nanotubes and nanorings can be readily controlled in the range of 14-37 nm and 2-32 nm, respectively. We further demonstrated that the nanotubes with ultrathin side walls showed superior catalytic performance in oxygen reduction reaction. © 2016 American Chemical Society.

  11. Same-Side Platinum Electrodes for Metal Assisted Etching of Porous Silicon (United States)


    depth by varying the local electrode/silicon (Si) ratio, the electrode will need to be cut up into electrically isolated sections or else the carriers...hydrogen peroxide (H2O2), and ethanol etch solution. The H2O2 reacts with hydrogen ions from the HF at the catalytic metal surface to become water ...the sample, or by hot gases at the flame front jetting across to a nearby PSi line. 4. Conclusions We have developed new procedures for etching

  12. Two mixed-NH3/amine platinum (II) anticancer complexes featuring a dichloroacetate moiety in the leaving group (United States)

    Liu, Weiping; Su, Jia; Jiang, Jing; Li, Xingyao; Ye, Qingsong; Zhou, Hongyu; Chen, Jialin; Li, Yan


    Two mixed-NH3/amine platinum (II) complexes of 3-dichoroacetoxylcyclobutane-1, 1-dicarboxylate have been prepared in the present study and characterized by elemental analysis and IR, HPLC-MS and 1H, 13C-NMR. The complexes exist in equilibrium between two position isomeric forms and undergo hydrolysis reaction in aqueous solution, releasing the platinum pharmacophores and dichloroacetate which is a small-molecular cell apoptosis inducer. Both complexes were evaluated for in vitro cytotoxic profile in A549, SGC-7901 and SK-OV-3 caner cells as well as in BEAS-2B normal cells. They exhibit markedly cytoxicity toward cancer cells by selectively inducing the apoptosis of cancer cells, whereas leaving normal cells less affected. They have also the ability to overcome the resistance of SK-OV-3 cancer cells to cisplatin. Our findings offer an alternative novel way to develop platinum drugs which can both overcome the drug resistance and selectively target tumor cells.

  13. Thiosemicarbazone complexes of the platinum metals. A story of variable coordination modes

    Indian Academy of Sciences (India)

    Indrani Pal; Falguni Basuli; Samaresh Bhattacharya


    Salicylaldehyde thiosemicarbazone (H2saltsc) reacts with [M(PPh3)3X2] (M = Ru, Os; X = Cl, Br) to afford complexes of type [M(PPh3)2(Hsaltsc)2], in which the salicylaldehyde thiosemicarbazone ligand is coordinated to the metal as a bidentate N,S-donor forming a four-membered chelate ring. Reaction of benzaldehyde thiosemicarbazones (Hbztsc-R) with [M(PPh3)3X2] also affords complexes of similar type, viz. [M(PPh3)2(bztsc-R)2], in which the benzaldehyde thiosemicarbazones have also been found to coordinate the metal as a bidentate N,S-donor forming a fourmembered chelate ring as before. Reaction of the Hbztsc-R ligands has also been carried out with [M(bpy)2X2] (M = Ru, Os; X = Cl, Br), which has afforded complexes of type [M(bpy)2(bztsc-R)]+, which have been isolated as perchlorate salts. Coordination mode of bztsc-R has been found to be the same as before. Structure of the Hbztsc-OMe ligand has been determined and some molecular modelling studies have been carried out determine the reason for the observed mode of coordination. Reaction of acetone thiosemicarbazone (Hactsc) has then been carried out with [M(bpy)2X2] to afford the [M(bpy)2(actsc)]ClO4 complexes, in which the actsc ligand coordinates the metal as a bidentate N,S-donor forming a five-membered chelate ring. Reaction of H2saltsc has been carried out with [Ru(bpy)2Cl2] to prepare the [Ru(bpy)2(Hsaltsc)]ClO4 complex, which has then been reacted with one equivalent of nickel perchlorate to afford an octanuclear complex of type [{Ru(bpy)2(saltsc-H)}4Ni4](ClO4)4.

  14. Magnesium, zinc, arsenic, selenium and platinum urinary excretion from cancer patients of Antofagasta region, Chile: multi-metal approach (United States)

    Pizarro, I; Rivera, L; Ávila, J; Cortés, P


    Objectives To evaluate the short-term 24 h urinary excretion of platinum, arsenic, selenium, magnesium and zinc in patients with lung cancer and with cancer other than lungs treated with cisplatin or/and carboplatin from Antofagasta, Chile. Design Urine measurements of Pt and Se were made by inductively coupled plasma optical emission spectrometry, As by hydride-generation atomic absorption spectrometry and Mg and Zn by means of flame furnace atomic absorption spectrometry. Setting All samples were provided by the Oncological Centre of Antofagasta Regional Hospital (Region of Antofagasta, Chile). Participants Ninety 24-h urine samples from cancer patients after the infusion of Pt-base drugs and 10 24-h urine samples from cancer patients not treated with metal-base drugs. Main outcome measures Concentrations of Pt, Se, As, Zn and Mg coming from 24-h urine samples. Results Pt excreted was not significantly different between patients with lung and other cancers treated with cisplatin. The excretion of Mg, Zn and Se was greater than As. Then, Pt favours the excretion of essential elements. For lung and other types of cancers treated with drugs without Pt, excretion of Mg, Zn and Se was also greater than that of As, suggesting antagonism Mg-Zn-Se–anti-cancer drug relationship. Conclusions The amounts of Mg, Zn and Se excreted were greater than for As either with or without Pt-containing drugs, suggesting antagonist Mg-Zn-Se–anti-cancer drug relationships. The excretion of As, Mg, Zn and Se is induced by Pt. Knowledge obtained can contribute to understanding the arsenic cancer mechanism and the As-Mg-Zn-Se-Pt inter-element association for lung cancer and other types of cancer. PMID:27757244

  15. Platinum group elements and gold in ferromanganese crusts from Afanasiy-Nikitin seamount, equatorial Indian Ocean: Sources and fractionation (United States)

    Banakar, V.K.; Hein, J.R.; Rajani, R.P.; Chodankar, A.R.


    The major element relationships in ferromanganese (Fe-Mn) crusts from Afanasiy-Nikitin seamount (ANS), eastern equatorial Indian Ocean, appear to be atypical. High positive correlations (r = 0.99) between Mn/Co and Fe/Co ratios, and lack of correlation of those ratios with Co, Ce, and Ce/Co, indicate that the ANS Fe-Mn crusts are distinct from Pacific seamount Fe-Mn crusts, and reflect region-specific chemical characteristics. The platinum group elements (PGE: Ir, Ru, Rh, Pt, and Pd) and Au in ANS Fe-Mn crusts are derived from seawater and are mainly of terrestrial origin, with a minor cosmogenic component. The Ru/Rh (0.5-2) and Pt/Ru ratios (7-28) are closely comparable to ratios in continental basalts, whereas Pd/Ir ratios exhibit values ( 0.75) correlations between water depth and Mn/Co, Fe/Co, Ce/Co, Co, and the PGEs. Fractionation of the PGE-Au from seawater during colloidal precipitation of the major-oxide phases is indicated by well-defined linear positive correlations (r > 0.8) of Co and Ce with Ir, Ru, Rh, and Pt; Au/Co with Mn/Co; and by weak or no correlations of Pd with water depth, Co-normalized major-element ratios, and with the other PGE (r elements, which likely involves an oxidation reaction on the Mn-oxide and Fe-oxyhydroxide surfaces. The documented fractionation of PGE-Au and their positive association with redox sensitive Co and Ce may have applications in reconstructing past-ocean redox conditions and water masses.

  16. Anthropogenic platinum group element (Pt, Pd, Rh) concentrations in PM10 and PM2.5 from Kolkata, India. (United States)

    Diong, Huey Ting; Das, Reshmi; Khezri, Bahareh; Srivastava, Bijayen; Wang, Xianfeng; Sikdar, Pradip K; Webster, Richard D


    This study investigates platinum group elements (PGEs) in the breathable (PM10) and respirable (PM2.5) fractions of air particulates from a heavily polluted Indian metro city. The samples were collected from traffic junctions at the heart of the city and industrial sites in the suburbs during winter and monsoon seasons of 2013-2014. PGE concentrations were determined by inductively coupled plasma-mass spectrometry (ICP-MS). The PGE concentrations in the samples from traffic junctions are within the range of 2.7-111 ng/m(3) for Pd, 0.86-12.3 ng/m(3) for Pt and 0.09-3.13 ng/m(3) for Rh, and from industrial sites are within the range of 3.12-32.3 ng/m(3) for Pd, 0.73-7.39 ng/m(3) for Pt and 0.1-0.69 ng/m(3) for Rh. Pt concentrations were lower in the monsoon compared to winter while Pd concentrations increased during monsoon and Rh stayed relatively unaffected across seasons. For all seasons and locations, concentrations of Pd > Pt > Rh, indicating dominance of Pd-containing exhaust converters. Most of the PGEs were concentrated in the PM2.5 fraction. A strong correlation (R ≥ 0.62) between the PGEs from traffic junction indicates a common emission source viz. catalytic converters, whereas a moderate to weak correlation (R ≤ 0.5) from the industrial sites indicate mixing of different sources like coal, raw materials used in the factories and automobile. A wider range of Pt/Pd, Pt/Rh and Pd/Rh ratios measured in the traffic junction possibly hint towards varying proportions of PGEs used for catalyst productions in numerous rising and established car brands.

  17. Platinum-Catalyzed Selective Hydration of Hindered Nitriles and Nitriles with Acid- or Base-Sensitive Groups

    NARCIS (Netherlands)

    Jiang, Xiao-bin; Minnaard, Adriaan J.; Vries, Johannes G. de; Feringa, Bernard


    Hindered tertiary nitriles can be hydrolyzed under neutral and mild conditions to the corresponding amides using platinum(II) catalysts with dimethylphosphine oxide or other secondary phosphine oxides (SPOs, phosphinous acids) as ligands. We have found that this procedure also works well for

  18. Fractionation of the platinum-group elments and Re during crystallization of basalt in Kilauea Iki Lava Lake, Hawaii (United States)

    Pitcher, L.; Helz, R.T.; Walker, R.J.; Piccoli, P.


    Kilauea Iki lava lake formed during the 1959 summit eruption of Kilauea Volcano, then crystallized and differentiated over a period of 35??years. It offers an opportunity to evaluate the fractionation behavior of trace elements in a uniquely well-documented basaltic system. A suite of 14 core samples recovered from 1967 to 1981 has been analyzed for 5 platinum-group elements (PGE: Ir, Os, Ru, Pt, Pd), plus Re. These samples have MgO ranging from 2.4 to 26.9??wt.%, with temperatures prior to quench ranging from 1140????C to ambient (110????C). Five eruption samples were also analyzed. Osmium and Ru concentrations vary by nearly four orders of magnitude (0.0006-1.40??ppb for Os and 0.0006-2.01??ppb for Ru) and are positively correlated with MgO content. These elements behaved compatibly during crystallization, mostly likely being concentrated in trace phases (alloy or sulfide) present in olivine phenocrysts or included chromite. Iridium also correlates positively with MgO, although less strongly than Os and Ru. The somewhat poorer correlation for Ir, compared with Os and Ru, may reflect variable loss of Ir as volatile IrF6 in some of the most magnesian samples. Rhenium is negatively correlated with MgO, behaving as an incompatible trace element. Its behavior in the lava lake is complicated by apparent volatile loss of Re, as suggested by a decrease in Re concentration with time of quenching for lake samples vs. eruption samples. Platinum and Pd concentrations are negatively, albeit weakly, correlated with MgO, so these elements were modestly incompatible during crystallization of the major silicate phases. Palladium contents peaked before precipitation of immiscible sulfide liquid, however, and decline sharply in the most differentiated samples. In contrast, Pt appears to have been unaffected by sulfide precipitation. Microprobe data confirm that Pd entered the sulfide liquid before Re, and that Pt is not strongly chalcophile in this system. Occasional high Pt values

  19. Global mining risk footprint of critical metals necessary for low-carbon technologies: the case of neodymium, cobalt, and platinum in Japan. (United States)

    Nansai, Keisuke; Nakajima, Kenichi; Kagawa, Shigemi; Kondo, Yasushi; Shigetomi, Yosuke; Suh, Sangwon


    Meeting the 2-degree global warming target requires wide adoption of low-carbon energy technologies. Many such technologies rely on the use of precious metals, however, increasing the dependence of national economies on these resources. Among such metals, those with supply security concerns are referred to as critical metals. Using the Policy Potential Index developed by the Fraser Institute, this study developed a new footprint indicator, the mining risk footprint (MRF), to quantify the mining risk directly and indirectly affecting a national economy through its consumption of critical metals. We formulated the MRF as a product of the material footprint (MF) of the consuming country and the mining risks of the countries where the materials are mined. A case study was conducted for the 2005 Japanese economy to determine the MF and MRF for three critical metals essential for emerging energy technologies: neodymium, cobalt and platinum. The results indicate that in 2005 the MFs generated by Japanese domestic final demand, that is, the consumption-based metal output of Japan, were 1.0 × 10(3) t for neodymium, 9.4 × 10(3) t for cobalt, and 2.1 × 10 t for platinum. Export demand contributes most to the MF, accounting for 3.0 × 10(3) t, 1.3 × 10(5) t, and 3.1 × 10 t, respectively. The MRFs of Japanese total final demand (domestic plus export) were calculated to be 1.7 × 10 points for neodymium, 4.5 × 10(-2) points for cobalt, and 5.6 points for platinum, implying that the Japanese economy is incurring a high mining risk through its use of neodymium. This country's MRFs are all dominated by export demand. The paper concludes by discussing the policy implications and future research directions for measuring the MFs and MRFs of critical metals. For countries poorly endowed with mineral resources, adopting low-carbon energy technologies may imply a shifting of risk from carbon resources to other natural resources, in particular critical metals, and a trade

  20. Ba 3A2PtCu 2O 10 ( A = Y or Ho): The crystal structure of a reaction by-product of high transition temperature superconductors with platinum metal (United States)

    Geiser, Urs; Porter, Leigh C.; Wang, Hau H.; Allen, Thomas A.; Williams, Jack M.


    Mixtures of CuO, BaCO 3, and A2O 3 ( A = Y, rare earth) react at temperatures between 600 and 1000°C with platinum containers to produce crystals of composition Ba 3A2PtCu 2O 10. The crystal structures of the compounds with A = Y or Ho were determined from single-crystal X-ray diffraction data. They are isostructural, monoclinic, space group {C2}/{m}, with Z = 2. Lattice parameters for Ba 3Y 2PtCu 2O 10 are a = 12.520(3) Å, b = 5.817(1) Å, c = 7.357(1) Å, β = 105.53(2)°, V = 516.2(2) Å 3. Lattice parameters for Ba 3Ho 2PtCu 2O 10 are a = 12.516(3) Å, b = 5.813(1)Å, c = 7.350(3) Å, β = 105.54(2)°, V = 515.2(3)Å 3. The structure of these complex oxides has the four metal ions in five distinct coordination environments: two barium sites with coordination numbers (CN) 8 and 11, yttrium or holmium with CN 7, platinum(IV) with CN 6, and copper with CN 5.

  1. Diarylplatinum(II Compounds as Versatile Metallating Agents in the Synthesis of Cyclometallated Platinum Compounds with N-Donor Ligands

    Directory of Open Access Journals (Sweden)

    Margarita Crespo


    Full Text Available This review deals with the reactions of diarylplatinum(II complexes with N-donor ligands to produce a variety of cycloplatinated compounds including endo-five-, endo-seven-, endo-six- or exo-five-membered platinacycles. The observed reactions result from a series of oxidative addition/reductive elimination processes taking place at platinum(II/platinum(IV species and involving C–X (X = H, Cl, Br bond activation, arene elimination, and, in some cases, Caryl–Caryl bond formation.

  2. Platinum group and chalcophile element systematics of serpentinized peridotites from the St. Elena ophiolite in Costa Rica (United States)

    Holm, J.; Bizimis, M.; Schwarzenbach, E. M.; Foustoukos, D.; Frisby, C. P.; Brandon, A. D.; Gazel, E.


    We present in situ LA-ICPMS data on platinum group element (PGE) and chalcophile element (namely Cu, Ag, Te, Au, Pb) systematics in sulfides from partially serpentinized peridotites of the St. Elena ophiolite, Costa Rica. PGE are strong indicators of primary mantle processes, though their behavior during low temperature alteration processes such as serpentinization is not well understood. St. Elena sulfides are dominantly pentlandites that coexist with Fe-Ni alloys and native Cu. This indicates extremely low fO2 and fS2 conditions likely established during the early stages of serpentinization. We observe extremely variable PGE-Re concentrations in the sulfides, (e.g. [Os] = 2 - 100,000 times primitive mantle, PM). Low [Os] sulfides have high Pd/Os, which in turn correlates positively with Cu concentrations, suggesting Pd enrichment through Cu-rich fluids (e.g. Schwarzenbach et al., 2014, CMP) as opposed to melt-rock reaction. Sulfide PM-normalized PGE-Re patterns are dominated by strong Pt depletions (e.g., Pt/Pd = 0.80-0.0009). Occasional Pt enrichments over Pd and Ru (or Rh) in a PM-normalized pattern (~5% of the sulfide population) often correlate with Te and/or Au enrichments. Pt enrichment was also observed in a composite pentlandite-awaruite, suggesting possible exsolution of Pt from sulfides under extremely low fS2 conditions. Pb concentrations do not correlate with other chalcophiles or PGE. Pb ranges from 0.01-31.64 ppm with the majority of sulfides <5 ppm, and an average concentration of 2.77 ppm (n=64). Assuming that this Pb concentration is representative of mantle sulfides, this implies that Pb is not dominantly held in sulfides in the upper mantle. Combination of in situ and bulk rock PGE analyses will be used to distinguish the effects of primary magmatic signatures (e.g., melt depletion, melt-rock interaction) and secondary processes such as serpentinization on the PGE-Re and chalcophile element systematics of these sulfides.

  3. Platinum group elements and gold in ferromanganese crusts from Afanasiy–Nikitin seamount, equatorial Indian Ocean: Sources and fractionation

    Indian Academy of Sciences (India)

    V K Banakar; J R Hein; R P Rajani; A R Chodankar


    The major element relationships in ferromanganese (Fe-Mn) crusts from Afanasiy-Nikitin seamount (ANS), eastern equatorial Indian Ocean, appear to be atypical. High positive correlations ( = 0.99) between Mn/Co and Fe/Co ratios, and lack of correlation of those ratios with Co, Ce, and Ce/Co, indicate that the ANS Fe-Mn crusts are distinct from Pacific seamount Fe-Mn crusts, and reflect region-specific chemical characteristics. The platinum group elements (PGE: Ir, Ru, Rh, Pt, and Pd) and Au in ANS Fe-Mn crusts are derived from seawater and are mainly of terrestrial origin, with a minor cosmogenic component. The Ru/Rh (0.5-2) and Pt/Ru ratios (7-28) are closely comparable to ratios in continental basalts, whereas Pd/Ir ratios exhibit values (> 2) similar to CI-chondrite (∼1). The chondrite-normalized PGE patterns are similar to those of igneous rocks, except that Pd is relatively depleted. The water depth of Fe-Mn crust formation appears to have a first-order control on both major element and PGE enrichments. These relationships are defined statistically by significant ( < 0.75) correlations between water depth and Mn/Co, Fe/Co, Ce/Co, Co, and the PGEs. Fractionation of the PGE-Au from seawater during colloidal precipitation of the major-oxide phases is indicated by well-defined linear positive correlations ( < 0.8) of Co and Ce with Ir, Ru, Rh, and Pt; Au/Co with Mn/Co; and by weak or no correlations of Pd with water depth, Co-normalized major-element ratios, and with the other PGE ( < 0.5). The strong enrichment of Pt (up to 1 ppm) relative to the other PGE and its positive correlations with Ce and Co demonstrate a common link for the high concentrations of all three elements, which likely involves an oxidation reaction on the Mn-oxide and Fe-oxyhydroxide surfaces. The documented fractionation of PGE-Au and their positive association with redox sensitive Co and Ce may have applications in reconstructing past-ocean redox conditions and water masses.

  4. Platinum-group element concentrations in pyrite from the Main Sulfide Zone of the Great Dyke of Zimbabwe (United States)

    Piña, R.; Gervilla, F.; Barnes, S.-J.; Oberthür, T.; Lunar, R.


    The Main Sulfide Zone (MSZ) of the Great Dyke of Zimbabwe hosts the world's second largest resource of platinum-group elements (PGE) after the Bushveld Complex in South Africa. The sulfide assemblage of the MSZ comprises pyrrhotite, pentlandite, chalcopyrite, and minor pyrite. Recently, several studies have observed in a number of Ni-Cu-PGE ore deposits that pyrite may host significant amounts of PGE, particularly Pt and Rh. In this study, we have determined PGE and other trace element contents in pyrite from the Hartley, Ngezi, Unki, and Mimosa mines of the Great Dyke by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). Based on the textures and PGE contents, two types of pyrite can be differentiated. Py1 occurs as individual euhedral or subhedral grains or clusters of crystals mostly within chalcopyrite and pentlandite, in some cases in the form of symplectitic intergrowths, and is PGE rich (up to 99 ppm Pt and 61 ppm Rh; 1.7 to 47.1 ppm Ru, 0.1 to 7.8 ppm Os, and 1.2 to 20.2 ppm Ir). Py2 occurs as small individual euhedral or subhedral crystals within pyrrhotite, pentlandite, and less frequently within chalcopyrite and silicates and has low PGE contents (<0.11 ppm Pt, <0.34 ppm Rh, <2.5 ppm Ru, <0.37 ppm Ir, and <0.40 ppm Os). Py1 contains higher Os, Ir, Ru, Rh, and Pt contents than the associated pyrrhotite, pentlandite, and chalcopyrite, whereas Py2 has similar PGE contents as coexisting pyrrhotite and pentlandite. Based on the textural relationships, two different origins are attributed for each pyrite type. Py1 intergrowth with pentlandite and chalcopyrite is inferred to have formed by late, low temperature (<300 °C) decomposition of residual Ni-rich monosulfide solid solution, whereas Py2 is suggested to have formed by replacement of pyrrhotite and pentlandite caused by late magmatic/hydrothermal fluids.

  5. Synthesis and assembly with mesoporous silica of platinum (II) porphyrin complexes bearing carbazyl groups: Luminescent and oxygen sensing properties

    Institute of Scientific and Technical Information of China (English)

    HUO Cheng; ZHANG Huidong; GUO Jianhua; ZHANG Hongyu; ZHANG Ping; WANG Yue


    A series of platinum meso-tetrakis [3-methoxy-4-(N-carbazyl)n-alkyloxyphenyl]porphyrin (Pt-4Cn-TPP, n = 4, 6 and 8) are synthesized. Pt-4C4-TPP, Pt-4C6-TPP and Pt-4C8-TPP exhibit similar luminescent properties in solution and solid state. Three protonated platinum (II) porphyrins are assembled with mesoporous silica MCM-48, respectively, resulting in assembly materials Pt-4Cn-TPP4+/ MCM-48 (n = 4, 6 and 8). The luminescent intensity of Pt-4Cn-TPP4+/MCM-48 can be extremely quenched by molecular oxygen with high sensitivity (I0/I100>9). The Stern-Volmer plots of these assembly materials display considerable linearity within a wide range of oxygen concentration (0 to 100%). The response time is all ≤ 1 s and recovery time ≤ 22 s for these assembly materials.

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


    ... § 23.7 Misuse of the words “platinum,” “iridium,” “palladium,” “ruthenium,” “rhodium,” and “osmium.” (a) It is unfair or deceptive to use the words “platinum,” “iridium,” “palladium,” “ruthenium,” “rhodium... marking or description misrepresents the product's true composition. The Platinum Group Metals (PGM)...

  7. Organometallic complexes of the platinum metals: Synthesis, structure, and catalytic applications

    Indian Academy of Sciences (India)

    Piyali Paul; Samaresh Bhattacharya


    Reaction of a group of N-(aryl)picolinamides (pic-R) with [Ru(PPh3)2(CO)2Cl2] in refluxing 2-methoxyethanol in the presence of a base affords hydrido complexes of two types (1-R and 2-R), which are geometric isomers. Similar reaction with N-(naphthyl)picolinamide (pic-nap) yields an organoruthenium complex (3) via formation of a hydrido intermediate. Reaction of 2-(arylazo)phenols (ap-R) with [Ir(PPh3)3Cl] in refluxing ethanol affords a mono-hydrido intermediate (4-R), a di-hydrido intermediate (5-R) and an organoiridium complex (6-R) as the final product, where the azo-ligand is coordinated as CNO-donor. Reaction of ap-R ligands with [Rh(PPh3)3Cl] yields organorhodium complexes (7-R) analogous to 6-R, but without any hydrido intermediate. N-(2'-hydroxyphenyl)benzaldimines (hpbz-R) react with [Rh(PPh3)3Cl] to yield a group of organorhodium complexes (8-R), where the hpbz-R ligands are coordinated in CNO-fashion. Upon interaction with [Ir(PPh3)3Cl] 2-(2',6'-dimethylphenylazo)-4-methylphenol (dmap) undergoes a methyl C-H activation and affords organoiridium complex 9, while 2-(2'-methylphenylazo)-4-methylphenol (mmap) undergoes a phenyl C-H activation and gives organoiridium complex 10. Reaction of benzaldehyde thiosemicarbazones (bztsc-R) with [Pd(PPh3)2Cl2], carried out with the expectation of inducing CNS-mode of coordination, actually has yielded complexes (11-R) where the bztsc-R is coordinated in an uncommon NS-mode forming a fivemembered chelate ring associated with a restricted rotation around the imine (C=N) bond. These palladium complexes are found to catalyse C-C cross coupling reactions very efficiently. Crystal structures of selected complexes of each type have been determined by X-ray crystallography.

  8. Tetracarboxylatoplatinum(IV) complexes featuring monodentate leaving groups - A rational approach toward exploiting the platinum(IV) prodrug strategy. (United States)

    Höfer, Doris; Varbanov, Hristo P; Legin, Anton; Jakupec, Michael A; Roller, Alexander; Galanski, Markus; Keppler, Bernhard K


    A series of novel symmetrically and unsymmetrically coordinated platinum(IV) complexes with monodentate carboxylato ligands was synthesized. The compounds exhibit a general coordination sphere of [Pt(en)(OCOR)2(OCOR')(OCOR″)], where the carboxylato ligands are represented by acetato and succinic acid monoester ligands. Dicarboxylatoplatinum(II) complexes were synthesized and oxidized symmetrically or unsymmetrically to obtain platinum(IV) complexes, which were subsequently carboxylated with noncyclic anhydrides. The compounds were investigated in detail by elemental analysis, mass spectrometry, infrared and multinuclear ((1)H, (13)C, (15)N, (195)Pt) NMR spectroscopy as well as by X-ray diffraction in some cases. The reduction behavior was followed by NMR spectroscopy, while stability and lipophilicity were examined by analytical reversed phase HPLC measurements. Cytotoxic properties were studied in three human cancer cell lines derived from cisplatin sensitive ovarian teratocarcinoma (CH1/PA-1), cisplatin insensitive colon carcinoma (SW480) and non-small cell lung cancer (A549). Thereby, the most lipophilic (yet water soluble) platinum(IV) complexes showed promising IC50 values in the low micromolar and even nanomolar range, demonstrating the significant advantage of using equatorially coordinated monodentate carboxylato ligands. Copyright © 2015 Elsevier Inc. All rights reserved.

  9. Toxicity of platinum compounds. (United States)

    Hartmann, Jörg Thomas; Lipp, Hans-Peter


    Since the introduction of platinum-based combination chemotherapy, particularly cisplatin, the outcome of the treatment of many solid tumours has changed. The leading platinum compounds in cancer chemotherapy are cisplatin, carboplatin and oxaliplatin. They share some structural similarities; however, there are marked differences between them in therapeutic use, pharmacokinetics and adverse effects profiles [1-4]. Compared to cisplatin, carboplatin has inferior efficacy in germ-cell tumour, head and neck cancer and bladder and oesophageal carcinoma, whereas both drugs seem to have comparable efficacy in advanced non-small cell and small cell lung cancer as well as ovarian cancer [5-7]. Oxaliplatin belongs to the group of diaminocyclohexane platinum compounds. It is the first platinum-based drug that has marked efficacy in colorectal cancer when given in combination with 5-fluorouracil and folinic acid [8,9]. Other platinum compounds such as oral JM216, ZD0473, BBR3464 and SPI-77, which is a pegylated liposomal formulation of cisplatin, are still under investigation [10-13], whereas nedaplatin has been approved in Japan for the treatment of non-small cell lung cancer and other solid tumours. This review focuses on cisplatin, carboplatin and oxaliplatin.

  10. New heteronuclear gold(I)-platinum(II) complexes with cytotoxic properties : Are two metals better than one?

    NARCIS (Netherlands)

    Wenzel, Margot; Bigaeva, Emilia; Richard, Philippe; Le Gendre, Pierre; Picquet, Michel; Casini, Angela; Bodio, Ewen


    A series of mono- and heterodinuclear gold(I) and platinum(II) complexes with a new bipyridylamine-phosphine ligand have been synthesized and characterized. The X-ray structures of the ligand precursor 4-iodo-N,N-di(pyridin-2-yl)benzamide, and of one gold derivative are reported. All the complexes d

  11. Accelerated growth from amorphous clusters to metallic nanoparticles observed in electrochemical deposition of platinum within nanopores of porous silicon

    NARCIS (Netherlands)

    Munoz-Noval, Alvaro; Fukami, Kazuhiro; Koyama, Akira; Gallach, Dario; Hermida-Merino, Daniel; Portale, Giuseppe; Kitada, Atsushi; Murase, Kuniaki; Abe, Takeshi; Hayakawa, Shinjiro; Sakka, Tetsuo


    This study examined the formation of amorphous platinum (Pt) clusters in nanopores of porous silicon at an initial stage of pore filling. The time dependency of the chemical state and local structure of Pt in the nanoporous silicon were characterized by X-ray absorption fine structure spectroscopy (

  12. Distribution of platinum group elements (Pt, Pd, Rh) in environmental and clinical matrices: Composition, analytical techniques and scientific outlook: Status report. (United States)

    Hees, T; Wenclawiak, B; Lustig, S; Schramel, P; Schwarzer, M; Schuster, M; Verstraete, D; Dams, R; Helmers, E


    Trace concentrations of the platinum group elements (PGE; here: Pt, Pd and Rh) play an important role in environmental analysis and assessment. Their importance is based on 1. their increasing use as active compartments in automobile exhaust catalysts, 2. their use as cancer anti-tumor agents in medicine. Due to their allergenic and cytotoxic potential, it is necessary to improve selectivity and sensitivity during analytical investigation of matrices like soil, grass, urine or blood. This paper summarizes the present knowledge of PGE in the fields of analytical chemistry, automobile emission rates, bioavailability, toxicology and medicine.

  13. Tolerance of non-platinum group metals cathodes proton exchange membrane fuel cells to air contaminants (United States)

    Reshetenko, Tatyana; Serov, Alexey; Artyushkova, Kateryna; Matanovic, Ivana; Sarah Stariha; Atanassov, Plamen


    The effects of major airborne contaminants (SO2, NO2 and CO) on the spatial performance of Fe/N/C cathode membrane electrode assemblies were studied using a segmented cell system. The injection of 2-10 ppm SO2 in air stream did not cause any performance decrease and redistribution of local currents due to the lack of stably adsorbed SO2 molecules on Fe-Nx sites, as confirmed by density functional theory (DFT) calculations. The introduction of 5-20 ppm of CO into the air stream also did not affect fuel cell performance. The exposure of Fe/N/C cathodes to 2 and 10 ppm NO2 resulted in performance losses of 30 and 70-75 mV, respectively. DFT results showed that the adsorption energies of NO2 and NO were greater than that of O2, which accounted for the observed voltage decrease and slight current redistribution. The cell performance partially recovered when the NO2 injection was stopped. The long-term operation of the fuel cells resulted in cell performance degradation. XPS analyses of Fe/N/C electrodes revealed that the performance decrease was due to catalyst degradation and ionomer oxidation. The latter was accelerated in the presence of air contaminants. The details of the spatial performance and electrochemical impedance spectroscopy results are presented and discussed.

  14. Gamma Prime Morphology and Creep Properties of Nickel Based Superalloys With Platinum Group Metal Additions (Preprint) (United States)


    creep resistance. Polycrystalline superalloy MAR - M247 can sustain a creep rate of 10-8 s-1 at 982°C at a stress of 172 MPa [44], while the alloys...Nathal, R.D. Maier, and L.J. Ebert, “The Influence of Cobalt on the Tensile and Stress Rupture Properties of the Nickel-Base Superalloy MAR - M247 ,” Metallurgical Transactions A, 13 (A) (1982), 1767-1774.           10

  15. Experimental investigations of the hydrothermal geochemistry of platinum and palladium: V. Equilibria between platinum metal, Pt(II), and Pt(IV) chloride complexes at 25 to 300°C (United States)

    Gammons, Christopher H.


    The solubility of metallic Pt in HCl solutions was determined at 200 to 300°C at oxidation states buffered near the aqueous Pt(II)/Pt(IV) boundary. Equilibrium constants were obtained for the following disproportionation reactions: log K, 200° 250° 300°C 2PtCl 42- = PtCl 42- + Pt(s) + 2Cl - 1.47 1.70 1.54 (a) 2PtCl 3- = PtCl 5- + Pt(s) + Cl - 1.77 1.74 1.37 (b) with experimental uncertainties of approximately ±0.20 log units. These results are found to be in good agreement with previously published estimates for reaction at 60 to 152.5°C. The data indicate that the relative stability of the Pt(II) and Pt(IV) chloride complexes does not change appreciably with temperature. This is in contrast to previous work in the Au(0)/Au(I)/Au(III) system which demonstrates that the Au(I) chloride complexes are unstable with respect to Au (III) at low temperature, but become the dominant aqueous species at 300°C. Pt(IV) chloride complexes are unlikely to be important in high temperature hydrothermal fluids, as unrealistically high aqueous platinum concentrations are required to stabilize these species relative to Pt(II). In contrast, thermodynamic calculations suggest that Pt(IV) chloride or hydroxychloride complexes may be the dominant form of dissolved platinum in low temperature brines that are strongly oxidized (e.g., seawater). In oxygenated, Cl-rich solutions, the solubility of Pt is extremely high at pH < 6, such that the mobility of this metal will most likely be limited by surface adsorption reactions and/ or its abundance and rate of dissolution in the enclosing rock or soil. At neutral to alkaline pH, calculated solubilities are much lower, and saturation with Pt oxide phases may occur, as has recently been described in nature.

  16. Choirs H I galaxy groups: The metallicity of dwarf galaxies

    Energy Technology Data Exchange (ETDEWEB)

    Sweet, Sarah M.; Drinkwater, Michael J. [School of Mathematics and Physics, University of Queensland, Qld 4072 (Australia); Meurer, Gerhardt; Bekki, Kenji [School of Physics, University of Western Australia, 35 Stirling Highway, Crawley, WA 6009 (Australia); Dopita, Michael A.; Nicholls, David C. [Research School of Astronomy and Astrophysics, Australian National University, Cotter Road, Weston ACT 2611 (Australia); Kilborn, Virginia, E-mail: [Swinburne University of Technology, Mail number H30, PO Box 218, Hawthorn, Victoria 3122 (Australia)


    We present a recalibration of the luminosity-metallicity relation for gas-rich, star-forming dwarfs to magnitudes as faint as M{sub R} ∼ –13. We use the Dopita et al. metallicity calibrations to calibrate the relation for all the data in this analysis. In metallicity-luminosity space, we find two subpopulations within a sample of high-confidence Sloan Digital Sky Survey (SDSS) DR8 star-forming galaxies: 52% are metal-rich giants and 48% are metal-medium galaxies. Metal-rich dwarfs classified as tidal dwarf galaxy (TDG) candidates in the literature are typically of metallicity 12 + log(O/H) = 8.70 ± 0.05, while SDSS dwarfs fainter than M{sub R} = –16 have a mean metallicity of 12 + log(O/H) = 8.28 ± 0.10, regardless of their luminosity, indicating that there is an approximate floor to the metallicity of low-luminosity galaxies. Our hydrodynamical simulations predict that TDGs should have metallicities elevated above the normal luminosity-metallicity relation. Metallicity can therefore be a useful diagnostic for identifying TDG candidate populations in the absence of tidal tails. At magnitudes brighter than M{sub R} ∼ –16, our sample of 53 star-forming galaxies in 9 H I gas-rich groups is consistent with the normal relation defined by the SDSS sample. At fainter magnitudes, there is an increase in dispersion of the metallicity of our sample, suggestive of a wide range of H I content and environment. In our sample, we identify three (16% of dwarfs) strong TDG candidates (12 + log(O/H) > 8.6) and four (21%) very metal-poor dwarfs (12 + log(O/H) < 8.0), which are likely gas-rich dwarfs with recently ignited star formation.

  17. New surfactant phosphine ligands and platinum(II) metallosurfactants. Influence of metal coordination on the critical micelle concentration and aggregation properties. (United States)

    Parera, Elisabet; Comelles, Francesc; Barnadas, Ramon; Suades, Joan


    We have prepared the first platinum(II) metallosurfactants from a new family of linear surfactant phosphines Ph(2)P(CH(2))(n)SO(3)Na {1 (n = 2), 2 (n = 6), and 3 (n = 10)}, which were synthesized by reaction between the halosulfonates X(CH(2))(n)SO(3)Na and sodium diphenylphosphide. The metallosurfactants cis-[PtCl(2)L(2)] (L = 1-3) were obtained after reaction between the phosphines and PtCl(2) in dimethylsulfoxide. All compounds were fully characterized by the usual methods {NMR ((1)H, (13)C, (31)P, (195)Pt), IR, MS-ESI and HRMS}. By exploring the surfactant properties of phosphines 1-3 and their respective platinum metallosurfactants cis-[PtCl(2)L(2)] (L = 1-3) through surface tension measurements, dynamic light scattering spectroscopy, and cryo-TEM microscopy, we were able to analyze the influence of the metal coordination on the critical micelle concentration (cmc) and the aggregation properties. The cmc values of platinum metallosurfactants were considerably lower than those obtained for the free phosphines 1-3. This behavior could be understood by an analogy between the structure of cis-[PtCl(2)L(2)] complexes and bolaform surfactants. The calculated values of area per molecule also showed different tendencies between 1-3 and cis-[PtCl(2)L(2)] complexes, which could be explained on the basis of the possible conformations of these compounds in the air-water interface. The study of aggregates by dynamic light scattering spectroscopy and cryo-TEM microscopy showed the formation of spherical disperse medium size vesicles in all cases. However, substantial differences were observed between the three free phosphines (the population of micellar aggregates increased with long chain length) and also between phosphines and their respective metallosurfactants.

  18. Coating Carbon Fibers With Platinum (United States)

    Effinger, Michael R.; Duncan, Peter; Coupland, Duncan; Rigali, Mark J.


    A process for coating carbon fibers with platinum has been developed. The process may also be adaptable to coating carbon fibers with other noble and refractory metals, including rhenium and iridium. The coated carbon fibers would be used as ingredients of matrix/fiber composite materials that would resist oxidation at high temperatures. The metal coats would contribute to oxidation resistance by keeping atmospheric oxygen away from fibers when cracks form in the matrices. Other processes that have been used to coat carbon fibers with metals have significant disadvantages: Metal-vapor deposition processes yield coats that are nonuniform along both the lengths and the circumferences of the fibers. The electrical resistivities of carbon fibers are too high to be compatible with electrolytic processes. Metal/organic vapor deposition entails the use of expensive starting materials, it may be necessary to use a furnace, and the starting materials and/or materials generated in the process may be hazardous. The present process does not have these disadvantages. It yields uniform, nonporous coats and is relatively inexpensive. The process can be summarized as one of pretreatment followed by electroless deposition. The process consists of the following steps: The surfaces of the fiber are activated by deposition of palladium crystallites from a solution. The surface-activated fibers are immersed in a solution that contains platinum. A reducing agent is used to supply electrons to effect a chemical reduction in situ. The chemical reduction displaces the platinum from the solution. The displaced platinum becomes deposited on the fibers. Each platinum atom that has been deposited acts as a catalytic site for the deposition of another platinum atom. Hence, the deposition process can also be characterized as autocatalytic. The thickness of the deposited metal can be tailored via the duration of immersion and the chemical activity of the solution.

  19. Platinum Complexes with Edda (Ethylenediamine -N, N - Diacetate Ligands as Potential Anticancer Agents

    Directory of Open Access Journals (Sweden)

    Jurisevic Milena


    Full Text Available The design of platinum based drugs is not a new field of interest. Platinum complexes are widely used as anticancer agents and currently, approximately 30 platinum(II and platinum(IV entered into some of the phases of clinical trials. A special place in today’s research belongs to platinum complexes with diammine ligands. A large number of edda (ethylenediamine- N, N’-diacetate-type ligands and their corresponding metal complexes has been successfully synthesized. This article summarizes recent progress in research on edda-type-platinum complexes. Some of these agents achieves better effect compared to the gold standard (cisplatin. It has been shown that there is a possible relationship between the length of the ligand ester group carbon chain and its cytotoxic effect. In most cases the longer the ester chain is the greater is the antitumor activity. Of particular interest are the noticeable effects of some new platinum compound with edda-type ligand on cell lines that are known to have a high level of cisplatin-resistance. Exanimate complexes appear to have a different mode of mechanism of action compared with cisplatin which includes apoptotic and necrotic cell death. There are indications that further investigations of these compounds may be very useful in overcoming the problems associated global cancer statistic.

  20. Ultraviolet Spectroscopy of Metal-Poor Stars: New Detections of Phosphorus, Germanium, Arsenic, Selenium, Cadmium, Tellurium, Lutetium, Osmium, Iridium, Platinum, Gold, and More! (United States)

    Roederer, Ian U.


    Ultraviolet spectroscopy with HST/STIS provides a 30% increase in the number of elements that can be detected in metal-poor stars. Although nearly every element from hydrogen through bismuth is probably present in most metal-poor stars, not all elements can be detected. The resonance lines of the dominant species of some elements are only found in the UV in late-type stars. The chemical compositions of these stars reflect the history of stellar nucleosynthesis from the first stars to today. Here, I present a summary of recent work that has expanded the chemical inventory in metal-poor stars using UV spectroscopy conducted using HST/STIS. The highlights include new detections of phosphorus, germanium, arsenic, selenium, cadmium, tellurium, lutetium, osmium, iridium, platinum, and gold in metal-poor stars. These detections reveal new insights into stellar nucleosynthesis in the earliest generations of massive stars, provide new constraints on the r-process, and open new channels for chemically-tagging stars that have assembled to form the Milky Way stellar halo.

  1. Photophysics of organometallic platinum(II) derivatives of the diketopyrrolopyrrole chromophore

    KAUST Repository

    Goswami, Subhadip


    A pair of diketopyrrolopyrrole (DPP) chromophores that are end-functionalized with platinum containing "auxochromes" were subjected to electrochemical and photophysical study. The chromophores contain either platinum acetylide or ortho-metalated 2-thienylpyridinyl(platinum) end-groups (DPP-Pt(CC) and DPP-Pt(acac), respectively). The ground state redox potentials of the chromophores were determined by solution electrochemistry, and the HOMO and LUMO levels were estimated. The chromophores\\' photophysical properties were characterized by absorption, photoluminescence, and time-resolved absorption spectroscopy on time scales from sub-picoseconds to microseconds. Density functional theory (DFT) computations were performed to understand the molecular orbitals involved in both the singlet and triplet excited state photophysics. The results reveal that in both platinum DPP derivatives the organometallic auxochromes have a significant effect on the chromophores\\' photophysics. The most profound effect is a reduction in the fluorescence yields accompanied by enhanced triplet yields due to spin-orbit coupling induced by the metal centers. The effects are most pronounced in DPP-Pt(acac), indicating that the orthometalated platinum auxochrome is able to induce spin-orbital coupling to a greater extent compared to the platinum acetylide units. (Figure Presented).

  2. The extractive metallurgy of south africa's platinum ores (United States)

    Cramer, Larry A.


    The extraction technology for platinum-group metals (PGMs) has changed dramatically in the last 80 years, and the changes are likely to continue for years to come. This article will review advances in PGM extraction, including developments in semi-autogenous and fully autogenous milling; flotation equipment applications for treating high-chrome ores; increases in power densities for future smelting furnaces, and new methods for meeting rising environmental standards.

  3. The platinum group elements and gold: analysis by radiochemical and instrumental neutron activation analysis and relevance to geological exploration and related problems

    Energy Technology Data Exchange (ETDEWEB)

    Reeves, S.; Plimer, I. R. [Melbourne Univ., Parkville, VIC (Australia). School of Physics


    This paper presents an overview of research conducted with the support of the Australian Institute of Nuclear Science and Engineering, at the University of Melbourne, School of Earth Sciences, Radiochemical Neutron Activation Laboratory. The primary objective of this research is to realize the high potential of the platinum group elements (PGE) and gold to the solution of petrogenetic problems, the study of magma generation and magmatic processes in mafic/ultramafic rock suites, as tracers in hydrothermal ore formation. The PGEs (Os, Ru, Ir, Pt, Pd and Rh) are among the least abundant of all elements on earth with unique properties such as high melting points, high electrical and thermal conductivity, high density, strength and toughness as alloys. They exhibit both siderophile and chalcophile characteristics and are valuable tools in providing information about magmatic processes, in particular S-saturation, as well as crystal fractionation trends. Two distinct groups of PGEs are discerned; the IPGEs (Ru, Os, Ir) and the PPGEs (Pt, Pd, Rh, Au) on the basis of their behaviour during fractionation processes. Using chondrite normalized PGE patterns it is possible to distinguish between sulphides that segregated from primitive magmas, such as komatiites, and sulphides which segregated from more fractionated magmas, such as tholeiites. It is critical to the understanding of these processes to be able to analyse key elements, such as the PGE and gold, in the parts per billion to parts per trillion range. Platinum group elements and Au were determined by radiochemical neutron activation analysis using a modified NiS fire-assay preconcentration technique, adapted from procedures first used by Robert, R.V. D. and van Wyk, E. (1975) . Detection limits are generally 0.005-0.01 ppb (Au and Ir), 0.1-0.2 ppb (Pd and Pt), and 0.1-0.5 ppb for Ru. 9 refs.

  4. Simple cerium-triethanolamine complex: Synthesis, characterization, thermal decomposition and its application to prepare ceria support for platinum catalysts used in methane steam reforming (United States)

    Wattanathana, Worawat; Nootsuwan, Nollapan; Veranitisagul, Chatchai; Koonsaeng, Nattamon; Laosiripojana, Navadol; Laobuthee, Apirat


    Cerium-triethanolamine complex was synthesized by simple complexation method in 1-propanol solvent using cerium(III) chloride as a metal source and triethanolamine as a ligand. The structures of the prepared complex were proposed based on FT-IR, FT-Raman and ESI-MS results as equimolar of triethanolamine and cerium chelated complex having monomeric tricyclic structure with and without chloride anion as another coordinating group known as ceratrane. The complex was used as a precursor for ceria material done by thermal decomposition. XRD result revealed that when calcined at 600 °C for 2 h, the cerium complex was totally turned into pure ceria with cubic fluorite structure. The obtained ceria was then employed to synthesize platinum doped ceria catalysts for methane steam reforming. Various amounts of platinum i.e. 1, 3, 5 and 10 mol percents were introduced on the ceria support by microwave-assisted wetness impregnation using ammonium tetrachloroplatinate(II). The platinum-impregnated ceria powders were subjected to calcination in 10% hydrogen/helium atmosphere at 500 °C for 3 h to reduce platinum(II) to platinum(0). XRD patterns of the catalysts confirmed that the platinum particles doped on the ceria support were in the form of platinum(0). Catalytic activity test showed that the catalytic activities got higher as the amounts of platinum doped increased. Besides, the portions of coke formation on the surface of catalysts were reduced as the amounts of platinum doped increased.

  5. Platinum-group Elements Geochemistry of the Yangliuping Magmatic Ni-Cu-PGE Sulfide Deposit:Implications of Its Genetic Link with the Extrusive Basalts

    Institute of Scientific and Technical Information of China (English)

    ZHENG Jianbin; CAO Zhimin; SONG Xieyan; AN Wei; LIU Ji


    Primitive mantle-normalized Platinum-group elements (PGE) concentration patterns for the Zhengziyanwo intrusion and Dashibao Formation basalts are of positive slope, similar to most of the world-class magmatic Ni-Cu-PGE sulfide deposits. Characters of this intrusion and its related ores and Dashibao Formation basalts are their negative Pt-anomaly and high concentration of Rh relative to Pt and Pd, facts being interpreted to be the results of crystallization and fractionation of Pt-alloys and spinel phase-free crystallization history for the magma, respectively. PGE parameters of the Dashibao Formation basalts are consistent with the general trend of those found for the Zhengziyanwo intrusion, and this might infer a genetic link between them.

  6. Merensky pillar strength formulae based on back-analysis of pillar failures at Impala Platinum

    CSIR Research Space (South Africa)

    Watson, BP


    Full Text Available The Bushveld platinum group metal deposits are two distinct, shallow-dipping stratiform tabular orebodies and strike for many hundreds of kilometres. Mining is extensive, with depths ranging from close-to-surface to 2 000 m. The mining method is a...

  7. 同位素稀释-ICPMS法测定地质标准物质中铂族元素%Determination of Platinum-group Elements in the Geological Standard Reference Materials by Isotope Dilution-ICPMS

    Institute of Scientific and Technical Information of China (English)

    胡明月; 何红蓼


    Platinum group elements (PGEs) includes platinum, palladium, iridium, osmium, rhodium and ruthenium. It has very high economic and scientific value in the field of geoscience and environmental science. But the analysis data referred by the different lab are very disperse because of the difficulty of the determination of PGEs. It makes very difficult to fix the value of the PGEs in the standard reference materials. In the article, the values of the PGEs in the standard reference materials of ocean sediment are determined by isotope dilution technique and dependable values of these elements are provided.

  8. Dipicolinate complexes of main group metals with hydrazinium cation

    Indian Academy of Sciences (India)

    K Saravanan; S Govindarajan


    Some new coordination complexes of hydrazinium main group metal dipicolinate hydrates of formulae (N2H5)2M(dip)2.H2O (where, M =Ca, Sr, Ba or Pb and = 0, 2, 4 and 3 respectively and dip = dipicolinate), N2H5Bi(dip)2.3H2O and (N2H5)3Bi(dip)3.4H2O have been prepared and characterized by physico-chemical techniques. The infrared spectra of the complexes reveal the presence of tridentate dipicolinate dianions and non-coordinating hydrazinium cations. Conductance measurements show that the mono, di and trihydrazinium complexes behave as 1:1, 2:1 and 3:1 electrolytes respectively, in aqueous solution. Thermal decomposition studies show that these compounds lose water followed by endothermic decomposition of hydrazine to give respective metal hydrogendipicolinate intermediates, which further decompose exothermically to the final product of either metal carbonates (Ca, Sr, Ba and Pb) or metal oxycarbonates (Bi). The coordination numbers around the metal ions differ from compound to compound. The various coordination numbers exhibited by these metals are six (Ca), seven (Ba), eight (Sr) and nine (Pb and Bi). In all the complexes the above coordination number is attained by tridentate dipicolinate dianions and water molecules. The X-ray diffraction patterns of these compounds differ from one another suggesting that they are not isomorphous.

  9. Geochemistry of Platinum Group and Rare Earth Elements of the Polymetallic Layer in the Lower Cambrian,Weng'an,Guizhou Province

    Institute of Scientific and Technical Information of China (English)

    FU Yong; WU Chaodong; GUAN Ping; QU Wenjun; CHEN Jiafu


    The black shales of the Lower Cambrian Niutitang Formation in Weng'an.on the Yangtze platform of south China,contain voluminous polymetallic sulfide deposits.A comprehensive geochemical investigation of trace,rare earth,and platinum group elements(PGE)has been undertaken in order to discuss its ore genesis and correlation with the tectono.depositional setting.The ore-bearing layers enrich molybdenum(Mo),nickeI(Ni),vanadium(V),lead(Pb),strontium(Sr), bariam(Ba),uranium(U),arsenic(As),and rare earth elements(REE)in abundance.High uranium/thorium(U/Th)ratios(U/Th>1)indicated that mineralization was mainly influenced by the hydrothermal process.The δU value Was above 1.9.showing a reducing sedimentary condition.The REE patterns showed high enrichment in Iight rare earth elements (LREE)(heavy rare earth elements (HREE)(LREE/HREE=5-17),slightly negative europium(EU)and cerium(Ce)anomalies(δEu=0.81-0.93).and positive Ce anomalies(δCe=0.76-1.12).PGE abundance was characterized by the PGE-type distribution patterns,enriching platinum(Pt),palladium(Pd),ruthenium(RuJ and osmium(Os).The Pt,Pd ratio was 0.8.which is close to the ratios of seawater and ultramafic rocks.AII of these geochemical features suggest that the mineralization was triggered by hydrothermal activity in an extensionai setting in the context of break-up of the Rodinian supercontinent.

