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Sample records for osmium phosphides

  1. Aluminum phosphide

    Integrated Risk Information System (IRIS)

    Aluminum phosphide ; CASRN 20859 - 73 - 8 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments for Noncarcinoge

  2. Osmium in the rivers

    SciTech Connect

    Sharma, M. |; Wasserburg, G.J.

    1997-12-01

    There is a large uncertainty in our understanding of the behavior of osmium during weathering and transport into deep oceans and the osmium budget of the oceans. The problem stems chiefly from the lack of osmium data on the dissolved load in the rivers and in the estuaries. In this study, the concentration and isotopic composition of osmium have been determined in three North American rivers (the Mississippi, the Columbia, and the Connecticut) and one river draining central Europe and flowing into the Baltic Sea (the Vistula). Osmium concentration in the Mississippi and the Vistula is about 45 femto mol kg{sup -1}; it is about 14 and 15 femto mol kg{sup -1} for the Connecticut and the Columbia, respectively. The {sup 187}Os/{sup 186}Os ratios estimated for the Mississippi and the Vistula are 10.4 and 10.7, respectively. For the Connecticut and the Columbia {sup 187}Os/{sup 186}Os = 8.8 and 14.4, respectively. Of all the rivers examined, the Mississippi is by far the largest, supplying {approximately}1.6% of the total annual world river flow. Its osmium isotopic composition is identical to the upper Mississippi valley loesses indicating (1) congruent dissolution of the bedrock and (2) little or no impact of anthropogenic sources on the osmium isotopic composition of the dissolved load. The latter observation indicates that the upper limit of the anthropogenic input in the dissolved osmium load of the Mississippi outflow is about 250 g yr{sup -1}. While the osmium concentration of the Vistula is high the isotopic composition does not appear to have been affected by substantial pollution. The river data can be used to put limits on the mean residence time of osmium in the oceans ({bar {tau}}{sub Os}) and on the osmium budget of the oceans. 17 refs., 1 fig., 1 tab.

  3. Osmium in the rivers

    NASA Astrophysics Data System (ADS)

    Sharma, M.; Wasserburg, G. J.

    1997-12-01

    There is a large uncertainty in our understanding of the behavior of osmium during weathering and transport into deep oceans and the osmium budget of the oceans. The problem stems chiefly from the lack of osmium data on the dissolved load in the rivers and in the estuaries. In this study, the concentration and isotopic composition of osmium have been determined in three North American rivers (the Mississippi, the Columbia, and the Connecticut) and one river draining central Europe and flowing into the Baltic Sea (the Vistula). Osmium concentration in the Mississippi and the Vistula is about 45 femto mol kg -1; it is about 14 and 15 femto mol kg -1 for the Connecticut and the Columbia, respectively. The 187Os/186Os ratios estimated for the Mississippi and the Vistula are 10.4 and 10.7, respectively. For the Connecticut and the Columbia 187Os/186Os = 8.8 and 14.4 , respectively. Of all the rivers examined, the Mississippi is by far the largest, supplying ˜1.6% of the total annual world river flow. Its osmium isotopic composition is identical to the upper Mississippi valley loesses (Esser and Turekian, 1993a) indicating (1) congruent dissolution of the bedrock and (2) little or no impact of anthropogenic sources on the osmium isotopic composition of the dissolved load. The latter obserbation indicates that the upper limit of the anthropogenic input in the dissolved osmium load of the Mississippi outflow is about 250 g yr -1. While the osmium concentration of the Vistula is high the isotopic composition does not appear to have been affected by substantial pollution. The river data can be used to put limits on the mean residence time of osmium in the oceans ( overlineτOs) and on the osmium budget of the oceans. If the bulk river influx of dissolved osmium into the oceans is similar to that of the Mississippi, we get a value for the net riverine inflow of osmium of 1680 mol yr -1. If there were no sequestering of osmium in the estuaries, this would give a value of

  4. Photovoltaic cells employing zinc phosphide

    DOEpatents

    Barnett, Allen M.; Catalano, Anthony W.; Dalal, Vikram L.; Masi, James V.; Meakin, John D.; Hall, Robert B.

    1984-01-01

    A photovoltaic cell having a zinc phosphide absorber. The zinc phosphide can be a single or multiple crystal slice or a thin polycrystalline film. The cell can be a Schottky barrier, heterojunction or homojunction device. Methods for synthesizing and crystallizing zinc phosphide are disclosed as well as a method for forming thin films.

  5. Photovoltaic cells employing zinc phosphide

    SciTech Connect

    Barnett, A.M.; Catalano, A.W.; Dalal, V.L.; Hall, R.B.; Masi, J.V.; Meakin, J.D.

    1984-10-16

    A photovoltaic cell having a zinc phosphide absorber. The zinc phosphide can be a single or multiple crystal slice or a thin polycrystalline film. The cell can be a Schottky barrier, heterojunction or homojunction device. Methods for synthesizing and crystallizing zinc phosphide are disclosed as well as a method for forming thin films.

  6. Synthesis of indium phosphide

    NASA Astrophysics Data System (ADS)

    Adamski, Joseph A.

    1983-11-01

    Polycrystalline ingots of indium phosphide have been synthesized using the direct reaction technique. Indium phosphide has been grown under various phosphorus pressures (3 to 30 atm). Several temperature profiles were used to study the effect of temperature on mobility, carrier concentration, grain size, homogeneity, and stoichiometry. Quartz and pyrolytic boron nitride boats are used. Several experiments were performed placing the PBN and quartz boats inside born nitride and aluminum oxide tubes in an attempt to lower silicon contamination. In-situ vacuum baking of the raw indium charge has resulted in a significant improvement in the purity of the synthesized InP.

  7. Osmium Recycling in Subduction Zones

    PubMed

    Brandon; Creaser; Shirey; Carlson

    1996-05-10

    Peridotite xenoliths from the Cascade arc in the United States and in the Japan arc have neodymium and osmium isotopic compositions that are consistent with addition of 5 to 15 percent of subducted material to the present-day depleted mantle. These observations suggest that osmium can be partitioned into oxidized and chlorine-rich slab-derived fluids or melts. These results place new constraints on the behavior of osmium (and possibly other platinum group elements) during subduction of oceanic crust by showing that osmium can be transported into the mantle wedge. PMID:8662577

  8. Osmium Recycling in Subduction Zones

    PubMed

    Brandon; Creaser; Shirey; Carlson

    1996-05-10

    Peridotite xenoliths from the Cascade arc in the United States and in the Japan arc have neodymium and osmium isotopic compositions that are consistent with addition of 5 to 15 percent of subducted material to the present-day depleted mantle. These observations suggest that osmium can be partitioned into oxidized and chlorine-rich slab-derived fluids or melts. These results place new constraints on the behavior of osmium (and possibly other platinum group elements) during subduction of oceanic crust by showing that osmium can be transported into the mantle wedge.

  9. Solar abundance of osmium

    PubMed Central

    Jacoby, George; Aller, Lawrence H.

    1976-01-01

    The abundance parameter, log gfA, where g is the statistical weight of the lower level, f is the oscillator strength, and A is the abundance (by numbers of atoms with respect to hydrogen), has been derived for three lines of osmium by a method of spectrum synthesis. An apparent discordance of the derived abundance with that found from the carbonaceous chondrites is probably to be attributed primarily to errors in the f-values, and blending with unknown contributors. PMID:16592314

  10. Gallium phosphide energy converters

    NASA Technical Reports Server (NTRS)

    Sims, P. E.; DiNetta, Louis C.; DuganCavanagh, K.; Goetz, M. A.

    1996-01-01

    Betavoltaic power supplies based on gallium phosphide can supply long term low-level power with high reliability. Results are presented for GaP devices powered by Ni-63 and tritiarated phosphors. Leakage currents as low as 1.2 x 10(exp -17) A/cm(exp 2) have been measured and the temperature dependence of the reverse saturation current is found to have ideal behavior. A small demonstration system has been assembled that generates and stores enough electricity to light up an LED.

  11. Osmium: An Appraisal of Environmental Exposure

    PubMed Central

    Smith, Ivan C.; Carson, Bonnie L.; Ferguson, Thomas L.

    1974-01-01

    In the U.S., the chief source of new osmium is copper refining, where this metal is produced as a byproduct. Probably less than 10% of the osmium in the original copper ore is recovered, and 1000–3000 oz troy of osmium is lost each year to the environment as the toxic, volatile tetroxide from copper smelters. In 1971, about 2000 oz troy of osmium was domestically refined, most of which was from secondary sources. An additional 4169 oz troy of osmium was toll-refined. Major uses for osmium tetroxide identified are for catalysis, especially in steroid synthesis, and for tissue staining. Minor uses of osmium metal are for electrical contacts and for imparting hardness to alloys for mechanical pivots, etc. Unreclaimed osmium tetroxide that reaches wastewater streams is probably rapidly reduced by organic matter to nontoxic osmium dioxide or osmium metal, which would settle out in the sediment of the water course. Waste osmium metal, itself innocuous and chemically resistant, would be oxidized to the toxic tetroxide if incinerated. Because of the small amounts used and their wide dispersal, the amounts of osmium tetroxide in wastewater and air should pose no hazard to man or the environment. The chief acute toxic effects of osmium tetroxide are well known and include eye and respiratory-tract damage. Few data are available that provide information on possible effects of nonacute exposure resulting from environmental contamination by osmium. However, workers continually exposed to osmium tetroxide vapors (refiners and histologists) and rheumatoid arthritis patients who have received intra-articular injections of osmic acid solutions have shown no apparent damage from exposure to low levels of osmium. PMID:4470919

  12. Gallium phosphide energy converters

    NASA Technical Reports Server (NTRS)

    Sims, P. E.; Dinetta, L. C.; Goetz, M. A.

    1995-01-01

    Gallium phosphide (GaP) energy converters may be successfully deployed to provide new mission capabilities for spacecraft. Betavoltaic power supplies based on the conversion of tritium beta decay to electricity using GaP energy converters can supply long term low-level power with high reliability. High temperature solar cells, also based on GaP, can be used in inward-bound missions greatly reducing the need for thermal dissipation. Results are presented for GaP direct conversion devices powered by Ni-63 and compared to the conversion of light emitted by tritiarated phosphors. Leakage currents as low as 1.2 x 10(exp -17) A/sq cm have been measured and the temperature dependence of the reverse saturation current is found to have ideal behavior. Temperature dependent IV, QE, R(sub sh), and V(sub oc) results are also presented. These data are used to predict the high-temperature solar cell and betacell performance of GaP devices and suggest appropriate applications for the deployment of this technology.

  13. Fundamental studies of the metallurgical, electrical, and optical properties of gallium phosphide and gallium phosphide alloys

    NASA Technical Reports Server (NTRS)

    1972-01-01

    Abstracts, bibliographic data, oral presentations, and published papers on (1) Diffusion of Sulfur in Gallium Phosphide and Gallium Arsenide, and (2) Properties of Gallium Phosphide Schottky Barrier Rectifiers for Use at High Temperature are presented.

  14. Phonon properties of americium phosphide

    NASA Astrophysics Data System (ADS)

    Arya, B. S.; Aynyas, Mahendra; Sanyal, S. P.

    2016-05-01

    Phonon properties of AmP have been studied by using breathing shell models (BSM) which includes breathing motion of electrons of the Am atoms due to f-d hybridization. The phonon dispersion curves, specific heat calculated from present model. The calculated phonon dispersion curves of AmP are presented follow the same trend as observed in uranium phosphide. We discuss the significance of this approach in predicting the phonon dispersion curves of these compounds and examine the role of electron-phonon interaction.

  15. Phosphide poisoning: a review of literature.

    PubMed

    Bumbrah, Gurvinder Singh; Krishan, Kewal; Kanchan, Tanuj; Sharma, Madhulika; Sodhi, Gurvinder Singh

    2012-01-10

    Metal phosphides in general and aluminium phosphide in particular are potent insecticides and rodenticides. These are commercially used for protection of crops during storage, as well as during transportation. However, these are highly toxic substances. Their detrimental effects may range from nausea and headache to renal failure and death. It is, therefore, pertinent to ensure their circumspect handling to avoid poisoning episodes. Its poisoning has a high mortality and recent years have seen an increase in the number of poisoning cases and deaths caused by suicidal ingestion. Yet due to their broad spectrum applications, these chemicals cannot be written off. The present communication reviews the various aspects of toxicity associated with metal phosphides.

  16. Can Ni phosphides become viable hydroprocessing catalysts?

    SciTech Connect

    Soled, S.; Miseo, S.; Baumgartner, J.; Guzman, J.; Bolin, T.; Meyer, R.

    2015-05-15

    We prepared higher surface area nickel phosphides than are normally found by reducing nickel phosphate. To do this, we hydrothermally synthesized Ni hydroxy phosphite precursors with low levels of molybdenum substitution. The molybdenum substitution increases the surface area of these precursors. During pretreatment in a sulfiding atmosphere (such as H2S/H2) dispersed islands of MoS2 segregate from the precursor and provide a pathway for H2 dissociation that allows reduction of the phosphite precursor to nickel phosphide at substantially lower temperatures than in the absence of MoS2. The results reported here show that to create nickel phosphides with comparable activity to conventional supported sulfide catalysts, one would have to synthesize the phosphide with surface areas exceeding 400 m2/g (i.e. with nanoparticles less than 30 Å in lateral dimension).

  17. New osmium-based reagent for the dihydroxylation of alkenes.

    PubMed

    Donohoe, Timothy J; Harris, Robert M; Butterworth, Sam; Burrows, Jeremy N; Cowley, Andrew; Parker, Jeremy S

    2006-06-01

    The cis dihydroxylation of alkenes is most efficiently accomplished by reaction with osmium tetroxide. Recently, the expense and toxicity of osmium tetroxide have led to a number of attempts to harness alternative osmium-based reagents, including microencapsulation and solid support techniques. We describe here the development of a new nonvolatile, stable, and recoverable osmium-based reagent devised for the stoichiometric cis dihydroxylation of alkenes. Although attempts to make this new dihydroxylation work with catalytic amounts of this reagent were unsuccessful, we did develop a sensitive test for free osmium tetroxide leached from the reagent in situ: this test may well have uses in probing future applications of derivatized osmium reagents.

  18. Development of anticancer agents: wizardry with osmium.

    PubMed

    Hanif, Muhammad; Babak, Maria V; Hartinger, Christian G

    2014-10-01

    Platinum compounds are one of the pillars of modern cancer chemotherapy. The apparent disadvantages of existing chemotherapeutics have led to the development of novel anticancer agents with alternative modes of action. Many complexes of the heavy metal osmium (Os) are potent growth inhibitors of human cancer cells and are active in vivo, often superior or comparable to cisplatin, as the benchmark metal-based anticancer agent, or clinically tested ruthenium (Ru) drug candidates. Depending on the choice of ligand system, osmium compounds exhibit diverse modes of action, including redox activation, DNA targeting or inhibition of protein kinases. In this review, we highlight recent advances in the development of osmium anticancer drug candidates and discuss their cellular mechanisms of action.

  19. Development of anticancer agents: wizardry with osmium.

    PubMed

    Hanif, Muhammad; Babak, Maria V; Hartinger, Christian G

    2014-10-01

    Platinum compounds are one of the pillars of modern cancer chemotherapy. The apparent disadvantages of existing chemotherapeutics have led to the development of novel anticancer agents with alternative modes of action. Many complexes of the heavy metal osmium (Os) are potent growth inhibitors of human cancer cells and are active in vivo, often superior or comparable to cisplatin, as the benchmark metal-based anticancer agent, or clinically tested ruthenium (Ru) drug candidates. Depending on the choice of ligand system, osmium compounds exhibit diverse modes of action, including redox activation, DNA targeting or inhibition of protein kinases. In this review, we highlight recent advances in the development of osmium anticancer drug candidates and discuss their cellular mechanisms of action. PMID:24955838

  20. The concentration and isotopic composition of osmium in the oceans

    SciTech Connect

    Sharma, M.; Papanastassiou, D.A.; Wasserburg, G.J.

    1997-08-01

    Osmium is one of the rarer elements in seawater. Analytical difficulties have previously prevented the direct measurement of the osmium concentration and isotopic composition in seawater. We report a chemical separation procedure that yields quantitative extraction of osmium standard and of osmium tracer by iron hydroxide precipitation from seawater doped with osmium standard, osmium tracer, and FeCl{sub 3}. The iron hydroxide precipitate is processed to extract osmium, using techniques developed for iron meteorites. Utilizing this procedure, water samples from the Pacific and Atlantic oceans were analyzed for osmium concentration and isotopic composition. Direct determination of the osmium concentration of seawater gives between 15 and 19 fM kg{sup -1}. Detailed experiments on different aliquots of one seawater sample from the North Atlantic Ocean, keeping the amounts of reagents constant, yield concentrations from 16 to 19 fM kg{sup -1}. The variability in concentration is outside the uncertainty introduced because of blanks and indicates a lack of full equilibration between the osmium tracer and seawater osmium. The most reliable osmium concentration of the North Atlantic deep ocean water is 19 fM kg {sup -1} with the {sup 187}Os/{sup 186}Os ratio being 8.7{+-}2 (2{sigma}). Detailed experiments on one seawater sample from the Central Pacific Ocean indicate that the most reliable osmium concentration of the deep ocean water from the Central Pacific is 19 fM kg{sup -1} with the {sup 187}Os/{sup 186}Os ratio being 8.7{+-}0.3 (2{sigma}). The directly measured osmium isotopic composition of the oceans is in good agreement with that obtained from the analysis of some rapidly accumulating organic rich sediments. A sample of ambient seawater around the Juan de Fuca Ridge gave {sup 187}Os/{sup 186}Os = 6.9{+-} 0.4. 42 refs., 6 figs., 4 tabs.

  1. Development of gallium aluminum phosphide electroluminescent diodes

    NASA Technical Reports Server (NTRS)

    Chicotka, R. J.; Lorenz, M. R.; Nethercot, A. H.; Pettit, G. D.

    1972-01-01

    Work done on the development of gallium aluminum phosphide alloys for electroluminescent light sources is described. The preparation of this wide band gap semiconductor alloy, its physical properties (particularly the band structure, the electrical characteristics, and the light emitting properties) and work done on the fabrication of diode structures from these alloys are broadly covered.

  2. Transition Metal Phosphide Hydroprocessing Catalysts: A review

    SciTech Connect

    Oyama, S.; Gott, T; Zhao, H; Lee, Y

    2009-01-01

    The diminishing quality of oil feedstocks coupled with increasingly more stringent environmental regulations limiting the content of sulfur in transportation fuels have given rise to a need for improved hydroprocessing technology. This review begins with a summary of the major improvements in hydrodesulfurization (HDS) and hydrodenitrogenation (HDN) catalysts and processes that have been reported in recent years. It then describes a new class of hydroprocessing catalysts, the transition metal phosphides, which have emerged as a promising group of high-activity, stable catalysts. The phosphides have physical properties resembling ceramics, so are strong and hard, yet retain electronic and magnetic properties similar to metals. Their crystal structures are based on trigonal prisms, yet they do not form layered structures like the sulfides. They display excellent performance in HDS and HDN, with the most active phosphide, Ni{sub 2}P, having activity surpassing that of promoted sulfides on the basis of sites titrated by chemisorption (CO for the phosphides, O{sub 2} for the sulfides). In the HDS of difficult heteroaromatics like 4,6-dimethyldibenzothiophene Ni{sub 2}P operates by the hydrogenation pathway, while in the HDN of substituted nitrogen compounds like 2-methylpiperidine it carries out nucleophilic substitution. The active sites for hydrogenation in Ni{sub 2}P have a square pyramidal geometry, while those for direct hydrodesulfurization have a tetrahedral geometry. Overall, Ni{sub 2}P is a promising catalyst for deep HDS in the presence of nitrogen and aromatic compounds.

  3. Sinterless Formation Of Contacts On Indium Phosphide

    NASA Technical Reports Server (NTRS)

    Weizer, Victor G.; Fatemi, Navid S.

    1995-01-01

    Improved technique makes it possible to form low-resistivity {nearly equal to 10(Sup-6) ohm cm(Sup2)} electrical contacts on indium phosphide semiconductor devices without damaging devices. Layer of AgP2 40 Angstrom thick deposited on InP before depositing metal contact. AgP2 interlayer sharply reduces contact resistance, without need for sintering.

  4. Osmium-191/iridium-191m radionuclide

    DOEpatents

    Knapp, Jr., Furn F.; Butler, Thomas A.; Brihaye, Claude

    1987-01-01

    A generator system to provide iridium-191m for clinical imaging applications comprises an activated carbon adsorbent loaded with a compound containing the parent nuclide, osmium-191. The generator, which has a shelf-life in excess of two weeks and does not require a scavenger column, can be eluted with physiologically compatible saline.

  5. Osmium-191/iridium-191m radionuclide

    DOEpatents

    Knapp, F.F. Jr.; Butler, T.A.; Brihaye, C.

    1985-08-26

    A generator system to provide iridium-191m for clinical imaging applications comprises an activated carbon adsorbent loaded with a compound containing the parent nuclide, osmium-191. The generator, which has a shelf-life in excess of two weeks and does not require a scavenger column, can be eluted with physiologically compatible saline. 4 figs. 3 tabs.

  6. Car Catalysts Impact on Anthropogenic Osmium Budget

    NASA Astrophysics Data System (ADS)

    Poirier, A.; Gariepy, C.

    2004-05-01

    A few sources of anthropogenic osmium have been identified that clearly contribute to the observed increase in unradiogenic osmium in recent urban sediments (a major one being biomedical use of OsO4 as a lipid stain used to enhance cell structures for optical and electron microscopy (1,2,3,4)). Previous studies suggested the possibility that automobile catalytic converters might also contribute to this Os pollution, even though this metal is not directly employed in car catalysts (1,4). The importance of this potential source has never been quantitatively tested. Here, we present results for the Os isotope analysis of 4 new catalytic converters. The unradiogenic 187Os/188Os composition of all catalytic converters is similar to typical platinum group elements ore (5). The measured Os concentrations are in the pg/g range (6-228 pg/g). The physical conditions in catalysts (oxidising environment and 300 \\deg C) are effective in promoting the oxidation of osmium to its gaseous form. We therefore expect that osmium volatility plays an important role in releasing Os from the catalysts. Based on measured concentrations, we estimate that car catalysts could be responsible for up to several picograms of anthropogenic osmium deposited per square meter in urban areas every year. Our results strengthen the idea that automobile catalytic converters might be a significant source of Os pollution. 1.Ravizza, G. E. and Bothner, M. H. (1996) Geochimica et Cosmochimica Acta, 60; 15, 2753-2763. 2.Smith, I. C., Carson, B. L., and Ferguson T.L. (1974) Environmental Health Perspectives, 8, 201-213. 3.Esser, B. K. and Turekian, K. K. (1993) Environmental Science and Technology, 27; 13, 2719-2724. 4.Rauch S., Hemond H.F., and Peucker-Ehrenbrink, B. (2004) Environmental Science and Technology, 38, 396-402. 5.McCandless, T. and Ruiz, J. (1991) Geology, 19, 1225-1228.

  7. InP (Indium Phosphide): Into the future

    NASA Technical Reports Server (NTRS)

    Brandhorst, Henry W., Jr.

    1989-01-01

    Major industry is beginning to be devoted to indium phosphide and its potential applications. Key to these applications are high speed and radiation tolerance; however the high cost of indium phosphide may be an inhibitor to progress. The broad applicability of indium phosphide to many devices will be discussed with an emphasis on photovoltaics. Major attention is devoted to radiation tolerance and means of reducing cost of devices. Some of the approaches applicable to solar cells may also be relevant to other devices. The intent is to display the impact of visionary leadership in the field and enable the directions and broad applicability of indium phosphide.

  8. Osmium complex binding to mismatched methylcytosine: effect of adjacent bases.

    PubMed

    Nomura, Akiko; Tainaka, Kazuki; Okamoto, Akimitsu

    2009-01-01

    We investigated the efficiency of osmium complex formation at 5-methylcytosine in mismatched DNA duplexes. Osmium complexation was not observed in fully matched duplexes, whereas the complexation site and efficiency in mismatched duplexes depended on the 5'-neighboring base of the 5-methylcytosine. In particular, when the base adjacent to the 5' side of the mismatched base pair was thymine, a unique side reaction was observed. However, the mismatched base pairs did not influence the selectivity of osmium complexation with methylated DNA.

  9. Synthesis and controlled growth of osmium nanoparticles by electron irradiation.

    PubMed

    Pitto-Barry, Anaïs; Perdigao, Luis M A; Walker, Marc; Lawrence, James; Costantini, Giovanni; Sadler, Peter J; Barry, Nicolas P E

    2015-12-21

    We have synthesised osmium nanoparticles of defined size (1.5-50 nm) on a B- and S-doped turbostratic graphitic structure by electron-beam irradiation of an organometallic osmium complex encapsulated in self-spreading polymer micelles, and characterised them by transmission electron microscopy (TEM), high-resolution TEM (HRTEM), and atomic force microscopy (AFM) on the same grid. Oxidation of the osmium nanoparticles after exposure to air was detected by X-ray photoelectron spectroscopy (XPS). PMID:26418726

  10. Gallium arsenide phosphide top solar cell

    SciTech Connect

    McNeely, J.B.; Barnett, A.M.

    1986-04-15

    This patent describes a tandem solar cell having a silicon solar cell for a low energy gap bottom cell and a high energy gap top cell. The improvement which a gallium arsenide phosphide top solar cell which described here is a. a transparent gallium phosphide substrate; b. a first active semiconductor layer of GaAs/sub 1-Y/P/sub Y/ and of a first conductivity type overlying the substrate; c. a second active semiconductor layer of GaAs/sub 1-X/P/sub X/ and of a second conductivity type opposite the first conductivity type overlying and forming a photovoltaic junction therewith; d. a transparent first electrical contact in ohmic contact with the substrate; and e. a transparent second electrical contact in ohmic contact with the second active semiconductor layer.

  11. Efficient water reduction with gallium phosphide nanowires

    PubMed Central

    Standing, Anthony; Assali, Simone; Gao, Lu; Verheijen, Marcel A.; van Dam, Dick; Cui, Yingchao; Notten, Peter H. L.; Haverkort, Jos E. M.; Bakkers, Erik P. A. M.

    2015-01-01

    Photoelectrochemical hydrogen production from solar energy and water offers a clean and sustainable fuel option for the future. Planar III/V material systems have shown the highest efficiencies, but are expensive. By moving to the nanowire regime the demand on material quantity is reduced, and new materials can be uncovered, such as wurtzite gallium phosphide, featuring a direct bandgap. This is one of the few materials combining large solar light absorption and (close to) ideal band-edge positions for full water splitting. Here we report the photoelectrochemical reduction of water, on a p-type wurtzite gallium phosphide nanowire photocathode. By modifying geometry to reduce electrical resistance and enhance optical absorption, and modifying the surface with a multistep platinum deposition, high current densities and open circuit potentials were achieved. Our results demonstrate the capabilities of this material, even when used in such low quantities, as in nanowires. PMID:26183949

  12. Microwave-assisted synthesis of transition metal phosphide

    DOEpatents

    Viswanathan, Tito

    2014-12-30

    A method of synthesizing transition metal phosphide. In one embodiment, the method has the steps of preparing a transition metal lignosulfonate, mixing the transition metal lignosulfonate with phosphoric acid to form a mixture, and subjecting the mixture to a microwave radiation for a duration of time effective to obtain a transition metal phosphide.

  13. The concentration and isotopic composition of osmium in the oceans

    NASA Astrophysics Data System (ADS)

    Sharma, M.; Papanastassiou, D. A.; Wasserburg, G. J.

    1997-08-01

    Osmium is one of the rarer elements in seawater. Analytical difficulties have previously prevented the direct measurement of the osmium concentration and isotopic composition in seawater. We report a chemical separation procedure that yields quantitative extraction of osmium standard and of osmium tracer by iron hydroxide precipitation from seawater doped with osmium standard, osmium tracer, and FeCl 3. The iron hydroxide precipitate is processed to extract osmium, using techniques developed for iron meteorites. Utilizing this procedure, water samples from the Pacific and Atlantic oceans were analyzed for osmium concentration and isotopic composition. Direct determination of the osmium concentration of seawater gives between 15 and 19 fM kg -1. Detailed experiments on different aliquots of one seawater sample from the North Atlantic Ocean, keeping the amounts of reagents constant, yield concentrations from 16 to 19 fM kg -1. The variability in concentration is outside the uncertainty introduced because of blanks and indicates a lack of full equilibration between the osmium tracer and seawater osmium. The most reliable osmium concentration of the North Atlantic deep ocean water is 19 fM kg -1 with the 187Os 186Os ratio being 8.7 ± 0.2 (2σ). Detailed experiments on one seawater sample from the Central Pacific Ocean indicate that the most reliable osmium concentration of the deep ocean water from the Central Pacific is 19 fM kg -1 with the 187Os 186Os ratio being 8.7 ± 0.3 (2σ). The directly measured osmium isotopic composition of the oceans is in good agreement with that obtained from the analysis of some rapidly accumulating organic rich sediments ( Ravizza and Turekian, 1992). A sample of ambient seawater around the Juan de Fuca Ridge gave 187Os 186Os= 6.9 ± 0.4. This is distinctly lower than the deep-sea water value and may reflect local hydrothermal activity or some analytical difficulty with this sample. The osmium isotopic composition of the deep oceans

  14. Stability and bonding of new superalkali phosphide species.

    PubMed

    Cochran, Elizabeth; Muller, Giel; Meloni, Giovanni

    2015-09-01

    New superalkali phosphide species with the molecular formulas F2Li3P, F2Li3P2, and F4Li6P were investigated. Using the CBS-QB3 composite method to optimize geometry and energetic parameters, four monophosphides, two diphosphides, and one disuperalkali phosphide were discovered that contain intriguing structural features, including hyperlithiation, phosphorus-phosphorus bonds, and planar tetracoordinated phosphorus. It is believed that these features lend to the stability of these structures and may warrant further experimental investigation of these phosphide species to determine if they could play some role in the development of novel chemical reactions and/or materials. PMID:26219751

  15. A systematic review of aluminium phosphide poisoning.

    PubMed

    Mehrpour, Omid; Jafarzadeh, Mostafa; Abdollahi, Mohammad

    2012-03-01

    Every year, about 300,000 people die because of pesticide poisoning worldwide. The most common pesticide agents are organophosphates and phosphides, aluminium phosphide (AlP) in particular. AlP is known as a suicide poison that can easily be bought and has no effective antidote. Its toxicity results from the release of phosphine gas as the tablet gets into contact with moisture. Phosphine gas primarily affects the heart, lungs, gastrointestinal tract, and kidneys. Poisoning signs and symptoms include nausea, vomiting, restlessness, abdominal pain, palpitation, refractory shock, cardiac arrhythmias, pulmonary oedema, dyspnoea, cyanosis, and sensory alterations. Diagnosis is based on clinical suspicion, positive silver nitrate paper test to phosphine, and gastric aspirate and viscera biochemistry. Treatment includes early gastric lavage with potassium permanganate or a combination with coconut oil and sodium bicarbonate, administration of charcoal, and palliative care. Specific therapy includes intravenous magnesium sulphate and oral coconut oil. Moreover, acidosis can be treated with early intravenous administration of sodium bicarbonate, cardiogenic shock with fluid, vasopresor, and refractory cardiogenic shock with intra-aortic baloon pump or digoxin. Trimetazidine may also have a useful role in the treatment, because it can stop ventricular ectopic beats and bigeminy and preserve oxidative metabolism. This article reviews the epidemiological, toxicological, and clinical/pathological aspects of AlP poisoning and its management.

  16. Anthropogenic forcings on the surficial osmium cycle.

    PubMed

    Rauch, Sebastien; Peucker-Ehrenbrink, Bernhard; Kylander, Malin E; Weiss, Dominik J; Martinez-Cortizas, Antonio; Heslop, David; Olid, Carolina; Mighall, Tim M; Hemond, Harold F

    2010-02-01

    Osmium is among the least abundant elements in the Earth's continental crust. Recent anthropogenic Os contamination of the environment from mining and smelting activities, automotive catalytic converter use, and hospital discharges has been documented. Here we present evidence for anthropogenic overprinting of the natural Os cycle using a ca. 7000-year record of atmospheric Os deposition and isotopic composition from an ombrotrophic peat bog in NW Spain. Preanthropogenic Os accumulation in this area is 0.10 +/- 0.04 ng m(-2) y(-1). The oldest strata showing human influence correspond to early metal mining and processing on the Iberian Peninsula (ca. 4700-2500 cal. BP). Elevated Os accumulation rates are found thereafter with a local maximum of 1.1 ng m(-2) y(-1) during the Roman occupation of the Iberian Peninsula (ca. 1930 cal. BP) and a further increase starting in 1750 AD with Os accumulation reaching 30 ng m(-2) y(-1) in the most recent samples. Osmium isotopic composition ((187)Os/(188)Os) indicates that recent elevated Os accumulation results from increased input of unradiogenic Os from industrial and automotive sources as well as from enhanced deposition of radiogenic Os through increased fossil fuel combustion and soil erosion. We posit that the rapid increase in catalyst-equipped vehicles, increased fossil fuel combustion, and changes in land-use make the changes observed in NW Spain globally relevant.

  17. Anticancer activity of osmium metalla-rectangles.

    PubMed

    Barry, Nicolas P E; Edafe, Fabio; Dyson, Paul J; Therrien, Bruno

    2010-03-21

    A series of cationic metalla-rectangles of the general formula [(p-cymene)(4)Os(4)(OO[intersection]OO)(2)(N[intersection]N)(2)](4+) have been obtained in methanol from the dinuclear arene osmium precursors [(p-cymene)(2)Os(2)(OO[intersection]OO)(2)Cl(2)] (OO[intersection]OO = 2,5-dioxydo-1,4-benzoquinonato (dhbq), 2,5-dichloro-1,4-benzoquinonato (dcbq)) by reaction with bipyridine linkers (N[intersection]N = 4,4'-bipyridine, 1,2-bis(4-pyridyl)ethylene) in the presence of AgCF(3)SO(3). All complexes were isolated as triflate salts and characterised by NMR, IR and UV-visible spectroscopy. The cytotoxicities of the dinuclear and tetranuclear osmium complexes were established using ovarian A2780 cancer cell lines. The most active metalla-rectangle, [(p-cymene)(4)Os(4)(dhbq)(2)(4,4'-bipyridine)(2)](4+), shows an IC(50) value of 5.7 microM (comparable to cisplatin) against A2780 cancer cells and 7.5 microM against the cisplatin resistant A2780cisR cells.

  18. Thin boron phosphide coating as a corrosion-resistant layer

    DOEpatents

    Not Available

    1982-08-25

    A surface prone to corrosion in corrosive environments is rendered anticorrosive by CVD growing a thin continuous film, e.g., having no detectable pinholes, thereon, of boron phosphide. In one embodiment, the film is semiconductive. In another aspect, the invention is an improved photoanode, and/or photoelectrochemical cell with a photoanode having a thin film of boron phosphide thereon rendering it anticorrosive, and providing it with unexpectedly improved photoresponsive properties.