  10. Metallicity of the Fossil Group NGC 1550 Observed with Suzaku (United States)

    Sato, Kosuke; Kawaharada, Madoka; Nakazawa, Kazuhiro; Matsushita, Kyoko; Ishisaki, Yoshitaka; Yamasaki, Noriko Y.; Ohashi, Takaya


    We studied the temperature and metal abundance distributions of the intra-cluster medium (ICM) in a group of galaxies, NGC 1550, observed with Suzaku. NGC 1550 is classified as a fossil group, which has few bright member galaxies, except for the central galaxy. Thus, such a type of galaxy is important to investigate how metals are enriched to the ICM. With the Suzaku XIS instrument, we directly measured not only the Si, S, and Fe lines, but also the O and Mg lines, and obtained those abundances to an outer region of ˜0.5r180 for the first time, and confirmed that the metals in the ICM of such a fossil group are indeed extending to a large radius. We found steeper gradients for the Mg, Si, S, and Fe abundances, while O showed an almost flat abundance distribution. Abundance ratios of α-elements to Fe were similar to those of the other groups and poor clusters. We calculated the number ratio of type II to type Ia supernovae for the ICM enrichment to be 2.9±0.5 within 0.1r180; the value is consistent with those for the other groups and poor clusters observed with Suzaku. We also calculated the metal mass-to-light ratios (MLRs) for Fe, O, and Mg with the B-band and K-band luminosities of the member galaxies of NGC 1550. The derived MLRs are comparable to those of the NGC 5044 group in the r region, while those of NGC 1550 are slightly higher than those of NGC 5044 in the outer region.


    Institute of Scientific and Technical Information of China (English)

    Xiao-ping Yan; Bao-lin He; Jie Zhang; Han-fan Liu


    Modification of transition metal cations to polymer-stabilized Pt colloidal clusters modified with cinchonidine was studied in enantioselective hydrogenation of methyl pyruvate. Compared to the enantiomeric excess (e.e.) value (71.4%)obtained without the presence of metal cations, obvious e.e. enhancement (up to 82.5%) was resulted from the addition of Zn2+ but with a certain decrease in activity. The reaction parameters in the presence of Zn2+ were also studied. It was found that the Pt colloidal catalysts in the presence of metal cations performed very differently from that in the absence of metal cations.

  12. Transformations and reactions of Re2(CO)8(mu-SbPh2)(mu-H) induced by the addition of a platinum(tri-t-butylphosphine) group. (United States)

    Adams, Richard D; Hall, Michael B; Pearl, William C; Yang, Xinzheng


    Three products Re(2)[Pt(PBu(t)(3))](mu-SbPh(2))(CO)(8)(mu-H), 2, Re(2)[Pt(CO)(PBu(t)(3))]Ph(CO)(8)(mu(3)-SbPh)(mu-H), 3, and Re(2)[Pt(PBu(t)(3))](2)(CO)(8)(mu(4)-Sb(2)Ph(2))(mu-H)(2), 4, were obtained from the reaction of Re(2)(CO)(8)(mu-SbPh(2))(mu-H), 1, with Pt(PBu(t)(3))(2). Compound 3 was also obtained from 2 by further reaction with Pt(PBu(t)(3))(2). Compound 2 is a Pt(PBu(t)(3)) adduct of 1 formed by the insertion of the platinum atom into one of the Re-Sb bonds of 1 with formation of two Pt-Re bonds. Compound 3 contains an open Re(2)Pt cluster and was also obtained in a low yield by the addition of CO to 2. The addition of SbPh(3) to 2 yielded the compound Re(2)Pt(PBu(t)(3))(Ph)(CO)(8)(SbPh(3))(mu(3)-SbPh)(mu-H), 5, a SbPh(3) derivative of 3. Compound 4 can be viewed as a dimer of the fragment Re[Pt(PBu(t)(3))](CO)(4)(SbPh)(mu-H). The two halves of the molecule are held together by Pt-Sb bonds and a significant interaction directly between the Sb atoms, Sb-Sb distance, 2.9834(7) A. The Sb-Sb bonding in 4 was explained by density functional calculations. Compound 4 adds 2 equiv of CO at 1 atm/25 degrees C, one to each platinum atom, to yield the compound [Re(CO)(4)Pt(H)(CO)(PBu(t)(3))(mu(3)-SbPh)](2) which exists as a mixture of two noninterconverting isomers, cis-6 and trans-6. Both isomers of 6 were isolated and structurally characterized. Each isomer of 6 consists of a central planar Re(2)Sb(2) core composed of two Re(CO)(4) groups with two bridging SbPh ligands. There is a Pt(H)(CO)(PBu(t)(3)) group coordinated to each antimony atom of 6. In the cis-isomer both Pt(H)(CO)(PBu(t)(3)) groups lie on the same side of the Re(2)Sb(2) plane. In the trans-isomer the Pt(H)(CO)(PBu(t)(3)) groups lie on opposite sides of the Re(2)Sb(2) plane.

  13. Improved and selective platinum recovery from spent alpha-alumina supported catalysts using pretreated anionic ion exchange resin. (United States)

    Shams, K; Goodarzi, F


    Improved and selective recovery of platinum from a spent dehydrogenation platinum alpha-alumina supported catalyst using a strong basic ion exchange resin is reported. Platinum and other precious metal group (PMG) complexes are leached using concentrated hydrochloric acid along with about 0.20 vol.% nitric acid as an oxidizing agent from de-coked and crushed spent catalyst. Effects of hydrochloric acid concentration, time, and temperature in leaching stage are investigated. The strong basic anionic resin is treated by sodium hydroxide solution to replace chloride anion by hydroxyl group ion. The supernatant of the leaching process is passed through a fixed column of hydroxylated strong base anionic resin. The treated resin on which the platinum complex is adsorbed is dried and burned in an oxidizing atmosphere at 750-800 degrees C. The recovered gray metallic powder is mainly platinum. Results compared with those obtained from untreated anionic resin show that adsorption of platinum complexes onto the treated anionic resin is more selective and the yield of separation is considerably improved. The breakthrough curves of the pretreated anion exchanger and that of untreated exchange resin reveals that the capacity of the hyroxilated resin is decreased by about 14%. These breakthrough curves can be used for calculation of height of a practical exchange plate (HPEP) for design purposes.

  14. Chemical Reactivity Perspective into the Group 2B Metals Halides. (United States)

    Özen, Alimet Sema; Akdeniz, Zehra


    Chemical reactivity descriptors within the conceptual density functional theory can be used to understand the nature of the interactions between two monomers of the Group 2B metal halides. This information might be valuable in the development of adequate force law parameters for simulations in the liquid state. In this study, MX2 monomers and dimers, where M = Zn, Cd, Hg and X = F, Cl, Br, I, were investigated in terms of chemical reactivity descriptors. Relativistic effects were taken into account using the effective core potential (ECP) approach. Correlations were produced between global and local reactivity descriptors and dimerization energies. Results presented in this work represent the first systematic investigation of Group 2B metal halides in the literature from a combined point of view of both relativistic effects and chemical reactivity descriptors. Steric effects were found to be responsible for the deviation from the chemical reactivity principles. They were introduced into the chemical reactivity descriptors such as local softness.

  15. Primary endpoint results of the OMEGA Study: One-year clinical outcomes after implantation of a novel platinum chromium bare metal stent

    Energy Technology Data Exchange (ETDEWEB)

    Wang, John C., E-mail: [MedStar Union Memorial Hospital, Baltimore MD (United States); Carrié, Didier, E-mail: [Centre Hôpital Universitaire Rangueil, Toulouse (France); Masotti, Monica, E-mail: [Hospital Clinic, University of Barcelona (Spain); Erglis, Andrejs, E-mail: [Pauls Stradins Clinical University Hospital, University of Latvia, Riga (Latvia); Mego, David, E-mail: [Arkansas Heart Hospital, Little Rock, AR (United States); Watkins, Matthew W., E-mail: [University of Vermont Medical Center, Burlington VT (United States); Underwood, Paul, E-mail: [Boston Scientific, Marlborough MA USA (United States); Allocco, Dominic J., E-mail: [Boston Scientific, Marlborough MA USA (United States); Hamm, Christian W., E-mail: [Kerckhoff Heart and Thoraxcenter, Bad Nauheim (Germany)


    Background/purpose: Bare metal stents (BMS) have similar rates of death and myocardial infarction (MI) compared to drug-eluting stents (DES). DES lower repeat revascularization rates compared to BMS, but may have higher rates of late stent thrombosis (ST) potentially due to impaired endothelialization requiring longer dual anti-platelet therapy (DAPT). OMEGA evaluated a novel BMS designed to have improved deliverability and radiopacity, in comparison to currently available platforms. Methods/materials: OMEGA was a prospective, multicenter, single-arm study enrolling 328 patients at 37 sites (US and Europe). Patients received the OMEGA stent (bare platinum chromium element stent) for the treatment of de novo native coronary artery lesions (≤ 28 mm long; diameter ≥ 2.25 mm to ≤ 4.50 mm). The primary endpoint was 9-month target lesion failure (TLF: cardiac death, target vessel-related MI, target lesion revascularization [TLR]) compared to a prespecified performance goal (PG) based on prior generation BMS. All major cardiac events were independently adjudicated. DAPT was required for a minimum of 1 month post procedure. Results: In the OMEGA study, the mean age was 65; 17% had diabetes mellitus. The primary endpoint was met; 9 month TLF rate was 11.5%, and the upper 1-sided 95% confidence bound of 14.79% was less than the prespecified PG of 21.2% (p < 0.0001). One-year event rates were low including a TLF rate of 12.8% and an ST rate of 0.6% at 12 months. Conclusions: One-year outcomes of OMEGA show low rates of TLF, revascularization and ST. This supports safety and efficacy of the OMEGA BMS for the treatment of coronary artery disease. - Highlights: • The OMEGA study evaluated a novel platinum chromium bare metal stent. • OMEGA enrolled 328 patients at 37 sites (US and Europe). • The primary endpoint of 9 month target lesion failure was 11.5%. • One-year event rates were low including an ST rate of 0.6% at 12 months.

  16. Zwitterionic Group VIII transition metal initiators supported by olefin ligands (United States)

    Bazan, Guillermo C.; Chen, Yaofeng


    A zwitterionic Group VIII transition metal complex containing the simple and relatively small 3-(arylimino)-but-1-en-2-olato ligand that catalyzes the formation of polypropylene and high molecular weight polyethylene. A novel feature of this catalyst is that the active species is stabilized by a chelated olefin adduct. The present invention also provides methods of polymerizing olefin monomers using zwitterionic catalysts, particularly polypropylene and high molecular weight polyethylene.

  17. DNA interaction studies of a platinum (II) complex containing an antiviral drug, ribavirin: the effect of metal on DNA binding. (United States)

    Shahabadi, Nahid; Mirzaei kalar, Zeinab; Moghadam, Neda Hosseinpour


    The water-soluble Pt (II) complex, [PtCl (DMSO)(N(4)N(7)-ribavirin)]· H(2)O (ribavirin is an antiviral drug) has been synthesized and characterized by physico-chemical and spectroscopic methods. The binding interactions of this complex with calf thymus DNA (CT-DNA) were investigated using fluorimetry, spectrophotometry, circular dichroism and viscosimetry. The complex binds to CT-DNA in an intercalative mode. The calculated binding constant, K(b), was 7.2×10(5) M(-1). In fluorimetric studies, the enthalpy (ΔH0) changes of the reaction between the Pt (II) complex with CT-DNA showed hydrophobic interaction. In addition, CD study showed stabilization of the right-handed B form of CT-DNA. All these results prove that the complex interacts with CT-DNA via intercalative mode of binding. In comparison with the previous study of the DNA interaction with ribavirin, these results show that platinum complex has greater affinity to CT-DNA.

  18. Investigations on the bioavailability of traffic-related platinum group elements (PGE) to the aquatic fauna with special consideration being given to palladium; Untersuchungen zur Bioverfuegbarkeit Kfz-emittierter Platingruppenelemente (PGE) fuer die aquatische Fauna unter besonderer Beruecksichtigung von Palladium

    Energy Technology Data Exchange (ETDEWEB)

    Sures, B.; Thielen, F.; Zimmermann, S. [Karlsruhe Univ. (T.H.) (Germany). Zoologisches Inst.


    The uptake and accumulation of the traffic-related platinum group elements (PGE) Pt, Pd and Rh by the aquatic fauna was investigated. Zebra mussels, eels and barbels were maintained in water containing either road dust or ground catalytic converter material. Following the exposure, samples of fish liver and kidney, as well as the soft tissues of the mussels, were analysed. Our results revealed that all three catalytic noble metals were accumulated by aquatic organisms. The highest bioavailability was found for Pd, followed by Pt and Rh. The concentration factor of Pd for Dreissena polymorpha was 5 times higher compared with Pb and only 6 times lower than the essential element Cu. With regard to the increasing emission of Pd the level of this metal has to be monitored very carefully in the environment. (orig.) [German] Die Aufnahme und Anreicherung der Kfz-buertigen Platingruppenelemente (PGE) Pt, Pd und Rh durch aquatische Tiere wurde an Dreikantmuscheln, Aalen und Barben untersucht. Hierzu wurden die Testorganismen in Wasser mit Strassenstaub einer stark befahrenen Strasse oder mit zerriebenem Autokatalysatormaterial ueber mehrere Wochen exponiert und anschliessend Leber und Niere der Fische sowie das Weichgewebe der Muscheln analysiert. Im Rahmen dieser Studien konnte nachgewiesen werden, dass alle drei Edelmetalle durch Fische wie durch Muscheln aufgenommen und angereichert werden. Fuer Pd fand sich die hoechste Bioverfuegbarkeit, gefolgt von Pt und Rh. Das Ausmass der Aufnahme von Pd durch Dreissena polymorpha war ca. 5fach hoeher als von Pb und 6fach niedriger verglichen mit dem essenziellen Element Cu. In Anbetracht der steigenden Emission von Pd sollte ein Umweltmonitoring die Verbreitung von Pd in der Umwelt klaeren. (orig.)

  19. 2-Methoxycycloocta-1,5-dienyl platinum complexes as precursors for platinum nanoparticles

    Indian Academy of Sciences (India)

    Ninad Ghavale; Sandip Dey; Vimal K Jain; R Tewari


    Thermolysis of [Pt2 (-OR)2 (C8H12OMe)2] (R = Me or Ac) in hexadecylamine (HDA) at 210°C under argon atmosphere gave platinum nanoparticles which were characterized by XRD, EDAX and TEM analysis. Both spherical (∼ 10 nm) and rod-like (∼ 19 nm length with aspect ratio of 2.3) face centred cubic (fcc) platinum metal nanoparticles could be isolated. The thermogravimetric analyses of these complexes revealed that they undergo a single step decomposition leading to the formation of platinum metal powder.

  20. Formation and geochemical significance of micrometallic aggregates including fissiogenic platinum group elements in the Oklo natural reactor, Gabon (United States)

    Kikuchi, Makiko; Hidaka, Hiroshi; Gauthier-Lafaye, François


    Metallic aggregates with a size of a few tens μm and consisting mainly of Ru, Rh, Pd, Te, Pb, As, Sb, S and Bi were found in the acid residue of SD37-S2/CD uraninite taken from Oklo natural reactor zone (RZ) 13. Quantitative analyses of major elements using an electron probe microanalyzer and in situ isotopic analyses of Zr, Mo, Ru, Pb and U using a sensitive high-resolution ion microprobe were performed on the metallic aggregates to determine the geochemical behaviors of fission products and actinides and to ascertain the processes of formation of the aggregates in the RZs. The chemical compositions of the aggregates investigated in this study are significantly different from those reported previously, showing lower Pb content and no correlation between the contents of Pb and S in the individual grains. The 235U/ 238U ratios in metallic aggregates vary significantly from 0.00478 to 0.01466, indicating chemical fractionation between U and Pu during the formation of the aggregates. The Pb isotopic data indicate that most of the Pb in the aggregates decayed from 2.05 Ga-old uraninite that existed in the RZ originally and that there was chemical fractionation between U and Pb in some aggregates. The Zr and Mo isotopic ratios, 90Zr/ 91Zr and 95Mo/ 97Mo, for most of the aggregates had small variations, which can be simply explained by constant separate mixing of fissiogenic and nonfissiogenic components. On the other hand, a large variation in the 99Ru/ 101Ru ratio (0.324-1.73) cannot be explained only by a two component mixing theory; thus, chemical fractionation between Tc and Ru during the reactor criticality is suggested. The large variations in the 235U/ 238U and 99Ru/ 101Ru isotopic ratios suggest that the aggregates formed under various redox conditions owing to the radiolysis of water.

  1. Nafion-Induced Metal-Metal Interactions in a Platinum(Ⅱ) Terpyridyl Acetylide Complex:a Luminescent Sensor for Detection of Volatile Organic Compounds

    Institute of Scientific and Technical Information of China (English)

    TONG,Qing-Xiao(佟庆笑); LI,Xiao-Hong(李晓红); WU,Li-Zhu(吴骊珠); YANG,Qing-Zheng(杨清正); ZHANG,Li-Ping(张丽萍); TUNG,Chen-Ho(佟振合)


    The platinum(Ⅱ) terpyridyl acetylide complex [Pt(terpy)(C≡CR)]C1O4 (terpy=2,2′: 6′2″-terpyridine, R=CH2CH2CH3) (1) was incorporated into Nafion membranes. At high loading the dry membranes exhibit intense photoluminescence with λmax at 707 nm from the 3MMLCT state, which was not observed in fluid solution. Upon exposure to the vapor of polar volatile organic compounds (VOC), this photoluminescence was significantly red-shifed. This process was fully reversible when the VOC-incorporated membrane was dried in air. The dramatic and reversible changes in the emission spectra made the Nafion-supported complex as an interesting sensor candidate for polar VOC.

  2. Search for a meteoritic component in drill cores from the Bosumtwi impact structure, Ghana: Platinum group element contents and osmium isotopic characteristics (United States)

    McDonald, Iain; Peucker-Ehrenbrink, Bernhard; Coney, Louise; Ferrière, Ludovic; Reimold, Wolf Uwe; Koeberl, Christian

    An attempt was made to detect a meteoritic component in both crater-fill (fallback) impact breccias and fallout suevites (outside the crater rim) at the Bosumtwi impact structure in Ghana. Thus far, the only clear indication for an extraterrestrial component related to this structure has been the discovery of a meteoritic signature in Ivory Coast tektites, which formed during the Bosumtwi impact event. Earlier work at Bosumtwi indicated unusually high levels of elements that are commonly used for the identification of meteoritic contamination (i.e., siderophile elements, including the platinum group elements [PGE]) in both target rocks and impact breccias from surface exposures around the crater structure, which does not allow unambiguous verification of an extraterrestrial signature. The present work, involving PGE abundance determinations and Os isotope measurements on drill core samples from inside and outside the crater rim, arrives at the same conclusion. Despite the potential of the Os isotope system to detect even small amounts of extraterrestrial contribution, the wide range in PGE concentrations and Os isotope composition observed in the target rocks makes the interpretation of unradiogenic, high-concentration samples as an impact signature ambiguous.

  3. Determination of the platinum - Group elements (PGE) and gold (Au) in manganese nodule reference samples by nickel sulfide fire-assay and Te coprecipitation with ICP-MS (United States)

    Balaram, V.; Mathur, R.; Banakar, V.K.; Hein, J.R.; Rao, C.R.M.; Gnaneswara, Rao T.; Dasaram, B.


    Platinum group elements (PGE) and Au data in polymetallic oceanic ferromanganese nodule reference samples and crust samples obtained by inductively coupled plasma mass spectrometry (ICP-MS), after separation and pre-concentration by nickel sulfide fire-assay and Te coprecipitation, are presented. By optimizing several critical parameters such as flux composition, matrix matching calibration, etc., best experimental conditions were established to develop a method suitable for routine analysis of manganese nodule samples for PGE and Au. Calibrations were performed using international PGE reference materials, WMG-1 and WMS-1. This improved procedure offers extremely low detection limits in the range of 0.004 to 0.016 ng/g. The results obtained in this study for the reference materials compare well with previously published data wherever available. New PGE data arc also provided on some international manganese nodule reference materials. The analytical methodology described here can be used for the routine analysis of manganese nodule and crust samples in marine geochemical studies.

  4. Milli-PIXE determination of trace elements in osmium-rich platinum-group minerals from the Witwatersrand basin, South Africa

    Energy Technology Data Exchange (ETDEWEB)

    Merkle, R.K.W. E-mail:; Franklyn, C.B


    Osmium-rich platinum-group minerals (PGM), like osmiridium or native osmium, are an integral, though rare, part of the mineralogy of the Witwatersrand paleoplacer. Usually these grains are small, on average <100 {mu}m in size, and the characteristics of their source areas are unknown. In the mineralogical literature on these PGM in the Witwatersrand gold reefs, no information on the trace elements in these minerals is available. The milli-PIXE system at the van de Graaff accelerator at the Atomic Energy Corporation of South Africa was used in a first attempt to determine a range of minor and trace elements, such as Co, Cu, Fe, Rh and Ru, in PGM from the Witwatersrand basin. This attempt is directed towards fingerprinting individual grains and to obtain possible information on the sources for these grains. It also serves as a first step towards a database of trace elements, which could allow a genetical classification of Os-rich PGM of unknown provenance.

  5. The pH-dependent release of platinum group elements (PGEs) from gasoline and diesel fuel catalysts: Implication for weathering in soils. (United States)

    Suchá, Veronika; Mihaljevič, Martin; Ettler, Vojtěch; Strnad, Ladislav


    Powdered samples of new and old gasoline catalysts (Pt, Pd, Rh) and new and old diesel (Pt) catalysts were subjected to a pH-static leaching procedure (pH 2-9) coupled with thermodynamic modeling using PHREEQC-3 to verify the release and mobility of PGEs (platinum group elements). PGEs were released under acidic conditions, mostly exhibiting L-shaped leaching patterns: diesel old: 5.47, 0.005, 0.02; diesel new: 68.5, 0.23, 0.11; gasoline old: 0.1, 11.8, 4.79; gasoline new 2.6, 25.2, 35.9 in mg kg(-1) for Pt, Pd and Rh, respectively. Only the new diesel catalyst had a strikingly different leaching pattern with elevated concentrations at pH 4, probably influenced by the dissolution of the catalyst carrier and washcoat. The pH-static experiment coupled with thermodynamic modeling was found to be an effective instrument for understanding the leaching behavior of PGEs under various environmental conditions, and indicated that charged Pt and Rh species may be adsorbed on the negatively charged surface of kaolinite or Mn oxides in the soil system, whereas uncharged Pd and Rh species may remain mobile in soil solutions.

  6. [Platinum compounds: metabolism, toxicity and supportive strategies]. (United States)

    Lipp, H P; Hartmann, J T


    Although the leading platinum compounds, cisplatin, carboplatin, and oxaliplatin, share some structural similarities, there are marked differences between them in therapeutic uses, pharmacokinetics, and adverse effects profiles. Compared with cisplatin, carboplatin has inferior efficacy in germ-cell tumors, head and neck cancers, and bladder and esophageal carcinomas, whereas the two drugs appear to have comparable efficacy in ovarian cancer, extensive small-cell lung cancers (SCLC), and advanced non-small-cell lung cancers (NSCLC). Oxaliplatin belongs to the group of diaminocyclohexane (DACH) platinum compounds. It is the first platinum-based drug that has marked efficacy in colorectal cancer when given in combination with 5-fluorouracil and folinic acid. Nedaplatin has been registered in Japan, whereas other derivatives, like JM216 (which is the only orally available platinum derivative), ZD0473, BBR3464, and SPI-77 (a liposomal formulation of cisplatin), are still under investigation. The adverse effects of platinum compounds are reviewed together with possible prevention strategies.

  7. PLATINUM AND FUEL CELLS (United States)

    Platinum requirements for fuel cell vehicles (FCVS) have been identified as a concern and possible problem with FCV market penetration. Platinum is a necessary component of the electrodes of fuel cell engines that power the vehicles. The platinum is deposited on porous electrodes...

  8. Characterization of electrochemically modified polycrystalline platinum surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Krebs, L.C.; Ishida, Takanobu.


    The characterization of electrochemically modified polycrystalline platinum surfaces has been accomplished through the use of four major electrochemical techniques. These were chronoamperometry, chronopotentiommetry, cyclic voltammetry, and linear sweep voltammetry. A systematic study on the under-potential deposition of several transition metals has been performed. The most interesting of these were: Ag, Cu, Cd, and Pb. It was determined, by subjecting the platinum electrode surface to a single potential scan between {minus}0.24 and +1.25 V{sub SCE} while stirring the solution, that the electrocatalytic activity would be regenerated. As a consequence of this study, a much simpler method for producing ultra high purity water from acidic permanganate has been developed. This method results in water that surpasses the water produced by pyrocatalytic distillation. It has also been seen that the wettability of polycrystalline platinum surfaces is greatly dependent on the quantity of oxide present. Oxide-free platinum is hydrophobic and gives a contact angle in the range of 55 to 62 degrees. We have also modified polycrystalline platinum surface with the electrically conducting polymer poly-{rho}-phenylene. This polymer is very stable in dilute sulfuric acid solutions, even under applied oxidative potentials. It is also highly resistant to electrochemical hydrogenation. The wettability of the polymer modified platinum surface is severely dependent on the choice of supporting electrolyte chosen for the electrochemical polymerization. Tetraethylammonium tetrafluoroborate produces a film that is as hydrophobic as Teflon, whereas tetraethylammonium perchlorate produces a film that is more hydrophilic than oxide-free platinum.

  9. The metal to metal interface and its effect on adhesion and friction (United States)

    Buckley, D. H.


    The paper considers the interface between two bulk metals and the effect of this interface on adhesive bonding, resistance to tangential displacements, friction and the interfacial transport from one surface to another. Using Auger emission spectroscopy, field ion microscopy, and low energy electron diffraction techniques, the influence of surface orientation, lattice registry, crystal lattice structure and defects, metal surface chemistry and alloying on the characteristics of the interface was studied for noble, platinum, transition, and Group 4B metals. With dissimilar metals in contact, epitaxial transfer of the cohesively weaker to the cohesively stronger metal has been observed. Surface chemical activity of the noble and platinum metals is shown to affect interfacial behavior as does a valence bonding in the transition metals, and the degree of metallic nature in the Group 4B elements. Alloying elements, e.g., Si and Fe, can alter interfacial behavior by segregation to the surface of metals or by altering bulk properties such as crystal transformation kinetics.

  10. Behaviour of palladium(II), platinum(IV), and rhodium(III) in artificial and natural waters: influence of reactor surface and geochemistry on metal recovery. (United States)

    Cobelo-Garcia, Antonio; Turner, Andrew; Millward, Geoffrey E; Couceiro, Fay


    The recovery of dissolved platinum group elements (PGE: Pd(II), Pt(IV) and Rh(III)) added to Milli-Q water, artificial freshwater and seawater and filtered natural waters has been studied, as a function of pH and PGE concentration, in containers of varying synthetic composition. The least adsorptive and/or precipitative loss was obtained for borosilicate glass under most of the conditions employed, whereas the greatest loss was obtained for low-density polyethylene. Of the polymeric materials tested, the adsorptive and/or precipitative loss of PGE was lowest for fluorinated ethylene propylene (Teflon). The loss of Pd(II) in freshwater was significant due to its affinity for surface adsorption and its relatively low solubility. The presence of natural dissolved organic matter increases the recovery of Pd(II) but enhances the loss of Pt(IV). The loss of Rh(III) in seawater was significant and was mainly due to precipitation, whereas Pd(II) recovery was enhanced, compared to freshwater, because of its complexation with chloride. The results have important implications regarding protocols employed for sample preservation and controlled laboratory experiments used in the study of the speciation and biogeochemical behaviour of PGE.

  11. Direct determination of platinum group elements and their distributions in geological and environmental samples at the ng g(-1) level using LA-ICP-IDMS. (United States)

    Boulyga, Sergei F; Heumann, Klaus G


    Laser ablation inductively coupled plasma isotope dilution mass spectrometry (LA-ICP-IDMS) was applied to the direct and simultaneous determination of the platinum group elements (PGEs) Pt, Pd, Ru, and Ir in geological and environmental samples. A special laser ablation system with high ablation rates was used, along with sector field ICP-MS. Special attention was paid to deriving the distributions of PGEs in the pulverized samples. IDMS could not be applied to the (mono-isotopic) Rh, but the similar ablation behavior of Ru and Rh allowed Rh to be simultaneously determined via relative sensitivity coefficients. The laser ablation process produces hardly any oxide ions (which usually cause interference in PGE analysis with liquid sample injection), so the ICP-MS can be run in its low mass resolution but high-sensitivity mode. The detection limits obtained for the geological samples were 0.16 ng g(-1), 0.14 ng g(-1), 0.08 ng g(-1), 0.01 ng g(-1) and 0.06 ng g(-1) for Ru, Rh, Pd, Ir and Pt, respectively. LA-ICP-IDMS was applied to different geological reference materials (TDB-1, WGB-1, UMT-1, WMG-1, SARM-7) and the road dust reference material BCR-723, which are only certified for some of the PGEs. Comparisons with certified values as well as with indicative values from the literature demonstrated the validity of the LA-ICP-IDMS method. The PGE concentrations in subsamples of the road dust reference material correspond to a normal distribution, whereas the distributions in the geological reference materials TDB-1, WGB-1, UMT-1, WMG-1, and SARM-7 are more complex. For example, in the case of Ru, a logarithmic normal distribution best fits the analyzed concentrations in TDB-1 subsamples, whereas a pronounced nugget effect was found for Pt in most geological samples.

  12. Direct determination of platinum group elements and their distributions in geological and environmental samples at the ng g{sup -1} level using LA-ICP-IDMS

    Energy Technology Data Exchange (ETDEWEB)

    Boulyga, Sergei F.; Heumann, Klaus G. [Johannes Gutenberg-University Mainz, Institute of Inorganic Chemistry and Analytical Chemistry, Mainz (Germany)


    Laser ablation inductively coupled plasma isotope dilution mass spectrometry (LA-ICP-IDMS) was applied to the direct and simultaneous determination of the platinum group elements (PGEs) Pt, Pd, Ru, and Ir in geological and environmental samples. A special laser ablation system with high ablation rates was used, along with sector field ICP-MS. Special attention was paid to deriving the distributions of PGEs in the pulverized samples. IDMS could not be applied to the (mono-isotopic) Rh, but the similar ablation behavior of Ru and Rh allowed Rh to be simultaneously determined via relative sensitivity coefficients. The laser ablation process produces hardly any oxide ions (which usually cause interference in PGE analysis with liquid sample injection), so the ICP-MS can be run in its low mass resolution but high-sensitivity mode. The detection limits obtained for the geological samples were 0.16 ng g{sup -1}, 0.14 ng g{sup -1}, 0.08 ng g{sup -1}, 0.01 ng g{sup -1} and 0.06 ng g{sup -1} for Ru, Rh, Pd, Ir and Pt, respectively. LA-ICP-IDMS was applied to different geological reference materials (TDB-1, WGB-1, UMT-1, WMG-1, SARM-7) and the road dust reference material BCR-723, which are only certified for some of the PGEs. Comparisons with certified values as well as with indicative values from the literature demonstrated the validity of the LA-ICP-IDMS method. The PGE concentrations in subsamples of the road dust reference material correspond to a normal distribution, whereas the distributions in the geological reference materials TDB-1, WGB-1, UMT-1, WMG-1, and SARM-7 are more complex. For example, in the case of Ru, a logarithmic normal distribution best fits the analyzed concentrations in TDB-1 subsamples, whereas a pronounced nugget effect was found for Pt in most geological samples. (orig.)

  13. Effects of mother lode-type gold mineralization on 187Os/188Os and platinum group element concentrations in peridotite: Alleghany District, California (United States)

    Walker, R.J.; Böhlke, J.K.; McDonough, W.F.; Li, J.


    Osmium isotope compositions and concentrations of Re, platinum group elements (PGE), and Au were determined for host peridotites (serpentinites and barzburgites) and hydrothermally altered ultramafic wall rocks associated with Mother Lode-type hydrothermal gold-quartz vein mineralization in the Alleghany district, California. The host peridotites have Os isotope compositions and Re, PGE, and Au abundances typical of the upper mantle at their presumed formation age during the late Proterozoic or early Paleozoic. The hydrothermally altered rocks have highly variable initial Os isotope compositions with ??os, values (% deviation of 187OS/188OS from the chondritic average calculated for the approx. 120 Ma time of mineralization) ranging from -1.4 to -8.3. The lowest Os isotope compositions are consistent with Re depletion of a chondritic source (e.g., the upper mantle) at ca. 1.6 Ga. Most of the altered samples are enriched in Au and have depleted and fractionated abundances of Re and PGE relative to their precursor peridotites. Geoehemical characteristics of the altered samples suggest that Re and some PGE were variably removed from the ultramafic rocks during the mineralization event. In addition to Re, the Pt and Pd abundances of the most intensely altered rocks appear to have been most affected by mineralization. The 187Os-depleted isotopic compositions of some altered rocks are interpreted to be a result of preferential 187Os loss via destruction of Re-rich phases during the event. For these rocks, Os evidently is not a useful tracer of the mineralizing fluids. The results do, however, provide evidence for differential mobility of these elements, and mobility of 187Os relative to the initial bulk Os isotope composition during hydrothermal metasomatic alteration of ultramafic rocks. ?? 2007 Society of Economic Geologists, Inc.

  14. Bioavailability of very finely distributed metallic platinum in the lungs and first orienting studies on effects. Part 1; Bioverfuegbarkeit von feinstverteiltem metallischem Platin in der Lunge und erste orientierende Wirkungsuntersuchungen (VPT 09; 1. Teil)

    Energy Technology Data Exchange (ETDEWEB)

    Artelt, S. [Fraunhofer-Institut fuer Toxikologie und Aerosolforschung, Hannover (Germany)


    Projects 07 VPT 08 and 07 VPT 08A revealed that platinum from automotive catalytic converters are largely emitted in metallic form as bound to the support material (aluminium oxide). Platinum emissions from this source are on the order of ng per km. The aim of the still ongoing project 07 VPT 09 is to estimate any health hazards that might grow from the deposition in the human lung by inhalation of very fine platinum particles. To answer this question it is necessary to have sufficient quantities of abraded material at one`s disposal. [Deutsch] Im Rahmen des Projektes 07 VPT 08 und 07 VPT 08A wurde festgestellt, dass Platin aus Automobilabgaskatalysatoren zum ueberwiegenden Teil in metallischer Form, gebunden an Traegermaterial (Aluminiumoxid), emittiert wird. Dabei liegt die Platinemission in der Groessenordnung von ng Platin/km. Im noch laufenden Vorhaben 07 VPT 09 soll ein eventuell auftretendes gesundheitliches Risiko, das durch die inhalative Aufnahme von sehr feinen Platinpartikeln in die Lunge des Menschen entstehen koennte, abgeschaetzt werden. Versuche zur Beantwortung dieser Frage setzen voraus, dass eine genuegend grosse Menge an Abriebmaterial zur Verfuegung steht. (orig.)

  15. Platinum Metal-Free Catalysts for Selective Soft Oxidative Methane → Ethylene Coupling. Scope and Mechanistic Observations. (United States)

    Peter, Matthias; Marks, Tobin J


    Using abundant soft oxidants, a high methane-to-ethylene conversion might be achievable due to the low thermodynamic driving force for over-oxidation. Here we report on the oxidative coupling of methane by gaseous S2 (SOCM). The catalytic properties of Pd/Fe3O4 are compared with those of Fe3O4, and it is found that high ethylene selectivities can be achieved without noble metals; conversion and selectivity on Fe3O4 are stable for at least 48 h at SOCM conditions. SOCM data for 10 oxides are compared, and ethylene selectivities as high as 33% are found; the C2H4/C2H6 ratios of 9-12 observed at the highest S2 conversions are significantly higher than the C2H4/C2H6 ratios usually found in the CH4 coupling with O2. Complementary in-detail analytical studies show that, on Mg, Zr, Sm, W, and La catalysts, which strongly coke during the reaction, lower ethylene selectivities are observed than on Fe, Ti, and Cr catalysts, which only coke to a minor extent. Further catalyst-dependent changes during SOCM in surface area, surface composition, and partial conversion to oxysulfides and sulfides are discussed. Evidence concerning the reaction mechanism is obtained taking into account the selectivity for the different reaction products versus the contact time. CH4 coupling proceeds non-oxidatively with the evolution of H2 on some catalysts, and evidence is presented that C2H4 and C2H2 formation occur via C2H6 and C2H4 dehydrogenation, respectively.

  16. Metal-Support Interactions of Platinum Nanoparticles Decorated N-Doped Carbon Nanofibers for the Oxygen Reduction Reaction. (United States)

    Melke, Julia; Peter, Benedikt; Habereder, Anja; Ziegler, Juergen; Fasel, Claudia; Nefedov, Alexei; Sezen, Hikmet; Wöll, Christof; Ehrenberg, Helmut; Roth, Christina


    N-doped carbon materials are discussed as catalyst supports for the electrochemical oxygen reduction reaction (ORR) in fuel cells. This work deals with the preparation of Pt nanoparticles (NPs) supported on N-doped carbon nanofibers (N-CNF) from a polyaniline nanofiber (PANI NF) precursor, and investigates the ORR activity of the produced materials. Initially, Pt NPs are deposited on PANI NFs. The PANI NF precursors are characterized by near-edge X-ray absorption fine structure (NEXAFS) and transmission electron microscopy (TEM) measurements. It is shown, that in the PANI NF precursor materials electrons from the Pt are being transferred toward the π-conjugated systems of the aromatic ring. This strong interaction of Pt atoms with PANI explains the high dispersion of Pt NPs on the PANI NF. Subsequently, the PANI NF precursors are carbonized at different heat-treatment conditions resulting in structurally different N-CNFs which are characterized by NEXAFS, X-ray photoelectron spectroscopy (XPS) ,and TEM measurements. It is shown that an interaction between N-groups and Pt NPs exists in all investigated N-CNFs. However, the N-CNFs differ in the composition of the N-species and the dispersion of the Pt NPs. A small mean Pt NP size with a narrow size distribution is attributed to the presence of pyrdinic N-groups in the N-CNFs, whereas, for the N-CNFs with mainly graphitic and pyrrolic N-groups, an increase in the average Pt NP size with a broad size distribution is found. The ORR activity in alkaline media investigated by Koutecky-Levich analysis of rotating disk electrode measurements showed a largely enhanced ORR activity in comparison to a conventional Pt/C catalyst.

  17. The concept of platinum sensitivity could be applied to recurrent cervical cancer: a multi-institutional retrospective study from the Japanese Gynecologic Oncology Group. (United States)

    Takekuma, Munetaka; Mori, Keita; Iida, Tetsuji; Kurihara, Kazuko; Saitou, Motoaki; Tokunaga, Hideki; Kawana, Kei; Ikeda, Masae; Satoh, Toyomi; Saito, Toshiaki; Miyagi, Etsuko; Nagai, Yutaka; Furusawa, Akiko; Kawano, Yoshiaki; Kawano, Kouichiro; Tabata, Tsutomu; Ota, Yukinobu; Hayase, Ryoji; Mikami, Mikio; Sugiyama, Toru


    This study aimed at evaluating the applicability of the concept of platinum sensitivity to recurrent cervical cancer. The clinical information of patients with recurrent cervical cancer, who were initially treated with platinum-based chemotherapy and received second-line platinum-based chemotherapy at the time of recurrence between January 2008 and December 2012, was retrospectively reviewed. A total of 677 patients from 71 medical centers were analyzed. The median overall survival (OS) for patients with platinum-free interval (PFI) of <6, 6-11, 12-17, and ≥18 months was 12.1 (95% CI 11.0-14.1) months, 17.4 (15.5-20.4) months, 20.2 (17.9-27.6) months, and 29.9 (26.7-36.0) months, respectively (P < 0.0001, log-rank). The best cut-off value of PFI that affected OS was 7 months, analyzed by the minimum P value method. The median progression-free survival (PFS) for patients with less than and more than PFI of 7 months was 6.2 months (95% CI 4.8-9.3) and 21.0 months (18.9-24.8) (P < 0.0001, log-rank), respectively, and the median OS for patients with less than and more than PFI of 7 months was 12.3 months (11.2-14.1) and 24.2 months (20.8-25.8) (P < 0.0001, log-rank). Multivariate analysis revealed that PFI (P < 0.0001, HR 0.449, 95% CI 0.369-0.548) alone had a statistically significant association with OS. This study showed that the concept of platinum sensitivity could be applied to recurrent cervical cancer and PFI could be one of the independent prognostic factors for patients with recurrent cervical cancer who have previously been treated with platinum-based chemotherapy.

  18. Molecular early main group metal hydrides : synthetic challenge, structures and applications

    NARCIS (Netherlands)

    Harder, Sjoerd


    Within the general area of early main group metal chemistry, the controlled synthesis of well-defined metal hydride complexes is a rapidly developing research field. As group 1 and 2 metal complexes are generally highly dynamic and lattice energies for their [MH](infinity) and [MH2](infinity) salts

  19. Molecular early main group metal hydrides : synthetic challenge, structures and applications

    NARCIS (Netherlands)

    Harder, Sjoerd


    Within the general area of early main group metal chemistry, the controlled synthesis of well-defined metal hydride complexes is a rapidly developing research field. As group 1 and 2 metal complexes are generally highly dynamic and lattice energies for their [MH](infinity) and [MH2](infinity) salts

  20. Synthesis of Group IVB Metals Oxicarbides by Carboreduction Reactions

    Directory of Open Access Journals (Sweden)

    A.D. Mazzoni


    Full Text Available The metals of the group IV B (Ti, Zr, Hf present a series of carbides and oxicarbides with scientific and technological interest. Many of these compounds belong to the subsystem "MO - MC" of the pseudoternary "MO - MN - MC" system (where M = Ti, Zr or Hf. In this work carboreduction reactions of TiO2 and ZrO2 were performed in argon atmosphere, using temperatures from 1250° to 1650° and reaction times of 120 min. The oxicarbides obtained were in the range TiC0.16O0.84 to TiC0.73O0.27 and ZrC0.46O0.54 to ZrC0.90O0.10. respectively. The reaction products were characterized by X-ray diffraction (XRD, with the calculation of their cell constants by means of the Rietveld method. Scanning Electron Microscopy (SEM was used in the characterization of powdered materials. Additionally, the carborreduction reaction was followed by weight loss.

  1. Modification of the sulphur resistance of platinum by addition of metals for aromatics hydrogenation; Modification de la thioresistance du platine par ajouts d'elements metalliques pour l'hydrogenation d'aromatiques

    Energy Technology Data Exchange (ETDEWEB)

    Guillon, E.


    The aim of this study is based on the understanding of sulphur resistance of platinum catalytic systems. In this work, bimetallic systems (Pt-Ge, Pt-Au and Pt-Pd) supported on {gamma}-alumina have been studied. Preparation methods have been chosen to give the best control of the physicochemical properties of final system. Electronic and geometrical properties of the metallic phase were characterised by various techniques (TPR, infrared spectroscopy of adsorbed CO (IR(CO)), EXAFS, LEIS). Ortho-xylene hydrogenation in presence of 100 ppm of sulphur was used as model catalytic test in order to study the sulphur resistance of the catalysts. It has been shown that germanium and palladium act as electro-acceptors toward platinum. The ranking of catalytic activity in presence of sulphur is as followed: Pt-Pd > Pt-Au {approx_equal} Pt >> Pt-Ge {approx_equal} 0. The best sulphur resistance for Pt-Pd was obtained for the composition Pt{sub 20}Pd{sub 80} (Pd/Pt=4). An eggshell PdS structure with Pt (sulfur free) core is proposed. These works show that the sulphur resistance of platinum is not only linked with its electronic properties. They allow us to propose an original concept of sulphur resistant catalyst taking into account each catalytic parameters such as chemical bonding of S and aromatic compounds on the metallic site, physico-chemical characteristics of the bimetallic aggregates (particle size, structure, surface composition) and electronic modification of surface atoms in bimetallic catalysts. (author)

  2. Molecular early main group metal hydrides: synthetic challenge, structures and applications. (United States)

    Harder, Sjoerd


    Within the general area of early main group metal chemistry, the controlled synthesis of well-defined metal hydride complexes is a rapidly developing research field. As group 1 and 2 metal complexes are generally highly dynamic and lattice energies for their [MH](∞) and [MH(2)](∞) salts are high, the synthesis of well-defined soluble hydride complexes is an obvious challenge. Access to molecular early main group metal hydrides, however, is rewarding: these hydrocarbon-soluble metal hydrides are highly reactive, have found use in early main group metal catalysis and are potentially also valuable molecular model systems for polar metal hydrides as a hydrogen storage material. The article focusses specifically on alkali and alkaline-earth metal hydride complexes and discusses the synthetic challenge, molecular structures, reactivity and applications.

  3. Optoelectronic method for determining platinum in biological products (United States)

    Radu, Simona; Ionicǎ, Mihai; Macovei, Radu Alexandru; Caragea, Genica; Forje, Mǎrgǎrita; Grecu, Iulia; Vlǎdescu, Marian; Viscol, Oana


    Of all platinum metals, platinum has the most uses and it's the most abundant and most easily to be processed. Its use in auto catalysts results in environmental contamination of crowded cities and high-traffic roads. In medicine, Pt is used as a cytostatic drug. In order to study the degree of contamination of the population with Pt or the correctness of treatment with Pt, it has been developed a method for its determination from urine or blood samples with a system Graphite Furnance - Atomic Absorption Spectrometer, (GF-AAS) Varian. There are presented the methods of sampling processing for blood or urine that followed the digest of the organic matrix. In the determination of the operating parameters for the system GF-AAS, was aimed the reducing of the nonanatomic absorbance by optimizing the drying temperatures, the calcination and atomization temperatures and the removal of the nonanatomic absorbance with D2 lamp. As a result of the use of the method are presented the concentrations of Pt in the blood or urine of a group of patients in Bucharest, a city with heavy traffic of vehicles. GF-AAS method presented is sensitive, reproducible, and relatively easy to apply with an acceptable cost. With this method, the concentration of Pt can be determined from blood and urine, both in order to establish the degree of contamination with Pt and for monitoring cancer therapy with platinum compounds.

  4. In vitro permeation of platinum through African and Caucasian skin. (United States)

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


    The majority of the South African workforce are Africans, therefore potential racial differences should be considered in risk and exposure assessments in the workplace. Literature suggests African skin to be a superior barrier against permeation and irritants. Previous in vitro studies on metals only included skin from Caucasian donors, whereas this study compared the permeation of platinum through African and Caucasian skin. A donor solution of 0.3 mg/ml of potassium tetrachloroplatinate (K₂PtCl₄) dissolved in synthetic sweat was applied to the vertical Franz diffusion cells with full thickness abdominal skin. Skin from three female African and three female Caucasian donors were included (n=21). The receptor solution was removed at various intervals during the 24 h experiment, and analysed with high resolution inductively coupled plasma-mass spectrometry (ICP-MS). Skin was digested and analysed by inductively coupled plasma-optical emission spectrometry (ICP-OES). Significantly higher permeation of platinum through intact African skin (p=0.044), as well as a significantly higher mass of platinum retention in African skin in comparison with Caucasian skin (p=0.002) occurred. Significant inter-donor variation was found in both racial groups (pplatinum salts. These results are contradictory to limited literature suggesting a superior barrier in African skin and further investigation is necessary to explain the higher permeation through African skin.

  5. Selective oxidation of glycerol by using a hydrotalcite-supported platinum catalyst under atmospheric oxygen pressure in water. (United States)

    Tsuji, Akihiro; Rao, Kasanneni Tirumala Venkateswara; Nishimura, Shun; Takagaki, Atsushi; Ebitani, Kohki


    A hydrotalcite-supported platinum (Pt/HT) catalyst was found to be a highly active and selective heterogeneous catalyst for glycerol oxidation in pure water under atmospheric oxygen pressure in a high glycerol/metal molar ratio up to 3125. High selectivity toward glyceric acid (78 %) was obtained even at room temperature under air atmosphere. The Pt/HT catalyst selectively oxidized the primary hydroxyl group of 1,2-propandiol to give the corresponding carboxylic acid (lactic acid) as well as glycerol. The activity of the catalyst was greatly influenced by the Mg/Al ratio of hydrotalcite. Glycerol conversion increased with increasing the Mg/Al ratio of hydrotalcite (from trace to 56 %). X-ray absorption fine structure (XAFS) measurements indicated that the catalytic oxidation activity was proportional to the metallic platinum concentration, and more than 35 % of metallic platinum was necessary for this reaction. TEM measurements and titration analysis by using benzoic acid suggested that the solid basicity of hydrotalcite plays important roles in the precise control of platinum size and metal concentration as well as the initial promotion of alcohol oxidation.

  6. Asymptomatic prospective and retrospective cohorts with metal-on-metal hip arthroplasty indicate acquired lymphocyte reactivity varies with metal ion levels on a group basis. (United States)

    Hallab, Nadim J; Caicedo, Marco; McAllister, Kyron; Skipor, Anastasia; Amstutz, Harlan; Jacobs, Joshua J


    Some tissues from metal-on-metal (MoM) hip arthroplasty revisions have shown evidence of adaptive-immune reactivity (i.e., excessive peri-implant lymphocyte infiltration/activation). We hypothesized that, prior to symptoms, some people with MoM hip arthroplasty will develop quantifiable metal-induced lymphocyte reactivity responses related to peripheral metal ion levels. We tested three cohorts (Group 1: n = 21 prospective longitudinal MoM hip arthroplasty; Group 2: n = 17 retrospective MoM hip arthroplasty; and Group 3: n = 20 controls without implants). We compared implant position, metal-ion release, and immuno-reactivity. MoM cohorts had elevated (p Group 1:1.2 ppb Co, 1.5 ppb Cr; Group 2: 3.4 ppb Co, 5.4 ppb Cr; Group 3: 0.01 ppb Co, 0.1 ppb Cr). However, only after 1-4 years post-op did 56% of Group 1 develop metal-reactivity (vs. 5% pre-op, metal-LTT, SI > 2), compared with 76% of Group 2, and 15% of Group 3 controls (patch testing was a poor diagnostic indicator with only 1/21 Group 1 positive). Higher cup-abduction angles (50° vs. 40°) in Group 1 were associated with higher serum Cr (p Group-1 participants (p Group 1 participants. Our results showed that lymphocyte reactivity to metals can develop within the first 1-4 years after MoM arthroplasty in asymptomatic patients and lags increases in metal ion levels. This increased metal reactivity was more prevalent in those individuals with extreme cup angles and higher amounts of circulating metal. Copyright © 2012 Orthopaedic Research Society.

  7. Multinuclear group 4 catalysis: olefin polymerization pathways modified by strong metal-metal cooperative effects. (United States)

    McInnis, Jennifer P; Delferro, Massimiliano; Marks, Tobin J


    homogeneous and heterogeneous systems, macromolecules with dramatically altered properties, and large-scale industrial processes. It is noteworthy that many metalloenzymes employ multiple active centers operating in close synergistic proximity to achieve high activity and selectivity. Such enzymes were the inspiration for the research discussed in this Account, focused on the properties of multimetallic olefin polymerization catalysts. Here we discuss how modifications in organic ligand architecture, metal···metal proximity, and cocatalyst can dramatically modify polyolefin molecular weight, branch structure, and selectively for olefinic comonomer enchainment. We first discuss bimetallic catalysts with identical group 4 metal centers and then heterobimetallic systems with either group 4 or groups 4 + 6 catalytic centers. We compare and contrast the polymerization properties of the bimetallic catalysts with their monometallic analogues, highlighting marked cooperative enchainment effects and unusual polymeric products possible via the proximate catalytic centers. Such multinuclear olefin polymerization catalysts exhibit the following distinctive features: (1) unprecedented levels of polyolefin branching; (2) enhanced enchainment selectivity for linear and encumbered α-olefin comonomers; (3) enhanced polyolefin tacticity and molecular weight; (4) unusual 1,2-insertion regiochemistry for styrenic monomers; (5) modified chain transfer kinetics, such as M-polymer β-hydride transfer to the metal or incoming monomer; (6) LLDPE synthesis with a single binuclear catalyst and ethylene.

  8. A randomized phase II study of carboplatin plus pegylated liposomal doxorubicin versus carboplatin plus paclitaxel in platinum sensitive ovarian cancer patients: a Hellenic Cooperative Oncology Group study

    Directory of Open Access Journals (Sweden)

    Briasoulis Evangelos


    Full Text Available Abstract Background Platinum-based combinations are the standard second-line treatment for platinum-sensitive ovarian cancer (OC. This randomized phase II study was undertaken in order to compare the combination of carboplatin and pegylated liposomal doxorubicin (LD with carboplatin and paclitaxel (CP in this setting. Methods Patients with histologically confirmed recurrent OC, at the time of or more than 6 months after platinum-based chemotherapy, were randomized to six cycles of CP (carboplatin AUC5 + paclitaxel 175 mg/m2, d1q21 or CLD (carboplatin AUC5 + pegylated LD 45 mg/m2, d1q28. Results A total of 189 eligible patients (CP 96, CLD 93, with a median age of 63 years, median Performance Status (PS 0 and a median platinum free interval (PFI of 16.5 months, entered the study. Discontinuation due to toxicity was higher in the CP patients (13.5% versus 3%, P = 0.016. The overall response rate was similar: CP 58% versus CLD 51%, P = 0.309 (Complete Response; CR 34% versus 23% and there was no statistical difference in time-to-progression (TTP or overall survival (OS; TTP 10.8 months CP versus 11.8 CLD, P = 0.904; OS 29.4 months CP versus 24.7 CLD, P = 0.454. No toxic deaths were recorded. Neutropenia was the most commonly seen severe toxicity (CP 30% versus CLD 35%. More frequent in CLD were severe thrombocytopenia (11% versus 2%, P = 0.016, skin toxicity and Palmar-plantar erythrodysesthesia (PPE grade 1-2 (38% versus 9%, PP = 0.029, 20% versus 5%, P = 0.003. PS and PFI were independent prognostic factors for TTP and OS. Conclusions The combination of pegylated LD with carboplatin is effective, showing less neurotoxicity and alopecia than paclitaxel-carboplatin. It thus warrants a further phase III evaluation as an alternative treatment option for platinum-sensitive OC patients. Trial Registration Australian New Zealand Clinical Trials Registry: ACTRN12609000436279

  9. Synthesis and characterization of new platinum(II) and platinum(IV) triphyrin complexes. (United States)

    Xue, Zhaoli; Kuzuhara, Daiki; Ikeda, Shinya; Okujima, Tetsuo; Mori, Shigeki; Uno, Hidemitsu; Yamada, Hiroko


    Metalation of 6,13,20,21-tetrakis(4-methylphenyl)-22H-tribenzo[14]triphyrin(2.1.1) with PtCl(2) gave a platinum(II) complex having a square-planar coordination structure with two pyrrolic nitrogen atoms and two chloride ions, with a saddle-shaped macrocycle. This platinum(II) complex was easily oxidized by air to an octahedral platinum(IV) complex coordinated by three pyrrolic nitrogen atoms as a tridentate monoanionic cyclic ligand and three chloride ions. When platinum(II) triphyrin was crystallized in air, an oxygen atom was incorporated between two α-carbon atoms of the pyrroles as an oxygen bridge to intercept the 14π aromatic system.

  10. Study of supported platinum catalysts by anomalous scattering

    Energy Technology Data Exchange (ETDEWEB)

    Georgopoulos, P.; Cohen, J.B.


    Platinum metal catalysts supported on silica gel and alumina were examined by wide-angle anomalous x-ray scattering at the Cornell High Energy Synchrotron Source. Complete removal of the support background features is achieved by this method, eliminating errors due to inaccurate background estimation. Platinum diffraction patterns from very-high-percentage metal-exposed catalysts were obtained for the first time, as well as from platinum supported on alumina. This technique is suitable for examining catalysts under working conditions and is superior to EXAFS for determinations of particle morphology and size distribution. 10 references, 8 figures.

  11. Occurrence model for magmatic sulfide-rich nickel-copper-(platinum-group element) deposits related to mafic and ultramafic dike-sill complexes: Chapter I in Mineral deposit models for resource assessment (United States)

    Schulz, Klaus J.; Woodruff, Laurel G.; Nicholson, Suzanne W.; Seal, Robert R., II; Piatak, Nadine M.; Chandler, Val W.; Mars, John L.


    Magmatic sulfide deposits containing nickel (Ni) and copper (Cu), with or without (±) platinum-group elements (PGE), account for approximately 60 percent of the world’s nickel production. Most of the remainder of the Ni production is derived from lateritic deposits, which form by weathering of ultramafic rocks in humid tropical conditions. Magmatic Ni-Cu±PGE sulfide deposits are spatially and genetically related to bodies of mafic and/or ultramafic rocks. The sulfide deposits form when the mantle-derived mafic and/or ultramafic magmas become sulfide-saturated and segregate immiscible sulfide liquid, commonly following interaction with continental crustal rocks.

  12. Redeposition of electrochemically dissolved platinum as nanoparticles on carbon

    DEFF Research Database (Denmark)

    Norgaard, C. F.; Stamatin, S. N.; Skou, E. M.


    Electrochemical dissolution of platinum has been proposed by several research groups as an environmentally friendly way to recover platinum from catalytic structures such as fuel cell electrodes. For the case of electrochemical dissolution of platinum in hydrochloric acid electrolyte, the present...... on carbon was then identified, quantified, and the particle size evaluated by powder X-ray diffraction, thermogravimetric analysis and cyclic voltammetry. Copyright (C) 2014, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved....

  13. The role of macrocyclic compounds in the extraction and possible separation of platinum and rhodium from chloride solutions (United States)

    Jyothi, Rajesh Kumar; Lee, Jin-Young


    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).

  14. The use of high performance liquid chromatography and solid phase extraction for separation of platinum, palladium and rhodium



    Platinum group metals (PGMs) have received much attention in the fields of industry, geochemistry and medicine. Due to scarcity of PGMs and their high industrial demands, recycling of PGM bearing materials such as industrial wastes, automobile catalytic converters and similar products gained much attention in recent times. Particularly, separation of PGMs as a group from the material bearing the elements followed by their individual separation is crucial. In this study, an attempt was made to...

  15. Platinum single crystal electrodes for the electrocatalysis of methane oxidation

    Directory of Open Access Journals (Sweden)

    Mayara Munaretto


    Full Text Available The main objective of this paper is to characterize the voltammetric profiles of platinum single crystals of low Miller indexes Pt(100 and Pt(110 and study their catalytic activities on the oxidation of methane. In this way, it was developed a metallic surface modified by presence of other metal oxide, which presents catalytic activity for this reaction. It is well known that the electrooxidation of methane (CH4 leads mainly to the formation of CO2 and H2O, however, the oxidation can also lead to the formation of CO, a reaction intermediate that has strong interaction with metal surfaces, such as platinum. This molecule tends to accumulate on the platinum surface and to passive it, due to the self-poisoning, decreasing its catalytic activity. Therefore, the main aim of this work was the development of a platinum electrode modified by deposition of titanium oxide, which presented electrocatalytic properties for the oxidation of methane.


    Energy Technology Data Exchange (ETDEWEB)

    Ross, Teresa L.; Holtzman, Jon [Department of Astronomy, New Mexico State University, P.O. Box 30001, MSC 4500, Las Cruces, NM 88003-8001 (United States); Saha, Abhijit [NOAO, 950 Cherry Avenue, Tucson, AZ 85726-6732 (United States); Anthony-Twarog, Barbara J., E-mail:, E-mail:, E-mail: [Department of Physics and Astronomy, University of Kansas, Lawrence, KS 66045-7582 (United States)


    We present stellar metallicities in Leo I, Leo II, IC 1613, and Phoenix dwarf galaxies derived from medium (F390M) and broad (F555W, F814W) band photometry using the Wide Field Camera 3 instrument on board the Hubble Space Telescope. We measured metallicity distribution functions (MDFs) in two ways, (1) matching stars to isochrones in color–color diagrams and (2) solving for the best linear combination of synthetic populations to match the observed color–color diagram. The synthetic technique reduces the effect of photometric scatter and produces MDFs 30%–50% narrower than the MDFs produced from individually matched stars. We fit the synthetic and individual MDFs to analytical chemical evolution models (CEMs) to quantify the enrichment and the effect of gas flows within the galaxies. Additionally, we measure stellar metallicity gradients in Leo I and II. For IC 1613 and Phoenix our data do not have the radial extent to confirm a metallicity gradient for either galaxy. We find the MDF of Leo I (dwarf spheroidal) to be very peaked with a steep metal-rich cutoff and an extended metal-poor tail, while Leo II (dwarf spheroidal), Phoenix (dwarf transition), and IC 1613 (dwarf irregular) have wider, less peaked MDFs than Leo I. A simple CEM is not the best fit for any of our galaxies; therefore we also fit the “Best Accretion Model” of Lynden-Bell. For Leo II, IC 1613, and Phoenix we find similar accretion parameters for the CEM even though they all have different effective yields, masses, star formation histories, and morphologies. We suggest that the dynamical history of a galaxy is reflected in the MDF, where broad MDFs are seen in galaxies that have chemically evolved in relative isolation and narrowly peaked MDFs are seen in galaxies that have experienced more complicated dynamical interactions concurrent with their chemical evolution.

  17. Abundances of platinum group elements in native sulfur condensates from the Niuatahi-Motutahi submarine volcano, Tonga rear arc: Implications for PGE mineralization in porphyry deposits (United States)

    Park, Jung-Woo; Campbell, Ian H.; Kim, Jonguk


    Some porphyry Cu-Au deposits, which are enriched in Pd, are potentially an economic source of Pd. Magmatic volatile phases are thought to transport the platinum group elements (PGEs) from the porphyry source magma to the point of deposition. However, the compatibilities of the PGEs in magmatic volatile phases are poorly constrained. We report PGE and Re contents in native sulfur condensates and associated altered dacites from the Niuatahi-Motutahi submarine volcano, Tonga rear arc, in order to determine the compatibility of PGEs and Re in magmatic volatile phases, and their mobility during secondary hydrothermal alteration. The native sulfur we analyzed is the condensate of a magmatic volatile phase exsolved from the Niuatahi-Motutahi magma. The PGEs are moderately enriched in the sulfur condensates in comparison to the associated fresh dacite, with enrichment factors of 11-285, whereas Au, Cu and Re are strongly enriched with enrichment factors of ∼20,000, ∼5000 and ∼800 respectively. Although the PGEs are moderately compatible into magmatic volatile phases, their compatibility is significantly lower than that of Au, Cu and Re. Furthermore, the compatibility of PGEs decrease in the order: Ru > Pt > Ir > Pd. This trend is also observed in condensates and sublimates from other localities. PGE mineralization in porphyry Cu-Au deposits is characterized by substantially higher Pd/Pt (∼7-60) and Pd/Ir (∼100-10,500) than typical orthomagmatic sulfide deposits (e.g. Pd/Pt ∼0.6 and Pd/Ir ∼20 for the Bushveld). It has previously been suggested that the high mobility of Pd, relative to the other PGEs, may account for the preferential enrichment of Pd in porphyry Cu-Au deposits. However, the low compatibility of Pd in the volatile phase relative to the other PGEs, shown in this study, invalidates this explanation. We suggest that the PGE geochemistry of Pd-rich Cu-Au deposits is principally derived from the PGE characteristics of the magma from which the ore

  18. Adsorption of volatile polonium species on metals in various gas atmospheres. Pt. II. Adsorption of volatile polonium on platinum, silver and palladium

    Energy Technology Data Exchange (ETDEWEB)

    Maugeri, Emilio Andrea; Joerg Neuhausen; Dressler, Rugard; Piguet, David; Voegele, Alexander; Schumann, Dorothea [Paul Scherrer Institut (PSI), Villigen (Switzerland). Lab. for Radiochemistry; Misiak, Ryszard [The Henryk Niewodniczanski Institute of Nuclear Physics, Krakow (Poland); Eichler, Robert [Paul Scherrer Institut (PSI), Villigen (Switzerland). Lab. for Radiochemistry; Bern Univ. (Switzerland). Dept. for Chemistry and Biochemistry


    This work presents the results obtained from studying the interaction between polonium compounds formed in different atmospheres and platinum, palladium and silver surfaces obtained by thermochromatography. These results are of crucial importance for the design of cover gas filter systems for lead-bismuth eutectic (LBE)-based nuclear facilities such as accelerator driven systems (ADS). The results obtained from studying the interaction of polonium and platinum under inert atmosphere and reducing atmospheres with and without addition of moisture show that polonium is deposited at temperatures between 993 and 1221 K, with adsorption enthalpies ranging from -235 to -291 kJ mol{sup -1}, indicating a very strong adsorption of the polonium species present on platinum surfaces. The interaction between polonium and silver was investigated using purified inert, reducing and oxidizing carrier gases. Results show a deposition temperature between 867 and 990 K, with adsorption enthalpies ranging from -205 to -234 kJ mol{sup -1}. The interaction of polonium and palladium was studied in purified helium and purified hydrogen. For both conditions a deposition temperature of 1221 K was observed corresponding to an adsorption enthalpy of -340 kJ mol{sup -1}. No highly volatile polonium species was formed at any of the applied experimental conditions.

  19. Possibilities Of Metals Extracton From Spent Metallic Automotive Catalytic Converters By Using Biometallurgical Method

    Directory of Open Access Journals (Sweden)

    Willner J.


    Full Text Available The main task of automotive catalytic converters is reducing the amount of harmful components of exhaust gases. Metallic catalytic converters are an alternative to standard ceramic catalytic converters. Metallic carriers are usually made from FeCrAl steel, which is covered by a layer of Precious Group Metals (PGMs acting as a catalyst. There are many methods used for recovery of platinum from ceramic carriers in the world, but the issue of platinum and other metals recovery from metallic carriers is poorly described. The article presents results of preliminary experiments of metals biooxidation (Fe, Cr and Al from spent catalytic converters with metallic carrier, using bacteria of the Acidithiobacillus genus.

  20. Metallicities and kinematics for dwarf spheroidals in the local group

    NARCIS (Netherlands)

    Battaglia, G.; Tolstoy, E.; Helmi, A.; Irwin, M.; Randich, S; Pasquini, L


    We present the first results of Call triplet observations from VLT/FLAMES for Sculptor, Fornax and Sextans dSphs. For each galaxy, we obtained accurate velocity and metallicity measurements for hundreds of stars out to and beyond the tidal radius. In each case, we find clear evidence for the presenc

  1. Metallicity Distribution Functions of Four Local Group dwarf galaxies

    CERN Document Server

    Ross, Teresa L; Saha, Abhijit; Anthony-Twarog, Barbara J


    We present stellar metallicities in Leo I, Leo II, IC 1613, and Phoenix dwarf galaxies derived from medium (F390M) and broad (F555W, F814W) band photometry using the Wide Field Camera 3 (WFC3) instrument aboard the Hubble Space Telescope. We measured metallicity distribution functions (MDFs) in two ways, 1) matching stars to isochrones in color-color diagrams, and 2) solving for the best linear combination of synthetic populations to match the observed color-color diagram. The synthetic technique reduces the effect of photometric scatter, and produces MDFs 30-50 % narrower than the MDFs produced from individually matched stars. We fit the synthetic and individual MDFs to analytical chemical evolution models (CEM) to quantify the enrichment and the effect of gas flows within the galaxies. Additionally, we measure stellar metallicity gradients in Leo I and II. For IC 1613 and Phoenix our data do not have the radial extent to confirm a metallicity gradient for either galaxy. We find the MDF of Leo I (dwarf spher...

  2. Metals and metal compounds in cancer treatment. (United States)

    Desoize, Bernard


    Metals and metal compounds have been used in medicine for several thousands of years. In this review we summarized the anti-cancer activities of the ten most active metals: arsenic, antimony, bismuth, gold, vanadium, iron, rhodium, titanium, gallium and platinum. The first reviewed metal, arsenic, presents the anomaly of displaying anti-cancer and oncogenic properties simultaneously. Some antimony derivatives, such as Sb2O3, salt (tartrate) and organic compounds, show interesting results. Bismuth directly affects Helicobacter pylori and gastric lymphoma; the effects of bismuth complexes of 6-mercaptopurine are promising. Gold(I) and (III) compounds show anti-tumour activities, although toxicity remains high. Research into the potential use of gold derivatives is still ongoing. Several derivatives of vanadium show anti-proliferative activity, but their toxicity must be overcome. Several pieces of evidence indicate that iron deprivation could be an excellent therapeutic approach; furthermore, it is synergistic with classic anti-cancer drugs. Rhodium belongs to the same group as platinum and it also presents interesting activity, but with the same nephrotoxicity. Several rhodium compounds have entered phase I clinical trials. In contrast to the platinum complexes, titanium derivatives showed no evidence of nephrotoxicity or myelotoxicity; titanocene dichloride is undergoing clinical trial. The anti-proliferative effect of gallium could be related to its competition with the iron atom; in addition a derivative appears to reverse the multidrug resistance. The last metal reviewed, platinum, has given some of the very best anti-cancer drugs. Four derivatives are used today in the clinic; their mechanism of action and of resistance are described.

  3. High-pressure/high-temperature synthesis and characterization of the first palladium or platinum containing lithium transition-metal sulfides Li2M3S4 (M=Pd, Pt) (United States)

    Heymann, Gunter; Niehaus, Oliver; Krüger, Hannes; Selter, Philipp; Brunklaus, Gunther; Pöttgen, Rainer


    The new lithium transition-metal sulfides Li2M3S4 (M=Pd, Pt) were obtained via multianvil high-pressure/high-temperature syntheses at 8 GPa and 1150 °C starting from a stoichiometric mixture of lithium nitride, sulfur, and palladium or platinum. Single crystal structure analyses indicated the space group P21/c (no. 14) with the following lattice parameters and refinement results: a=492.9(1), b=1005.9(2), c=614.9(2) pm, β=110.9 (1)°, R1=0.0165, wR2=0.0308 (all data) for Li2Pd3S4 and a=498.2(1), b=1005.5(2), c=613.0(2) pm, β=110.8(1)°, R1=0.0215, wR2=0.0450 (all data) for Li2Pt3S4. The crystal structures are built up from two distinct Pd/Pt sites, one of which is a special position (0,0,0), two sulfur sites, and one lithium site. The atoms Pd2/Pt2 form isolated square planar PdS4/PtS4 units, whereas the Pd1/Pt1 atoms form pairs of square planar PdS4/PtS4 units, which are connected via a common edge. These two structural motives built up a three-dimensional network structure by linking through common corners. The lithium atoms are positioned inside of the so formed channels. Li2M3S4 (M=Pd, Pt) are isostructural to the minerals jaguéite, Cu2Pd3Se4 and chrisstanleyite, Ag2Pd3Se4, which are up to now the only representatives of this structure type. Both compounds were studied with respect to their magnetic properties and can be classified as Pauli paramagnetic or diamagnetic. Regarding the possibility of lithium mobility inside the channels, of the structure, solid state 7Li NMR and high-temperature single crystal investigations revealed localization of the lithium atoms on their crystallographic sites.

  4. Decomposition of the Precursor [Pt(NH3)4](OH)2, Genesis and Structure of the Metal-Support Interface of Alumina Supported Platinum Particles: A Structural Study Using TPR, MS and XAFS Spectroscopy.

    NARCIS (Netherlands)

    Koningsberger, D.C.; Muñoz-Paez, A.


    During the preparation of alumina supported platinum catalysts, the precursor [Pt(NH3)4](OH)2 decomposes to a neutral Pt(NH3)zO species during the drying process at 120 'C. Treatment in flowing hydrogen at 180 'C leads to partial reduction of the platinum ammine complex and formation of platinum met

  5. Simultaneous Platinum and Copper Ion Attachment to a Human Copper Chaperone Protein (United States)

    Hodak, Miroslav; Cvitkovic, John; Yu, Corey; Dmitriev, Oleg; Kaminski, George; Bernholc, Jerry


    Cisplatin is a potent anti-cancer drug based on a platinum ion. However, its effectiveness is decreased by cellular resistance, which involves cisplatin attaching to copper transport proteins. One of such proteins is Atox1, where cisplatin attaches to the copper binding site. Surprisingly, it was shown that both cisplatin and copper can attach to Atox1 at the same time. To study this double metal ion attachment, we use the KS/FD DFT method, which combines Kohn-Sham DFT with frozen-density DFT to achieve efficient quantum-mechanical description of explicit solvent. Calculations have so far investigated copper ion attachment to CXXC motifs present in Atox1. The addition of the platinum ion and the competition between the two metals is currently being studied. These calculations start from a molecular mechanics (MM) structural model, in which glutathione groups provide additional ligands to the Pt ion. Our goals are to identify possible Cu-Pt structures and to determine whether copper/platinum attachment is competitive, independent, or cooperative. Results will be compared to the 1H, N1 5 -HSQC NMR experiments, in which binding of copper and cisplatin to Atox1 produces distinct secondary chemical shift signatures, allowing for kinetic studies of simultaneous metal binding.

  6. Concentrations of Platinum Group Elements (Pt, Pd, Rh in Airborne Particulate Matter (PM2.5 and PM10-2.5 Collected at Selected Canadian Urban Sites: a Case Study

    Directory of Open Access Journals (Sweden)

    Celo V.


    Full Text Available Increasing environmental concentrations of platinum group elements (PGEs, in particular platinum (Pt, palladium (Pd and rhodium (Rh, from catalytic converters has been reported worldwide. Initially it was believed that the emitted PGEs remain in the roadside environment, but recent studies have shown that fine PGE-containing particles can be transported and distributed at regional and long-range levels. Therefore, the monitoring of PGEs in airborne particulate matter (PM is important for the estimation of potential risks to human health and to the ecosystem. The aim of this study is to present the first results from an analysis on the concentration and distribution of Pt, Pd and Rh in PM collected on Teflon filters at two selected urban sites (Toronto, Ontario; Edmonton, Alberta collected within the Canadian National Air Pollution Surveillance (NAPS network. In this work, a quadruple inductively coupled plasma mass spectrometry (ICP-MS, combined with microwave assisted acid digestion using aqua regia was used. A cation exchange separation was used to alleviate the matrix-induced spectral and nonspectral interferences prior to ICP-MS analysis. To obtain sufficient material needed for PGEs analysis, fine PM (particles with aerodynamic diameter less than 2.5 mm; PM2.5 and coarse PM (with aerodynamic diameter between 2.5 and 10 mm; PM10-2.5 samples were combined into composite samples on a seasonal basis. The obtained results will be discussed and compared with literature data.

  7. Platinum hypersensitivity and desensitization. (United States)

    Miyamoto, Shingo; Okada, Rika; Ando, Kazumichi


    Platinum agents are drugs used for various types of cancer. With increased frequency of administration of platinum agents, hypersensitivity reactions appear more frequently, occurring in over 25% of cases from the seventh cycle or second line onward. It then becomes difficult to conduct treatment using these agents. Various approaches have been investigated to address hypersensitivity reactions to platinum agents. Desensitization, which gradually increases the concentration of the anticancer drug considered to be the antigen until the target dosage, has been reported as being particularly effective, with a success rate of 80-100%. The aims of this paper are to present the current findings regarding hypersensitivity reactions to platinum agents and to discuss attempts of using desensitization against hypersensitivity reactions worldwide. © The Author 2015. Published by Oxford University Press. All rights reserved. For Permissions, please email:

  8. 溶胶-凝胶法制备金属铂高分散的二氧化钛薄膜%Preparation of Titania Thin Film with Highly-Dispersed Platinum Metal by Sol-Gel Method

    Institute of Scientific and Technical Information of China (English)

    黄妙良; 伴隆幸; 大矢丰; 高桥康隆


    Uniform and crack-free TiO2 thin films with highly-dispersed platinum were p repared from i-PrOH-TTIP-DEA-H2O system containing H2PtCl6*6H 2O as metal source by sol-gel method. The microstructure and morphology of th e films were characterized by TEM and XRD respectively. It was found that the Pt particles dispersed in the films and had a homogeneous distribution in the shap e of sphere with an average size of about 5 nm. This study also showed that the doping with few percent of Pt resulted in the formation of pure rutile phase at a temperature as low as 550 ℃, whereas the same pure phase was formed at the te mperature higher than 650 ℃ in TiO2 or Au/TiO2 thin films.

  9. Interfacial electronic effects control the reaction selectivity of platinum catalysts (United States)

    Chen, Guangxu; Xu, Chaofa; Huang, Xiaoqing; Ye, Jinyu; Gu, Lin; Li, Gang; Tang, Zichao; Wu, Binghui; Yang, Huayan; Zhao, Zipeng; Zhou, Zhiyou; Fu, Gang; Zheng, Nanfeng


    Tuning the electronic structure of heterogeneous metal catalysts has emerged as an effective strategy to optimize their catalytic activities. By preparing ethylenediamine-coated ultrathin platinum nanowires as a model catalyst, here we demonstrate an interfacial electronic effect induced by simple organic modifications to control the selectivity of metal nanocatalysts during catalytic hydrogenation. This we apply to produce thermodynamically unfavourable but industrially important compounds, with ultrathin platinum nanowires exhibiting an unexpectedly high selectivity for the production of N-hydroxylanilines, through the partial hydrogenation of nitroaromatics. Mechanistic studies reveal that the electron donation from ethylenediamine makes the surface of platinum nanowires highly electron rich. During catalysis, such an interfacial electronic effect makes the catalytic surface favour the adsorption of electron-deficient reactants over electron-rich substrates (that is, N-hydroxylanilines), thus preventing full hydrogenation. More importantly, this interfacial electronic effect, achieved through simple organic modifications, may now be used for the optimization of commercial platinum catalysts.

  10. The RSC Faraday prize lecture of 1989 on platinum. (United States)

    Thomas, John Meurig


    In 1861, Michael Faraday gave one of his last Friday Evening Discourses at the Royal Institution of Great Britain, London, on platinum, which he described as "this beautiful, magnificent and valuable metal". More than a hundred and twenty years later (in 1989), the author re-enacted, at the Royal Institution, many of the demonstrations that Faraday carried out in his memorable Discourse. This article outlines many of Faraday's views on, and experiments with, platinum. It also describes the continuing importance and utilization of platinum, both as perceived in 1989 and from present perspectives.

  11. Research on New Technology for Extracting Precious Metals from Low Grade Gold Platinum Palladium Material%从低品位金铂钯物料中提取贵金属新工艺研究

    Institute of Scientific and Technical Information of China (English)

    马玉天; 陈大林; 郭晓辉; 潘从明; 张燕; 王立


    金川集团股份有限公司产生的低品位金钯铂物料为蒸残渣,通常是由贵金属精矿蒸馏分离锇、钌,水溶液氯化产生。现有蒸残渣处理工艺为反复氯化,由于受氯化效率的影响,依然有部分贵金属残留在外付渣中,造成贵金属流失。为提高贵金属回收率,金川集团贵金属冶炼厂组织进行了从蒸残渣中提纯贵金属的实验研究。通过长期实验探索,确定了蒸残渣氯化焙烧-盐酸浸出-有机溶剂萃取分离金铂钯的工艺路线。之后,又进行了工业化扩大试验,确定了最佳工艺技术条件,金、铂、钯直收率≥95%。与水溶液氯化工艺相比,该工艺具有贵金属直收率高、劳动强度低、生产周期短及生产成本低等特点。%The company produced platinum and palladium low grade gold material that was a kind of steamed residue,additionally,the steamed residue was produced during the process of precious metals concentrate distillation separation of osmium,ruthenium and aqueous chlorination.The existing steamed residue treatment technique of chloride repeatedly,because the effect of the efficiency of chloride,there were still some precious metal residues in the outside pay residue,has the problem of precious metals lossing.In order to improve the precious metal recovery,the smelting plant in the company completed a series of experimental studies on purification of precious metals from the steamed residue.Thus,after the experimental exploration for a long time, the steamed residue chloridizing roasting-hydrochloric acid leaching gold platinum palladium-organic solvent extraction separation process was determined.Then,the industrialized expanding test and the optimum technology conditions were also determined,meanwhile,the direct recovery rate was more than or equal to 95%during the technological process of gold,platinum and palladium.Compared with aqueous chlorination process,the method applied in the paper

  12. Oxidation of Group 8 transition-Metal Hydrides and Ionic Hydrogenation of Ketones and Aldehydes

    Energy Technology Data Exchange (ETDEWEB)

    Smith, Kjell-Tore


    Transition-metal hydrides have received considerable attention during the last decades because of their unusual reactivity and their potential as homogeneous catalysts for hydrogenation and other reactions of organic substrates. An important class of catalytic processes where transition-metal hydrides are involved is the homogeneous hydrogenation of alkenes, alkynes, ketones, aldehydes, arenes and nitro compounds. This thesis studies the oxidation of Group 8 transition-metal hydrides and the ionic hydrogenation of ketones and aldehydes.

  13. Arbuscular mycorrhizal fungal phylogenetic groups differ in affecting host plants along heavy metal levels. (United States)

    He, Lei; Yang, Haishui; Yu, Zhenxing; Tang, Jianjun; Xu, Ligen; Chen, Xin


    Arbuscular mycorrhizal fungi (AMF) are important components of soil microbial communities, and play important role in plant growth. However, the effects of AMF phylogenetic groups (Glomeraceae and non-Glomeraceae) on host plant under various heavy metal levels are not clear. Here we conducted a meta-analysis to compare symbiotic relationship between AMF phylogenetic groups (Glomeraceae and non-Glomeraceae) and host plant functional groups (herbs vs. trees, and non-legumes vs. legumes) at three heavy metal levels. In the meta-analysis, we calculate the effect size (ln(RR)) by taking the natural logarithm of the response ratio of inoculated to non-inoculated shoot biomass from each study. We found that the effect size of Glomeraceae increased, but the effect size of non-Glomeraceae decreased under high level of heavy metal compared to low level. According to the effect size, both Glomeraceae and non-Glomeraceae promoted host plant growth, but had different effects under various heavy metal levels. Glomeraceae provided more benefit to host plants than non-Glomeraceae did under heavy metal condition, while non-Glomeraceae provided more benefit to host plants than Glomeraceae did under no heavy metal. AMF phylogenetic groups also differed in promoting plant functional groups under various heavy metal levels. Interacting with Glomeraceae, herbs and legumes grew better than trees and non-legumes did under high heavy metal level, while trees and legumes grew better than herbs and non-legumes did under medium heavy metal level. Interacting with non-Glomeraceae, herbs and legumes grew better than trees and non-legumes did under no heavy metal. We suggested that the combination of legume with Glomeraceae could be a useful way in the remediation of heavy metal polluted environment.

  14. Platinum recycling going green via induced surface potential alteration enabling fast and efficient dissolution (United States)

    Hodnik, Nejc; Baldizzone, Claudio; Polymeros, George; Geiger, Simon; Grote, Jan-Philipp; Cherevko, Serhiy; Mingers, Andrea; Zeradjanin, Aleksandar; Mayrhofer, Karl J. J.


    The recycling of precious metals, for example, platinum, is an essential aspect of sustainability for the modern industry and energy sectors. However, due to its resistance to corrosion, platinum-leaching techniques rely on high reagent consumption and hazardous processes, for example, boiling aqua regia; a mixture of concentrated nitric and hydrochloric acid. Here we demonstrate that complete dissolution of metallic platinum can be achieved by induced surface potential alteration, an ‘electrode-less' process utilizing alternatively oxidative and reductive gases. This concept for platinum recycling exploits the so-called transient dissolution mechanism, triggered by a repetitive change in platinum surface oxidation state, without using any external electric current or electrodes. The effective performance in non-toxic low-concentrated acid and at room temperature is a strong benefit of this approach, potentially rendering recycling of industrial catalysts, including but not limited to platinum-based systems, more sustainable. PMID:27767178

  15. Platinum recycling going green via induced surface potential alteration enabling fast and efficient dissolution (United States)

    Hodnik, Nejc; Baldizzone, Claudio; Polymeros, George; Geiger, Simon; Grote, Jan-Philipp; Cherevko, Serhiy; Mingers, Andrea; Zeradjanin, Aleksandar; Mayrhofer, Karl J. J.


    The recycling of precious metals, for example, platinum, is an essential aspect of sustainability for the modern industry and energy sectors. However, due to its resistance to corrosion, platinum-leaching techniques rely on high reagent consumption and hazardous processes, for example, boiling aqua regia; a mixture of concentrated nitric and hydrochloric acid. Here we demonstrate that complete dissolution of metallic platinum can be achieved by induced surface potential alteration, an `electrode-less' process utilizing alternatively oxidative and reductive gases. This concept for platinum recycling exploits the so-called transient dissolution mechanism, triggered by a repetitive change in platinum surface oxidation state, without using any external electric current or electrodes. The effective performance in non-toxic low-concentrated acid and at room temperature is a strong benefit of this approach, potentially rendering recycling of industrial catalysts, including but not limited to platinum-based systems, more sustainable.

  16. Gemcitabine-oxaliplatin combination for ovarian cancer resistant to taxane-platinum treatment: a phase II study from the GINECO group. (United States)

    Ray-Coquard, I; Weber, B; Cretin, J; Haddad-Guichard, Z; Lévy, E; Hardy-Bessard, A C; Gouttebel, M C; Geay, J-F; Aleba, A; Orfeuvre, H; Agostini, C; Provencal, J; Ferrero, J M; Fric, D; Dohollou, N; Paraiso, D; Salvat, J; Pujade-Lauraine, E


    Advanced ovarian carcinoma in early progression (<6 months) (AOCEP) is considered resistant to most cytotoxic drugs. Gemcitabine (GE) and oxaliplatin (OXA) have shown single-agent activity in relapsed ovarian cancer. Their combination was tested in patients with AOCEP in phase II study. Fifty patients pre-treated with platinum-taxane received q3w administration of OXA (100 mg m(-2), d1) and GE (1000 mg m(-2), d1, d8, 100-min infusion). Patient characteristics were a : median age 64 years (range 46-79),and 1 (84%) or 2 (16%) earlier lines of treatment. Haematological toxicity included grade 3-4 neutropaenia (33%), anaemia (8%), and thrombocytopaenia (19%). Febrile neutropaenia occurred in 3%. Non-haematological toxicity included grade 2-3 nausea or vomiting (34%), grade 3 fatigue (25%),and grade 2 alopecia (24%). Eighteen (37%) patients experienced response. Median progression-free (PF) and overall survivals (OS) were 4.6 and 11.4 months, respectively. The OXA-GE combination has high activity and acceptable toxicity in AOCEP patients. A comparison of the doublet OXA-GE with single-agent treatment is warranted.

  17. Structurally defined allyl compounds of main group metals: coordination and reactivity. (United States)

    Lichtenberg, Crispin; Okuda, Jun


    Organometallic allyl compounds are important as allylation reagents in organic synthesis, as polymerization catalysts, and as volatile metal precursors in material science. Whereas the allyl chemistry of synthetically relevant transition metals such as palladium and of the lanthanoids is well-established, that of main group metals has been lagging behind. Recent progress on allyl complexes of Groups 1, 2, and 12-16 now provides a more complete picture. This is based on a fundamental understanding of metal-allyl bonding interactions in solution and in the solid state. Furthermore, reactivity trends have been rationalized and new types of allyl-specific reactivity patterns have been uncovered. Key features include 1) the exploitation of the different types of metal-allyl bonding (highly ionic to predominantly covalent), 2) the use of synergistic effects in heterobimetallic compounds, and 3) the adjustment of Lewis acidity by variation of the charge of allyl compounds.

  18. Copper Production of Jinchuan Group Sees Rapid Growth

    Institute of Scientific and Technical Information of China (English)


    <正> Last year,Jinchuan Group Co.,Ltd.,the No.1rare metals production base of the nickel,cobaltand platinum family in China produced a totalof 60,500 tons of nickel,102,800 tons of cop-per,15.09 tons of cobalt,14.58 kilograms of

  19. Monofunctional and Higher-Valent Platinum Anticancer Agents (United States)

    Johnstone, Timothy C.; Wilson, Justin J.


    Platinum compounds represent one of the great success stories of metals in medicine. Following the serendipitous discovery of the anticancer activity of cisplatin by Rosenberg, a large number of cisplatin variants have been prepared and tested for their ability to kill cancer cells and inhibit tumor growth. These efforts continue today with increased realization that new strategies are needed to overcome issues of toxicity and resistance inherent to treatment by the approved platinum anticancer agents. One approach has been the use of so-called “non-traditional” platinum(II) and platinum(IV) compounds that violate the structure-activity relationships that governed platinum drug-development research for many years. Another is the use of specialized drug delivery strategies. Here we describe recent developments from our laboratory involving monofunctional platinum(II) complexes together with an historical account of the manner by which we came to investigate these compounds and their relationship to previously studied molecules. We also discuss work carried out using platinum(IV) prodrugs and the development of nanoconstructs designed to deliver them in vivo. PMID:23738524

  20. Oxygen Reduction on Platinum

    DEFF Research Database (Denmark)

    Nesselberger, Markus

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

  1. First German scyscraper is awarded with LEED platinum. ''The Cube'' - the new headquarter of the Deutsche Boerse group; Erstes deutsches Hochhaus mit LEED-Platin ausgezeichnet. ''The Cube'' - die neue Konzernzentrale der Deutschen Boerse

    Energy Technology Data Exchange (ETDEWEB)

    Wissenbach, Wolfgang [TGAgentur GmbH, Borgstedt (Germany)


    'Platinum for a German skyscraper.' - This headline is worth to inspect this building thus distinguished more exactly. The new building of the Deutsche Boerse group (Frankfurt (Main), Federal Republic of Germany) has an intelligent energy concept and attracts attention particularly by its 80 m high entrance hall.

  2. Predictive and Prognostic Value of Ribonucleotide Reductase Regulatory Subunit M1 and Excision Repair Cross-Complementation Group 1 in Advanced Urothelial Carcinoma (UC Treated with First-Line Gemcitabine Plus Platinum Combination Chemotherapy.

    Directory of Open Access Journals (Sweden)

    Miso Kim

    Full Text Available Preclinical and clinical studies have suggested that expression of ribonucleotide reductase regulatory subunit M1 (RRM1 and excision repair cross-complementation group 1 (ERCC1 is associated with resistance to gemcitabine and cisplatin, respectively. We evaluated the significance of RRM1 and ERCC1 expression to predict tumor response to gemcitabine plus platinum chemotherapy (GP and survival in advanced UC. We retrospectively collected tumor samples and reviewed clinical data of 53 patients with unresectable or metastatic UC, who were treated with first-line GP. RRM1 and ERCC1 expression were measured by immunohistochemistry. Among 53 patients, 12 (22.6% and 26 (49.1% patients had tumors that demonstrated a high expression for RRM1 and ERCC1, respectively. Twenty-nine (70.7% of 41 patients with low RRM1 expression achieved a clinical response (complete + partial responses, but only 3 (25.0% of 12 patients with high RRM1 expression achieved a clinical response after GP (P=0.007. Nineteen (70.4% of 27 patients with low ERCC1 expression achieved a clinical response, while 13 (50.0% of 26 patients with high ERCC1 expression achieved a clinical response (P=0.130. High RRM1 expression was associated with shorter progression free survival and overall survival (PFS P=0.006, OS P=0.006. Multivariate analysis confirmed that patients with high RRM1 expression had a significantly greater risk of progression and death than those with low RRM1 expression. ERCC1 status was not a significant predictor for PFS and OS. RRM1 expression was predictive and prognostic of clinical outcome in advanced UC treated with gemcitabine plus platinum combination chemotherapy.

  3. Biomineralization of platinum by microorganisms (United States)

    Pavlova, L. M.; Radomskaya, V. I.; Shumilova, L. P.; Ionov, A. M.; Sorokin, P.


    The mechanism of platinum biomineralization by microscopic fungi is displayed based on data of electron microscopy, infrared and X-ray photoelectronic spectroscopy. It was suggested the platinum sorption process by microscopic fungi has some stages. The initial interaction is carried out by the mechanisms of physical and chemical sorption. Hereafter the reduction process of adsorbed platinum ions up to zero state is performed, probably, for account of organic compounds, which are produced by fungi biomass as metabolism result, and the process terminates by nulvalent particles aggregating up to nanosize forms. Obtained data on the platinum biomineralization extends the concept concerning the character of forming platinum nanoparticles in carbonous paleobasin.

  4. Interaction of DNA with Bis(diiminosuccinonitrilo)platinum(Ⅱ)

    Institute of Scientific and Technical Information of China (English)

    ZHANG Zhi-Gang; SUN Yuan-Yuan; JIANG Xiao-Ming


    Interaction of DNA with bis(diiminosuccinonitrilo)platinum(Ⅱ) has been studied by UV-visible absorbance spectra, fluorescence spectra and viscosity measurements. The UV-visible absorption spectra of the metal complex exhibit hypochromism with a small blue shift on interaction with DNA. Scatchard plot analyses indicate that the binding sites of the metal complex on DNA are different from those of ethidium bromide. Viscosity experiments reveal that the binding of the metal complex decreases the relative viscosity of DNA. These results suggest that the platinum diimine complex interact with DNA by surface binding. These studies are helpful for us to understand the action mechanism of bis(diiminosuccinonitrilo)platinum(Ⅱ) as a potential photodynamic therapeutic agent, and further to develop it.

  5. Platinum blue staining of cells grown in electrospun scaffolds. (United States)

    Yusuf, Mohammed; Millas, Ana Luiza G; Estandarte, Ana Katrina C; Bhella, Gurdeep K; McKean, Robert; Bittencourt, Edison; Robinson, Ian K


    Fibroblast cells grown in electrospun polymer scaffolds were stained with platinum blue, a heavy metal stain, and imaged using scanning electron microscopy. Good contrast on the cells was achieved compared with samples that were gold sputter coated. The cell morphology could be clearly observed, and the cells could be distinguished from the scaffold fibers. Here we optimized the required concentration of platinum blue for imaging cells grown in scaffolds and show that a higher concentration causes platinum aggregation. Overall, platinum blue is a useful stain for imaging cells because of its enhanced contrast using scanning electron microscopy (SEM). In the future it would be useful to investigate cell growth and morphology using three-dimensional imaging methods.

  6. [Comparison of the effectiveness of platinum-based chemotherapy versus non-platinum-based chemotherapy for triple-negative breast cancer with metastases confined to the lungs]. (United States)

    Hong, Ruoxi; Ma, Fei; Shi, Xiuqing; Li, Qing; Zhang, Pin; Yuan, Peng; Wang, Jiayu; Fan, Ying; Cai, Ruigang; Li, Qiao; Xu, Binghe


    To compare the effect of first-line treatment with platinum-based chemotherapy and non-platinum-based chemotherapy in patients with lung metastases from triple negative breast cancer (TNBC). Sixty-five eligible patients were divided into platinum-treated group and non-platinum-treated group according to the first-line therapy. Factors predicting the chemotherapeutic efficacy included overall survival (OS), progression-free survival (PFS) and objective response (OR). In the platinum-treated group of 32 patients, 2 cases (6.3%) achieved CR, 16 cases (50.0%) achieved PR, 11 (34.4%) cases achieved SD, and 3 patients (9.4%) achieved PD. In the non-platinum-treated group of 33 patients, 2 cases (6.1%) achieved CR, 6 cases (18.2%) achieved PR, 16 cases (48.5%) achieved SD, and 9 cases (27.3%) achieved PD. Median PFS was significantly longer in the platinum-treated group than in the non-platinum-treated group (10 months vs. 6.0 months, P = 0.012), and OS was also improved (32 months vs. 22 months, P = 0.006). Multivariate analysis of several factors including local-regional lymph node involvement, lung metastasis-related symptoms, first-line platinum-based chemotherapy, disease-free interval, size and number of lung lesions, showed that first-line platinum-based chemotherapy was an independent prognostic factor for TNBC patients with lung metastases. Compared with non-platinum-based chemotherapy, the first-line platinum-based chemotherapy can improve PFS and OS in TNBC patients with metastases confined to the lungs.

  7. Addition of platinum and silver nanoparticles to toughen dental porcelain. (United States)

    Fujieda, Tokushi; Uno, Mitsunori; Ishigami, Hajime; Kurachi, Masakazu; Wakamatsu, Nobukazu; Doi, Yutaka


    Several studies have investigated toughening porcelain that is layered over a frame or a core. The introduction of residual compressive stress to the surface of porcelain has been shown to be effective to strengthen it. In the present study, nanoparticles of precious metals of silver and platinum (rather than non-precious metals) were used to evaluate if they could increase the fracture resistance of porcelain. The addition of silver and platinum nanoparticles was found to improve the mechanical properties of porcelain since it increased both the Young's modulus and the fracture toughness of commercial porcelain.

  8. Concurrent chemoradiotherapy comparison of taxanes and platinum versus 5-fluorouracil and platinum in nasopharyngeal carcinoma treatment

    Institute of Scientific and Technical Information of China (English)

    Chen Xichuang; Hong Yuan; Feng Jinhua; Ye Jianlin; Zheng Panpan; Guan Xiyin; You Xiaohong


    Background Nasopharyngeal carcinoma (NPC) is a squamous-cell carcinoma especially prevailing among the natives of southern China.The regimen of concurrent chemoradiotherapy (CCRT) that include platinum and 5-fluorouracil (5-FU)is considered to be the standard treatment for NPC.However,its clinical use is limited by its toxicity.Our purpose was to evaluate the efficacy and safety of the regimen of CCRT with taxanes and platinum versus the regimen of CCRT with 5-FU and platinum in NPC treatment.Methods Medline,the Cochrane library,and the Chinese medical literature database were searched for eligible studies.Meta-analysis was performed using Review Manager (Version 5.2).Results Six random controlled trials (RCTs) including 514 patients met our criteria.Meta-analysis showed that the regimen of CCRT with taxanes and platinum had an improved significant difference in complete remission (CR) and less incidence rate in adverse reactions such as gastrointestinal impairment grades Ⅲll-Ⅳ,liver and kidney impairment grades Ⅰ-Ⅱ,and radiodermatitis grades Ⅲ-Ⅳ versus the conventional regimen of CCRT with 5-FU and platinum,while the long-term effectiveness rate of overall survival,Iocoregional failure-free survival,or distant metastasis failure-free survival between the two groups was therapeutic equivalence.Conclusions The regimen of CCRT with taxanes and platinum in NPC therapy may be more efficient and safe compared to the conventional modality of 5-FU and platinum in CCRT.However,we need more high-quality studies of multi-center and randomized double-blind clinical trials to further compare,analyze,and confirm the findings.

  9. Unsaturated platinum-rhenium cluster complexes. Synthesis, structures and reactivity. (United States)

    Adams, Richard D; Captain, Burjor; Smith, Mark D; Beddie, Chad; Hall, Michael B


    Two new compounds PtRe3(CO)12(PBut3)(micro-H)3, 9, and PtRe2(CO)9(PBut3)(micro-H)2, 10, were obtained from the reaction of Pt(PBut3)2 with Re3(CO)12(micro-H3), 8, at room temperature. Compound 9 contains a butterfly cluster of four metals formed by the insertion of the platinum atom from a Pt(PBut3) group into one of the hydride-bridged metal-metal bonds of 8. The three hydrido ligands are bridging ligands across each of three new Pt-Re bonds. Compound 10 contains a triangular PtRe2 cluster with two hydrido ligands; one bridges a Pt-Re bond, and the other bridges the Re-Re bond. The new compound Pt2Re2(CO)7(PBut3)2(micro-H)2, 11, was obtained from the reaction of 8 with Pt(PBut3)2 in hexane at reflux. Compound 11 was also obtained from 10 by reaction with an additional quantity of Pt(PBut3)2. Compound 11 contains a tetrahedral cluster of four metal atoms with two dynamically active hydrido ligands. A CO ligand on one of the two platinum atoms also exchanges between the two platinum atoms rapidly on the NMR time scale. Compound 11 is electronically unsaturated and was found to add hydrogen at room temperature to form the tetrahydrido cluster complex, Pt2Re2(CO)7(PBut3)2(micro-H)4, 12. Compound 12 has a structure similar to 11 but contains one triply bridging hydrido ligand, two edge bridging hydrido ligands, and one terminal hydrido ligand on one of the two platinum atoms. A kinetic isotope effect D/H of 1.5(1) was determined for the addition of H2 to 11. Hydrogen can be eliminated from 12 by heating to 97 degrees C or by the application of UV-vis irradiation at room temperature. Compound 12 adds CO at room temperature to yield the complex Pt2Re2(CO)8(PBut3)2(micro-H)4, 13, which contains a planar cluster of four metal atoms with a Pt-Pt bond and four edge bridging hydrido ligands. Compounds 11 and 12 react with Pt(PBut3)2 to yield the known five metal cluster complexes Pt3Re2(CO)6(PBut3)3(micro-H)2, 14, and Pt3Re2(CO)6(PBut3)3(micro-H)4, 15, respectively. Density

  10. Interaction of novel bis(platinum) complexes with DNA.


    Roberts, J D; Van Houten, B; Qu, Y; Farrell, N P


    Bis(platinum) complexes [[cis-PtCl2(NH3)]2H2N(CH2)nNH2] are a novel series of potential anticancer agents in which two cis-diamine(platinum) groups are linked by an alkyldiamine of variable length. These complexes are potentially tetrafunctional, a unique feature in comparison with known anticancer agents. Studies of DNA interactions of bis(platinum) complexes in comparison with cisplatin demonstrate significant differences. Investigations of interstrand crosslink formation in which crosslink...

  11. Bio-inspired routes for synthesizing efficient nanoscale platinum electrocatalysts

    Energy Technology Data Exchange (ETDEWEB)

    Cha, Jennifer N. [Univ. of California, San Diego, CA (United States); Wang, Joseph [Univ. of California, San Diego, CA (United States)


    controlled, the nanocrystals boast a defined shape, morphology, orientation and size and are synthesized at benign reaction conditions. Adapting the methods of biomineralization towards the synthesis of platinum nanocrystals will allow effective control at a molecular level of the synthesis of highly active metal electrocatalysts, with readily tailored properties, through tuning of the biochemical inputs. The proposed research will incorporate many facets of biomineralization by: (1) isolating peptides that selectively bind particular crystal faces of platinum (2) isolating peptides that promote the nucleation and growth of particular nanocrystal morphologies (3) using two-dimensional DNA scaffolds to control the spatial orientation and density of the platinum nucleating peptides, and (4) combining bio-templating and soluble peptides to control crystal nucleation, orientation, and morphology. The resulting platinum nanocrystals will be evaluated for their electrocatalytic behavior (on common carbon supports) to determine their optimal size, morphology and crystal structure. We expect that such rational biochemical design will lead to highly uniform and efficient platinum nanocrystal catalysts for fuel cell applications.

  12. Synthesis of Bimetallic Platinum Nanoparticles for Biosensors

    Directory of Open Access Journals (Sweden)

    Gerard M. Leteba


    Full Text Available The use of magnetic nanomaterials in biosensing applications is growing as a consequence of their remarkable properties; but controlling the composition and shape of metallic nanoalloys is problematic when more than one precursor is required for wet chemistry synthesis. We have developed a successful simultaneous reduction method for preparation of near-spherical platinum-based nanoalloys containing magnetic solutes. We avoided particular difficulties in preparing platinum nanoalloys containing Ni, Co and Fe by the identification of appropriate synthesis temperatures and chemistry. We used transmission electron microscopy (TEM to show that our particles have a narrow size distribution, uniform size and morphology, and good crystallinity in the as-synthesized condition. Energy dispersive spectroscopy (EDS and X-ray diffraction (XRD confirms the coexistence of Pt with the magnetic solute in a face-centered cubic (FCC solid solution.

  13. Dissolution of Metal Supported Spent Auto Catalysts in Acids

    Directory of Open Access Journals (Sweden)

    Fornalczyk A.


    Full Text Available Metal supported auto catalysts, have been used in sports and racing cars initially, but nowadays their application systematically increases. In Metal Substrate (supported Converters (MSC, catalytic functions are performed by the Platinum Group Metals (PGM: Pt, Pd, Rh, similarly to the catalysts on ceramic carriers. The contents of these metals make that spent catalytic converters are valuable source of precious metals. All over the world there are many methods for the metals recovery from the ceramic carriers, however, the issue of platinum recovery from metal supported catalysts has not been studied sufficiently yet. The paper presents preliminary results of dissolution of spent automotive catalyst on a metal carrier by means of acids: H2SO4, HCl, HNO3, H3PO4. The main assumption of the research was the dissolution of base metals (Fe, Cr, Al from metallic carrier of catalyst, avoiding dissolution of PGMs. Dissolution was the most effective when concentrated hydrochloric acid, and 2M sulfuric acid (VI was used. It was observed that the dust, remaining after leaching, contained platinum in the level of 0.8% and 0.7%, respectively.

  14. Determinations of Platinum-Group Element (PGE) Distributions Using Whole-rock, SEM, EMPA, Image Analysis, and LA-ICP-MS Techniques in the Kelly Lake Ni-Cu-PGE Deposit, Sudbury (United States)

    Huminicki, M. A.; Cabri, L.; Sylvester, P. J.; Tubrett, M. N.


    The Kelly Lake deposit is a Ni-Cu-PGE offset-style deposit that occurs at the south end of the Copper Cliff Offset (CCO), Sudbury. The deposit consists of four ore bodies (710, 720, 725, and 740) that were first identified in 1997 and contain a published 10.5 million tonnes of ore at 1.77% Ni, 1.34% Cu, and 3.6 g/tonne combined Pt + Pd + Au. The ore bodies have a sub-vertical orientation and plunge to the south. The CCO consists of an inclusion-and sulfide-poor marginal zone of quartz diorite (QD) and an inclusion- and sulfide-rich core of QD. The sulfide assemblage is similar to other deposits along the CCO, comprising pentlandite (Pn), pyrrhotite (Po), and chalcopyrite (Ccp) with minor pyrite (Py) and trace amounts of galena [PbS]. The platinum-group mineral assemblage consists of michenerite [(Pd,Pt)BiTe], sperrylite [PtAs2], and microinclusions of hollingworthite [(Rh,Pt,Pd)AsS] and ruarsite [RuAsS], which are associated with the bismuth-telluride, tsumoite [BiTe] and the sulfarsenide, cobaltite-gersdorfitte [(Co,Fe)AsS-NiAsS]. The purpose of this study was to determine the distribution of the platinum-group elements (PGE) within the Kelly Lake ores. Analyses were carried out using a combination of: 1) lead and nickel-sulfide fire-assay for whole rock PGE abundances; 2) scanning-electron-microscopy (SEM) image analysis, quantitative energy dispersive X-ray spectrometry (EDXS), and quantitative electron probe microanalysis (EPMA) to determine size, shape, location, association, and mineral chemistry of discrete platinum-group minerals; and 3) laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) to determine low-level PGE contents in solid solution and as microinclusions within the sulfides and sulfarsenides. SEM, EPMA, and LA-ICP-MS results indicate that the PGE occur: 1) primarily as discrete PGM (sperrylite and michenerite), 2) in solid-solution in cobaltite-gersdorfitte, and 3) as micro-inclusions of hollingworthite and ruarsite in

  15. Platinum Acetylide Two-Photon Chromophores (Preprint) (United States)


    the higher energy range that lead to its photodegradation . Secondly, because there is a quadratic dependence of two-photon absorption (2PA) on either an electron donating amino- fluorenyl or electron withdrawing benzothiazolyl-fluorene that are themselves known as two-photon absorbing dyes ...groups in place of phenyl groups have shown a doubling of the intrinsic cr2value at 740 nm.40,41In this paper we describe novel platinum dyes that

  16. New water-soluble azido- and derived tetrazolato-platinum(II) complexes with PTA. Easy metal-mediated synthesis and isolation of 5-substituted tetrazoles. (United States)

    Smoleński, Piotr; Mukhopadhyay, Suman; Guedes da Silva, M Fátima C; Charmier, M Adília Januário; Pombeiro, Armando J L


    The water-soluble four- and five-coordinate diazido-platinum(II) complexes cis-[Pt(N3)2(PTA)2] (1) (PTA = 1,3,5-triaza-7-phosphaadamantane), cis-[Pt(N3)2(Me-PTA)2]I2 (2) (Me-PTA = N-methyl-1,3,5-triaza-7-phosphaadamantane cation) and [Pt(N3)2(PTA)3] (3) were obtained by reactions of cis-[Pt(N3)2(PPh3)2] with PTA or [Me-PTA]I in dichloromethane. [2 + 3] cycloadditions of with organonitriles NCR gave the bis(tetrazolato) complexes trans-[Pt(N4CR)2(PTA)2] (R = Ph (4), 4-ClC6H4 (5) or 3-NC5H4 (6)), the reactions being greatly accelerated by microwave irradiation. 5-R-1H-Tetrazoles N4CR (R = Ph, 4-ClC6H4 and 3-NC5H4) were easily liberated from the tetrazolato complexes and isolated in high yields, in a single-pot process, upon reaction with aqueous diluted HCl, with concomitant formation of the water soluble cis-[Pt(Cl)2(PTA-H)2] complex 7. Alternatively, in a less convenient method, the tetrazoles could be liberated on reaction of 4-6 with propionitrile which also leads to the dicyano trans-[Pt(CN)2(PTA)2] complex 8. The compounds were characterized by IR, 1H, 13C and 31P[1H] NMR spectroscopies, FAB+-MS or ESI-MS, elemental analyses and (for and 4) also by X-ray diffraction.