  19. Carbon monoxide adsorption on platinum-osmium and platinum-ruthenium-osmium mixed nanoparticles.

    PubMed

    Dimakis, Nicholas; Navarro, Nestor E; Smotkin, Eugene S

    2013-05-01

    Density functional calculations (DFT) on carbon monoxide (CO) adsorbed on platinum, platinum-osmium, and platinum-ruthenium-osmium nanoclusters are used to elucidate changes on the adsorbate internal bond and the carbon-metal bond, as platinum is alloyed with osmium and ruthenium atoms. The relative strengths of the adsorbate internal bond and the carbon-metal bond upon alloying, which are related to the DFT calculated C-O and C-Pt stretching frequencies, respectively, cannot be explained by the traditional 5σ-donation/2π*-back-donation theoretical model. Using a modified π-attraction σ-repulsion mechanism, we ascribe the strength of the CO adsorbate internal bond to changes in the polarization of the adsorbate-substrate hybrid orbitals towards carbon. The strength of the carbon-metal bond is quantitatively related to the CO contribution to the adsorbate-substrate hybrid orbitals and the sp and d populations of adsorbing platinum atom. This work complements prior work on corresponding slabs using periodic DFT. Similarities and differences between cluster and periodic DFT calculations are discussed. PMID:23656149

  20. Cavity optomechanics in gallium phosphide microdisks

    NASA Astrophysics Data System (ADS)

    Mitchell, Matthew; Hryciw, Aaron C.; Barclay, Paul E.

    2014-04-01

    We demonstrate gallium phosphide (GaP) microdisk optical cavities with intrinsic quality factors >2.8 × 105 and mode volumes <10(λ/n)3, and study their nonlinear and optomechanical properties. For optical intensities up to 8.0 × 104 intracavity photons, we observe optical loss in the microcavity to decrease with increasing intensity, indicating that saturable absorption sites are present in the GaP material, and that two-photon absorption is not significant. We observe optomechanical coupling between optical modes of the microdisk around 1.5 μm and several mechanical resonances, and measure an optical spring effect consistent with a theoretically predicted optomechanical coupling rate g0/2π˜30 kHz for the fundamental mechanical radial breathing mode at 488 MHz.

  1. Direct band gap wurtzite gallium phosphide nanowires.

    PubMed

    Assali, S; Zardo, I; Plissard, S; Kriegner, D; Verheijen, M A; Bauer, G; Meijerink, A; Belabbes, A; Bechstedt, F; Haverkort, J E M; Bakkers, E P A M

    2013-04-10

    The main challenge for light-emitting diodes is to increase the efficiency in the green part of the spectrum. Gallium phosphide (GaP) with the normal cubic crystal structure has an indirect band gap, which severely limits the green emission efficiency. Band structure calculations have predicted a direct band gap for wurtzite GaP. Here, we report the fabrication of GaP nanowires with pure hexagonal crystal structure and demonstrate the direct nature of the band gap. We observe strong photoluminescence at a wavelength of 594 nm with short lifetime, typical for a direct band gap. Furthermore, by incorporation of aluminum or arsenic in the GaP nanowires, the emitted wavelength is tuned across an important range of the visible light spectrum (555-690 nm). This approach of crystal structure engineering enables new pathways to tailor materials properties enhancing the functionality.

  2. Successful management of zinc phosphide poisoning

    PubMed Central

    Shakoori, Vahid; Agahi, Mahsa; Vasheghani-Farahani, Maryam; Marashi, Sayed Mahdi

    2016-01-01

    Zinc phosphide (Zn2P3) rodenticide, is generally misused intentionally for suicidal purpose in Iran. For many years, scientists believe that liberation of phosphine (PH3) on contact with acidic content of the stomach is responsible for clinical presentations. However, relatively long time interval between ingestion of Zn2P3 and presentation of its systemic toxicity, and progression of acute liver failure could not be explained by the current opinion. Hence, an innovative theory intended that phosphonium, as an intermediate product will create and pass through the stomach, which then will reduce to produce PH3in the luminal tract. Here, we present a case of massive Zn2P3 poisoning. In our case, we used repeated doses of castor oil to induce bowel movement with an aim of removing unabsorbed toxin, which was proved by radiography. Interestingly, the patient presents only mild symptoms of toxicity such as transient metabolic acidosis and hepatic dysfunction. PMID:27390464

  3. Cavity optomechanics in gallium phosphide microdisks

    SciTech Connect

    Mitchell, Matthew; Barclay, Paul E.; Hryciw, Aaron C.

    2014-04-07

    We demonstrate gallium phosphide (GaP) microdisk optical cavities with intrinsic quality factors >2.8 × 10{sup 5} and mode volumes <10(λ/n){sup 3}, and study their nonlinear and optomechanical properties. For optical intensities up to 8.0 × 10{sup 4} intracavity photons, we observe optical loss in the microcavity to decrease with increasing intensity, indicating that saturable absorption sites are present in the GaP material, and that two-photon absorption is not significant. We observe optomechanical coupling between optical modes of the microdisk around 1.5 μm and several mechanical resonances, and measure an optical spring effect consistent with a theoretically predicted optomechanical coupling rate g{sub 0}/2π∼30 kHz for the fundamental mechanical radial breathing mode at 488 MHz.

  4. BP: synthesis and properties of boron phosphide

    NASA Astrophysics Data System (ADS)

    Woo, Katherine; Lee, Kathleen; Kovnir, Kirill

    2016-07-01

    Cubic boron phosphide, BP, is notorious for its difficult synthesis, thus preventing it from being a widely used material in spite of having numerous favorable technological properties. In the current work, three different methods of synthesis are developed and compared: from the high temperature reaction of elements, Sn flux assisted synthesis, and a solid state metathesis reaction. Structural and optical properties of the products synthesized from the three methods were thoroughly characterized. Solid state metathesis is shown to be the cleanest and most efficient method in terms of reaction temperature and time. Synthesis by Sn flux resulted in a novel Sn-doped BP compound. Undoped BP samples exhibit an optical bandgap of ∼2.2 eV while Sn-doped BP exhibits a significantly smaller bandgap of 1.74 eV. All synthesized samples show high stability in concentrated hydrochloric acid, saturated sodium hydroxide solutions, and fresh aqua regia.

  5. Direct Band Gap Wurtzite Gallium Phosphide Nanowires

    PubMed Central

    2013-01-01

    The main challenge for light-emitting diodes is to increase the efficiency in the green part of the spectrum. Gallium phosphide (GaP) with the normal cubic crystal structure has an indirect band gap, which severely limits the green emission efficiency. Band structure calculations have predicted a direct band gap for wurtzite GaP. Here, we report the fabrication of GaP nanowires with pure hexagonal crystal structure and demonstrate the direct nature of the band gap. We observe strong photoluminescence at a wavelength of 594 nm with short lifetime, typical for a direct band gap. Furthermore, by incorporation of aluminum or arsenic in the GaP nanowires, the emitted wavelength is tuned across an important range of the visible light spectrum (555–690 nm). This approach of crystal structure engineering enables new pathways to tailor materials properties enhancing the functionality. PMID:23464761

  6. Successful management of zinc phosphide poisoning.

    PubMed

    Shakoori, Vahid; Agahi, Mahsa; Vasheghani-Farahani, Maryam; Marashi, Sayed Mahdi

    2016-06-01

    Zinc phosphide (Zn2P3) rodenticide, is generally misused intentionally for suicidal purpose in Iran. For many years, scientists believe that liberation of phosphine (PH3) on contact with acidic content of the stomach is responsible for clinical presentations. However, relatively long time interval between ingestion of Zn2P3 and presentation of its systemic toxicity, and progression of acute liver failure could not be explained by the current opinion. Hence, an innovative theory intended that phosphonium, as an intermediate product will create and pass through the stomach, which then will reduce to produce PH3in the luminal tract. Here, we present a case of massive Zn2P3 poisoning. In our case, we used repeated doses of castor oil to induce bowel movement with an aim of removing unabsorbed toxin, which was proved by radiography. Interestingly, the patient presents only mild symptoms of toxicity such as transient metabolic acidosis and hepatic dysfunction. PMID:27390464

  7. Method for production of free-standing polycrystalline boron phosphide film

    DOEpatents

    Baughman, Richard J.; Ginley, David S.

    1985-01-01

    A process for producing a free-standing polycrystalline boron phosphide film comprises growing a film of boron phosphide in a vertical growth apparatus on a metal substrate. The metal substrate has a coefficient of thermal expansion sufficiently different from that of boron phosphide that the film separates cleanly from the substrate upon cooling thereof, and the substrate is preferably titanium. The invention also comprises a free-standing polycrystalline boron phosphide film for use in electronic device fabrication.

  8. Free-standing polycrystalline boron phosphide film and method for production thereof

    DOEpatents

    Baughman, R.J.; Ginley, D.S.

    1982-09-09

    A process for producing a free-standing polycrystalline boron phosphide film comprises growing a film of boron phosphide in a vertical growth apparatus on a metal substrate. The metal substrate has a coefficient of thermal expansion sufficiently different from that of boron phosphide that the film separates cleanly from the substrate upon cooling thereof, and the substrate is preferably titanium. The invention also comprises a free-standing polycrystalline boron phosphide film for use in electronic device fabrication.

  9. Osmium conductive metal coating for SEM specimen using sublimated osmium tetroxide in negative glow phase of DC glow discharge.

    PubMed

    Tanaka, A

    1994-08-01

    A new method of osmium conductive metal coating for scanning electron microscopy specimens using osmium tetroxide in direct current glow discharge and its apparatus have been devised. Anode and cathode plates are placed in a gas reactor, sublimated osmium tetroxide is introduced, and glow discharge is generated. As a result, the gas between the electrodes instantaneously becomes plasma. At the specimen surface, which is placed in the negative glow phase on the cathode plate, positively ionized osmium molecules are directly adhered and deposited, thereby leaving a completely amorphous metal coating of osmium. As a result, the formed coating precisely matched the fine structure of the specimen surface, and even when irradiated with a strong electron beam was free of heat damage, electrification and contamination. The secondary electron emission efficiency of the coating was also good. Furthermore, no granularity of the film surface was observed even when viewed at a high magnification. In this way, a superior osmium conductive metal coating was obtained. PMID:7996076

  10. Successful Management of Aluminium Phosphide Poisoning Resulting in Cardiac Arrest.

    PubMed

    Hakimoğlu, Sedat; Dikey, İsmail; Sarı, Ali; Kekeç, Leyla; Tuzcu, Kasım; Karcıoğlu, Murat

    2015-08-01

    Aluminum phosphide has high toxicity when it is ingested, and in case of contact with moisture, phosphine gas is released. Aluminum phosphide poisoning causes metabolic acidosis, arrhythmia, acute respiratory distress syndrome and shock, and there is no specific antidote. A 17-year-old male patient was referred to our hospital because of aluminum phosphide poisoning with 1500 mg of aluminum phosphide tablets. The patient's consciousness was clear but he was somnolent. Vital parameters were as follows: blood pressure: 85/56 mmHg, pulse: 88 beats/min, SpO2: 94%, temperature: 36.4°C. Because of hypotension, noradrenaline and dopamine infusions were started. The patient was intubated because of respiratory distress and loss of consciousness. Severe metabolic acidosis was determined in the arterial blood gas, and metabolic acidosis was corrected by sodium bicarbonate treatment. In addition to supportive therapy of the poisoning, haemodialysis was performed. Cardiac arrest occurred during follow-ups in the intensive care unit, and sinus rhythm was achieved after 10 min of cardiopulmonary resuscitation. The patient was discharged after three sessions of haemodialysis on the ninth day. As a result, haemodialysis contributed to symptomatic treatment of aluminum phosphide poisoning in this case report. PMID:27366514

  11. Osmium coated diffraction grating in the Space Shuttle environment - Performance

    NASA Technical Reports Server (NTRS)

    Torr, M. R.

    1985-01-01

    Samples coated with osmium were flown on the early Shuttle test flights, and on the return of these samples, the osmium coating was found to have disappeared, evidently due to the oxidation of the material in the atomic oxygen atmosphere. An instrument flown on the Spacelab 1 mission comprised an array of five spectrometers covering the extreme ultraviolet (EUV) to near-IR wavelengths. The EUV spectrometer contained an osmium-coated reflective grating located fairly deep within the instruments. Here, results of an assessment of the reflectivity and stability of the osmium surface over the course of the ten-day mission are reported. It is concluded that the osmium reflective coating remained stable relative to the spectrometer coated with MgF2 over the course of the mission. In addition, the ratio of sensitivity of these two spectrometers did not change in any major way from the time of the laboratory calibration until the time of flight two years later. Any changes are within the 50-percent calibration uncertainty.

  12. Carbon phosphide monolayers with superior carrier mobility.

    PubMed

    Wang, Gaoxue; Pandey, Ravindra; Karna, Shashi P

    2016-04-28

    Two dimensional (2D) materials with a finite band gap and high carrier mobility are sought after materials from both fundamental and technological perspectives. In this paper, we present the results based on the particle swarm optimization method and density functional theory which predict three geometrically different phases of the carbon phosphide (CP) monolayer consisting of sp2 hybridized C atoms and sp3 hybridized P atoms in hexagonal networks. Two of the phases, referred to as α-CP and β-CP with puckered or buckled surfaces are semiconducting with highly anisotropic electronic and mechanical properties. More remarkably, they have the lightest electrons and holes among the known 2D semiconductors, yielding superior carrier mobility. The γ-CP has a distorted hexagonal network and exhibits a semi-metallic behavior with Dirac cones. These theoretical findings suggest that the binary CP monolayer is a yet unexplored 2D material holding great promise for applications in high-performance electronics and optoelectronics. PMID:27067002

  13. Phosphide-based materials as hard optical coatings

    NASA Astrophysics Data System (ADS)

    Lewis, Keith L.; Savage, James A.

    1990-08-01

    A requirement exists for more durable windows for airborne applications to improve their survivability under highly erosive conditions. A range of materials show potential including nitrides, phosphides, carbides and diamond. This paper will address the phosphide materials system and review the various possibilities available. Materials such as gallium phosphide show promise for use In the infrared on the basis of their behaviour in bulk form, with significant lattice absorption bands only apparent at wavelengths beyond l2jnn. Other known phosphides include those of Al, B, Si, Mg, In, Zn, Cd, Rb, Ir, Ni, Go, Y, Sc, Ti, Nb, Mo, W, Th as well as several of the rare earth elements. Ternary systen have also been examined, largely as bulk materials. Recently the potential of phosphide materials for infra-red applications has been highlighted by the deinstration of high durability in amorphous coatings of boron phosphide deposited by plasma assisted chemcal vapour deposition. The levels of durability obtained have exceeded those characteristic of diamond-like carbon, whilst allowing simultaneous transmission of both IR bands and the important 1.O6im wavelength. Here there is significant evidence of the role of non-stoichiometry, with P/B ratios of as high as 7 being typical. Some forms of amorphous phosphorus itself have been known to demonstrate remarkable stability, with samples remaining atomically clean in dry air for significant periods of time. Various other forms of high phosphorus polyphosphides are known, such as those containing alkali metals in a bridging configuration between phosphorus skeletons. These can be produced as thin films and exhibit high levels of stability and adhesion.

  14. A mild reduction phosphidation approach to nanocrystalline GaP

    NASA Astrophysics Data System (ADS)

    Chen, Luyang; Luo, Tao; Huang, Mingxing; Gu, Yunle; Shi, Liang; Qian, Yitai

    2004-12-01

    Nanocrystalline gallium phosphide (GaP) has been prepared through a reduction-phosphidation by using Ga, PCl 3 as gallium and phosphorus sources and metallic sodium as reductant at 350 °C. The XRD pattern can be indexed as cublic GaP with the lattice constant of a=5.446 Å. The TEM image shows particle-like polycrystals and flake-like single crystals. The PL spectrum exhibits one peak at 330 nm for the as-prepared nanocrystalline GaP.

  15. Carbon phosphide monolayers with superior carrier mobility

    NASA Astrophysics Data System (ADS)

    Wang, Gaoxue; Pandey, Ravindra; Karna, Shashi P.

    2016-04-01

    Two dimensional (2D) materials with a finite band gap and high carrier mobility are sought after materials from both fundamental and technological perspectives. In this paper, we present the results based on the particle swarm optimization method and density functional theory which predict three geometrically different phases of the carbon phosphide (CP) monolayer consisting of sp2 hybridized C atoms and sp3 hybridized P atoms in hexagonal networks. Two of the phases, referred to as α-CP and β-CP with puckered or buckled surfaces are semiconducting with highly anisotropic electronic and mechanical properties. More remarkably, they have the lightest electrons and holes among the known 2D semiconductors, yielding superior carrier mobility. The γ-CP has a distorted hexagonal network and exhibits a semi-metallic behavior with Dirac cones. These theoretical findings suggest that the binary CP monolayer is a yet unexplored 2D material holding great promise for applications in high-performance electronics and optoelectronics.Two dimensional (2D) materials with a finite band gap and high carrier mobility are sought after materials from both fundamental and technological perspectives. In this paper, we present the results based on the particle swarm optimization method and density functional theory which predict three geometrically different phases of the carbon phosphide (CP) monolayer consisting of sp2 hybridized C atoms and sp3 hybridized P atoms in hexagonal networks. Two of the phases, referred to as α-CP and β-CP with puckered or buckled surfaces are semiconducting with highly anisotropic electronic and mechanical properties. More remarkably, they have the lightest electrons and holes among the known 2D semiconductors, yielding superior carrier mobility. The γ-CP has a distorted hexagonal network and exhibits a semi-metallic behavior with Dirac cones. These theoretical findings suggest that the binary CP monolayer is a yet unexplored 2D material holding great

  16. Manganese phosphide thin films and nanorods grown on gallium phosphide and on glass substrates

    NASA Astrophysics Data System (ADS)

    Nateghi, N.; Lambert-Milot, S.; Ménard, D.; Masut, R. A.

    2016-05-01

    We report a simple and fast route to grow ferromagnetic manganese phosphide polycrystalline films and nanorods on GaP and on glass substrates using metalorganic vapor phase deposition. Increasing the growth temperature (≥600 °C) and growth time (≥30 min) results in nucleation of secondary MnP crystals on the primary grains. The secondary crystals grow faster along a specific direction of orthorhombic MnP (c-axis) and form long rods (up to ~10 μm) whose diameters are in the nanoscale (20-100 nm). The nanorods can be easily detached from the glass substrate. The films exhibit ferromagnetic behavior with a range of transition temperatures, depending on the growth conditions.

  17. Thin-film cadmium telluride and zinc phosphide solar cells

    NASA Astrophysics Data System (ADS)

    Chu, T. L.

    1981-06-01

    Major efforts during this quarter were directed to the deposition and characterization of zinc phosphide and cadmium telluride films and solar cells. The deposition of zinc phosphide films by the reaction of zinc and phosphine in a hydrogen atmosphere was continued and the composition of deposited films was determined. For more efficient utilization of phosphine, a 8500 C zone was added to the deposition. The in-situ annealing of zinc phosphide in phosphine was carried out. Attempts to prepare solar cell structures by depositing a thin film of zinc phosphide on an annealed film were made; however, the results are inconclusive. The deposition of cadmium telluride films by the direct combination of the elements under reduced pressure and under atmospheric pressure was carried out. Films deposited under reduced pressure exhibited more compact grain structures, however, they showed poor photoresponse. The composition of the films deposited under atmospheric pressure were analyzed and the dependence of short circuit density on the reactant composition was investigated.

  18. Responses of Siberian ferrets to secondary zinc phosphide poisoning

    USGS Publications Warehouse

    Hill, E.F.; Carpenter, J.W.

    1982-01-01

    The hazard of operational-type applications of zinc phosphide (Zn3P2) on a species closely related to the black-footed ferret (Mustela nigripes), was evaluated by feeding 16 Siberian ferrets (M. eversmanni) rats that had been killed by consumption of 2% zinc phosphide treated bait or by an oral dose of 40, 80, or 160 mg of Zn3P2. All ferrets accepted rats and a single emesis by each of 3 ferrets was the only evidence of acute intoxication. All ferrets learned to avoid eating gastrointestinal tracts of the rats. Subacute zinc phosphide toxicity in the ferrets was indicated by significant decreases (18-48%) in hemoglobin, increases of 35-91 % in serum iron, and elevated levels of serum globulin, cholesterol, and triglycerides. Hemoglobin/iron, urea nitrogen/creatinine, and albumin/globulin ratios also were altered by the treatments. This study demonstrated that Siberian ferrets, or other species with a sensitive emetic reflex, are afforded a degree of protection from acute zinc phosphide poisoning due to its emetic action. The importance of toxicity associated with possible respiratory, liver, and kidney damage indicated by altered blood chemistries is not known.

  19. Visible light electroluminescent diodes of indium-gallium phosphide

    NASA Technical Reports Server (NTRS)

    Clough, R.; Richman, D.; Tietjen, J.

    1970-01-01

    Vapor deposition and acceptor impurity diffusion techniques are used to prepare indium-gallium phosphide junctions. Certain problems in preparation are overcome by altering gas flow conditions and by increasing the concentration of phosphine in the gas. A general formula is given for the alloy's composition.

  20. Solvo-thermal synthesis of crystalline dinickel phosphide

    NASA Astrophysics Data System (ADS)

    Lü, Bo; Bai, Yu-Jun; Feng, Xin; Zhao, Yong-Rui; Yang, Jie; Chi, Jie-Ru

    2004-01-01

    Nanocrystalline dinickel phosphide was synthesized via a solvo-thermal route using PCl 3 and NiCl 2 as precursors, and Na as reductant. The crystals were characterized by X-ray powder diffraction and transmission electronic microscopy. It was shown that the product is pure Ni 2P which crystallizes very well with an average size of about 80 nm.

  1. Ab initio melting curve of osmium

    NASA Astrophysics Data System (ADS)

    Burakovsky, L.; Burakovsky, N.; Preston, D. L.

    2015-11-01

    The melting curve of osmium up to a pressure P of 500 GPa is obtained from an extensive suite of ab initio quantum molecular dynamics (QMD) simulations using the Z method. The ab initio P =0 melting point of Os is 3370 ±75 K; this range encompasses all of the available data in the literature and corroborates the conclusion of J. W. Arblaster [Platinum Metals Rev. 49, 166 (2005)], 10.1595/147106705X70264 that the melting temperature of pure Os is 3400 ±50 K and that the 3300 K typically quoted in the literature is the melting point of impure Os. The T =0 equation of state (EOS) of Os and the P dependence of the optimized c /a ratio for the hexagonal unit cell, both to pressures ˜900 GPa, are obtained in the ab initio approach as validation of its use. Although excellent agreement with the available experimental data (P ≲80 GPa) is found, it is the third-order Birch-Murnaghan EOS with B0'=5 rather than the more widely accepted B0'=4 that describes the QMD data to higher pressures, in agreement with the more recent experimental EOS by Godwal et al. The theoretical melting curve of Os obtained earlier by Joshi et al. is shown to be inconsistent with our QMD results, and the possible reason for this discrepancy is suggested. Regularities in the melting curves of Os and five other third-row transition metals (Ta, W, Re, Pt, Au) could be used to estimate the currently unknown melting curves of Hf and Ir.

  2. Production of negative osmium ions by laser desorption and ionization.

    PubMed

    Rodríguez, D; Sonnenschein, V; Blaum, K; Block, M; Kluge, H-J; Lallena, A M; Raeder, S; Wendt, K

    2010-01-01

    The interest to produce negative osmium ions is manifold in the realm of high-accuracy ion trap experiments: high-resolution nearly Doppler-free laser spectroscopy, antihydrogen formation in its ground state, and contributions to neutrino mass spectrometry. Production of these ions is generally accomplished by sputtering an Os sample with Cs(+) ions at tens of keV. Though this is a well-established method commonly used at accelerators, these kind of sources are quite demanding and tricky to operate. Therefore, the development of a more straightforward and cost effective production scheme will be of benefit for ion trap and other experiments. Such a scheme makes use of desorption and ionization with pulsed lasers and identification of the ions by time-of-flight mass spectrometry. First investigations of negative osmium ion production using a pulsed laser for desorption and ionization and a commercial matrix-assisted laser desorption/ionization time-of-flight system for identification has demonstrated the suitability of this technique. More than 10(3) negative osmium ions per shot were registered after bombarding pure osmium powder with a 5 ns pulse width Nd:yttrium aluminum garnet laser. The limitation in the ion number was imposed by the detection limit of the microchannel plate detector.

  3. Discovery of tantalum, rhenium, osmium, and iridium isotopes

    SciTech Connect

    Robinson, R.; Thoennessen, M.

    2012-09-15

    Currently, thirty-eight tantalum, thirty-eight rhenium, thirty-nine osmium, and thirty-eight iridium isotopes have been observed and the discovery of these isotopes is described here. For each isotope a brief synopsis of the first refereed publication, including the production and identification method, is presented.

  4. Improved microbial electrocatalysis with osmium polymer modified electrodes.

    PubMed

    Patil, Sunil A; Hasan, Kamrul; Leech, Dónal; Hägerhäll, Cecilia; Gorton, Lo

    2012-10-21

    Using the well-known exoelectrogen Shewanella oneidensis MR-1, an osmium redox polymer modified anode exhibited ca. 4-fold increase in current generation. Additionally, a significant decrease in the start-up time for electrocatalysis was observed. The findings suggest that the inherent extracellular electron transfer capabilities of electrogens coupled with such polymers could enhance electrocatalysis.

  5. Osmium isotopic tracing of atmospheric emissions from an aluminum smelter

    NASA Astrophysics Data System (ADS)

    Gogot, Julien; Poirier, André; Boullemant, Amiel

    2015-09-01

    We present for the first time the use of osmium isotopic composition as a tracer of atmospheric emissions from an aluminum smelter, where alumina (extracted from bauxite) is reduced through electrolysis into metallic aluminum using carbonaceous anodes. These anodes are consumed in the process; they are made of petroleum coke and pitch and have high Re/Os elementary ratio. Due to the relatively large geological age of their source material, their osmium shows a high content of radiogenic 187Os produced from in situ187Re radioactive decay. The radiogenic isotopic composition (187Os/188Os ∼ 2.5) of atmospheric particulate emissions from this smelter is different from that of other typical anthropogenic osmium sources (that come from ultramafic geological contexts with unradiogenic Os isotopes, e.g., 187Os/188Os < 0.2) and also different from average eroding continental crust 187Os/188Os ratios (ca. 1.2). This study demonstrates the capacity of osmium measurements to monitor particulate matter emissions from the Al-producing industry.

  6. Osmium Isotopic Composition of the Sumbar Cretaceous- Tertiary Boundary, Turkmenia

    NASA Astrophysics Data System (ADS)

    Meisel, T.; Krahenbuhl, U.; Nazarov, M. A.

    1992-07-01

    Turekian (1982) propagated the use of the osmium isotopic composition as a cosmic indicator for the origin of the high osmium (and iridium) layers at the K/T boundaries. He did not consider the osmium isotopic signature of the terrestrial mantle, which also has a chondritic evolution of the Re-Os system. Osmium cannot serve alone as an infallible indicator of the impact theory, but interesting results can be obtained from their investigation. Different K/T boundary section have been analyzed so far for ^187Os/^186Os. An overview of the values is presented in the table. Boundary Clay layer Os ratio Reference Stevns Klint fish clay 1.66 Luck and Turekian, 1983 Woodside Creek 1.12 Lichte et al., 1986 Raton Basin 1.23 Kraehenbuehl et al., 1988 Raton Basin (several) 1.15-1.23 Esser and Turekian, 1989 Sumbar (0-1 cm) 1.16 This work We obtained a complete marine section of the K/T boundary in southern Turkmenia (decribed by Alekseyev, 1988). It shows a very high Ir concentration (66 ppb) at the boundary layer and a remarkable Ir enrichment over crustal rocks continuing up to 30 cm above the boundary. Our aim of this investigation is to analyze several samples from above and below the boundary for the ^187Os/^186Os ratio to obtain a complete picture of the isotopic evolution of the section. We want to evaluate mixing of Os with chondritic ratios with Os from upper crustal rocks. Another goal is to investigate a mobilization of Os. So far only one sample has been analyzed with NTI-MS after fire assay digestion of the sample. The sample 0 to 1 cm has an ^187Os/^186Os ratio of 1.162 +- 13, which is quite low. We expect an even lower value for the boundary clay (0 cm) itself not taking into account a contribution of radiogenic osmium from the decay of terrestrial rhenium. This might put this K/T boundary section closest of all to the present day chondritic value (approx. 1.05). Further analysis will be presented at the meeting. References Alekseyev A. S., Nazarov M. A

  7. Rational Design of Zinc Phosphide Heterojunction Photovoltaics

    NASA Astrophysics Data System (ADS)

    Bosco, Jeffrey Paul

    The prospect of terawatt-scale electricity generation using a photovoltaic (PV) device places strict requirements on the active semiconductor optoelectronic properties and elemental abundance. After reviewing the constraints placed on an ``earth-abundant'' solar absorber, we find zinc phosphide (α-Zn 3P2) to be an ideal candidate. In addition to its near-optimal direct band gap of 1.5 eV, high visible-light absorption coefficient (>10. 4cm-1), and long minority-carrier diffusion length (>5 μm), Zn3P 2 is composed of abundant Zn and P elements and has excellent physical properties for scalable thin-film deposition. However, to date, a Zn 3P2 device of sufficient efficiency for commercial applications has not been demonstrated. Record efficiencies of 6.0% for multicrystalline and 4.3% for thin-film cells have been reported, respectively. Performance has been limited by the intrinsic p-type conductivity of Zn3P 2 which restricts us to Schottky and heterojunction device designs. Due to our poor understanding of Zn3P2 interfaces, an ideal heterojunction partner has not yet been found. The goal of this thesis is to explore the upper limit of solar conversion efficiency achievable with a Zn3P2 absorber through the design of an optimal heterojunction PV device. To do so, we investigate three key aspects of material growth, interface energetics, and device design. First, the growth of Zn3P2 on GaAs(001) is studied using compound-source molecular-beam epitaxy (MBE). We successfully demonstrate the pseudomorphic growth of Zn3P2 epilayers of controlled orientation and optoelectronic properties. Next, the energy-band alignments of epitaxial Zn3P2 and II-VI and III-V semiconductor interfaces are measured via high-resolution x-ray photoelectron spectroscopy in order to determine the most appropriate heterojunction partner. From this work, we identify ZnSe as a nearly ideal n-type emitter for a Zn3P 2 PV device. Finally, various II-VI/Zn3P2 heterojunction solar cells designs are

  8. Himalayan uplift and osmium isotopes in oceans and rivers

    SciTech Connect

    Sharma, M.; Wasserburg, G.J.; Hofmann, A.W.; Chakrapani, G.J.

    1999-12-01

    Previous studies have shown that {sup 187}Os/{sup 188}Os in seawater has become increasingly radiogenic over the last 409 Ma in a manner analogous to strontium. This rapid rise in the marine {sup 187}Os/{sup 188}Os over the last 17 Ma has been attributed to an increase in the bulk silicate weathering rates resulting from the rise of the Himalayas and/or selective weathering and erosion of highly radiogenic organic rich ancient sediments. The key test of this hypothesis is the {sup 187}Os/{sup 188}Os and the total osmium concentration of the Himalayan rivers. The authors report the concentration and isotopic composition of osmium in the Ganges, the Brahmaputra, and the Indus rivers. The {sup 187}Os/{sup 188}Os of the Ganges close to its source (at Kaudiyal) is 2.65 and [Os] = 45 fM/kg. A second sample of the lower reaches of the Ganges at Patna gives {sup 187}Os/{sup 188}Os = 1.59 and [Os] = 171 fM/kg. The {sup 187}Os/{sup 188}Os of the Brahmaputra at Guwahati is 1.07 and [Os] = 52 fM/kg. A sample of the Indus (Besham) has a {sup 187}Os/{sup 188}Os of 1.2 and [Os] = 59 fM/kg. The authors infer that the Himalayas do not provide either a high flow of osmium of a highly radiogenic osmium component to the oceans. The overall trend for osmium and strontium could be explained by a regularly increasing input of global continental weathering sources but the Himalayas themselves appear not to be the dominant source.

  9. Osmium-187 enrichment in some plumes: Evidence for core-mantle interaction?

    USGS Publications Warehouse

    Walker, R.J.; Morgan, J.W.; Horan, M.F.

    1995-01-01

    Calculations with data for asteroidal cores indicate that Earth's outer core may have a rhenium/osmium ratio at least 20 percent greater than that of the chondritic upper mantle, potentially leading to an outer core with an osmium-187/osmium-188 ratio at least 8 percent greater than that of chondrites. Because of the much greater abundance of osmium in the outer core relative to the mantle, even a small addition of metal to a plume ascending from the D??? layer would transfer the enriched isotopic signature to the mixture. Sources of certain plume-derived systems seem to have osmium-187/osmium-188 ratios 5 to 20 percent greater than that for chondrites, consistent with the ascent of a plume from the core-mantle boundary.

  10. Synthesis of transition-metal phosphides from oxidic precursors by reduction in hydrogen plasma

    SciTech Connect

    Guan Jie; Wang Yao; Qin Minglei; Yang Ying; Li Xiang; Wang Anjie

    2009-06-15

    A series of transition metal phosphides, including MoP, WP, CoP, Co{sub 2}P, and Ni{sub 2}P, were synthesized from their oxidic precursors by means of hydrogen plasma reduction under mild conditions. The effects of reduction conditions, such as metal to phosphorus molar ratio, power input, and reduction time, on the synthesis of metal phosphides were investigated. The products were identified by means of XRD characterization. It is indicated that metal phosphides were readily synthesized stoichiometrically from their oxides in hydrogen plasma under mild conditions. - Graphical abstract: Metal phosphides were obtained stoichiometrically from their oxidic precursors by hydrogen plasma reaction under mild conditions.

  11. Histopathological changes in cases of aluminium phosphide poisoning.

    PubMed

    Sinha, U S; Kapoor, A K; Singh, A K; Gupta, A; Mehrotra, Ravi

    2005-04-01

    Of a total of 205 poisoning deaths in our hospital in 2003, 83 cases were due to Aluminium phosphide poisoning and were further analyzed. Most vulnerable age group was 21-40 years and M:F ratio was 2:1. On naked eye examination, almost all the vital organs were found to be congested. On microscopic study, the liver showed central venous congestion, degeneration, haemorrhage, sinusoidal dilation, bile stasis, centrilobular necrosis, Kupffer cell hyperplasia, infiltration by mononuclear cells and fatty change. Microscopy of the lungs revealed alveolar thickening, oedema, dilated capillaries, collapsed alveoli and haemorrhage. In the kidney, changes were degeneration, infiltration, tubular dilation and cloudy swelling. Changes in the brain included congestion and coagulative necrosis and in the stomach, congestion and haemorrhage. Easy availability of this cheap and highly toxic substance was responsible for the sudden spurt of poisoning with aluminium phosphide. PMID:16758658

  12. Determination of series resistance of indium phosphide solar cells

    NASA Technical Reports Server (NTRS)

    Jain, Raj K.; Weinberg, Irving

    1991-01-01

    The series resistance of a solar cell is an important parameter, which must be minimized to achieve high cell efficiencies. The cell series resistance is affected by the starting material, its design, and processing. The theoretical approach proposed by Jia, et. al., is used to calculate the series resistance of indium phosphide solar cells. It is observed that the theoretical approach does not predict the series resistance correctly in all cases. The analysis was modified to include the use of effective junction ideality factor. The calculated results were compared with the available experimental results on indium phosphide solar cells processed by different techniques. It is found that the use of process dependent junction ideality factor leads to better estimation of series resistance. An accurate comprehensive series resistance model is warranted to give proper feedback for modifying the cell processing from the design state.