  17. Cyclometalated platinum(Ⅱ) complexes with sterically bulky camphor-derived groups as β-diketonate ancillary ligand:a new route to efficiently reducing π-π interactions and Pt-Pt interactions

    Institute of Scientific and Technical Information of China (English)


    A new series of mono-cyclometalated square planar platinum(Ⅱ) complexes have been synthesized and the single-crystal X-ray structures of complex 1 and 2 have been determined.The complexes have the general formula ppyPt(OO),where ppy is 2-phenylpyridyl,and OO is β-diketonate ancillary ligands with the acyl substituent group in position 3 of(D)-(+)-camphor.Although,like the many Pt(Ⅱ) complexes with square-planar geometry,these complexes have plane stacking modes in crystal structure,the sterically bulky camphor-derived groups compel extensive slipping of the molecular stacking planes,resulting in the negligible overlapping of the aromatic ring fragments between molecules and the considerable Pt-Pt distance.The resolved spectra and a little shifted emission in solid state of complexes show that there is significant reduction of π-π interactions and Pt-Pt interactions,and suggest these complexes may be good candidates for doped phosphorescent organic light emitting diodes(PhOLEDs) and even for nondoped PhOLEDs.

  18. The oldest and most metal-poor stars in the APOSTLE Local Group simulations (United States)

    Starkenburg, Else; Oman, Kyle A.; Navarro, Julio F.; Crain, Robert A.; Fattahi, Azadeh; Frenk, Carlos S.; Sawala, Till; Schaye, Joop


    We examine the spatial distribution of the oldest and most metal-poor stellar populations of Milky Way-sized galaxies using the A Project Of Simulating The Local Environment (APOSTLE) cosmological hydrodynamical simulations of the Local Group. In agreement with earlier work, we find strong radial gradients in the fraction of the oldest (tform stars, both of which increase outwards. The most metal-poor stars form over an extended period of time; half of them form after z = 5.3, and the last 10 per cent after z = 2.8. The age of the metal-poor stellar population also shows significant variation with environment; a high fraction of them are old in the galaxy's central regions and an even higher fraction in some individual dwarf galaxies, with substantial scatter from dwarf to dwarf. We investigate the dependence of these results on the assumptions made for metal mixing. Overall, over half of the stars that belong to both the oldest and most metal-poor population are found outside the solar circle. Somewhat counter-intuitively, we find that dwarf galaxies with a large fraction of metal-poor stars that are very old are systems where metal-poor stars are relatively rare, but where a substantial old population is present. Our results provide guidance for interpreting the results of surveys designed to hunt for the earliest and most pristine stellar component of our Milky Way.

  19. Inhibition of Aβ42 peptide aggregation by a binuclear ruthenium(II)-platinum(II) complex: Potential for multi-metal organometallics as anti-amyloid agents. (United States)

    Kumar, Amit; Moody, Lamaryet; Olaivar, Jason F; Lewis, Nerissa A; Khade, Rahul L; Holder, Alvin A; Zhang, Yong; Rangachari, Vijayaraghavan


    Design of inhibitors for amyloid-β (Aβ) peptide aggregation has been widely investigated over the years towards developing viable therapeutic agents for Alzheimer's disease (AD). The biggest challenge seems to be inhibiting Aβ aggregation at the early stages of aggregation possibly at the monomeric level, as oligomers are known to be neurotoxic. In this regard, exploiting the metal chelating property of Aβ to generate molecules that can overcome this impediment presents some promise. Recently, one such metal complex containing Pt(II) ([Pt(BPS)Cl(2)]) was reported to effectively inhibit Aβ42 aggregation and toxicity (1). This complex was able bind to Aβ42 at the N-terminal part of the peptide and triggered a conformational change resulting in effective inhibition. In the current report, we have generated a mixed-binuclear metal complex containing Pt(II) and Ru(II) that inhibited Aβ42 aggregation at an early stage of aggregation and seemed to have different modes of interaction than the previously reported Pt(II) complex, suggesting an important role of the second metal center. This 'proof-of-concept' compound will help in developing more effective molecules against Aβ aggregation by modifying the two metal centers as well as their ligands, which will open doors to new rationale for Aβ inhibition.

  20. Mechanical, thermal and laser damage threshold analyses of II group metal complexes of thiourea

    Energy Technology Data Exchange (ETDEWEB)

    Dhanuskodi, S., E-mail: [School of Physics, Bharathidasan University, Tiruchirappalli 620 024, Tamil Nadu (India); Sabari Girisun, T.C. [School of Physics, Bharathidasan University, Tiruchirappalli 620 024, Tamil Nadu (India); Department of Physics, Bishop Heber College, Tiruchirappalli 620 017, Tamil Nadu (India); Bhagavannarayana, G. [Material Characterization Division, National Physical laboratory, New Delhi 110 012 (India); Uma, S.; Phillip, J. [Sophisticated Test and Instrumentation Center, Cochin University of Science and Technology, Cochin 682 022 (India)


    Research highlights: {yields} The role of the Group II metal ions in improving the stability is discussed. {yields} BTCC has a higher heat capacity than BTZC. {yields} Elastic stiffness is found to be higher for BTCC than BTZC. {yields} Microscopy studies confirm the damage is due to thermo-chemical ablation. {yields} BTCC has a higher laser damage threshold than BTZC. - Abstract: Single crystals of thiourea metal complexes with selected Group II metal ions, Zinc and Cadmium, have been grown by solvent evaporation technique. The crystals grown are bisthiourea zinc chloride (BTZC) and bisthiourea cadmium chloride (BTCC). Following an improved photopyroelectric technique, the thermal transport properties have been determined. It is found that BTCC has a higher heat capacity (304.09 J kg{sup -1} K{sup -1}) than BTZC (255.24 J kg{sup -1} K{sup -1}), and hence BTCC has better thermal stability. Vicker's microhardness measurements reveal that these materials have reverse indentation size effect and belong to the category of soft materials. Elastic stiffness is found to be higher for BTCC (1.57 GPa) than BTZC (0.76 GPa). The roles of the Group II metal ions in improving the mechanical and thermal stability of the metal complexes are discussed. Multi-shot laser damage studies on these materials reveal that BTCC has a higher laser damage threshold (15 GW cm{sup -2}) than BTZC (6 GW cm{sup -2}).

  1. Olaparib for Maintenance Treatment of BRCA 1 or 2 Mutated, Relapsed, Platinum-Sensitive Ovarian, Fallopian Tube and Peritoneal Cancer in People Whose Relapsed Disease has Responded to Platinum-Based Chemotherapy: An Evidence Review Group Perspective of a NICE Single Technology Appraisal. (United States)

    Tappenden, Paul; Harnan, Sue; Ren, Shijie; Thokala, Praveen; Wong, Ruth; Mukuria, Clara; Green, Clare; Pledge, Simon; Tidy, John


    As part of its Single Technology Appraisal process, the National Institute for Health and Care Excellence (NICE) invited the manufacturer of olaparib (AstraZeneca) to submit evidence on the clinical and cost effectiveness of olaparib for the maintenance treatment of BRCA1/2 mutated (BRCAm), platinum-sensitive relapsed (PSR) ovarian, fallopian tube and peritoneal cancer in people whose relapsed disease has responded to platinum-based chemotherapy. The Evidence Review Group (ERG) produced a critical review of the evidence contained within the company's submission (CS) to NICE. The clinical evidence related to one phase II, double-blind randomised controlled trial that recruited 265 patients with PSR serous ovarian cancer (OC) regardless of BRCAm status. Patients received olaparib 400 mg twice daily (b.i.d.) or matched placebo. In the whole population, the primary endpoint of progression-free survival (PFS) was met (hazard ratio [HR] 0.35; 95 % confidence interval [CI] 0.25-0.49, p group (HR 0.88; 95 % CI 0.64-1.21; p = 0.44) or the BRCAm subgroup (0.73; 95 % CI 0.45-1.17; p = 0.19), though treatment switching may have confounded results. The exclusion of data from sites allowing crossover resulted in an HR for overall survival (OS) of 0.52 (95 % CI 0.28-0.97, p = 0.039) in the BRCAm group. Health-related quality-of-life measures were not significantly different between groups. All post hoc exploratory outcomes (time to treatment discontinuation/death, time to first subsequent therapy/death, and time to second subsequent therapy/death) were statistically significantly better in the olaparib arm in the whole population and the BRCAm subgroup analyses. Adverse events were more frequent for olaparib but were largely minor or manageable. The company's semi-Markov model assessed the cost effectiveness of olaparib versus routine surveillance in patients with BRCAm PSR OC from a National Health Service (NHS) and Personal Social Services (PSS) perspective over a


    Institute of Scientific and Technical Information of China (English)


    Narrow disperse poly(ethyleneglycol dimethacrylate-co-4-vinylpyridine) (poly(EGDMA-co-4-VPy)) microspheres were prepared by distillation-precipitation copolymerization of ethyleneglycol dimethacrylate (EGDMA) and 4-vinylpyridine (4-VPy) with 2,2'-azobisisobutyronitrile (AIBN) as initiator in neat acetonitrile. The polymer microspheres containing pyridyl group were then utilized as stabilizer for gold metallic colloids with the diameter around 7 nm, which were prepared by the in situ reduction of gold chloride trihydrate with sodium borohydride through the coordination of the pyridyl group on the gel layer and surface of the microsphere with the gold metallic nano-particles. The catalytic properties of the pyridyl-functionalized microsphere-stabilized gold metallic colloids and the behavior of the stabilized-catalyst for the recycling were investigated with reduction of 4-nitrophenol to 4-aminophenol as a model reaction.

  3. Aromatic H/D Exchange Reaction Catalyzed by Groups 5 and 6 Metal Chlorides

    Institute of Scientific and Technical Information of China (English)

    郭巧霞; 申宝剑; 郭海卿; 高桥保


    Groups 5 and 6 metal chlorides such as MoCl5, WCI6, NbCl5 and TaCl5 were found to be simple and very efficientcatalysts for the aromatic H/D exchange reactions. Compared with other metal chlorides such as ZnCl2, SnCl4 and TiCl4, groups 5 and 6 metal chlorides showed better catalytic activity in the H/D exchange reaction of naphthalene with C6D6. Deuteration of anthracene using MoC15 as a catalyst proceeded within 24 h at room temperature. Other aromatic compounds such as toluene, diphenylmethane and 1,1,2-triphenylethane were also deuterated smoothly in C6D6 within 24 h at room temperature.

  4. The prognostic and predictive value of excision repair cross-complementation group 1 (ERCC1) protein in 1288 patients with head and neck squamous cell carcinoma treated with platinum-based therapy: a meta-analysis. (United States)

    Bišof, Vesna; Zajc Petranović, Matea; Rakušić, Zoran; Samardžić, Kristina Ruža; Juretić, Antonio


    Excision repair cross-complementation group 1 (ERCC1) protein has been extensively investigated as a prognostic and predictive factor for platinum-based treatment in head and neck squamous cell carcinoma (HNSCC) but with inconsistent results. We performed the present meta-analysis to better elucidate this issue in advanced HNSCC. A literature search was conducted using the PubMed and Web of Science databases. The inclusion criteria were head and neck cancer patients with platinum-based treatment and evaluation of the correlation between ERCC1 expression and clinical outcomes [objective response rate (ORR), progression-free survival (PFS), and overall survival (OS), both unadjusted and adjusted estimates]. In high vs. low pooled analyses, high ERCC1 expression was associated with unfavorable OS [hazard ratio (HR) = 1.95, 95 % confidence interval (CI) 1.18-3.21, p = 0.009], PFS (HR = 2.39, 95 % CI 1.74-3.28, p = 0.000) and ORR (odds ratio = 0.48, 95 % CI 0.23-0.98, p = 0.044). In the subgroup analysis of adjusted OS estimates, ERCC1 was a predictor of shorter survival in Asians (HR = 3.13, 95 % CI 2.09-4.70, p = 0.000) and Caucasians (HR = 2.02, 95 % CI 1.32-3.07, p = 0.001) but of longer survival in South Americans (HR = 0.17, 95 % CI 0.07-0.40, p = 0.000). Immunohistochemistry proved to be of predictive value irrespective of used antibody (p = 0.009). In the stratified analysis according to the tumor site, ERCC1 expression was associated with OS in nasopharyngeal cancer (HR = 2.72, 95 % CI 1.79-4.13, p = 0.000). ERCC1 has a potential to become predictive and prognostic factor enabling treatment tailoring in HNSCC patients.

  5. Platinum supported catalysts for carbon monoxide preferential oxidation: Study of support influence

    Energy Technology Data Exchange (ETDEWEB)

    Padilla, R.; Rodriguez, L.; Serrano-Lotina, A.; Daza, L. [Instituto de Catalisis y Petroleoquimica (CSIC), C/Marie Curie 2, Campus Cantoblanco, 28049 Madrid (Spain); Benito, M. [Instituto de Catalisis y Petroleoquimica (CSIC), C/Marie Curie 2, Campus Cantoblanco, 28049 Madrid (Spain); Centro de Investigaciones Energeticas Medioambientales y Tecnologicas (CIEMAT), Av. Complutense 22, 28040 Madrid (Spain)


    The aim of this work is to study the influence of the addition of different oxides to an alumina support, on surface acidity and platinum reducibility in platinum-based catalysts, as well as their effect on the activity and selectivity in CO preferential oxidation, in presence of hydrogen. A correlation between surface acidity and acid strength of surface sites and metal reducibility was obtained, being Pt-support interaction a function of the acid sites concentration under a particular temperature range. In platinum supported on alumina catalysts, CO oxidation follows a Langmuir-Hinshelwood mechanism, where O{sub 2} and CO compete in the adsorption on the same type of active sites. It is noteworthy that the addition of La{sub 2}O{sub 3} modifies the reaction mechanism. In this case, CO is not only adsorbed on the Pt active sites but also on La{sub 2}O{sub 3}, forming bridge bonded carbonates which leads to high reactivity at low temperatures. An increase on temperature produces CO desorption from Pt surface sites and favours oxygen adsorption producing CO{sub 2}. CO oxidation with surface hydroxyl groups was activated producing simultaneously CO{sub 2} and H{sub 2}. (author)

  6. Group 3 metal stilbene complexes: Synthesis, reactivity, and electronic structure studies


    Huang, W.; Abukhalil, PM; Khan, SI; Diaconescu, PL


    Group 3 metal (E)-stilbene complexes supported by a ferrocene diamide ligand were synthesized and characterized. Reactivity studies showed that they behave similar to analogous naphthalene complexes. Experimental and computational results indicated that the double bond was reduced and not a phenyl ring, in contrast to a previously reported uranium (E)-stilbene complex. © the Partner Organisations 2014.

  7. Lattice-Inversion Embedded-Atom-Method Interatomic Potentials for Group-VA Transition Metals

    Institute of Scientific and Technical Information of China (English)

    袁晓俭; 陈难先; 申江


    The lattice-inversion embedded-atom-method (LI-EAM) interatomic potential we developed previously [J. Phys.: Condens. Matter 22 (2010) 375503] is extended to group- VA transition metals (V, Nb and Ta). It is found that considering interatomic interactions up to appropriate-distance-neighbor atoms is crucial to constructing accurate EAM potentials, especially for the prediction of surface energy. The LI-EAM interatomic potentials for group-VA transition metals are successfully built by considering interatomic interactions up to the fifth neighbor atoms. These angular-independent potentials drastically promote the accuracy of the predicted surface energies, which match the experimental resuits well.%The lattice-inversion embedded-atom-method(LI-EAM)interatomic potential we developed previously[J.Phys.:Condens.Matter 22(2010)375503]is extended to group-VA transition metals(V,Nb and Ta).It is found that considering interatomic interactions up to appropriate-distance-neighbor atoms is crucial to constructing accurate EAM potentials,especially for the prediction of surface energy.The LI-EAM interatomic potentials for group-VA transition metals are successfully built by considering interatomic interactions up to the fifth neighbor atoms.These angular-independent potentials drastically promote the accuracy of the predicted surface energies,which match the experimental results well.

  8. Using amino acids for the chromatofocusing of metal ions on silica with bonded tetraethylenepentamine groups (United States)

    Ivanov, A. V.


    Amino acid-based eluents are used for the chromatofocusing of metal ions on Tetren-SiO2 chelating sorbent (silica with bonded tetraethylenepentamine groups) for the first time. The smoothest quasilinear pH gradients form for eluents based on glutamic and aspartic acids. The separation of Mn2+, Cr3+, Co2+, Ni2+, and Cu2+ is achieved.

  9. Xinjiang Nonferrous Metals Group Achieved Annual Sales Revenue of RMB 50 Billion

    Institute of Scientific and Technical Information of China (English)


    <正>Xinjiang Nonferrous Metals Group has officially presented the following ideas for development in the 12th Five-Year Plan period: "take effective measures such as resource integration, scale expansion, capital operation and technological innovation, etc. to boost the

  10. The use of cation exchange matrix separation coupled with ICP-MS to directly determine platinum group element (PGE) and other trace element emissions from passenger cars equipped with diesel particulate filters (DPF)

    Energy Technology Data Exchange (ETDEWEB)

    Cairns, Warren R.L.; Cozzi, Giulio [Institute for the Dynamics of Environmental Processes-CNR, Venice (Italy); De Boni, Antonella; Gabrieli, Jacopo [University of Venice, Department of Environmental Science, Venice (Italy); Asti, Massimo; Merlone Borla, Edoardo; Parussa, Flavio [Centro Ricerche Fiat, Orbassano (Italy); Moretto, Ezio [FIAT Powertrain Technologies S.p.A, Turin (Italy); Cescon, Paolo; Barbante, Carlo [University of Venice, Department of Environmental Science, Venice (Italy); Institute for the Dynamics of Environmental Processes-CNR, Venice (Italy); Boutron, Claude [Laboratoire de Glaciologie et Geophysique de l' Environnement, UMR CNRS 5183, B.P. 96, Saint Martin d' Heres Cedex (France)


    Inductively coupled plasma-mass spectrometry coupled with cation exchange matrix separation has been optimised for the direct determination of platinum group element (PGE) and trace element emissions from a diesel engine car. After matrix separation method detection limits of 1.6 ng g{sup -1} for Pd, 0.4 ng g{sup -1} for Rh and 4.3 ng g{sup -1} for Pt were achieved, the method was validated against the certified reference material BCR 723, urban road dust. The test vehicle was fitted with new and aged catalytic converters with and without diesel particulate filters (DPF). Samples were collected after three consecutive New European Driving Cycle (NEDC) of the particulate and ''soluble'' phases using a home-made sampler optimised for trace element analysis. Emission factors for the PGEs ranged from 0.021 ng km{sup -1} for Rh to 70.5 ng km{sup -1} for Pt; when a DPF was fitted, the emission factors for the PGEs actually used in the catalysts dropped by up to 97% (for Pt). Trace element emission factors were found to drop by a maximum of 92% for Ni to a minimum of 18% for Y when a DPF was fitted; a new DPF was also found to cause a reduction of up to 86% in the emission of particulate matter. (orig.)

  11. Platinum-Group Minerals in Chromitites of the Niquelândia Layered Intrusion (Central Goias, Brazil: Their Magmatic Origin and Low-Temperature Reworking during Serpentinization and Lateritic Weathering

    Directory of Open Access Journals (Sweden)

    Nelson Angeli


    Full Text Available A variety of platinum-group-minerals (PGM have been found to occur associated with the chromitite and dunite layers in the Niquelândia igneous complex. Two genetically distinct populations of PGM have been identified corresponding to phases crystallized at high temperatures (primary, and others formed or modified during post-magmatic serpentinization and lateritic weathering (secondary. Primary PGM have been found in moderately serpentinized chromitite and dunite, usually included in fresh chromite grains or partially oxidized interstitial sulfides. Due to topographically controlled lateritic weathering, the silicate rocks are totally transformed to a smectite-kaolinite-garnierite-amorphous silica assemblage, while the chromite is changed into a massive aggregate of a spinel phase having low-Mg and a low Fe3+/Fe2+ ratio, intimately associated with Ti-minerals, amorphous Fe-hydroxides, goethite, hematite and magnetite. The PGM in part survive alteration, and in part are corroded as a result of deep chemical weathering. Laurite is altered to Ru-oxides or re-crystallizes together with secondary Mg-ilmenite. Other PGM, especially the Pt-Fe alloys, re-precipitate within the altered chromite together with kaolinite and Fe-hydroxides. Textural evidence suggests that re-deposition of secondary PGM took place during chromite alteration, controlled by variation of the redox conditions on a microscopic scale.

  12. Coulombic amino group-metal bonding: adsorption of adenine on Cu110. (United States)

    Preuss, M; Schmidt, W G; Bechstedt, F


    The interaction between molecular amino groups and metal surfaces is analyzed from first-principles calculations using the adsorption of adenine on Cu110 as a model case. The amino group nitrogens are found to adsorb on top of the surface copper atoms. However, the bonding clearly cannot be explained in terms of covalent interactions. Instead, we find it to be largely determined by mutual polarization and Coulomb interaction between substrate and adsorbate.

  13. Investigation of complexing ability of ionites with various groups to some heavy and transition metal ions

    Directory of Open Access Journals (Sweden)

    Yedil Yergozhin


    Full Text Available The physico-chemical and complexing properties of the sorbent based on chloromethylated styrene and divinylbenzene copolymer with nicotinamide groups and copolymers based on metacryloilaminobenzene acids with 2-methyl-5-vinylpyridineisomers are studied. By potentiometric titration method the constant of polyelectrolytes functional groups ionization, the composition and strength of the resulting complexes with ions of some heavy and transition metals are determined.

  14. The oldest and most metal poor stars in the APOSTLE Local Group simulations

    CERN Document Server

    Starkenburg, Else; Navarro, Julio F; Crain, Robert A; Fattahi, Azadeh; Frenk, Carlos S; Sawala, Till; Schaye, Joop


    We examine the spatial distribution of the oldest and most metal poor stellar populations of Milky Way-sized galaxies using the APOSTLE cosmological hydrodynamical simulations of the Local Group. In agreement with earlier work, we find strong radial gradients in the fraction of the oldest (tform < 0.8 Gyr) and most metal poor ([Fe/H]< -2.5) stars, both of which increase outwards. The most metal poor stars form over an extended period of time; half of them form after z = 5.3, and the last 10% after z = 2.8. The age of the metal poor stellar population also shows significant variation with environment; a high fraction of them are old in the galaxy's central regions and an even higher fraction in some individual dwarf galaxies, with substantial scatter from dwarf to dwarf. Overall, over half of the stars that belong to both the oldest and most metal-poor population are found outside the solar circle. Somewhat counter-intuitively, we find that dwarf galaxies with a large fraction of metal poor stars that ar...

  15. Effect of functionalization of boron nitride flakes by main group metal clusters on their optoelectronic properties (United States)

    Chakraborty, Debdutta; Chattaraj, Pratim Kumar


    The possibility of functionalizing boron nitride flakes (BNFs) with some selected main group metal clusters, viz. OLi4, NLi5, CLi6, BLI7 and Al12Be, has been analyzed with the aid of density functional theory (DFT) based computations. Thermochemical as well as energetic considerations suggest that all the metal clusters interact with the BNF moiety in a favorable fashion. As a result of functionalization, the static (first) hyperpolarizability (β ) values of the metal cluster supported BNF moieties increase quite significantly as compared to that in the case of pristine BNF. Time dependent DFT analysis reveals that the metal clusters can lower the transition energies associated with the dominant electronic transitions quite significantly thereby enabling the metal cluster supported BNF moieties to exhibit significant non-linear optical activity. Moreover, the studied systems demonstrate broad band absorption capability spanning the UV–visible as well as infra-red domains. Energy decomposition analysis reveals that the electrostatic interactions principally stabilize the metal cluster supported BNF moieties.

  16. Unmetallated and metallated phthalocyanines bearing oxadiazole groups: Synthesis, photophysical and photochemical studies

    Energy Technology Data Exchange (ETDEWEB)

    Nas, Asiye [Department of Chemistry, Karadeniz Technical University, 61080 Trabzon (Turkey); Kantekin, Halit, E-mail: [Department of Chemistry, Karadeniz Technical University, 61080 Trabzon (Turkey); Durmuş, Mahmut [Gebze Institute of Technology, Department of Chemistry, PO Box 141, Gebze, 41400 Kocaeli (Turkey); Gümrükçüoğlu, Nurhan [Department of Chemistry, Karadeniz Technical University, 61080 Trabzon (Turkey)


    Unmetallated (4) and metallated (zinc(II), cobalt(II), lead(II)) phthalocyanines (5–7) carrying four 4-(4-(5-phenyl-1,3,4-oxadiazol-2-yl)phenoxy) groups on the peripheral positions were synthesized by cyclotetramerization of 4-(4-(5-phenyl-1,3,4-oxadiazol-2-yl)phenoxy)phthalonitrile (3) in the presence of corresponding metal salts (zinc(II) acetate, cobalt(II) chloride, lead(II) oxide) for metallated and without any metal for unmetallated phthalocyanines. The obtained organo-soluble phthalocyanines were characterized by infrared, electronic absorption, nuclear magnetic resonance and mass spectral techniques and elemental analysis as well. The photophysical and photochemical properties of newly synthesized tetra-substituted unmetallated (4), zinc(II) (5) and lead(II) (7) phthalocyanines were reported in N,N-dimetilformamid (DMF). The synthesized phthalocyanine compound 6 was not evaluated for photophysical and photochemical studies due to open shell and paramagnetic behavior of cobalt(II) metal ions in the phthalocyanine cavity. - Highlights: • Synthesis of unmetallated and metallated phthalocyanines. • Photophysical and photochemical properties of tetra-substituted phthalocyanines. • Characterization of organosoluble phthalocyanines by several spectral techniques.

  17. Main Group Lewis Acid-Mediated Transformations of Transition-Metal Hydride Complexes. (United States)

    Maity, Ayan; Teets, Thomas S


    This Review highlights stoichiometric reactions and elementary steps of catalytic reactions involving cooperative participation of transition-metal hydrides and main group Lewis acids. Included are reactions where the transition-metal hydride acts as a reactant as well as transformations that form the metal hydride as a product. This Review is divided by reaction type, illustrating the diverse roles that Lewis acids can play in mediating transformations involving transition-metal hydrides as either reactants or products. We begin with a discussion of reactions where metal hydrides form direct adducts with Lewis acids, elaborating the structure and dynamics of the products of these reactions. The bulk of this Review focuses on reactions where the transition metal and Lewis acid act in cooperation, and includes sections on carbonyl reduction, H2 activation, and hydride elimination reactions, all of which can be promoted by Lewis acids. Also included is a section on Lewis acid-base secondary coordination sphere interactions, which can influence the reactivity of hydrides. Work from the past 50 years is included, but the majority of this Review focuses on research from the past decade, with the intent of showcasing the rapid emergence of this field and the potential for further development into the future.

  18. Size-dependent metal-insulator transition in platinum-dispersed silicon dioxide thin film: A candidate for future non-volatile memory (United States)

    Chen, Albert B. K.

    Non-volatile random access memories (NVRAM) are promising data storage and processing devices. Various NVRAM, such as FeRAM and MRAM, have been studied in the past. But resistance switching random access memory (RRAM) has demonstrated the most potential for replacing flash memory in use today. In this dissertation, a novel RRAM material design that relies upon an electronic transition, rather than a phase change (as in chalcogenide Ovonic RRAM) or a structural change (such in oxide and halide filamentary RRAM), is investigated. Since the design is not limited to a single material but applicable to general combinations of metals and insulators, the goal of this study is to use a model material to delineate the intrinsic features of the electronic metal/insulator transition in random systems and to demonstrate their relevance to reliable memory storage and retrieval. We fabricated amorphous SiO2 thin films embedded with randomly dispersed Pt atoms. Macroscopically, this random material exhibits a percolation transition in electric conductivity similar to the one found in various insulator/metal granular materials. However, at Pt concentrations well below the bulk percolation limit, a distinct insulator to metal transition occurs in the thickness direction as the film thickness falls below electron's "diffusion" distance, which is the tunneling distance at 0K. The thickness-triggered metal- to-insulator transition (MIT) can be similarly triggered by other conditions: (a) a changing Pt concentration (a concentration-triggered MIT), (b) a changing voltage/polarity (voltage-triggered MIT), and (c) an UV irradiation (photon-triggered MIT). The resistance switching characteristics of this random material were further investigated in several device configurations under various test conditions. These include: materials for the top and bottom electrodes, fast pulsing, impedance spectroscopy, static stressing, retention, fatigue and temperature from 10K to 448K. The SiO2-Pt


    Institute of Scientific and Technical Information of China (English)


    Objective To evaluate the anti-tumor effect and toxicity of gemcitabine combined with platinum chemotherapy on recurrent epithelial ovarian cancer.Methods Phase Ⅱ study of gemcitabine combined with platinum chemotherapy was carried out in 22 patients with recurrent epithelial ovarian cancer. Median age of patients was 50. 5 years old. Seven patients were platinum-sensitive and 15 patients were platinum-resistant or -refractor. All patients received gemcitabine combined with carboplatin or oxaliplatin chemotherapy. Patients' response rate (RR) and toxicity of gemcitabine combined with platinum chemotherapy were evaluated.Results A total of 98 gemcitabine-based chemotherapy cycles were performed. Total RR was 36.4%, RR of platinum-sensitive patients was 4/7 and platinum-resistant and -refractory patients was 4/15. The estimated median survival time was 10. 0 months (95% CI: 7.0-13.0) after initiation of gemcitabine combined with platinum chemotherapy.There was no significant difference in survival time between platinum-resistant/refractory group and platinum-sensitive group (P = 0. 061 ). Side effects of gemcitabine combined with platinum chemotherapy were observed in 81.8 % of patients. Grade Ⅱ/Ⅲ anemia (54.5%) and grade Ⅲ/Ⅳ neutropenia (54.5%) were most common toxicities. Ten (45.5%) patients had to delay their chemotherapy cycles or reduce the dose of chemotherapeutic drugs because of the severe side effects. Fourteen (63.6%) patients received granulocyte colony-stimulating factor to relieve neutropenia,and 8 (36. 4% ) patients received component blood transfusion to treat anemia or thrombocytopenia. There was no treatment-associated death.Conclusion Gemcitabine combined with platinum chemotherapy appears to be an effective and well-tolerant treatment for recurrent epithelial ovarian cancer, including platinum-resistant or -refractory diseases.

  20. Platinum in Earth surface environments (United States)

    Reith, F.; Campbell, S. G.; Ball, A. S.; Pring, A.; Southam, G.


    Platinum (Pt) is a rare precious metal that is a strategic commodity for industries in many countries. The demand for Pt has more than doubled in the last 30 years due to its role in the catalytic conversion of CO, hydrocarbons and NOx in modern automobiles. To explore for new Pt deposits, process ores and deal with ecotoxicological effects of Pt mining and usage, the fundamental processes and pathways of Pt dispersion and re-concentration in surface environments need to be understood. Hence, the aim of this review is to develop a synergistic model for the cycling of Pt in Earth surface environments. This is achieved by integrating the geological/(biogeo)chemical literature, which focuses on naturally occurring Pt mobility around ore deposits, with the environmental/ecotoxicological literature dealing with anthropogenic Pt dispersion. In Pt deposits, Pt occurs as sulfide-, telluride- and arsenide, native metal and alloyed to other PGEs and iron (Fe). Increased mining and utilization of Pt combined with the burning of fossil fuels have led to the dispersion of Pt-containing nano- and micro-particles. Hence, soils and sediments in industrialized areas, urban environments and along major roads are now commonly Pt enriched. Platinum minerals, nuggets and anthropogenic particles are transformed by physical and (bio)geochemical processes. Complexation of Pt ions with chloride, thiosulfate, ammonium, cyanide, low- and high molecular weight organic acids (LMWOAs and HMWOAs) and siderophores can facilitate Pt mobilization. Iron-oxides, clays, organic matter and (micro)biota are known to sequester Pt-complexes and -particles. Microbes and plants are capable of bioaccumulating and reductively precipitating mobile Pt complexes. Bioaccumulation can lead to toxic effects on plants and animals, including humans. (Bio)mineralization in organic matter-rich sediments can lead to the formation of secondary Pt particles and -grains. Ultimately, Pt is enriched in oceanic sediments

  1. A 3D analysis of the metal distribution in the compact group of galaxies HCG 31 (United States)

    Torres-Flores, Sergio; Mendes de Oliveira, Claudia; Alfaro-Cuello, Mayte; Rodrigo Carrasco, Eleazar; de Mello, Duilia; Amram, Philippe


    We present new Gemini/GMOS integral field unit observations of the central region of the merging compact group of galaxies HCG 31. Using this data set, we derive the oxygen abundances for the merging galaxies HCG 31A and HCG 31C. We found a smooth metallicity gradient between the nuclei of these galaxies, suggesting a mixing of metals between these objects. These results are confirmed by high-resolution Fabry-Perot data, from which we infer that gas is flowing between HCG 31A and HCG 31C.

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

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


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

  3. μ2-Iodido-bis{dimethyl[methylbis(quinolin-8-ylsilanyl-κ3N,Si,N′]platinum(IV} tetrakis(pentafluorophenylborate dichloromethane 0.66-solvate

    Directory of Open Access Journals (Sweden)

    Marcus I. Gibson


    Full Text Available The title complex, [Pt2(CH34(C19H15N2Si2I][B(C6F54]·0.66CH2Cl2, resulted from an attempt to synthesize a stable five-coordinate platinum species via ligand abstraction of a six-coordinate platinum precursor. However, dimerization occurred after ligand abstraction, thereby yielding the compound described in this study. The cation is a dinuclear PtIV organometallic complex, in which the metal centers are bridged by an I− anion. Both metal centers display a coordination geometry close to octahedral, including cis-arranged quinoline ligands connected by Si atoms, which form Pt—Si bonds, two cis-methyl groups, and the bridging I− anion. In the crystal structure, voids between cations and anions are partially filled with an average of 0.66 molecules of dichloromethane solvent.

  4. NGC 6845: metallicity gradients and star formation in a complex compact group

    CERN Document Server

    Olave-Rojas, D; Carrasco, E R; de Oliveira, C Mendes; de Mello, D F; Scarano, S


    We have obtained Gemini/GMOS spectra of 28 regions located across the interacting group NGC 6845, spanning from the inner regions of the four major galaxies (NGC 6845A, B, C, D) to the tidal tails of NGC 6845A. All regions in the tails are star-forming objects with ages younger than 10 Myr. We derived the gas-phase metallicity gradients across NGC 6845A and its two tails and we find that these are shallower than those for isolated galaxies. NGC 6845A has a gas-phase oxygen central metallicity of \\mbox{12+log(O/H)$\\sim$8.5} and a flat gas-phase metallicity gradient ($\\beta$=0.002$\\pm$0.004 dex kpc$^{-1}$) out to $\\sim$4 $\\times$ R$_{25}$ (to the end of the longest tidal tail). Considering the mass-metallicity relation, the central region of NGC 6845A displays a lower oxygen abundance than the expected for its mass. Taking into account this fact and considering the flat oxygen distribution measured along the eastern tidal tail, we suggest that an interaction event has produced a dilution in the central metallic...

  5. Probing the bonding of CO to heteronuclear group 4 metal-nickel clusters by photoelectron spectroscopy. (United States)

    Zou, Jinghan; Xie, Hua; Yuan, Qinqin; Zhang, Jumei; Dai, Dongxu; Fan, Hongjun; Tang, Zichao; Jiang, Ling


    A series of heterobinuclear group 4 metal-nickel carbonyls MNi(CO)n(-) (M = Ti, Zr, Hf; n = 3-7) has been generated via a laser vaporization supersonic cluster source and characterized by mass-selected photoelectron velocity-map imaging spectroscopy. Quantum chemical calculations have been carried out to elucidate the geometric and electronic structures and support the spectral assignments. The n = 3 cluster is determined to be capable of simultaneously accommodating three different types of CO bonds (i.e., side-on-bonded, bridging, and terminal modes), resulting in a MNi[η(2)(μ2-C, O)](μ-CO)(CO)(-) structure, which represents the smallest metal carbonyl with the involvement of all the main modes of metal-CO coordination to date. The building block of three bridging CO molecules is favored at n = 4, the structure of which persists up to n = 7. The additional CO ligands are bonded terminally to the metal atoms. The present findings provide important new insight into the structure and bonding mechanisms of CO molecules with heteronuclear transition metals, which would have important implications for understanding chemisorbed CO molecules on alloy surfaces.

  6. High-temperature mass spectrometry - Vaporization of group 4-B metal carbides. [using Knudsen effusion (United States)

    Stearns, C. A.; Kohl, F. J.


    The high temperature vaporization of the metal-carbon systems TiC, ZrC, HfC, and ThC was studied by the Knudsen effusion - mass spectrometric method. For each system the metal dicarbide and tetracarbide molecular species were identified in the gas phase. Relative ion currents of the carbides and metals were measured as a function of temperature. Second- and third-law methods were used to determine enthalpies. Maximum values were established for the dissociation energies of the metal monocarbide molecules TiC, ZrC, HfC, and ThC. Thermodynamic functions used in the calculations are discussed in terms of assumed molecular structures and electronic contributions to the partition functions. The trends shown by the dissociation energies of the carbides of Group 4B are compared with those of neighboring groups and discussed in relation to the corresponding oxides and chemical bonding. The high temperature molecular beam inlet system and double focusing mass spectrometer are described.

  7. TP53 status and taxane-platinum versus platinum-based therapy in ovarian cancer patients: A non-randomized retrospective study

    Directory of Open Access Journals (Sweden)

    Markowska Janina


    Full Text Available Abstract Background Taxane-platinum therapy (TP has replaced platinum-based therapy (PC or PAC, DNA damaging chemotherapy in the postoperative treatment of ovarian cancer patients; however, it is not always effective. TP53 protein plays a differential role in response to DNA-damaging agents and taxanes. We sought to define profiles of patients who benefit the most from TP and also of those who can be treated with PC. Methods We compared the effectiveness of PC/PAC (n = 253 and TP (n = 199 with respect to tumor TP53 accumulation in ovarian cancer patients with FIGO stage IIB-IV disease; this was a non-randomized retrospective study. Immunohistochemical analysis was performed on 452 archival tumors; univariate and multivariate analysis by the Cox's and logistic regression models was performed in all patients and in subgroups with [TP53(+] and without TP53 accumulation [TP53(-]. Results The advantage of taxane-platinum therapy over platinum-based therapy was seen in the TP53(+, and not in the TP53(- group. In the TP53(+ group taxane-platinum therapy enhanced the probability of complete remission (p = .018, platinum sensitivity (p = .014, platinum highly sensitive response (p = .038 and longer survival (OS, p = .008. Poor tumor differentiation diminished the advantage from taxane-platinum therapy in the TP53(+ group. In the TP53(- group PC/PAC was at least equally efficient as taxane-platinum therapy and it enhanced the chance of platinum highly sensitive response (p = .010. However, in the TP53(- group taxane-platinum therapy possibly diminished the risk of death in patients over 53 yrs (p = .077. Among factors that positively interacted with taxane-platinum therapy in some analyses were endometrioid and clear cell type, FIGO III stage, bulky residual tumor, more advanced age of patient and moderate tumor differentiation. Conclusion Our results suggest that taxane-platinum therapy is particularly justified in patients with TP53(+ tumors or older

  8. Platinum and Other Transition Metal Nanoclusters (Pd, Rh) Stabilized by PAMAM Dendrimer as Excellent Heterogeneous Catalysts: Application to the Methylcyclopentane (MCP) Hydrogenative Isomerization. (United States)

    Deraedt, Christophe; Melaet, Gérôme; Ralston, Walter T; Ye, Rong; Somorjai, Gabor A


    Pt, Rh, and Pd nanoclusters stabilized by PAMAM dendrimer are used for the first time in a gas flow reactor at high temperature (150-250 °C). Pt nanoclusters show a very high activity for the hydrogenation of the methylcyclopentane (MCP) at 200-225 °C with turnover freqency (TOF) up to 334 h(-1) and selectivity up to 99.6% for the ring opening isomerization at very high conversion (94%). Rh nanoclusters show different selectivity for the reaction, that is, ring opening isomerization at 175 °C and cracking at higher temperature whereas Pd nanoclusters perform ring enlargement plus dehydrogenation, while maintaining a high activity. The difference in these results as compared to unsupported/uncapped nanoparticles, demonstrates the crucial role of dendrimer. The tunability of the selectivity of the reaction as well as the very high activity of the metal nanoclusters stabilized by dendrimer under heterogeneous conditions open a new application for dendrimer catalysts.

  9. Clinical pharmacology and pharmacokinetics of cis-platinum and analogs. (United States)

    Ribaud, P; Gouveia, J; Bonnay, M; Mathe, G


    cis-Platinum (DDP), the first metal coordination complex introduced into clinical trials, is remarkable for its therapeutic index. A short review of the numerator of this index, ie, the clinical activities of DDP given as a single agent or in combination therapy is presented. Toxicity of DDP, the denominator of the index, is given more attention, particularly nephrotoxicity, whose cumulative character and molecular mechanism are still in question and which can most often be prevented by following certain safety rules that are detailed in this paper. Pharmacokinetics data of free and filterable platinum are reviewed and discussed according to the different modalities of administration of DDP, and to what is known about its toxicity and its mechanism of cell kill. The rationale for using DDP in combination treatment is presented and the question of possible long-term toxicities is raised. cis-platinum analogs are sought for the purpose of enlarging the spectrum of activity, increasing selectivity and diminishing toxicity. Malonato-platinum has been shown not to be cross-resistant with DDP and to be clinically effective in adult acute leukemia. In a phase I study, malonato-platinum, which is poorly soluble, was administered in 6-24-hour infusions to 49 patients in doses ranging from 3 to 32 mg/kg. GI toxicity was universal. Hematological toxicity appeared to be mild and not clearly dose-related (the 3-32 mg/kg patients were not yet evaluable). Platinum pharmacokinetics in urine and plasma were performed using flameless absorption spectrophotometry. Preliminary results have suggested that malonato-platinum presented several pharmacokinetic features in common with DDP. Minor responses were seen in four solid tumor patients, three of whom were refractory to DDP. Other analogs soon to be introduced into clinical trials are listed.

  10. Xinjiang Nonferrous Metal Group is Developing on Low-cost Expanding

    Institute of Scientific and Technical Information of China (English)


    <正>Xinjiang Xinxin Mining Industry Co.,Ltd., whose shareholder is Xinjiang Nonferrous Metal Group,issued a report through the Stock Exchange of Hong Kong Limited,or SEHK, that the company had made a 542.25 million yuan takeover of Yakesi Resources Develop- ment Co.,Ltd.and Hami Jubao Resource De- velopment Co.,Ltd.,the biggest copper nickel exploitation company in Hami area.This is the largest scale takeover since Xinxin became a

  11. Retention of heavy metals by carboxyl functional groups of biochars in small arms range soil. (United States)

    Uchimiya, Minori; Bannon, Desmond I; Wartelle, Lynda H


    Long-term effectiveness of biochar for heavy metal stabilization depends upon biochar's sorptive property and recalcitrance in soil. To understand the role of carboxyl functional groups on heavy metal stabilization, cottonseed hull biochar and flax shive steam-activated biochar having a low O/C ratio (0.04-0.06) and high fixed carbon content (~80% dry weight basis) were oxidized using concentrated H(2)SO(4)/HNO(3) and 30% HNO(3). Oxidized and unoxidized biochars were characterized for O/C ratio, total acidity, pH, moisture, ash, volatile matter, and fixed carbon contents, Brunauer-Emmett-Teller surface area, and attenuated total reflectance Fourier transform infrared spectral features. Characterized biochars were amended (2%, 5%, 10%, and 20% in grams of biochar per gram of soil) on a sandy, slightly acidic (pH 6.27) heavy metal contaminated small arms range soil fraction (carbon (0.518%) and low cation exchange capacity (0.95 cmol(c) kg(-1)). Oxidized biochars rich in carboxyl functional groups exhibited significantly greater Pb, Cu, and Zn stabilization ability compared to unoxidized biochars, especially in pH 4.9 acetate buffer (standard solution for the toxicity characteristic leaching procedure). Oppositely, only oxidized biochars caused desorption of Sb, indicating a counteracting impact of carboxyl functional groups on the solubility of anions and cations. The results suggested that appropriate selection of biochar oxidant will produce recalcitrant biochars rich in carboxyl functional groups for a long-term heavy metal stabilization strategy in contaminated soils.

  12. Dichlorostannylene complexes of group 10 metals, a unique bonding mode stabilized by bridging 2-pyridyldiphenylphosphine ligands

    NARCIS (Netherlands)

    Cabon, Y.; Kleijn, H.; Siegler, M. A.; Spek, A.L.; Klein Gebbink, R.J.M.; Deelman, B.J.


    The reaction of tin dichloride with catalytically-relevant group 10 metal precursors [M(Cl)(X)(2-PyPPh2)2] (M = Ni, Pd, Pt; 2-PyPPh2 = 2-pyridyldiphenylphosphine; X = Cl, Me) provides easy access to unprecedented cationic dichlorostannylene complexes [M(X)(2-PyPPh2)2(SnCl2)]+ where the M–Sn bond is

  13. Platinum-Iridium Alloy Films Prepared by MOCVD

    Institute of Scientific and Technical Information of China (English)

    WEI Yan; CHEN Li; CAI Hongzhong; ZHENG Xu; YANG Xiya; HU Changyi


    Platinum-Iridium alloy films were prepared by MOCVD on Mo substrate using metal-acetylacetonate precursors.Effects of deposition conditions on composition,microstructure and mechanical properties were determined.In these experimental conditions,the purities of films are high and more than 99.0%.The films are homogeneous and monophase solid solution of Pt and Ir.Weight percentage of platinum are much higher than iridium in the alloy.Lattice constant of the alloy changes with the platinum composition.Iridium composition showing an up-down-up trend at the precursor temperature of 190~230℃ and the deposition temperature at 400~550℃.The hardness of Pt-Ir alloys prepared by MOCVD is three times more than the alloys prepared by casting.

  14. Comparison between alkalimetal and group 11 transition metal halide and hydride tetramers: molecular structure and bonding. (United States)

    El-Hamdi, Majid; Solà, Miquel; Frenking, Gernot; Poater, Jordi


    A comparison between alkalimetal (M = Li, Na, K, and Rb) and group 11 transition metal (M = Cu, Ag, and Au) (MX)4 tetramers with X = H, F, Cl, Br, and I has been carried out by means of the Amsterdam Density Functional software using density functional theory at the BP86/QZ4P level of theory and including relativistic effects through the ZORA approximation. We have obtained that, in the case of alkalimetals, the cubic isomer of Td geometry is more stable than the ring structure with D4h symmetry, whereas in the case of group 11 transition metal tetramers, the isomer with D4h symmetry (or D2d symmetry) is more stable than the Td form. To better understand the results obtained we have made energy decomposition analyses of the tetramerization energies. The results show that in alkalimetal halide and hydride tetramers, the cubic geometry is the most stable because the larger Pauli repulsion energies are compensated by the attractive electrostatic and orbital interaction terms. In the case of group 11 transition metal tetramers, the D4h/D2d geometry is more stable than the Td one due to the reduction of electrostatic stabilization and the dominant effect of the Pauli repulsion.

  15. Development of Platinum(iv) Complexes as Anticancer Prodrugs: the Story so Far (United States)

    Wong, Daniel Yuan Qiang; Ang, Wee Han


    The serendipitous discovery of the antitumor properties of cisplatin by Barnett Rosenberg some forty years ago brought about a paradigm shift in the field of medicinal chemistry and challenged conventional thinking regarding the role of potentially toxic heavy metals in drugs. Platinum(II)-based anticancer drugs have since become some of the most effective and widely-used drugs in a clinician's arsenal and have saved countless lives. However, they are limited by high toxicity, severe side-effects and the incidence of drug resistance. In recent years, attention has shifted to stable platinum(IV) complexes as anticancer prodrugs. By exploiting the unique chemical and structural attributes of their scaffolds, these platinum(IV) prodrugs offer new strategies of targeting and killing cancer cells. This review summarizes the development of anticancer platinum(IV) prodrugs to date and some of the exciting strategies that utilise the platinum(IV) construct as targeted chemotherapeutic agents against cancer.

  16. Carbide-forming groups IVB-VIB metals: a new territory in the periodic table for CVD growth of graphene. (United States)

    Zou, Zhiyu; Fu, Lei; Song, Xiuju; Zhang, Yanfeng; Liu, Zhongfan


    Early transition metals, especially groups IVB-VIB metals, can form stable carbides, which are known to exhibit excellent "noble-metal-like" catalytic activities. We demonstrate herein the applications of groups IVB-VIB metals in graphene growth using atmospheric pressure chemical vapor deposition technique. Similar to the extensively studied Cu, Ni, and noble metals, these transition-metal foils facilitate the catalytic growth of single- to few-layer graphene. The most attractive advantage over the existing catalysts is their perfect control of layer thickness and uniformity with highly flexible experimental conditions by in situ converting the dissolved carbons into stable carbides to fully suppress the upward segregation/precipitation effect. The growth performance of graphene on these transition metals can be well explained by the periodic physicochemical properties of elements. Our work has disclosed a new territory of catalysts in the periodic table for graphene growth and is expected to trigger more interest in graphene research.

  17. Platinum-Free Counter Electrode Comprised of Metal-Organic-Framework (MOF)-Derived Cobalt Sulfide Nanoparticles for Efficient Dye-Sensitized Solar Cells (DSSCs) (United States)

    Hsu, Shao-Hui; Li, Chun-Ting; Chien, Heng-Ta; Salunkhe, Rahul R.; Suzuki, Norihiro; Yamauchi, Yusuke; Ho, Kuo-Chuan; Wu, Kevin C.-W.


    We fabricated a highly efficient (with a solar-to-electricity conversion efficiency (η) of 8.1%) Pt-free dye-sensitized solar cell (DSSC). The counter electrode was made of cobalt sulfide (CoS) nanoparticles synthesized via surfactant-assisted preparation of a metal organic framework, ZIF-67, with controllable particle sizes (50 to 320 nm) and subsequent oxidation and sulfide conversion. In contrast to conventional Pt counter electrodes, the synthesized CoS nanoparticles exhibited higher external surface areas and roughness factors, as evidenced by X-ray diffraction (XRD), scanning electron microscopy (SEM) element mapping, and electrochemical analysis. Incident photon-to-current conversion efficiency (IPCE) results showed an increase in the open circuit voltage (VOC) and a decrease in the short-circuit photocurrent density (Jsc) for CoS-based DSSCs compared to Pt-based DSSCs, resulting in a similar power conversion efficiency. The CoS-based DSSC fabricated in the study show great potential for economically friendly production of Pt-free DSSCs.


    Energy Technology Data Exchange (ETDEWEB)

    Torres-Flores, S.; Alfaro-Cuello, M. [Departamento de Física, Universidad de La Serena, Av. Cisternas 1200, La Serena (Chile); De Oliveira, C. Mendes [Instituto de Astronomia, Geofísica e Ciências Atmosféricas da Universidade de São Paulo, Cidade Universitária, CEP:05508-900, São Paulo, SP (Brazil); Amram, P. [Aix Marseille Université, CNRS, LAM (Laboratoire d' Astrophysique de Marseille) UMR 7326, F-13388, Marseille (France); Carrasco, E. R. [Gemini Observatory/AURA, Southern Operations Center, Casilla 603, La Serena (Chile); De Mello, D. F., E-mail: [Catholic University of America, Washington, DC 20064 (United States)


    We present for the first time direct evidence that in a merger of disk galaxies, the pre-existing central metallicities will mix as a result of gas being transported in the merger interface region along the line that joins the two coalescing nuclei. This is shown using detailed two-dimensional kinematics as well as metallicity measurements for the nearby ongoing merger in the center of the compact group HCG 31. We focus on the emission line gas, which is extensive in the system. The two coalescing cores display similar oxygen abundances. While in between the two nuclei, the metallicity changes smoothly from one nucleus to the other indicating a mix of metals in this region, which is confirmed by the high-resolution Hα kinematics (R = 45,900). This nearby system is especially important because it involves the merging of two fairly low-mass and clumpy galaxies (LMC-like galaxies), making it an important system for comparison with high-redshift galaxies.

  19. Energetics of small clusters of group IB metals (Cu, Ag, and Au) adsorbed on graphene (United States)

    Kaur, Gagandeep; Gupta, Shuchi; Dharamvir, Keya


    The 2D structure of graphene maximizes the interaction of adsorbate on the layer. Many experiments have been devised to form stable metallic clusters of different sizes. We study the structure and binding energies of group IB clusters Mn (M=Au, Ag, Cu n=1, 3) adsorbed on graphene using Gupta potential [1] (for M-M interaction) and Lennard-Jones potential [2] (for metal-carbon interaction). The total energy of the system has been obtained by placing each of Mn cluster a certain distance above the graphene sheet at various positions and in various orientations. The minimized energy configurations, for all Mn clusters, lie above the center of a hexagon and parallel to the graphene sheet. Binding energy per atom for Ag and Cu metal clusters are less than those of respective Au indicating the lower stability of Ag/Cu metal-graphene system. Using various energy barriers, we can calculate the energy required to move small cluster from one position of minimum energy to another on graphene.