  13. Synthesis and Hydrodeoxygenation Properties of Ruthenium Phosphide Catalysts

    SciTech Connect

    Bowker, Richard H.; Smith, Mica C.; Pease, Melissa; Slenkamp, Karla M.; Kovarik, Libor; Bussell, Mark E.

    2011-07-01

    Ru2P/SiO2 and RuP/SiO2 catalysts were prepared by the temperature-programmed reduction (TPR) of uncalcined precursors containing hypophosphite ion (H2PO2-) as the phosphorus source. The Ru2P/SiO2 and RuP/SiO2 catalysts had small average particle sizes (~4 nm) and high CO chemisorption capacities (90-110 umol/g). The Ru phosphide catalysts exhibited similar or higher furan (C4H4O) hydrodeoxygenation (HDO) activities than did a Ru/SiO2 catalyst, and the phosphide catalysts favored C4 hydrocarbon products while the Ru metal catalyst produced primarily C3 hydrocarbons.

  14. Ternary transition metal phosphides: High-temperature superconductors

    PubMed Central

    Barz, H.; Ku, H. C.; Meisner, G. P.; Fisk, Z.; Matthias, B. T.

    1980-01-01

    Two systems of ternary transition metal phosphides with the ordered Fe2P-type hexagonal structure are reported. They have the general formula MRuP and MOsP, in which M can be Ti, Zr, or Hf. An onset of the superconducting transition temperature as high as 13.0 K is reported for the ZrRuP compound. PMID:16592838

  15. Status of indium phosphide solar cell development at Spire

    NASA Technical Reports Server (NTRS)

    Spitzer, M. B.; Keavney, C. J.; Vernon, S. M.

    1987-01-01

    On-going development of indium phosphide solar cells for space applications is presented. The development is being carried out with a view towards both high conversion efficiency and simplicity of manufacture. The cell designs comprise the ion-implanted cell, the indium tin oxide top contact cell, and the epitaxial cell grown by metal organic chemical vapor deposition. Modelling data on the limit to the efficiency are presented and comparison is made to measured performance data.

  16. Heat capacity and absolute entropy of iron phosphides

    SciTech Connect

    Dobrokhotova, Z.V.; Zaitsev, A.I.; Litvina, A.D.

    1994-09-01

    There is little or no data on the thermodynamic properties of iron phosphides despite their importance for several areas of science and technology. The information available is of a qualitative character and is based on assessments of the heat capacity and absolute entropy. In the present work, we measured the heat capacity over the temperature range of 113-873 K using a differential scanning calorimeter (DSC) and calculated the absolute entropy.

  17. Indium phosphide nanowires and their applications in optoelectronic devices

    PubMed Central

    Zafar, Fateen

    2016-01-01

    Group IIIA phosphide nanocrystalline semiconductors are of great interest among the important inorganic materials because of their large direct band gaps and fundamental physical properties. Their physical properties are exploited for various potential applications in high-speed digital circuits, microwave and optoelectronic devices. Compared to II–VI and I–VII semiconductors, the IIIA phosphides have a high degree of covalent bonding, a less ionic character and larger exciton diameters. In the present review, the work done on synthesis of III–V indium phosphide (InP) nanowires (NWs) using vapour- and solution-phase approaches has been discussed. Doping and core–shell structure formation of InP NWs and their sensitization using higher band gap semiconductor quantum dots is also reported. In the later section of this review, InP NW-polymer hybrid material is highlighted in view of its application as photodiodes. Lastly, a summary and several different perspectives on the use of InP NWs are discussed. PMID:27118920

  18. Diphacinone and zinc phosphide toxicity in a flock of Peafowl.

    PubMed

    Shivaprasad, H L; Galey, F

    2001-12-01

    Toxicity probably due to a combination of diphacinone and zinc phosphide was diagnosed in a flock of peafowl, in which 35 birds in a flock of 80 died over a span of 10 days without any apparent clinical signs. Chickens and guinea fowl, 30 each on the same premises, were not affected. Plastic tubes containing diphacinone and zinc phosphide were used on the premises to control ground squirrels. Most of the six dead peafowl, which ranged in age from 6 months to 4 years, had an accumulation of serosanguinous fluid in the abdominal cavity, semi-clotted blood over the liver lobes, increased pericardial fluid, and enlarged and pale kidneys. Pellets of diphacinone and zinc phosphide were found in the crop and gizzard contents from most of the birds. Microscopically, most of the birds had mild to moderate centrolobular degeneration of hepatocytes and multifocal degeneration of myofibres in the heart with infiltration by a few mononuclear cells. Acute nephrosis and mucosal oedema in the oesophagus and crop were also observed. Toxicological analysis of the crop and gizzard contents revealed the presence of diphacinone and phosphine gas, and analysis of the crop contents from two birds for heavy metals revealed zinc levels of up to 6600 parts/10 6 . It was suspected that only the peafowl and not the chickens and guinea fowl were affected because peafowl, with their longer necks, were able to reach into the plastic tubes and eat the pellets.

  19. Diphacinone and zinc phosphide toxicity in a flock of Peafowl.

    PubMed

    Shivaprasad, H L; Galey, F

    2001-12-01

    Toxicity probably due to a combination of diphacinone and zinc phosphide was diagnosed in a flock of peafowl, in which 35 birds in a flock of 80 died over a span of 10 days without any apparent clinical signs. Chickens and guinea fowl, 30 each on the same premises, were not affected. Plastic tubes containing diphacinone and zinc phosphide were used on the premises to control ground squirrels. Most of the six dead peafowl, which ranged in age from 6 months to 4 years, had an accumulation of serosanguinous fluid in the abdominal cavity, semi-clotted blood over the liver lobes, increased pericardial fluid, and enlarged and pale kidneys. Pellets of diphacinone and zinc phosphide were found in the crop and gizzard contents from most of the birds. Microscopically, most of the birds had mild to moderate centrolobular degeneration of hepatocytes and multifocal degeneration of myofibres in the heart with infiltration by a few mononuclear cells. Acute nephrosis and mucosal oedema in the oesophagus and crop were also observed. Toxicological analysis of the crop and gizzard contents revealed the presence of diphacinone and phosphine gas, and analysis of the crop contents from two birds for heavy metals revealed zinc levels of up to 6600 parts/10 6 . It was suspected that only the peafowl and not the chickens and guinea fowl were affected because peafowl, with their longer necks, were able to reach into the plastic tubes and eat the pellets. PMID:19184953

  20. Osmium isotope constraints on Earth's late accretionary history

    USGS Publications Warehouse

    Morgan, J.W.

    1985-01-01

    Osmium isotope measurements reported by Alle??gre and Luck 1,2 indicate that terrestrial osmiridiums evolved in a mantle source region in which the osmium/rhenium ratio falls strictly within the range found in chondrites. This suggests that the highly siderophile elements in the Earth's mantle were introduced by a late influx of chondritic material and are not a result of endogenous processes. I have now examined the available data in more detail and conclude that the inferred Os/Re ratio of the Earth's mantle matches the E group and C3 chondrites, but that C1 and probably C2 chondrites were not major components of the material accreted in the late stages of mantle formation. ?? 1985 Nature Publishing Group.

  1. Enzyme Biosensor Based on an Electropolymerized Osmium Redox Polymer

    NASA Astrophysics Data System (ADS)

    Tsujimoto, Masaki; Maruyama, Kenichi; Mishima, Yuji; Motonaka, Junko

    Electrochemical polymerizations of metal complex as electron mediator in aqueous solution have been developed. The metal complexes as electron mediator of biosensor for practical application have a rapid electron transfer rate, a chemical stability, and an accessible manipulation. The electro-polymerized redox polymer relatively decreased the enzyme and catalytic activity, although these could be treated in organic solvent. In this work, the water-soluble osmium complex-modified pyrrole derivatives with long, flexible spacer chain were synthesized. The electro-polymerized redox polymer was generally produced by potential sweep copolymerization (-400 mV -/+1200 mV (vs. Ag|AgCl(sat.KCl))) of water-soluble osmium complex-modified pyrrole monomer and glucose oxidase (GOD) on the top of a Pt electrode in aqueous solution. With the electro-polymerized osmium redox polymer modified electrode, calibration graphs for measurements of glucose and the effect of concomitant compounds, dissolved oxygen and the lifetimes of the sensor were electrochemistry examined, respectively. Under optimal conditions, the response of the sensors was in the concentration ranges of 0.6 mM-100 mM for glucose.

  2. Elastic constants of osmium between 5 and 300 K

    NASA Astrophysics Data System (ADS)

    Pantea, C.; Stroe, I.; Ledbetter, H.; Betts, J. B.; Zhao, Y.; Daemen, L. L.; Cynn, H.; Migliori, A.

    2009-07-01

    Using two measurement methods, pulse-echo ultrasound and resonance ultrasound spectroscopy, we measured the elastic constants of both monocrystal and polycrystal osmium between 5 and 300 K. Our measurements help to resolve the current measurement-and-theory controversy concerning whether osmium’s bulk modulus exceeds diamond’s. It does not at any temperature (for osmium, we find a zero-temperature bulk modulus of 410 GPa and a 300 K value of 405 GPa, while diamond’s value being 442 GPa). From the zero-temperature elastic constants, we extract a Debye temperature of 477 K. From Grüneisen’s first rule, we extract a Grüneisen parameter of 2.1, agreeing well with handbook values. Osmium shows near elastic anisotropy and small elastic constant changes with temperature (for example, the bulk modulus increases only about 1.2% upon cooling through the studied temperature interval). In all cases, the Cij(T) measurements agree well with an Einstein-oscillator model. We consider especially the Poisson ratio, which is low and anisotropic ( ν12=0.242 , ν13=0.196 ) and suggests some covalent interatomic bonding, which may account for osmium’s extreme high hardness and the departure of the 5d elements from Friedel’s parabolic bulk-modulus/atomic-number model.

  3. Indium phosphide space solar cell research: Where we are and where we are going

    NASA Technical Reports Server (NTRS)

    Jain, R. K.; Flood, D. J.; Weinberg, Irving

    1995-01-01

    Indium phosphide is considered to be a strong contender for many photovoltaic space applications because of its radiation resistance and its potential for high efficiency. An overview of recent progress is presented, and possible future research directions for indium phosphide space solar cells are discussed. The topics considered include radiation damage studies and space flight experiments.

  4. Isotopic determinations of rhenium and osmium in meteorites by using fusion, distillation and ion-exchange separations

    USGS Publications Warehouse

    Morgan, J.W.; Walker, R.J.

    1989-01-01

    A stable isotope-dilution method using resonance ionization mass spectrometry is suitable for the determination of rhenium and osmium abundances and osmium isotopic composition in carbonaceous chondrites and iron meteorites. The chemical procedure involves sodium peroxide fusion, followed by distillation of osmium from sulfuric acid/hydrogen peroxide and subsequent anion-exchange separation of rhenium from the same solution. ?? 1989.

  5. Methods for the separation of rhenium, osmium and molybdenum applicable to isotope geochemistry

    USGS Publications Warehouse

    Morgan, J.W.; Golightly, D.W.; Dorrzapf, A.F.

    1991-01-01

    Effective methods are described for the chemical separation of rhenium, osmium and molybdenum. The methods are based on distillation and anion-exchange chromatography, and have been the basis for rhenium-osmium isotope studies of ore deposits and meteorites. Successful anion-exchange separation of osmium requires both recognition and careful control of the osmium species in solution; thus, distillation of osmium tetroxide from a mixture of sulfuric acid and hydrogen peroxide is preferred to anion-exchange. Distribution coefficients measured for perrhenate in sulfuric acid media are sufficiently high (Kd > 500) for rhenium to be directly loaded onto an ion-exchange column from a distillation residue and subsequently eluted with nitric acid. Polymerization of molybdenum species during elution is prevented by use of a solution that is 1M in hydrochloric acid and 1M in sodium chloride. ?? 1991.

  6. A gallium phosphide high-temperature bipolar junction transistor

    NASA Technical Reports Server (NTRS)

    Zipperian, T. E.; Dawson, L. R.; Chaffin, R. J.

    1981-01-01

    Preliminary results are reported on the development of a high temperature (350 C) gallium phosphide bipolar junction transistor (BJT) for geothermal and other energy applications. This four-layer p(+)n(-)pp(+) structure was formed by liquid phase epitaxy using a supercooling technique to insure uniform nucleation of the thin layers. Magnesium was used as the p-type dopant to avoid excessive out-diffusion into the lightly doped base. By appropriate choice of electrodes, the device may also be driven as an n-channel junction field-effect transistor. The initial design suffers from a series resistance problem which limits the transistor's usefulness at high temperatures.

  7. Indium phosphide solar cells for laser power beaming applications

    NASA Technical Reports Server (NTRS)

    Jain, Raj K.; Landis, Geoffrey A.

    1992-01-01

    Lasers can be used to transmit power to photovoltaic cells. Solar cell efficiencies are enhanced significantly under monochromatic light, and therefore a laser beam of proper wavelength could be a very effective source of illumination for a solar array operating at very high efficiencies. This work reviews the modeling studies made on indium phosphide solar cells for such an application. These cells are known to be very radiation resistant and have a potential for high efficiency. Effects of cell series resistance, laser intensity, and temperature on cell performance have been discussed.

  8. Aluminum Phosphide Poisoning-Related Deaths in Tehran, Iran, 2006 to 2013.

    PubMed

    Etemadi-Aleagha, Afshar; Akhgari, Maryam; Iravani, Fariba Sardari

    2015-09-01

    Metal phosphides such as aluminum phosphide are potent insecticides. This highly toxic substance is used for rice and other grains protection in Iran. Due to its high toxicity potential and easy availability, it is widely used as a suicide poison. This substance has no effective antidote and the incidence of deaths due to its poisoning is increasing day by day in Iran. The present study was conducted to show the increasing incidence of fatal aluminum phosphide poisoning and its toxicological and forensic aspects in an 8-year study, 2006 to 2013. Autopsy sheets were reviewed and cases with the history of aluminum phosphide poisoning were selected. Toxicological analysis results, demographic and necroscopic examination findings were studied. A total of 51.8% of studied cases were female. Most of the cases were between 10 and 40 years old. The manner of death was self-poisoning in 85% of cases. Morphine, ethanol, and amitriptyline were the most common additional drugs detected in toxicological analysis. The incidence of fatal aluminum phosphide poisoning cases referred for phosphine analysis was 5.22 and 37.02 per million of population of Tehran in 2006 and 2013, respectively. The results of this study showed that in spite of ban and restrictions, there was a dramatic increase in the incidence of fatal aluminum phosphide poisoning in Tehran from 2006 to 2013. Safety alert should be highlighted in training program for all population groups about the toxic effects of aluminum phosphide tablets.

  9. Aluminum Phosphide Poisoning-Related Deaths in Tehran, Iran, 2006 to 2013

    PubMed Central

    Etemadi-Aleagha, Afshar; Akhgari, Maryam; Iravani, Fariba Sardari

    2015-01-01

    Abstract Metal phosphides such as aluminum phosphide are potent insecticides. This highly toxic substance is used for rice and other grains protection in Iran. Due to its high toxicity potential and easy availability, it is widely used as a suicide poison. This substance has no effective antidote and the incidence of deaths due to its poisoning is increasing day by day in Iran. The present study was conducted to show the increasing incidence of fatal aluminum phosphide poisoning and its toxicological and forensic aspects in an 8-year study, 2006 to 2013. Autopsy sheets were reviewed and cases with the history of aluminum phosphide poisoning were selected. Toxicological analysis results, demographic and necroscopic examination findings were studied. A total of 51.8% of studied cases were female. Most of the cases were between 10 and 40 years old. The manner of death was self-poisoning in 85% of cases. Morphine, ethanol, and amitriptyline were the most common additional drugs detected in toxicological analysis. The incidence of fatal aluminum phosphide poisoning cases referred for phosphine analysis was 5.22 and 37.02 per million of population of Tehran in 2006 and 2013, respectively. The results of this study showed that in spite of ban and restrictions, there was a dramatic increase in the incidence of fatal aluminum phosphide poisoning in Tehran from 2006 to 2013. Safety alert should be highlighted in training program for all population groups about the toxic effects of aluminum phosphide tablets. PMID:26402837

  10. Incompressibility of osmium metal at ultrahigh pressures and temperatures

    SciTech Connect

    Armentrout, Matt M.; Kavner, Abby

    2010-07-23

    Osmium is one of the most incompressible elemental metals, and is used as a matrix material for synthesis of ultrahard materials. To examine the behavior of osmium metal under extreme conditions of high pressure and temperature, we measured the thermal equation of state of osmium metal at pressures up to 50 GPa and temperatures up to 3000 K. X-ray diffraction measurements were conducted in the laser heated diamond anvil cell at GeoSoilEnviroCARS and the High Pressure at the Advanced Photon Source and beamline 12.2.2 at the advanced light source. Ambient temperature data give a zero pressure bulk modulus of 421 (3) GPa with a first pressure derivative fixed at 4. Fitting to a high temperature Birch-Murnaghan equation of state gives a room pressure thermal expansion of 1.51(0.06) x 10{sup -5} K{sup -1} with a first temperature derivative of 4.9(0.7) x 10{sup -9} K{sup -2} and the first temperature derivative of bulk modulus of be dK{sub 0}/dT = -0.055 (0.004). Fitting to a Mie-Grueneisen-Debye equation of state gives a Grueneisen parameter of 2.32 (0.08) with a q of 7.2 (1.4). A comparison of the high pressure, temperature behavior among Re, Pt, Os, shows that Os has the highest bulk modulus and lowest thermal expansion of the three, suggesting that Os-based ultrahard materials may be especially mechanically stable under extreme conditions.

  11. A quantitative link between recycling and osmium isotopes.

    PubMed

    Sobolev, Alexander V; Hofmann, Albrecht W; Brügmann, Gerhard; Batanova, Valentina G; Kuzmin, Dmitry V

    2008-07-25

    Recycled subducted ocean crust has been traced by elevated 187Os/188Os in some studies and by high nickel and low manganese contents in others. Here, we show that these tracers are linked for Quaternary lavas of Iceland, strengthening the recycling model. An estimate of the osmium isotopic composition of both the recycled crust and the mantle peridotite implies that Icelandic Quaternary lavas are derived in part from an ancient crustal component with model ages between 1.1 _ 109 and 1.8 _ 109 years and from a peridotitic end-member close to present-day oceanic mantle. PMID:18653885

  12. Osmium isotope constraints on ore metal recycling in subduction zones

    PubMed

    McInnes; McBride; Evans; Lambert; Andrew

    1999-10-15

    Veined peridotite xenoliths from the mantle beneath the giant Ladolam gold deposit on Lihir Island, Papua New Guinea, are 2 to 800 times more enriched in copper, gold, platinum, and palladium than surrounding depleted arc mantle. Gold ores have osmium isotope compositions similar to those of the underlying subduction-modified mantle peridotite source region, indicating that the primary origin of the metals was the mantle. Because the mantle is relatively depleted in gold, copper, and palladium, tectonic processes that enhance the advective transport and concentration of these fluid soluble metals may be a prerequisite for generating porphyry-epithermal copper-gold deposits. PMID:10521343

  13. New modes for the osmium-catalyzed oxidative cyclization.

    PubMed

    Donohoe, Timothy J; Lindsay-Scott, Peter J; Parker, Jeremy S; Callens, Cedric K A

    2010-03-01

    The osmium-catalyzed oxidative cyclization of amino alcohol initiators formally derived from 1,4-dienes is an effective method for the construction of pyrrolidines, utilizing a novel reoxidant (4-nitropyridine N-oxide = NPNO). The cyclization of enantiopure syn- and anti-amino alcohols gives rise to enantiopure cis- and trans-2,5-disubstituted pyrrolidines, respectively. Moreover, the cyclization of bis-homoallylic amines bearing an exocyclic chelating group is shown to be a complementary method for trans-pyrrolidine formation.

  14. Osmium Metal Studied under High Pressure and Nonhydrostatic Stress

    SciTech Connect

    Weinberger,M.; Tolbert, S.; Kavner, A.

    2008-01-01

    Interest in osmium as an ultra-incompressible material and as an analog for the behavior of iron at high pressure has inspired recent studies of its mechanical properties. We have measured elastic and plastic deformation of Os metal at high pressures using in situ high pressure x-ray diffraction in the radial geometry. We show that Os has the highest yield strength observed for any pure metal, supporting up to 10 GPa at a pressure of 26 GPa. Furthermore, our data indicate changes in the nonhydrostatic apparent c/a ratio and clear lattice preferred orientation effects at pressures above 15 GPa.

  15. Organometallic osmium arene complexes with potent cancer cell cytotoxicity.

    PubMed

    Fu, Ying; Habtemariam, Abraha; Pizarro, Ana M; van Rijt, Sabine H; Healey, David J; Cooper, Patricia A; Shnyder, Steven D; Clarkson, Guy J; Sadler, Peter J

    2010-11-25

    Iodido osmium(II) complexes [Os(η(6)-arene)(XY)I](+) (XY = p-hydroxy or p-dimethylaminophenylazopyridine, arene = p-cymene or biphenyl) are potently cytotoxic at nanomolar concentrations toward a panel of human cancer cell lines; e.g., IC(50) = 140 nM for [Os(η(6)-bip)(azpy-NMe(2))I](+) toward A2780 ovarian cancer cells. They exhibit low toxicity and negligible deleterious effects in a colon cancer xenograft model, giving rise to the possibility of a broad therapeutic window. The most active complexes are stable and inert toward aquation. Their cytotoxic activity appears to involve redox mechanisms.

  16. Osmium isotope constraints on ore metal recycling in subduction zones

    PubMed

    McInnes; McBride; Evans; Lambert; Andrew

    1999-10-15

    Veined peridotite xenoliths from the mantle beneath the giant Ladolam gold deposit on Lihir Island, Papua New Guinea, are 2 to 800 times more enriched in copper, gold, platinum, and palladium than surrounding depleted arc mantle. Gold ores have osmium isotope compositions similar to those of the underlying subduction-modified mantle peridotite source region, indicating that the primary origin of the metals was the mantle. Because the mantle is relatively depleted in gold, copper, and palladium, tectonic processes that enhance the advective transport and concentration of these fluid soluble metals may be a prerequisite for generating porphyry-epithermal copper-gold deposits.

  17. A quantitative link between recycling and osmium isotopes.

    PubMed

    Sobolev, Alexander V; Hofmann, Albrecht W; Brügmann, Gerhard; Batanova, Valentina G; Kuzmin, Dmitry V

    2008-07-25

    Recycled subducted ocean crust has been traced by elevated 187Os/188Os in some studies and by high nickel and low manganese contents in others. Here, we show that these tracers are linked for Quaternary lavas of Iceland, strengthening the recycling model. An estimate of the osmium isotopic composition of both the recycled crust and the mantle peridotite implies that Icelandic Quaternary lavas are derived in part from an ancient crustal component with model ages between 1.1 _ 109 and 1.8 _ 109 years and from a peridotitic end-member close to present-day oceanic mantle.

  18. Osmium complexation of mismatched DNA: effect of the bases adjacent to mismatched 5-methylcytosine.

    PubMed

    Nomura, Akiko; Tainaka, Kazuki; Okamoto, Akimitsu

    2009-03-18

    The efficiency of osmium complex formation at 5-methylcytosine in mismatched DNA duplexes is a key point for the design of sequence-specific detection of DNA methylation. Osmium complexation was not observed in fully matched duplexes, whereas the complexation site and efficiency in mismatched duplexes changed depending on the type of 5'-neighboring base of the 5-methylcytosine forming a mismatched base pair. In particular, when the base adjacent to the 5' side of the mismatched base pair was thymine, a unique "side reaction" was observed. However, the nature of the mismatched base pairs in the reaction site did not influence the selectivity of osmium complex formation with methylated DNA.

  19. Recent advances in osmium-catalyzed hydrogenation and dehydrogenation reactions.

    PubMed

    Chelucci, Giorgio; Baldino, Salvatore; Baratta, Walter

    2015-02-17

    CONSPECTUS: A current issue in metal-catalyzed reactions is the search for highly efficient transition-metal complexes affording high productivity and selectivity in a variety of processes. Moreover, there is also a great interest in multitasking catalysts that are able to efficiently promote different organic transformations by careful switching of the reaction parameters, such as temperature, solvent, and cocatalyst. In this context, osmium complexes have shown the ability to catalyze efficiently different types of reactions involving hydrogen, proving at the same time high thermal stability and simple synthesis. In the catalytic reduction of C═X (X = O, N) bonds by both hydrogenation (HY) and transfer hydrogenation (TH) reactions, the most interest has been focused on homogeneous systems based on rhodium, iridium, and in particular ruthenium catalysts, which have proved to catalyze chemo- and stereoselective hydrogenations with remarkable efficiency. By contrast, osmium catalysts have received much less attention because they are considered less active on account of their slower ligand exchange kinetics. Thus, this area remained almost neglected until recent studies refuted these prejudices. The aim of this Account is to highlight the impressive developments achieved over the past few years by our and other groups on the design of new classes of osmium complexes and their applications in homogeneous catalytic reactions involving the hydrogenation of carbon-oxygen and carbon-nitrogen bonds by both HY and TH reactions as well as in alcohol deydrogenation (DHY) reactions. The work described in this Account demonstrates that osmium complexes are emerging as powerful catalysts for asymmetric and non-asymmetric syntheses, showing a remarkably high catalytic activity in HY and TH reactions of ketones, aldehydes, imines, and esters as well in DHY reactions of alcohols. Thus, for instance, the introduction of ligands with an NH function, possibly in combination with a

  20. Optimal design study of high efficiency indium phosphide space solar cells

    NASA Technical Reports Server (NTRS)

    Jain, Raj K.; Flood, Dennis J.

    1990-01-01

    Recently indium phosphide solar cells have achieved beginning of life AMO efficiencies in excess of 19 pct. at 25 C. The high efficiency prospects along with superb radiation tolerance make indium phosphide a leading material for space power requirements. To achieve cost effectiveness, practical cell efficiencies have to be raised to near theoretical limits and thin film indium phosphide cells need to be developed. The optimal design study is described of high efficiency indium phosphide solar cells for space power applications using the PC-1D computer program. It is shown that cells with efficiencies over 22 pct. AMO at 25 C could be fabricated by achieving proper material and process parameters. It is observed that further improvements in cell material and process parameters could lead to experimental cell efficiencies near theoretical limits. The effect of various emitter and base parameters on cell performance was studied.

  1. Earth's Phosphides in Levant and insights into the source of Archean prebiotic phosphorus

    PubMed Central

    Britvin, Sergey N.; Murashko, Michail N.; Vapnik, Yevgeny; Polekhovsky, Yury S.; Krivovichev, Sergey V.

    2015-01-01

    Natural phosphides - the minerals containing phosphorus in a redox state lower than zero – are common constituents of meteorites but virtually unknown on the Earth. Herein we present the first rich occurrence of iron-nickel phosphides of terrestrial origin. Phosphide-bearing rocks are exposed in three localities in the surroundings of the Dead Sea, Levant: in the northern Negev Desert, Israel and Transjordan Plateau, south of Amman, Jordan. Seven minerals from the ternary Fe-Ni-P system have been identified with five of them, NiP2, Ni5P4, Ni2P, FeP and FeP2, previously unknown in nature. The results of the present study could provide a new insight on the terrestrial origin of natural phosphides – the most likely source of reactive prebiotic phosphorus at the times of the early Earth. PMID:25667163

  2. Earth's Phosphides in Levant and insights into the source of Archean prebiotic phosphorus.

    PubMed

    Britvin, Sergey N; Murashko, Michail N; Vapnik, Yevgeny; Polekhovsky, Yury S; Krivovichev, Sergey V

    2015-01-01

    Natural phosphides--the minerals containing phosphorus in a redox state lower than zero--are common constituents of meteorites but virtually unknown on the Earth. Herein we present the first rich occurrence of iron-nickel phosphides of terrestrial origin. Phosphide-bearing rocks are exposed in three localities in the surroundings of the Dead Sea, Levant: in the northern Negev Desert, Israel and Transjordan Plateau, south of Amman, Jordan. Seven minerals from the ternary Fe-Ni-P system have been identified with five of them, NiP2, Ni5P4, Ni2P, FeP and FeP2, previously unknown in nature. The results of the present study could provide a new insight on the terrestrial origin of natural phosphides--the most likely source of reactive prebiotic phosphorus at the times of the early Earth. PMID:25667163

  3. Photoelectrochemical cell having photoanode with thin boron phosphide coating as a corrosion resistant layer

    DOEpatents

    Baughman, Richard J.; Ginley, David S.

    1984-01-01

    A surface prone to corrosion in corrosive environments is rendered anticorrosive by CVD growing a thin continuous film, e.g., having no detectable pinholes, thereon, of boron phosphide. In one embodiment, the film is semiconductive. In another aspect, the invention is an improved photoanode, and/or photoelectrochemical cell with a photoanode having a thin film of boron phosphide thereon rendering it anitcorrosive, and providing it with unexpectedly improved photoresponsive properties.

  4. Surface reactions of molecular and atomic oxygen with carbon phosphide films.

    PubMed

    Gorham, Justin; Torres, Jessica; Wolfe, Glenn; d'Agostino, Alfred; Fairbrother, D Howard

    2005-11-01

    The surface reactions of atomic and molecular oxygen with carbon phosphide films have been studied using X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM). Carbon phosphide films were produced by ion implantation of trimethylphosphine into polyethylene. Atmospheric oxidation of carbon phosphide films was dominated by phosphorus oxidation and generated a carbon-containing phosphate surface film. This oxidized surface layer acted as an effective diffusion barrier, limiting the depth of phosphorus oxidation within the carbon phosphide film to < 3 nm. The effect of atomic oxygen (AO) exposure on this oxidized carbon phosphide layer was subsequently probed in situ using XPS. Initially AO exposure resulted in a loss of carbon atoms from the surface, but increased the surface concentration of phosphorus atoms as well as the degree of phosphorus oxidation. For more prolonged AO exposures, a highly oxidized phosphate surface layer formed that appeared to be inert toward further AO-mediated erosion. By utilizing phosphorus-containing hydrocarbon thin films, the phosphorus oxides produced during exposure to AO were found to desorb at temperatures >500 K under vacuum conditions. Results from this study suggest that carbon phosphide films can be used as AO-resistant surface coatings on polymers.

  5. Ruthenium or osmium complexes and their uses as catalysts for water oxidation

    DOEpatents

    Concepcion Corbea, Javier Jesus; Chen, Zuofeng; Jurss, Jonah Wesley; Templeton, Joseph L; Hoertz, Paul; Meyer, Thomas J

    2014-10-28

    The present invention provides ruthenium or osmium complexes and their uses as a catalyst for catalytic water oxidation. Another aspect of the invention provides an electrode and photo-electrochemical cells for electrolysis of water molecules.

  6. Ruthenium or osmium complexes and their uses as catalysts for water oxidation

    DOEpatents

    Corbea, Javier Jesus Concepcion; Chen, Zoufeng; Jurss, Jonah Wesley; Templeton, Joseph L.; Hoertz, Paul; Meyer, Thomas J.

    2016-06-07

    The present invention provides ruthenium or osmium complexes and their uses as a catalyst for catalytic water oxidation. Another aspect of the invention provides an electrode and photo-electrochemical cells for electrolysis of water molecules.

  7. Ruthenium or osmium complexes and their uses as catalysts for water oxidation

    SciTech Connect

    Corbea, Javier Jesus Concepcion; Chen, Zuofeng; Jurss, Jonah Wesley; Templeton, Joseph L.; Hoertz, Paul; Meyer, Thomas J.

    2013-09-03

    The present invention provides ruthenium or osmium complexes and their uses as a catalyst for catalytic water oxidation. Another aspect of the invention provides an electrode and photo-electrochemical cells for electrolysis of water molecules.

  8. Osmium (VI) complexes of the 3', 5'-dinucleoside monophosphates, ApU and UpA.

    PubMed

    Daniel, F B; Behrman, E J

    1976-02-10

    The dinucleoside monophosphates, ApU and UpA, react with potassium osmate (VI) and 2,2'-bipyridyl to form the corresponding oxo-osmium (VI) bipyridyl sugar ester in which the osmate group is bonded to the terminal 2',3'-glycol. Osmium (VIII) tetroxide and 2,2'-bipyridyl react with the dinucleosides to form the corresponding oxo-osmium (VI) bipyridyl heterocyclic esters which result from addition of the tetroxide to the 5,6-double bond of the uracil residue. Although capable of transesterification reactions, these heterocyclic esters are exceptionally stable toward exchange reactions in solution. No apparent exchange was observed after 1 month. This reaction thus seems promising for single-site osmium labeling in polynucleotides.

  9. An osmium-DNA interstrand complex: application to facile DNA methylation analysis.

    PubMed

    Tanaka, Kazuo; Tainaka, Kazuki; Umemoto, Tadashi; Nomura, Akiko; Okamoto, Akimitsu

    2007-11-21

    Nucleic acids often acquire new functions by forming a variety of complexes with metal ions. Osmium, in an oxidized state, also reacts with C5-methylated pyrimidines. However, control of the sequence specificity of osmium complexation with DNA is still immature, and the value of the resulting complexes is unknown. We have designed a bipyridine-attached adenine derivative for sequence-specific osmium complexation. Sequence-specific osmium complexation was achieved by hybridization of a short DNA molecule containing this functional nucleotide to a target DNA sequence and resulted in the formation of a cross-linked structure. The interstrand cross-link clearly distinguished methylated cytosines from unmethylated cytosines and was used to quantify the degree of methylation at a specific cytosine in the genome.

  10. A Terminal Osmium(IV) Nitride: Ammonia Formation and Ambiphilic Reactivity.

    PubMed

    Schendzielorz, Florian S; Finger, Markus; Volkmann, Christian; Würtele, Christian; Schneider, Sven

    2016-09-12

    Low-valent osmium nitrides are discussed as intermediates in nitrogen fixation schemes. However, rational synthetic routes that lead to isolable examples are currently unknown. Here, the synthesis of the square-planar osmium(IV) nitride [OsN(PNP)] (PNP=N(CH2 CH2 P(tBu)2 )2 ) is reported upon reversible deprotonation of osmium(VI) hydride [Os(N)H(PNP)](+) . The Os(IV) complex shows ambiphilic nitride reactivity with SiMe3 Br and PMe3 , respectively. Importantly, the hydrogenolysis with H2 gives ammonia and the polyhydride complex [OsH4 (HPNP)] in 80 % yield. Hence, our results directly demonstrate the role of low-valent osmium nitrides and of heterolytic H2 activation for ammonia synthesis with H2 under basic conditions. PMID:27529412

  11. Organometallic osmium(II) arene anticancer complexes containing picolinate derivatives.

    PubMed

    van Rijt, Sabine H; Peacock, Anna F A; Johnstone, Russell D L; Parsons, Simon; Sadler, Peter J

    2009-02-16

    Chlorido osmium(II) arene [(eta(6)-biphenyl)Os(II)(X-pico)Cl] complexes containing X = Br (1), OH (2), and Me (3) as ortho, or X = Cl (4), CO(2)H (5), and Me (6) as para substituents on the picolinate (pico) ring have been synthesized and characterized. The X-ray crystal structures of 1 and 6 show typical "piano-stool" geometry with intermolecular pi-pi stacking of the biphenyl outer rings of 6. At 288 K the hydrolysis rates follow the order 2 > 6 > 4 > 3 > 5 > 1 with half-lives ranging from minutes to 4.4 h illustrating the influence of both electronic and steric effects of the substituents. The pK(a) values of the aqua adducts 3A, 4A, 5A, and 6A were all in the range of 6.3-6.6. The para-substituted pico complexes 4-6 readily formed adducts with both 9-ethyl guanine (9EtG) and 9-ethyl adenine (9EtA), but these were less favored for the ortho-substituted complexes 1 and 3 showing little reaction with 9EtG and 9EtA, respectively. Density-functional theory calculations confirmed the observed preferences for nucleobase binding for complex 1. In cytotoxicity assays with A2780, cisplatin-resistant A2780cis human ovarian, A549 human lung, and HCT116 colon cancer cells, only complexes 4 (p-Cl) and 6 (p-Me) exhibited significant activity (IC(50) values < 25 microM). Both of these complexes were as active as cisplatin in A2780 (ovarian) and HCT116 (colon) cell lines, and even overcome cisplatin resistance in the A2780cis (ovarian) cell line. The inactivity of 5 is attributed to the negative charge on its para carboxylate substituent. These data illustrate how the chemical reactivity and cancer cell cytotoxicity of osmium arene complexes can be controlled and "fine-tuned" by the use of steric and electronic effects of substituents on a chelating ligand to give osmium(II) arene complexes which are as active as cisplatin but have a different mechanism of action.

  12. Metal and phosphide phases in Luna 24 soil fragments

    NASA Astrophysics Data System (ADS)

    Axon, H. J.; Nasir, M. J.; Knowles, F.

    1980-06-01

    Soil fragments in the 106-150 and 150-250 micron size ranges were selected for metallographic and microprobe examination on the basis of their magnetic properties. Serial sections of the mounted fragments were examined. One fragment proved to be a compositionally zoned crystal of phosphide with no metal phase but partly embedded in glass. Another was a coarse-grained association of silica with ilmenite and fayalite with a 5-micron particle of metallic iron in troilite. One splinter of oxide contained a central spine of metallic iron. The remaining six fragments contained 10-micron particles of iron-nickel-cobalt alloy with compositions in either the 'meteoritic' or the low Ni-low Co sub-meteoritic composition ranges of Ni, Co content. In some fragments separate particles of alloy had different Ni, Co contents. No particles of high Co metal were encountered.

  13. Vapor-Phase Synthesis of Gallium Phosphide Nanowires

    SciTech Connect

    Gu, Dr Zhanjun; Paranthaman, Mariappan Parans; Pan, Zhengwei

    2009-01-01

    Gallium phosphide (GaP) nanowires were synthesized in a high yield by vapor-phase reaction of gallium vapor and phosphorus vapor at 1150 C in a tube furnace system. The nanowires have diameters in the range of 25-100 nm and lengths of up to tens of micrometers. Twinning growth occurs in GaP nanowires, and as a result most nanowires contain a high density of twinning faults. Novel necklacelike GaP nanostructures that were formed by stringing tens of amorphous Ga-P-O microbeads upon one crystalline GaP nanowires were also found in some synthesis runs. This simple vapor-phase approach may be applied to synthesize other important group III-V compound nanowires.

  14. Rapid thermal annealing of indium phosphide compound semiconductors

    NASA Technical Reports Server (NTRS)

    Biedenbender, Michael D.; Kapoor, Vik J.; Williams, W. D.

    1987-01-01

    The rapid thermal annealing (RTA) of indium phosphide (InP) substrates using a proximity contact method and silicon nitride encapsulation is investigated. The surface conditions of the InP substrates following cleaning with procedures A and B are analyzed. Procedure A involves using an iodic acid solution to remove work-damage InP surface layers and B is a degasssing process and hydrofluoric acid solution for native oxide removal. AES, XPS, and SIMS data of the proximity contact and silicon nitride encapsulated annealed samples are examined. The data reveal that RTA using proximity contact with silicon wafers does not provide adequate protection; however, the InP sample is successfully annealed when protected by a silicon nitride encapsulant.

  15. Band structures in silicene on monolayer gallium phosphide substrate

    NASA Astrophysics Data System (ADS)

    Ren, Miaojuan; Li, Mingming; Zhang, Changwen; Yuan, Min; Li, Ping; Li, Feng; Ji, Weixiao; Chen, Xinlian

    2016-07-01

    Opening a sizable band gap in the zero-gap silicene is a key issue for its application in nanoelectronics. We design new 2D silicene and GaP heterobilayer (Si/GaP HBL) composed of silicene and monolayer (ML) GaP. Based on first-principles calculations, we find that the interaction energies are in the range of -295.5 to -297.5 meV per unit cell, indicating a weak interaction between silicene and gallium phosphide (GaP) monolayer. The band gap changes ranging from 0.06 to 0.44 eV in hybrid HBLs. An unexpected indirect-direct band gap crossover is also observed in HBLs, dependent on the stacking pattern. These provide a possible way to design effective FETs out of silicene on GaP monolayer.

  16. Zinc phosphide intoxication of wild turkeys (Meleagris gallopavo).

    PubMed

    Poppenga, Robert H; Ziegler, Andre F; Habecker, Perry L; Singletary, Don L; Walter, Mark K; Miller, Paul G

    2005-01-01

    Zinc phosphide (Zn3P2) is a rodenticide used to control a variety of small mammal species. It is available over-the-counter or as a restricted-use pesticide depending on how it is to be applied. The toxicity of Zn3P2 is dependent on the species exposed, whether the animal is able to vomit or not, and whether it is ingested on a full or empty stomach. Nontarget species can be exposed through inadvertent or intentional product misapplication. In this article we describe four mortality events in which wild turkeys (Meleagris gallopavo) were believed to have been intoxicated following the ingestion of baits containing Zn3P2.

  17. Elasto-optic effect anisotropy in gallium phosphide crystals.

    PubMed

    Mytsyk, B G; Demyanyshyn, N M; Sakharuk, O M

    2015-10-01

    Elasto-optic coefficients of gallium phosphide (GaP) crystals were calculated on the basis of their piezo-optic and elastic coefficients. Surfaces of the spatial distribution of piezo- and elasto-optic effects in these crystals were built. The maxima of the surfaces of the elasto-optic effect and the geometries of acousto-optic interaction that correspond to these maxima were found. Ratios that describe the rotation of optical indicatrix, depending on direction of the action of uniaxial pressure or deformation on cubic crystal, were recorded. It was shown that such rotations induced by mechanical stress do not exceed 1.5° in GaP, but in some cubic crystals they can reach tens of degrees. PMID:26479633

  18. Fabrication and properties of gallium phosphide variable colour displays

    NASA Technical Reports Server (NTRS)

    Effer, D.; Macdonald, R. A.; Macgregor, G. M.; Webb, W. A.; Kennedy, D. I.

    1973-01-01

    The unique properties of single-junction gallium phosphide devices incorporating both red and green radiative recombination centers were investigated in application to the fabrication of monolithic 5 x 7 displays capable of displaying symbolic and alphanumeric information in a multicolor format. A number of potentially suitable material preparation techniques were evaluated in terms of both material properties and device performance. Optimum results were obtained for double liquid-phase-epitaxial process in which an open-tube dipping technique was used for n-layer growth and a sealed tipping procedure for subsequent p-layer growth. It was demonstrated that to prepare devices exhibiting a satisfactory range of dominant wavelengths which can be perceived as distinct emission colors extending from the red through green region of the visible spectrum involves a compromise between the material properties necessary for efficient red emission and those considered optimum for efficient green emission.

  19. Cyclometalated Osmium-Amine Electronic Communication through the p-Oligophenylene Wire.

    PubMed

    Shen, Jun-Jian; Shao, Jiang-Yang; Gong, Zhong-Liang; Zhong, Yu-Wu

    2015-11-16

    A series of bis-tridentate cyclometalated osmium complexes with a redox-active triarylamine substituent have been prepared, where the amine substituent is separated from the osmium ion by a p-oligophenylene wire of various lengths. X-ray crystallographic data of complexes 3(PF6) and 4(PF6) with three or four repeating phenyl units between the osmium ion and the amine substituent are presented. These complexes show two consecutive anodic redox couples between +0.1 and +0.9 V vs Ag/AgCl, with the potential splitting in the range of 300-390 mV. A combined experimental and theoretical study suggests that, in the one-electron-oxidized state, the odd electron is delocalized for short congeners and localized on the osmium component for long congeners. The electronic coupling parameter (Vab) was estimated by the Marcus-Hush analysis. The distance dependence plot of ln(Vab) versus the osmium-amine geometrical distance (Rab) gives a negative linear relationship with a decay slope of -0.19 Å(-1), which is slightly steeper with respect to the previously reported ruthenium-amine series with the same molecular wire. DFT calculations with the long-range-corrected UCAM-B3LYP functional gave more reasonable results for the osmium complexes with respect to those with UB3LYP. PMID:26567859

  20. Similar Biological Activities of Two Isostructural Ruthenium and Osmium Complexes

    SciTech Connect

    Maksimoska,J.; Williams, D.; Atilla-Gokcumen, G.; Smalley, K.; Carroll, P.; Webster, R.; Filippakopoulos, P.; Knapp, S.; Herlyn, M.; Meggers, E.

    2008-01-01

    In this study, we probe and verify the concept of designing unreactive bioactive metal complexes, in which the metal possesses a purely structural function, by investigating the consequences of replacing ruthenium in a bioactive half-sandwich kinase inhibitor scaffold by its heavier congener osmium. The two isostructural complexes are compared with respect to their anticancer properties in 1205?Lu melanoma cells, activation of the Wnt signaling pathway, IC50 values against the protein kinases GSK-3? and Pim-1, and binding modes to the protein kinase Pim-1 by protein crystallography. It was found that the two congeners display almost indistinguishable biological activities, which can be explained by their nearly identical three-dimensional structures and their identical mode of action as protein kinase inhibitors. This is a unique example in which the replacement of a metal in an anticancer scaffold by its heavier homologue does not alter its biological activity.

  1. Electronic transport experiments on osmium-adatom-decorated graphene

    NASA Astrophysics Data System (ADS)

    Elias, Jamie; Henriksen, Erik

    Monolayer graphene is theoretically predicted to inherit a spin-orbit coupling from a dilute coating of certain transition metal adatoms. To explore these predictions we have constructed a cryogenic probe capable of in situ thermal annealing of graphene followed immediately by electronic transport measurements and controlled deposition of sub-monolayer coatings of most any metal. Previously a light coating of indium on graphene was investigated, and found to transfer electrons to graphene and reduce the mobility although no evidence of an induced spin-orbit coupling was seen. We are now depositing osmium and tungsten on graphene devices. Our initial results show an unexpected hole-doping and a sizable increase in resistance of the sample. We will report our progress on characterizing these samples by electronic transport measurements.

  2. Mechanical mixtures of metal oxides and phosphorus pentoxide as novel precursors for the synthesis of transition-metal phosphides.

    PubMed

    Guo, Lijuan; Zhao, Yu; Yao, Zhiwei

    2016-01-21

    This study presents a new type of precursor, mechanical mixtures of metal oxides (MOs) and phosphorus pentoxide (P2O5) are used to synthesize Ni2P, Co2P and MoP phosphides by the H2 reduction method. In addition, this is first report of common solid-state P2O5 being used as a P source for the synthesis of metal phosphides. The traditional precursors are usually prepared via a complicated preparation procedure involving dissolution, drying and calcination steps. However, these novel MOs/P2O5 precursors can be obtained only by simple mechanical mixing of the starting materials. Furthermore, unlike the direct transformation from amorphous phases to phosphides, various specific intermediates were involved in the transformation from MOs/P2O5 to phosphides. It is worthy to note that the dispersions of Ni2P, Co2P and MoP obtained from MOs/P2O5 precursors were superior to those of the corresponding phosphides prepared from the abovementioned traditional precursors. It is suggested that the morphology of the as-prepared metal phosphides might be inherited from the corresponding MOs. Based on the results of XRD, XPS, SEM and TEM, the formation pathway of phosphides can be defined as MOs/P2O5 precursors → complex intermediates (metals, metal phosphates and metal oxide-phosphates) → metal phosphides.

  3. Novel, high-activity hydroprocessing catalysts: Iron group phosphides

    NASA Astrophysics Data System (ADS)

    Wang, Xianqin

    A series of iron, cobalt and nickel transition metal phosphides was synthesized by means of temperature-programmed reduction (TPR) of the corresponding phosphates. The same materials, Fe2P, CoP and NO, were also prepared on a silica (SiO2) support. The phase purity of these catalysts was established by x-ray diffraction (XRD), and the surface properties were determined by N2 BET specific surface area (Sg) measurements and CO chemisorption. The activities of the silica-supported catalysts were tested in a three-phase trickle bed reactor for the simultaneous hydrodenitrogenation (HDN) of quinoline and hydrodesulfurization (HDS) of dibenzothiophene using a model liquid feed at realistic conditions (30 atm, 370°C). The reactivity studies showed that the nickel phosphide (Ni2P/SiO2) was the most active of the catalysts. Compared with a commercial Ni-Mo-S/gamma-Al 2O3 catalyst at the same conditions, Ni2P/silica had a substantially higher HDS activity (100% vs. 76%) and HDN activity (82% vs. 38%). Because of their good hydrotreating activity, an extensive study of the preparation of silica supported nickel phosphides, Ni2P/SiO 2, was carried out. The parameters investigated were the phosphorus content and the weight loading of the active phase. The most active composition was found to have a starting synthesis Ni/P ratio close to 1/2, and the best loading of this sample on silica was observed to be 18 wt.%. Extended x-ray absorption fine structure (EXAFS) and x-ray absorption near edge spectroscopy (XANES) measurements were employed to determine the structures of the supported samples. The main phase before and after reaction was found to be Ni2P, but some sulfur was found to be retained after reaction. A comprehensive scrutiny of the HDN reaction mechanism was also made over the Ni2P/SiO2 sample (Ni/P = 1/2) by comparing the HDN activity of a series of piperidine derivatives of different structure. It was found that piperidine adsorption involved an alpha-H activation

  4. Synthesis and catalytic activity of the metastable phase of gold phosphide

    NASA Astrophysics Data System (ADS)

    Fernando, Deshani; Nigro, Toni A. E.; Dyer, I. D.; Alia, Shaun M.; Pivovar, Bryan S.; Vasquez, Yolanda

    2016-10-01

    Recently, transition metal phosphides have found new applications as catalysts for the hydrogen evolution reaction that has generated an impetus to synthesize these materials at the nanoscale. In this work, Au2P3 was synthesized utilizing the high temperature decomposition of tri-n-octylphosphine as a source of elemental phosphorous. Gold nanorods were used as morphological templates with the aim of controlling the shape and size of the resulting gold phosphide particles. We demonstrate that the surface capping ligand of the gold nanoparticle precursors can influence the purity and extent to which the gold phosphide phase will form. Gold nanorods functionalized with 1-dodecanethiol undergo digestive ripening to produce discrete spherical particles that exhibit reduced reactivity towards phosphorous, resulting in low yields of the gold phosphide. In contrast, gold phosphide was obtained as a phase pure product when cetyltrimethylammonium bromide functionalized gold nanorods are used instead. The Au2P3 nanoparticles exhibited higher activity than polycrystalline gold towards the hydrogen evolution reaction.

  5. Andreyivanovite: A Second New Phosphide from the Kaidun Meteorite

    NASA Technical Reports Server (NTRS)

    Zolensky, Michael

    2008-01-01

    Andreyivanovite (ideally FeCrP) is another new phosphide species from the Kaidun meteorite, which fell in South Yemen in 1980. Kaidun is a unique breccia containing an unprecedented variety of fragments of different chondritic as well as achondritic lithologies. Andreyivanovite was found as individual grains and linear arrays of grains with a maximum dimension of 8 m within two masses of Fe-rich serpentine. In one sample it is associated with Fe-Ni-Cr sulfides and florenskyite (FeTiP). Andreyivanovite is creamy white in reflected light, and its luster is metallic. The average of nine electron microprobe analyses yielded the formula Fe(Cr0.587 Fe0.150 V0.109 Ti0.081 Ni0.060 Co0.002)P. Examination of single grains of andreyivanovite using Laue patterns collected by in-situ synchrotron X-ray diffraction (XRD), and by electron backscattered diffraction revealed that it is isostructural with florenskyite; we were unable to find single crystals of sufficient quality to perform a complete structure analysis. Andreyivanovite crystallizes in the space group Pnma, and has the anti-PbCl2 structure. Previously-determined cell constants of synthetic material [a = 5.833(1), b = 3.569(1), c = 6.658(1) A] were consistent with our XRD work. We used the XPOW program to calculate a powder XRD pattern; the 5 most intense reflections are d = 2.247 (I = 100), 2.074 (81), 2.258 (46), 1.785 (43), and 1.885 A (34). Andreyivanovite is the second new phosphide to be described from the Kaidun meteorite. Andreyivanovite could have formed as a result of cooling and crystallization of a melted precursor consisting mainly of Fe-Ni metal enriched in P, Ti, and Cr. Serpentine associated with andreyivanovite would then have formed during aqueous alteration on the parent asteroid. It is also possible that the andreyivanovite could have formed during aqueous alteration, however, artificial FeTiP has been synthesized only during melting experiments, at low oxygen fugacity, and there is no evidence that

  6. Sequential separation and spectrophotometric determination of osmium and platinum with 5-chloro-2-hydroxythiobenzhydrazide.

    PubMed

    Sawant, Shakuntala S

    2009-06-01

    Osmium was determined spectrophotometrically after coprecipitation with 5-chloro-2-hydroxythiobenzhydrazide at room temperature in the pH range 2.5-5.0 and collection on microcrystalline naphthalene. Beer's law was obeyed in the concentration range 1.8-14.4 ppm of osmium in a chloroform solution at 510 nm. The molar absorptivity and Sandell sensitivity were 1.056 x 10(4) l mol(-1) cm(-1) and 0.018 ppm, respectively. Six replicate analyses of a solution containing 7.2 ppm of osmium gave a mean absorbance of 0.405 with a standard deviation of 0.013 and a relative standard deviation of 0.92%. The complex was stable for over 72 h. The metal-to-ligand ratio in the complex was 1:2. Interference from various ions was studied, and the method was applied to the determination of osmium in various synthetic mixtures containing commonly associated metals and corresponding to the alloy composition. The sequential separation and determination of osmium and platinum is reported.

  7. Early Archean Osmium in Chromitites from the Beartooth Range, Montana

    NASA Astrophysics Data System (ADS)

    Minarik, W. G.; Henry, D.

    2004-05-01

    Metamorphosed chromitites from the Hellroaring Plateau (Beartooth Mountains, Montana, USA) were analyzed for osmium isotopes and Re and Os contents. The chromitites are exposed at the surface in pit mines above Quad Creek. Euhedral spinels (Mg# 43-44, Cr# 74-76) are set in a matrix of phlogopite and talc. Chromites are free of ferrichromite rims and have only minor exsolution lamellae. Samples were dissolved in carius tubes using aqua regia and analyzed using MC-NTIMS (Os) and MC-ICPMS (Re). Zircons from the Hellroaring Plateau give average Lu-Hf ages of 3.5 Ga (Stevenson and Patchett, 1990). Quartzites (3.1-2.7 Ga depositional age) from this area contain detrital zircons with U-Pb ages up to 4.0 Ga. The main zircon population dates a major crust-forming event at 3.2-3.4 Ga (Mueller et al. 1998). The Main Beartooth Massif area has seen several generations of amphibolite- to granulite-facies metamorphism before the area was uplift during the Laramide orogeny. Sample QC81-19 contains 43 ppb Os with a 187Os/188Os of 0.1048 (±0.0001, 2σ ). Low Re/Os makes correction for 187Os production since the Archean minimal. Assuming an igneous age of 3.2 Ga, the sample formed with an initial 187Os/188Os of 0.1046, close to the chondritic Re/Os evolution line. A sample aggressively acid leached with still contained considerable osmium of nearly the same 187Os/188Os as the unleached sample. This suggests that the Os is not hosted by grain boundary sulfides, and that fluid influx and recrystallization was not accompanied by either Re or Os mobility. The present-day 187Os/188Os of this sample (0.1048) is one of the least radiogenic bulk sample Os ratios reported to date, slightly more radiogenic than the ratios reported (0.1026) for the 3.8 Ga peridotites of SW Greenland (Bennett et al., 2002). Both suggest the upper mantle source had a chondritic Re/Os in the early Archean. Mantle xenoliths from the Highwood mountains on the northern margin of the Wyoming Craton give minimum model

  8. Method of synthesizing bulk transition metal carbide, nitride and phosphide catalysts

    DOEpatents

    Choi, Jae Soon; Armstrong, Beth L; Schwartz, Viviane

    2015-04-21

    A method for synthesizing catalyst beads of bulk transmission metal carbides, nitrides and phosphides is provided. The method includes providing an aqueous suspension of transition metal oxide particles in a gel forming base, dropping the suspension into an aqueous solution to form a gel bead matrix, heating the bead to remove the binder, and carburizing, nitriding or phosphiding the bead to form a transition metal carbide, nitride, or phosphide catalyst bead. The method can be tuned for control of porosity, mechanical strength, and dopant content of the beads. The produced catalyst beads are catalytically active, mechanically robust, and suitable for packed-bed reactor applications. The produced catalyst beads are suitable for biomass conversion, petrochemistry, petroleum refining, electrocatalysis, and other applications.

  9. Gas phase catalytic hydrodechlorination of chlorobenzene over cobalt phosphide catalysts with different P contents.

    PubMed

    Cecilia, J A; Infantes-Molina, A; Rodríguez-Castellón, E; Jiménez-López, A

    2013-09-15

    The gas phase catalytic hydrodechlorination (HDC) of chlorobenzene (CB) at atmospheric pressure was investigated over silica-supported cobalt and cobalt phosphide catalysts containing different P loading and a fixed amount of cobalt (5 wt.%). The effect of the initial P/Co molar ratio on the stoichiometry of the cobalt phosphide phase, the acidity and the hydrogen activation capability were discussed and these properties correlated with the catalytic activity. Catalytic results indicated that the cobalt phosphide phase is much more active than the monometallic cobalt one. The activity raised with the P content present in the sample due to the formation of the CoP phase instead of the Co₂P one, which favored the formation of hydrogen spillover species, increased the amount of weak acid sites and the number of exposed superficial cobalt atoms probably related to a better dispersion of the active phase. All the catalysts gave rise benzene as the main reaction product.

  10. A case of accidental fatal aluminum phosphide poisoning involving humans and dogs.

    PubMed

    Behera, Chittaranjan; Krishna, Karthik; Bhardwaj, Daya Nand; Rautji, Ravi; Kumar, Arvind

    2015-05-01

    Aluminum phosphide is one of the commonest poisons encountered in agricultural areas, and manner of death in the victims is often suicidal and rarely homicidal or accidental. This paper presents an unusual case, where two humans (owner and housemaid) and eight dogs were found dead in the morning hours inside a room of a house, used as shelter for stray dogs. There was allegation by the son of the owner that his father had been killed. Crime scene visit by forensic pathologists helped to collect vital evidence. Autopsies of both the human victims and the dogs were conducted. Toxicological analysis of viscera, vomitus, leftover food, and chemical container at the crime scene tested positive for aluminum phosphide. The cause of death in both humans and dogs was aluminum phosphide poisoning. Investigation by police and the forensic approach to the case helped in ascertaining the manner of death, which was accidental.

  11. Protective Role of G6PD Deficiency in Aluminium Phosphide Poisoning.

    PubMed

    Humayun, Mohammad; Haider, Iqbal; Badshah, Aliena; Subhan, Fazle

    2015-04-01

    A 15-year-old boy was referred to the hospital from the periphery with a history of ingestion of 5 wheat pills (aluminium phosphide) 5 days back. He had been given a stomach wash in his village hospital prior to referral. On arrival, he was jaundiced and had developed haematuria too, but otherwise appeared well in himself. Four days after admission, his haemoglobin showed a marked drop and he was shifted to intensive care, keeping in mind the high mortality rate associated with aluminium phosphide intoxication. His G6PD levels were checked, and he turned out to be G6PD deficient. The patient was given intravenous magnesium sulphate and supportive care and he improved subsequently. Wheat pill poisoning carries a high mortality of 98% in some cases; despite the high mortality, this patient survived. This may mean that G6PD deficiency has a protective role in poisoning due to aluminium phosphide.

  12. Comparative performance of diffused junction indium phosphide solar cells

    NASA Technical Reports Server (NTRS)

    Weinberg, I.; Swartz, C. K.; Hart, R. E., Jr.; Ghandhi, S. K.; Borrego, J. M.; Parat, K. K.

    1987-01-01

    A comparison is made between indium phosphide solar cells whose p-n junctions were processed by open tube capped diffusion, and closed tube uncapped diffusion, of sulfur into Czochralski grown p-type substrates. Air mass zero, total area, efficiencies ranged from 10 to 14.2 percent, the latter value attributed to cells processed by capped diffusion. The radiation resistance of these latter cells was slightly better, under 1 MeV electron irradiation. However, rather than being process dependent, the difference in radiation resistance could be attributed to the effects of increased base dopant concentration. In agreement with previous results, both cells exhibited radiation resistance superior to that of gallium arsenide. The lowest temperature dependency of maximum power was exhibited by the cells prepared by open tube capped diffusion. Contrary to previous results, no correlation was found between open circuit voltage and the temperature dependency of Pmax. It was concluded that additional process optimization was necessary before concluding that one process was better than another.

  13. Therapeutic role of hyperinsulinemia/euglycemia in aluminum phosphide poisoning

    PubMed Central

    Hassanian-Moghaddam, Hossein; Zamani, Nasim

    2016-01-01

    Abstract Background: Different protocols have been suggested to treat aluminum phosphide (ALP) poisoning. We aimed to evaluate the possible therapeutic effect of hyperinsulinemia/euglycemia (HIE) in treatment of ALP poisoning. Methods: In a prospective interventional study, a total of 88 ALP-poisoned patients were included and assigned into HIE group undergoing glucose/insulin/potassium (GIK) protocol and a control group that was managed by routine conventional treatments. The 2 groups were then compared regarding the signs and symptoms of toxicity and their progression, development of complications, and final outcome to detect the possible effect of GIK protocol on the patients’ course of toxicity and outcome. Results: The 2 groups were similar in terms of demographic characteristics and on-arrival vital signs and lab tests. Using GIK protocol resulted in significantly longer hospital stays (24 vs 60 hours; P < 0.001) and better outcomes (72.7% vs 50% mortality; P = 0.03). Regression analysis showed that GIK duration was an independent variable that could prognosticate mortality (odds ratio [95% confidence interval] = 1.045 [1.004,1.087]). The risk of mortality decreased by 4.5% each hour after initiation of GIK. Conclusion: GIK protocol improves the outcome of ALP poisoning and increases the length of hospital stay. PMID:27495040

  14. Optical Properties of Strained Wurtzite Gallium Phosphide Nanowires.

    PubMed

    Greil, J; Assali, S; Isono, Y; Belabbes, A; Bechstedt, F; Valega Mackenzie, F O; Silov, A Yu; Bakkers, E P A M; Haverkort, J E M

    2016-06-01

    Wurtzite gallium phosphide (WZ GaP) has been predicted to exhibit a direct bandgap in the green spectral range. Optical transitions, however, are only weakly allowed by the symmetry of the bands. While efficient luminescence has been experimentally shown, the nature of the transitions is not yet clear. Here we apply tensile strain up to 6% and investigate the evolution of the photoluminescence (PL) spectrum of WZ GaP nanowires (NWs). The pressure and polarization dependence of the emission together with a theoretical analysis of strain effects is employed to establish the nature and symmetry of the transitions. We identify the emission lines to be related to localized states with significant admixture of Γ7c symmetry and not exclusively related to the Γ8c conduction band minimum (CBM). The results emphasize the importance of strongly bound state-related emission in the pseudodirect semiconductor WZ GaP and contribute significantly to the understanding of the optoelectronic properties of this novel material. PMID:27175743

  15. Optical Properties of Strained Wurtzite Gallium Phosphide Nanowires

    PubMed Central

    2016-01-01

    Wurtzite gallium phosphide (WZ GaP) has been predicted to exhibit a direct bandgap in the green spectral range. Optical transitions, however, are only weakly allowed by the symmetry of the bands. While efficient luminescence has been experimentally shown, the nature of the transitions is not yet clear. Here we apply tensile strain up to 6% and investigate the evolution of the photoluminescence (PL) spectrum of WZ GaP nanowires (NWs). The pressure and polarization dependence of the emission together with a theoretical analysis of strain effects is employed to establish the nature and symmetry of the transitions. We identify the emission lines to be related to localized states with significant admixture of Γ7c symmetry and not exclusively related to the Γ8c conduction band minimum (CBM). The results emphasize the importance of strongly bound state-related emission in the pseudodirect semiconductor WZ GaP and contribute significantly to the understanding of the optoelectronic properties of this novel material. PMID:27175743

  16. Optical Properties of Strained Wurtzite Gallium Phosphide Nanowires.

    PubMed

    Greil, J; Assali, S; Isono, Y; Belabbes, A; Bechstedt, F; Valega Mackenzie, F O; Silov, A Yu; Bakkers, E P A M; Haverkort, J E M

    2016-06-01

    Wurtzite gallium phosphide (WZ GaP) has been predicted to exhibit a direct bandgap in the green spectral range. Optical transitions, however, are only weakly allowed by the symmetry of the bands. While efficient luminescence has been experimentally shown, the nature of the transitions is not yet clear. Here we apply tensile strain up to 6% and investigate the evolution of the photoluminescence (PL) spectrum of WZ GaP nanowires (NWs). The pressure and polarization dependence of the emission together with a theoretical analysis of strain effects is employed to establish the nature and symmetry of the transitions. We identify the emission lines to be related to localized states with significant admixture of Γ7c symmetry and not exclusively related to the Γ8c conduction band minimum (CBM). The results emphasize the importance of strongly bound state-related emission in the pseudodirect semiconductor WZ GaP and contribute significantly to the understanding of the optoelectronic properties of this novel material.

  17. Identification of phases in thin amorphous films of zinc phosphides

    SciTech Connect

    Aleinikova, K. B.; Zinchenko, E. N. Lesovoi, M. V.

    2007-03-15

    Analysis of the experimental atomic radial distribution functions for thin amorphous films of zinc phosphides obtained by explosive laser sputtering has been performed within a fragmentary model. The experiment was carried out with an Emp-10a electron diffractometer in transmitted light at accelerating voltages of 50 and 75 kV. The films obtained by sputtering of {beta}-ZnP{sub 2} single crystals contained nanoparticles of this phase. The films based on Zn{sub 3}P{sub 2} turned out to be two-phase and consisted of dispersed Zn{sub 3}P{sub 2} and {beta}-ZnP{sub 2} nanoparticles. The composition of the film obtained on the basis of {alpha}-ZnP{sub 2} corresponded neither to any one of the known phases in the Zn-P system nor to any mixture of these phases. Crystallization of films in a divergent electron beam confirmed the results of the phase analysis performed using the model atomic radial distribution functions.

  18. Allende meteorite: Isotopically anomalous xenon is accompanied by normal osmium.

    PubMed

    Takahashi, H; Higuchi, H; Gros, J; Morgan, J W; Anders, E

    1976-12-01

    The (184)Os/(190)Os ratio of six Allende meteorite samples was determined by neutron activation analysis. Four chromite concentrates gave a ratio differing from the terrestrial ratio by only -0.1 +/- 0.4%, although they contained highly anomalous xenon enriched by up to 67% in (124)Xe and 93% in (136)Xe. In view of this result and the normal isotopic composition of carbon and oxygen in these fractions, it seems very unlikely that the xenon anomalies were produced in a supernova by the p and r processes. More probably, the xenon anomalies were established in the early solar system, by mass fractionation during trapping of noble gases in solids and by spontaneous fission of a superheavy element.Two other samples, containing osmium from the calcium,aluminum-rich inclusions, also gave an (184)Os/(190)Os ratio within -0.1 +/- 0.5% of the terrestrial value, although these inclusions show well-established anomalies in the light elements oxygen and magnesium, which appear to be due to pre-solar dust grains of distinctive nuclear history. Apparently the stellar source of the anomalous oxygen and magnesium did not synthesize heavier elements.

  19. Allende meteorite: Isotopically anomalous xenon is accompanied by normal osmium

    PubMed Central

    Takahashi, H.; Higuchi, H.; Gros, Jacques; Morgan, John W.; Anders, Edward

    1976-01-01

    The 184Os/190Os ratio of six Allende meteorite samples was determined by neutron activation analysis. Four chromite concentrates gave a ratio differing from the terrestrial ratio by only -0.1 ± 0.4%, although they contained highly anomalous xenon enriched by up to 67% in 124Xe and 93% in 136Xe. In view of this result and the normal isotopic composition of carbon and oxygen in these fractions, it seems very unlikely that the xenon anomalies were produced in a supernova by the p and r processes. More probably, the xenon anomalies were established in the early solar system, by mass fractionation during trapping of noble gases in solids and by spontaneous fission of a superheavy element. Two other samples, containing osmium from the calcium,aluminum-rich inclusions, also gave an 184Os/190Os ratio within -0.1 ± 0.5% of the terrestrial value, although these inclusions show well-established anomalies in the light elements oxygen and magnesium, which appear to be due to pre-solar dust grains of distinctive nuclear history. Apparently the stellar source of the anomalous oxygen and magnesium did not synthesize heavier elements. PMID:16592365

  20. Theoretical survey of the reaction between osmium and acetaldehyde

    NASA Astrophysics Data System (ADS)

    Dai, Guo-Liang; Wang, Chuan-Feng

    2012-05-01

    The mechanism of the reaction of osmium atom with acetaldehyde has been investigated with a DFT approach. All the stationary points are determined at the UB3LYP/ sdd/6-311++G** level of the theory. Both ground and excited state potential energy surfaces are investigated in detail. The present results show that the title reaction start with the formation of a CH3CHO-metal complex followed by C-C, aldehyde C-H, C-O, and methyl C-H activation. These reactions can lead to four different products (HOsCH3 + CO, OsCO + CH4, OsCOCH3 + H, and OsO + C2H4). The minimum energy reaction path is found to involve the spin inversion in the initial reaction step. This potential energy curve-crossing dramatically affects reaction exothermic. The present results may be helpful in understanding the mechanism of the title reaction and further experimental investigation of the reaction.

  1. Rhenium-osmium isotope systematics of carbonaceous chondrites

    USGS Publications Warehouse

    Walker, R.J.; Morgan, J.W.

    1989-01-01

    Rhenium and osmium concentrations and Os isotopic compositions of eight carbonaceous chondrites, one LL3 ordinary chondrite, and two iron meteorites were determined by resonance ionization mass spectrometry. Iron meteorite 187Re/186Os and 187OS/186Os ratios plot on the previously determined iron meteorite isochron, but most chondrite data plot 1 to 2 percent above this meteorite isochron. This suggests either that irons have significantly younger Re-Os closure ages than chondrites or that chondrites were formed from precursor materials with different chemical histories from the precursors of irons. Some samples of Semarkona (LL3) and Murray (C2M) meteorites plot 4 to 6 percent above the iron meteorite isochron, well above the field delineated by other chondrites. Murray may have lost Re by aqueous leaching during its preterrestrial history. Semarkona could have experienced a similar loss of Re, but only slight aqueous alteration is evident in the meteorite. Therefore, the isotopic composition of Semarkona could reflect assembly of isotopically heterogeneous components subsequent to 4.55 billion years ago or Os isotopic heterogeneities in the primordial solar nebula.