  20. Process for applying a catalytically active coating, particularly one containing platinum and/or palladium on catalyst carrier. Verfahren zum Aufbringen eines katalytisch aktiven, insbesondere Platin und/oder Palladium enthaltenden Ueberzugs auf Katalysatortraeger

    Energy Technology Data Exchange (ETDEWEB)

    Bozon, A.; Lakatos, E.; Koberstein, E.; Pletka, H.D.; Voelker, H.


    The invention concerns an improved process for applying a platinum and/or palladium, coating or films, possibly one containing other platinum group metals and/or nonprecious metals, by means of solutions of the metal compounds on the outer surface of porous catalyst carriers, i.e. those having a large surface. It was found that aquaeous solutions of ammonium chloride can be used to advantage to pre-charge the catalyst carrier, instead of the previously used organic solvents, where the saturation of the catalyst carrier must not be exceeded. After impregnation with an aquaeous solution of the catalytically active elements, the liquid is finally removed by heating. In the engine exhaust gas test, the catalysts according to the invention proved superior to the conventional ones.

  1. Designer ligands: The search for metal ion selectivity

    Directory of Open Access Journals (Sweden)

    Perry T. Kaye


    Full Text Available The paper reviews research conducted at Rhodes University towards the development of metal-selective ligands. The research has focused on the rational design, synthesis and evaluation of novel ligands for use in the formation of copper complexes as biomimetic models of the metalloenzyme, tyrosinase, and for the selective extraction of silver, nickel and platinum group metal ions in the presence of contaminating metal ions. Attention has also been given to the development of efficient, metal-selective molecular imprinted polymers.

  2. Cycloadditions to Epoxides Catalyzed by GroupIII-V Transition-Metal Complexes

    KAUST Repository

    D'Elia, Valerio


    Complexes of groupIII-V transition metals are gaining increasing importance as Lewis acid catalysts for the cycloaddition of dipolarophiles to epoxides. This review examines the latest reports, including homogeneous and heterogeneous applications. The pivotal step for the cycloaddition reactions is the ring opening of the epoxide following activation by the Lewis acid. Two modes of cleavage (C-C versus C-O) have been identified depending primarily on the substitution pattern of the epoxide, with lesser influence observed from the Lewis acid employed. The widely studied cycloaddition of CO2 to epoxides to afford cyclic carbonates (C-O bond cleavage) has been scrutinized in terms of catalytic efficiency and reaction mechanism, showing that unsophisticated complexes of groupIII-V transition metals are excellent molecular catalysts. These metals have been incorporated, as well, in highly performing, recyclable heterogeneous catalysts. Cycloadditions to epoxides with other dipolarophiles (alkynes, imines, indoles) have been conducted with scandium triflate with remarkable performances (C-C bond cleavage). © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Highly Fluorescent Group 13 Metal Complexes with Cyclic, Aromatic Hydroxamic Acid Ligands

    Energy Technology Data Exchange (ETDEWEB)

    Seitz, Michael; Moore, Evan G.; Raymond, Kenneth N.


    The neutral complexes of two ligands based on the 1-oxo-2-hydroxy-isoquinoline (1,2-HOIQO) motif with group 13 metals (Al, Ga, In) show bright blue-violet luminescence in organic solvents. The corresponding transition can be attributed to ligand-centered singlet emission, characterized by a small Stokes shifts of only a few nm combined with lifetimes in the range between 1-3 ns. The fluorescence efficiency is high, with quantum yields of up to 37% in benzene solution. The crystal structure of one of the indium(III) complexes (trigonal space group R-3, a = b = 13.0384(15) {angstrom}, c = 32.870(8) {angstrom}, ? = {beta} = 90{sup o}, {gamma} = 120{sup o}, V = 4839.3(14) {angstrom}{sup 3}, Z = 6) shows a six-coordinate geometry around the indium center which is close to trigonal-prismatic, with a twist angle between the two trigonal faces of 20.7{sup o}. Time-dependent density functional theory (TD-DFT) calculations (Al and Ga: B3LYP/6-31G(d)); In: B3LYP/LANL2DZ of the fac and mer isomers with one of the two ligands indicate that there is no clear preference for either one of the isomeric forms of the metal complexes. In addition, the metal centers do not have a significant influence on the electronic structure, and as a consequence, on the predominant intraligand optical transitions.


    Energy Technology Data Exchange (ETDEWEB)

    Landa, A; Soderlind, P


    The change in phase stability of Group-VB (V, Nb, and Ta) transition metals due to pressure and alloying is explored by means of first-principles electronic-structure calculations. It is shown that under compression stabilization or destabilization of the ground-state body-centered cubic (bcc) phase of the metal is mainly dictated by the band-structure energy that correlates well with the position of the Kohn anomaly in the transverse acoustic phonon mode. The predicted position of the Kohn anomaly in V, Nb, and Ta is found to be in a good agreement with data from the inelastic x-ray or neutron scattering measurements. In the case of alloying the change in phase stability is defined by the interplay between the band-structure and Madelung energies. We show that band-structure effects determine phase stability when a particular Group-VB metal is alloyed with its nearest neighbors within the same d-transition series: the neighbor with less and more d electrons destabilize and stabilize the bcc phase, respectively. When V is alloyed with neighbors of a higher (4d- or 5d-) transition series, both electrostatic Madelung and band-structure energies stabilize the body-centered-cubic phase. The opposite effect (destabilization) happens when Nb or Ta is alloyed with neighbors of the 3d-transition series.

  5. Platinum germanium ordering in UPtGe (United States)

    Hoffmann, Rolf-Dieter; Pöttgen, Rainer; Lander, Gerry H.; Rebizant, Jean


    The non-centrosymmetric structure of UPtGe was investigated by X-ray diffraction on both powders and single crystals: EuAuGe type, Imm2, a=432.86(5), b=718.81(8), c=751.66(9) pm, wR2=0.0738 for 399 F2 values and 22 variables. The platinum and germanium atoms form two-dimensional layers of puckered Pt 3Ge 3 hexagons with short PtGe intralayer distances of 252 and 253 pm. These condensed two-dimensionally infinite nets are interconnected to each other via weak PtPt contacts with bond distances of 300 pm. The two crystallographically independent uranium atoms are situated above and below the six-membered platinum-germanium rings. The U1 atoms have six closer germanium neighbors while the U2 atoms have six closer platinum neighbors. The group-subgroup relation with the KHg 2 type structure is presented.

  6. Porous platinum-based catalysts for oxygen reduction (United States)

    Erlebacher, Jonah D; Snyder, Joshua D


    A porous metal that comprises platinum and has a specific surface area that is greater than 5 m.sup.2/g and less than 75 m.sup.2/g. A fuel cell includes a first electrode, a second electrode spaced apart from the first electrode, and an electrolyte arranged between the first and the second electrodes. At least one of the first and second electrodes is coated with a porous metal catalyst for oxygen reduction, and the porous metal catalyst comprises platinum and has a specific surface area that is greater than 5 m.sup.2/g and less than 75 m.sup.2/g. A method of producing a porous metal according to an embodiment of the current invention includes producing an alloy consisting essentially of platinum and nickel according to the formula Pt.sub.xNi.sub.1-x, where x is at least 0.01 and less than 0.3; and dealloying the alloy in a substantially pH neutral solution to reduce an amount of nickel in the alloy to produce the porous metal.

  7. Highly trifluoromethylated platinum compounds. (United States)

    Martínez-Salvador, Sonia; Forniés, Juan; Martín, Antonio; Menjón, Babil


    The homoleptic, square-planar organoplatinum(II) compound [NBu(4)](2) [Pt(CF(3))(4)] (1) undergoes oxidative addition of CF(3) I under mild conditions to give rise to the octahedral organoplatinum(IV) complex [NBu(4)](2) [Pt(CF(3))(5)I] (2). This highly trifluoromethylated species reacts with Ag(+) salts of weakly coordinating anions in Me(2)CO under a wet-air stream to afford the aquo derivative [NBu(4)][Pt(CF(3))(5) (OH(2))] (4) in around 75% yield. When the reaction of 2 with the same Ag(+) salts is carried out in MeCN, the solvento compound [NBu(4) ][Pt(CF(3))(5)(NCMe)] (5) is obtained in around 80% yield. The aquo ligand in 4 as well as the MeCN ligand in 5 are labile and can be cleanly replaced by neutral and anionic ligands to furnish a series of pentakis(trifluoromethyl)platinate(IV) compounds with formulae [NBu(4)][Pt(CF(3))(5) (L)] (L=CO (6), pyridine (py; 7), tetrahydrothiophene (tht; 8)) and [NBu(4)](2) [Pt(CF(3))(5)X] (X=Cl (9), Br (10)). The unusual carbonyl-platinum(IV) derivative [NBu(4)][Pt(CF(3))(5) (CO)] (6) is thermally stable and has a ν(CO) of 2194 cm(-1). The crystal structures of 2⋅CH(2)Cl(2), 5, [PPh(4) ][Pt(CF(3))(5)(CO)] (6'), and 7 have been established by X-ray diffraction methods. Compound 2 has shown itself to be a convenient entry to the chemistry of highly trifluoromethylated platinum compounds. To the best of our knowledge, compounds 2 and 4-10 are the organoelement compounds with the highest CF(3) content to have been isolated and adequately characterized to date.

  8. Understanding platinum-induced ototoxicity. (United States)

    Langer, Thorsten; am Zehnhoff-Dinnesen, Antoinette; Radtke, Susanne; Meitert, Johannes; Zolk, Oliver


    Childhood cancer survival rates are now nearly 80% in more developed European countries because of improved therapies and better supportive care. Platinum chemotherapy drugs, such as cisplatin and carboplatin, are the cornerstone of many effective therapeutic protocols for childhood cancer. However, the antitumor efficacy of cisplatin and carboplatin comes at the cost of ototoxicity, which affects at least 60% of pediatric patients. Although ototoxicity is not life threatening, it can have debilitating effects on patients' quality of life. Recently, many initiatives have been launched with the ultimate goal of reducing cisplatin and high-dose carboplatin ototoxicity without compromising antitumor efficacy. This review addresses the incidence of platinum ototoxicity and its clinical presentation, time course, and early diagnostic evaluation. Genetic and non-genetic risk factors for platinum-associated ototoxicity, and their predictive value, are discussed. Recent developments in the prevention of platinum ototoxicity are also summarized. Copyright © 2013 Elsevier Ltd. All rights reserved.

  9. Polyamide platinum anticancer complexes designed to target specific DNA sequences. (United States)

    Jaramillo, David; Wheate, Nial J; Ralph, Stephen F; Howard, Warren A; Tor, Yitzhak; Aldrich-Wright, Janice R


    Two new platinum complexes, trans-chlorodiammine[N-(2-aminoethyl)-4-[4-(N-methylimidazole-2-carboxamido)-N-methylpyrrole-2-carboxamido]-N-methylpyrrole-2-carboxamide]platinum(II) chloride (DJ1953-2) and trans-chlorodiammine[N-(6-aminohexyl)-4-[4-(N-methylimidazole-2-carboxamido)-N-methylpyrrole-2-carboxamido]-N-methylpyrrole-2-carboxamide]platinum(II) chloride (DJ1953-6) have been synthesized as proof-of-concept molecules in the design of agents that can specifically target genes in DNA. Coordinate covalent binding to DNA was demonstrated with electrospray ionization mass spectrometry. Using circular dichroism, these complexes were found to show greater DNA binding affinity to the target sequence: d(CATTGTCAGAC)(2), than toward either d(GTCTGTCAATG)(2,) which contains different flanking sequences, or d(CATTGAGAGAC)(2), which contains a double base pair mismatch sequence. DJ1953-2 unwinds the DNA helix by around 13 degrees , but neither metal complex significantly affects the DNA melting temperature. Unlike simple DNA minor groove binders, DJ1953-2 is able to inhibit, in vitro, RNA synthesis. The cytotoxicity of both metal complexes in the L1210 murine leukaemia cell line was also determined, with DJ1953-6 (34 microM) more active than DJ1953-2 (>50 microM). These results demonstrate the potential of polyamide platinum complexes and provide the structural basis for designer agents that are able to recognize biologically relevant sequences and prevent DNA transcription and replication.

  10. Platinum availability for future automotive technologies. (United States)

    Alonso, Elisa; Field, Frank R; Kirchain, Randolph E


    Platinum is an excellent catalyst, can be used at high temperatures, and is stable in many aggressive chemical environments. Consequently, platinum is used in many current industrial applications, notably automotive catalytic converters, and prospective vehicle fuel cells are expected to rely upon it. Between 2005 and 2010, the automotive industry used approximately 40% of mined platinum. Future automotive industry growth and automotive sales shifts toward new technologies could significantly alter platinum demand. The potential risks for decreased platinum availability are evaluated, using an analysis of platinum market characteristics that describes platinum's geophysical constraints, institutional efficiency, and dynamic responsiveness. Results show that platinum demand for an automotive fleet that meets 450 ppm greenhouse gas stabilization goals would require within 10% of historical growth rates of platinum supply before 2025. However, such a fleet, due largely to sales growth in fuel cell vehicles, will more strongly constrain platinum supply in the 2050 time period. While current platinum reserves are sufficient to satisfy this increased demand, decreasing platinum ore grade and continued concentration of platinum supply in a single geographic area are availability risk factors to platinum end-users.

  11. The Next Generation of Platinum Drugs: Targeted Pt(II) Agents, Nanoparticle Delivery, and Pt(IV) Prodrugs. (United States)

    Johnstone, Timothy C; Suntharalingam, Kogularamanan; Lippard, Stephen J


    The platinum drugs, cisplatin, carboplatin, and oxaliplatin, prevail in the treatment of cancer, but new platinum agents have been very slow to enter the clinic. Recently, however, there has been a surge of activity, based on a great deal of mechanistic information, aimed at developing nonclassical platinum complexes that operate via mechanisms of action distinct from those of the approved drugs. The use of nanodelivery devices has also grown, and many different strategies have been explored to incorporate platinum warheads into nanomedicine constructs. In this Review, we discuss these efforts to create the next generation of platinum anticancer drugs. The introduction provides the reader with a brief overview of the use, development, and mechanism of action of the approved platinum drugs to provide the context in which more recent research has flourished. We then describe approaches that explore nonclassical platinum(II) complexes with trans geometry or with a monofunctional coordination mode, polynuclear platinum(II) compounds, platinum(IV) prodrugs, dual-threat agents, and photoactivatable platinum(IV) complexes. Nanoparticles designed to deliver platinum(IV) complexes will also be discussed, including carbon nanotubes, carbon nanoparticles, gold nanoparticles, quantum dots, upconversion nanoparticles, and polymeric micelles. Additional nanoformulations, including supramolecular self-assembled structures, proteins, peptides, metal-organic frameworks, and coordination polymers, will then be described. Finally, the significant clinical progress made by nanoparticle formulations of platinum(II) agents will be reviewed. We anticipate that such a synthesis of disparate research efforts will not only help to generate new drug development ideas and strategies, but also will reflect our optimism that the next generation of approved platinum cancer drugs is about to arrive.

  12. The two metallicity groups of the globular cluster M22: a chemical perspective

    CERN Document Server

    Marino, A F; Kraft, R P; Wallerstein, G; Norris, J E; Da Costa, G; Milone, A P; Ivans, I I; Gonzalez, G; Fulbright, J P; Hilker, M; Piotto, G; Zoccali, M; Stetson, P B


    We present a detailed chemical composition analysis of 35 red giant stars in the globular cluster M22. High resolution spectra for this study were obtained at five observatories, and analyzed in a uniform manner. We have determined abundances of representative light proton-capture, alpha, Fe-peak and neutron-capture element groups. Our aim is to better understand the peculiar chemical enrichment history of this cluster, in which two stellar groups are characterized by a different content in iron, neutron capture elements Y, Zr and Ba, and alpha element Ca. The principal results of this study are: (i) substantial star-to-star metallicity scatter (-2.0<[Fe/H]<-1.6); (ii) enhancement of s-process/r-process neutron-capture abundance ratios in a fraction of giants, positively correlated with metallicity; (iii) sharp separation between the s-process rich and s-process poor groups by [La/Eu] ratio; (iv) possible increase of [Cu/Fe] ratios with increasing [Fe/H], suggesting that this element also has a signific...

  13. Investigation of mechanical and structural characteristics of platinum and palladium at high temperatures

    Energy Technology Data Exchange (ETDEWEB)

    Trumie, B. T.; Gomidzelovie, L.; Marjanovic, S. R.; Krstic, V. R.


    In order to broaden future application of products based on platinum and palladium a comparative analysis of their high-temperature mechanical properties was performed. Platinum and palladium are of great importance and are widely used in chemical industry, electronics, for making laboratory dishes, to name a few. Mechanical properties of pure metals, such as: tensile strength, creep rate and rupture time were investigated using universal testing machine for tensile testing of materials. Microstructure of samples was investigated by optical microscopy. Based on obtained results it can be concluded that the platinum, compared to palladium, is superior for high-temperature applications. (Author)

  14. Selective hydrogenation of halogenated arenes using porous manganese oxide (OMS-2) and platinum supported OMS-2 catalysts. (United States)

    McManus, Iain J; Daly, Helen; Manyar, Haresh G; Taylor, S F Rebecca; Thompson, Jillian M; Hardacre, Christopher


    Porous manganese oxide (OMS-2) and platinum supported on OMS-2 catalysts have been shown to facilitate the hydrogenation of the nitro group in chloronitrobenzene to give chloroaniline with no dehalogenation. Complete conversion was obtained within 2 h at 25 °C and, although the rate of reaction increased with increasing temperature up to 100 °C, the selectivity to chloroaniline remained at 99.0%. Use of Pd/OMS-2 or Pt/Al2O3 resulted in significant dechlorination even at 25 °C and 2 bar hydrogen pressure giving a selectivity to chloroaniline of 34.5% and 77.8%, respectively, at complete conversion. This demonstrates the potential of using platinum group metal free catalysts for the selective hydrogenation of halogenated aromatics. Two pathways were observed for the analogous nitrobenzene hydrogenation depending on the catalyst used. The hydrogenation of nitrobenzene was found to follow a direct pathway to aniline and nitrosobenzene over Pd/OMS-2 in contrast to the OMS and Pt/OMS-2 catalysts which resulted in formation of nitrosobenzene, azoxybenzene and azobenzene/hydrazobenzene intermediates before complete conversion to aniline. These results indicate that for Pt/OMS-2 the hydrogenation proceeds predominantly over the support with the metal acting to dissociate hydrogen. In the case of Pd/OMS-2 both the hydrogenation and hydrogen adsorption occur on the metal sites.

  15. Surface decorated platinum carbonyl clusters (United States)

    Ciabatti, Iacopo; Femoni, Cristina; Iapalucci, Maria Carmela; Longoni, Giuliano; Zacchini, Stefano; Zarra, Salvatore


    Four molecular Pt-carbonyl clusters decorated by Cd-Br fragments, i.e., [Pt13(CO)12{Cd5(μ-Br)5Br2(dmf)3}2]2- (1), [Pt19(CO)17{Cd5(μ-Br)5Br3(Me2CO)2}{Cd5(μ-Br)5Br(Me2CO)4}]2- (2), [H2Pt26(CO)20(CdBr)12]8- (3) and [H4Pt26(CO)20(CdBr)12(PtBr)x]6- (4) (x = 0-2), have been obtained from the reactions between [Pt3n(CO)6n]2- (n = 2-6) and CdBr2.H2O in dmf at 120 °C. The structures of these molecular clusters with diameters of 1.5-2 nm have been determined by X-ray crystallography. Both 1 and 2 are composed of icosahedral or bis-icosahedral Pt-CO cores decorated on the surface by Cd-Br motifs, whereas 3 and 4 display a cubic close packed Pt26Cd12 metal frame decorated by CO and Br ligands. An oversimplified and unifying approach to interpret the electron count of these surface decorated platinum carbonyl clusters is suggested, and extended to other low-valent organometallic clusters and Au-thiolate nanoclusters.Four molecular Pt-carbonyl clusters decorated by Cd-Br fragments, i.e., [Pt13(CO)12{Cd5(μ-Br)5Br2(dmf)3}2]2- (1), [Pt19(CO)17{Cd5(μ-Br)5Br3(Me2CO)2}{Cd5(μ-Br)5Br(Me2CO)4}]2- (2), [H2Pt26(CO)20(CdBr)12]8- (3) and [H4Pt26(CO)20(CdBr)12(PtBr)x]6- (4) (x = 0-2), have been obtained from the reactions between [Pt3n(CO)6n]2- (n = 2-6) and CdBr2.H2O in dmf at 120 °C. The structures of these molecular clusters with diameters of 1.5-2 nm have been determined by X-ray crystallography. Both 1 and 2 are composed of icosahedral or bis-icosahedral Pt-CO cores decorated on the surface by Cd-Br motifs, whereas 3 and 4 display a cubic close packed Pt26Cd12 metal frame decorated by CO and Br ligands. An oversimplified and unifying approach to interpret the electron count of these surface decorated platinum carbonyl clusters is suggested, and extended to other low-valent organometallic clusters and Au-thiolate nanoclusters. CCDC 867747 and 867748. For crystallographic data in CIF or other electronic format see DOI: 10.1039/c2nr30400g

  16. Understanding hydrogen sorption in a metal-organic framework with open-metal sites and amide functional groups

    KAUST Repository

    Pham, Tony T.


    Grand canonical Monte Carlo (GCMC) studies of the mechanism of hydrogen sorption in an rht-MOF known as Cu-TPBTM are presented. The MOF is a decorated/substituted isostructural analogue to the unembellished rht-MOF, PCN-61, that was studied previously [ Forrest, K. A.J. Phys. Chem. C 2012, 116, 15538-15549. ]. The simulations were performed using three different hydrogen potentials of increasing complexity. Simulated hydrogen sorption isotherms and calculated isosteric heat of adsorption, Qst, values were in excellent agreement with the reported experimental data for only a polarizable model in one of four experimentally observed crystal structure configurations. The study demonstrates the ability of modeling to distinguish the differential sorption of distinct strucures; one configuration is found to be dominant due to favorable interactions with substrates. In addition, it was discovered that the presence of polar amide groups had a significant effect on the electrostatics of the Cu2+ ions and directs the low-pressure physisorption of hydrogen in the MOF. This is in contrast to what was observed in PCN-61, where an exterior copper ion had a higher relative charge and was the favored loading site. This tunability of the electrostatics of the copper ions via chemical substitution on the MOF framework can be explained by the presence of the negatively charged oxygen atom of the amide group that causes the interior Cu2+ ion to exhibit a higher positive charge through an inductive effect. Further, control simulations, taking advantage of the flexibility afforded by theoretical modeling, include artificially modified charges for both Cu2+ ions chosen equal to or with a higher charge on the exterior Cu2+ ion. This choice resulted in distinctly different hydrogen sorption characteristics in Cu-TPBTM with no direct sorption on the open-metal sites. Thus, this study demonstrates both the tunable nature of MOF platforms and the possibility for rational design of sorption

  17. Study of gold-platinum and platinum-gold surface modification and its influence on hydrogen evolution and oxygen reduction

    Directory of Open Access Journals (Sweden)



    Full Text Available Surface modification of the electrodes was conducted from sulfuric acid solutions containing the corresponding metal–chloride complexes using cyclic voltammetry. Comparing the charges of the hydrogen underpotential deposition region, and the corresponding oxide reduction regions, it is concluded that a platinum overlayer on gold forms 3D islands, while gold on platinum forms 2D islands. Foreign metals present in an amount of up to one monolayer exert an influence on the change in reaction rate with respect to both hydrogen evolution (HER and oxygen reduction (ORR reactions. Aplatinum overlayer on a gold substrate increases the activity forHER and for ORR, compared with pure gold. These results can be understood in terms of a simple model, in which the change in the H and OH binding energies are directly proportional to the shift of the d-bond center of the overlayer. On the contrary, a gold layer on platinum slightly decreases the activity for both reactions compared with pure platinum.

  18. Platinum contamination issues in ferroelectric memories (United States)

    Boubekeur, H.; Mikolajick, T.; Pamler, W.; Hopfner, J.; Frey, L.; Ryssel, H.


    The contamination risk of processing with platinum electrodes on device performance in ferroelectric memories is assessed in this work. Details of platinum diffusion to the active regions at annealing temperatures of 800 degC are investigated by secondary ion mass spectroscopy, deep level transient spectroscopy, and Rutherford backscattering spectrometry techniques. Cross sectional transmission electron microscopy and local elemental analysis by energy dispersive x-ray spectroscopy were used to examine the precipitation of Pt in defect free silicon as an eventual cause of gate oxide degradation. The impact of platinum contamination on device performance is evaluated under the typical ferroelectric memory processing conditions. Results from leakage current and charge to breakdown measurements of intentionally contaminated diode and metal-oxide-semiconductor (MOS) structures, respectively, are presented. The results show that the degradation depends strongly on device design and configuration. A phosphorus doped polysilicon plug, which has the function of connecting the select transistor to the capacitor module, provides effective gettering regions and prevents the diffusion of Pt atoms to the active regions. Under typical processing conditions, no evident Pt precipitates were observed and up to a concentration level of 4 x1014 atoms/cm2, the leakage current of intentionally contaminated diodes does not increase, if the contamination occurs after front-end phosphorus doped poly-Si processing. Results from constant current charge to breakdown show a small number of breakdown events due to redeposition of Pt at the periphery of the MOS structure. The risk of processing with Pt electrodes in ferroelectric memories requires great care. Precautions like sealing the back surface and incorporating phosphorus doped polysilicon as the plug material are necessary to avoid the detrimental effects of Pt.

  19. Extraction of gold, palladium, and platinum from acidic media with cyclic sulfoxide derivative

    Institute of Scientific and Technical Information of China (English)

    Songping Wu; Guobang Gu


    The extraction of gold (Ⅲ), palladium (Ⅱ), and platinum (Ⅳ) from the acidic media with the cyclic sulfoxide derivative of a-dodecyl-tetrahydrothiophene 1-oxide (dtmso) was investigated. Gold (Ⅲ), palladium (Ⅱ), and platinum (Ⅳ) could be separated from the acidic media with suitable sulfoxide concentration and acidity. The extraction reaction of gold (Ⅲ), palladium (Ⅱ) or platinum (Ⅳ) is exothermic when dtmso is used as an extracting reagent. The coordination number was studied by the slope method. The results indicate that, in high acidity, the dtmso coordination number for extracting gold (Ⅲ) or palladium (Ⅱ) is 3, and that for platinum (Ⅳ) is 2. UV and FT-IR spectra were used to analyze the structure of the complex. Gold (Ⅲ) is coordinated with the oxygen atom in S=O group in dtmso, and palladium (Ⅱ) or platinum (Ⅳ) is coordinated with the sulfur atom in S=O group in dtmso.

  20. Electrocatalysts having gold monolayers on platinum nanoparticle cores, and uses thereof (United States)

    Adzic, Radoslav; Zhang, Junliang


    The invention relates to gold-coated particles useful as fuel cell electrocatalysts. The particles are composed of an electrocatalytically active core at least partially encapsulated by an outer shell of gold or gold alloy. The invention more particularly relates to such particles having a noble metal-containing core, and more particularly, a platinum or platinum alloy core. In other embodiments, the invention relates to fuel cells containing these electrocatalysts and methods for generating electrical energy therefrom.

  1. Extrinsic Hardening of Superhard Tungsten Tetraboride Alloys with Group 4 Transition Metals. (United States)

    Akopov, Georgiy; Yeung, Michael T; Turner, Christopher L; Mohammadi, Reza; Kaner, Richard B


    Alloys of tungsten tetraboride (WB4) with the group 4 transition metals, titanium (Ti), zirconium (Zr), and hafnium (Hf), of different concentrations (0-50 at. % on a metals basis) were synthesized by arc-melting in order to study their mechanical properties. The phase composition and purity of the as-synthesized samples were confirmed using powder X-ray diffraction (PXRD) and energy dispersive X-ray spectroscopy (EDS). The solubility limit as determined by PXRD is 20 at. % for Ti, 10 at. % for Zr, and 8 at. % for Hf. Vickers indentation measurements of WB4 alloys with 8 at. % Ti, 8 at. % Zr, and 6 at. % Hf gave hardness values, Hv, of 50.9 ± 2.2, 55.9 ± 2.7 and 51.6 ± 2.8 GPa, respectively, compared to 43.3 GPa for pure WB4 under an applied load of 0.49 N. Each of the aforementioned compositions are considered superhard (Hv > 40 GPa), likely due to extrinsic hardening that plays a key role in these superhard metal borides. Furthermore, these materials exhibit a significantly reduced indentation size effect, which can be seen in the plateauing hardness values for the W1-xZrxB4 alloy. In addition, W0.92Zr0.08B4, a product of spinoidal decomposition, possesses nanostructured grains and enhanced grain hardening. The hardness of W0.92Zr0.08B4 is 34.7 ± 0.65 GPa under an applied load of 4.9 N, the highest value obtained for any superhard metal at this relatively high loading. In addition, the WB4 alloys with Ti, Zr, and Hf showed a substantially increased oxidation resistance up to ∼460 °C, ∼510 °C, and ∼490 °C, respectively, compared to ∼400 °C for pure WB4.

  2. Witnessing Gas Mixing in the Metal Distribution of the Hickson Compact Group HCG 31 (United States)

    Torres-Flores, S.; Mendes de Oliveira, C.; Amram, P.; Alfaro-Cuello, M.; Carrasco, E. R.; de Mello, D. F.


    We present for the first time direct evidence that in a merger of disk galaxies, the pre-existing central metallicities will mix as a result of gas being transported in the merger interface region along the line that joins the two coalescing nuclei. This is shown using detailed two-dimensional kinematics as well as metallicity measurements for the nearby ongoing merger in the center of the compact group HCG 31. We focus on the emission line gas, which is extensive in the system. The two coalescing cores display similar oxygen abundances. While in between the two nuclei, the metallicity changes smoothly from one nucleus to the other indicating a mix of metals in this region, which is confirmed by the high-resolution Hα kinematics (R = 45,900). This nearby system is especially important because it involves the merging of two fairly low-mass and clumpy galaxies (LMC-like galaxies), making it an important system for comparison with high-redshift galaxies. Based on observations obtained at the Gemini Observatory, which is operated by the Association of Universities for Research in Astronomy, Inc., under a cooperative agreement with the NSF on behalf of the Gemini partnership: the National Science Foundation (United States), the Science and Technology Facilities Council (United Kingdom), the National Research Council (Canada), CONICYT (Chile), the Australian Research Council (Australia), Ministério da Ciência e Tecnologia (Brazil) and Ministerio de Ciencia, Tecnología e Innovación Productiva (Argentina) - Observing run: GS-2012B-Q-60.

  3. Detailed Iron-Group Abundances in a Very Metal-Poor Main Sequence Turnoff Star (United States)

    Sneden, Chris; Roederer, Ian U.; Boesgaard, Ann M.; Lawler, James E.; Den Hartog, Elizabeth; Cowan, John J.; Sobeck, Jennifer


    We have obtained Keck HIRES and HST STIS high resolution, high signal-to-noise spectra of the very metal-poor ([Fe/H] ~ -2.9) main-sequence turnoff star BD+03 740. A detailed chemical composition analysis based on synthetic spectrum computations has been conducted. Our initial focus has been on the iron-group elements in the Z = 21-28 range. This study takes advantage of recent improvements in neutral and ionzied species transition data for all of these elements except Sc (Z = 21) by the Wisconsin atomic physics group (see a companion presentation on Cr II at this meeting). Several metal-poor abundance surveys have concluded that there are large overabundances of Co and underabundances of Cr with respect to Fe for stars with [Fe/H] synthesis in the Galaxy.This work has been supported by HST STScI Program GO-14232; and NSF grants AST-1211585 and AST-1616040 to CS; AST-1516182 to JEL and EDH; NASA grant NNX16AE96G to JEL

  4. Photocatalytic performance of nitrogen-platinum group metal co-doped Tio2 supported on carbon nanotubes for visible-light degradation of organic pollutants in water



    D.Phil. (Chemistry) Elimination of toxic organic compounds from wastewater is currently one of the most important subjects in water-pollution control. Among the many organic pollutants are dyes and emerging pollutants such as natural organic matter (NOM). Dyes such as Eosin Yellow (EY), an anionic xanthene fluorescent dye, can originate from many sources such as textile industrial processes, paper pulp industries and agricultural processes. Most dyes are problematic because they are resist...

  5. Determination of platinum-group metals and lead in vegetable environmental bio-monitors by voltammetric and spectroscopic techniques: critical comparison. (United States)

    Locatelli, Clinio; Melucci, Dora; Torsi, Giancarlo


    This paper reports voltammetric sequential determination of Pt(II), Pd(II), and Rh(III), by square-wave adsorption stripping voltammetry (SWAdSV), and Pb(II), by square-wave anodic stripping voltammetry (SWASV), in vegetable environmental matrices. Analytical procedures were verified by the analysis of the standard reference materials: Olive Leaves BCR-CRM 062 and Tomato Leaves NIST-SRM 1573a. Precision and accuracy, expressed as relative standard deviation and relative error, respectively, were always less than 6% and the limits of detection (LOD) for each element were below 0.096 mug g(-1). Once set up on the standard reference materials, the analytical procedure was transferred and applied to laurel leaves sampled in proximity to a superhighway and in the Po river mouth area. A critical comparison with spectroscopic measurements is discussed.

  6. Invited: Tailoring Platinum Group Metals Towards Optimal Activity for Oxygen Electroreduction to H2o and H2O2: From Extended Surfaces to Nanoparticles

    DEFF Research Database (Denmark)

    Stephens, Ifan


    demonstrated the very high activity of Pt3Y and Pt5Gd on extended polycrystalline surfaces. However, we have more recently shown that model, size-selected nanoparticles of PtxY exhibit up to 3 Ag-1at 0.9 V. These promising results provide a strong impetus towards the large scale synthesis of these catalysts...... a catalyst that is active, stable and selective for H2O2 production. We recently discovered a set of electrocatalysts that showed an unprecedented combination of all three of these desired properties: alloys of Pt, Ag or Pd with Hg.(10, 11) I will present data collected a wide range of different methods...... ). The figure shows transmission electron miscroscopy images of 9 nm diameter PtxY nanoparticles, based on high angle annular dark field –scanning transmission electron microscopy (left) and Y, Pt and combined Pt+Y X-ray energy dispersive X-ray spectroscopy elemental maps. (a) as-prepared catalyst and (b) after...

  7. Study of half-sandwich mono and dinuclear complexes of platinum group metals containing pyrazolyl pyridine analogues: Synthesis and spectral characterization

    Indian Academy of Sciences (India)

    Venkateswara Rao Anna; Kota Thirumala Prasad; Peng Wang; Kollipara Mohan Rao


    The chelating ligands 3-chloro-6-(3-pyridyl-1-pyrazolyl)pyridazine (-Cl) and 3,6-bis(3-pyridyl-1-pyrazolyl)pyridazine (bppp), were prepared by the condensation of pyridylpyrazole and 3,6-dichloropyridazine. The mononuclear complexes [(6-arene)Ru(-Cl)Cl]+ {6-arene = C6H6 (1); -iPrC6H4Me (2)}, [(5-C5Me5)M(-Cl)]+ {M = Rh (3); Ir (4)}, [(6-arene)Ru()Cl]+ {6-arene = C6H6 (5); -iPrC6H4Me (6)}, [(5-C5Me5)M(bppp)]+ {M =Rh (7); Ir (8)} as well as the binuclear complexes [{(6-arene)RuCl}2(bppp)]2+ {6 -arene =C6H6 (9); -iPrC6H4Me (10)} and [{(5-C5Me5)MCl}2(bppp)]2+ {M = Rh (11); Ir (12)} have been synthesized from 3-chloro-6-(3-pyridyl-1-pyrazolyl)pyridazine (-Cl) or 3,6-bis(3-pyridyl-1-pyrazolyl)pyridazine (bppp) and the corresponding dimers [(6-arene)Ru(-Cl)Cl]2 and [Cp∗M(-Cl)Cl]2, respectively. All complexes were isolated as their hexafluorophosphate salts and characterized by IR, NMR, mass spectrometry and UV-visible spectroscopy. The molecular structures of [2]PF6 and [7]PF6 have been established by single crystal X-ray structure analysis.

  8. Oxidative addition of disulfide/diselenide to group 10 metal(0) and in situ functionalization to form neutral thiasalen/selenasalen group 10 metal(II) complexes. (United States)

    Dutta, Pradip Kr; Asatkar, Ashish K; Zade, Sanjio S; Panda, Snigdha


    Three components, one pot synthesis of thiasalen/selenasalen Ni(II), Pd(II) and Pt(II) complexes, 14-19, by the oxidative addition of S-S/Se-Se bond of bis(o-formylphenyl)disulfide/-diselenide to Ni(0), Pd(0) and Pt(0) followed by in situ Schiff base formation with ethylenediamine is reported. S-S or Se-Se bonds were cleaved and coordinated to the metal center as thiolate (ArS(-)) or selenolate (ArSe(-)) while the formal oxidation state of metal centers was changed from '0' to '+2'. The disulfide/diselenide reacted with zero-valent metals at room temperature to give only the monometallic complexes. All complexes (except Pd-thiolate complex 15) were studied by single crystal X-ray crystallography and revealed the square planar geometry around metal centers.

  9. Elution of platinum from carboplatin-impregnated calcium sulfate hemihydrate beads in vitro. (United States)

    Tulipan, Rachel J; Phillips, Heidi; Garrett, Laura D; Dirikolu, Levent; Mitchell, Mark A


    OBJECTIVE To characterize the elution of platinum from carboplatin-impregnated calcium sulfate hemihydrate (CSH) beads in vitro. SAMPLE 60 carboplatin-impregnated CSH beads and 9 CSH beads without added carboplatin (controls). PROCEDURES Carboplatin-impregnated CSH beads (each containing 4.6 mg of carboplatin [2.4 mg of platinum]) were placed into separate 10-mL plastic tubes containing 5 mL of PBSS in groups of 1, 3, 6, or 10; 3 control beads were placed into a single tube of PBSS at the same volume. Experiments were conducted in triplicate at 37°C and a pH of 7.4 with constant agitation. Eluent samples were collected at 1, 2, 3, 6, 12, 24, and 72 hours. Samples were analyzed for platinum content by inductively coupled plasma-mass spectrometry. RESULTS The mean concentration of platinum released per carboplatin-impregnated bead over 72 hours was 445.3 mg/L. Cumulative concentrations of platinum eluted increased as the number of beads per tube increased. There was a significant difference in platinum concentrations over time, with values increasing over the first 12 hours and then declining for all tubes. There was also a significant difference in percentage of total incorporated platinum released into tubes with different numbers of beads: the percentage of eluted platinum was higher in tubes containing 1 or 3 beads than in those containing 6 or 10 beads. CONCLUSIONS AND CLINICAL RELEVANCE Carboplatin-impregnated CSH beads eluted platinum over 72 hours. Further studies are needed to determine whether implantation of carboplatin-impregnated CSH beads results in detectable levels of platinum systemically and whether the platinum concentrations eluted locally are toxic to tumor cells.

  10. Nanostructured gold and platinum electrodes on silicon structures for biosensing (United States)

    Ogurtsov, V. I.; Sheehan, M. M.


    Gold and platinum metal electrodes on Si/SiO2 having undergone anisotropic potassium hydroxide (KOH) etch treatment are considered. This treatment etches at different rates and directions in the material resulting in creation of numerous pyramid shaped holes in the silicon substrate. This surface is used to make metal electrodes with increased electrode efficiency. The electrodes can serve as the sensors or as the sensor substrates (for surface polymer modification) and because both gold and platinum are inert they have applications for food safety biosensing. Wine, an economically significant food product, was chosen as a matrix, and impedance spectroscopy (EIS) was selected as a method of investigation of electrode behaviour. Based on results of EIS, different complexity equivalent circuits were determined by applying fitting mean square root optimisation of sensor complex impedance measurements.

  11. Quantitative study of the spin Hall magnetoresistance in ferromagnetic insulator/normal metal hybrids

    NARCIS (Netherlands)

    Althammer, M.; Meyer, S.; Nakayama, H.; Schreier, M.; Altmannshofer, S.; Weiler, M.; Huebl, H.; Gesprägs, S.; Opel, M.; Gross, R.; Meier, D.; Klewe, C.; Kuschel, T.; Schmalhorst, J.M.; Reiss, G.; Shen, L.; Gupta, A.; Chen, Y.T.; Bauer, G.E.W.; Saitoh, E.; Goennenwein, S.T.B.


    We experimentally investigate and quantitatively analyze the spin Hall magnetoresistance effect in ferromagnetic insulator/platinum and ferromagnetic insulator/nonferromagnetic metal/platinum hybrid structures. For the ferromagnetic insulator, we use either yttrium iron garnet, nickel ferrite, or ma


    Institute of Scientific and Technical Information of China (English)

    Cheuk-lam Ho; Wai-yeung Wong


    A new luminescent and thermally stable platinum(Ⅱ) polyyne polymer trans-[-Pt(PBu3)2C≡CArC≡C-]n (P1) containing the 2,7-fluorene chromophoric spacer substituted by pendant carbazolyl group via long alkyl bridges. The regiochemical structures of these compounds were studied by various spectroscopic analyses. We report the photophysical properties of this group 10 polymetallayne and a comparison was made to its binuclear model complex trans-[Pt(Ph)(PEt3)2C≡CArC≡CPt(Ph)(PEt3)2] (M1) as well as to those with non-carbazole-containing fluorene spacer (P2 and M2). Upon photoexcitation, each of P1 and M1 emits an intense purple-blue fluorescence emission in the near-UV to visible region in dilute fluid solutions at room temperature. Harvesting of organic triplet emissions harnessed through the strong heavy-atom effects of platinum metal was examined and at 77 K, each of the metalated compounds displayed dual emission bands, viz. Both the fluorescence and the lower-lying phosphorescence. Spectroscopic results revealed that the formation of excimers was suppressed by introducing carbazole side groups. The spatial extent of the lowest singlet and triplet excitons in PI and M1 was fully elucidated. Such organometallic poly(fluorenyleneethynylene)s anchored with the carbazole pendants was found to have an improved thermal stability and suppressed aggregation.

  13. Nanostructured silver and platinum modified carbon fiber microelectrodes coated with nafion for H2O2 determination

    Directory of Open Access Journals (Sweden)

    Vladimir Halouzka


    Full Text Available Carbon fiber microelectrodes equipped with nanostructured metals(platinum and silver and covered with a Nafion layer constitutesensitive H2O2 sensors. Metallic layers on carbon fibers wereprepared by surfactant assisted electrodeposition. In the case ofsilver, the procedure leads to coating which is composed of porous,partially aggregated and crystalline deposits containing silvernanoparticles. The electrodeposition of platinum leads to carbonfiber decorated with clusters of platinum nanoparticles. Aftercoating the electrodes with protective and antiinterference barriermade of Nafion, the sensing properties of the preparedmicroelectrodes towards hydrogen peroxide are investigated.

  14. Cross-reactivity of Halogenated Platinum Salts (United States)

    Halogenated platinum (Pt) salts are well-known respiratory sensitizers associated with the development of asthma. People may be exposed to a variety of platinum compounds in different contexts (e.g. occupationally, automobile exhaust). Published reports suggest that sensitizati...

  15. Synthesis of platinum and palladium complexes with bis-(hydroxy imines

    Directory of Open Access Journals (Sweden)

    Lucas M. Arantes


    Full Text Available The Schiff bases are an important class of compounds well used as ligands in coordination chemistry. The functionalized bis-imines, that represent a specific group of Schiff base, have been studied in our research group both for the evaluation of biological activity, against fungi and cancer, as for organocatalyst. Here the bis-imines 1 and 4 were synthesized in good yields by condensation of hydroxylated benzaldehydes with phenylenediamines. After that they were matched with Platinum and palladium salts providing three metallic complex (2, 3 and 5 that were fully characterized by nuclear magnetic resonance and mass spectrometry with electrospray ionization. Now these complexes are being tested in cross-coupling reactions of Heck and Suzuki.

  16. Synthesis of platinum nanoparticle electrocatalysts by atomic layer deposition (United States)

    Lubers, Alia Marie

    Demand for energy continues to increase, and without alternatives to fossil fuel combustion the effects on our environment will become increasingly severe. Fuel cells offer a promising improvement on current methods of energy generation; they are able to convert hydrogen fuel into electricity with a theoretical efficiency of up to 83% and interface smoothly with renewable hydrogen production. Fuel cells can replace internal combustion engines in vehicles and are used in stationary applications to power homes and businesses. The efficiency of a fuel cell is maximized by its catalyst, which is often composed of platinum nanoparticles supported on carbon. Economical production of fuel cell catalysts will promote adoption of this technology. Atomic layer deposition (ALD) is a possible method for producing catalysts at a large scale when employed in a fluidized bed. ALD relies on sequential dosing of gas-phase precursors to grow a material layer by layer. We have synthesized platinum nanoparticles on a carbon particle support (Pt/C) by ALD for use in proton exchange membrane fuel cells (PEMFCs) and electrochemical hydrogen pumps. Platinum nanoparticles with different characteristics were deposited by changing two chemistries: the carbon substrate through functionalization; and the deposition process by use of either oxygen or hydrogen as ligand removing reactants. The metal depositing reactant was trimethyl(methylcyclopentadienyl)platinum(IV). Functionalizing the carbon substrate increased nucleation during deposition resulting in smaller and more dispersed nanoparticles. Use of hydrogen produced smaller nanoparticles than oxygen, due to a gentler hydrogenation reaction compared to using oxygen's destructive combustion reaction. Synthesized Pt/C materials were used as catalysts in an electrochemical hydrogen pump, a device used to separate hydrogen fuel from contaminants. Catalysts deposited by ALD on functionalized carbon using a hydrogen chemistry were the most

  17. Oscillatory instabilities in the electrooxidation of borohydride on platinum

    Energy Technology Data Exchange (ETDEWEB)

    Machado, Eduardo G.; Varela, Hamilton, E-mail: [Universidade de Sao Paulo (USP), Sao Carlos, SP (Brazil). Instituto de Quimica


    The borohydride ion has been pointed as a promising alternative fuel. Most of the investigation on its electrochemistry is devoted to the electrocatalytic aspects of its electrooxidation on platinum and gold surfaces. Besides the known kinetic limitations and intricate mechanism, our Group has recently found the occurrence of two regions of bi-stability and autocatalysis in the electrode potential during the open circuit interaction of borohydride and oxidized platinum surfaces. Following this previous contribution, the occurrence of more complicated phenomena is here presented: namely the presence of electrochemical oscillations during the electrooxidation of borohydride on platinum in alkaline media. Current oscillations were found to be associated to two distinct instability windows and characterized in the resistance-potential parameter plane. The dynamic features of such oscillations suggest the existence of distinct mechanisms according to the potential region. Previously published results obtained under non-oscillatory regime were used to give some hints on the surface chemistry behind the observed dynamics. (author)

  18. Tunable magneto-optical effects in hole-doped group-IIIA metal-monochalcogenide monolayers (United States)

    Feng, Wanxiang; Guo, Guang-Yu; Yao, Yugui


    Because of unusual properties and fascinating prospects for next-generation device applications, two-dimensional (2D) materials have attracted enormous attention since graphene was discovered in 2004. Among the 2D materials beyond graphene, group-IIIA metal-monochalcogenide (MX) monolayers (MLs), are receiving increasing interests because their excellent applications on electronics and optoelectronics. Recently, ferromagnetism and half-metallicity have been predicted in hole-doped GaS and GaSe MLs, which promise exciting potentials for semiconductor spintronics. Detection and measurement of spontaneous magnetization in these 2D materials will be essential for their spintronic applications. The magneto-optical (MO) effects not only are a powerful probe of magnetism in 2D materials but also have valuable applications in high-density data-storage technology. Furthermore, anomalous Hall effect is not only an ideal transport probe of itinerant magnetism but also of considerable current interest because of its topological nature. Here we perform a systematic first-principles density functional study on the MO Kerr and Faraday effects as well as such important magnetic and transport properties as magneto-crystalline anisotropy energy (MAE) and anomalous Hall conductivity (AHC) of all hole-doped MX (M = Ga, In; X = S, Se, Te) MLs. In this paper, we report the following important findings: (a) gate-tunable MO effects in MX MLs in a broad range of hole concentration; (b) large Kerr and Faraday rotation angles with Kerr angles comparable to well-known MO 3d-transition-metal multilayers and Faraday angles being among the largest ones reported; (c) tunable MAE and large AHC, making MX MLs suitable for magnetic memory devices current-driven via spin-transfer torque and also promising materials for magnetic field nanosensors with high sensitivity. Superior MO characteristics, together with the other interesting properties, would make MX MLs an excellent family of 2D materials for

  19. Separation of gold, palladium and platinum in chromite by anion exchange chromatography for inductively coupled plasma atomic emission spectrometric analysis

    Energy Technology Data Exchange (ETDEWEB)

    Choi, Kwang Soon; Lee, Chang Heon; Park, Yeong Jae; Joe, Kih Soo; Kim, Won Ho [KAERI, Taejon (Korea, Republic of)


    A study has been carried out on the separation of gold, iridium, palladium, rhodium, ruthenium and platinum in chromite samples and their quantitative determination using inductively coupled plasma atomic emission spectrometry (ICP-AES). The dissolution condition of the minerals by fusion with sodium peroxide was optimized and chromatographic elution behavior of the rare metals was investigated by anion exchange chromatography. Spectral interference of chromium, a matrix of the minerals, was investigated on determination of gold. Chromium interfered on determination of gold at the concentration of 500 mg/L and higher. Gold plus trace amounts of iridium, palladium, rhodium and ruthenium, which must be preconcentrated before ICP-AES was separated by anion exchange chromatography after reducing Cr(VI) to Cr(III) by H{sub 2}O{sub 2}. AuCl{sup -}{sub 4} retained on the resin column was selectively eluted with acetone- HNO{sub 3}-H{sub 2}O as an eluent. In addition, iridium, palladium, rhodium and ruthenium remaining on the resin column were eluted as a group with concentrated HCl. However, platinum was eluted with concentrated HNO{sub 3}. The recovery yield of gold with acetone-HNO{sub 3}-H{sub 2}O was 100.7 {+-} 2.0 % , and the yields of palladium and platinum with concentrated HCl and HNO{sub 3} were 96.1 {+-} 1.8% and 96.6 {+-} 1.3%, respectively. The contents of gold and platinum in a Mongolian chromite sample were 32.6 {+-} 2.2 {mu}g/g and 1.6 {+-} 0.14 {mu}g/g, respectively. Palladium was not detected.

  20. ICP-MS Determination of Platinum Metals in Black Shale Enriched by Tin Fire Assay%锡试金富集-电感耦合等离子体质谱法测定黑色页岩中的铂族元素

    Institute of Scientific and Technical Information of China (English)

    王君玉; 孙自军; 袁润蕾; 王盈; 李杰; 王敏捷


    黑色页岩中的铂族元素经锡试金富集后,所得贵金属沉淀物用盐酸-硝酸(3+1)混合酸溶解,用电感耦合等离子体质谱法测定样品中的铂族元素.以镥为内标元素,用轻质氧化镁-高纯碳化硅(2+1)作覆盖剂,以防止锇和钌的挥发损失.铂族元素在一定的质量浓度范围内与其光谱强度呈线性关系,检出限(3σ)在0.018~0.20 ng· g-1之间.方法的加标回收率在80.0%~110%之间,相对标准偏差(n=11)在5.9%~14%之间.%Platinum metals in black shale were enriched by the method of tin fire assay.The precious metal precipitate obtained was dissolved in mixed acid of HCl-HNC3 (3 + 1),and contents of platinum metals in the solution were determined by ICP-MS.Lutetium was used as internal standard; and a mixture of light MgO and high purity SiC (2 + 1) was used as covering reagent to avoid the volatilization of Os and Ru.Linear relationships between values of spectral intensity and mass concentration of the platinum metals were kept in definite ranges.Detection limits (3σ) found were in the range of 0.018-0.20 ng · g-1.Tests for recovery were made by standard addition method,giving values of recovery in the range of 80.0%-110% with RSD's (n=11) in the range of 5.9%-14%.

  1. Uptake of platinum by zebrafish (Danio rerio) and ramshorn snail (Marisa cornuarietis) and resulting effects on early embryogenesis. (United States)

    Osterauer, Raphaela; Haus, Nadine; Sures, Bernd; Köhler, Heinz-R


    Platinum group elements (PGEs), platinum, palladium and rhodium are widely used in automobile catalytic converters. PGEs are emitted into the environment and enter the aquatic ecosystem via runoff rainwater. The present study investigated the bioavailability of platinum chloride for the zebrafish (Danio rerio) and the ramshorn snail (Marisa cornuarietis) and determined the bioaccumulation rate of platinum. Applying the fish early life stage assay for D. rerio (DarT) and the Marisa embryo toxicity test ("Mariett") for M. cornuarietis, effects of platinum chloride on the embryonic development were investigated. Platinum concentrations tested in this study ranged from environmentally relevant concentrations of 38 ng L(-1) up to a concentration of 74.2 microg L(-1) for D. rerio and of 200 ngL(-1) up to 98.7 microg L(-1) for M. cornuarietis. Platinum was found to be accumulated in both organisms. Bioaccumulation factors (BAFs) were in the range of 5-55 for D. rerio and of 218.4-723.9 for M. cornuarietis, depending on the tested Pt concentrations. During the embryonic development, platinum was shown to alter the heart rate of both organisms already at the lowest tested concentration. At higher concentrations, platinum decelerated the hatching rate of the embryos of both species. Additionally, a retardation of the general development and a loss of weight due to platinum exposure was observed in M. cornuarietis. Results of this study contribute important data on the ecotoxicity of a rarely studied element.

  2. Electron-energy-loss spectroscopy on group-III nitrides and transition- metal oxides

    CERN Document Server

    Niessner, W


    A main topic represent electron-energy-loss spectroscopy (EELS) studies of the group-III nitrides AlN, GaN, InN, as well as their mixing systems Al sub x Ga sub 1 sub - sub x N, In sub x Ga sub 1 sub - sub x N. In EELS measurements with excitation energies above 1 keV clear collective excitations in AlN at 21 eV and in GaN at 15 eV were observed. In the mixing system Al sub x Ga sub 1 sub - sub x M a 2-mode behaviour is observed. Up to x=0.2 a GaN-like excitation remains preserved, while from x=0.44 the eigenfrequency of a AlN-like resonance shifts continuously. With vanadium dioxide a d sup 1 transition metal oxide was studied, which passes at 68 C a semiconductor-metal transition. In the EELS valence band spectra beside band transitions from the O2p subsigma and O2p subpi band an intense signal with a loss energy of 1 eV occurs. EELS studies on W- and F-doped VO sub 2 show, that it deals with a band transition from the V3d into the pd subpi band. EELS studies were for the first time also performed at lead t...

  3. Platinum on Carbon Nanofibers as Catalyst for Cinnamaldehyde Hydrogenation

    NARCIS (Netherlands)

    Plomp, A.J.


    The aim of the work described in this thesis was to investigate the role and nature of nanostructured carbon materials, oxygen surface groups and promoters on platinum-based catalysts for the selective hydrogenation of cinnamaldehyde. The selective hydrogenation of cinnamaldehyde to cinnamyl alcohol

  4. Platinum on Carbon Nanofibers as Catalyst for Cinnamaldehyde Hydrogenation

    NARCIS (Netherlands)

    Plomp, A.J.


    The aim of the work described in this thesis was to investigate the role and nature of nanostructured carbon materials, oxygen surface groups and promoters on platinum-based catalysts for the selective hydrogenation of cinnamaldehyde. The selective hydrogenation of cinnamaldehyde to cinnamyl alcohol

  5. Responses of fibroblasts and glial cells to nanostructured platinum surfaces (United States)

    Pennisi, C. P.; Sevcencu, C.; Dolatshahi-Pirouz, A.; Foss, M.; Lundsgaard Hansen, J.; Nylandsted Larsen, A.; Zachar, V.; Besenbacher, F.; Yoshida, K.


    The chronic performance of implantable neural prostheses is affected by the growth of encapsulation tissue onto the stimulation electrodes. Encapsulation is associated with activation of connective tissue cells at the electrode's metallic contacts, usually made of platinum. Since surface nanotopography can modulate the cellular responses to materials, the aim of the present work was to evaluate the 'in vitro' responses of connective tissue cells to platinum strictly by modulating its surface nanoroughness. Using molecular beam epitaxy combined with sputtering, we produced platinum nanostructured substrates consisting of irregularly distributed nanopyramids and investigated their effect on the proliferation, cytoskeletal organization and cellular morphology of primary fibroblasts and transformed glial cells. Cells were cultured on these substrates and their responses to surface roughness were studied. After one day in culture, the fibroblasts were more elongated and their cytoskeleton less mature when cultured on rough substrates. This effect increased as the roughness of the surface increased and was associated with reduced cell proliferation throughout the observation period (4 days). Morphological changes also occurred in glial cells, but they were triggered by a different roughness scale and did not affect cellular proliferation. In conclusion, surface nanotopography modulates the responses of fibroblasts and glial cells to platinum, which may be an important factor in optimizing the tissue response to implanted neural electrodes.

  6. Stimuli-Responsive Metal-Organic Frameworks with Photoswitchable Azobenzene Side Groups. (United States)

    Kanj, Anemar Bruno; Müller, Kai; Heinke, Lars


    Metal-organic frameworks (MOFs) are nanoporous, crystalline hybrid materials, which enable various functionalities by incorporating functional organic molecules. By using organic linker molecules that possess photoswitchable azobenzene side groups, the remote control over certain properties was introduced to MOFs. Different MOF materials in the form of powders and thin films have been used to demonstrate the photoswitching. The applications of these stimuli-responsive nanoporous solids range from switching the adsorption capacity of various gases over remote-controlled release of guest molecules to continuously tunable membrane separation of molecular mixtures. A particular focus of this review is the effect of the azobenzene photoswitching on the host-guest interaction, enabling smart applications of the material. Steric hindrance, which may suppress the photoswitching in some MOF structures, is also discussed. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. HM+ and HM+-He (M = Group 2 metal): Chemical or physical interactions? (United States)

    Harris, Joe P.; Dodson, Hannah; Breckenridge, W. H.; Wright, Timothy G.


    We investigate the HM+-He complexes (M = Group 2 metal) using quantum chemistry. Equilibrium geometries are linear for M = Be and Mg, and bent for M = Ca-Ra; the explanation for this lies in the differing nature of the highest occupied molecular orbitals in the two sets of complexes. The difference primarily occurs as a result of the formation of the H-M+ bond, and so the HM+ diatomics are also studied as part of the present work. The position of the He atom in the complexes is largely determined by the form of the electron density. HM+…He binding energies are obtained and are surprisingly high for a helium complex. The HBe+…He value is almost 3000 cm-1, which is high enough to suspect contributions from chemical bonding. This is explored by examining the natural orbital density and by population analyses.

  8. Materials design by evolutionary optimization of functional groups in metal-organic frameworks. (United States)

    Collins, Sean P; Daff, Thomas D; Piotrkowski, Sarah S; Woo, Tom K


    A genetic algorithm that efficiently optimizes a desired physical or functional property in metal-organic frameworks (MOFs) by evolving the functional groups within the pores has been developed. The approach has been used to optimize the CO2 uptake capacity of 141 experimentally characterized MOFs under conditions relevant for postcombustion CO2 capture. A total search space of 1.65 trillion structures was screened, and 1035 derivatives of 23 different parent MOFs were identified as having exceptional CO2 uptakes of >3.0 mmol/g (at 0.15 atm and 298 K). Many well-known MOF platforms were optimized, with some, such as MIL-47, having their CO2 adsorption increase by more than 400%. The structures of the high-performing MOFs are provided as potential targets for synthesis.

  9. Bioavailability of very finely distributed metallic platinum in the lungs and first orienting studies on effects. Part 2; Bioverfuegbarkeit von feinstverteiltem metallischem Platin in der Lunge und erste orientierende Wirkungsuntersuchungen (VPT 09; 2. Teil)

    Energy Technology Data Exchange (ETDEWEB)

    Emmendoerffer, A. [Fraunhofer-Institut fuer Toxikologie und Aerosolforschung, Hannover (Germany)


    Platinum is emitted from automotive catalytic converters in particulate form. The first organ to be exposed to it after its uptake by the organism is the lung. Lung macrophages therefore constitute the first barrier of the immune system which can to react to platinum. In this study the production of nitrogen oxides and cytokines was studied. These parameters play an important role in the initiation of inflammation and in the maintenance of chronic inflammatory processes that can lead to fibrosis of the lung. [Deutsch] Platin wird partikulaer aus Automobilabgaskatalysatoren emittiert. Das erste Zielorgan fuer eine Aufnahme im Organismus ist deshalb die Lunge. Die Lungenmakrophagen stellen also die erste Barriere des Immunsystems dar, das auf Platin reagieren kann. In vitro wurde die Produktion von Stickoxiden und Zytokinen untersucht. Diese Parameter spielen eine Rolle bei der Initiation von Entzuendungen und auch bei der Aufrechterhaltung chronisch entzuendlicher Prozesse, die in der Lunge zu einer Fibrose fuehren koennen. (orig.)

  10. Explorations of new selenites of the group IIIA and IVA metals (United States)

    Kong, Fang; Li, Pei-Xin; Zhang, Su-Yun; Mao, Jiang-Gao


    Systematic explorations of new phases in the GaIII/InIII/GeIV-SeIV-O systems by hydrothermal syntheses or solid-state reactions at high-temperature led to six new ternary compounds, namely, M2Se2O7 (M=Ga 1, In 2), M(OH)(SeO3) (M=Ga 3, In 4), α-Ge(SeO3)25 and β-Ge(SeO3)26. Ga2Se2O71 displays a 3D open framework composed of 2D gallium oxide layers being further bridged and capped by SeO3 groups. In2Se2O72 features a 3D indium oxide framework formed by corner- and edge- sharing InO6 octahedra with SeO3 groups attached on the cavities and the 8-member ring tunnels of the structure. The isostructural of M(OH)(SeO3) (M=Ga 3, In 4) exhibit a 2D metal selenite layer composed of 1D edge-sharing MO6 octahedral chains that are interconnected by SeO3 groups. α-Ge(SeO3)2 (P21/n) 5 displays a 3D open framework with 1D 8-member ring tunnels along the a-axis while β-Ge(SeO3)2 (Pa-3) 6 exhibits a condensed 3D network.

  11. Multiconfiguration pair-density functional theory: barrier heights and main group and transition metal energetics. (United States)

    Carlson, Rebecca K; Li Manni, Giovanni; Sonnenberger, Andrew L; Truhlar, Donald G; Gagliardi, Laura


    Kohn-Sham density functional theory, resting on the representation of the electronic density and kinetic energy by a single Slater determinant, has revolutionized chemistry, but for open-shell systems, the Kohn-Sham Slater determinant has the wrong symmetry properties as compared to an accurate wave function. We have recently proposed a theory, called multiconfiguration pair-density functional theory (MC-PDFT), in which the electronic kinetic energy and classical Coulomb energy are calculated from a multiconfiguration wave function with the correct symmetry properties, and the rest of the energy is calculated from a density functional, called the on-top density functional, that depends on the density and the on-top pair density calculated from this wave function. We also proposed a simple way to approximate the on-top density functional by translation of Kohn-Sham exchange-correlation functionals. The method is much less expensive than other post-SCF methods for calculating the dynamical correlation energy starting with a multiconfiguration self-consistent-field wave function as the reference wave function, and initial tests of the theory were quite encouraging. Here, we provide a broader test of the theory by applying it to bond energies of main-group molecules and transition metal complexes, barrier heights and reaction energies for diverse chemical reactions, proton affinities, and the water dimerization energy. Averaged over 56 data points, the mean unsigned error is 3.2 kcal/mol for MC-PDFT, as compared to 6.9 kcal/mol for Kohn-Sham theory with a comparable density functional. MC-PDFT is more accurate on average than complete active space second-order perturbation theory (CASPT2) for main-group small-molecule bond energies, alkyl bond dissociation energies, transition-metal-ligand bond energies, proton affinities, and the water dimerization energy.

  12. Surface chemistry of the atomic layer deposition of metals and group III oxides (United States)

    Goldstein, David Nathan

    Atomic Layer Deposition (ALD) is a thin-film growth technique offering precise control of film thickness and the ability to coat high-aspect-ratio features such as trenches and nanopowders. Unlike other film growth techniques, ALD does not require harsh processing conditions and is not limited by line-of-sight deposition. Emerging applications for ALD materials include semiconductor devices, gas sensors, and water-diffusion barriers. The chemistry behind ALD involves understanding how the precursors interact with surfaces to deposit the desired material. All ALD precursors need to be stable on the substrate to ensure self-limiting behavior yet reactive enough to be easily removed with the second reagent. Recent precursor development has provided many volatile organometallic compounds for most of the periodic table. As the number of precursors increases, proper precursor choice becomes crucial. This is because the film properties, growth rates, and growth temperature vary widely between the precursors. Many of the above traits can be predicted with knowledge of the precursor reaction mechanisms. This thesis aims to link surface reaction mechanisms to observed growth and nucleation trends in metal and oxide ALD systems. The first portion of this thesis explores the mechanisms of two ALD oxide systems. First, I examine the mechanism of ALD alumina with ozone. Ozone is used as an oxidant in the semiconductor industry because the deposited Al 2O3 films possess better insulating properties and ozone is easier to purge from a vacuum system. FT-IR analysis reveals a complicated array of surface intermediates such as formate, carbonate, and methoxy groups that form during Al2O3 growth with ozone. Next, a new method to deposit thin films of Ga2O3 is introduced. Gallium oxide is a transparent conducting oxide that needs expensive solid precursors to be deposited by ALD. I show that trimethylgallium is a good high-temperature ALD precursor that deposits films of Ga2O 3 with

  13. Asymmetric partitioning of metals among cluster anions and cations generated via laser ablation of mixed aluminum/Group 6 transition metal targets. (United States)

    Waller, Sarah E; Mann, Jennifer E; Jarrold, Caroline Chick


    While high-power laser ablation of metal alloys indiscriminately produces gas-phase atomic ions in proportion to the abundance of the various metals in the alloy, gas-phase ions produced by moderate-power laser ablation sources coupled with molecular beams are formed by more complicated mechanisms. A mass spectrometric study that directly compares the mass distributions of cluster anions and cations generated from laser ablation of pure aluminum, an aluminum/molybdenum mixed target, and an aluminum/tungsten mixed target is detailed. Mass spectra of anionic species generated from the mixed targets showed that both tungsten and molybdenum were in higher abundance in the negatively charged species than in the target material. Mass spectra of the cationic species showed primarily Al(+) and aluminum oxide and hydroxide cluster cations. No molybdenum- or tungsten-containing cluster cations were definitively assigned. The asymmetric distribution of aluminum and Group 6 transition metals in cation and anion cluster composition is attributed to the low ionization energy of atomic aluminum and aluminum suboxide clusters. In addition, the propensity of both molybdenum and tungsten to form metal oxide cluster anions under the same conditions that favor metallic aluminum cluster anions is attributed to differences in the optical properties of the surface oxide that is present in the metal powders used to prepare the ablation targets. Mechanisms of mixed metal oxide clusters are considered.

  14. Metal-free annulation of arenes with 2-aminopyridine derivatives: the methyl group as a traceless non-chelating directing group. (United States)

    Manna, Srimanta; Matcha, Kiran; Antonchick, Andrey P


    A novel annulation reaction between 2-aminopyridine derivatives and arenes under metal-free conditions is described. The presented intermolecular transformation provided straightforward access to the important pyrido[1,2-a]benzimidazole scaffold under mild reaction conditions. The unprecedented application of the methyl group of methylbenzenes as a traceless, non-chelating, and highly regioselective directing group is reported. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Bioaccessibility of palladium and platinum in urban aerosol particulates (United States)

    Puls, Christoph; Limbeck, Andreas; Hann, Stephan


    To evaluate potential health hazards caused by environmental Platinum Group Elements (PGEs), bioaccessibility of the metals in question needs to be assessed. To gain appropriate data, airborne particulate matter samples of different size fractions (total suspended particles as well as PM10 and PM2.5) were taken in downtown Vienna, an urban site primarily polluted by traffic. Total PGE concentrations in these samples were in the low picogram per cubic meter range, as determined by ID-ICP-MS after microwave digestion. For elimination of elements interfering with the accurate quantification, the digested samples were subjected to a cleaning procedure involving cation exchange. For determination of the bioaccessible fraction, it was assumed that inhaled particles are removed from the respiratory system by mucociliary clearance and subsequently ingested. Accordingly, the solubility of PGE in synthetic gastric juice was investigated by batch extraction of particulate matter samples followed by microwave assisted UV-digestion, cation exchange cleanup and ID-ICP-MS. The acquired data was used to calculate the bioaccessible fraction of Pd and Pt in airborne particulate matter. Average GIT-extractable fractions for Pd and Pt in TSP were 41% and 27%, in PM10 34% and 26%, respectively, thus exceeding previously determined values for bioaccessibility of PGE from ground catalyst materials by up to an order of magnitude.

  16. Characterization of Platinum Nanoparticles Deposited on Functionalized Graphene Sheets

    Directory of Open Access Journals (Sweden)

    Yu-Chun Chiang


    Full Text Available Due to its special electronic and ballistic transport properties, graphene has attracted much interest from researchers. In this study, platinum (Pt nanoparticles were deposited on oxidized graphene sheets (cG. The graphene sheets were applied to overcome the corrosion problems of carbon black at operating conditions of proton exchange membrane fuel cells. To enhance the interfacial interactions between the graphene sheets and the Pt nanoparticles, the oxygen-containing functional groups were introduced onto the surface of graphene sheets. The results showed the Pt nanoparticles were uniformly dispersed on the surface of graphene sheets with a mean Pt particle size of 2.08 nm. The Pt nanoparticles deposited on graphene sheets exhibited better crystallinity and higher oxygen resistance. The metal Pt was the predominant Pt chemical state on Pt/cG (60.4%. The results from the cyclic voltammetry analysis showed the value of the electrochemical surface area (ECSA was 88 m2/g (Pt/cG, much higher than that of Pt/C (46 m2/g. The long-term test illustrated the degradation in ECSA exhibited the order of Pt/C (33% > Pt/cG (7%. The values of the utilization efficiency were calculated to be 64% for Pt/cG and 32% for Pt/C.

  17. Selective speciation improves efficacy and lowers toxicity of platinum anticancer and vanadium antidiabetic drugs. (United States)

    Doucette, Kaitlin A; Hassell, Kelly N; Crans, Debbie C


    Improving efficacy and lowering resistance to metal-based drugs can be addressed by consideration of the coordination complex speciation and key reactions important to vanadium antidiabetic drugs or platinum anticancer drugs under biological conditions. The methods of analyses vary depending on the specific metal ion chemistry. The vanadium compounds interconvert readily, whereas the reactions of the platinum compounds are much slower and thus much easier to study. However, the vanadium species are readily differentiated due to vanadium complexes differing in color. For both vanadium and platinum systems, understanding the processes as the compounds, Lipoplatin and Satraplatin, enter cells is needed to better combat the disease; there are many cellular metabolites, which may affect processing and thus the efficacy of the drugs. Examples of two formulations of platinum compounds illustrate how changing the chemistry of the platinum will result in less toxic and better tolerated drugs. The consequence of the much lower toxicity of the drug, can be readily realized because cisplatin administration requires hospital stay whereas Lipoplatin can be done in an outpatient manner. Similarly, the properties of Satraplatin allow for development of an oral drug. These forms of platinum demonstrate that the direct consequence of more selective speciation is lower side effects and cheaper administration of the anticancer agent. Therefore we urge that as the community goes forward in development of new drugs, control of speciation chemistry will be considered as one of the key strategies in the future development of anticancer drugs.

  18. 中国部分城市铂族元素环境地球化学特征研究%Environmental Geochemical Characteristics of Platinum-group Elements in Some Major Cities of China

    Institute of Scientific and Technical Information of China (English)

    赵正; 漆亮; 黄小文; 刘莹莹; 王怡昌


    The platinum-group elements (PGEs) (mosdy, Pt, Pd and Rh) have been used as automobile catalytic converters in automobile industry to transform greenhouse gases, such as carbon monoxide, nitrogen oxides (NOχ) and hydrocarbons to carbon dioxide, nitrogen, and water since 1990. Although automobile catalytic converters can reduce the exhaust of greenhouse gases, the emission of PGEs has led to the concentration of PGE in road dusts and roadside soils in urban areas that are well above natural background levels. Reported in this paper is the evaluation of contamination of all the PGEs and Au recorded in road dusts and roadside soils from the four major cities: Beijing, Shenzhen, Guangzhou and Guiyang in China. Samples were digested with a carius tube and analyzed by isotope dilution ICP-MS, Os was separated by distillation and the other PGEs by Te-copreeipitation. PGE concentrations of all the samples have been elevated above the background values of uncontaminated soil, and higher Pt, Pd and Rh contents than the other PGEs. There are clearly positive correlations between Pt and Pd, Pt and Rh and Pd and Rh for all the samples, indicating that the compositions of automobile catalyst are Pt, Pd and Rh. The concentrations of Ir, Ru and Os in all the samples are higher than the background values of uncontaminated soil. Dust samples with higher Os contents have lower 187 Os/188. Os ratios, suggesting that Ir, Ru and Os come also from automobile catalytic converters, and may be present as impurities of the automobile catalysts.%自上世纪90年代起,汽车工业中大量引入铂族元素催化剂,将有害气体转交为二氧亿碳和氮气,以降低这些温室气体的排放.但铂族元素催亿剂释放约Pt,Pd和Rh等元素在城市道路尘主和路边土壤中聚积,其含量大大的超过正常背景值.本次研究在深圳,广州,北京和贵阳等城市的主要交通路段采集了尘土、土壤及新鲜土壤样品,采用改进的卡洛斯管法和蒸馏

  19. Synthesis and characterisation of platinum (II) salphen complex and its interaction with calf thymus DNA

    Energy Technology Data Exchange (ETDEWEB)

    Sukri, Shahratul Ain Mohd; Heng, Lee Yook; Karim, Nurul Huda Abd [School of Chemical Sciences and Food Technology, Faculty of Science and Technology, Universiti Kebangsaan Malaysia, 43650 Bangi, Selangor (Malaysia)


    A platinum (II) salphen complex was synthesised by condensation reaction of 2,4-dihydroxylbenzaldehyde and o-phenylenediamine with potassium tetrachloroplatinate to obtain N,N′-Bis-4-(hydroxysalicylidene)-phenylenediamine-platinum (II). The structure of the complex was confirmed by {sup 1}H and {sup 13}C NMR spectroscopy, FTIR spectroscopy, CHN elemental analyses and ESI-MS spectrometry. The platinum (II) salphen complex with four donor atoms N{sub 2}O{sub 2} from its salphen ligand coordinated to platinum (II) metal centre were determined. The binding mode and interaction of this complex with calf thymus DNA was determined by UV/Vis DNA titration and emission titration. The intercalation between the DNA bases by π-π stacking due to its square planar geometry and aromatic rings structures was proposed.

  20. Synthesis and characterisation of platinum (II) salphen complex and its interaction with calf thymus DNA (United States)

    Sukri, Shahratul Ain Mohd; Heng, Lee Yook; Karim, Nurul Huda Abd


    A platinum (II) salphen complex was synthesised by condensation reaction of 2,4-dihydroxylbenzaldehyde and o-phenylenediamine with potassium tetrachloroplatinate to obtain N,N'-Bis-4-(hydroxysalicylidene)-phenylenediamine-platinum (II). The structure of the complex was confirmed by 1H and 13C NMR spectroscopy, FTIR spectroscopy, CHN elemental analyses and ESI-MS spectrometry. The platinum (II) salphen complex with four donor atoms N2O2 from its salphen ligand coordinated to platinum (II) metal centre were determined. The binding mode and interaction of this complex with calf thymus DNA was determined by UV/Vis DNA titration and emission titration. The intercalation between the DNA bases by π-π stacking due to its square planar geometry and aromatic rings structures was proposed.

  1. Tungsten/Platinum Hybrid Nanowire Growth via Field Emission Using Nanorobotic Manipulation

    Directory of Open Access Journals (Sweden)

    Zhan Yang


    Full Text Available This paper reports tungsten-platinum hybrid nanowire growth via field emission, based on nanorobotic manipulation within a field emission scanning electron microscope (FESEM. A multiwalled carbon nanotube (MWCNT was used as the emitter, and a tungsten probe was used as the anode at the counterposition, by way of nanomanipulation. By independently employing trimethylcyclopentadienyl platinum (CpPtMe3 and tungsten hexacarbonyl (W(CO6 as precursors, the platinum nanowire grew on the tip of the MWCNT emitter. Tungsten nanowires then grew on the tip of the platinum nanowire. The hybrid nanowire length wascontrolled by nanomanipulation. Their purity was evaluated using energy-dispersive X-ray spectroscopy (EDS. Thus, it is possible to fabricate various metallic hybrid nanowires by changing the precursor materials. Hybrid nanowires have various applications in nanoelectronics, nanosensor devices, and nanomechanical systems.

  2. Bioinspired hierarchical nanotubular titania immobilized with platinum nanoparticles for photocatalytic hydrogen production. (United States)

    Liu, Xiaoyan; Li, Jiao; Zhang, Yiming; Huang, Jianguo


    A bioinspired nanocomposite composed of platinum nanoparticles and nanotubular titania was fabricated in which the titania matter was templated by natural cellulose substance. The composite possesses three- dimensional hierarchical structures, and ultrafine metallic platinum particles with sizes of ca. 2 nm were immobilized uniformly on the surfaces of the titania nanotubes. Such a nanocomposite with 1.06 wt % of platinum content shows the optimal photocatalytic hydrogen production activity from water splitting of 16.44 mmol h(-1)  g(-1) , and excessive loading of platinum results in poorer photocatalytic performance. The structural integrity of the nanocomposite upon cyclic water-splitting processes results in its sufficient photocatalytic stability.

  3. Synthesis and photophysical and electrochemical properties of new cyclometalated platinum complex containing oxadiazole ligand

    Institute of Scientific and Technical Information of China (English)

    DENG Ji-yong; LIU Yu; HU Zheng-yong; ZHU Mei-xiang; ZHU Wei-guo


    A new cyclometalated platinum complex containing 2, 5-bis(naphthalene-1-y1)-1,3,4-oxadiazole ligand was synthesized and characterized. The UV-Vis absorptions and photoluminescent properties of the ligand and its platinum complex were investigated.A characteristic metal-ligand charge transfer absorption peak at 439 nm in the UV spectrum and a strong emission peak at 625 nm in the photoluminescence spectrum were observed for this complex in dichloromethane. Cyclic voltammtry (CV) analysis shows that the EHOMO (energy level of the highest occupied molecular orbital) and ELUMO (energy level of the lowest unoccupied molecular orbital) of the platinum complex are about -5.69 and -3.25 eV, respectively, indicating that the oxadiazole-based platinum complex has a potential application in electrophosphorescent devices used as a red-emitting material.

  4. Bibliography of the technical literature of the Materials Joining Group, Metals and Ceramics Division, 1951 through June 1987

    Energy Technology Data Exchange (ETDEWEB)

    David, S.A.; Goodwin, G.M.; Gardner, K. (comps.)


    This document contains a listing of the written scientific information originating in the Materials Joining Group (formerly the Welding and Brazing Group), Metals and Ceramics Division, Oak Ridge National Laboratory during 1951 through June 1987. It is a registry of about 400 documents as nearly as possible in the order in which they were issued.

  5. Nanocarriers for delivery of platinum anticancer drugs☆ (United States)

    Oberoi, Hardeep S.; Nukolova, Natalia V.; Kabanov, Alexander V.; Bronich, Tatiana K.


    Platinum based anticancer drugs have revolutionized cancer chemotherapy, and continue to be in widespread clinical use especially for management of tumors of the ovary, testes, and the head and neck. However, several dose limiting toxicities associated with platinum drug use, partial anti-tumor response in most patients, development of drug resistance, tumor relapse, and many other challenges have severely limited the patient quality of life. These limitations have motivated an extensive research effort towards development of new strategies for improving platinum therapy. Nanocarrier-based delivery of platinum compounds is one such area of intense research effort beginning to provide encouraging preclinical and clinical results and may allow the development of the next generation of platinum chemotherapy. This review highlights current understanding on the pharmacology and limitations of platinum compounds in clinical use, and provides a comprehensive analysis of various platinum–polymer complexes, micelles, dendrimers, liposomes and other nanoparticles currently under investigation for delivery of platinum drugs. PMID:24113520

  6. Functionalization of metal-organic frameworks through the postsynthetic transformation of olefin side groups. (United States)

    Hindelang, Konrad; Kronast, Alexander; Vagin, Sergei I; Rieger, Bernhard


    For the first time, the adaptability of the C=C double bond as a versatile precursor for the postsynthetic modification (PSM) of microporous materials was extensively investigated and evaluated. Therefore, an olefin-tagged 4,4'-bipyridine linker was synthesized and successfully introduced as pillar linker within a 9,10-triptycenedicarboxylate (TDC) zinc paddle-wheel metal-organic framework (MOF) through microwave-assisted synthesis. Different reactions, predominately used in organic chemistry, were tested, leading to the development of new postsynthetic reactions for the functionalization of solid materials. The postsynthetic oxidation of the olefin side groups applying osmium tetroxide (OsO₄) as a catalyst led to the formation of a microporous material with free vicinal diol functionalities. The epoxidation with dimethyldioxirane (DMDO) enabled the synthesis of epoxy-functionalized MOFs. In addition to that, reaction procedures for a postsynthetic hydroboration with borane dimethyl sulfide as well as a photoinduced thiol-ene click reaction with ethyl mercaptan were developed. For all of these PSMs, yields of more than 90% were obtained, entirely maintaining the crystallinity of the MOFs. Since the direct introduction of the corresponding groups by means of pre-synthetic approaches is hardly possible, these new PSMs are useful tools for the functionalization of porous solids towards applications such as selective adsorption, separation, and catalysis.

  7. Comparison of the interactions in the rare gas hydride and Group 2 metal hydride anions. (United States)

    Harris, Joe P; Manship, Daniel R; Breckenridge, W H; Wright, Timothy G


    We study both the rare gas hydride anions, RG-H(-) (RG = He-Rn) and Group 2 (Group IIa) metal hydride anions, MIIaH(-) (MIIa = Be-Ra), calculating potential energy curves at the CCSD(T) level with augmented quadruple and quintuple basis sets, and extrapolating the results to the basis set limit. We report spectroscopic parameters obtained from these curves; additionally, we study the Be-He complex. While the RG-H(-) and Be-He species are weakly bound, we show that, as with the previously studied BeH(-) and MgH(-) species, the other MIIaH(-) species are strongly bound, despite the interactions nominally also being between two closed shell species: M(ns(2)) and H(-)(1s(2)). We gain insight into the interactions using contour plots of the electron density changes and population analyses. For both series, the calculated dissociation energy is significantly less than the ion/induced-dipole attraction term, confirming that electron repulsion is important in these species; this effect is more dramatic for the MIIaH(-) species than for RG-H(-). Our analyses lead us to conclude that the stronger interaction in the case of the MIIaH(-) species arises from sp and spd hybridization, which allows electron density on the MIIa atom to move away from the incoming H(-).

  8. The Versatile Behavior of Platinum Alkyne Complexes towards XeF2 : Formation of Fluorovinyl and Fluorido Complexes. (United States)

    Berger, Josefine; Braun, Thomas; Ahrens, Theresia; Kläring, Paul; Laubenstein, Reik; Braun-Cula, Beatrice


    Reactions of platinum(0) tolane complexes, bearing a chelating ligand with P and N donor atoms, with the electrophilic fluorinating agent XeF2 give facile access to platinum(II) β-fluorovinyl fluorido complexes. A series of new platinum(II) β-fluorovinyl complexes have been synthesized and were structurally characterized. Further oxidation with XeF2 led to ortho-metalated platinum(IV) fluorido compounds. Additional reactions of platinum(0) tolane complexes, bearing a chelating P,P donor ligand, with XeF2 led to a variety of fluorido and fluorovinyl complexes. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Bibliography of the technical literature of the Materials Joining Group, Metals and Ceramics Division, 1951--June 1989

    Energy Technology Data Exchange (ETDEWEB)

    David, S.A.; Goodwin, G.M.; Gardner, K. (comps.)


    This document contains a listing of the written scientific information originating in the Materials Joining (formerly the Welding and Brazing Group), Metals and Ceramics Division, Oak Ridge National Laboratory during 1951 through June 1989. This registry of documents is as much as possible, in the order of issue date. A complete cross-referenced listing of the technical literature of the Metals and Ceramics Division is also available.

  10. [Formylation of porphyrin platinum complexes]. (United States)

    Rumiantseva, V D; Konovalenko, L I; Nagaeva, E A; Mironov, A F


    The formylation reaction of platinum complexes of beta-unsubstituted porphyrins was studied. The interaction of deuteroporphyrin IX derivatives with the Vilsmeyer reagent led to the selective formylation of their macrocycles in the beta position. The resulting formyl derivatives of the porphyrins are of interest for fluorescent immunoassay.

  11. Hydrogen as a Modifier of the Structure and Electronic Properties of Platinum in Acidic Zeolite. LTL: A Combined Infrared and X-ray Absorption Spectroscopy Study.

    NARCIS (Netherlands)

    Koningsberger, D.C.; Vaarkamp, M.; Mojet, B.L.; Kappers, M.J.; Miller, J.T.


    The structure and electronic properties of platinum in WH-LTL after reduction at 300 'C and heating in helium to 500 or 690 'C were determined using X-ray absorption and infrared spectroscopy. After reduction at 300 'C, the platinum particles were metallic, consisted of 4 or 5 atoms, and were locate

  12. The Origin of Sulfur Tolerance in Supported Platinum Catalysts: The Relationship between Structural and Catalytic Properties in Acidic and Alkaline Pt/LTL.

    NARCIS (Netherlands)

    Koningsberger, D.C.; Miller, J.T.


    The reactivity, structure, and sulfur tolerance is compared for platinum supported on acidic and alkaline LTL zeolite. In the absence of sulfur, EXAFS spectroscopy indicates that small metallic platinum particles of approximately 6 to 14 atoms/cluster are present. The TOF for neopentane hydrogenolys

  13. Direct intermolecular force measurements between functional groups and individual metallic or semiconducting single-walled carbon nanotubes. (United States)

    Thong, Ya Xuan; Poon, Yin Fun; Chen, Tzu-Yin; Li, Lain-Jong; Chan-Park, Mary B


    Many electronic applications of single-walled carbon nanotubes (SWNTs) require electronic homogeneity in order to maximally exploit their outstanding properties. Non-covalent separation is attractive as it is scalable and results in minimal alteration of nanotube properties. However, fundamental understanding of the metallicity-dependence of functional group interactions with nanotubes is still lacking; this lack is compounded by the absence of methods to directly measure these interactions. Herein, a novel technology platform based on a recently developed atomic force microscopy (AFM) mode is reported which directly quantifies the adhesion forces between a chosen functional group and individual nanotubes of known metallicity, permitting comparisons between different metallicity. These results unambiguously show that this technology platform is able to discriminate the subtle adhesion force differences of a chosen functional group with pure metallic as opposed to pure semiconducting nanotubes. This new method provides a route towards rapid advances in understanding of non-covalent interactions of large libraries of compounds with nanotubes of varying metallicity and diameter; presenting a superior tool to assist the discovery of more effective metallicity-based SWNT separation agents.

  14. Study of Interaction Platinum Salts (Ii and Palladium (Ii on the Biologically Active Ligand

    Directory of Open Access Journals (Sweden)

    Asmat Nizami Kyzy Azizova


    Full Text Available Studied complexing ability of platinum (II and palladium (II with a time of personal gray-oxygen and sulfur-containing ligands donor nitrogens in different taniyah. A combination of functional groups. It is found that the complexation unimportant role nature of the starting metal salts, the pH of the medium, the nature of the solvent and the ratio of reactants. Determine the actual denticity tiodiuksusnoy, tiodipro propionic acid, mercaptoethanol, and bis -- hydroxyethyl sulfide. Discovered that a molecule entering the reaction of cysteamine origin walks splitting S–S communication and the resulting deproto-bined mercamine enter into complexation. In non-aqueous medium splitting S–S communication occurs.

  15. Determination of platinum traces contamination by graphite furnace atomic absorption spectrometry after preconcentration by cloud point extraction

    Energy Technology Data Exchange (ETDEWEB)

    Chappuy, M. [Analytical Development Laboratory, Pharmaceutical Establishment of Paris Hospitals, 7 rue du Fer a Moulin, 75005 Paris (France); Caudron, E., E-mail: [Analytical Development Laboratory, Pharmaceutical Establishment of Paris Hospitals, 7 rue du Fer a Moulin, 75005 Paris (France); Groupe de Chimie Analytique de Paris-Sud, EA 4041, IFR 141, School of Pharmacy, Univ Paris-Sud, 92296 Chatenay-Malabry (France); Bellanger, A. [Department of Pharmacy, Pitie-Salpetriere Hospital (Paris Public Hospital Authority), 47 boulevard de l' hopital, 75013 Paris (France); Pradeau, D. [Analytical Development Laboratory, Pharmaceutical Establishment of Paris Hospitals, 7 rue du Fer a Moulin, 75005 Paris (France)


    A simple and sensitive method is described for the determination of platinum surface contamination originating from cisplatin, carboplatin and oxaliplatin. Following extraction from swabs and preconcentration with the cloud point extraction (CPE) method, detection was by graphite furnace atomic absorption spectrometry (GFAAS). After desorption of platinum compounds from the swab, CPE involved on preconcentration of platinum in aqueous solution with diethyldithiocarbamate (DDTC) as chelating agent and Triton X-114 as extraction medium. DDTC is not only a chelating agent, but may also be a good candidate for the inactivation of platinum compounds. DDTC is recommended by the Word Health Organization (WHO) for the destruction of platinum-based anticancer drugs. The main factors affecting CPE efficiency, pH of the sample solution, concentrations of DDTC and Triton X-114, equilibration temperature and incubation time, were evaluated in order to enhance sensitivity of the method. The desorption of platinum compounds from the swab was investigated in parallel. Since platinum is bound to DDTC, it must exchange with copper in order to enhance platinum atomizing by GFAAS. A preconcentration factor of 29 was obtained for 10 mL of a platinum solution at 10 {mu}g mL{sup -1}. In optimal conditions, the limit of detection was 0.2 ng mL{sup -1}, corresponding to 2.0 ng of platinum metal on the swab. Absorbance was linear between 0.7 and 15 ng mL{sup -1}. The proposed method was applied for the determination of surface contamination by platinum compounds with correct results.

  16. A new platinum complex with tryptophan: synthesis, structural characterization, DFT studies and biological assays in vitro over human tumorigenic cells. (United States)

    Carvalho, Marcos A; Shishido, Silvia M; Souza, Bárbara C; de Paiva, Raphael E F; Gomes, Alexandre F; Gozzo, Fábio C; Formiga, André L B; Corbi, Pedro P


    A new platinum(II) complex with the amino acid L-tryptophan (trp), named Pt-trp, was synthesized and characterized. Elemental, thermogravimetric and ESI-QTOF mass spectrometric analyses led to the composition [Pt(C11H11N2O2)2]⋅6H2O. Infrared spectroscopic data indicate the coordination of trp to Pt(II) through the oxygen of the carboxylate group and also through the nitrogen atom of the amino group. The (13)C CP/MAS NMR spectroscopic data confirm coordination through the oxygen atom of the carboxylate group, while the (15)N CP/MAS NMR data confirm coordination of the nitrogen of the NH2 group to the metal. Density functional theory (DFT) studies were applied to evaluate the cis and trans coordination modes of trp to platinum(II). The trans isomer was shown to be energetically more stable than the cis one. The Pt-trp complex was evaluated as a cytotoxic agent against SK-Mel 103 (human melanoma) and Panc-1 (human pancreatic carcinoma) cell lines. The complex was shown to be cytotoxic over the considered cells.

  17. Surface oxide growth on platinum electrode in aqueous trifluoromethanesulfonic acid (United States)

    Furuya, Yoshihisa; Mashio, Tetsuya; Ohma, Atsushi; Dale, Nilesh; Oshihara, Kenzo; Jerkiewicz, Gregory


    Platinum in the form of nanoparticles is the key and most expensive component of polymer electrolyte membrane fuel cells, while trifluoromethanesulfonic acid (CF3SO3H) is the smallest fluorinated sulfonic acid. Nafion, which acts as both electrolyte and separator in fuel cells, contains -CF2SO3H groups. Consequently, research on the electrochemical behaviour of Pt in aqueous CF3SO3H solutions creates important background knowledge that can benefit fuel cell development. In this contribution, Pt electro-oxidation is studied in 0.1 M aqueous CF3SO3H as a function of the polarization potential (Ep, 1.10 ≤ Ep ≤ 1.50 V), polarization time (tp, 100 ≤ tp ≤ 104 s), and temperature (T, 278 ≤ T ≤ 333 K). The critical thicknesses (X1), which determines the applicability of oxide growth theories, is determined and related to the oxide thickness (dox). Because X1 > dox for the entire range of Ep, tp, and T values, the formation of Pt surface oxide follows the interfacial place-exchange or the metal cation escape mechanism. The mechanism of Pt electro-oxidation is revised and expanded by taking into account possible interactions of cations, anions, and water molecules with Pt. A modified kinetic equation for the interfacial place exchange is proposed. The application of the interfacial place-exchange and metal cation escape mechanisms leads to an estimation of the Ptδ+-Oδ- surface dipole (μPtO), and the potential drop (Vox) and electric field (Eox) within the oxide. The Pt-anion interactions affect the oxidation kinetics by indirectly influencing the electric field within the double layer and the surface oxide.

  18. No Evidence of Genotoxic Damage in a Group of Patients with Titanium Dental Implants and Different Metal Restorations in the Oral Cavity. (United States)

    Camacho-Alonso, Fabio; Sánchez-Siles, Mariano; Gilbel-del Águila, Osmundo


    Titanium is the most widely used metal in implant dentistry. In spite of its biocompatibility, when it is released into the oral environment, it can have local negative biological effects. The aims of this study were to detect the concentration of metal ions in patients with dental implants, to evaluate whether or not their release might be influenced by the presence of other metals, and to assay whether these ions might provoke genotoxic damage in oral mucosa cells. One hundred five patients with a total of 180 dental implants were included. The sample was divided into seven groups (n = 15 per group). Group 1 consisted of patients with metal-porcelain fixed crowns on dental implants; Group 2, patients with metal-porcelain fixed crowns on teeth; Group 3, patients with dental amalgams; Group 4, patients with metal-porcelain fixed crowns on dental implants and metal-porcelain fixed crowns on teeth; Group 5, patients with metal-porcelain fixed crowns on dental implants and dental amalgams; and Group 6, patients with metal-porcelain fixed crowns on dental implants, metal-porcelain fixed crowns on teeth, and dental amalgams. Group 7 was the control group, without any dental treatment. The concentration of metal ions was detected using inductively coupled plasma mass spectrometry; genotoxicity was measured using the buccal micronucleus cytome assay protocol. Group 5 displayed the highest concentration of metal ions in parts per billion (Ti, Co, Ni, Zn, Pd, Sn, and Pb). Group 6 was characterized by the highest presence of Hg. No signs of genotoxic damage were found in any of the study groups. Patients with titanium dental implants combined with other metal restorations presented higher concentrations of metal ions, but no genotoxic damage was observed in oral mucosal epithelial cells. © 2013 Wiley Periodicals, Inc.

  19. Novel dinuclear platinum(II) complexes containing mixed nitrogen-sulfur donor ligands. (United States)

    Hochreuther, Stephanie; Puchta, Ralph; van Eldik, Rudi


    A series of novel dinuclear platinum(II) complexes were synthesized containing a mixed nitrogen-sulfur donor bidentate chelate system in which the two platinum centers are connected by an aliphatic chain of variable length. The bidentate chelating ligands were selected to stabilize the complex toward decomposition. The pK(a) values and reactivity of the four synthesized complexes, namely, [Pt(2)(S(1),S(4)-bis(2-pyridylmethyl)-1,4-butanedithioether)(OH(2))(4)](4+) (4NSpy), [Pt(2)(S(1),S(6)-bis(2-pyridylmethyl)-1,6-hexanedithioether)(OH(2))(4)](4+) (6NSpy), [Pt(2)(S(1),S(8)-bis(2-pyridylmethyl)-1,8-octanedithioether)(OH(2))(4)](4+) (8NSpy), and [Pt(2)(S(1),S(10)-bis(2-pyridylmethyl)-1,10-decanedithioether)(OH(2))(4)](4+) (10NSpy), were investigated. This system is of special interest because only little is known about the substitution behavior of dinuclear platinum complexes that contain a bidentate chelate that forms part of the aliphatic bridging ligand. Moreover, the ligands as well as the dinuclear complexes were examined in terms of their cytotoxic activity, and the 10NSpy complex was found to be active. Spectrophotometric acid-base titrations were performed to determine the pK(a) values of all the coordinated water molecules. The substitution of coordinated water by thiourea was studied under pseudo-first-order conditions as a function of nucleophile concentration, temperature, and pressure, using stopped-flow techniques and UV-vis spectroscopy. The results for the dinuclear complexes were compared to those for the corresponding mononuclear reference complex [Pt(methylthiomethylpyridine)(OH(2))(2)](2+) (Pt(mtp)), by which the effect of the increasing aliphatic chain length of the bridged complexes could be investigated. The results indicate that there is a clear interaction between the two platinum centers, which becomes weaker as the chain length between the metal centers increases. Furthermore, differences and similarities of the N,S-system were compared to

  20. Synthesising carbo-nitrides of some d-group transition metals using a solar furnace at PSA


    Shohoji, Nobumitsu; Oliveira, F. A. Costa; Rosa, Luís Guerra; Fernandes, Jorge Cruz; Magalhães, Teresa; Coelho, Manuel Caldeira; Rodriguez,José; Canadas, Inmaculada; Ramos, Carlos; Martinez, Diego


    Carbo-nitride synthesis was undertaken using a solar furnace at PSA in flowing N2/Ar gas mixture under total pressure 1 atm and processing temperature T = 1600ºC for some d-group transition elements (Ti; Zr, V, Nb, Mo, W) starting from 1.5G/M (graphite/metal powder mixture with mole ratio 1.5:1) compact to ensure co-presence of free carbon with the reaction product. Clear X-ray diffraction (XRD) evidence of formation of carbo-nitride was detected for Ti (IVa group metal) showing higher N cont...

  1. Alkali Metal Cation Affinities of Anionic Main Group-Element Hydrides Across the Periodic Table. (United States)

    Boughlala, Zakaria; Fonseca Guerra, Célia; Bickelhaupt, F Matthias


    We have carried out an extensive exploration of gas-phase alkali metal cation affinities (AMCA) of archetypal anionic bases across the periodic system using relativistic density functional theory at ZORA-BP86/QZ4P//ZORA-BP86/TZ2P. AMCA values of all bases were computed for the lithium, sodium, potassium, rubidium and cesium cations and compared with the corresponding proton affinities (PA). One purpose of this work is to provide an intrinsically consistent set of values of the 298 K AMCAs of all anionic (XHn-1(-) ) constituted by main group-element hydrides of groups 14-17 along the periods 2-6. In particular, we wish to establish the trend in affinity for a cation as the latter varies from proton to, and along, the alkali cations. Our main purpose is to understand these trends in terms of the underlying bonding mechanism using Kohn-Sham molecular orbital theory together with a quantitative bond energy decomposition analyses (EDA). © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Iron-Group Abundances in the Metal-Poor Main Sequence Turnoff Star HD~84937

    CERN Document Server

    Sneden, Christopher; Kobayashi, Chiaki; Pignatari, Marco; Lawler, James E; Hartog, Elizabeth A Den; Wood, Michael P


    We have derived new very accurate abundances of the Fe-group elements Sc through Zn (Z = 21-30) in the bright main-sequence turnoff star HD 84937, based on high-resolution spectra covering the visible and ultraviolet spectral regions. New or recent laboratory transition data for 14 species of seven elements have been used. Abundances from more than 600 lines of non-Fe species have been combined with about 550 Fe lines in HD 84937 to yield abundance ratios of high precision. The abundances have been determined from both neutral and ionized transitions, which generally are in agreement with each other. We find no substantial departures from standard LTE Saha ionization balance in this [Fe/H] = -2.32 star. Noteworthy among the abundances are: [Co/Fe] = 0.14 and [Cu/Fe] = -0.83, in agreement with past studies abundance trends in this and other low metallicity stars; and = 0.31, which has not been noted previously. A detailed examination of scandium, titanium, and vanadium abundances in large-sample spectroscopic...

  3. Facile preparation of mono-, di- and mixed-carboxylato platinum(IV) complexes for versatile anticancer prodrug design. (United States)

    Zhang, Jenny Z; Bonnitcha, Paul; Wexselblatt, Ezequiel; Klein, Alice V; Najajreh, Yousef; Gibson, Dan; Hambley, Trevor W


    Facile strategies were developed for the versatile functionalization of platinum(IV) axial sites, allowing for easy accessibility to unsymmetric mono- and mixed-carboxylato, as well as symmetric di-substituted platinum(IV) complexes. The first method involves the direct oxidation and carboxylation of the platinum(II) center using an appropriate peroxide and the carboxylate of choice to firstly yield a monocarboxylato monohydroxido platinum(IV) complex. This platinum(IV) intermediate can undergo further carboxylation to give rise to a mixed-carboxylato platinum(IV) complex. The second method involves the activation of the carboxylate of choice by a common carbodiimide coupling reagent, and its reaction with a dihydroxido platinum(IV) precursor to give the monocarboxylato platinum(IV) complex. Uronium salts can be employed to promote efficient dicarboxylation of the dihydroxido platinum(IV) precursor. Lastly, an axial azide pendant group was demonstrated to be suitable for orthogonal "click" conjugation reactions. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. The Utilization of Amide Groups To Expand and Functionalize Metal-Organic Frameworks Simultaneously. (United States)

    Lu, Zhiyong; Bai, Junfeng; Hang, Cheng; Meng, Fei; Liu, Wenlong; Pan, Yi; You, Xiaozeng


    A new stepwise ligand-elongation strategy by amide spacers is utilized to prepare isoreticularly high-porous metal-organic frameworks (MOFs), namely, quasi-mesoporous [Cu2 (PDBAD)(H2 O)]n (H4 PDBAD=5,5'-((4,4'-((pyridine-3,5-dicarbonyl)bis(azanediyl))bis(benzoyl))bis(azanediyl))diisophthalic acid; NJU-Bai22: NJU-Bai for Nanjing University Bai's group), and mesoporous [Cu2 (PABAD)(H2 O)]n (H4 PABAD=5,5'-((4,4'-((4,4'-((pyridine-3,5-dicarbonyl)bis(azanediyl))bis(benzoyl))bis (azanediyl))bis(benzoyl))bis(azanediyl))diisophthalic acid; NJU-Bai23). Compared with the prototypical MOF of [Cu2 (PDAD)(H2 O)]n (H4 PDAD=5,5'-(pyridine-3,5-dicarbonyl)bis(azanediyl)diisophthalic acid; NJU-Bai21, also termed as PCN-124), both MOFs exhibit almost the same CO2 adsorption enthalpy and CO2 selectivity values, and better capacity for CO2 storage under high pressure; these results make them promising candidate materials for CO2 capture and sequestration. Interestingly, this new method, in comparison with traditional strategies of using phenyl or triple-bond spacers, is easier and cheaper, resulting in a better ability to retain high CO2 affinity and selectivity in MOFs with large pores and high CO2 storage capacity. Additionally, it may lead to the high thermal stability of the MOFs and also their tolerance to water, which is related to the balance between the density of functional groups and pore sizes. Therefore, this strategy could provide new opportunities to explore more functionalized mesoporous MOFs with high performance. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Modification of platinum surfaces by spontaneous deposition: Methanol oxidation electrocatalysis

    Energy Technology Data Exchange (ETDEWEB)

    MacDonald, J.P.; Gualtieri, B.; Runga, N.; Teliz, E.; Zinola, C.F. [Fundamental Electrochemistry Laboratory, School of Sciences, Universidad de la Republica, Igua Street No. 4225, CP 11400, Montevideo (Uruguay)


    The presence of a second metal on platinum surfaces affects the performance of methanol oxidation. However, most of the electrocatalytic reactions are studied by using electrochemically deposited platinum alloys, but in the case of spontaneous deposition the situation is not so clear since the surface distribution, stability and morphology are usually not well documented. The formation of surface decorated samples on mono- and poly-crystalline platinum is followed by electrochemical and spectroscopic techniques and analysis of their performance towards methanol adsorption and oxidation compared with that on pure platinum. Pt/Sn and Pt/Ru are of special interest because of their well-known performance in methanol fuel cells. Methanol oxidation on Pt(111)/Ru, Pt(111)/Sn and Pt(111) shows that ruthenium is the only one able to promote the reaction since the simultaneous dissolution of tin occurs and competes with the process of interest. The in situ infrared spectroscopy is used to compare methanol oxidation on Pt(111)/Ru and Pt(111) in acid media using p-polarized light. The formation of bridge bound carbon monoxide is inhibited in the presence of ruthenium ad-species, whereas on Pt(111) the three adsorption configurations are observed. Linear sweep polarization curves and Tafel slopes (calculated from steady state potentiostatic plots) for methanol oxidation are compared on polycrystalline surfaces modified by tin or ruthenium at different coverages. There is almost no change in the Tafel slopes due to the presence of the foreign metal except for Pt/Ru, where a 0.09 V decade{sup -1} slope was calculated below 0.55 V due to hydroxyl adsorbates on ruthenium islands. The anodic stripping of methanol residues on the three surfaces indicates a lower amount of carbon monoxide-type adsorbates on Pt/Ru, and the simultaneous tin dissolution process leading to residues oxidation on Pt/Sn electrodes. (author)

  6. Platinum(II), palladium(II), rhodium(III) and lead(II) voltammetric determination in sites differently influenced by vehicle traffic. (United States)

    Melucci, Dora; Locatelli, Clinio


    The present work reports analytical results relevant to voltammetric determination of Pt(II), Pd(II), Rh(III) [Platinum Group Metals (PGMs)] and Pb(II) in superficial water sampled in sites differently influenced by vehicle traffic, especially considering their temporal behaviour. For all the elements, in addition to detection limits, precision, expressed as relative standard deviation (s(r) %) and accuracy, expressed as percentage recovery (R %) are also reported. In all cases they show to be good, being the former lower than 6% and the latter in the range 94-105%. A critical comparison with spectroscopic measurements is also discussed.

  7. Defect-Induced Optoelectronic Response in Single-layer Group-VI Transition-Metal Dichalcogenides (United States)

    Chow, Philippe K.