  2. Osmium isotope stratigraphy of a marine ferromanganese crust

    USGS Publications Warehouse

    Klemm, V.; Levasseur, S.; Frank, M.; Hein, J.R.; Halliday, A.N.

    2005-01-01

    Ferromanganese crusts provide records of long term change in ocean circulation and continental weathering. However, calibrating their age prior to 10 Ma has been entirely based on empirical growth rate models using Co concentrations, which have inherently large uncertainties and fail to detect hiatuses and erosional events. We present a new method for dating these crusts by measuring their osmium (Os) isotope record and matching it to the well-known marine Os isotope evolution of the past 80 Ma. The well-characterised crust CD29-2 from the central Pacific, was believed to define a record of paleooceanographic change from 50 Ma. Previous growth rate estimates based on the Co method are consistent with the new Os isotope stratigraphy but the dating was grossly inaccurate due to long hiatuses that are now detectable. The new chronology shows that it in fact started growing prior to 70 Ma in the late Cretaceous and stopped growing or was eroded between 13.5 and 47 Ma. With this new technique it is now possible to exploit the full potential of the oceanographic and climatic records stored in Fe-Mn crusts. ?? 2005 Elsevier B.V. All rights reserved.

  3. Osmium isotope evidence for a large Late Triassic impact event.

    PubMed

    Sato, Honami; Onoue, Tetsuji; Nozaki, Tatsuo; Suzuki, Katsuhiko

    2013-01-01

    Anomalously high platinum group element concentrations have previously been reported for Upper Triassic deep-sea sediments, which are interpreted to be derived from an extraterrestrial impact event. Here we report the osmium (Os) isotope fingerprint of an extraterrestrial impact from Upper Triassic chert successions in Japan. Os isotope data exhibit a marked negative excursion from an initial Os isotope ratio ((187)Os/(188)Osi) of ~0.477 to unradiogenic values of ~0.126 in a platinum group element-enriched claystone layer, indicating the input of meteorite-derived Os into the sediments. The timing of the Os isotope excursion coincides with both elevated Os concentrations and low Re/Os ratios. The magnitude of this negative Os isotope excursion is comparable to those found at Cretaceous-Paleogene boundary sites. These geochemical lines of evidence demonstrate that a large impactor (3.3-7.8 km in diameter) produced a global decrease in seawater (187)Os/(188)Os ratios in the Late Triassic.

  4. Osmium isotope evidence for a large Late Triassic impact event

    PubMed Central

    Sato, Honami; Onoue, Tetsuji; Nozaki, Tatsuo; Suzuki, Katsuhiko

    2013-01-01

    Anomalously high platinum group element concentrations have previously been reported for Upper Triassic deep-sea sediments, which are interpreted to be derived from an extraterrestrial impact event. Here we report the osmium (Os) isotope fingerprint of an extraterrestrial impact from Upper Triassic chert successions in Japan. Os isotope data exhibit a marked negative excursion from an initial Os isotope ratio (187Os/188Osi) of ∼0.477 to unradiogenic values of ∼0.126 in a platinum group element-enriched claystone layer, indicating the input of meteorite-derived Os into the sediments. The timing of the Os isotope excursion coincides with both elevated Os concentrations and low Re/Os ratios. The magnitude of this negative Os isotope excursion is comparable to those found at Cretaceous–Paleogene boundary sites. These geochemical lines of evidence demonstrate that a large impactor (3.3–7.8 km in diameter) produced a global decrease in seawater 187Os/188Os ratios in the Late Triassic. PMID:24036603

  5. Osmium isotope evidence for a large Late Triassic impact event.

    PubMed

    Sato, Honami; Onoue, Tetsuji; Nozaki, Tatsuo; Suzuki, Katsuhiko

    2013-01-01

    Anomalously high platinum group element concentrations have previously been reported for Upper Triassic deep-sea sediments, which are interpreted to be derived from an extraterrestrial impact event. Here we report the osmium (Os) isotope fingerprint of an extraterrestrial impact from Upper Triassic chert successions in Japan. Os isotope data exhibit a marked negative excursion from an initial Os isotope ratio ((187)Os/(188)Osi) of ~0.477 to unradiogenic values of ~0.126 in a platinum group element-enriched claystone layer, indicating the input of meteorite-derived Os into the sediments. The timing of the Os isotope excursion coincides with both elevated Os concentrations and low Re/Os ratios. The magnitude of this negative Os isotope excursion is comparable to those found at Cretaceous-Paleogene boundary sites. These geochemical lines of evidence demonstrate that a large impactor (3.3-7.8 km in diameter) produced a global decrease in seawater (187)Os/(188)Os ratios in the Late Triassic. PMID:24036603

  6. Indium phosphide solar cells - Recent developments and estimated performance in space

    NASA Technical Reports Server (NTRS)

    Weinberg, Irving; Brinker, David J.

    1990-01-01

    The current status of indium phosphide solar cell research is reviewed. In the NASA research program, efficiencies of 18.8 percent were achieved for standard n/p homojunction InP cells while 17 percent was achieved for ITO/InP cells processed by sputtering n-type indium tin oxide onto p-type indium phosphide. The latter represents a cheaper, simpler processing alternative. Computer modeling calculations indicate that efficiencies of over 21 percent are feasible. Relatively large area cells are produced in Japan with a maximum efficiency of 16.6 percent.

  7. Osmium isotopic ratio measurements by inductively coupled plasma source mass spectrometry

    SciTech Connect

    Russ, G.P. III; Bazan, J.M.; Date, A.R.

    1987-04-01

    The isotopic composition of nanogram quantities of osmium was measured by using an inductively coupled plasma source mass spectrometer. Sensitivity was enhanced a factor of approx.100 by the use of an osmium tetraoxide vapor generator rather than nebulization of solution. For samples less than or equal to5 ng, the ratios /sup 190/Os//sup 192/Os, /sup 189/Os//sup 192/Os, and /sup 188/Os//sup 192/Os were determined to better than +/- 0.5% (1sigma/sub m/) precision. For the minor isotopes, the ratios /sup 187/Os//sup 192/Os and /sup 186/Os//sup 192/Os were determined to +/-1%, and /sup 184/Os//sup 192/Os (4 x 10/sup -4/) was determined to approx.10%. Isotope ratios for common osmium are reported.

  8. Rhenium-osmium-isotope constraints on the age of iron meteorites

    NASA Technical Reports Server (NTRS)

    Horan, M. F.; Morgan, J. W.; Walker, R. J.; Grossman, J. N.

    1992-01-01

    Rhenium and osmium concentrations and the osmium isotopic compositions of iron meteorites were determined by negative thermal ionization mass spectrometry. Data for the IIA iron meteorites define an isochron with an uncertainty of approximately +/-31 million years for meteorites about 4500 million years old. Although an absolute rhenium-osmium closure age for this iron group cannot be as precisely constrained because of uncertainty in the decay constant of Re-187, an age of 4460 million years ago is the minimum permitted by combined uncertainties. These age constraints imply that the parent body of the IIAB magmatic irons melted and subsequently cooled within 100 million years after the formation of the oldest portions of chondrites. Other iron meteorites plot above the IIA isochron, indicating that the planetary bodies represented by these iron groups may have cooled significantly later than the parent body of the IIA irons.

  9. Rhenium-osmium isotope constraints on the age of iron meteorites

    USGS Publications Warehouse

    Horan, M.F.; Morgan, J.W.; Walker, R.J.; Grossman, J.N.

    1992-01-01

    Rhenium and osmium concentrations and the osmium isotopic compositions of iron meteorites were determined by negative thermal ionization mass spectrometry. Data for the IIA iron meteorites define an isochron with an uncertainty of approximately ??31 million years for meteorites ???4500 million years old. Although an absolute rhenium-osmium closure age for this iron group cannot be as precisely constrained because of uncertainty in the decay constant of 187Re, an age of 4460 million years ago is the minimum permitted by combined uncertainties. These age constraints imply that the parent body of the IIAB magmatic irons melted and subsequently cooled within 100 million years after the formation of the oldest portions of chondrites. Other iron meteorites plot above the IIA isochron, indicating that the planetary bodies represented by these iron groups may have cooled significantly later than the parent body of the IIA irons.

  10. Estimating the Compressibility of Osmium from Recent Measurements of Ir-Os Alloys under High Pressure.

    PubMed

    Sarlis, Nicholas V; Skordas, Efthimios S

    2016-03-10

    Several fcc- and hcp-structured Ir-Os alloys have been recently studied up to 30 GPa at room temperature by means of synchrotron-based X-ray powder diffraction in diamond anvil cells. Using their bulk moduli, which increase with increasing osmium content, showing a deviation from linearity, and after employing a thermodynamical model, it was concluded that the bulk modulus for osmium is slightly smaller than that for diamond. Here, a similar conclusion is obtained upon employing an alternative model, thus strengthening the conclusion that osmium is the densest but not the most incompressible element. This is particularly interesting for Earth Sciences because it may be of key importance toward clarifying the anomalous elastic properties of the Earth's core. PMID:26890719

  11. Osmium isotopic evidence for ancient subcontinental lithospheric mantle beneath the kerguelen islands, southern indian ocean

    PubMed

    Hassler; Shimizu

    1998-04-17

    Upper mantle xenoliths found in ocean island basalts are an important window through which the oceanic mantle lithosphere may be viewed directly. Osmium isotopic data on peridotite xenoliths from the Kerguelen Islands, an archipelago that is located on the northern Kerguelen Plateau in the southern Indian Ocean, demonstrate that pieces of mantle of diverse provenance are present beneath the Islands. In particular, peridotites with unradiogenic osmium and ancient rhenium-depletion ages (to 1.36 x 10(9) years old) may be pieces of the Gondwanaland subcontinental lithosphere that were incorporated into the Indian Ocean lithosphere as a result of the rifting process. PMID:9545216

  12. Cluster decay in osmium isotopes using Hartree-Fock-Bogoliubov theory

    NASA Astrophysics Data System (ADS)

    Ashok, Nithu; Joseph, Deepthy Maria; Joseph, Antony

    2016-02-01

    Cluster radioactivity is a rare cold nuclear process which is intermediate between alpha decay and spontaneous fission. The present work is a theoretical investigation of the feasibility of alpha decay and cluster radioactivity from proton rich Osmium (Os) isotopes with mass number ranging from 162-190. Osmium forms a part of the transition region between highly deformed and spherical nuclei. Calculations have been done using unified fission model and Hartree-Fock-Bogoliubov (HFB) theory. We have chosen only those decays with half-lives falling in measurable range. Geiger-Nuttall plot has been successfully reproduced. The isotope which is most favorable to each decay mode has a magic daughter nucleus.

  13. Chitosan-cross-linked osmium polymer composites as an efficient platform for electrochemical biosensors.

    PubMed

    Jirimali, Harishchandra Digambar; Nagarale, Rajaram Krishna; Lee, Jong Myung; Saravanakumar, Durai; Shin, Woonsup

    2013-07-22

    A new family of chitosan-cross-linked osmium polymer composites was prepared and its electrochemical properties were examined. The composites were prepared by quaternization of the poly(4-vinylpyridine) osmium bipyridyl polymer (PVP-Os) which was then cross-linked with chitosan, yielding PVP-Os/chitosan. Films made of the composites showed improved mass and electron transport owing to the porous and hydrophilic structure which is derived from the cross-links between the Os polymer and chitosan. The rate for glucose oxidation was enhanced four times when glucose oxidase (GOx) was immobilized on PVP-Os/chitosan compared immobilization on PVP-Os.

  14. Spectrophotometric determination of hydrogen peroxide with osmium(VIII) and m-carboxyphenylfluorone.

    PubMed

    Hoshino, Mitsuru; Kamino, Shinichiro; Doi, Mitsunobu; Takada, Shingo; Mitani, Shota; Yanagihara, Rika; Asano, Mamiko; Yamaguchi, Takako; Fujita, Yoshikazu

    2014-01-01

    Spectrophotometric determination of hydrogen peroxide was accomplished with osmium(VIII) and m-carboxyphenylfluorone (MCPF) in the presence of cetyltrimethylammonium chloride (CTAC). In the determination of hydrogen peroxide based on the fading of the color of osmium(VIII)-MCPF complex, Beer's law was obeyed in the range 20-406 ng mL(-1), with an effective molar absorption coefficient (at 580 nm) of 5.21×10(4) L mol(-1) cm(-1) and a relative standard deviation of 0.33% (n=6). Further, we performed the characterization of MCPF and obtained the crystal structure.

  15. Wiring of pyranose dehydrogenase with osmium polymers of different redox potentials.

    PubMed

    Zafar, Muhammad Nadeem; Tasca, Federico; Boland, Susan; Kujawa, Magdalena; Patel, Ilabahen; Peterbauer, Clemens K; Leech, Dónal; Gorton, Lo

    2010-11-01

    In this study, five different flexible osmium based redox polymers were investigated for their ability to efficiently "wire" the oxidoreductase pyranose dehydrogenase (PDH, EC 1.1.99.29) from Agaricus meleagris, on graphite electrodes for possible applications in biofuel cells. A series of newly synthesised osmium based redox polymers covering the potential range between -270 and +160 mV vs. Ag|AgCl (0.1M KCl) was used. The performance of the redox polymers for enzyme wiring was investigated using glucose as substrate. The optimal operational conditions such as pH and potential were investigated.

  16. Low earth orbit environmental effects on osmium and related optical thin-film coatings

    NASA Technical Reports Server (NTRS)

    Gull, T. R.; Herzig, H.; Osantowski, J. F.; Toft, A. R.

    1985-01-01

    A number of samples of optical thin film materials were flown on Shuttle flight STS-8 as part of an experiment to evaluate their interaction with residual atomic oxygen in low earth orbit. Osmium was selected because of its usefulness as a reflective optical coating for far-UV instruments and for confirmation of results from previous Shuttle flights in which such coatings disappeared. Reflectance data and photographic evidence are presented to support the hypothesis that the osmium disappearance is due to reaction with oxygen to form a volatile oxide. Platinum and iridium, which were included for comparison, fared much better.

  17. Conductive polymers derived from iron, ruthenium, and osmium metalloporphyrins: The shish-kebab approach

    PubMed Central

    Collman, James P.; McDevitt, John T.; Yee, Gordon T.; Leidner, Charles R.; McCullough, Laughlin G.; Little, William A.; Torrance, Jerry B.

    1986-01-01

    The synthesis and characterization of pyrazine-bridged polymers of iron(II/III), ruthenium(II/III), and osmium(II/III) octaethylporphyrin (dubbed “shish-kebab” polymers) are presented. Optical and dc conductivity measurements reveal that the ruthenium and osmium polymers, when partially oxidized, are highly conductive. Electrochemical and ESR results are presented that indicate the existence of an interesting metal-centered conduction pathway. Unlike most of the previously reported porphyrinic molecular metals in which the conduction electrons are macrocyclic-based, electron transport in these materials proceeds exclusively along the metal-pyrazine backbone. PMID:16593717

  18. Osmium isotopic evidence for ancient subcontinental lithospheric mantle beneath the kerguelen islands, southern indian ocean

    PubMed

    Hassler; Shimizu

    1998-04-17

    Upper mantle xenoliths found in ocean island basalts are an important window through which the oceanic mantle lithosphere may be viewed directly. Osmium isotopic data on peridotite xenoliths from the Kerguelen Islands, an archipelago that is located on the northern Kerguelen Plateau in the southern Indian Ocean, demonstrate that pieces of mantle of diverse provenance are present beneath the Islands. In particular, peridotites with unradiogenic osmium and ancient rhenium-depletion ages (to 1.36 x 10(9) years old) may be pieces of the Gondwanaland subcontinental lithosphere that were incorporated into the Indian Ocean lithosphere as a result of the rifting process.

  19. Boron Arsenide and Boron Phosphide for High Temperature and Luminescent Devices. [semiconductor devices - crystal growth/crystal structure

    NASA Technical Reports Server (NTRS)

    Chu, T. L.

    1975-01-01

    The crystal growth of boron arsenide and boron phosphide in the form of bulk crystals and epitaxial layers on suitable substrates is discussed. The physical, chemical, and electrical properties of the crystals and epitaxial layers are examined. Bulk crystals of boron arsenide were prepared by the chemical transport technique, and their carrier concentration and Hall mobility were measured. The growth of boron arsenide crystals from high temperature solutions was attempted without success. Bulk crystals of boron phosphide were also prepared by chemical transport and solution growth techniques. Techniques required for the fabrication of boron phosphide devices such as junction shaping, diffusion, and contact formation were investigated. Alloying techniques were developed for the formation of low-resistance ohmic contacts to boron phosphide. Four types of boron phosphide devices were fabricated: (1) metal-insulator-boron phosphide structures, (2) Schottky barriers; (3) boron phosphide-silicon carbide heterojunctions; and (4) p-n homojunctions. Easily visible red electroluminescence was observed from both epitaxial and solution grown p-n junctions.

  20. Indium Phosphide Window Layers for Indium Gallium Arsenide Solar Cells

    NASA Technical Reports Server (NTRS)

    Jain, Raj K.

    2005-01-01

    Window layers help in reducing the surface recombination at the emitter surface of the solar cells resulting in significant improvement in energy conversion efficiency. Indium gallium arsenide (In(x)Ga(1-x)As) and related materials based solar cells are quite promising for photovoltaic and thermophotovoltaic applications. The flexibility of the change in the bandgap energy and the growth of InGaAs on different substrates make this material very attractive for multi-bandgap energy, multi-junction solar cell approaches. The high efficiency and better radiation performance of the solar cell structures based on InGaAs make them suitable for space power applications. This work investigates the suitability of indium phosphide (InP) window layers for lattice-matched In(0.53)Ga(0.47)As (bandgap energy 0.74 eV) solar cells. We present the first data on the effects of the p-type InP window layer on p-on-n lattice-matched InGaAs solar cells. The modeled quantum efficiency results show a significant improvement in the blue region with the InP window. The bare InGaAs solar cell performance suffers due to high surface recombination velocity (10(exp 7) cm/s). The large band discontinuity at the InP/InGaAs heterojunction offers a great potential barrier to minority carriers. The calculated results demonstrate that the InP window layer effectively passivates the solar cell front surface, hence resulting in reduced surface recombination and therefore, significantly improving the performance of the InGaAs solar cell.

  1. Anthropogenic osmium in rain and snow reveals global-scale atmospheric contamination

    PubMed Central

    Chen, Cynthia; Sedwick, Peter N.; Sharma, Mukul

    2009-01-01

    Osmium is one of the rarer elements in seawater, with typical concentration of ≈10 × 10−15 g g−1 (5.3 × 10−14 mol kg−1). The osmium isotope composition (187Os/188Os ratio) of deep oceans is 1.05, reflecting a balance between inputs from continental crust (≈1.3) and mantle/cosmic dust (≈0.13). Here, we show that the 187Os/188Os ratios measured in rain and snow collected around the world range from 0.16 to 0.48, much lower than expected (>1), but similar to the isotope composition of ores (≈0.2) that are processed to extract platinum and other metals to be used primarily in automobile catalytic converters. Present-day surface seawater has a lower 187Os/188Os ratio (≈0.95) than deep waters, suggesting that human activities have altered the isotope composition of the world's oceans and impacted the global geochemical cycle of osmium. The contamination of the surface ocean is particularly remarkable given that osmium has few industrial uses. The pollution may increase with growing demand for platinum-based catalysts. PMID:19416862

  2. High-resolution scanning-electron microscopy of stereocilia using the osmium-thiocarbohydrazide coating technique.

    PubMed

    Furness, D N; Hackney, C M

    1986-01-01

    Further observations on the detailed morphology of stereocilia have been made using high-resolution scanning-electron microscopy of osmium-thiocarbohydrazide-coated guinea pig cochleae. Three types of cross-link have been observed between stereocilia. Side-to-side and row-to-row linkages are composed of a filamentous network whilst upward-pointing links are a fine single strand, often with a terminal widening. The stereocilia have rough surfaces. These features are observed on both inner and outer hair cells despite reported sensitivity to long periods of osmium fixation. We suggest that osmium sensitivity may be altered by the buffering conditions used during preparation. The observations on osmium-coated material correspond more closely with those made using transmission-electron microscopy than those made using other scanning-electron microscopical preparation techniques, since gold-coating artefacts are absent and the degree of specimen collapse is less. This has enabled us to observe fine details of the links and their attachments which have not been reported previously in SEM.

  3. Synthesis and antitumor activity of a series of osmium(VI) nitrido complexes bearing quinolinolato ligands.

    PubMed

    Tang, Quan; Ni, Wen-Xiu; Leung, Chi-Fai; Man, Wai-Lun; Lau, Kenneth King-Kwan; Liang, Yimin; Lam, Yun-Wah; Wong, Wai-Yeung; Peng, Shie-Ming; Liu, Gui-Jian; Lau, Tai-Chu

    2013-11-01

    A series of osmium(VI) nitrido complexes supported by quinolinolato ligands have been prepared and they exhibit promising in vitro anti-cancer activities. These results establish that Os(VI)≡N is a potentially versatile and promising platform for the design of a variety of high-valent anti-cancer drugs.

  4. Anthropogenic osmium in rain and snow reveals global-scale atmospheric contamination.

    PubMed

    Chen, Cynthia; Sedwick, Peter N; Sharma, Mukul

    2009-05-12

    Osmium is one of the rarer elements in seawater, with typical concentration of approximately 10 x 10(-15) g g(-1) (5.3 x 10(-14) mol kg(-1)). The osmium isotope composition ((187)Os/(188)Os ratio) of deep oceans is 1.05, reflecting a balance between inputs from continental crust (approximately 1.3) and mantle/cosmic dust (approximately 0.13). Here, we show that the (187)Os/(188)Os ratios measured in rain and snow collected around the world range from 0.16 to 0.48, much lower than expected (>1), but similar to the isotope composition of ores (approximately 0.2) that are processed to extract platinum and other metals to be used primarily in automobile catalytic converters. Present-day surface seawater has a lower (187)Os/(188)Os ratio (approximately 0.95) than deep waters, suggesting that human activities have altered the isotope composition of the world's oceans and impacted the global geochemical cycle of osmium. The contamination of the surface ocean is particularly remarkable given that osmium has few industrial uses. The pollution may increase with growing demand for platinum-based catalysts.

  5. Osmium-catalyzed vicinal oxyamination of alkenes by N-(4-toluenesulfonyloxy)carbamates.

    PubMed

    Masruri; Willis, Anthony C; McLeod, Malcolm D

    2012-10-01

    N-(4-toluenesulfonyloxy)carbamates based on a range of common amine protecting groups serve as preformed nitrogen sources in the intermolecular osmium-catalyzed oxyamination reaction of a variety of mono-, di-, and trisubstituted alkenes. The reactions occur with low catalyst loadings and good yields and afford high regioselectivity for unsymmetrically substituted alkenes.

  6. Electrical wiring of live, metabolically enhanced Bacillus subtilis cells with flexible osmium-redox polymers.

    PubMed

    Coman, Vasile; Gustavsson, Tobias; Finkelsteinas, Arnonas; von Wachenfeldt, Claes; Hägerhäll, Cecilia; Gorton, Lo

    2009-11-11

    The present study explores genetic engineering of the respiratory chain and the application of two different flexible osmium redox polymers to achieve efficient electric communication between the gram-positive organism Bacillus subtilis and an electrode. Poly(1-vinylimidazole)(12)-[Os-(4,4'-dimethyl-2,2'-bipyridyl)(2)Cl(2)](+/2+) (osmium redox polymer I) and poly(vinylpyridine)-[Os-(N,N'-methylated-2,2'-biimidazole)(3)](2+/3+) (osmium redox polymer II) were investigated for efficient electrical "wiring" of viable gram-positive bacterial cells to electrodes. Using a B. subtilis strain that overproduces succinate/quinone oxidoreductase (respiratory complex II), we were able to improve the current response several fold using succinate as substrate, in both batch and flow analysis modes, and using gold and graphite electrodes. The efficiency of the osmium redox polymer, working as electron transfer mediator between the cells and the electrode, was compared with that of a soluble mediator (hexacyanoferrate). The results demonstrated that mediators did not have to pass the cytosolic membrane to bring about an efficient electronic communication between bacterial cells with a thick cell wall and electrodes.

  7. Facile synthesis of hydroxymethylcytosine-containing oligonucleotides and their reactivity upon osmium oxidation.

    PubMed

    Sugizaki, Kaori; Ikeda, Shuji; Yanagisawa, Hiroyuki; Okamoto, Akimitsu

    2011-06-01

    DNA strands containing a 5-hydroxymethylcytosine ((hm)C), which have recently been found in neuron cells and embryonic stem cells, were synthesized through a facile synthetic technique. The (hm)C-containing strands were efficiently oxidized at (hm)C using an osmium oxidation assay. The (hm)C was oxidized as easily as 5-methylcytosine, which can be distinguished from unmethylated cytosine.

  8. DNA-osmium complexes: recent developments in the operative chemical analysis of DNA epigenetic modifications.

    PubMed

    Okamoto, Akimitsu

    2014-09-01

    The development of a reaction for the detection of one epigenetic modification in a long DNA strand is a chemically and biologically challenging research subject. Herein, we report and discuss the formation of 5-methylcytosine-osmium complexes that are used as the basis for a bisulfite-free chemical assay for DNA methylation analysis. Osmium in the oxidized state reacts with C5-methylated pyrimidines in the presence of a bipyridine ligand to give a stable ternary complex. On the basis of this reaction, an adenine derivative with a tethered bipyridine moiety has been designed for sequence-specific osmium complex formation. Osmium complexation is then achieved by hybridization of a short DNA molecule containing this functional nucleotide to a target DNA sequence and results in the formation of a cross-linked structure. This novel concept of methylation-specific reaction, based on a straightforward chemical process, expands the range of methods available for the analysis of epigenetic modifications. Advantages of the described method include amplification-insensitive detection, 5-hydroxymethylcytosine complexation, and visualization through methylation-specific in situ hybridization.

  9. Reply to "Comment on two-phonon gamma-vibrational strength in osmium nuclei"

    SciTech Connect

    Wu, C.Y.; Cline, D.; Hayes, A.B.; Simon, M.W.; Krueken, R.; Cooper, J.R.; Barton, C.J.; Beausang, C.W.; Bialik, C.; Caprio, M.A.; Casten, R.F.; Hecht, A.A.; Newman, H.; Novak, J.; Pietralla, N.; Zyromski, K.; Zamfir, N.V.

    2002-09-03

    The claim that the two-phonon gamma-vibrational configuration constitutes a major component for the I=4+ states in osmium nuclei is based on solid experimental evidence. A non-negligible two-quasiparticle or hexadecapole component must also exist in order to explain the data.

  10. The potential impact of municipal solid waste incinerators ashes on the anthropogenic osmium budget.

    PubMed

    Funari, Valerio; Meisel, Thomas; Braga, Roberto

    2016-01-15

    Osmium release from Municipal Solid Waste Incinerators (MSWI), even if acknowledged to occur at least over the last fifteen years, remains overlooked in the majority of recent studies. We present the osmium concentration and (187)Os/(188)Os isotopic measurements of different kinds of bottom and fly ash samples from MSWI plants and reference materials of incinerator fly ash (BCR176 and BCR176R). The analysis of the unknown ash samples shows a relatively wide range of (187)Os/(188)Os ratios (0.24-0.70) and Os concentrations (from 0.026 ng/g to 1.65 ng/g). Osmium concentrations and isotopic signatures differ from those of other known Os sources, either natural or manmade, suggesting a mixture of both contributions in the MSWI feedstock material. Furthermore, the comparison between the BCR176 and the renewed BCR176R indicates a decrease in Os concentration of one order of magnitude over the years (from 1 to 0.1 ng/g) due to improved recycling efficiency of Os-bearing waste. The estimated annual amount of Os from a typical incinerator (using average Os values and MSWI mass balance) is 13.4 g/a. The osmium potentially released from MSWI smokestacks is predicted to be from 16 to 38 ng Os/m(2)/a, considering a medium size country having 50 MSWI facilities; therefore much higher than the naturally transported osmium from continental dust in the atmosphere (about 1 pg Os/m(2)/a). MSWI systems are considered one of the best options for municipal solid waste management in industrialised countries, but their contribution to the Os budget can be significant. PMID:26490532

  11. An Entry to Stable Mixed Phosphine-Osmium-NHC Polyhydrides.

    PubMed

    Buil, María L; Cardo, Juan J F; Esteruelas, Miguel A; Fernández, Israel; Oñate, Enrique

    2016-05-16

    An entry to mixed phosphine-osmium-NHC polyhydride complexes is described, starting from the five-coordinate hydrido-alkylidyne compounds [OsHCl(≡CPh)(IPr)(PR3)]OTf (IPr = 1,3-bis(2,6-disopropylphenyl)imidazolylidene; OTf = CF3SO3; PR3 = P(i)Pr3 (1), PPh3 (2)). The experimental procedure involves the borylation of the Os-C triple bond of 1 and 2 with NaBH4 and the subsequent alcoholysis of the borylation products OsH2Cl(η(2)-H-BCH2Ph)(IPr)(PR3) (PR3 = P(i)Pr3 (3), PPh3 (4)) or OsH2(η(2):η(2):H2BCH2Ph)(IPr)(P(i)Pr3) (5). Stirring of 3 in 2-propanol affords the five coordinate chloride-trihydride OsH3Cl(IPr)(P(i)Pr3)2 (6), which reacts with NaBH4 to give OsH3(κ(2)-H2BH2)(IPr)(P(i)Pr3) (7). This trihydride-tetrahydrideborate derivative and its PPh3 counterpart OsH3(κ(2)-H2BH2)(IPr)(PPh3) (8) can be also obtained in a one-pot procedure, starting from 1 and 2 and using methanol at -60 °C instead of 2-propanol as alcoholysis agent. The bonding situation in 7 and 8, analyzed by DFT calculations using AIM and NBO methods, resembles that found in B2H6 and contrasts with the bonding situation in the bis-σ-borane derivative 5. Stirring of 7 and 8 in 2-propanol leads to the corresponding d(2)-hexahydride derivatives OsH6(IPr)(PR3) (PR3 = P(i)Pr3 (9), PPh3 (10)), which reduce the C≡N triple bond of benzonitrile and promote the subsequent chelate-assisted ortho-CH bond activation of the resulting phenylmethanimine, to form the trihydride compounds OsH3{κ(2)-N,C-(NH═CH-C6H4)}(IPr)(PR3)2 (PR3 = P(i)Pr3 (11), PPh3 (12)), containing a stabilized orthometalated aldimine.

  12. An Entry to Stable Mixed Phosphine-Osmium-NHC Polyhydrides.

    PubMed

    Buil, María L; Cardo, Juan J F; Esteruelas, Miguel A; Fernández, Israel; Oñate, Enrique

    2016-05-16

    An entry to mixed phosphine-osmium-NHC polyhydride complexes is described, starting from the five-coordinate hydrido-alkylidyne compounds [OsHCl(≡CPh)(IPr)(PR3)]OTf (IPr = 1,3-bis(2,6-disopropylphenyl)imidazolylidene; OTf = CF3SO3; PR3 = P(i)Pr3 (1), PPh3 (2)). The experimental procedure involves the borylation of the Os-C triple bond of 1 and 2 with NaBH4 and the subsequent alcoholysis of the borylation products OsH2Cl(η(2)-H-BCH2Ph)(IPr)(PR3) (PR3 = P(i)Pr3 (3), PPh3 (4)) or OsH2(η(2):η(2):H2BCH2Ph)(IPr)(P(i)Pr3) (5). Stirring of 3 in 2-propanol affords the five coordinate chloride-trihydride OsH3Cl(IPr)(P(i)Pr3)2 (6), which reacts with NaBH4 to give OsH3(κ(2)-H2BH2)(IPr)(P(i)Pr3) (7). This trihydride-tetrahydrideborate derivative and its PPh3 counterpart OsH3(κ(2)-H2BH2)(IPr)(PPh3) (8) can be also obtained in a one-pot procedure, starting from 1 and 2 and using methanol at -60 °C instead of 2-propanol as alcoholysis agent. The bonding situation in 7 and 8, analyzed by DFT calculations using AIM and NBO methods, resembles that found in B2H6 and contrasts with the bonding situation in the bis-σ-borane derivative 5. Stirring of 7 and 8 in 2-propanol leads to the corresponding d(2)-hexahydride derivatives OsH6(IPr)(PR3) (PR3 = P(i)Pr3 (9), PPh3 (10)), which reduce the C≡N triple bond of benzonitrile and promote the subsequent chelate-assisted ortho-CH bond activation of the resulting phenylmethanimine, to form the trihydride compounds OsH3{κ(2)-N,C-(NH═CH-C6H4)}(IPr)(PR3)2 (PR3 = P(i)Pr3 (11), PPh3 (12)), containing a stabilized orthometalated aldimine. PMID:27145380

  13. On line vapor generation of osmium based on solution cathode glow discharge for the determination by ICP-OES.

    PubMed

    Zhu, Zhenli; Huang, Chunying; He, Qian; Xiao, Qing; Liu, Zhifu; Zhang, Suicheng; Hu, Shenghong

    2013-03-15

    A novel plasma induced vapor generation method is proposed to determine osmium in solutions. Without any chemical oxidizing agents, osmium ion can be readily converted to volatile osmium tetraoxide vapor in the solution cathode glow discharge (SCGD) system. The generated osmium vapor is then transported to inductively coupled plasma for determination by optical emission spectrometry. The influences of background electrolyte, carrier gas flow rate, sample flow rate, ICP power and discharge current were investigated. The analytical performances of this proposed technique were evaluated under optimized conditions. The detection limit of Os was calculated to be 0.51 ng mL(-1). The reproducibility, expressed as the relative standard deviation (n=11) of a 2.0 μg mL(-1) standard solution, was 1.9%. This SCGD induced vapor generation is sensitive and simple, oxidation reagents free, providing an alternative analytical method for measuring Os in geological or environmental water samples. PMID:23598105

  14. On line vapor generation of osmium based on solution cathode glow discharge for the determination by ICP-OES.

    PubMed

    Zhu, Zhenli; Huang, Chunying; He, Qian; Xiao, Qing; Liu, Zhifu; Zhang, Suicheng; Hu, Shenghong

    2013-03-15

    A novel plasma induced vapor generation method is proposed to determine osmium in solutions. Without any chemical oxidizing agents, osmium ion can be readily converted to volatile osmium tetraoxide vapor in the solution cathode glow discharge (SCGD) system. The generated osmium vapor is then transported to inductively coupled plasma for determination by optical emission spectrometry. The influences of background electrolyte, carrier gas flow rate, sample flow rate, ICP power and discharge current were investigated. The analytical performances of this proposed technique were evaluated under optimized conditions. The detection limit of Os was calculated to be 0.51 ng mL(-1). The reproducibility, expressed as the relative standard deviation (n=11) of a 2.0 μg mL(-1) standard solution, was 1.9%. This SCGD induced vapor generation is sensitive and simple, oxidation reagents free, providing an alternative analytical method for measuring Os in geological or environmental water samples.

  15. Dinuclear osmium(II) probes for high-resolution visualisation of cellular DNA structure using electron microscopy.

    PubMed

    Wragg, Ashley; Gill, Martin R; Hill, Christopher J; Su, Xiaodi; Meijer, Anthony J H M; Smythe, Carl; Thomas, Jim A

    2014-12-01

    Two dinuclear osmium polypyridyl complexes function as convenient, easy to handle TEM contrast agents and facilitate the high-resolution visualisation of intracellular structure, particularly sub-nuclear detail.

  16. Scaling Mesa Indium Phosphide DHBTs to Record Bandwidths

    NASA Astrophysics Data System (ADS)

    Lobisser, Evan

    Indium phosphide heterojunction bipolar transistors are able to achieve higher bandwidths at a given feature size than transistors in the Silicon material system for a given feature size. Indium phosphide bipolar transistors demonstrate higher breakdown voltages at a given bandwidth than both Si bipolars and field effect transistors in the InP material system. The high bandwidth of InP HBTs results from both intrinsic material parameters and bandgap engineering through epitaxial growth. The electron mobility in the InGaAs base and saturation velocity in the InP collector are both approximately three times higher than their counterparts in the SiGe material system. Resistance of the base can be made very low due to the large offset in the valence band between the InP emitter and the InGaAs base, which allows the base to be doped on the order of 1020 cm-3 with negligible reduction in emitter injection efficiency. This thesis deals with type-I, NPN dual-heterojunction bipolar transistors. The emitters are InP, and the base is InGaAs. There is a thin (˜ 10 nm) n-type InGaAs "setback" region, followed by a chirped superlattice InGaAs/InAlAs grade to the InP collector. The setback, grade, and collector are all lightly doped n-type. The emitter and collector are contacted through thin (˜ 5 nm) heavily doped n-type InGaAs layers to reduce contact resistivity. The primary focus of this work is increasing the bandwidth of InP HBTs through the proportional scaling of the device dimensions, both layer thicknesses and junction areas, as well as the reduction of the contact resistivities associated with the transistor. Essentially, all RC time constants and transit times must be reduced by a factor of two to double a transistor's bandwidth. Chapter 2 describes in detail the scaling laws and design principles for high frequency bipolar transistor design. A low-stress, blanket sputter deposited composite emitter metal process was developed. Refractory metal base contacts were

  17. Molecular beam epitaxy growth and characterization of dysprosium phosphide and dysprosium arsenide in gallium arsenide and gallium phosphide

    NASA Astrophysics Data System (ADS)

    Lee, Paul Piyawong

    The ability to grow thermally stable Schottky/ohmic contacts and buried, epitaxial metallic or semimetallic layers on semiconductors has many potential applications in novel device structures. Many rare earth group-V compounds with the sodium chloride structure possess the properties that make them potential candidates for stable contacts, buried layers, and other applications. In this work, two novel rare earth compounds, namely dysprosium phosphide (DyP) and dysprosium arsenide (DyAs) have been studied for high temperature ohmic/Schottky contacts to III-V semiconductors as well as for buried metal layers in semiconductor/metal/semiconductor structures. DyP and DyAs have been grown by molecular beam epitaxy on GaAs and GaP substrates. Both DyP and DyAs display metallic behavior and have room temperature resistivities of 8 x 10--5 and 1 x 10--4 Ocm, respectively. The electron concentrations for DyP and DyAs are about 4 x 1020 and 1 x 1021 cm--3, respectively. High quality DyP films as determined by XRD, AFM, and TEM can be achieved at a wide range of substrate temperatures (500°C to 600°C) with excess phosphorus pressure. Unlike most rare earth-group V compounds, DyP films are stable in air with no sign of oxidation. DyP films deposited on n-type GaAs and GaP exhibit Schottky behavior with room temperature barrier heights of 0.83 and 0.90 eV, respectively, with ideality factors close to unity and low reverse bias leakage current densities. These contacts are stable up to 250°C and 350°C for GaAs and GaP, respectively. DyAs films on the other hand, oxidize in air and display weak Schottky behavior on n-type GaAs. DyP has been grown as buried layers in both GaAs/DyP/GaAs and GaAs/DyP/GaP structures. Although high quality DyP layers have been achieved, the GaAs overlayers contain defects such as twins. The poor wetting of GaAs on DyP and the crystal symmetry between the two materials are responsible for the three-dimensional growth and the defects found in the Ga

  18. New method for the measurement of osmium isotopes applied to a New Zealand Cretaceous/Tertiary boundary shale

    USGS Publications Warehouse

    Lichte, F.E.; Wilson, S.M.; Brooks, R.R.; Reeves, R.D.; Holzbecher, J.; Ryan, D.E.

    1986-01-01

    The determination of osmium content and isotopic abundances in geological materials has received increasing attention in recent years following the proposal of Alvarez et al.1 that mass extinctions at the end of the Cretaceous period were caused by the impact of a large (???10km) meteorite which left anomalously high iridium levels as a geochemical signature in the boundary shales. Here we report a new and simple method for measuring osmium in geological materials, involving fusion of the sample with sodium peroxide, distillation of the osmium as the tetroxide using perchloric acid, extraction into chloroform, and absorption of the chloroform extract onto graphite powder before instrumental neutron activation analysis. In a variant of this technique, the chloroform extract is back-extracted into an aqueous phase and the osmium isotopes are determined by plasma-source mass spectrometry (ICPMS). We have used this method on the Woodside Creek (New Zealand) Cretaceous/Tertiary boundary clay and have obtained the first osmium content (6g ng g-1) for this material. The 187Os/186Os ratio is 1.12??0.16, showing a typical non-crustal signature. This combined distillation-extraction- ICPMS method will prove to be useful for measuring osmium isotopes in other geological materials. ?? 1986 Nature Publishing Group.

  19. Heteroepitaxy of group-III phosphides on silicon

    NASA Astrophysics Data System (ADS)

    Sukidi, Nkadi

    The objective of this thesis is to advance fundamental understanding of heteroepitaxial processes. The approach taken is real-time optical monitoring of growth rate and surface composition in conjunction with ex-situ characterization of the evolution of surface topography and microstructure at various stages of nucleation, island growth, coalescence, and contiguous film growth of group III phosphides on silicon substrates. The deposition method, pulsed chemical beam epitaxy (PCBE), chosen for this investigation, affords ballistic beams of source vapor molecules, such as triethylgallium (TEG), trimethylindium (TMI), and tertiary-butylphosphine (TBP) which mix and interact on the surface of the heated substrate. Therefore, gas phase reactions and transport do not complicate the analysis of the time-dependent optical signal, and ambient effects on the signal-to-noise ratio are absent. Primary in-situ methods of optical real-time process monitoring employed here are p-polarized reflectance (PR) and laser light scattering (LLS). Background information, experimental details, data analysis, and discussions of the results of this investigation are presented in the following order: (1) introduction, (2) general experimental procedure, (3) methods of surface temperature measurements, (4) investigation of initial stages of heteroepitaxy of GaP on silicon, (5) initial results of epitaxial layer overgrowth (ELO) of GaP on SiOsb2-masked silicon substrates, (6) investigation of steady-state PCBE of GaP on Si including (i) heteroepitaxy of GaP on Si(100), (ii) real-time monitoring of steady-state PCBE by PR, (iii) molecular layer epitaxy of real-time optical process monitoring, and (iv) real-time monitoring of kinetics of steady-state GaP growth, and (7) Gasb{x}Insb{1-x}P/GaP heterostructures on Si (100). The introduction encompasses (a) a review of the literature regarding relevant prior work, and (b) description of CBE, PR, and LLS. This is followed by general experimental

  20. Nickel Phosphide as a Copper Free Back Contact for CdTe-Based Solar Cells

    NASA Astrophysics Data System (ADS)

    Sunderland, Brian; Gupta, Akhlesh; Compaan, Alvin D.

    2002-03-01

    Nickel phosphide back contacts were deposited onto polycrystalline, thin-film, CdS/CdTe solar cells using DC magnetron sputtering. The effects of the etching procedure, substrate temperature, deposition duration, post-deposition diffusion temperature, and ambient on the initial performance and on the long term stability of the devices were studied. We found that the initial performance of nickel phosphide contacts was lower than typical Cu-based back contacts. However, the stability of the cells at open circuit under one-sun light soak for several months is better than for our standard contact with evaporated Cu and Au. The use of sputtered graphite as an interfacial layer improved the performance. Average efficiencies of over 8.6were achieved. The excellent stability makes Ni2P an attractive candidate for a Cu-free back contact to CdTe-based solar cells. Work supported by NREL and by NSF-REU.

  1. Osmium isotopes and the Upper Devonian "Kellwasser" event

    NASA Astrophysics Data System (ADS)

    Brauns, M.

    2001-12-01

    at least for the studied localities: (I) The Os isotopic composition of all limestone and shale samples as well as separated biogenic/diagenetic rock components is very radiogenic. Even the conodonts reveal no obvious contribution of primitive Os supplied by extraterrestrial material, as would be expected when considering the meteoric impact theory. Thus, such an event at the Frasne/Famenne boundary appears to be highly improbable. (II) A drastic peak reflecting elevated Re, Os concentrations during the upper gigas subzone may point to an enhanced clastic input of upper crustal material to the Kellwasser sea. Brauns, M. (2001): A rapid, low-blank technique for the extraction of Osmium from geological samples. Chem. Geol. In press. Schindler, E. (1990): Die Kellwasser - Krise (hohe Frasne-Stufe, Ober-Devon). Diss. Göttingen. 116 S. Tagami, K. & Uchida, S. (2000): Separation of rhenium by an extraction chromatograpic resin for determination by inductively coupled plasma-mass-spectrometry. Anal. Chim. Acta. 405, 227-229.

  2. Successful management of aluminium phosphide poisoning using intravenous lipid emulsion: Report of two cases

    PubMed Central

    Baruah, Udismita; Sahni, Ameeta; Sachdeva, Harish C.

    2015-01-01

    Aluminum phosphide (ALP) is a cheap, easily available agricultural pesticide which causes lethal poisoning by liberation of phosphine and inhibition of cytochrome c oxidase thereby leading to cellular hypoxia. Although there is no known specific antidote, clinical trials are still going on. We present here two cases of ALP poisoning who were successfully managed by treatment with lipid emulsion and intravenous magnesium sulfate. PMID:26816450

  3. Ultra-fast mechanochemical synthesis of boron phosphides, BP and B12P2.

    PubMed

    Mukhanov, Vladimir A; Vrel, Dominique; Sokolov, Petr S; Le Godec, Yann; Solozhenko, Vladimir L

    2016-06-21

    Here we propose a new approach to the synthesis of single-phase boron phosphides (BP and B12P2) by mechanochemical reactions between boron phosphate and magnesium/magnesium diboride in the presence of an inert diluent (sodium chloride). The proposed method is characterized by the simplicity of implementation, high efficiency, low cost of the product, and good perspectives for large-scale production.

  4. Cobalt phosphide nanowires: an efficient electrocatalyst for enzymeless hydrogen peroxide detection

    NASA Astrophysics Data System (ADS)

    Liu, Danni; Chen, Tao; Zhu, Wenxin; Cui, Liang; Asiri, Abdullah M.; Lu, Qun; Sun, Xuping

    2016-08-01

    In this letter, we demonstrate for the first time that cobalt phosphide nanowires (CoP NWs) exhibit remarkable catalytic activity toward electrochemical detection of hydrogen peroxide (H2O2). As an enzymeless H2O2 sensor, such CoP NWs show a fast amperometric response within 5 s and a low detection limit of 0.48 μM. In addition, this nonenzymatic sensor displays good selectivity, long-term stability and excellent reproducibility.

  5. Hepatotoxicity due to zinc phosphide poisoning in two patients: role of N-acetylcysteine.

    PubMed

    Oghabian, Zohreh; Afshar, Arefeh; Rahimi, Hamid Reza

    2016-08-01

    Zinc phosphide (Zn3P2/ZnP) is used as a rodenticide. The most common signs of toxicity are nausea, vomiting, hypotension, and metabolic acidosis; patients presenting such signs are referred to the emergency department (ED) of the hospitals. Therefore, this study aimed to report two cases of hepatotoxicity following accidental and intentional ZnP poisoning and successful management with N-acetylcysteine (NAC). PMID:27525081

  6. Ingestion of gallium phosphide nanowires has no adverse effect on Drosophila tissue function.

    PubMed

    Adolfsson, Karl; Schneider, Martina; Hammarin, Greger; Häcker, Udo; Prinz, Christelle N

    2013-07-19

    Engineered nanoparticles have been under increasing scrutiny in recent years. High aspect ratio nanoparticles such as carbon nanotubes and nanowires have raised safety concerns due to their geometrical similarity to asbestos fibers. III-V epitaxial semiconductor nanowires are expected to be utilized in devices such as LEDs and solar cells and will thus be available to the public. In addition, clean-room staff fabricating and characterizing the nanowires are at risk of exposure, emphasizing the importance of investigating their possible toxicity. Here we investigated the effects of gallium phosphide nanowires on the fruit fly Drosophila melanogaster. Drosophila larvae and/or adults were exposed to gallium phosphide nanowires by ingestion with food. The toxicity and tissue interaction of the nanowires was evaluated by investigating tissue distribution, activation of immune response, genome-wide gene expression, life span, fecundity and somatic mutation rates. Our results show that gallium phosphide nanowires applied through the diet are not taken up into Drosophila tissues, do not elicit a measurable immune response or changes in genome-wide gene expression and do not significantly affect life span or somatic mutation rate. PMID:23787695

  7. Ingestion of gallium phosphide nanowires has no adverse effect on Drosophila tissue function.

    PubMed

    Adolfsson, Karl; Schneider, Martina; Hammarin, Greger; Häcker, Udo; Prinz, Christelle N

    2013-07-19

    Engineered nanoparticles have been under increasing scrutiny in recent years. High aspect ratio nanoparticles such as carbon nanotubes and nanowires have raised safety concerns due to their geometrical similarity to asbestos fibers. III-V epitaxial semiconductor nanowires are expected to be utilized in devices such as LEDs and solar cells and will thus be available to the public. In addition, clean-room staff fabricating and characterizing the nanowires are at risk of exposure, emphasizing the importance of investigating their possible toxicity. Here we investigated the effects of gallium phosphide nanowires on the fruit fly Drosophila melanogaster. Drosophila larvae and/or adults were exposed to gallium phosphide nanowires by ingestion with food. The toxicity and tissue interaction of the nanowires was evaluated by investigating tissue distribution, activation of immune response, genome-wide gene expression, life span, fecundity and somatic mutation rates. Our results show that gallium phosphide nanowires applied through the diet are not taken up into Drosophila tissues, do not elicit a measurable immune response or changes in genome-wide gene expression and do not significantly affect life span or somatic mutation rate.

  8. Evaluation of Metal Phosphide Nanocrystals as Anode Materials for Na-ion Batteries.

    PubMed

    Walter, Marc; Bodnarchuk, Maryna I; Kravchyk, Kostiantyn V; Kovalenko, Maksym V

    2015-01-01

    Sodium-ion batteries (SIBs) are potential low-cost alternatives to lithium-ion batteries (LIBs) because of the much greater natural abundance of sodium salts. However, developing high-performance electrode materials for SIBs is a challenging task, especially due to the ∼50% larger ionic radius of the Na(+) ion compared to Li(+), leading to vastly different electrochemical behavior. Metal phosphides such as FeP, CoP, NiP(2), and CuP(2) remain unexplored as electrode materials for SIBs, despite their high theoretical charge storage capacities of 900-1300 mAh g(-1). Here we report on the synthesis of metal phosphide nanocrystals (NCs) and discuss their electrochemical properties as anode materials for SIBs, as well as for LIBs. We also compare the electrochemical characteristics of phosphides with their corresponding sulfides, using the environmentally benign iron compounds, FeP and FeS(2), as a case study. We show that despite the appealing initial charge storage capacities of up to 1200 mAh g(-1), enabled by effective nanosizing of the active electrode materials, further work toward optimization of the electrode/electrolyte pair is needed to improve the electrochemical performance upon cycling. PMID:26842319

  9. Ingestion of gallium phosphide nanowires has no adverse effect on Drosophila tissue function

    NASA Astrophysics Data System (ADS)

    Adolfsson, Karl; Schneider, Martina; Hammarin, Greger; Häcker, Udo; Prinz, Christelle N.

    2013-07-01

    Engineered nanoparticles have been under increasing scrutiny in recent years. High aspect ratio nanoparticles such as carbon nanotubes and nanowires have raised safety concerns due to their geometrical similarity to asbestos fibers. III-V epitaxial semiconductor nanowires are expected to be utilized in devices such as LEDs and solar cells and will thus be available to the public. In addition, clean-room staff fabricating and characterizing the nanowires are at risk of exposure, emphasizing the importance of investigating their possible toxicity. Here we investigated the effects of gallium phosphide nanowires on the fruit fly Drosophila melanogaster. Drosophila larvae and/or adults were exposed to gallium phosphide nanowires by ingestion with food. The toxicity and tissue interaction of the nanowires was evaluated by investigating tissue distribution, activation of immune response, genome-wide gene expression, life span, fecundity and somatic mutation rates. Our results show that gallium phosphide nanowires applied through the diet are not taken up into Drosophila tissues, do not elicit a measurable immune response or changes in genome-wide gene expression and do not significantly affect life span or somatic mutation rate.

  10. Bidentate ligands on osmium(VI) nitrido complexes control intracellular targeting and cell death pathways.

    PubMed

    Suntharalingam, Kogularamanan; Johnstone, Timothy C; Bruno, Peter M; Lin, Wei; Hemann, Michael T; Lippard, Stephen J

    2013-09-25

    The cellular response evoked by antiproliferating osmium(VI) nitrido compounds of general formula OsN(N^N)Cl3 (N^N = 2,2'-bipyridine 1, 1,10-phenanthroline 2, 3,4,7,8-tetramethyl-1,10-phenanthroline 3, or 4,7-diphenyl-1,10-phenanthroline 4) can be tuned by subtle ligand modifications. Complex 2 induces DNA damage, resulting in activation of the p53 pathway, cell cycle arrest at the G2/M phase, and caspase-dependent apoptotic cell death. In contrast, 4 evokes endoplasmic reticulum (ER) stress leading to the upregulation of proteins of the unfolded protein response pathway, increase in ER size, and p53-independent apoptotic cell death. To the best of our knowledge, 4 is the first osmium compound to induce ER stress in cancer cells.

  11. Electrochemical communication between microbial cells and electrodes via osmium redox systems.

    PubMed

    Hasan, Kamrul; Patil, Sunil A; Leech, Dónal; Hägerhäll, Cecilia; Gorton, Lo

    2012-12-01

    Electrochemical communication between micro-organisms and electrodes is the integral and fundamental part of BESs (bioelectrochemical systems). The immobilization of bacterial cells on the electrode and ensuring efficient electron transfer to the electrode via a mediator are decisive features of mediated electrochemical biosensors. Notably, mediator-based systems are essential to extract electrons from the non-exoelectrogens, a major group of microbes in Nature. The advantage of using polymeric mediators over diffusible mediators led to the design of osmium redox polymers. Their successful use in enzyme-based biosensors and BFCs (biofuel cells) paved the way for exploring their use in microbial BESs. The present mini-review focuses on osmium-bound redox systems used to date in microbial BESs and their role in shuttling electrons from viable microbial cells to electrodes.

  12. Rhenium-osmium concentration and isotope systematics in group IIAB iron meteorites

    USGS Publications Warehouse

    Morgan, J.W.; Horan, M.F.; Walker, R.J.; Grossman, J.N.

    1995-01-01

    Rhenium and osmium abundances, and osmium isotopic compositions were measured by negative thermal ionization mass spectrometry in thirty samples, including replicates, of five IIA and eight IIB iron meteorites. Log plots of Os vs. Re abundances for IIA and IIB irons describe straight lines that approximately converge on Lombard, which has the lowest Re and Os abundances and highest 187Re/188Os measured in a IIA iron to date. The linear IIA trend may be exactly reproduced by fractional crystallization, but is not well fitted using variable partition coefficients. The IIB iron trend, however, cannot be entirely explained by simple fractional crystallization. One explanation is that small amounts of Re and Os were added to the asteroid core during the final stages of crystallization. Another possibility is that diffusional enrichment of Os may have occurred in samples most depleted in Re and Os. -from Authors

  13. Use of an osmium complex as a universal luminescent probe for enzymatic reactions.

    PubMed

    Virel, Ana; Sanchez-Lopez, Jose; Saa, Laura; García, Ana Carla; Pavlov, Valeri

    2009-06-15

    The water-soluble bis(bipyridine)chloro(4-picolinic acid) osmium complex, [Os(III)(bpy)2Cl(PyCOOH)]2+ (bpy=2,2'-bipyridine, Py=pyridine), is fluorescent in aqueous solution, whereas the reduced form of the complex, [Os(II)(bpy)2Cl(PyCOOH)]+, shows no significant fluorescence under the same conditions. Such reversible redox control of the fluorescence of the complex can be easily adapted to follow any enzymatic reaction to yield oxidising or reducing products that are capable of interacting with [Os(III)(bpy)2Cl(PyCOOH)]2+ or [Os(II)(bpy)2Cl(PyCOOH)]+. Based on the redox reaction between products of biocatalytic reactions and the osmium complex, we have designed a simple bioanalytical assay for the detection of nerve gases, alpha-ketoglutarate, hydrogen peroxide and glucose.

  14. Stability and mobility of rhenium and osmium in tungsten: first principles study

    NASA Astrophysics Data System (ADS)

    Suzudo, T.; Yamaguchi, M.; Hasegawa, A.

    2014-10-01

    We report a series of ab initio studies based upon density functional theory for the behavior of rhenium and osmium atoms in body-centered-cubic tungsten crystal. Contrary to the fast one-dimensional migration of self-interstitial atoms, interstitials of these solute elements in tungsten have three-dimensional motion because they form a mixed dumbbell having a low rotation energy barrier. The migration of these solute elements strongly influences the effects of radiation upon the materials, and our results suggest that the low rotation energy barrier leading to three-dimensional migration is a property that is key to the explanation of the radiation effects experimentally observed in tungsten-rhenium and tungsten-osmium alloys.

  15. FIXATION OF NEURAL TISSUES FOR ELECTRON MICROSCOPY BY PERFUSION WITH SOLUTIONS OF OSMIUM TETROXIDE

    PubMed Central

    Palay, Sanford L.; McGee-Russell, S. M.; Gordon, Spencer; Grillo, Mary A.

    1962-01-01

    This paper describes in detail a method for obtaining nearly uniform fixation of the nervous system by vascular perfusion with solutions of osmium tetroxide. Criteria are given for evaluating the degree of success achieved in the preservation of all the cellular components of the nervous system. The method permits analysis of the structural relations between cells at the electron microscopic level to an extent that has not been possible heretofore. PMID:14483299

  16. DNA photocleavage by an osmium(II) complex in the PDT window.

    PubMed

    Sun, Yujie; Joyce, Lauren E; Dickson, Nicole M; Turro, Claudia

    2010-09-28

    The extended pi-delocalization of dppn (benzo[i]dipyrido[3,2-a:2,3-c]phenazine) results in a (3)pipi* state as the lowest triplet excited state in [Os(bpy)(2)(dppn)](2+) (bpy = 2,2'-bipyridine), which generates a (1)O(2) quantum yield of 0.42. Together with its (3)MLCT absorption, this new osmium complex shows efficient DNA cleavage under irradiation of lambda(irr) > or = 645 nm.

  17. Ligand-free osmium clusters supported on MgO. A density functional study

    SciTech Connect

    Goellner, J.F.; Neyman, K.M.; Mayer, M.; Noertemann, F.; Gates, B.C.; Roesch, N.

    2000-03-21

    The interactions of Os{sub 4}, Os{sub 5}, and Os{sub 5}C clusters with various sites of a MgO(001) support were investigated theoretically with the aid of a scalar-relativistic density functional cluster model method. Adsorption geometries of C{sub 4{upsilon}} clusters centered above a magnesium cation and the Os atoms oriented either to the nearest surface oxygen anions (A) or between them (B) were considered. The influence of surface V{sub s} and V{sub s}{sup 2{minus}} defects on the adsorption of the clusters was also investigated. The calculated base Os-Os distances in supported Os{sub 5} and Os{sub 5}C square-pyramidal clusters are at most 0.1 {angstrom} longer (2.5--2.6{angstrom}) than the values calculated for the corresponding free osmium cluster but about 0.4{angstrom} (or more) shorter than the values determined by EXAFS spectroscopy for MgO-powder-supported clusters formed by decarbonylation of [Os{sub 5}C(CO){sub 14}]{sup 2{minus}} and shown to retains the Os{sub 5}C frame. The experimental Os-Os distances characterizing the supported clusters are close to the experimental and calculated bond lengths for coordinatively saturated osmium carbonyl clusters; the result favors the suggestion that the supported clusters characterized by EXAFS spectroscopy were not entirely ligand-free. The models reported here are inferred to be too simplified to capture all the pertinent structural details of MgO-powder-supported osmium clusters, but they are sufficient to indicate a significant role of defect sites in the adsorption of supported osmium clusters and, the authors infer, other transition metal clusters.

  18. Isotopic signature and impact of car catalysts on the anthropogenic osmium budget.

    PubMed

    Poirier, André; Gariépy, Clement

    2005-06-15

    Higher osmium concentrations and lower 187Os/188Os ratios in sediments from urban areas have been linked to anthropogenic osmium sources. Automobile catalytic converters that use platinum group metals (PGM) are a potential source for this Os pollution. We present the first direct Os concentrations and isotopic measurements of catalytic converters for major automobile brands to test the assumption that car catalysts release Os with a distinct signature in the environment. The analysis of four new catalytic converters yields similar low 187Os/188Os ratios (0.1-0.2), suggesting a similar source for the PGM. The Os concentrations measured are in the ppt range (6-228 ppt). From our results, the osmium contribution of the car catalysts to the environment through attrition (wearing and grinding down of the catalyst by friction) is predicted to be low, <0.2 pg Os/m2/year in highly urbanized environment. We show that Os loss from catalysts as volatile OsO4 is important at car catalyst operating temperatures. Moreover, we estimate that car catalysts may be responsible for up to approximately 120 pg Os/m2 deposited per year in urban areas and that part of it may be exported to sedimentary sinks. Car catalytic converters are thus an important anthropogenic osmium source in densely populated areas. The NIST car catalyst standard (SRM-2557, made from recycled used catalysts) yields higher concentrations (up to 721 ppt Os) and a more radiogenic isotopic composition (approximately 0.38), perhaps indicative of Os contamination during its preparation.

  19. Osmium and neodymium isotopic constraints on the temporal and spatial evolution of Siberian flood basalt sources

    USGS Publications Warehouse

    Horan, M.F.; Walker, R.J.; Fedorenko, V.A.; Czamanske, G.K.

    1995-01-01

    Picrites from the Gudchikhinsky suite, the oldest rocks examined, have ??Os of +5.3 to +6.1 and ??Nd of +3.7 to +4.0. The osmium and neodymium isotopic compositions of these rocks are similar to some modern ocean-island basalts (OIB), consistent with their derivation from an mantle plume. Picrites from the stratigraphically higher Tuklonsky suite have similar ??Os of +3.4 to +6.5, but ??Nd of -0.9 to -2.6. The similar ??Os, but lower ??Nd , suggest that some magmas from the same OIB-type, mantle source were contaminated by lithospheric components. A differentiated ankaramite flow, associated with the top of the stratigraphically higher Morongovsky suite, has ??Os of +9.8 to +10.2 and ??Nd of +1.3 to +1.4. The higher ??Os may indicate that the plume source was heterogeneous with respect to osmium isotopic composition, consistent with osmium isotopic measurements in rocks from other plume sources. Mg-rich, alkaline rocks (meymechites) from the Guli area that erupted much nearer the end of the flood-basalt event have ??Os of -1.2 to -2.6 and ??Nd of +3.7 to +4.9. These rocks were probably produced by low degrees of partial melting of mantle after the main stages of flood-basalt production. -from Authors

  20. Osmium(II)--versus ruthenium(II)--arene carbohydrate-based anticancer compounds: similarities and differences.

    PubMed

    Hanif, Muhammad; Nazarov, Alexey A; Hartinger, Christian G; Kandioller, Wolfgang; Jakupec, Michael A; Arion, Vladimir B; Dyson, Paul J; Keppler, Bernhard K

    2010-08-21

    The synthesis and in vitro anticancer activity of Os(II)-arene complexes with carbohydrate-derived phosphite co-ligands are reported. The compounds were characterized by standard methods and the molecular structure of dichlorido(eta(6)-p-cymene)(3,5,6-bicyclophosphite-1,2-O-isopropylidene-alpha-D-glucofuranoside)osmium(II) was determined by X-ray diffraction analysis. Complexes with chlorido leaving groups undergo hydrolysis by consecutive formation of aqua compounds, followed by cleavage of a P-O bond of sugar phosphite ligands, as demonstrated by NMR studies. These observations are similar to those of analogous Ru(II)-arene complexes; however the rate of hydrolysis is very slow for osmium compounds. The complexes with oxalato leaving groups resist hydrolysis; no hydrolytic species were detected by (31)P{(1)H} NMR spectroscopy over several days. Within this series of Os compounds, in vitro anticancer activity is highest for the most lipophilic chlorido complex dichlorido(eta(6)-p-cymene)(3,5,6-bicyclophosphite-1,2-O-cyclohexylidene-alpha-D-glucofuranoside)osmium(II).

  1. Glycosaminoglycans in the rat aorta. Ultrastructural localization with toluidine blue O and osmium--ferrocyanide procedure.

    PubMed Central

    Coltoff-Schiller, B.; Goldfischer, S.

    1981-01-01

    Glycosaminoglycans (GAGs) have been implicated in the pathogenesis of sclerotic vascular disease. The localization of GAGs in the rat aorta was examined by two different ultrastructural cytochemical approaches. These procedures are believed to demonstrate 1) anionic sites, with fixatives that contain either toluidine blue or ruthenium red, both cationic dyes, and 2) polysaccharides, proteoglycans, and glycoproteins, with an osmium--ferrocyanide mixture that binds to vicinal diols. Both procedures stain a network of insoluble, 2--8-nm filaments that bridge collagen fibers, elastin, basement membranes, and plasma membranes. These structures resist digestion with chondroitinase ABC and appear to be identical to the filaments that have previously been demonstrated with ruthenium red. Focal 6--12-nm densities are present where filaments intersect. However, the large granules that are made visible with ruthenium red are not seen in toluidine blue or osmium--ferrocyanide preparations. A soluble and relatively amorphous component surrounds the tightly packed bundles of collagen in the media and is preserved and stained by toluidine blue and osmium--ferrocyanide mixtures. Images Figure 1 Figure 2 Figure 3 Figure 4 Figure 5 Figure 6 Figure 7 Figure 8 Figure 9 Figure 10 Figure 11 Figure 12 PMID:6172040

  2. Biological properties of novel ruthenium- and osmium-nitrosyl complexes with azole heterocycles.

    PubMed

    Novak, Maria S; Büchel, Gabriel E; Keppler, Bernhard K; Jakupec, Michael A

    2016-06-01

    Since the discovery that nitric oxide (NO) is a physiologically relevant molecule, there has been great interest in the use of metal nitrosyl compounds as antitumor pharmaceuticals. Particularly interesting are those complexes which can deliver NO to biological targets. Ruthenium- and osmium-based compounds offer lower toxicity compared to other metals and show different mechanisms of action as well as different spectra of activity compared to platinum-based drugs. Novel ruthenium- and osmium-nitrosyl complexes with azole heterocycles were studied to elucidate their cytotoxicity and possible interactions with DNA. Apoptosis induction, changes of mitochondrial transmembrane potential and possible formation of reactive oxygen species were investigated as indicators of NO-mediated damage by flow cytometry. Results suggest that ruthenium- and osmium-nitrosyl complexes with the general formula (indazolium)[cis/trans-MCl4(NO)(1H-indazole)] have pronounced cytotoxic potency in cancer cell lines. Especially the more potent ruthenium complexes strongly induce apoptosis associated with depolarization of mitochondrial membranes, and elevated reactive oxygen species levels. Furthermore, a slight yet not unequivocal trend to accumulation of intracellular cyclic guanosine monophosphate attributable to NO-mediated effects was observed. PMID:26961253

  3. Engineering absorption and blackbody radiation in the far-infrared with surface phonon polaritons on gallium phosphide

    SciTech Connect

    Streyer, W.; Law, S.; Rosenberg, A.; Wasserman, D.; Roberts, C.; Podolskiy, V. A.; Hoffman, A. J.

    2014-03-31

    We demonstrate excitation of surface phonon polaritons on patterned gallium phosphide surfaces. Control over the light-polariton coupling frequencies is demonstrated by changing the pattern periodicity and used to experimentally determine the gallium phosphide surface phonon polariton dispersion curve. Selective emission via out-coupling of thermally excited surface phonon polaritons is experimentally demonstrated. Samples are characterized experimentally by Fourier transform infrared reflection and emission spectroscopy, and modeled using finite element techniques and rigorous coupled wave analysis. The use of phonon resonances for control of emissivity and excitation of bound surface waves offers a potential tool for the exploration of long-wavelength Reststrahlen band frequencies.

  4. Zinc iodide-osmium staining of membrane-coating granules in keratinized and non-keratinized mammalian oral epithelium.

    PubMed

    Squier, C A

    1982-01-01

    Specimens of keratinized and non-keratinized oral epithelium were examined in the electron microscope after being stained with zinc iodide-osmium. In both types of tissue, reaction was seen in unmyelinated nerves, in the specific granules of epithelial Langerhans cells and within lysosome-like organelles and small vesicles associated with Golgi systems. In keratinized epithelia, the reaction was also present in the membrane-coating granules and between the deepest cells of the keratinized layer. In contrast, the membrane-coating granules of non-keratinized epithelia lacked Zn iodide-osmium staining despite the presence of reaction in adjacent Golgi systems. It is suggested that Zn iodide-osmium stains glycolipid or glycoprotein material in the cell. This material is elaborated in the Golgi systems from which lysosomes and the membrane-coating granules of keratinized tissues are probably derived.

  5. Essential elucidation for preparation of supported nickel phosphide upon nickel phosphate precursor

    SciTech Connect

    Liu, Xuguang; Xu, Lei; Zhang, Baoquan

    2014-04-01

    Preparation of supported nickel phosphide (Ni{sub 2}P) depends on nickel phosphate precursor, generally related to its chemical composition and supports. Study of this dependence is essential and meaningful for the preparation of supported Ni{sub 2}P with excellent catalytic activity. The chemical nature of nickel phosphate precursor is revealed by Raman and UV–vis spectra. It is found that initial P/Ni mole ratio ≥0.8 prohibits the Ni-O-Ni bridge bonding (i.e., nickel oxide). This chemical bonding will not result in Ni{sub 2}P structure, verified by XRD characterization results. The alumina (namely, γ-Al{sub 2}O{sub 3}, θ-Al{sub 2}O{sub 3}, or α-Al{sub 2}O{sub 3}) with distinct physiochemical properties also results in diverse chemical nature of nickel phosphate, and then different nickel phosphides. The influence of alumina support on producing Ni{sub 2}P was explained by the theory of surface energy heterogeneity, calculated by the NLDFT method based on N{sub 2}-sorption isotherm. The uniform surface energy of α-Al{sub 2}O{sub 3} results only in the nickel phosphosate precursor and thus the Ni{sub 2}P phase. - Graphical abstract: Surface energy heterogeneity in alumina (namely α-Al{sub 2}O{sub 3}, θ-Al{sub 2}O{sub 3}, and γ-Al{sub 2}O{sub 3}) supported multi-oxidic precursors with different reducibilities and thus diverse nickel phosphides (i.e., Ni{sub 3}P, Ni{sub 12}P{sub 5}, Ni{sub 2}P). - Highlights: • Preparing pure Ni{sub 2}P. • Elucidating nickel phosphate precursor. • Associating with surface energy.