    The ever-evolving symbiosis between mankind and nanoelectronics-driven technology pushes the limits of its constituent materials, largely due to the dominance of undesirable hetero-interfacial physiochemical behavior at the few-nanometer length scale, which dominates over bulk material characteristics. Driven by such instabilities, research into two-dimensional (2D) van der Waals-layered materials (e.g. graphene, transition metal dichalcogenides (TMDCs), boron nitride), which have characteristically inert surface chemistry, has virtually exploded over the past few years. The discovery of an indirect- to direct-gap conversion in semiconducting group-VI TMDCs (e.g. MoS2) upon thinning to a single atomic layer provided the critical link between metallic and insulating 2D materials. While proof-of-concept demonstrations of single-layer TMDC-based devices for visible-range photodetection, light-emission and solar energy conversion have showed promising results, the exciting qualities are downplayed by poorly-understood defectinduced photocarrier traps, limiting the best-achieved external quantum efficiencies to approximately ~1%. This thesis explores the behavior of defects in atomically-thin TMDC layers in response to optical stimuli using a combination of steady-state photoluminescence, reflectance and Raman spectroscopy at room-temperature. By systematically varying the defect density using plasma-irradiation techniques, an unprecedented room-temperature defect-induced monolayer PL feature was discovered. High-resolution transmission electron microscopy correlated the defect-induced PL with plasma-generation of sulfur vacancy defects while reflectance measurements indicate defect-induced sub-bandgap light absorption. Excitation intensity-dependent PL measurements and exciton rate modeling further help elucidate the origin of the defect-induced PL response and highlights the role of non-radiative recombination on exciton conversion processes. The results in this

  8. Cosmetic comparison of gold weight and platinum chain insertion in primary upper eyelid loading for lagophthalmos. (United States)

    Bladen, John C; Norris, Jonathan H; Malhotra, Raman


    Platinum chains are thinner than gold weights (GWs) and may confer a better eyelid curvature profile with reduced visibility. Outcomes compared eyelid measurements, cosmesis, and complications. Forty-two primary GW and 17 primary platinum chain insertions were identified and subsequently matched for laterality, pathology, and weight of implant. Twenty-two patients were randomly allocated into 2 groups for comparison; those receiving a GW (n = 11) or platinum chain (n = 11) to formulate a retrospective case-controlled study. Primary upper eyelid loading surgery with both implants involved a standard technique of a high tarsal placement with levator recession. Blinded assessment of preoperative and 6-month postoperative photographs calculated eyelid parameters: upper marginal reflex distance and lagophthalmos. Standardized photographs were used to define cosmesis in terms of abnormal eyelid contour and prominence. Gold weights demonstrated an improvement in eyelid parameters. Nine eyelids had prominent implants: mild (2), moderate (3), and severe (4). Eyelid contour was affected in 7 patients, 5 with droop, and 2 with flattened contour. Platinum chain improved eyelid measurements. Mild eyelid prominence was noted in 2 cases, but eyelid contour remained normal in all patients. No complications were noted with either the GW or the platinum chain implants. Both devices are successful in treating complications of lagophthalmos. Platinum chains appear less prominent and maintain normal eyelid contour. Although more expensive, platinum chains appear to be as safe and effective as GWs yet provide better cosmesis.

  9. [Search of heavy metals biosorbents among yeasts of different taxonomic groups]. (United States)

    Lozovaia, O G; Kasatkina, T P; Podgorskiĭ, V S


    The use of microbial cells as heavy metal biosorbents is a potential alternative for the existing methods of the environment treatment for pollution by these metals. Yeast may be successfully used in the metals sorption. An agar-plate screening method was used for rapid isolation of metal-accumulating strains of yeast and preliminary estimation of their biosorption capacity. The capacity to accumulate heavy metals, such as copper, zinc, lead, chrome and cobalt was estimated in 68 pigmented and pigmentless yeast strains isolated from different sources. The best capacity of copper and zinc accumulation was shown by pink-coloured Rhodotorula mucilaginosa, Rhodotorula aurantiaca, Rhodotorula glutinis and pigmentless strains of the yeast Candida krusei, Williopsis california.

  10. Conducting metal dithiolate complexes

    DEFF Research Database (Denmark)

    Underhill, A. E.; Ahmad, M. M.; Turner, D. J.;


    Further work on the chemical composition of the one-dimensional metallic metal dithiolene complex Li-Pt(mnt) is reported. The electrical conduction and thermopower properties of the nickel and palladium complexes are reported and compared with those of the platinum compound...

  11. Production of Platinum Atom Nanoclusters at One End of Helical Plant Viruses

    Directory of Open Access Journals (Sweden)

    Yuri Drygin


    Full Text Available Platinum atom clusters (Pt nanoparticles, Pt-NPs were produced selectively at one end of helical plant viruses, tobacco mosaic virus (TMV and potato virus X (PVX, when platinum coordinate compounds were reduced chemically by borohydrides. Size of the platinum NPs depends on conditions of the electroless deposition of platinum atoms on the virus. Results suggest that the Pt-NPs are bound concurrently to the terminal protein subunits and the 5′ end of encapsidated TMV RNA. Thus, a special structure of tobacco mosaic virus and potato X virus particles with nanoparticles of platinum, which looks like a push-pin with platinum head and virus needle, was obtained. Similar results were obtained with ultrasonically fragmented TMV particles. By contrast, the Pt-NPs fully filled the central axial hole of in vitro assembled RNA-free TMV-like particles. We believe that the results presented here will be valuable in the fundamental understanding of interaction of viral platforms with ionic metals and in a mechanism of nanoparticles formation.

  12. Cubic nitrides of the sixth group of transition metals formed by nitrogen ion irradiation during metal condensation

    Energy Technology Data Exchange (ETDEWEB)

    Ensinger, W. [Augsburg Univ. (Germany). Inst. fuer Physik; Kiuchi, M. [Osaka National Research Institute, Midorigaoka 1-8-31, Ikeda, Osaka 563 (Japan)


    Nitrogen-containing phases of chromium, molybdenum and tungsten were formed by evaporation of the metal under simultaneous nitrogen ion irradiation. With gradually increasing ion irradiation intensity, chromium forms initially Cr and Cr{sub 2}N phase mixtures, then additionally CrN appears, and at the highest intensities pure CrN films are formed. Molybdenum also forms pure nitride MoN under intense ion bombardment. However, in this case two different crystal structures are found, the stable hexagonal phase and the metastable cubic high-temperature phase. The latter is favoured under intense ion irradiation. In the case of tungsten, even at the highest intensities, only phase mixtures of W and W{sub 2}N were formed. These observed differences can be explained by the low reactivity of these metals towards nitrogen and the low chemical stability of the nitrides, particularly of WN. The metastable high-temperature structure of MoN is formed under the particular conditions of ion bombardment with rapid energy dissipation. (orig.)

  13. Surface characterization of platinum electrodes. (United States)

    Solla-Gullón, José; Rodríguez, Paramaconi; Herrero, Enrique; Aldaz, Antonio; Feliu, Juan M


    The quantitative analysis of the different surface sites on platinum samples is attempted from pure voltammetric data. This analysis requires independent knowledge of the fraction of two-dimensional (111) and (100) domains. Specific site-probe reactions are employed to achieve this goal. Irreversibly-adsorbed bismuth and tellurium have been revealed to be sensitive to the presence of (111) terrace domains of different width whereas almost all sites involved in (100) ordered domains have been characterized through germanium adatoms. The experimental protocol follows that used with well-defined single-crystal electrodes and, therefore, requires careful control of the surface cleanliness. Platinum basal planes and their vicinal stepped surfaces have been employed to obtain calibration plots between the charge density measured under the adatom redox peak, specific for the type of surface site, and the corresponding terrace size. The evaluation of the (100) bidimensional domains can also be achieved using the voltammetric profiles, once the fraction of (111) ordered domains present in the polyoriented platinum has been determined and their featureless contribution has been subtracted from the whole voltammetric response. Using that curve, it is possible to perform a deconvolution of the adsorption states of the polycrystalline sample different from those related to (111) domains. The fraction of (100)-related states in the deconvoluted voltammogram can then be compared to that expected from the independent estimation coming from the charge involved in the redox process undergone by the irreversibly-adsorbed germanium and thus check the result of the deconvolution. The information about the surface-site distribution can also be applied to analyze the voltammetric profile of nanocrystalline platinum electrodes.

  14. Modifications of chemical functional groups of Pandanus amaryllifolius Roxb and its effect towards biosorption of heavy metals (United States)

    Abdullah, Mohd. Zamri; Ismail, Siti Salwa


    The utilization of non-living biomass as an alternative biosorbent for heavy metal removal has gain a tremendous consideration through the years. Pandanus amaryllifolius Roxb or pandan leaves, which is widely used as food additives in the South East Asia region, has been selected for its viability in the said effort due to the presence of chemical functional groups on its cellular network that enables the sorption to occur. In order to elucidate the possible mechanisms participated during the heavy metal removal process, the biosorbent undergone a series of modification techniques to alter the chemical functional groups present on its constituent. From the outcome of the chemically-modified biosorbent being subjected to the contact with metal cations, nitrogen- and oxygen-containing groups present on the biosorbent are believed to be responsible for the metal uptake to occur through complexation mechanism. Modifying amine groups causes 14% reduction of Cu(II) uptake, whereas removing protein element increases the uptake to 26% as compared to the unmodified biosorbent. Also, scanning electron micrographs further suggested that the adsorption mechanism could perform in parallel, as attributed to the evidence of porous structure throughout the biosorbent fibrous nature.

  15. Modifications of chemical functional groups of Pandanus amaryllifolius Roxb and its effect towards biosorption of heavy metals

    Energy Technology Data Exchange (ETDEWEB)

    Abdullah, Mohd Zamri, E-mail:; Ismail, Siti Salwa [Chemical Engineering Department, Universiti Teknologi PETRONAS, 31750 Bandar Seri Iskandar, Perak (Malaysia)


    The utilization of non-living biomass as an alternative biosorbent for heavy metal removal has gain a tremendous consideration through the years. Pandanus amaryllifolius Roxb or pandan leaves, which is widely used as food additives in the South East Asia region, has been selected for its viability in the said effort due to the presence of chemical functional groups on its cellular network that enables the sorption to occur. In order to elucidate the possible mechanisms participated during the heavy metal removal process, the biosorbent undergone a series of modification techniques to alter the chemical functional groups present on its constituent. From the outcome of the chemically-modified biosorbent being subjected to the contact with metal cations, nitrogen- and oxygen-containing groups present on the biosorbent are believed to be responsible for the metal uptake to occur through complexation mechanism. Modifying amine groups causes 14% reduction of Cu(II) uptake, whereas removing protein element increases the uptake to 26% as compared to the unmodified biosorbent. Also, scanning electron micrographs further suggested that the adsorption mechanism could perform in parallel, as attributed to the evidence of porous structure throughout the biosorbent fibrous nature.

  16. Mining Critical Metals and Elements from Seawater: Opportunities and Challenges. (United States)

    Diallo, Mamadou S; Kotte, Madhusudhana Rao; Cho, Manki


    The availability and sustainable supply of technology metals and valuable elements is critical to the global economy. There is a growing realization that the development and deployment of the clean energy technologies and sustainable products and manufacturing industries of the 21st century will require large amounts of critical metals and valuable elements including rare-earth elements (REEs), platinum group metals (PGMs), lithium, copper, cobalt, silver, and gold. Advances in industrial ecology, water purification, and resource recovery have established that seawater is an important and largely untapped source of technology metals and valuable elements. This feature article discusses the opportunities and challenges of mining critical metals and elements from seawater. We highlight recent advances and provide an outlook of the future of metal mining and resource recovery from seawater.

  17. Platinum catalysts recovery of the proton exchange membrane fuel cell; Recuperacao de catalisadores de platina da celula a combustibel de membrana polimerica trocadora de protons

    Energy Technology Data Exchange (ETDEWEB)

    Fukurozaki, S.H.; Seo, E.S.M. [Instituto de Pesquisas Energeticas e Nucleares (IPEN/CNEN-SP), Sao Paulo, SP (Brazil). Centro de Ciencia e Tecnologia de Materiais. Lab. de Processamento de Residuos


    Currently, platinum is the most feasible catalyst for the Proton Exchange Membrane Fuel Cells - PEMFC. Along with platinum's significant importance in this energy system are the high cost of this noble metal and its detrimental effects on the environment. Therefore, recycling this material seems as an alternative to decrease its impacts on the environment and, at the same time, to provide a reduction of the system's costs. A search was conducted for literature and studies about platinum recycling methods. However, only two techniques of platinum recovery, which are still in development, were found. In face of this situation, a recovery method of platinum from deactivated Membrane Electrode Assembly - MEA's was developed, with attention to aspects related to the environment and the necessary requirements for its primary recycling. The results found showed a high recovery ratio and a possibility to reintroduce this metal into the production cycle. (author)

  18. Electrochemical behaviour of platinum at polymer-modified glassy carbon electrodes

    Indian Academy of Sciences (India)

    Carmem L P S Zanta; C A Martínez-Huitle


    In this paper, the preparations and voltammetric characteristics of chitosan-modified glassy carbon (Ct-MGC) and platinum electrodes are studied. Ct-MGC can be used for pre-concentration and quantification of trace amounts of platinum in solution. At low pH medium, the complex of Pt with protonated group -NH3+ in the chitosan molecule has been confirmed by FT-IR spectra studies.

  19. Characterization of TiO[sub 2] films modified by platinum doping

    Energy Technology Data Exchange (ETDEWEB)

    Avalle, L.; Santos, E.; Leiva, E.; Macagno, V.A. (Dept. de Fisicoquimica, Univ. Nacional de Cordoba, INFIQC (Argentina))


    TiO[sub 2]-Pt films were prepared through galvanostatic platinum deposition from acidic H[sub 2]PtCl[sub 6] solutions, followed by potentiodynamic TiO[sub 2] growth in Na[sub 2]SO[sub 4] solutions. The characterization of the doped films was carried out by means of Auger electron spectroscopy and X-ray photoelectron spectroscopy (XPS) in combination with argon bombardment. The dopant concentration profiles and the valence states of the elements present within the films were also determined. The predominant species present is metallic platinum, although oxidized species probably make some contributions. Titanium changed from TiO[sub 2] to lower oxidation states in going from the surface to the film depth. XPS indicates the presence of hydrated oxides at the surface. Scanning electron microscopy (SEM) analyses indicate that platinum deposition occurs preferentially on grain boundaries. At high platinum content, clusters are evident and the substructure of titanium substrate is reproduced. At low platinum content, SEM cannot detect its presence at the surface in spite of the electrochemical evidence. The electrochemical behaviour of modified oxide films was also analysed. The potentiodynamic response correlates with the response of a polycrystalline platinum electrode. Electron transfer reactions reveal a catalytic effect due to the platinum incorporated into the TiO[sub 2] layer. The oxygen evolution reaction was investigated using impedance as a function of both the platinum content and the thickness of the TiO[sub 2] layer. Finally, an approximate physical model for the system is proposed.

  20. Influence of Dose on Particle Size and Optical Properties of Colloidal Platinum Nanoparticles

    Directory of Open Access Journals (Sweden)

    Elias Saion


    Full Text Available Attempts to produce colloidal platinum nanoparticles by using steady absorption spectra with various chemical-based reduction methods often resulted in the fast disappearance of the absorption maxima leaving reduced platinum nanoparticles with little information on their optical properties. We synthesized colloidal platinum nanoparticles in an aqueous solution of polyvinyl pyrrolidone by gamma radiolytic reduction method, which produced steady absorption spectra of fully reduced and highly pure platinum nanoparticles free from by-product impurities or reducing agent contamination. The average particle size was found to be in the range of 3.4–5.3 nm and decreased with increasing dose due to the domination of nucleation over ion association in the formation of metal nanoparticles by the gamma radiolytic reduction method. The platinum nanoparticles exhibit optical absorption spectra with two absorption peaks centered at about 216 and 264 nm and the peaks blue shifted to lower wavelengths with decreasing particle size. The absorption spectra of platinum nanoparticles were also calculated using quantum mechanical treatment and coincidently a good agreement was obtained between the calculated and measured absorption peaks at various particle sizes. This indicates that the 216 and 264-nm absorption peaks of platinum nanoparticles conceivably originated from the intra-band transitions of conduction electrons of (n = 5, l = 2 and (n = 6, l = 0 energy states respectively to higher energy states. The absorption energies, i.e., conduction band energies of platinum nanoparticles derived from the absorption peaks increased with increasing dose and decreased with increasing particle size.

  1. Recent Progress on the Photonic Properties of Conjugated Organometallic Polymers Built Upon the trans-Bis(para-ethynylbenzene)bis(phosphine)platinum(II) Chromophore and Related Derivatives. (United States)

    Wong, Wai-Yeung; Harvey, Pierre D


    This review article surveys the electronic and photophysical properties of conjugated organometallic polymers built upon the title compound and its related derivatives focussing primarily on systems investigated in our laboratories. The general structure of the polymers is (trans-bis(para-ethynylbenzene)bis(phosphine)platinum(II)-G)(n) where G is a conjugated group such as thiophene, fluorene, carbazole, substituted silole, quinone derivative, and metalloporphyrin residue, or a non-conjugated main-group moiety. Systems based on substituted phenylene units and other related fused rings are also discussed. The phosphine ligands are generally triethyl- or tri-n-butylphosphine groups. These trans-platinum(II) polymers and the corresponding model compounds are compared to the corresponding ortho-derivatives in the quinone series, and the newly prepared paracyclophane-containing polymers. For the porphyrin series, a comparison of fully conjugated oligomers exhibiting the general structure (trans-bis(para-ethynyl(zinc(porphyrin)))bis(phosphine)platinum(II))(n) (i.e., the C(6) H(4) group is absent from the main chain) will be made. This contribution also includes a description of the properties of the mononuclear chromophore itself, properties that define those of the polymers. Potential applications with regard to electronic and optical devices will be highlighted. These soluble and stable materials feature both the processing advantages of polymers and the functionality provided by the presence of metal centers. These multifunctional organometallic polyyne polymers exhibit convenient structural variability as well as optical and electronic properties, which renders them important for use in different research domains as chemical sensors and sensor protectors, as converters for light/electricity signals, and as patternable precursors to magnetic metal alloy nanoparticles.

  2. Phosphoric acid fuel cell platinum use study (United States)

    Lundblad, H. L.


    The U.S. Department of Energy is promoting the private development of phosphoric acid fuel cell (PAFC) power plants for terrestrial applications. Current PAFC technology utilizes platinum as catalysts in the power electrodes. The possible repercussions that the platinum demand of PAFC power plant commercialization will have on the worldwide supply and price of platinum from the outset of commercialization to the year 2000 are investigated. The platinum demand of PAFC commercialization is estimated by developing forecasts of platinum use per unit of generating capacity and penetration of PAFC power plants into the electric generation market. The ability of the platinum supply market to meet future demands is gauged by assessing the size of platinum reserves and the capability of platinum producers to extract, refine and market sufficient quantities of these reserves. The size and timing of platinum price shifts induced by the added demand of PAFC commercialization are investigated by several analytical methods. Estimates of these price shifts are then used to calculate the subsequent effects on PAFC power plant capital costs.

  3. Ionization of the group 3 metals La, Y and Sc in H2---O2---Ar flames (United States)

    Patterson, Patricia M.; Goodings, John M.


    Four pairs of premixed, fuel-rich/fuel-lean (FR/FL; equivalence ratio [Phi] = 1.5/0.75). H2---O2---Ar flames at four temperatures in the range 1900-2425 K, all at atmospheric pressure, were doped with about 10-6 mole fraction of the group 3 metals La, Y and Sc using atomizer techniques. The metals produce solid particles in the flames and gaseous metallic species. The latter include free metallic atoms, A, near the flame reaction zone, but only the monoxide AO and the oxide-hydroxide OAOH further downstream at equilibrium; the [OAOH]/[AO] ratio varies in FR/FL flames. Metallic ions (produce AO+; further downstream, the ionization level is sustained by the thermal (collisional) ionization of AO to produce AO+ and/or the chemi-ionization of OAOH with H to produce A(OH)2+. The ions AO+, A(OH)2+ and higher hydrates are all rapidly equilibrated by three-body association reactions with water. Ions are lost by dissociative electron-ion recombination of A(OH)2+ and possibly higher hydrates. The chemical ionization of the metallic species by H3O+ was investigated by adding a small quantity of CH4 to the flames. The ion chemistry is discussed in detail. An estimate of the bond dissociation energy D0°(OLa---OH) = 408 ± 40 kJ mol-1 (4.23 ± 0.41 eV) was obtained.

  4. Capacitance of the double electrical layer on the copper-group metals in molten alkali metal halides (United States)

    Kirillova, E. V.; Stepanov, V. P.


    The electrochemical impedance is measured to study the capacitance of the double electrical layer of metallic Au, Ag, and Cu as a function of potential and temperature in nine molten salts, namely, the chlorides, bromides, and iodides of sodium, potassium, and cesium. The C- E curve of a gold electrode has an additional minimum in the anodic branch. This minimum for silver is less pronounced and is only observed at low ac signal frequencies in cesium halides. The additional minimum is not detected for copper in any salt under study. This phenomenon is explained on the assumption that the adsorption of halide anions on a positively charged electrode surface has a predominantly chemical rather than an electrostatic character. The specific adsorption in this case is accompanied by charge transfer through the interface and the formation of an adsorbent-adsorbate covalent bond.

  5. Electrochemical sensors and devices for heavy metals assay in water: the French groups' contribution

    National Research Council Canada - National Science Library

    Pujol, Luca; Evrard, David; Groenen-Serrano, Karine; Freyssinier, Mathilde; Ruffien-Cizsak, Audrey; Gros, Pierre


    A great challenge in the area of heavy metal trace detection is the development of electrochemical techniques and devices which are user-friendly, robust, selective, with low detection limits and allowing fast analyses...

  6. Study of Noble Metal Elements in Lower Cambrian Black Rock Series of Guizhou-Hunan Provinces, China

    Institute of Scientific and Technical Information of China (English)


    Systematic analyses of noble metal elements in the Lower Cambrian black rock series of South China are reported. Correlations of w(Os)/w(Ir), w(Au)/w(Ir), w(Ag)/w(Au), w(Pt+Pd)/w(Os+Ru+Rh+Ir), relations of noble metal and platinum group element (PGE) distribution patterns reveal that the noble metals are not directly from extraterrestrial materials. Studying the data of 9 aspects, the authors conclude that the noble metals were mainly from ultramafic-mafic igneous rocks and their enrichment in black rocks is mainly controlled by hydrothermal fluid.

  7. Oxygen Reduction on Platinum

    DEFF Research Database (Denmark)

    Nesselberger, Markus

    bands are observed on the Pt/C layer: bands arising from the functional groups of the carbon support, bands related to water and hydronium, and bands related to the sulfur anion interaction with the catalyst. The correlation of the anion absorption to the ORR current leads to the proposition that anion...

  8. Ion mobility studies of carbohydrates as group I adducts: isomer specific collisional cross section dependence on metal ion radius. (United States)

    Huang, Yuting; Dodds, Eric D


    Carbohydrates play numerous critical roles in biological systems. Characterization of oligosaccharide structures is essential to a complete understanding of their functions in biological processes; nevertheless, their structural determination remains challenging in part due to isomerism. Ion mobility spectrometry provides the means to resolve gas phase ions on the basis of their shape-to-charge ratios, thus providing significant potential for separation and differentiation of carbohydrate isomers. Here, we report on the determination of collisional cross sections for four groups of isomeric carbohydrates (including five isomeric disaccharides, four isomeric trisaccharides, two isomeric pentasaccharides, and two isomeric hexasaccharides) as their group I metal ion adducts (i.e., [M + Li](+), [M + Na](+), [M + K](+), [M + Rb](+), and [M + Cs](+)). In all, 65 collisional cross sections were measured, the great majority of which have not been previously reported. As anticipated, the collisional cross sections of the carbohydrate metal ion adducts generally increase with increasing metal ion radius; however, the collisional cross sections were found to scale with the group I cation size in isomer specific manners. Such measurements are of substantial analytical value, as they illustrate how the selection of charge carrier influences carbohydrate ion mobility determinations. For example, certain pairs of isomeric carbohydrates assume unique collisional cross sections upon binding one metal ion, but not another. On the whole, these data suggest a role for the charge carrier as a probe of carbohydrate structure and thus have significant implications for the continued development and application of ion mobility spectrometry for the distinction and resolution of isomeric carbohydrates.

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

    Institute of Scientific and Technical Information of China (English)

    施意华; 王晟; 杨仲平; 靳晓珠; 胡圣虹; 邓水平


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

  10. The role of support and promoter on the oxidation of sulfur dioxide using platinum based catalysts

    DEFF Research Database (Denmark)

    Koutsopoulos, Sotiris; Rasmussen, Søren Birk; Eriksen, Kim Michael


    The catalytic oxidation of SO2 to SO3 was studied over platinum based catalysts in the absence and the presence of dopants. The active metal was supported on silica gel or titania (anatase) by impregnation. The activities of the silica supported catalysts were found to follow the order PtRh/SiO2...

  11. Ostwald Ripening of Platinum Nanoparticles Confined in a Carbon Nanotube/Silica-Templated Cylindrical Space

    Directory of Open Access Journals (Sweden)

    Cintia Mateo-Mateo


    Full Text Available Sintering of nanoparticles mediated by an Ostwald ripening mechanism is generally assessed examining the final particle size distributions. Based on this methodology, a general approach for depositing platinum nanoparticles onto carbon nanotubes in solution has been employed in order to evaluate the sintering process of these metallic nanoparticles at increasing temperatures in a carbon nanotube/silica-templated confined space.

  12. Understanding the electrocatalysis of oxygen reduction on platinum and its alloys

    DEFF Research Database (Denmark)

    Stephens, Ifan E. L.; Bondarenko, Alexander S.; Grønbjerg, Ulrik;


    by alloying it with other metals. In this perspective paper we provide an overview of the fundamentals underlying the reduction of oxygen on platinum and its alloys. We also report the ORR activity of Pt5La for the first time, which shows a 3.5- to 4.5-fold improvement in activity over Pt in the range 0...

  13. Investigation of morphological changes in platinum-containing nanostructures created by electron-beam-induced deposition

    NARCIS (Netherlands)

    Botman, A.; Hesselberth, M.; Mulders, J.J.L.


    Focused electron-beam-induced deposition (EBID) allows the rapid fabrication of three-dimensional nanodevices and metallic wiring of nanostructures, and is a promising technique for many applications in nanoresearch. The authors present two topics on platinum-containing nanostructures created by EBI

  14. Synthesis and ion-binding studies of platinum(Ⅱ) phenanthroline complexes containing crown ether moiety

    Institute of Scientific and Technical Information of China (English)


    Two new benzo-[15]-crown-5 attached phenanthroline platinum(Ⅱ) complexes with the general formula Pt(phen)X2, where X = Cl (1), C≡CC6H5 (2) have been synthesized, and their absorption and luminescence response towards metal ions have been studied.

  15. Rhenium-osmium isotope constraints on the age and source of the platinum mineralization in the Lower Cambrian black rock series of Hunan-Guizhou provinces, China

    Institute of Scientific and Technical Information of China (English)

    李胜荣; 肖启云; 申俊峰; 孙丽; 刘波; 阎柏琨; 江永宏


    The shale at the bottom of the Lower Cambrian black series in South China is rich in nonferrous metals, noble metals, rare and dispersed elements and radioactive elements, known as "polyelement-rich bed". In order to date and trace the source of the platinum group elements, 6 samples were collected from the Zhongnan region of Guizhou Province, and the Ganzi- ping-Sancha region of Hunan Province. The contents and isotopes of Re and Os were measured. Re and Os are positively correlated with each other and the correlation coefficient between 187Os/188Os and 187Re/188Os is 0.99856. On the 187Os/188Os-187Re/188Os diagram, 6 sample points are well-distributed along the (542±11) Ma fitting isochron in high coincidence and with 0.84±0.12 as the initial 187Os/188Os value. The result displays that the age value of the major mineralization of Re, Os and other platinum group elements is (542±11) Ma, which is identical with the stratigraphical age of the wall rocks; the 'polyelement beds' in Hunan and Guizhou provinces bear high isochroneity; the differences of the forming times of different materials in the 'polyelement bed' of the same area do not surpass the error limit permissible for Re-Os date fitting; there exists no distinct time interval between the formation of the diagenetic veinlets and that of the 'polyelement bed', or the Re-Os isotope composition has not been distinctly changed by the former process; basaltic crust might be the major source of Re, Os, other platinum group and trace elements in the Lower Cambrian 'polyelement bed' of Hunan and Guizhou provinces.

  16. Carbon-rich dust production in metal-poor galaxies in the Local Group

    CERN Document Server

    Sloan, G C; Lagadec, E; van Loon, J Th; Kraemer, K E; McDonald, I; Groenewegen, M A T; Wood, P R; Bernard-Salas, J; Zijlstra, A A


    We have observed a sample of 19 carbon stars in the Sculptor, Carina, Fornax, and Leo I dwarf spheroidal galaxies with the Infrared Spectrograph on the Spitzer Space Telescope. The spectra show significant quantities of dust around the carbon stars in Sculptor, Fornax, and Leo I, but little in Carina. Previous comparisons of carbon stars with similar pulsation properties in the Galaxy and the Magellanic Clouds revealed no evidence that metallicity affected the production of dust by carbon stars. However, the more metal-poor stars in the current sample appear to be generating less dust. These data extend two known trends to lower metallicities. In more metal-poor samples, the SiC dust emission weakens, while the acetylene absorption strengthens. The bolometric magnitudes and infrared spectral properties of the carbon stars in Fornax are consistent with metallicities more similar to carbon stars in the Magellanic Clouds than in the other dwarf spheroidals in our sample. A study of the carbon budget in these sta...

  17. Stabilization of 200-atom platinum nanoparticles by organosilane fragments

    KAUST Repository

    Pelzer, Katrin


    Three\\'s a charm: Platinum nanoparticles of 2 nm diameter and containing approximately 200 atoms covered with n-octylsilyl groups (see picture, right; Pt blue, Si red, C gray, H turquoise) form when [Pt(dba)2] (dba=dibenzylideneacetone) decomposes in the presence of n-octylsilane. The particles adopt a cuboctahedral structure with an edge length of three atoms. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Platinum(II) complexes as spectroscopic probes for biomolecules

    Energy Technology Data Exchange (ETDEWEB)

    Ratilla, E.


    The use of platinum(II) complexes as tags and probes for biomolecules is indeed advantageous for their reactivities can be selective for certain purposes through an interplay of mild reaction conditions and of the ligands bound to the platinum. The use of {sup 195}Pt NMR as a method of detecting platinum and its interactions with biomolecules was carried out with the simplest model of platinum(II) tagging to proteins. Variable-temperature {sup 195}Pt NMR spectroscopy proved useful in studying the stereodynamics of complex thioethers like methionine. The complex, Pt(trpy)Cl{sup +}, with its chromophore has a greater potential for probing proteins. It is a noninvasive and selective tag for histidine and cysteine residues on the surface of cytochrome c at pH 5. The protein derivatives obtained are separable, and the tags are easily quantitated and differentiated through the metal-to-ligand charge transfer bands which are sensitive to the environment of the tag. Increasing the pH to 7.0 led to the modification by Pt(trpy)Cl{sup +}of Arg 91 in cytochrome c. Further studies with guanidine-containing ligands as models for arginine modification by Pt(trpy)Cl{sup +} showed that guanidine can act as a terminal ligand and as a bridging ligand. Owing to the potential utility of Pt(trpy)L{sup n+} as electron dense probes of nucleic acid structure, interactions of this bis-Pt(trpy){sup 2+} complex with nucleic acids was evaluated. Indeed, the complex interacts non-covalently with nucleic acids. Its interactions with DNA are not exactly the same as those of its precedents. Most striking is its ability to form highly immobile bands of DNA upon gel electrophoresis. 232 refs.

  19. Electrochemical sensors and devices for heavy metals assay in water: the French groups' contribution

    Directory of Open Access Journals (Sweden)

    Luca ePUJOL


    Full Text Available A great challenge in the area of heavy metal trace detection is the development of electrochemical techniques and devices which are user-friendly, robust, selective, with low detection limits and allowing fast analyses. This review presents the major contribution of the French scientific academic community in the field of electrochemical sensors and electroanalytical methods within the last 20 years. From the well-known polarography to the up-to-date generation of functionalized interfaces, the different strategies dedicated to analytical performances improvement are exposed: stripping voltammetry, solid mercury-free electrode, ion selective sensor, carbon based materials, chemically modified electrodes, nano-structured surfaces. The paper particularly emphasizes their advantages and limits face to the last Water Frame Directive devoted to the Environmental Quality Standards for heavy metals. Recent trends on trace metal speciation as well as on automatic on line monitoring devices are also evoked.

  20. Group 4 Metalloporphyrin diolato Complexes and Catalytic Application of Metalloporphyrins and Related Transition Metal Complexes

    Energy Technology Data Exchange (ETDEWEB)

    Du, Guodong [Iowa State Univ., Ames, IA (United States)


    In this work, the first examples of group 4 metalloporphyrin 1,2-diolato complexes were synthesized through a number of strategies. In general, treatment of imido metalloporphyrin complexes, (TTP)M=NR, (M = Ti, Zr, Hf), with vicinal diols led to the formation of a series of diolato complexes. Alternatively, the chelating pinacolate complexes could be prepared by metathesis of (TTP)MCl2 (M = Ti, Hf) with disodium pinacolate. These complexes were found to undergo C-C cleavage reactions to produce organic carbonyl compounds. For titanium porphyrins, treatment of a titanium(II) alkyne adduct, (TTP)Ti(η2-PhC≡CPh), with aromatic aldehydes or aryl ketones resulted in reductive coupling of the carbonyl groups to produce the corresponding diolato complexes. Aliphatic aldehydes or ketones were not reactive towards (TTP)Ti(η2-PhC≡CPh). However, these carbonyl compounds could be incorporated into a diolato complex on reaction with a reactive precursor, (TTP)Ti[O(Ph)2C(Ph)2O] to provide unsymmetrical diolato complexes via cross coupling reactions. In addition, an enediolato complex (TTP)Ti(OCPhCPhO) was obtained from the reaction of (TTP)Ti(η2-PhC≡CPh) with benzoin. Titanium porphyrin diolato complexes were found to be intermediates in the (TTP)Ti=O-catalyzed cleavage reactions of vicinal diols, in which atmospheric oxygen was the oxidant. Furthermore, (TTP)Ti=O was capable of catalyzing the oxidation of benzyl alcohol and α-hydroxy ketones to benzaldehyde and α-diketones, respectively. Other high valent metalloporphyrin complexes also can catalyze the oxidative diol cleavage and the benzyl alcohol oxidation reactions with dioxygen. A comparison of Ti(IV) and Sn(IV) porphyrin chemistry was undertaken. While chelated diolato complexes were invariably obtained for titanium porphyrins on treatment with 1,2-diols, the reaction of vicinal diols with tin porphyrins gave a number of products, including mono

  1. Group 4 Metalloporphyrin diolato Complexes and Catalytic Application of Metalloporphyrins and Related Transition Metal Complexes

    Energy Technology Data Exchange (ETDEWEB)

    Guodong Du


    In this work, the first examples of group 4 metalloporphyrin 1,2-diolato complexes were synthesized through a number of strategies. In general, treatment of imido metalloporphyrin complexes, (TTP)M=NR, (M = Ti, Zr, Hf), with vicinal diols led to the formation of a series of diolato complexes. Alternatively, the chelating pinacolate complexes could be prepared by metathesis of (TTP)MCl{sub 2} (M = Ti, Hf) with disodium pinacolate. These complexes were found to undergo C-C cleavage reactions to produce organic carbonyl compounds. For titanium porphyrins, treatment of a titanium(II) alkyne adduct, (TTP)Ti({eta}{sup 2}-PhC{triple_bond}CPh), with aromatic aldehydes or aryl ketones resulted in reductive coupling of the carbonyl groups to produce the corresponding diolato complexes. Aliphatic aldehydes or ketones were not reactive towards (TTP)Ti({eta}{sup 2}-PhC{triple_bond}CPh). However, these carbonyl compounds could be incorporated into a diolato complex on reaction with a reactive precursor, (TTP)Ti[O(Ph){sub 2}C(Ph){sub 2}O] to provide unsymmetrical diolato complexes via cross coupling reactions. In addition, an enediolato complex (TTP)Ti(OCPhCPhO) was obtained from the reaction of (TTP)Ti({eta}{sup 2}-PhC{triple_bond}CPh) with benzoin. Titanium porphyrin diolato complexes were found to be intermediates in the (TTP)Ti=O-catalyzed cleavage reactions of vicinal diols, in which atmospheric oxygen was the oxidant. Furthermore, (TTP)Ti=O was capable of catalyzing the oxidation of benzyl alcohol and {alpha}-hydroxy ketones to benzaldehyde and {alpha}-diketones, respectively. Other high valent metalloporphyrin complexes also can catalyze the oxidative diol cleavage and the benzyl alcohol oxidation reactions with dioxygen. A comparison of Ti(IV) and Sn(IV) porphyrin chemistry was undertaken. While chelated diolato complexes were invariably obtained for titanium porphyrins on treatment with 1,2-diols, the reaction of vicinal diols with tin porphyrins gave a number of

  2. Hall measurements on carbon nanotube paper modified with electroless deposited platinum. (United States)

    Petrik, Leslie; Ndungu, Patrick; Iwuoha, Emmanuel


    Carbon nanotube paper, sometimes referred to as bucky paper, is a random arrangement of carbon nanotubes meshed into a single robust structure, which can be manipulated with relative ease. Multi-walled carbon nanotubes were used to make the nanotube paper, and were subsequently modified with platinum using an electroless deposition method based on substrate enhanced electroless deposition. This involves the use of a sacrificial metal substrate that undergoes electro-dissolution while the platinum metal deposits out of solution onto the nanotube paper via a galvanic displacement reaction. The samples were characterized using SEM/EDS, and Hall-effect measurements. The SEM/EDS analysis clearly revealed deposits of platinum (Pt) distributed over the nanotube paper surface, and the qualitative elemental analysis revealed co-deposition of other elements from the metal substrates used. When stainless steel was used as sacrificial metal a large degree of Pt contamination with various other metals was observed. Whereas when pure sacrificial metals were used bimetallic Pt clusters resulted. The co-deposition of a bimetallic system upon carbon nanotubes was a function of the metal type and the time of exposure. Hall-effect measurements revealed some interesting fluctuations in sheet carrier density and the dominant carrier switched from N- to P-type when Pt was deposited onto the nanotube paper. Perspectives on the use of the nanotube paper as a replacement to traditional carbon cloth in water electrolysis systems are also discussed.

  3. Hall Measurements on Carbon Nanotube Paper Modified With Electroless Deposited Platinum

    Directory of Open Access Journals (Sweden)

    Iwuoha Emmanuel


    Full Text Available Abstract Carbon nanotube paper, sometimes referred to as bucky paper, is a random arrangement of carbon nanotubes meshed into a single robust structure, which can be manipulated with relative ease. Multi-walled carbon nanotubes were used to make the nanotube paper, and were subsequently modified with platinum using an electroless deposition method based on substrate enhanced electroless deposition. This involves the use of a sacrificial metal substrate that undergoes electro-dissolution while the platinum metal deposits out of solution onto the nanotube paper via a galvanic displacement reaction. The samples were characterized using SEM/EDS, and Hall-effect measurements. The SEM/EDS analysis clearly revealed deposits of platinum (Pt distributed over the nanotube paper surface, and the qualitative elemental analysis revealed co-deposition of other elements from the metal substrates used. When stainless steel was used as sacrificial metal a large degree of Pt contamination with various other metals was observed. Whereas when pure sacrificial metals were used bimetallic Pt clusters resulted. The co-deposition of a bimetallic system upon carbon nanotubes was a function of the metal type and the time of exposure. Hall-effect measurements revealed some interesting fluctuations in sheet carrier density and the dominant carrier switched from N- to P-type when Pt was deposited onto the nanotube paper. Perspectives on the use of the nanotube paper as a replacement to traditional carbon cloth in water electrolysis systems are also discussed.

  4. Isotope exchange of indoles with D/sub 2/O over group VIII metals

    Energy Technology Data Exchange (ETDEWEB)

    Karakhanov, E.A.; Dedov, A.G.; Kurts, A.L.; Luzikov, Yu.N.


    Results of H - D exchange between indole and its methyl derivatives and D/sub 2/O over metallic Pt, Rh, and Pd are reported. The composition of the reaction mixture after the isotopic exchange was determined by mass spectrometry. The order of reactivity of the metals was Pt>Pd>Rh. It was determined that it was only the heterocycle ..pi..-electron system that interacts with the surface and mainly the hydrogens at C/sub 2/ and C/sub 3/ that undergo exchange and not those bonded to the N. (BLM)

  5. Platinum nanoparticles: a promising material for future cancer therapy? (United States)

    Porcel, Erika; Liehn, Samuel; Remita, Hynd; Usami, Noriko; Kobayashi, Katsumi; Furusawa, Yoshiya; Le Sech, Claude; Lacombe, Sandrine


    Recently, the use of gold nanoparticles as potential tumor selective radiosensitizers has been proposed as a breakthrough in radiotherapy. Experiments in living cells and in vivo have demonstrated the efficiency of the metal nanoparticles when combined with low energy x-ray radiations (below conventional 1 MeV Linac radiation). Further studies on DNA have been performed in order to better understand the fundamental processes of sensitization and to further improve the method. In this work, we propose a new strategy based on the combination of platinum nanoparticles with irradiation by fast ions effectively used in hadron therapy. It is observed in particular that nanoparticles enhance strongly lethal damage in DNA, with an efficiency factor close to 2 for double strand breaks. In order to disentangle the effect of the nano-design architecture, a comparison with the effects of dispersed metal atoms at the same concentration has been performed. It is thus shown that the sensitization in nanoparticles is enhanced due to auto-amplified electronic cascades inside the nanoparticles, which reinforces the energy deposition in the close vicinity of the metal. Finally, the combination of fast ion radiation (hadron therapy) with platinum nanoparticles should strongly improve cancer therapy protocols.

  6. Novel compliant electrodes based on platinum salt reduction (United States)

    Delille, Remi; Urdaneta, Mario; Hsieh, Kuangwen; Smela, Elisabeth


    A compliant electrode material is presented that was inspired by the electroding process used to manufacture ionic polymer-metal composites (IPMCs). However, instead of an ion-exchange membrane, a UV-curable acrylated urethane elastomer is employed. The electrode material consists of the UV-curable elastomer (Loctite 3108) loaded with tetraammineplatinum(II) chloride salt particles through physical mixing and homogenization. The composite material is made conductive by immersion in a reducing agent, sodium borohydride, which reduces the salt to platinum metal on the surface of the elastomer film. Because the noble metal is mixed into the elastomer precursor as a salt, the amount of UV light absorbed by the precursor is not significantly reduced, and the composite loses little photopatternability. As a result meso-scale electrodes of varying geometries can be formed by exposing the precursor/salt mixture through a mask. The materials are mechanically and electrically characterized. The percolation threshold of the composite is estimated to be 9 vol. % platinum salt, above which the compliant electrode material exhibits a maximum conductivity of 1 S/cm. The composite maintains its electrical conductivity under axial tensile strains of up to 40%.

  7. Green Synthesis, Characterization and Uses of Palladium/Platinum Nanoparticles (United States)

    Siddiqi, Khwaja Salahuddin; Husen, Azamal


    Biogenic synthesis of palladium (Pd) and platinum (Pt) nanoparticles from plants and microbes has captured the attention of many researchers because it is economical, sustainable and eco-friendly. Plant and their parts are known to have various kinds of primary and secondary metabolites which reduce the metal salts to metal nanoparticles. Shape, size and stability of Pd and Pt nanoparticles are influenced by pH, temperature, incubation time and concentrations of plant extract and that of the metal salt. Pd and Pt nanoparticles are broadly used as catalyst, as drug, drug carrier and in cancer treatment. They have shown size- and shape-dependent specific and selective therapeutic properties. In this review, we have discussed the biogenic fabrication of Pd/Pt nanoparticles, their potential application as catalyst, medicine, biosensor, medical diagnostic and pharmaceuticals.

  8. Group 4 Transition-Metal Complexes of an Aniline–Carbene–Phenol Ligand

    KAUST Repository

    Despagnet-Ayoub, Emmanuelle


    Attempts to install a tridentate aniline-NHC-phenol (NCO) ligand on titanium and zirconium led instead to complexes resulting from unexpected rearrangement pathways that illustrate common behavior in carbene-early- transition-metal chemistry. © 2013 American Chemical Society.

  9. Phosphine and phosphine oxide groups in metal-organic frameworks detected by P K-edge XAS. (United States)

    Morel, F L; Pin, S; Huthwelker, T; Ranocchiari, M; van Bokhoven, J A


    Phosphine metal-organic frameworks (P-MOFs) are crystalline porous coordination polymers that contain phosphorus functional groups within their pores. We present the use of X-ray absorption spectroscopy (XAS) at the P K-edge to determine the phosphine to phosphine oxide ratio in two P-MOFs with MIL-101 topology. The phosphorus oxidation state is of particular interest as it strongly influences the coordination affinity of these materials for transition metals. This method can determine the oxidation state of phosphorus even when the material contains paramagnetic nuclei, differently from NMR spectroscopy. We observed that phosphine in LSK-15 accounts for 72 ± 4% of the total phosphorus groups and that LSK-12 contains only phosphine oxide.

  10. Platinum Interference with siRNA Non-seed Regions Fine-Tunes Silencing Capacity

    DEFF Research Database (Denmark)

    Hedman, Hanna K; Kirpekar, Finn; Elmroth, Sofi K C


    , cisplatin and oxaliplatin, on siRNA's silencing capacity has been evaluated. More specifically, siRNAs targeting the 3' UTR region of Wnt-5a mRNA (NM_003352) were constructed, and the biologically active antisense RNA strand was pre-platinated. Platinum adducts were detected and characterized...... of the platination sites, i.e., with altered degradation patterns compared to native RNAs. The MALDI-MS method was successfully used to further identify and characterize platinated RNA, with the naturally occurring platinum isotopic patterns serving as sensitive fingerprints for metalated sites. Expression assays...


    Institute of Scientific and Technical Information of China (English)

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


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

  12. Nanolithographic Fabrication and Heterogeneous Reaction Studies ofTwo-Dimensional Platinum Model Catalyst Systems

    Energy Technology Data Exchange (ETDEWEB)

    Contreras, Anthony Marshall [Univ. of California, Berkeley, CA (United States)


    In order to better understand the fundamental components that govern catalytic activity, two-dimensional model platinum nanocatalyst arrays have been designed and fabricated. These catalysts arrays are meant to model the interplay of the metal and support important to industrial heterogeneous catalytic reactions. Photolithography and sub-lithographic techniques such as electron beam lithography, size reduction lithography and nanoimprint lithography have been employed to create these platinum nanoarrays. Both in-situ and ex-situ surface science techniques and catalytic reaction measurements were used to correlate the structural parameters of the system to catalytic activity.

  13. The synthesis and characterization of organometallic copolymers with Mn-Re binuclear transition-metal group in the side chain

    Institute of Scientific and Technical Information of China (English)

    XU; Zhi; FENG; Gang; BAI; Zhifeng; MA; Yongqiang; CHANG; Weixing; LI; Jing


    Novel organometallic copolymers with Mn-Re binuclear transition-metal groups in the side chain are synthesized and characterized. The structure and properties of the copolymers are characterized by GPC, DSC, TG, NMR, FT-IR, UV-Vis spectra and elemental analysis. The glass transition temperature and UV-Vis spectra properties of these three organometallic copolymers are found to be different from the normal polystyrene. New synthetic strategy for the synthesis of organometallic copolymer is developed.

  14. Development of Novel Non-Pt Group Metal Electrocatalysts for PEM Fuel Cell Applications

    Energy Technology Data Exchange (ETDEWEB)

    Mukerjee, Sanjeev [Northeastern Univ., Boston, MA (United States). Dept. of Chemistry and Chemical Biology; Atanassov, Plamen [Univ. of New Mexico, Albuquerque, NM (United States); Barton, Scott [Michigan State Univ., East Lansing, MI (United States); Dale, Nilesh [Nissan Technical Center North America (NTCNA), Farmington Hills, MI (United States); Halevi, Bar [Pajarito Powder LLC, Albuquerque, NM (United States)


    The objective of this multi-institutional effort was to comprehensively pursue the goal of eliminating noble metal (Pt group metals, PGM) from the cathodic oxygen reduction reaction (ORR) electrode thereby providing a quantum leap in lowering the overall PGM loading in a polymer electrolyte fuel cell (PEMFC). The overall project scope encompassed (a) comprehensive materials discovery effort, (b) a concomitant effort to scale up these materials with very high ( ±5%) reproducibility, both intra and inter, (c) understanding mass transport in porous medium both in gas diffusion and micro-porous layers for enhanced areal activity, (d) understanding mechanistic aspects of active site structure and ORR electrocatalytic pathway. Overall project milestones and metrics were (a) first phase effort based on performance in oxygen where the project’s Go/No-Go decision point milestone of 100 mA/cm2 at 0.8 V (internal resistance-free, iR-free) at 80°C, pure H2/O2, with 1.5 bar total pressure was met. Subsequently, the principle objectives were to (a) transition the project from H2/O2 to H2/Air with slated target of exceeding 30 mA/cm2 @ 0.8 V, 2.5 bar total pressure and an end of the project target of 1 A/cm2 @ 0.4 V (same total pressure), both under 100% relative humidity. The target for catalyst material scale up was to achieve 100 g batch size at the end of the program. This scale up target had a quality control milestone of less than 5% variation of activity measured with H2/Air (2.5 bar total pressure) at 0.8 V. In addition, the project also aimed at arriving at a unified understanding of the nature of active sites in these catalysts as well as some preliminary understanding of the mechanistic pathway. Also addressed is the development of an integrated method for determination of mass transport parameters using a combination of Helox experiments and modeling of the gas

  15. Biosorption of platinum and palladium for their separation/preconcentration prior to graphite furnace atomic absorption spectrometric determination

    Energy Technology Data Exchange (ETDEWEB)

    Godlewska-Zylkiewicz, Beata E-mail:


    Inexpensive baker's yeast Saccharomyces cerevisiae and green algae Chlorella vulgaris, either free or immobilized on silica gel have been shown to selectively accumulate platinum and palladium from water samples in acidic medium (pH 1.6-1.8). Optimization of conditions of metals biosorption (sample pH, algae and yeast masses, adsorption time, temperature) was performed in batch mode. The procedure of matrix separation based on biosorption of platinum and palladium on algae C. vulgaris covalently immobilized on silica gel in flow mode was developed. The use of algae in flow procedure offers several advantages compared with its use in the batch mode. The procedure shows better reproducibility (<2%), improved efficiency of platinum retention on the column (93.3{+-}1.6%), is less laborious and less time consuming. The best recovery of biosorbed metals from column (87.7{+-}3.3% for platinum and 96.8{+-}1.1 for palladium) was obtained with solution of 0.3 mol l{sup -1} thiourea in 1 mol l{sup -1} hydrochloric acid. The influence of thiourea on analytical signals of examined metals during GFAAS determination is discussed. The procedure has been applied for separation of noble metals from tap and waste water samples spiked with platinum and palladium.

  16. Effect of platinum nanoparticle deposition parameters on hydrogen peroxide transduction for applications in wearable electrochemical glucose biosensors (United States)

    Cargill, Allison A.; Neil, Kathrine M.; Hondred, John A.; McLamore, Eric S.; Claussen, Jonathan C.


    Enhanced interest in wearable biosensor technology over the past decade is directly related to the increasing prevalence of diabetes and the associated requirement of daily blood glucose monitoring. In this work we investigate the platinum-carbon transduction element used in traditional first-generation glucose biosensors which rely on the concentration of hydrogen peroxide produced by the glucose-glucose oxidase binding scheme. We electrodeposit platinum nanoparticles on a commercially-available screen printed carbon electrode by stepping an applied current between 0 and 7.12 mA/cm2 for a varying number of cycles. Next, we examine the trends in deposition and the effect that the number of deposition cycles has on the sensitivity of electrochemical glucose sensing. Results from this work indicate that applying platinum nanoparticles to screen printed carbon via electrodeposition from a metal salt solution improves overall biosensor sensitivity. This work also pinpoints the amount of platinum (i.e., number of deposition cycles) that maximizes biosensor sensitivity in an effort to minimize the use of the precious metals, viz., platinum, in electrode fabrication. In summary, this work quantifies the relationship between platinum electrodeposition and sensor performance, which is crucial in designing and producing cost-effective sensors.