  6. An approach to preparing porous and hollow metal phosphides with higher hydrodesulfurization activity

    SciTech Connect

    Song Limin; Zhang Shujuan; Wei Qingwu

    2011-06-15

    This paper describes an effective method for the synthesis of metal phosphides. Bulk and supported Ni{sub 2}P, Cu{sub 3}P, and CoP were prepared by thermal treatment of metal and the amorphous red phosphorus mixtures. Porous and hollow Ni{sub 2}P particles were also synthesized successfully using this method. The structural properties of these products are investigated using X-ray powder diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM), inductively coupled plasma (ICP-AES) and X-ray photoemission spectroscopy (XPS). A rational mechanism was proposed for the selective formation of Ni{sub 2}P particles. In experimental conditions, the Ni{sub 2}P/SiO{sub 2} catalyst exhibits excellent hydrodesulfurization (HDS) activity for dibenzothiophene (DBT). - Graphical abstract: Bulk and supported Ni{sub 2}P, Cu{sub 3}P, and CoP were prepared by thermal treatment of their metal and amorphous red phosphorus mixtures. Porous and hollow Ni{sub 2}P particles were successfully synthesized by this method also. In the experimental condition, a Ni{sub 2}P/SiO{sub 2} catalyst exhibits excellent hydrodesulfurization activity for dibenzothiophene. Highlights: > A new synthetic route by heat treating mixtures of metal and red phosphorus in flowing N{sub 2} to prepare corresponding metal phosphides. > Porous and hollow Ni{sub 2}P particles may successfully be obtained using the route. > It is very easy to synthesize other bulk and supported metal phosphides using the mixing of bulk and supported metal and red phosphorus by the method. > The Ni{sub 2}P/SiO{sub 2} catalyst synthesized by the route shows a good HDS of dibenzothiophene. > Its operation is simple (only heat treating pure metal and red phosphorus), and the reaction time is short (only 0.5 h).

  7. Cobalt phosphide nanowall array as an efficient 3D catalyst electrode for methanol electro-oxidation

    NASA Astrophysics Data System (ADS)

    Liu, Danni; Lu, Wenbo; Wang, Kunyang; Du, Gu; Asiri, Abdullah M.; Lu, Qun; Sun, Xuping

    2016-11-01

    In this letter, we report on the use of a cobalt phosphide nanowall array on conductive carbon cloth (CoP NA/CC) as an efficient catalyst electrode for methanol electro-oxidation under alkaline conditions. This CoP NA/CC achieves a current density of 96 mA cm–2 toward 0.5 M methanol at 0.5 V (versus a saturated calomel electrode (SCE)) in 1 M KOH. Moreover, this electrode exhibits superior stability and 93% of the initial anodic current density can be retained after 1000 cyclic voltammetry cycles when re-measured in new electrolyte.

  8. An efficient bifunctional electrocatalyst for water splitting based on cobalt phosphide

    NASA Astrophysics Data System (ADS)

    Yang, Libin; Qi, Honglan; Zhang, Chengxiao; Sun, Xuping

    2016-06-01

    The development of highly efficient electrocatalysts for water splitting is critical for various renewable-energy technologies. In this letter, we demonstrate a cobalt phosphide nanowire array grown on a Ti mesh (CoP/TM) behaving as a bifunctional electrocatalyst for water splitting. The CoP/TM electrode delivers 10 mA cm-2 at an overpotential of 72 mV for the hydrogen evolution reaction (HER) and 310 mV for the oxygen evolution reaction (OER) in 1.0 M KOH. Furthermore, its corresponding two-electrode alkaline electrolyzer displays 10 mA cm-2 at 1.64 V.

  9. Cobalt phosphide nanowall array as an efficient 3D catalyst electrode for methanol electro-oxidation.

    PubMed

    Liu, Danni; Lu, Wenbo; Wang, Kunyang; Du, Gu; Asiri, Abdullah M; Lu, Qun; Sun, Xuping

    2016-11-01

    In this letter, we report on the use of a cobalt phosphide nanowall array on conductive carbon cloth (CoP NA/CC) as an efficient catalyst electrode for methanol electro-oxidation under alkaline conditions. This CoP NA/CC achieves a current density of 96 mA cm(-2) toward 0.5 M methanol at 0.5 V (versus a saturated calomel electrode (SCE)) in 1 M KOH. Moreover, this electrode exhibits superior stability and 93% of the initial anodic current density can be retained after 1000 cyclic voltammetry cycles when re-measured in new electrolyte. PMID:27671347

  10. An efficient bifunctional electrocatalyst for water splitting based on cobalt phosphide

    NASA Astrophysics Data System (ADS)

    Yang, Libin; Qi, Honglan; Zhang, Chengxiao; Sun, Xuping

    2016-06-01

    The development of highly efficient electrocatalysts for water splitting is critical for various renewable-energy technologies. In this letter, we demonstrate a cobalt phosphide nanowire array grown on a Ti mesh (CoP/TM) behaving as a bifunctional electrocatalyst for water splitting. The CoP/TM electrode delivers 10 mA cm‑2 at an overpotential of 72 mV for the hydrogen evolution reaction (HER) and 310 mV for the oxygen evolution reaction (OER) in 1.0 M KOH. Furthermore, its corresponding two-electrode alkaline electrolyzer displays 10 mA cm‑2 at 1.64 V.

  11. Theoretical Investigations on the Elastic and Thermodynamic Properties of Rhenium Phosphide

    NASA Astrophysics Data System (ADS)

    Wei, Qun; Yan, Haiyan; Zhu, Xuanmin; Lin, Zhengzhe; Yao, Ronghui

    2016-01-01

    Structural, mechanical, and electronic properties of orthorhombic rhenium phosphide (Re2P) are systematically investigated by using first principles calculations. The elastic constants and anisotropy of elastic properties are obtained. The metallic character of Re2P is demonstrated by density of state calculations. The quasi-harmonic Debye model is applied to the study of the thermodynamic properties. The thermal expansion, heat capacities, and Grüneisen parameter on the temperature and pressure have been determined as a function of temperature and pressure in the pressure range from 0 to 100 GPa and the temperature range from 0 to 1600 K.

  12. Cobalt phosphide nanowall array as an efficient 3D catalyst electrode for methanol electro-oxidation.

    PubMed

    Liu, Danni; Lu, Wenbo; Wang, Kunyang; Du, Gu; Asiri, Abdullah M; Lu, Qun; Sun, Xuping

    2016-11-01

    In this letter, we report on the use of a cobalt phosphide nanowall array on conductive carbon cloth (CoP NA/CC) as an efficient catalyst electrode for methanol electro-oxidation under alkaline conditions. This CoP NA/CC achieves a current density of 96 mA cm(-2) toward 0.5 M methanol at 0.5 V (versus a saturated calomel electrode (SCE)) in 1 M KOH. Moreover, this electrode exhibits superior stability and 93% of the initial anodic current density can be retained after 1000 cyclic voltammetry cycles when re-measured in new electrolyte.

  13. UV laser micromachining of silicon, indium phosphide and lithium niobate for telecommunications applications

    NASA Astrophysics Data System (ADS)

    Greuters, Jako; Rizvi, Nadeem H.

    2003-03-01

    The laser micromachining characteristics of indium phosphide, lithium niobate and silicon have been characterised using a 355nm neodymium vanadate laser and 193nm and 248nm excimer lasers. Etch rates for these materials are presented at the different laser wavelengths. High quality cutting of the three materials is demonstrated with the 355nm laser and an excimer laser mask projection method is subsequently used to micromachine precision V-grooves as fibre placement structures. Silicon microbenches, used for the integration of multiple-function devices, are also produced using the 355nm laser.

  14. Infrared reflection spectra in contactless nondestructive measurements of the electron density and mobility in indium phosphide

    SciTech Connect

    Il'in, M.A.; Karasev, P.Yu.; Denisova, N.A.; Rezvov, A.V.; Tyurina, S.V.

    1988-07-01

    On the basis of numerical calculations and experimental studies we analyze the possibilities of measuring the electrophysical parameters of indium phosphide by means of infrared reflection spectra at wavelengths ranging from 5 to 200 /mu/m. We demonstrate that contactless nondestructive measurements of the electron density in the range 10/sup 16/-10/sup 20/ cm/sup /minus/3/ can be made with a relative error not exceeding 15%, and of mobility with a relative error not exceeding 25%. A nomogram method is presented for rapid conversion of data form infrared reflection spectra into the parameters being measured.

  15. Comparative radiation resistance, temperature dependence and performance of diffused junction indium phosphide solar cells

    NASA Technical Reports Server (NTRS)

    Weinberg, I.; Swartz, C. K.; Hart, R. E., Jr.; Ghandhi, S. K.; Borrego, J. M.

    1987-01-01

    Indium phosphide solar cells whose p-n junctions were processed by the open tube capped diffusion and by the closed tube uncapped diffusion of sulfur into Czochralski-grown p-type substrates are compared. Differences found in radiation resistance were attributed to the effects of increased base dopant concentration. Both sets of cells showed superior radiation resistance to that of gallium arsenide cells, in agreement with previous results. No correlation was, however, found between the open-circuit voltage and the temperature dependence of the maximum power.

  16. A Flexible Electrode Based on Iron Phosphide Nanotubes for Overall Water Splitting.

    PubMed

    Yan, Ya; Xia, Bao Yu; Ge, Xiaoming; Liu, Zhaolin; Fisher, Adrian; Wang, Xin

    2015-12-01

    The design of cheap and efficient water splitting systems for sustainable hydrogen production has attracted increasing attention. A flexible electrode, based on carbon cloth substrate and iron phosphide nanotubes coated with an iron oxide/phosphate layer, is shown to catalyze overall water splitting. The as-prepared flexible electrode demonstrates remarkable electrocatalytic activity for both the hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER) at modest overpotentials. The surface iron oxide/phosphate, which is formed in situ, is proposed to improve the HER activity by facilitating the water-dissociation step and serves directly as the catalytically-active component for the OER process.

  17. Direct radiometric dating of hydrocarbon deposits using rhenium-osmium isotopes.

    PubMed

    Selby, David; Creaser, Robert A

    2005-05-27

    Rhenium-osmium (Re-Os) data from migrated hydrocarbons establish the timing of petroleum emplacement for the giant oil sand deposits of Alberta, Canada, at 112 +/- 5.3 million years ago. This date does not support models that invoke oil generation and migration for these deposits in the Late Cretaceous. Most Re-Os data from a variety of deposits within the giant hydrocarbon system show similar characteristics, supporting the notion of a single source for these hydrocarbons. The Re-Os data disqualify Cretaceous rocks as the primary hydrocarbon source but suggest an origin from older source rocks. This approach should be applicable to dating oil deposits worldwide.

  18. Features of the band structure for semiconducting iron, ruthenium, and osmium monosilicides

    SciTech Connect

    Shaposhnikov, V. L. Migas, D. B.; Borisenko, V. E.; Dorozhkin, N. N.

    2009-02-15

    The pseudopotential method has been used to optimize the crystal lattice and calculate the energy band spectra for iron, ruthenium and, osmium monosilicides. It is found that all these compounds are indirect-gap semiconductors with band gaps of 0.17, 0.22, and 0.50 eV (FeSi, RuSi, and OsSi, respectively). A distinctive feature of their band structure is the 'loop of extrema' both in the valence and conduction bands near the center of the cubic Brillouin zone.

  19. Osmium-catalyzed tethered aminohydroxylation of glycals: a stereodirected access to 2- and 3-aminosugars.

    PubMed

    Mirabella, Stefania; Cardona, Francesca; Goti, Andrea

    2015-02-01

    The osmium-catalyzed aminohydroxylation of glycals has been achieved with complete regio- and stereocontrol by taking advantage of the Donohoe tethering approach. Glucals and galactals showed complementary reactivity in dependence of the stage at which the reaction was performed, i.e., directly or after double-bond shift consequent to a Ferrier rearrangement (that is, on the 1,2 or 2,3-unsaturated sugar), allowing access to both classes of 2-amino (mannosamine) and 3-amino (talosamine) sugar derivatives, respectively.

  20. Photocurrent generation from thylakoid membranes on osmium-redox-polymer-modified electrodes.

    PubMed

    Hamidi, Hassan; Hasan, Kamrul; Emek, Sinan Cem; Dilgin, Yusuf; Åkerlund, Hans-Erik; Albertsson, Per-Åke; Leech, Dónal; Gorton, Lo

    2015-03-01

    Thylakoid membranes (TMs) are uniquely suited for photosynthesis owing to their distinctive structure and composition. Substantial efforts have been directed towards use of isolated photosynthetic reaction centers (PRCs) for solar energy harvesting, however, few studies investigate the communication between whole TMs and electrode surfaces, due to their complex structure. Here we report on a promising approach to generate photosynthesis-derived bioelectricity upon illumination of TMs wired with an osmium-redox-polymer modified graphite electrode, and generate a photocurrent density of 42.4 μA cm(-2).

  1. Photocurrent generation from thylakoid membranes on osmium-redox-polymer-modified electrodes.

    PubMed

    Hamidi, Hassan; Hasan, Kamrul; Emek, Sinan Cem; Dilgin, Yusuf; Åkerlund, Hans-Erik; Albertsson, Per-Åke; Leech, Dónal; Gorton, Lo

    2015-03-01

    Thylakoid membranes (TMs) are uniquely suited for photosynthesis owing to their distinctive structure and composition. Substantial efforts have been directed towards use of isolated photosynthetic reaction centers (PRCs) for solar energy harvesting, however, few studies investigate the communication between whole TMs and electrode surfaces, due to their complex structure. Here we report on a promising approach to generate photosynthesis-derived bioelectricity upon illumination of TMs wired with an osmium-redox-polymer modified graphite electrode, and generate a photocurrent density of 42.4 μA cm(-2). PMID:25703722

  2. Osmium Bisterpyridine Complexes with Redox-Active Amine Substituents: A Comparison Study with Ruthenium Analogues.

    PubMed

    Sun, Meng-Jia; Shao, Jiang-Yang; Yao, Chang-Jiang; Zhong, Yu-Wu; Yao, Jiannian

    2015-08-17

    Five osmium complexes with redox-active amine substituents, [Os(ttpy)(Ntpy)](PF6)2 (1(PF6)2), [Os(Ntpy)2](PF6)2 (2(PF6)2), [Os(ttpy)(NPhtpy)](PF6)2 (3(PF6)2), [Os(Ntpy)(NPhtpy)](PF6)2 (4(PF6)2), and [Os(NPhtpy)2](PF6)2 (5(PF6)2), have been prepared, where ttpy is 4'-tolyl-2,2':6',2″-terpyridine, Ntpy is 4'-(di-p-anisylamino)-2,2':6',2″-terpyridine, and NPhtpy is 4'-(di-p-anisylaminophen-4-yl)-2,2':6',2″-terpyridine. X-ray crystallographic data of 2(PF6)2 and 4(PF6)2 are presented. These complexes show rich visible absorptions attributed to the singlet metal-to-ligand charge-transfer ((1)MLCT), triplet MLCT, and intraligand charge-transfer transitions. Complexes 3(PF6)2 and 5(PF6)2 show weak emissions around 720 nm at room temperature. All complexes show stepwise oxidations of the osmium ion and the amine segment. However, the redox potentials and the order of the Os(III/II) and N(•+/0) processes vary significantly, depending on the electronic nature of the amine substituents. In the singly oxidized state, either Os(II) → N(•+) MLCT or N → Os(III) ligand-to-metal charge-transfer transitions in the near-infrared region have been observed. For complexes 2(PF6)2, 4(PF6)2, and 5(PF6)2 with two amine substituents, no evidence has been observed for the presence of osmium-mediated amine-amine electronic coupling. Density functional theory (DFT) and time-dependent DFT calculations have been performed to complement these experimental results. The one-electron-oxidized forms 3(3+) and 5(3+) show distinct electron paramagnetic resonance (EPR) signals in CH3CN at room temperature. However, complexes 1(3+), 2(3+), and 4(3+) are EPR silent under similar conditions. In addition, a comparison study has been made between these osmium complexes and the previously reported ruthenium analogues. PMID:26237331

  3. Proton-coupled electron transfer and multielectron oxidations in complexes of ruthenium and osmium

    SciTech Connect

    Dovletoglou, A.

    1992-01-01

    This doctoral research concerns the mechanism of proton-coupled electron transfer over an extended pH range. These processes between ruthenium and osmium complexes and hydroquinones have been studied using spectrophotometric methods and cyclic voltammetry. Elucidation of the mechanistic details has been attempted by using isotopic labelling, kinetic analysis, and numerical simulation of complex kinetic schemes. The coordination and redox chemistry of polypyridyl-acetylacetonato and -oxalato complexes of ruthenium and the role of ancillary ligands in defining the properties of Ru[sup IV]O complexes were explored. These studies represent the first attempt to probe possible 2e[sup [minus

  4. Anion Sensing by Solution- and Surface-Assembled Osmium(II) Bipyridyl Rotaxanes

    PubMed Central

    Lehr, Joshua; Lang, Thomas; Blackburn, Octavia A; Barendt, Timothy A; Faulkner, Stephen; Davis, Jason J; Beer, Paul D

    2013-01-01

    We report the preparation of [2]rotaxanes containing an electrochemically and optically active osmium(II) bipyridyl macrocyclic component mechanically bonded with cationic pyridinium axles. Such interlocked host systems are demonstrated to recognise and sense anionic guest species as shown by 1H NMR, luminescence and electrochemical studies. The rotaxanes can be surface assembled on to gold electrodes through anion templation under click copper(I)-catalysed Huisgen cycloaddition conditions to form rotaxane molecular films, which, after template removal, respond electrochemically and selectively to chloride. PMID:24127251

  5. Osmium(II) polypyridyl polyarginine conjugate as a probe for live cell imaging; a comparison of uptake, localization and cytotoxicity with its ruthenium(II) analogue.

    PubMed

    Byrne, Aisling; Dolan, Ciarán; Moriarty, Roisin D; Martin, Aaron; Neugebauer, Ute; Forster, Robert J; Davies, Anthony; Volkov, Yuri; Keyes, Tia E

    2015-08-28

    A first investigation into the application of a luminescent osmium(ii) bipyridine complex to live cell imaging is presented. Osmium(ii) (bis-2,2-bipyridyl)-2(4-carboxylphenyl) imidazo[4,5f][1,10]phenanthroline was prepared and conjugated to octaarginine, a cell penetrating peptide. The photophysics, cell uptake and cytotoxicity of this osmium complex conjugate were performed and compared with its ruthenium analogue. Cell uptake and distribution of both ruthenium and osmium conjugates were very similar with rapid transmembrane transport of the osmium probe (complete within approx. 20 min) and dispersion throughout the cytoplasm and organelles. The near-infrared (NIR) emission of the osmium complex (λmax 726 nm) coincides well with the biological optical window and this facilitated luminescent and luminescence lifetime imaging of the cell which was well resolved from cell autofluorescence. The large Stokes shift of the emission also permitted resonance Raman mapping of the dye within CHO cells. Rather surprisingly, the osmium conjugate exhibited very low cytotoxicity when incubated both in the dark and under visible irradiation. This was attributed to the remarkable stability of this complex which was reflected by the complete absence of photo-bleaching of the complex even under extended continuous irradiation. In addition, when compared to its ruthenium analogue its luminescence was short-lived in water therefore rendering it insensitive to O2. PMID:26197944

  6. Osmium(II) polypyridyl polyarginine conjugate as a probe for live cell imaging; a comparison of uptake, localization and cytotoxicity with its ruthenium(II) analogue.

    PubMed

    Byrne, Aisling; Dolan, Ciarán; Moriarty, Roisin D; Martin, Aaron; Neugebauer, Ute; Forster, Robert J; Davies, Anthony; Volkov, Yuri; Keyes, Tia E

    2015-08-28

    A first investigation into the application of a luminescent osmium(ii) bipyridine complex to live cell imaging is presented. Osmium(ii) (bis-2,2-bipyridyl)-2(4-carboxylphenyl) imidazo[4,5f][1,10]phenanthroline was prepared and conjugated to octaarginine, a cell penetrating peptide. The photophysics, cell uptake and cytotoxicity of this osmium complex conjugate were performed and compared with its ruthenium analogue. Cell uptake and distribution of both ruthenium and osmium conjugates were very similar with rapid transmembrane transport of the osmium probe (complete within approx. 20 min) and dispersion throughout the cytoplasm and organelles. The near-infrared (NIR) emission of the osmium complex (λmax 726 nm) coincides well with the biological optical window and this facilitated luminescent and luminescence lifetime imaging of the cell which was well resolved from cell autofluorescence. The large Stokes shift of the emission also permitted resonance Raman mapping of the dye within CHO cells. Rather surprisingly, the osmium conjugate exhibited very low cytotoxicity when incubated both in the dark and under visible irradiation. This was attributed to the remarkable stability of this complex which was reflected by the complete absence of photo-bleaching of the complex even under extended continuous irradiation. In addition, when compared to its ruthenium analogue its luminescence was short-lived in water therefore rendering it insensitive to O2.

  7. Silicon nanowire arrays coupled with cobalt phosphide spheres as low-cost photocathodes for efficient solar hydrogen evolution.

    PubMed

    Bao, Xiao-Qing; Fatima Cerqueira, M; Alpuim, Pedro; Liu, Lifeng

    2015-07-01

    We demonstrate the first example of silicon nanowire array photocathodes coupled with hollow spheres of the emerging earth-abundant cobalt phosphide catalysts. Compared to bare silicon nanowire arrays, the hybrid electrodes exhibit significantly improved photoelectrochemical performance toward the solar-driven H2 evolution reaction.

  8. C-H bond activation of the methyl group of the supporting ligand in an osmium(III) complex upon reaction with H2O2: formation of an organometallic osmium(IV) complex.

    PubMed

    Sugimoto, Hideki; Ashikari, Kenji; Itoh, Shinobu

    2013-01-18

    Oxidation of the hydroxoosmium(III) complex resulted in C-H bond activation of the methyl group of the supporting ligand (N,N'-dimethyl-2,11-diaza[3.3](2,6)pyridinophane). The product was an osmium(IV) complex exhibiting a seven-coordinate structure with an additional Os-CH(2) bond.

  9. ANALYSIS OF THE WATER-SPLITTING CAPABILITIES OF GALLIUM INDIUM PHOSPHIDE NITRIDE (GaInPN)

    SciTech Connect

    Head, J.; Turner, J.

    2007-01-01

    With increasing demand for oil, the fossil fuels used to power society’s vehicles and homes are becoming harder to obtain, creating pollution problems and posing hazard’s to people’s health. Hydrogen, a clean and effi cient energy carrier, is one alternative to fossil fuels. Certain semiconductors are able to harness the energy of solar photons and direct it into water electrolysis in a process known as photoelectrochemical water-splitting. P-type gallium indium phosphide (p-GaInP2) in tandem with GaAs is a semiconductor system that exhibits water-splitting capabilities with a solar-tohydrogen effi ciency of 12.4%. Although this material is effi cient at producing hydrogen through photoelectrolysis it has been shown to be unstable in solution. By introducing nitrogen into this material, there is great potential for enhanced stability. In this study, gallium indium phosphide nitride Ga1-yInyP1-xNx samples were grown using metal-organic chemical vapor deposition in an atmospheric-pressure vertical reactor. Photocurrent spectroscopy determined these materials to have a direct band gap around 2.0eV. Mott-Schottky analysis indicated p-type behavior with variation in fl atband potentials with varied frequencies and pH’s of solutions. Photocurrent onset and illuminated open circuit potential measurements correlated to fl atband potentials determined from previous studies. Durability analysis suggested improved stability over the GaInP2 system.

  10. Three-dimensional interconnected nickel phosphide networks with hollow microstructures and desulfurization performance

    SciTech Connect

    Zhang, Shuna; Zhang, Shujuan; Song, Limin; Wu, Xiaoqing; Fang, Sheng

    2014-05-01

    Graphical abstract: Three-dimensional interconnected nickel phosphide networks with hollow microstructures and desulfurization performance. - Highlights: • Three-dimensional Ni{sub 2}P has been prepared using foam nickel as a template. • The microstructures interconnected and formed sponge-like porous networks. • Three-dimensional Ni{sub 2}P shows superior hydrodesulfurization activity. - Abstract: Three-dimensional microstructured nickel phosphide (Ni{sub 2}P) was fabricated by the reaction between foam nickel (Ni) and phosphorus red. The as-prepared Ni{sub 2}P samples, as interconnected networks, maintained the original mesh structure of foamed nickel. The crystal structure and morphology of the as-synthesized Ni{sub 2}P were characterized by X-ray diffraction, scanning electron microscopy, automatic mercury porosimetry and X-ray photoelectron spectroscopy. The SEM study showed adjacent hollow branches were mutually interconnected to form sponge-like networks. The investigation on pore structure provided detailed information for the hollow microstructures. The growth mechanism for the three-dimensionally structured Ni{sub 2}P was postulated and discussed in detail. To investigate its catalytic properties, SiO{sub 2} supported three-dimensional Ni{sub 2}P was prepared successfully and evaluated for the hydrodesulfurization (HDS) of dibenzothiophene (DBT). DBT molecules were mostly hydrogenated and then desulfurized by Ni{sub 2}P/SiO{sub 2}.

  11. Performance enhancement of a graphene-zinc phosphide solar cell using the electric field-effect.

    PubMed

    Vazquez-Mena, Oscar; Bosco, Jeffrey P; Ergen, O; Rasool, Haider I; Fathalizadeh, Aidin; Tosun, Mahmut; Crommie, Michael; Javey, Ali; Atwater, Harry A; Zettl, Alex

    2014-08-13

    The optical transparency and high electron mobility of graphene make it an attractive material for photovoltaics. We present a field-effect solar cell using graphene to form a tunable junction barrier with an Earth-abundant and low cost zinc phosphide (Zn3P2) thin-film light absorber. Adding a semitransparent top electrostatic gate allows for tuning of the graphene Fermi level and hence the energy barrier at the graphene-Zn3P2 junction, going from an ohmic contact at negative gate voltages to a rectifying barrier at positive gate voltages. We perform current and capacitance measurements at different gate voltages in order to demonstrate the control of the energy barrier and depletion width in the zinc phosphide. Our photovoltaic measurements show that the efficiency conversion is increased 2-fold when we increase the gate voltage and the junction barrier to maximize the photovoltaic response. At an optimal gate voltage of +2 V, we obtain an open-circuit voltage of V oc = 0.53 V and an efficiency of 1.9% under AM 1.5 1-sun solar illumination. This work demonstrates that the field effect can be used to modulate and optimize the response of photovoltaic devices incorporating graphene.

  12. Spectrophotometric determination of osmium based on its catalytic effect on the oxidation of carminic acid by hydrogen peroxide.

    PubMed

    Manzoori, J L; Sorouraddin, M H; Amjadi, M

    2000-10-01

    A highly sensitive spectrophotometric method is described for the determination of trace amounts of osmium(VIII), based on its catalytic effect on the oxidation of carminic acid by hydrogen peroxide. The reaction was monitored spectrophotometrically by measuring the decrease in absorbance of carminic acid at 540 nm after 3 min of mixing the reagents. The optimum reaction conditions were 1x10(-4) mol l(-1) carminic acid, 0.013 mol l(-1) hydrogen peroxide and pH 10 at 25 degrees C. By using the recommended procedure, the calibration graph was linear from 0.1 to 1.5 ng ml(-1) of osmium; the detection limit was 0.02 ng ml(-1); the RSD for five replicate determinations of 0.2-1.4 ng ml(-1) was in the range of 1.8-4.7%. The influence of several foreign ions on osmium determination were studied and the effect of interfering ions were removed by extracting osmium into isobuthyl methyl ketone and back extracting into sodium hydroxide solution. PMID:18968089

  13. A simple protocol for paraffin-embedded myelin sheath staining with osmium tetroxide for light microscope observation.

    PubMed

    Di Scipio, Federica; Raimondo, Stefania; Tos, Pierluigi; Geuna, Stefano

    2008-07-01

    Experimental investigation of peripheral nerve fiber regeneration is attracting more and more attention among both basic and clinical researchers. Assessment of myelinated nerve fiber morphology is a pillar of peripheral nerve regeneration research. The gold standard for light microscopic imaging of myelinated nerve fibers is toluidine blue staining of resin-embedded semithin sections. However, many researchers are unaware that the dark staining of myelin sheaths typically produced by this procedure is due to osmium tetroxide postfixation and not due to toluidine blue. In this article, we describe a simple pre-embedding protocol for staining myelin sheaths in paraffin-embedded nerve specimens using osmium tetroxide. The method involves immersing the specimen in 2% osmium tetroxide for 2 h after paraformaldehyde fixation, followed by routine dehydration and paraffin embedding. Sections can then be observed directly under the microscope or counterstained using routine histological methods. Particularly good results were obtained with Masson's trichrome counterstain, which permits the imaging of connective structures in nerves that are not detectable in toluidine blue-stained resin sections. Finally, we describe a simple protocol for osmium etching of sections, which makes further immunohistochemical analysis possible on the same specimens. Taken together, our results suggest that the protocol described in this article is a valid alternative to the conventional resin embedding-based protocol: it is much cheaper, can be adopted by any histological laboratory, and allows immunohistochemical analysis to be conducted.

  14. Short review of high-pressure crystal growth and magnetic and electrical properties of solid-state osmium oxides

    NASA Astrophysics Data System (ADS)

    Yamaura, Kazunari

    2016-04-01

    High-pressure crystal growth and synthesis of selected solid-state osmium oxides, many of which are perovskite-related types, are briefly reviewed, and their magnetic and electrical properties are introduced. Crystals of the osmium oxides, including NaOsO3, LiOsO3, and Na2OsO4, were successfully grown under high-pressure and high-temperature conditions at 6 GPa in the presence of an appropriate amount of flux in a belt-type apparatus. The unexpected discovery of a magnetic metal-insulator transition in NaOsO3, a ferroelectric-like transition in LiOsO3, and high-temperature ferrimagnetism driven by a local structural distortion in Ca2FeOsO6 may represent unique features of the osmium oxides. The high-pressure and high-temperature synthesis and crystal growth has played a central role in the development of solid-state osmium oxides and the elucidation of their magnetic and electronic properties toward possible use in multifunctional devices.

  15. Three-Dimensional Structural Analysis of MgO-Supported Osmium Clusters by Electron Microscopy with Single-Atom Sensitivity

    SciTech Connect

    Aydin, C.; Kulkarni, Apoorva; Chi, Miaofang; Browning, Nigel D.; Gates, Bruce C.

    2013-05-10

    Size, shape, nuclearity: Aberration-corrected scanning transmission electron microscopy was used to determine the 3D structures of MgO-supported Os3, Os4, Os5, and Os10 clusters, which have structures nearly matching those of osmium carbonyl compounds with known crystal structures. The samples are among the best-defined supported catalysts.

  16. Ruthenium- and osmium-arene-based paullones bearing a TEMPO free-radical unit as potential anticancer drugs.

    PubMed

    Arion, Vladimir B; Dobrov, Anatolie; Göschl, Simone; Jakupec, Michael A; Keppler, Bernhard K; Rapta, Peter

    2012-09-01

    A modified paullone ligand bearing a TEMPO free-radical unit (HL) and its ruthenium(II) and osmium(II)-arene complexes [M(p-cymene)(HL)Cl]Cl·nH(2)O (M = Ru, Os) exhibit high antiproliferative activity in human cancer cell lines.

  17. Osmium-Based Pyrimidine Contrast Tags for Enhanced Nanopore-Based DNA Base Discrimination

    PubMed Central

    Henley, Robert Y.; Vazquez-Pagan, Ana G.; Johnson, Michael; Kanavarioti, Anastassia; Wanunu, Meni

    2015-01-01

    Nanopores are a promising platform in next generation DNA sequencing. In this platform, an individual DNA strand is threaded into nanopore using an electric field, and enzyme-based ratcheting is used to move the strand through the detector. During this process the residual ion current through the pore is measured, which exhibits unique levels for different base combinations inside the pore. While this approach has shown great promise, accuracy is not optimal because the four bases are chemically comparable to one another, leading to small differences in current obstruction. Nucleobase-specific chemical tagging can be a viable approach to enhancing the contrast between different bases in the sequence. Herein we show that covalent modification of one or both of the pyrimidine bases by an osmium bipyridine complex leads to measureable differences in the blockade amplitudes of DNA molecules. We qualitatively determine the degree of osmylation of a DNA strand by passing it through a solid-state nanopore, and are thus able to gauge T and C base content. In addition, we show that osmium bipyridine reacts with dsDNA, leading to substantially different current blockade levels than exhibited for bare dsDNA. This work serves as a proof of principle for nanopore sequencing and mapping via base-specific DNA osmylation. PMID:26657869

  18. Homogeneous electrochemical detection of hippuric acid in urine based on the osmium-antigen conjugate.

    PubMed

    Jeon, Won-Yong; Choi, Young-Bong; Kim, Hyug-Han

    2013-07-22

    A homogeneous electrochemical immunoassay is based on the interaction of osmium-antigen conjugate with its antibody. The novelty presented herein is the direct conjugation of the osmium complex to a small antigen and the application of the quantitative analysis of the antigen and its antibody as the electrical signal for homogeneous immunoassay. The small antigen chosen is hippuric acid (HA), a major urinary metabolite in toluene-exposed humans. As a redox mediator, [Os(4,4'-dimethoxy-2,2'-bipyridine)2(4-aminomethylpyridine-HA)Cl](+/2+) (Os-HA antigen) has been synthesized and characterized on screen-printed carbon electrodes. The synthesized Os-HA antigen shows reversible redox peaks at E(½)=0.056 V versus Ag/AgCl. The homogeneous competitive immunoassay relies on the interaction between Os-HA antigen conjugate and free antigen to its antibody, which can generate electrical signals linearly proportional to the free antigen monitored by cyclic voltammetry and differential pulse voltammetry in the range of 10 μg mL(-1) to 5.12 mg mL(-1). The cutoff concentration of HA in urine samples is 2.0 mg mL(-1), so the method can be used to develop a HA immunosensor. Moreover, the proposed homogeneous electrochemical immunoassay method can be applied to detect low concentrations of small antigens found in the healthcare area.