  17. Platinum incorporation in the Na Y zeolite through impregnation method, and characterization by XRD, FTIR and nitrogen adsorption

    Energy Technology Data Exchange (ETDEWEB)

    Araujo, A.S.; Sousa, B.V.; Andrade, A.C.C.; Rodrigues, M.G.F. [Universidade Federal de Campina Grande (UFCG), PB (Brazil). Centro de Ciencias e Tecnologia. Unidade Academica de Engenharia Quimica], e-mail:, e-mail:, e-mail:; Rangel, M.C. [Universidade Federal da Bahia (UFBA), Salvador, BA (Brazil). Inst. de Quimica. Grupo de Estudos em Cinetica e Catalise


    Supported metal catalysts are widely used in petroleum refining, chemical and petroleum industries. These catalysts are important in ammonia synthesis, conversion of hydrocarbons with water vapor to synthesis gas, reforming, hydrocracking, ... Platinum has long been used in cracking, hydrogenation and dehydrogenation processes. The aim of this project is the Na Y zeolitic sample preparation through impregnation for incipient humidity, with 0,5% concentration of platinum, aiming its use as a catalyst in the steam reforming reaction. The characterization techniques used were: X Rays Diffraction (XRD), Fourier Transform Infrared spectroscopy (FTIR) and Nitrogen Adsorption (BET Method). From the obtained results through the techniques mentioned previously it is possible to evidence that the platinum impregnation process did not change the Na Y zeolite structure. Through the superficial specific area (BET) it was possible to observe that the platinum impregnation process caused a decrease in the specific area due to the reduction to the accessibility to the micropores of the zeolitic structure. (author)

  18. Inhibition of Notch signaling in combination with paclitaxel reduces platinum-resistant ovarian tumor growth

    Directory of Open Access Journals (Sweden)

    Jolijn W Groeneweg


    Full Text Available Introduction: Ovarian cancer (OvCa is the most lethal gynecologic malignancy in the United States because of chemoresistant recurrent disease. Our objective was to investigate the efficacy of inhibiting the Notch pathway with a gamma-secretase inhibitor (GSI in an OvCa patient derived xenograft (PDX model as a single agent therapy and in combination with standard chemotherapy.Methods: Immunocompromised mice bearing xenografts derived from clinically platinum sensitive human ovarian serous carcinomas were treated with vehicle, GSI (MRK-003 alone, paclitaxel and carboplatin (P/C alone, or the combination of GSI and P/C. Mice bearing platinum resistant xenografts were given GSI with or without paclitaxel. Gene transcript levels of the Notch pathway target Hes1 were analyzed using RT-PCR. Notch1 and Notch3 protein levels were evaluated. The Wilcoxon rank-sum test was used to assess significance between the different treatment groups. Results: Expression of Notch1 and 3 was variable. GSI alone decreased tumor growth in two of three platinum sensitive ovarian tumors (p < 0.05, as well as in one of three platinum sensitive tumors (p = 0.04. The combination of GSI and paclitaxel was significantly more effective than GSI alone and paclitaxel alone in all platinum resistant ovarian tumors (all p <0.05. The addition of GSI did not alter the effect of P/C in platinum sensitive tumors. Interestingly, although the response of each tumor to chronic GSI exposure did not correlate with its endogenous level of Notch expression, GSI did negatively affect Notch signaling in an acute setting.Conclusions: Inhibiting the Notch signaling cascade with a GSI reduces primary human xenograft growth in vivo. GSI synergized with conventional cytotoxic chemotherapy only in the platinum resistant OvCa models with single agent paclitaxel. These findings suggest inhibition of the Notch pathway in concert with taxane therapy may hold promise for treatment of platinum resistant OvCa.

  19. Metal Organic Frameworks as Solid Catalysts in Condensation Reactions of Carbonyl Groups


    Dhakshina Moorthy, Amarajothi; Opanasenko, Maksym; Cejka, Jirí; García Gómez, Hermenegildo


    This review summarizes the use of metal organic frameworks (MOFs) as solid catalysts for condensation reactions. After an introductory section, in which condensation reactions are generally presented, a list of the MOFs employed as condensation catalyst is given. The main part of the present review is organized according to the use of MOFs as solid acids, solid bases or as bi-functional solids containing both acid and basic sites. Throughout the review, the emphasis has been made on discussin...

  20. Group III alcohol dehydrogenase from Pectobacterium atrosepticum: insights into enzymatic activity and organization of the metal ion-containing region. (United States)

    Elleuche, Skander; Fodor, Krisztian; von der Heyde, Amélie; Klippel, Barbara; Wilmanns, Matthias; Antranikian, Garabed


    NAD(P)(+)-dependent alcohol dehydrogenases (ADH) are widely distributed in all phyla. These proteins can be assigned to three nonhomologous groups of isozymes, with group III being highly diverse with regards to catalytic activity and primary structure. Members of group III ADHs share a conserved stretch of amino acid residues important for cofactor binding and metal ion coordination, while sequence identities for complete proteins are highly diverse (90 %). A putative group III ADH PaYqhD has been identified in BLAST analysis from the plant pathogenic enterobacterium Pectobacterium atrosepticum. The PaYqhD gene was expressed in the heterologous host Escherichia coli, and the recombinant protein was purified in a two-step purification procedure to homogeneity indicating an obligate dimerization of monomers. Four conserved amino acid residues involved in metal ion coordination were substituted with alanine, and their importance for catalytic activity was confirmed by circular dichroism spectrum determination, in vitro, and growth experiments. PaYqhD exhibits optimal activity at 40 °C with short carbon chain aldehyde compounds and NADPH as cofactor indicating the enzyme to be an aldehyde reductase. No oxidative activities towards alcoholic compounds were detectable. EDTA completely inhibited catalytic activity and was fully restored by the addition of Co(2+). Activity measurements together with sequence alignments and structure analysis confirmed that PaYqhD belongs to the butanol dehydrogenase-like enzymes within group III of ADHs.

  1. The Oldest Stars of the Extremely Metal-Poor Local Group Dwarf Irregular Galaxy Leo A

    CERN Document Server

    Schulte-Ladbeck, R E; Drozdovsky, I O; Greggio, L; Crone, M M; Schulte-Ladbeck, Regina E.; Hopp, Ulrich; Drozdovsky, Igor O.; Greggio, Laura; Crone, Mary M.


    We present deep Hubble Space Telescope single-star photometry of Leo A in B, V, and I. Our new field of view is offset from the centrally located field observed by Tolstoy et al. (1998) in order to expose the halo population of this galaxy. We report the detection of metal-poor red horizontal branch stars, which demonstrate that Leo A is not a young galaxy. In fact, Leo A is as least as old as metal-poor Galactic Globular Clusters which exhibit red horizontal branches, and are considered to have a minimum age of about 9 Gyr. We discuss the distance to Leo A, and perform an extensive comparison of the data with stellar isochrones. For a distance modulus of 24.5, the data are better than 50% complete down to absolute magnitudes of 2 or more. We can easily identify stars with metallicities between 0.0001 and 0.0004, and ages between about 5 and 10 Gyr, in their post-main-sequence phases, but lack the detection of main-sequence turnoffs which would provide unambiguous proof of ancient (>10 Gyr) stellar generation...

  2. Precise tuning in platinum-nickel/nickel sulfide interface nanowires for synergistic hydrogen evolution catalysis (United States)

    Wang, Pengtang; Zhang, Xu; Zhang, Jin; Wan, Sheng; Guo, Shaojun; Lu, Gang; Yao, Jianlin; Huang, Xiaoqing


    Comprising abundant interfaces, multicomponent heterostructures can integrate distinct building blocks into single entities and yield exceptional functionalities enabled by the synergistic components. Here we report an efficient approach to construct one-dimensional metal/sulfide heterostructures by directly sulfuring highly composition-segregated platinum-nickel nanowires. The heterostructures possess a high density of interfaces between platinum-nickel and nickel sulfide components, which cooperate synergistically towards alkaline hydrogen evolution reaction. The platinum-nickel/nickel sulfide heterostructures can deliver a current density of 37.2 mA cm−2 at an overpotential of 70 mV, which is 9.7 times higher than that of commercial Pt/C. The heterostructures also offer enhanced stability revealed by long-term chronopotentiometry measurements. The present work highlights a potentially powerful interface-engineering strategy for designing multicomponent heterostructures with advanced performance in hydrogen evolution reaction and beyond. PMID:28239145

  3. Thermally stable single-atom platinum-on-ceria catalysts via atom trapping

    Energy Technology Data Exchange (ETDEWEB)

    Jones, John; Xiong, Haifeng; DelaRiva, Andrew; Peterson, Eric J.; Pham, Hien; Challa, Sivakumar R.; Qi, Gongshin; Oh, Se H.; Wiebenga, Michelle H.; Pereira Hernandez, Xavier I.; Wang, Yong; Datye, Abhaya K.


    Catalysts based on single atoms of scarce precious metals can lead to more efficient use through enhanced reactivity and selectivity. However, single atoms on catalyst supports can be mobile and aggregate into nanoparticles when heated at elevated temperatures. High temperatures are detrimental to catalyst performance unless these mobile atoms can be trapped. We used ceria powders having similar surface areas but different exposed surface facets. When mixed with a platinum/ aluminum oxide catalyst and aged in air at 800°C, the platinum transferred to the ceria and was trapped. Polyhedral ceria and nanorods were more effective than ceria cubes at anchoring the platinum. Performing synthesis at high temperatures ensures that only the most stable binding sites are occupied, yielding a sinter-resistant, atomically dispersed catalyst.

  4. Extraction and separation studies of platinum(IV) with N-n-octylaniline. (United States)

    Lokhande, T N; Anuse, M A; Chavan, M B


    N-n-octylaniline in xylene is used for the extractive separation of platinum(IV) from acidic media. Platinum(IV) was extracted quantitatively with 10 ml of 3% reagent in xylene from 0.5 to 10 and 2.5 to 10 M hydrochloric and sulphuric acid, respectively. It was stripped from organic phase with water and estimated photometrically with stannous chloride. The effect of metal ion, acids, reagent concentration and of various foreign ions has been investigated. The method affords binary separation of platinum(IV) from iron(III), cobalt(II), nickel(II) and copper(II), and is applicable to the analysis of synthetic mixtures and alloys. The method is fast, accurate and precise.

  5. New transition metal-rich rare-earth palladium/platinum aluminides with RET{sub 5}Al{sub 2} composition. Structure, magnetism and {sup 27}Al NMR spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Benndorf, Christopher [Muenster Univ. (Germany). Inst. fuer Anorganische und Analytische Chemie; Muenster Univ. (Germany). Inst. fuer Physikalische Chemie; Stegemann, Frank; Janka, Oliver [Muenster Univ. (Germany). Inst. fuer Anorganische und Analytische Chemie; Eckert, Hellmut [Muenster Univ. (Germany). Inst. fuer Physikalische Chemie


    REPd{sub 5}Al{sub 2} compounds with RE = Ce-Gd as well as Y and Lu have been previously synthesized. Although some compounds with the small lanthanides also exist, the compounds with intermediate-sized rare-earth elements (RE = Tb-Yb) had not been prepared. We report on the missing members of the REPd{sub 5}Al{sub 2} (RE = Tb-Yb) series as well as on the new REPt{sub 5}Al{sub 2} (RE = Y, Gd-Tm, Lu) series, which we have synthesized and structurally as well as magnetically characterized. All members crystallize isostructurally in the ZrNi{sub 2}Al{sub 5} type with an anti-arrangement of the T = Pd/Pt and Al atoms. YPd{sub 5}Al{sub 2} and LuPd{sub 5}Al{sub 2}, as well as the respective platinum homologs, YPt{sub 5}Al{sub 2} and LuPt{sub 5}Al{sub 2}, have been characterized also by {sup 27}Al magic-angle spinning nuclear magnetic resonance spectroscopy. Consistent with the XRD analysis, the spectra indicate the existence of only one distinct Al site in the structure.

  6. Trace element geochemistry of CR chondrite metal

    CERN Document Server

    Jacquet, Emmanuel; Alard, Olivier; Kearsley, Anton T; Gounelle, Matthieu


    We report trace element analyses by laser ablation inductively coupled plasma mass spectrometry of metal grains from 9 different CR chondrites, distinguishing grains from chondrule interior ("interior grains"), chondrule surficial shells ("margin grains") and the matrix ("isolated grains"). Save for a few anomalous grains, Ni-normalized trace element patterns are similar for all three petrographical settings, with largely unfractionated refractory siderophile elements and depleted volatile Au, Cu, Ag, S. All types of grains are interpreted to derive from a common precursor approximated by the least melted, fine-grained objects in CR chondrites. This also excludes recondensation of metal vapor as the origin of the bulk of margin grains. The metal precursors presumably formed by incomplete condensation, with evidence for high-temperature isolation of refractory platinum-group-element (PGE)-rich condensates before mixing with lower temperature PGE-depleted condensates. The rounded shape of the Ni-rich, interior ...

  7. Room temperature synthesis of colloidal platinum nanoparticles

    Indian Academy of Sciences (India)

    G Sarala Devi; V J Rao


    Efficient preparation of stable dispersions of platinum nanoparticles from platinous chloride (K2PtCl4) was achieved by simultaneous addition of capping polymer material. The size of platinum nanoparticles was controlled by changing the ratio of concentration of capping polymer material to the concentration of platinum cation used. The morphology of colloidal particles were studied by means of UV-visible spectrophotometry and transmission electron microscopy (TEM). Particle size increased with low reagent concentration. The change in absorption spectra with the particle size was observed, i.e. blue shift attributed to decrease in particle size.

  8. Stabilizing platinum in phosphoric acid fuel cells (United States)

    Remick, R. J.


    A carbon substrate for use in fabricating phosphoric acid fuel cell cathodes was modified by catalytic oxidation to stabilize the platinum catalyst by retarding the sintering of small platinum crystallites. Results of 100-hour operational tests confirmed that the rate of platinum surface area loss observed on catalytically oxidized supports was less than that observed with unmodified supports of the same starting material. Fuel cell electrodes fabricated from Vulcan XC-72R, which was modified by catalytic in a nitric oxide atmosphere, produced low platium sintering rates and high activity for the reduction of oxygen in the phosphoric acid environment.

  9. Antitumor effect of arabinogalactan and platinum complex. (United States)

    Starkov, A K; Zamay, T N; Savchenko, A A; Ingevatkin, E V; Titova, N M; Kolovskaya, O S; Luzan, N A; Silkin, P P; Kuznetsova, S A


    The article presents the results of investigation of antitumor properties of platinum-arabinogalactan complex. We showed the ability of the complex to inhibit the growth of Ehrlich ascites tumor cells. It is found that the distribution of the platinum-arabinogalactan complex is not specific only for tumor cells in mice. The complex was found in all tissues and organs examined (ascites cells, embryonic cells, kidney, and liver). The mechanism of action of the arabinogalactan-platinum complex may be similar to cisplatin as the complex is able to accumulate in tumor cells.

  10. Mechanism of Platinum Derivatives Induced Kidney Injury

    Directory of Open Access Journals (Sweden)

    Feifei YAN


    Full Text Available Platinum derivatives are the most widely used chemotherapeutic agents to treat solid tumors including ovarian, head and neck, and testicular germ cell tumors, lung cancer, and colorectal cancer. Two major problems exist, however, in the clinic use of platinum derivatives. One is the development of tumor resistance to the drug during therapy, leading to treatment failure. The other is the drug’s toxicity such as the cisplatin’s nephrotoxicity, which limits the dose that can be administered. This paper describes the mechanism of platinum derivatives induced kidney injury.

  11. Elaboration, physical and electrochemical characterizations of CO tolerant PEMFC anode materials. Study of platinum-molybdenum and platinum-tungsten alloys and composites; Elaborations et caracterisations electrochimiques et physiques de materiaux d'anode de PEMFC peu sensibles a l'empoisonnement par CO: etude d'alliages et de composites a base de platine-molybdene et de platine-tungstene

    Energy Technology Data Exchange (ETDEWEB)

    Peyrelade, E.


    PEMFC development is hindered by the CO poisoning ability of the anode platinum catalyst. It has been previously shown that the oxidation potential of carbon monoxide adsorbed on the platinum atoms can be lowered using specific Pt based catalysts, either metallic alloys or composites. The objective is then to realize a catalyst for which the CO oxidation is compatible with the working potential of a PEMFC anode. In our approach, to enhance the CO tolerance of platinum based catalyst supported on carbon, we studied platinum-tungsten and platinum-molybdenum alloys and platinum-metal oxide materials (Pt-WO{sub x} and Pt-MoO{sub x}). The platinum based alloys demonstrate a small effect of the second metal towards the oxidation of carbon monoxide. The platinum composites show a better tolerance to carbon monoxide. Electrochemical studies on both Pt-MoO{sub x} and Pt-WO{sub x} demonstrate the ability of the metal-oxides to promote the ability of Pt to oxidize CO at low potentials. However, chrono-amperometric tests reveal a bigger influence of the tungsten oxide. Complex chemistry reactions on the molybdenum oxide surface make it more difficult to observe. (author)

  12. Transition metal ferrocenyl dithiocarbamates functionalized dye-sensitized solar cells with hydroxy as an anchoring group (United States)

    Yadav, Reena; Waghadkar, Yogesh; Kociok-Köhn, Gabriele; Kumar, Abhinav; Rane, Sunit B.; Chauhan, Ratna


    Three new transition-metal dithiocarbamates involving ferrocene (Fc), namely [Co(FcCH2EtOHdtc)3] (Co), [M(FcCH2EtOHdtc)2] M = Ni (Ni), Cu (Cu) (EtOHdtc = N-ethanol dithiocarbamate), have been synthesized and characterized by microanalyses, FTIR, 1H and 13C NMR spectroscopies and single crystal X-ray diffraction technique. The peak broadening in the 1H spectrum of the copper complex indicates the paramagnetic behavior of this compound. The observed single quasi-reversible cyclic voltammograms for the complexes indicate the stabilization of a metal center (except copper) other than Fe in their characteristic oxidation state. These complexes have been used as photo-sensitizer in dye-sensitized solar cells which indicates that Co displays the best photosensitization property with an overall conversion efficiency of 3.25 ± 0.04%. The low cell efficiency of Ni and Cu complexes may be due to slow regeneration of the dye by iodine/iodide redox couple followed by charge injection into TiO2.

  13. Effects triggered by platinum nanoparticles on primary keratinocytes

    Directory of Open Access Journals (Sweden)

    Konieczny P


    Full Text Available Piotr Konieczny,1,* Anna Grazyna Goralczyk,1,* Radoslaw Szmyd,1,* Lukasz Skalniak,1,* Joanna Koziel,2 Francesca Larese Filon,3 Matteo Crosera,4 Agnieszka Cierniak,1 Ewa K Zuba-Surma,5 Julia Borowczyk,5 Eliza Laczna,5 Justyna Drukala,5 Elzbieta Pyza,6 Danuta Semik,6 Olga Woznicka,6 Andrzej Klein,1 Jolanta Jura11Department of General Biochemistry, 2Department of Microbiology, Jagiellonian University, Kraków, Poland; 3Department of Public Health Sciences, 4Department of Chemical and Pharmaceutical Sciences, University of Trieste, Trieste, Italy; 5Department of Cell Biology, 6Department of Cell Biology and Imaging, Jagiellonian University, Kraków, Poland*These authors equally contributed to this workAbstract: The platinum (Pt-group elements (PGEs represent a new kind of environmental pollutant and a new hazard for human health. Since their introduction as vehicle-exhaust catalysts, their emissions into the environment have grown considerably compared with their low natural concentration in the earth crust. PGE emissions from vehicle catalysts can be also in the form of nanometer-sized particles (Pt nanoparticles [PtNPs]. These elements, both in their metallic form or as ions solubilized in biological media, are now recognized as potent allergens and sensitizers. Human skin is always exposed to toxic particles; therefore, in the present study we addressed the question of whether polyvinylpyrrolidone-coated PtNPs may have any negative effects on skin cells, including predominantly epidermal keratinocytes. In this study, PtNPs of two sizes were used: 5.8 nm and 57 nm, in concentrations of 6.25, 12.5, and 25 µg/mL. Both types of NPs were protected with polyvinylpyrrolidone. Primary keratinocytes were treated for 24 and 48 hours, then cytotoxicity, genotoxicity, morphology, metabolic activity, and changes in the activation of signaling pathways were investigated in PtNP-treated cells. We found that PtNPs trigger toxic effects on primary keratinocytes

  14. Comparison of different sample preparation methods for platinum determination in cultured cells by graphite furnace atomic absorption spectrometry

    Directory of Open Access Journals (Sweden)

    Man Xiao


    Full Text Available Background Platinum-based agents are widely used in chemotherapy against solid tumors and insufficient intracellular drug accumulation is one of the leading causes of platinum resistance which is associated with poor survival of tumor patients. Thus, the detection of intracellular platinum is pivotal for studies aiming to overcome platinum resistance. In the present study, we aimed to establish a reliable graphite furnace atomic absorption spectrometry (GFAAS-based assay to quantify the intracellular platinum content for cultured cells. Methods Several most commonly applied cell preparation methods, including 0.2% HNO3, 0.2% Triton X-100, concentrated nitric acid, RIPA combined with concentrated nitric acid and hydroxide, followed by GFAAS for platinum detection were compared in ovarian, cervical and liver cancer cell lines to obtain the optimal one, and parameters regarding linearity, accuracy, precision and sensitivity were evaluated. Influence of other metals on platinum detection and the storage conditions of samples were also determined. Results The treatment of cells with 0.2% HNO3 was superior to other approaches with fewer platinum loss and better repeatability. The recovery rate and precision of this method were 97.3%–103.0% and 1.4%–3.8%, respectively. The average recoveries in the presence of other metals were 95.1%–103.1%. The detection limit was 13.23 ug/L. The recovery rate of platinum remained acceptable even in cell samples stored in −20 °C or −80 °C for two months. Discussion After comparison, we found that 0.2% HNO3 was optimal for intracellular platinum quantification based on GFAAS, which presented values compatible with that of inductively-coupled plasma mass-spectrometry (ICP-MS, and this is partially attributed to the simplicity of this method. Moreover, the assay was proved to be accurate, sensitive, cost-effective and suitable for the research of platinum-based antitumor therapy.

  15. Expression of Drug-Resistant Factor Genes in Hepatocellular Carcinoma Patients Undergoing Chemotherapy with Platinum Complex by Arterial Infusion

    Directory of Open Access Journals (Sweden)

    Shiro Ueda


    Full Text Available This study investigated gene expression of drug resistance factors in biopsy tissue samples from hepatocellular carcinoma (HCC patients undergoing chemotherapy by platinum complex. Liver biopsy was performed to collect tissue from the tumor site (T and the non-tumor site (NT prior to the start of treatment. For drug-resistant factors, drug excretion transporters cMOAT and MDR-1, intracellular metal binding protein MT2, DNA repair enzyme ERCC-l and inter-nucleic cell transport protein MVP, were investigated. The comparison of the expression between T and NT indicated a significant decrease of MT2 and MDR-1 in T while a significant increase in ERCC-1 was noted in T. Further, expression was compared between the response cases and non-response cases using the ratios of expression in T to those in NT. The response rate was significantly low in the high expression group when the cutoff value of cMOAT and MT2 was set at 1.5 and 1.0, respectively. Furthermore, when the patients were classified into A group (cMOAT ≧ 1.5 or MT2 ≧ 1.0 and B group (cMOAT < 1.5 and MT2 < 1.0, the response rate of A group was significantly lower than B group when we combined the cutoff values of cMOAT and MT2. It is considered possible to estimate the therapeutic effect of platinum complex at a high probability by combining the expression condition of these two genes.

  16. Glycolate adsorption at gold and platinum electrodes: A theoretical and in situ spectroelectrochemical study

    Energy Technology Data Exchange (ETDEWEB)

    Delgado, Jose Manuel; Blanco, Raquel; Orts, Jose Manuel; Perez, Juan Manuel [Departamento de Quimica Fisica e Instituto Universitario de Electroquimica, Universidad de Alicante, Apartado 99, E-03080 Alicante (Spain); Rodes, Antonio, E-mail: Antonio.Rodes@ua.e [Departamento de Quimica Fisica e Instituto Universitario de Electroquimica, Universidad de Alicante, Apartado 99, E-03080 Alicante (Spain)


    The adsorption of glycolate anions at sputtered gold thin-film electrodes was studied in perchloric acid solutions by cyclic voltammetry experiments combined with in situ Surface Enhanced Raman Scattering (SERS) and Surface Enhanced Infrared Reflection Absorption Spectroscopy under attenuated total reflection conditions (ATR-SEIRAS). Theoretical harmonic vibrational frequencies and band intensities obtained from B3LYP/LANL2DZ,6-31+G(d) calculations for glycolate species adsorbed on Au clusters with (1 1 1) orientation were used to interpret the experimental spectra. Vibrational data confirm the bidentate bonding of glycolate anions through the oxygen atoms of the carboxylate group, in a bridge configuration with the OCO plane perpendicular to the metal surface. The DFT calculations show no significant effect of the total charge of the metal cluster-adsorbate adduct on the vibrational frequencies of adsorbed glycolate species. The infrared experimental study is extended to platinum films electrochemically deposited onto sputtered gold thin-film electrodes showing the potential-dependent formation of adsorbed CO upon dissociative adsorption of glycolate anions. As in the case of gold, the reversible adsorption of glycolate anions takes place in a bidentate configuration as predicted by DFT calculations for glycolate adsorbed on Pt(1 1 1) clusters. At low glycolic acid concentration, the in situ ATR-SEIRA spectra evidence the formation of adsorbed oxalate as reaction intermediate.

  17. The Oldest Stars of the Extremely Metal-Poor Local Group Dwarf Irregular Galaxy Leo A (United States)

    Schulte-Ladbeck, Regina E.; Hopp, Ulrich; Drozdovsky, Igor O.; Greggio, Laura; Crone, Mary M.


    We present deep Hubble Space Telescope (HST) single-star photometry of Leo A in B, V, and I. Our new field of view is offset from the centrally located field observed by Tolstoy et al. in order to expose the halo population of this galaxy. We report the detection of metal-poor red horizontal branch stars, which demonstrate that Leo A is not a young galaxy. In fact, Leo A is as least as old as metal-poor Galactic Globular Clusters that exhibit red horizontal branches and are considered to have a minimum age of about 9 Gyr. We discuss the distance to Leo A and perform an extensive comparison of the data with stellar isochrones. For a distance modulus of 24.5, the data are better than 50% complete down to absolute magnitudes of 2 or more. We can easily identify stars with metallicities between 0.0001 and 0.0004, and ages between about 5 and 10 Gyr, in their post-main-sequence phases, but we lack the detection of main-sequence turnoffs that would provide unambiguous proof of ancient (>10 Gyr) stellar generations. Blue horizontal branch stars are above the detection limits but difficult to distinguish from young stars with similar colors and magnitudes. Synthetic color-magnitude diagrams show it is possible to populate the blue horizontal branch in the halo of Leo A. The models also suggest ~50% of the total astrated mass in our pointing to be attributed to an ancient (>10 Gyr) stellar population. We conclude that Leo A started to form stars at least about 9 Gyr ago. Leo A exhibits an extremely low oxygen abundance, only 3% of solar, in its ionized interstellar medium. The existence of old stars in this very oxygen-deficient galaxy illustrates that a low oxygen abundance does not preclude a history of early star formation. Based on observations made with the NASA/ESA Hubble Space Telescope, obtained from the Space Telescope Science Institute, which is operated by the Association of Universities for Research in Astronomy, Inc., under NASA contract NAS 5-26555.

  18. Role of bonding mechanisms during transfer hydrogenation reaction on heterogeneous catalysts of platinum nanoparticles supported on zinc oxide nanorods (United States)

    Al-Alawi, Reem A.; Laxman, Karthik; Dastgir, Sarim; Dutta, Joydeep


    For supported heterogeneous catalysis, the interface between a metal nanoparticle and the support plays an important role. In this work the dependency of the catalytic efficiency on the bonding chemistry of platinum nanoparticles supported on zinc oxide (ZnO) nanorods is studied. Platinum nanoparticles were deposited on ZnO nanorods (ZnO NR) using thermal and photochemical processes and the effects on the size, distribution, density and chemical state of the metal nanoparticles upon the catalytic activities are presented. The obtained results indicate that the bonding at Pt-ZnO interface depends on the deposition scheme which can be utilized to modulate the surface chemistry and thus the activity of the supported catalysts. Additionally, uniform distribution of metal on the catalyst support was observed to be more important than the loading density. It is also found that oxidized platinum Pt(IV) (platinum hydroxide) provided a more suitable surface for enhancing the transfer hydrogenation reaction of cyclohexanone with isopropanol compared to zero valent platinum. Photochemically synthesized ZnO supported nanocatalysts were efficient and potentially viable for upscaling to industrial applications.

  19. Synthesis of Diacetyl Curcumin Metal ( Copper, Platinum)Complexes and Its Interaction with ctDNA%二乙酰姜黄素金属(铜,铂)配合物的合成及其与ctDNA的键合作用

    Institute of Scientific and Technical Information of China (English)

    姜波; 魏冬; 范九良; 汪佳凤; 周双生


    以姜黄素为原料,合成了二乙酰姜黄素(H2L)及其铜(Ⅱ)和铂(Ⅱ)配合物(CuL2和PtL2),其结构经1H NMR,IR,MS和元素分析确认.采用UV-Vis测定法和循环伏安法研究了CuL2和PtL2与ctDNA的相互作用.结果表明,CuL2和PtL2与ctDNA的作用属嵌插作用模式.%Diacetyl Curcumin(H2L) and its metal[copper( II ) , platinum( H ) ] complex, CuL2 and PtL2, were synthesized from curcumin. The structures were characterized by 1H NMR, IR, MS and elemental analysis. The interactions of the CuL2 and PtL2 with ctDNA were studied by UV-Vis test method and cyclic voltammetry method. The results showed that interactions model of CuL2 and PtL2 with ctDNA was presumably intercalative model.

  20. Platinum-Resistor Differential Temperature Sensor (United States)

    Kolbly, R. B.; Britcliffe, M. J.


    Platinum resistance elements used in bridge circuit for measuring temperature difference between two flowing liquids. Temperature errors with circuit are less than 0.01 degrees C over range of 100 degrees C.

  1. VB Platinum Tile & Carpet, Inc. Information Sheet (United States)

    VB Platinum Tile & Carpet, Inc. (the Company) is located in Bristow, Virginia. The settlement involves renovation activities conducted at a property constructed prior to 1978, located in Washington, DC.


    Institute of Scientific and Technical Information of China (English)

    Ya-lin Qiao; Ping Hu; Guo-xin Jin


    A series of half-sandwich groupmetal complexes with tridentate monoanionic phenoxy-imine arylsulfide[O-NS] ligand [2-But4-Me-6-((2-(SC6H5)C6H4N =CHC6H2O)]-(La) and dianionic phenoxy-amine arylsulfide [O-N-S]ligand [2-Bu'4-Me-6-((2-(SC6H5)C6H4N-CH2C6H2O)]2-(Lb) have been synthesized and characterized.Lb was obtained easily in high yield by reduction of ligand La with excess LiAlH4 in cool diethyl ether.Half-sandwich Groupmetal complexes CpTi[O-NS]C12 (1a),CpZr[O-NS]C12 (1b),CpTi[O-N-S]C1 (2a),CpZr[O-N-S]C1 (2b) and Cp*Zr[O-N-S]Cl (2c)were synthesized by the reactions of La and Lb with CpTiCl3,CpZrCl3 and Cp*ZrCl3,and characterized by IR,1H-NMR,13C-NMR and elemental analysis.In addition,an X-ray structure analysis was performed on ligand Lb.The title Group Ⅳ half-sandwich bearing tridentate [O,N,S] ligands show good catalytic activities for ethylene polymerization in the presence of methylaluminoxane (MAO) as co-catalyst up to 1.58 × 107 g-PE·mol-Zr-1·h-1.The good catalytic activities can be maintained even at high temperatures such as 100 ℃ exhibiting the excellent thermal stability for these half-sandwich metal pre-catalysts.

  3. Stabilizing platinum in phosphoric acid fuel cells (United States)

    Remick, R. J.


    Platinum sintering on phosphoric acid fuel cell cathodes is discussed. The cathode of the phosphoric acid fuel cell uses a high surface area platinum catalyst dispersed on a conductive carbon support to minimize both cathode polarization and fabrication costs. During operation, however, the active surface area of these electrodes decreases, which in turn leads to decreased cell performance. This loss of active surface area is a major factor in the degradation of fuel cell performance over time.

  4. A Robust Metal-Organic Framework Combining Open Metal Sites and Polar Groups for Methane Purification and CO2 /Fluorocarbon Capture. (United States)

    Chen, Cheng-Xia; Zheng, Shao-Ping; Wei, Zhang-Wen; Cao, Chen-Chen; Wang, Hai-Ping; Wang, Dawei; Jiang, Ji-Jun; Fenske, Dieter; Su, Cheng-Yong


    A 3D porous perchlorinated metal-organic framework (MOF), LIFM-26, featuring dual functionality, that is, functional polar groups and open metal sites, has been synthesized using perchlorinated linear dicarboxylate to link trigonal prismatic Fe3 (μ3 -O) units. LIFM-26 exhibits good thermal and chemical stability, and possesses high porosity with a BET surface area of 1513 m(2)  g(-1) , compared with isoreticular MOF-235 and Fe3 O(F4 BDC)3 (H2 O)3 (F4 BDC=2,3,5,6-tetrafluorobenzene-1,4-dicarboxylate). Most strikingly, LIFM-26 features good gas sorption/separation performance at 298 K and 1 atm with IAST selectivity values reaching up to 36, 93, 23, 11, 46, and 202 for CO2 /CH4 , CO2 /N2 , C2 H4 /CH4 , C2 H6 /CH4 , C3 H8 /CH4 , and R22/N2 (R22=CHClF2 ), respectively, showing potential for use in biogas/natural gas purification and CO2 /R22 capture. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. IUPAC-NIST Solubility Data Series. 85. Transition and 12-14 Main Group Metals, Lanthanide, Actinide, and Ammonium Halates (United States)

    Miyamoto, Hiroshi


    This paper is the fourth and final volume in the halate solubility series. The solubility data for halates of transition metals, lanthanides, actinides, ammonium, and metallic elements of the main groups 12-14 are reviewed. Where appropriate, binary, ternary, and multicomponent systems are critically evaluated. Most of the solubility results were obtained in water or aqueous solutions of electrolytes. The solubility in organic solvents and aqueous-organic solvent mixtures is also collected in this volume. All these data were critically examined for their reliability. The best values were selected on the basis of critical evaluations and presented in tabular form. Fitting equations and graphical plots are also provided. When numerical data were not reported in an original publication, they were read out from figures and digitized by the compilers. The quantities, units, and symbols used in this volume are in accord with IUPAC recommendations. We always reported the original data and, if necessary, transferred them into the IUPAC recommended units and symbols. The literature on the solubility data was researched through 2002. The halates of these metals play a role in industrial processes. For example, some halates are essential as catalysts, heat stabilizers, and blanching reagents for manufacturing polymer products such as textiles and resins. Some iodates are used in pyrotechnic compounds for weather modification and colored smoke generation. The nonlinear halate crystals are important in construction of optical devices.

  6. 从铂钯精矿中提取金、铂、钯工艺研究%Research on Extraction of Gold, Platinum and Palladium From Palladium-Platinum Concentrate

    Institute of Scientific and Technical Information of China (English)

    王兴; 崔家友; 张善辉; 陶明光


    针对在处理铜阳极泥过程中产生的铂钯精矿,采用电控除杂-大氯化溶解Au、Pt、Pd-氯化铵共沉铂钯-SO2还原金-水煮分离铂钯-铂钯精炼工艺提取金、铂、钯。铂、钯回收率98%以上,金的回收率为99%。该工艺具有成本低、操作简单、贵金属回收率高等优点。%In connection with the Platinum and Palladium Concentrates produced in the course of processing copper anode slime, utilizing the process of electronically controlled impurity-large chloride dissolving gold, platinum, palladium-ammonium chloride coprecipitating platinum and palladium-SO2 restoring gold-separation platinum and palladium by boiling to refine platinum and palladium. The recovery rate of platinum and palladium is over 98%, the recovery rate of gold reaches to 99%. The process has the advantage of low cost , simple operation, high precious metals recovery.

  7. Palladium, platinum, and rhodium contents of rocks near the lower margin of the Stillwater complex, Montana. (United States)

    Zientek, M.L.; Foose, M.P.; Leung, Mei


    Statistical summaries are reported for Pd, Pt and Rh contents of rocks from the lower part of the Stillwater complex, the underlying contact-metamorphosed sediments, and post-metamorphic dykes and sills wholly within the hornfelses. Variability of the data among the rock types is attributed largely to differences in sulphide content. Non-correlation of sulphur with platinum-group assays of many rock types leads to the suggestion that the immiscible sulphide and silicate liquids did not completely equilibrate with respect to platinum-group elements. -G.J.N.

  8. Metal-organic frameworks as selectivity regulators for hydrogenation reactions (United States)

    Zhao, Meiting; Yuan, Kuo; Wang, Yun; Li, Guodong; Guo, Jun; Gu, Lin; Hu, Wenping; Zhao, Huijun; Tang, Zhiyong


    Owing to the limited availability of natural sources, the widespread demand of the flavouring, perfume and pharmaceutical industries for unsaturated alcohols is met by producing them from α,β-unsaturated aldehydes, through the selective hydrogenation of the carbon-oxygen group (in preference to the carbon-carbon group). However, developing effective catalysts for this transformation is challenging, because hydrogenation of the carbon-carbon group is thermodynamically favoured. This difficulty is particularly relevant for one major category of heterogeneous catalyst: metal nanoparticles supported on metal oxides. These systems are generally incapable of significantly enhancing the selectivity towards thermodynamically unfavoured reactions, because only the edges of nanoparticles that are in direct contact with the metal-oxide support possess selective catalytic properties; most of the exposed nanoparticle surfaces do not. This has inspired the use of metal-organic frameworks (MOFs) to encapsulate metal nanoparticles within their layers or inside their channels, to influence the activity of the entire nanoparticle surface while maintaining efficient reactant and product transport owing to the porous nature of the material. Here we show that MOFs can also serve as effective selectivity regulators for the hydrogenation of α,β-unsaturated aldehydes. Sandwiching platinum nanoparticles between an inner core and an outer shell composed of an MOF with metal nodes of Fe3+, Cr3+ or both (known as MIL-101; refs 19, 20, 21) results in stable catalysts that convert a range of α,β-unsaturated aldehydes with high efficiency and with significantly enhanced selectivity towards unsaturated alcohols. Calculations reveal that preferential interaction of MOF metal sites with the carbon-oxygen rather than the carbon-carbon group renders hydrogenation of the former by the embedded platinum nanoparticles a thermodynamically favoured reaction. We anticipate that our basic design

  9. Catalysis by alkali and alkaline-earth metal ions in nucleophilic attack of methoxide ion on crown ethers bearing an intra-annular acetoxy group

    NARCIS (Netherlands)

    Cacciapaglia, Roberta; Lucente, Silvia; Mandolini, Luigi; Doorn, van Arie R.; Reinhoudt, David N.; Verboom, Willem


    Rates of reaction of methoxide ion with crown ethers bearing an intra-annular acetoxy group are markedly enhanced by alkali and alkaline-earth metal bromides as a result of much stronger interactions of the metal ions with transition states than with reactants. Rates of reactions of methoxide ion w

  10. Complexes of bis(cyclopentadienyl)hydridorhenium with group-II metal halides

    Energy Technology Data Exchange (ETDEWEB)

    Ishchenko, V.M.; Arkhireeva, T.M.; Bulychev, B.M.; Soloveichik, G.L.; Nikolaeva, S.N.


    It has been shown that the interaction of bis(cyclopentadienyl)hydridorhenium (Cp/sub 2/ReH, where Cp = eta/sup 5 -/C/sub 5/H/sub 5/) with the halides of zinc, cadmium, beryllium, and magnesium in diethyl ether results in the formation of complex compounds with the general formula Cp/sub 2/ReH MHal/sub 2/. The replacement of ether by tetrahydrofuran in the case of zinc derivatives gives monosolvates with the formula Cp/sub 2/ReH x ZnHal/sub 2/ x THF (Hal = Br, I). On the basis of data from IR and PMR spectroscopy it has been concluded that the bonding of the metal-containing fragments in these complexes is realized either as a result of an Re :..-->.. M donor-acceptor interaction (the complexes with ZnHal/sub 2/ and CdI/sub 2/) or as a result of the formation of a mixed bond (the complexes with BeCl/sub 2/ and MgHal/sub 2/).

  11. OB stars at the lowest Local Group metallicity: GTC-OSIRIS observations of Sextans A

    CERN Document Server

    Camacho, I; Herrero, A; Simón-Díaz, S


    Our aim is to find and classify OB stars in Sextans A, to later determine accurate stellar parameters of these blue massive stars in this low metallicity region $(Z \\sim 0.1 \\rm Z_{\\odot})$. Using UBV photometry, the reddening-free index Q and GALEX imaging, we built a list of blue massive star candidates in Sextans A. We obtained low resolution (R $\\sim$ 1000) GTC-OSIRIS spectra for a fraction of them and carried out spectral classification. For the confirmed O-stars we derive preliminary stellar parameters. The target selection criteria and observations were successful and have produced the first spectroscopic atlas of OB-type stars in Sextans A. From the whole sample of 18 observed stars, 12 were classified as early OB-types, including 5 O-stars. The radial velocities of all target stars are in agreement with their Sextans A membership, although three of them show significant deviations. We determined the stellar parameters of the O-type stars using the stellar atmosphere code FASTWIND, and revisited the s...

  12. Synthesis, Crystal Structure and Luminescent Property of a Novel Pt(II) Complex with Weak Metal-metal Interaction

    Institute of Scientific and Technical Information of China (English)

    YUE Cheng-Yang; JIANG Fei-Long; FENG Rui; HONG Mao-Chun


    The title complex cis-bis(tetrahydrothiophene)-bis(nitrate) platinum(II), (tht)2Pt(NO3)2, was the reducing product from potassium hexachloroplatinate(IV) K2PtCl6 where the platinum is tetra-valenced. Crystal data for C8H16N2O6PtS2: monoclinic, space group P21/c, a = 9.8833(5), b = 8.6744(4), c = 18.6407(9) (A), β = 114.401(3)°, V = 1455.35(12) (A)3, Z = 4, Mr = 495.44, Dc = 2.261 g/cm3, F(000) = 944, μ = 9.950 mm-1, λ(MoKα) = 0.71073 (A), T = 293(2) K, 2θmax = 54.96o, GOOF = 1.033, R = 0.0350 and wR = 0.0785 for 2572 observed reflections with I > 2σ(I). X-ray diffraction studies reveal that the title complex has interesting weak metal-metal interactions and two molecules linked by metal-metal interaction exist as a group. Luminescent spectrum illuminates red emission of the complex at room temperature.

  13. Catalytic co-pyrolysis of peat and polymeric wastes in the presence of iron sub-group metal chlorides

    Energy Technology Data Exchange (ETDEWEB)

    Sulman, E.M.; Kosivtsov, Y.Y.; Lugovoy, Y.V. [Tver Technical University, Tver (Russian Federation)


    The purpose of this investigation is the study of activity of iron sub-group metal chlorides in co-processing of peat and polymeric wastes by low-temperature catalytic pyrolysis method. Iron sub-group metal chlorides in concentration varied from 1 to 10% (wt) were used as the catalysts of pyrolysis. The process was conducted in fixed bed reactor in inert gaseous atmosphere at the temperature interval of 350-550{sup o}C. All the investigated catalysts were found to promote the increase of liquid fraction mass and the decrease of solid carbon-containing residue mass up to 10-30%. Cobalt catalyst revealed the highest selectivity with respect to liquid products formation. The use of the catalysts in low-temperature peat and polymeric wastes pyrolysis process was found to favour the increase gaseous products volume up to 20-50% as well as unsaturated hydrocarbons volume in 1.2 folds in comparison to uncatalysed process. 9 refs., 3 figs., 2 tabs.

  14. Effects triggered by platinum nanoparticles on primary keratinocytes. (United States)

    Konieczny, Piotr; Goralczyk, Anna Grazyna; Szmyd, Radoslaw; Skalniak, Lukasz; Koziel, Joanna; Filon, Francesca Larese; Crosera, Matteo; Cierniak, Agnieszka; Zuba-Surma, Ewa K; Borowczyk, Julia; Laczna, Eliza; Drukala, Justyna; Pyza, Elzbieta; Semik, Danuta; Woznicka, Olga; Klein, Andrzej; Jura, Jolanta


    The platinum (Pt)-group elements (PGEs) represent a new kind of environmental pollutant and a new hazard for human health. Since their introduction as vehicle-exhaust catalysts, their emissions into the environment have grown considerably compared with their low natural concentration in the earth crust. PGE emissions from vehicle catalysts can be also in the form of nanometer-sized particles (Pt nanoparticles [PtNPs]). These elements, both in their metallic form or as ions solubilized in biological media, are now recognized as potent allergens and sensitizers. Human skin is always exposed to toxic particles; therefore, in the present study we addressed the question of whether polyvinylpyrrolidone-coated PtNPs may have any negative effects on skin cells, including predominantly epidermal keratinocytes. In this study, PtNPs of two sizes were used: 5.8 nm and 57 nm, in concentrations of 6.25, 12.5, and 25 μg/mL. Both types of NPs were protected with polyvinylpyrrolidone. Primary keratinocytes were treated for 24 and 48 hours, then cytotoxicity, genotoxicity, morphology, metabolic activity, and changes in the activation of signaling pathways were investigated in PtNP-treated cells. We found that PtNPs trigger toxic effects on primary keratinocytes, decreasing cell metabolism, but these changes have no effects on cell viability or migration. Moreover, smaller NPs exhibited more deleterious effect on DNA stability than the big ones. Analyzing activation of caspases, we found changes in activity of caspase 9 and caspase 3/7 triggered mainly by smaller NPs. Changes were not so significant in the case of larger nanoparticles. Importantly, we found that PtNPs have antibacterial properties, as is the case with silver NPs (AgNPs). In comparison to our previous study regarding the effects of AgNPs on cell biology, we found that PtNPs do not exhibit such deleterious effects on primary keratinocytes as AgNPs and that they also can be used as potential antibacterial agents

  15. Removal of transition metals from dilute aqueous solution by carboxylic acid group containing absorbent polymers (United States)

    A new carboxylic acid group containing resin with cation exchange capacity, 12.67 meq/g has been used to remove Cu2+, Co2+ and Ni2+ ions from dilute aqueous solution. The resin has Cu2+, Co2+ and Ni2+ removal capacity, 216 mg/g, 154 mg/g and 180 mg/g, respectively. The selectivity of the resin to ...

  16. Performance of Platinum Nanoparticles / Multiwalled Carbon Nanotubes / Bacterial Cellulose Composite as Anode Catalyst for Proton Exchange Membrane Fuel Cells

    Directory of Open Access Journals (Sweden)

    Henry Fonda Aritonang


    Full Text Available Highly dispersed platinum (Pt nanoparticles / multiwalled carbon nanotubes (MWCNTs on bacterial cellulose (BC as anode catalysts for proton exchange membrane fuel cells (PEMFC were prepared with various precursors and their electro-catalytic activities towards hydrogen oxidation at 70 oC under non-humidified conditions. The composite was prepared by deposition of Pt nanoparticles and MWCNTs on BC gel by impregnation method using a water solution of metal precursors and MWCNTs followed by reducing reaction using a hydrogen gas. The composite was characterized by using TEM (transmission electron microscopy, EDS (energy dispersive spectroscopy, and XRD (X-ray diffractometry techniques. TEM images and XRD patterns both lead to the observation of spherical metallic Pt nanoparticles with mean diameter of 3-11 nm well impregnated into the BC fibrils. Preliminary tests on a single cell indicate that renewable BC is a good prospect to be explored as a membrane in fuel cell field. Copyright © 2017 BCREC Group. All rights reserved Received: 21st November 2016; Revised: 26th February 2017; Accepted: 27th February 2017 How to Cite: Aritonang, H.F., Kamu, V.S., Ciptati, C., Onggo, D., Radiman, C.L. (2017. Performance of Platinum Nanoparticles / Multiwalled Carbon Nanotubes / Bacterial Cellulose Composite as Anode Catalyst for Proton Exchange Membrane Fuel Cells. Bulletin of Chemical Reaction Engineering & Catalysis, 12 (2: 287-292 (doi:10.9767/bcrec.12.2.803.287-292 Permalink/DOI:

  17. Cytotoxicity of platinum(IV) and platinum(II) complexes containing 1R,2R-cyclohexanediamine as a ligand. (United States)

    Yamashita, T; Hirose, J; Noji, M; Saito, R; Tomida, H; Kidani, Y


    Several Pt(IV) and Pt(II) complexes containing 1R,2R-cyclohexanediamine (1R,2R-dach) as a carrier ligand were synthesized. The cytotoxicities and the uptake of the platinum complexes by leukemia L1210 cells were compared in order to study the correlation between their structures and cytotoxicities. [Pt(II)Cl2(1R,2R-dach)], [(Pt(II)(oxalato)(1R,2R-dach)], and [Pt(II)(malonato)(1R,2R-dach)], which have excellent anticancer properties, exhibited very high cytotoxicities and were easily taken up by leukemia L1210 cells. [Pt(IV)Cl4(1R,2R-dach)], trans(Cl)-[Pt(IV)Cl2(oxalato)(1R,2R-dach)], and trans(Cl)-[Pt(IV)Cl2(malonato)(1R,2R-dach)] also had high cytotoxicities. After a short incubation time, the uptake of [Pt(II)Cl2(1R,2R-dach)], [Pt(II)(oxalato)(1R,2R-dach)], and [Pt(II)(malonato)(1R,2R-dach)] by leukemia L1210 cells were respectively very similar to those of [Pt(IV)Cl4(1R,2R-dach)], trans(Cl)-[Pt(IV)Cl2(oxalato)(1R,2R-dach)], and trans(Cl)-[Pt(IV)Cl2(malonato)(1R,2R-dach)]. In addition, trans(OH)-[Pt(IV)(OH)2Y2(1R,2R-dach)] (Y2: oxalato or malonato) did not exhibit cytotoxicity towards leukemia L1210 cells, whereas trans(Cl)-[Pt(IV)Cl2Y2(1R,2R-dach)] (Y2: oxalato or malonato) were highly cytotoxic. The accumulation of trans(OH)-[Pt(IV)(OH)2Y2(1R,2R-dach)] in leukemia L1210 cells was much lower than that of trans(Cl)-[Pt(IV)Cl2Y2(1R,2R-dach)]. Platinum(IV) complexes, in which leaving groups are replaced by hydroxide groups, have decreased cytotoxic activity, because the hydroxide groups of the platinum(IV) complex reduce the uptake of platinum by the cells. trans(OH),cis(Cl)-[Pt(IV)(OH)2Cl2(1R,2R-dach)], which has hydroxide and chloride groups, was easily incorporated into the cells and exhibited the high cytotoxic activity. This behavior indicates that the chloride group apparently overcomes the ameliorating effect of the hydroxide group.

  18. On the electronic structure of nitro-substituted bipyridines and their platinum complexes. (United States)

    Murray, Paul R; Crawford, Stephen; Dawson, Alice; Delf, Alexander; Findlay, Calum; Jack, Lorna; McInnes, Eric J L; Al-Musharafi, Salma; Nichol, Gary S; Oswald, Iain; Yellowlees, Lesley J


    We report the preparation and electrochemical studies of a systematic series of mono- and di-nitro-substituted 2,2'-bipyridine (bipy) compounds [x-NO(2)-bipy (x = 3,4) and x,x'-(NO(2))(2)-bipy (x,x' = 3, 4, 5)] and their complexes with platinum(II), [Pt(x-NO(2)-bipy)Cl(2)] and [Pt(x,x'-(NO(2))(2)-bipy)Cl(2)]. The effect of the number and substitution pattern of the nitro groups on the low-lying acceptor molecular orbitals (involved in charge transfer transitions) is probed by in situ UV/Vis/NIR and EPR spectroelectrochemical methods, supported by DFT calculations. The LUMOs of x-NO(2)-bipy (x = 3-5) are largely localised on the NO(2)-pyridyl moiety; this is also true of their {PtCl(2)} complexes but with a small but significant shift of electron density from the nitro groups. The LUMOs of x,x'-(NO(2))(2)-bipy with x = 3 and 5 are delocalised over both NO(2)-pyridyl rings, but for 4,4'-(NO(2))(2)-bipy is localised on a single NO(2)-pyridyl ring. In all cases the LUMO of the [Pt(x,x'-(NO(2))(2)-bipy)Cl(2)] complexes is delocalised over both nitro-pyridyl rings. For all complexes, the 4(4') derivatives allows greatest overlap with metal valence orbitals in the LUMO.

  19. Formic Acid Electrooxidation by a Platinum Nanotubule Array Electrode

    Directory of Open Access Journals (Sweden)

    Eric Broaddus


    Full Text Available One-dimensional metallic nanostructures such as nanowires, rods, and tubes have drawn much attention for electrocatalytic applications due to potential advantages that include fewer diffusion impeding interfaces with polymeric binders, more facile pathways for electron transfer, and more effective exposure of active surface sites. 1D nanostructured electrodes have been fabricated using a variety of methods, typically showing improved current response which has been attributed to improved CO tolerance, enhanced surface activity, and/or improved transport characteristics. A template wetting approach was used to fabricate an array of platinum nanotubules which were examined electrochemically with regard to the electrooxidation of formic acid. Arrays of 100 and 200 nm nanotubules were compared to a traditional platinum black catalyst, all of which were found to have similar surface areas. Peak formic acid oxidation current was observed to be highest for the 100 nm nanotubule array, followed by the 200 nm array and the Pt black; however, CO tolerance of all electrodes was similar, as were the onset potentials of the oxidation and reduction peaks. The higher current response was attributed to enhanced mass transfer in the nanotubule electrodes, likely due to a combination of both the more open nanostructure as well as the lack of a polymeric binder in the catalyst layer.

  20. Surface segregations in platinum-based alloy nanoparticles (United States)

    Yamakawa, Shunsuke; Asahi, Ryoji; Koyama, Toshiyuki


    A phase-field model that describes the radial distributions of the ordered-disordered phase and surface segregation in a single-alloy nanoparticle is introduced to clarify the overall behavior of surface segregation of various Pt-based alloy nanoparticles. One of the obstacles to apply a platinum-transition metal alloy as a cathode electro-catalyst of a polymer electrolyte fuel cell is the need to ensure the retention of the designed surface composition in an alloy nanoparticle against the alloy combinations, a particle size, and heat treatment. From the results of calculations for CrPt, FePt, CoPt, NiPt, CuPt, PdPt, IrPt, and AuPt binary nanoparticles with diameters below 10 nm at 973.15 K, the compositional variation within a single particle was found to depend on the balance between the atomic interaction within particles and the surface free energy. In addition, the obtained specific steady-state composition of the surface varied significantly with alloy combination and particle diameter. Based on the general tendencies of a binary system to exhibit segregation, attempts to control the amount of platinum segregation on the surface using a ternary-alloy system were examined.