  19. Osmium-Based Pyrimidine Contrast Tags for Enhanced Nanopore-Based DNA Base Discrimination.

    PubMed

    Henley, Robert Y; Vazquez-Pagan, Ana G; Johnson, Michael; Kanavarioti, Anastassia; Wanunu, Meni

    2015-01-01

    Nanopores are a promising platform in next generation DNA sequencing. In this platform, an individual DNA strand is threaded into nanopore using an electric field, and enzyme-based ratcheting is used to move the strand through the detector. During this process the residual ion current through the pore is measured, which exhibits unique levels for different base combinations inside the pore. While this approach has shown great promise, accuracy is not optimal because the four bases are chemically comparable to one another, leading to small differences in current obstruction. Nucleobase-specific chemical tagging can be a viable approach to enhancing the contrast between different bases in the sequence. Herein we show that covalent modification of one or both of the pyrimidine bases by an osmium bipyridine complex leads to measureable differences in the blockade amplitudes of DNA molecules. We qualitatively determine the degree of osmylation of a DNA strand by passing it through a solid-state nanopore, and are thus able to gauge T and C base content. In addition, we show that osmium bipyridine reacts with dsDNA, leading to substantially different current blockade levels than exhibited for bare dsDNA. This work serves as a proof of principle for nanopore sequencing and mapping via base-specific DNA osmylation.

  20. Hydrolysis and cytotoxic properties of osmium(II)/(III)-DMSO-azole complexes. Short communication.

    PubMed

    Egger, Alexander; Cebrián-Losantos, Berta; Stepanenko, Iryna N; Krokhin, Artem A; Eichinger, Rene; Jakupec, Michael A; Arion, Vladimir B; Keppler, Bernhard K

    2008-08-01

    The antiproliferative properties of the osmium(II) complexes cis,fac-[Os(II)Cl(2)(DMSO)(3)(L)] and trans,cis,cis-[Os(II)Cl(2)(DMSO)(2)(L)(2)] (L = 1H-pyrazole, 1H-imidazole) were studied in three human cancer cell lines, namely 41M (ovary), SK-BR-3 (breast), and SW480 (colon). Their activities were compared with those of osmium(III) and ruthenium(III) NAMI-A type complexes on HT-29 (colon) and SK-BR-3 cancer cell lines. While IC(50) values of all the Os(II) complexes were found to be >1000 microM in all cell lines, Os and Ru-NAMI-A type complexes showed remarkable antiproliferative activity. The marginal in vitro cytotoxicity of the Os(II) compounds is presumably attributed to their resistance to hydrolysis. However, the Os-NAMI-A complexes, which are also kinetically stable in aqueous solution, showed reasonable antiproliferative activity in vitro when compared with the analogous Ru compounds and with the Os(II)-DMSO-azole species, indicating that hydrolysis might be not a prerequisite for the antitumor activity of Os-NAMI-A type complexes.

  1. Electrochemical communication between heterotrophically grown Rhodobacter capsulatus with electrodes mediated by an osmium redox polymer.

    PubMed

    Hasan, Kamrul; Patil, Sunil A; Górecki, Kamil; Leech, Dónal; Hägerhäll, Cecilia; Gorton, Lo

    2013-10-01

    The metabolically versatile purple bacteria Rhodobacter capsulatus was investigated to check its possible applicability in biofuel cells and electrochemical microbial biosensors. The wild type strain ATCC 17015 and mutant strain 37b4 lacking the lipopolysaccharide capsule was compared for their ability to communicate with electrodes modified with an osmium redox polymer. In this work, aerobic heterotrophically grown R. capsulatus were used to screen for efficient cell-electrode communication for later implementation using photoheterotrophically grown bacteria. The bacterial cells embedded in the osmium polymer matrix demonstrated efficient electrical "wiring" with the electrodes and were able to generate a noticeable current with succinate as substrate. Interestingly, at 2mM succinate the wild type strain showed much better bioelectrocatalytic current generation (4.25 μA/cm(2)) than the strain lacking capsule (1.55 μA/cm(2)). The wild type strain also exhibited a stable current response for longer time, demonstrating that the bacterial lipopolysaccharide in fact enhances the stability of the polymer matrix layer of the modified electrode. Control experiments with R. capsulatus without any mediator did not show any current irrespective of the capsule presence. This demonstrates that development of photosensors and other light driven bioelectrochemical devices could be feasible using R. capsulatus and will be at focus for future studies.

  2. Iridium- and Osmium-decorated Reduced Graphenes as Promising Catalysts for Hydrogen Evolution.

    PubMed

    Lim, Chee Shan; Sofer, Zdeněk; Toh, Rou Jun; Eng, Alex Yong Sheng; Luxa, Jan; Pumera, Martin

    2015-06-22

    Renewable energy sources are highly sought after as a result of numerous worldwide problems concerning the environment and the shortage of energy. Currently, the focus in the field is on the development of catalysts that are able to provide water splitting catalysis and energy storage for the hydrogen evolution reaction (HER). While platinum is an excellent material for HER catalysis, it is costly and rare. In this work, we investigated the electrocatalytic abilities of various graphene-metal hybrids to replace platinum for the HER. The graphene materials were doped with 4f metals, namely, iridium, osmium, platinum and rhenium, as well as 3d metals, namely, cobalt, iron and manganese. We discovered that a few hybrids, in particular iridium- and osmium-doped graphenes, have the potential to become competent electrocatalysts owing to their low costs and-more importantly-to their promising electrochemical performances towards the HER. One of the more noteworthy observations of this work is the superiority of these two hybrids over MoS2 , a well-known electrocatalyst for the HER. PMID:25908556

  3. Osmium-Based Pyrimidine Contrast Tags for Enhanced Nanopore-Based DNA Base Discrimination.

    PubMed

    Henley, Robert Y; Vazquez-Pagan, Ana G; Johnson, Michael; Kanavarioti, Anastassia; Wanunu, Meni

    2015-01-01

    Nanopores are a promising platform in next generation DNA sequencing. In this platform, an individual DNA strand is threaded into nanopore using an electric field, and enzyme-based ratcheting is used to move the strand through the detector. During this process the residual ion current through the pore is measured, which exhibits unique levels for different base combinations inside the pore. While this approach has shown great promise, accuracy is not optimal because the four bases are chemically comparable to one another, leading to small differences in current obstruction. Nucleobase-specific chemical tagging can be a viable approach to enhancing the contrast between different bases in the sequence. Herein we show that covalent modification of one or both of the pyrimidine bases by an osmium bipyridine complex leads to measureable differences in the blockade amplitudes of DNA molecules. We qualitatively determine the degree of osmylation of a DNA strand by passing it through a solid-state nanopore, and are thus able to gauge T and C base content. In addition, we show that osmium bipyridine reacts with dsDNA, leading to substantially different current blockade levels than exhibited for bare dsDNA. This work serves as a proof of principle for nanopore sequencing and mapping via base-specific DNA osmylation. PMID:26657869

  4. Aerobic Oxidation of an Osmium(III) N-Hydroxyguanidine Complex To Give Nitric Oxide.

    PubMed

    Xiang, Jing; Wang, Qian; Yiu, Shek-Man; Man, Wai-Lun; Kwong, Hoi-Ki; Lau, Tai-Chu

    2016-05-16

    The aerobic oxidation of the N-hydroxyguanidinum moiety of N-hydroxyarginine to NO is a key step in the biosynthesis of NO by the enzyme nitric oxide synthase (NOS). So far, there is no chemical system that can efficiently carry out similar aerobic oxidation to give NO. We report here the synthesis and X-ray crystal structure of an osmium(III) N-hydroxyguanidine complex, mer-[Os(III){NH═C(NH2)(NHOH)}(L)(CN)3](-) (OsGOH, HL = 2-(2-hydroxyphenyl)benzoxazole), which to the best of our knowledge is the first example of a transition metal N-hydroxyguanidine complex. More significantly, this complex readily undergoes aerobic oxidation at ambient conditions to generate NO. The oxidation is pH-dependent; at pH 6.8, fac-[Os(NO)(L)(CN)3](-) is formed in which the NO produced is bound to the osmium center. On the other hand, at pH 12, aerobic oxidation of OsGOH results in the formation of the ureato complex [Os(III)(NHCONH2)(L)(CN)3](2-) and free NO. Mechanisms for this aerobic oxidation at different pH values are proposed. PMID:27135258

  5. Enhanced multiplexing in mass cytometry using osmium and ruthenium tetroxide species.

    PubMed

    Catena, Raúl; Özcan, Alaz; Zivanovic, Nevena; Bodenmiller, Bernd

    2016-05-01

    Mass cytometry facilitates high-dimensional, quantitative, single-cell analysis. The method for sample multiplexing in mass cytometry, called mass-tag cellular barcoding (MCB), relies on the covalent reaction of bifunctional metal chelators with intracellular proteins. Here, we describe the use of osmium and ruthenium tetroxides (OsO4 and RuO4 ) that bind covalently with fatty acids in the cellular membranes and aromatic amino acids in proteins. Both OsO4 and RuO4 rapidly reacted and allowed for MCB with live cells, crosslinked cells, and permeabilized cells. Given the covalent nature of the labeling reaction, isotope leaching was not observed. OsO4 and RuO4 were used in a 20-sample barcoding protocol together with palladium isotopes. As mass channels occupied by osmium and ruthenium are not used for antibody detection the number of masses effectively utilized in a single experiment is expanded. OsO4 and RuO4 can therefore be used as MCB reagents for a wide range of mass cytometry workflows. © 2016 International Society for Advancement of Cytometry. PMID:27018769

  6. The effect of core level crossing on the high-pressure equation of state of osmium

    NASA Astrophysics Data System (ADS)

    Wills, John

    2015-03-01

    The equation of state of the 5d transition metal osmium has been studied with a combination of experiment and theory at pressures up to 500 GPa. The experimental results show a c/a ratio increasing by approximately 1 percent over this pressure range and displaying anomalies at pressures near 180 GPa and near 400 GPa. We have use all-electron fully relativistic density functional theory (DFT) calculations to study the cold equation of state and structural parameters of osmium at pressures up to 500 GPa, using one LDA and two GGA functionals. The increase in the c/a ratio agrees well with experiment, and we find anomalies, although less extreme, near the experimentally observed pressures. We find that the high pressure anomaly coincides with the crossing and hybridization of the 4f(7/2) and 5p(3/2) semi-core levels. In this talk we discuss the theoretical results and methodology and the possible implication for the equations of state of the 5d transition and actinide metals.

  7. A New Lifshitz Transition and the Equation of State of Osmium

    SciTech Connect

    Occelli, F; Aracne, C M; Teter, D M; Hanfland, M; Canny, B; Couzinet, B; Chervin, J; Badro, J; Farber, D L

    2003-11-05

    We have measured the equation of state (EoS) of osmium to 75 GPa under hydrostatic conditions at room temperature using angle dispersive x-ray diffraction. A least-squares fit of the data using a third order Birch-Murnaghan EoS yields K{sub 0} = 411 {+-} 6 GPa and K'{sub 0} = 4.0 {+-} 0.2, showing osmium is in fact more compressible than diamond. Most importantly, we have documented an anomaly in the compressibility at 20.3 GPa associated with a large discontinuity in the first pressure derivative of the c/a ratio. This discontinuity likely arises from the collapse of the small hole-ellipsoid in the Fermi surface near the L point. There has been much interest in the possibility of a Lifshitz [1] or electronic topological transition (ETT) in zinc at high-pressure near 10 GPa. Interestingly, while the experimental data remain somewhat ambiguous [2-5], most simulations suggest the ETT exists in this pressure range [6-8]. Recently, Steinle-Neumann et al. [8] have shown that the transition arises from changes in the band structure near the high-symmetry point K where three bands cross the Fermi surface upon compression. Thus one might expect that other hcp metals should exhibit similar phenomena. The hcp 4d and 5d transition elements Re, Os and Ru are known to be among the densest and stiffest metals [9,10] suggesting that these might in fact be poor candidates in which to look for such effects. In osmium however, experimental and theoretical results [11,12] have shown the existence of small local maxima in the band structure just above the Fermi energy near the high-symmetry point L on the zone boundary [11]. These structures might potentially fall below the Fermi energy upon compression and give rise to an ETT. Osmium is of further interest as recent EoS measurements by Cynn et al. [13] have suggested that Os (K{sub 0} = 462 GPa and K'{sub 0} = 2.4) has the lowest known compressibility, lower even than diamond (K{sub 0} = 446 GPa and K'{sub 0} = 3) [14]. This

  8. Correction: Unexpected higher stabilisation of two classical antiaromatic frameworks with a ruthenium fragment compared to the osmium counterpart: origin probed by DFT calculations.

    PubMed

    Wu, Jingjing; Hao, Yulei; An, Ke; Zhu, Jun

    2016-01-25

    Correction for 'Unexpected higher stabilisation of two classical antiaromatic frameworks with a ruthenium fragment compared to the osmium counterpart: origin probed by DFT calculations' by Jingjing Wu et al., Chem. Commun., 2016, 52, 272-275. PMID:26699929

  9. Transition Metal Phosphide Nanoparticles Supported on SBA-15 as Highly Selective Hydrodeoxygenation Catalysts for the Production of Advanced Biofuels.

    PubMed

    Yang, Yongxing; Ochoa-Hernández, Cristina; de la Peña O'Shea, Víctor A; Pizarro, Patricia; Coronado, Juan M; Serrano, David P

    2015-09-01

    A series of catalysts constituted by nanoparticles of transition metal (M = Fe, Co, Ni and Mo) phosphides (TMP) dispersed on SBA-15 were synthesized by reduction of the corresponding metal phosphate precursors previously impregnated on the mesostructured support. All the samples contained a metal-loading of 20 wt% and with an initial M/P mole ratio of 1, and they were characterized by X-ray diffraction (XRD), N2 sorption, H2-TPR and transmission electron microscopy (TEM). Metal phosphide nanocatalysts were tested in a high pressure continuous flow reactor for the hydrodeoxygenation (HDO) of a methyl ester blend containing methyl oleate (C17H33-COO-CH3) as main component (70%). This mixture constitutes a convenient surrogate of triglycerides present in vegetable oils, and following catalytic hydrotreating yields mainly n-alkanes. The results of the catalytic assays indicate that Ni2P/SBA-15 catalyst presents the highest ester conversion, whereas the transformation rate is about 20% lower for MoP/SBA-15. In contrast, catalysts based on Fe and Co phosphides show a rather limited activity. Hydrocarbon distribution in the liquid product suggests that both hydrodeoxygenation and decarboxylation/decarbonylation reactions occur simultaneously over the different catalysts, although MoP/SBA-15 possess a selectivity towards hydrodeoxygenation exceeding 90%. Accordingly, the catalyst based on MoP affords the highest yield of n-octadecane, which is the preferred product in terms of carbon atom economy. Subsequently, in order to conjugate the advantages of both Ni and Mo phosphides, a series of catalysts containing variable proportions of both metals were prepared. The obtained results reveal that the mixed phosphides catalysts present a catalytic behavior intermediate between those of the monometallic phosphides. Accordingly, only marginal enhancement of the yield of n-octadecane is obtained for the catalysts with a Mo/Ni ratio of 3. Nevertheless, owing to this high selectivity

  10. Transition Metal Phosphide Nanoparticles Supported on SBA-15 as Highly Selective Hydrodeoxygenation Catalysts for the Production of Advanced Biofuels.

    PubMed

    Yang, Yongxing; Ochoa-Hernández, Cristina; de la Peña O'Shea, Víctor A; Pizarro, Patricia; Coronado, Juan M; Serrano, David P

    2015-09-01

    A series of catalysts constituted by nanoparticles of transition metal (M = Fe, Co, Ni and Mo) phosphides (TMP) dispersed on SBA-15 were synthesized by reduction of the corresponding metal phosphate precursors previously impregnated on the mesostructured support. All the samples contained a metal-loading of 20 wt% and with an initial M/P mole ratio of 1, and they were characterized by X-ray diffraction (XRD), N2 sorption, H2-TPR and transmission electron microscopy (TEM). Metal phosphide nanocatalysts were tested in a high pressure continuous flow reactor for the hydrodeoxygenation (HDO) of a methyl ester blend containing methyl oleate (C17H33-COO-CH3) as main component (70%). This mixture constitutes a convenient surrogate of triglycerides present in vegetable oils, and following catalytic hydrotreating yields mainly n-alkanes. The results of the catalytic assays indicate that Ni2P/SBA-15 catalyst presents the highest ester conversion, whereas the transformation rate is about 20% lower for MoP/SBA-15. In contrast, catalysts based on Fe and Co phosphides show a rather limited activity. Hydrocarbon distribution in the liquid product suggests that both hydrodeoxygenation and decarboxylation/decarbonylation reactions occur simultaneously over the different catalysts, although MoP/SBA-15 possess a selectivity towards hydrodeoxygenation exceeding 90%. Accordingly, the catalyst based on MoP affords the highest yield of n-octadecane, which is the preferred product in terms of carbon atom economy. Subsequently, in order to conjugate the advantages of both Ni and Mo phosphides, a series of catalysts containing variable proportions of both metals were prepared. The obtained results reveal that the mixed phosphides catalysts present a catalytic behavior intermediate between those of the monometallic phosphides. Accordingly, only marginal enhancement of the yield of n-octadecane is obtained for the catalysts with a Mo/Ni ratio of 3. Nevertheless, owing to this high selectivity

  11. Strain tunable electronic and magnetic properties of pristine and semihydrogenated hexagonal boron phosphide

    SciTech Connect

    Yu, Jin; Guo, Wanlin

    2015-01-26

    Tunable electromagnetic properties of pristine two-dimensional boron phosphide (h-BP) nanosheet and its semihydrogenated structure were studied by density functional theory computations. In sharp contrast to previously reported tensile strain-induced red shift in two-dimensional semiconductors, the direct gap of h-BP undergoes blue shift under biaxial tensile strain. Once semihydrogenated, the h-BP not only transform from the nonmagnetic semiconductor into metal which is spin-resolved but also exhibits linear response between the magnetic moment and biaxial strain with a slope up to 0.005 μB/1%. These findings provide a simple and effective route to tune the electronic and magnetic properties of h-BP nanostructures in a wide range and should inspire experimental enthusiasm.

  12. Indium phosphide solar cells: status and prospects for use in space

    NASA Technical Reports Server (NTRS)

    Weinberg, I.; Brinker, D. J.

    1986-01-01

    The current status of indium phosphide cell research is reviewed and state of the art efficiencies compared to those of GaAs and Si. It is shown that the radiation resistance of InP cells is superior to that of either GaAs or Si under 1 MeV electron and 10 MeV proton irradiation. Using lightweight blanket technology, a SEP array structure and projected cell efficiencies, array specific powers are obtained for all three cell types. Array performance is calculated as a function of time in orbit. The results indicate that arrays using InP cells can outperform those using GaAs or Si in orbits where radiation is a significant cell degradation factor. It is concluded that InP solar cells are excellent prospects for future use in the space radiation environment.

  13. The metal-rich sulfides and phosphides of the early transition metals

    SciTech Connect

    Franzen, H.F. |

    1996-06-01

    Early work on the preparation of refractory metal-rich compounds of the early transition metals resulted in the understanding that metal-metal bonding results in a structural variety that plays an important role in the high-temperature chemistry of these systems. The binary metal-rich systems have been thoroughly studied at high temperatures, and the structures of most, if not all, of the refractory sulfides and phosphides are known. More recently new ternary phases have been discovered, and these have been shown to result from distributed fractional site occupation of metal atom sites in complex structures. The extent of metal-metal bonding has been quantified by Extended-Hueckel Tight-Bonding calculations using Mullikan Overlap Populations. Correlations of site occupancy with MOP based upon the DFSO model have been observed. 44 refs.

  14. Sc-Sc bonding in the new ternary phosphide ScNiP

    SciTech Connect

    Kleinke, H.; Franzen, H.F.

    1998-05-01

    The new phosphide ScNiP can be synthesized by arc-melting of ScP and Ni, or by arc-melting of Sc with NiP. The lattice constants, as obtained from the bulk sample, are a = 6.3343(8) {angstrom}, b = 3.7375(7) {angstrom}, c = 7.0917(8), and V = 167.89(4) {angstrom}{sup 3}. ScNiP crystallizes in the Co{sub 2}Si structure type. Although one might assign the trivalent state to Sc, corresponding to a formal ionic formula of Sc{sup 3+}Ni{sup {+-}0}P{sup 3{minus}}, the structure of ScNiP contains Sc-Sc bonds and shows weak metallic properties, as expected based on extended Hueckel calculations.

  15. Molybdenum Disulfide as a Protection Layer and Catalyst for Gallium Indium Phosphide Solar Water Splitting Photocathodes.

    PubMed

    Britto, Reuben J; Benck, Jesse D; Young, James L; Hahn, Christopher; Deutsch, Todd G; Jaramillo, Thomas F

    2016-06-01

    Gallium indium phosphide (GaInP2) is a semiconductor with promising optical and electronic properties for solar water splitting, but its surface stability is problematic as it undergoes significant chemical and electrochemical corrosion in aqueous electrolytes. Molybdenum disulfide (MoS2) nanomaterials are promising to both protect GaInP2 and to improve catalysis because MoS2 is resistant to corrosion and also possesses high activity for the hydrogen evolution reaction (HER). In this work, we demonstrate that GaInP2 photocathodes coated with thin MoS2 surface protecting layers exhibit excellent activity and stability for solar hydrogen production, with no loss in performance (photocurrent onset potential, fill factor, and light-limited current density) after 60 h of operation. This represents a 500-fold increase in stability compared to bare p-GaInP2 samples tested in identical conditions. PMID:27196435

  16. Synthesis and Superconducting Properties of a Hexagonal Phosphide ScRhP

    NASA Astrophysics Data System (ADS)

    Inohara, Takumi; Okamoto, Yoshihiko; Yamakawa, Youichi; Takenaka, Koshi

    2016-09-01

    We report the synthesis and superconducting properties of the ternary phosphide ScRhP. The crystal structure of ScRhP is determined to be the ordered Fe2P type with the hexagonal Pbar{6}2m space group by powder X-ray diffraction experiments. Resistivity, magnetization, and heat capacity data indicate that ScRhP is a bulk superconductor with a transition temperature Tc of 2 K. This Tc is lower than that of its 5d analogue, ScIrP (Tc = 3.4 K), although ScRhP is found to have larger electronic density of states at the Fermi energy and a higher Debye temperature than those of ScIrP.

  17. Treatment of Aluminium Phosphide Poisoning with a Combination of Intravenous Glucagon, Digoxin and Antioxidant Agents

    PubMed Central

    Oghabian, Zohreh; Mehrpour, Omid

    2016-01-01

    Aluminium phosphide (AlP) is used to protect stored grains from rodents. It produces phosphine gas (PH3), a mitochondrial poison thought to cause toxicity by blocking the cytochrome c oxidase enzyme and inhibiting oxidative phosphorylation, which results in cell death. AlP poisoning has a high mortality rate among humans due to the rapid onset of cardiogenic shock and metabolic acidosis, despite aggressive treatment. We report a 21-year-old male who was referred to the Afzalipour Hospital, Kerman, Iran, in 2015 after having intentionally ingested a 3 g AlP tablet. He was successfully treated with crystalloid fluids, vasopressors, sodium bicarbonate, digoxin, glucagon and antioxidant agents and was discharged from the hospital six days after admission in good clinical condition. For the treatment of AlP poisoning, the combination of glucagon and digoxin with antioxidant agents should be considered. However, evaluation of further cases is necessary to optimise treatment protocols.

  18. Effect of InAlAs window layer on efficiency of indium phosphide solar cells

    NASA Technical Reports Server (NTRS)

    Jain, Raj K.; Landis, Geoffrey A.

    1992-01-01

    Indium phosphide (InP) solar cell efficiencies are limited by surface recombination. The effect of a wide bandgap, lattice-matched indium aluminum arsenide (In(0.52)Al(0.48)As) window layer on the performance of InP solar cells was investigated by using the numerical code PC-1D. The p(+)n InP solar cell performance improved significantly with the use of the window layer. No improvement was seen for the n(+)p InP cells. The cell results were explained by the band diagram of the heterostructure and the conduction band energy discontinuity. The calculated current voltage and internal quantum efficiency results clearly demonstrated that In(0.52)Al(0.48)As is a very promising candidate for a window layer material for p(+)n InP solar cells.

  19. Molybdenum Disulfide as a Protection Layer and Catalyst for Gallium Indium Phosphide Solar Water Splitting Photocathodes.

    PubMed

    Britto, Reuben J; Benck, Jesse D; Young, James L; Hahn, Christopher; Deutsch, Todd G; Jaramillo, Thomas F

    2016-06-01

    Gallium indium phosphide (GaInP2) is a semiconductor with promising optical and electronic properties for solar water splitting, but its surface stability is problematic as it undergoes significant chemical and electrochemical corrosion in aqueous electrolytes. Molybdenum disulfide (MoS2) nanomaterials are promising to both protect GaInP2 and to improve catalysis because MoS2 is resistant to corrosion and also possesses high activity for the hydrogen evolution reaction (HER). In this work, we demonstrate that GaInP2 photocathodes coated with thin MoS2 surface protecting layers exhibit excellent activity and stability for solar hydrogen production, with no loss in performance (photocurrent onset potential, fill factor, and light-limited current density) after 60 h of operation. This represents a 500-fold increase in stability compared to bare p-GaInP2 samples tested in identical conditions.

  20. Treatment of Aluminium Phosphide Poisoning with a Combination of Intravenous Glucagon, Digoxin and Antioxidant Agents

    PubMed Central

    Oghabian, Zohreh; Mehrpour, Omid

    2016-01-01

    Aluminium phosphide (AlP) is used to protect stored grains from rodents. It produces phosphine gas (PH3), a mitochondrial poison thought to cause toxicity by blocking the cytochrome c oxidase enzyme and inhibiting oxidative phosphorylation, which results in cell death. AlP poisoning has a high mortality rate among humans due to the rapid onset of cardiogenic shock and metabolic acidosis, despite aggressive treatment. We report a 21-year-old male who was referred to the Afzalipour Hospital, Kerman, Iran, in 2015 after having intentionally ingested a 3 g AlP tablet. He was successfully treated with crystalloid fluids, vasopressors, sodium bicarbonate, digoxin, glucagon and antioxidant agents and was discharged from the hospital six days after admission in good clinical condition. For the treatment of AlP poisoning, the combination of glucagon and digoxin with antioxidant agents should be considered. However, evaluation of further cases is necessary to optimise treatment protocols. PMID:27606117

  1. Treatment of Aluminium Phosphide Poisoning with a Combination of Intravenous Glucagon, Digoxin and Antioxidant Agents.

    PubMed

    Oghabian, Zohreh; Mehrpour, Omid

    2016-08-01

    Aluminium phosphide (AlP) is used to protect stored grains from rodents. It produces phosphine gas (PH3), a mitochondrial poison thought to cause toxicity by blocking the cytochrome c oxidase enzyme and inhibiting oxidative phosphorylation, which results in cell death. AlP poisoning has a high mortality rate among humans due to the rapid onset of cardiogenic shock and metabolic acidosis, despite aggressive treatment. We report a 21-year-old male who was referred to the Afzalipour Hospital, Kerman, Iran, in 2015 after having intentionally ingested a 3 g AlP tablet. He was successfully treated with crystalloid fluids, vasopressors, sodium bicarbonate, digoxin, glucagon and antioxidant agents and was discharged from the hospital six days after admission in good clinical condition. For the treatment of AlP poisoning, the combination of glucagon and digoxin with antioxidant agents should be considered. However, evaluation of further cases is necessary to optimise treatment protocols. PMID:27606117

  2. High-efficiency indium tin oxide/indium phosphide solar cells

    NASA Technical Reports Server (NTRS)

    Li, X.; Wanlass, M. W.; Gessert, T. A.; Emery, K. A.; Coutts, T. J.

    1989-01-01

    Improvements in the performance of indium tin oxide (ITO)/indium phosphide solar cells have been realized by the dc magnetron sputter deposition of n-ITO onto an epitaxial p/p(+) structure grown on commercial p(+) bulk substrates. The highest efficiency cells were achieved when the surface of the epilayer was exposed to an Ar/H2 plasma before depositing the bulk of the ITO in a more typical Ar/O2 plasma. With H2 processing, global efficiencies of 18.9 percent were achieved. It is suggested that the excellent performance of these solar cells results from the optimization of the doping, thickness, transport, and surface properties of the p-type base, as well as from better control over the ITO deposition procedure.

  3. Effect of emitter parameter variation on the performance of heteroepitaxial indium phosphide solar cells

    NASA Technical Reports Server (NTRS)

    Jain, Raj K.; Flood, Dennis J.

    1990-01-01

    Metallorganic chemical-vapor-deposited heteroepitaxial indium phosphide (InP) solar cell experimental results were simulated by using a PC-1D computer model. The effect of emitter parameter variation on the performance of n(+)/p/p(+) heteroepitaxial InP/GaAs solar cell was presented. The thinner and lighter doped emitters were observed to offer higher cell efficiencies. The influence of emitter thickness and minority carrier diffusion length on the cell efficiency with respect to dislocation density was studied. Heteroepitaxial cells with efficiencies similar to present day homojunction InP efficiencies (greater than 16 percent AMO) were shown to be attainable if a dislocation density lower than 10(exp 6)/sq cm could be achieved. A realistic optimized design study yielded InP solar cells of over 22 percent AMO efficiency at 25 C.

  4. Effect of InAlAs window layer on the efficiency of indium phosphide solar cells

    NASA Technical Reports Server (NTRS)

    Jain, R. K.; Landis, G. A.

    1991-01-01

    Indium phosphide (InP) solar cell efficiencies are limited by surface recombination. The effect of a wide-bandgap lattice-matched indium aluminum arsenide (In0.52Al0.48As) window layer on the performance of InP solar cells was investigated using a numerical code PC-1D. The p(+)n InP solar cell performance improves significantly with the use of a window layer. No improvement is seen for n(+)p InP cells. Cell results are explained by the band diagram of the heterostructure and the conduction-band energy discontinuity. The calculated I-V and internal quantum efficiency results clearly demonstrate that In0.52Al0.48As is a promising candidate as a window layer material for p(+)n InP solar cells.

  5. Effect of emitter parameter variation on the performance of heteroepitaxial indium phosphide solar cells

    NASA Technical Reports Server (NTRS)

    Jain, R. K.; Flood, D. J.

    1990-01-01

    Metalorganic chemical-vapor-deposited heteroepitaxial indium phosphide (InP) solar cell experimental results were simulated by using a PC-1D computer model. The effect of emitter parameter variation on the performance of n(+)/p/p(+) heteroepitaxial InP/GaAs solar cell was presented. The thinner and lighter doped emitters were observed to offer higher cell efficiencies. The influence of emitter thickness and minority carrier diffusion length on the cell efficiency with respect to dislocation density was studied. Heteroepitaxial cells with efficiencies similar to present day homojunction InP efficiencies (greaater than 16 percent AM0) were shown to be attainable if a dislocation density lower than 10(exp 6)/sq cm could be achieved. A realistic optimized design study yielded InP solar cells of over 22 percent AM0 efficiency at 25 C.

  6. An approach to preparing porous and hollow metal phosphides with higher hydrodesulfurization activity

    NASA Astrophysics Data System (ADS)

    Song, Limin; Zhang, Shujuan; Wei, Qingwu

    2011-06-01

    This paper describes an effective method for the synthesis of metal phosphides. Bulk and supported Ni 2P, Cu 3P, and CoP were prepared by thermal treatment of metal and the amorphous red phosphorus mixtures. Porous and hollow Ni 2P particles were also synthesized successfully using this method. The structural properties of these products are investigated using X-ray powder diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM), inductively coupled plasma (ICP-AES) and X-ray photoemission spectroscopy (XPS). A rational mechanism was proposed for the selective formation of Ni 2P particles. In experimental conditions, the Ni 2P/SiO 2 catalyst exhibits excellent hydrodesulfurization (HDS) activity for dibenzothiophene (DBT).

  7. Ab-initio calculations of electronic, transport, and structural properties of boron phosphide

    SciTech Connect

    Ejembi, J. I.; Nwigboji, I. H.; Franklin, L.; Malozovsky, Y.; Zhao, G. L.; Bagayoko, D.

    2014-09-14

    We present results from ab-initio, self-consistent density functional theory calculations of electronic and related properties of zinc blende boron phosphide (zb-BP). We employed a local density approximation potential and implemented the linear combination of atomic orbitals formalism. This technique follows the Bagayoko, Zhao, and Williams method, as enhanced by the work of Ekuma and Franklin. The results include electronic energy bands, densities of states, and effective masses. The calculated band gap of 2.02 eV, for the room temperature lattice constant of a=4.5383 Å, is in excellent agreement with the experimental value of 2.02±0.05 eV. Our result for the bulk modulus, 155.7 GPa, agrees with experiment (152–155 GPa). Our predictions for the equilibrium lattice constant and the corresponding band gap, for very low temperatures, are 4.5269 Å and 2.01 eV, respectively.

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

    Code of Federal Regulations, 2012 CFR

    2012-01-01

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

  9. 16 CFR 23.7 - Misuse of the words “platinum,” “iridium,” “palladium,” “ruthenium,” “rhodium,” and “osmium.”

    Code of Federal Regulations, 2011 CFR

    2011-01-01

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

  10. 16 CFR 23.7 - Misuse of the words “platinum,” “iridium,” “palladium,” “ruthenium,” “rhodium,” and “osmium.”

    Code of Federal Regulations, 2014 CFR

    2014-01-01

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

  11. 16 CFR 23.7 - Misuse of the words “platinum,” “iridium,” “palladium,” “ruthenium,” “rhodium,” and “osmium.”

    Code of Federal Regulations, 2010 CFR

    2010-01-01

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

  12. 16 CFR 23.7 - Misuse of the words “platinum,” “iridium,” “palladium,” “ruthenium,” “rhodium,” and “osmium.”

    Code of Federal Regulations, 2013 CFR

    2013-01-01

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

  13. Phosphorus-Rich Copper Phosphide Nanowires for Field-Effect Transistors and Lithium-Ion Batteries.

    PubMed

    Li, Guo-An; Wang, Chiu-Yen; Chang, Wei-Chung; Tuan, Hsing-Yu

    2016-09-27

    Phosphorus-rich transition metal phosphide CuP2 nanowires were synthesized with high quality and high yield (∼60%) via the supercritical fluid-liquid-solid (SFLS) growth at 410 °C and 10.2 MPa. The obtained CuP2 nanowires have a high aspect ratio and exhibit a single crystal structure of monoclinic CuP2 without any impurity phase. CuP2 nanowires have progressive improvement for semiconductors and energy storages compared with bulk CuP2. Being utilized for back-gate field effect transistor (FET) measurement, CuP2 nanowires possess a p-type behavior intrinsically with an on/off ratio larger than 10(4) and its single nanowire electrical transport property exhibits a hole mobility of 147 cm(2) V(-1) s(-1), representing the example of a CuP2 transistor. In addition, CuP2 nanowires can serve as an appealing anode material for a lithium-ion battery electrode. The discharge capacity remained at 945 mA h g(-1) after 100 cycles, showing a good capacity retention of 88% based on the first discharge capacity. Even at a high rate of 6 C, the electrode still exhibited an outstanding result with a capacity of ∼600 mA h g(-1). Ex-situ transmission electron microscopy and CV tests demonstrate that the stability of capacity retention and remarkable rate capability of the CuP2 nanowires electrode are attributed to the role of the metal phosphide conversion-type lithium storage mechanism. Finally, CuP2 nanowire anodes and LiFePO4 cathodes were assembled into pouch-type lithium batteries offering a capacity over 60 mA h. The full cell shows high capacity and stable capacity retention and can be used as an energy supply to operate electronic devices such as mobile phones and mini 4WD cars. PMID:27603024

  14. Process Development of Gallium Nitride Phosphide Core-Shell Nanowire Array Solar Cell

    NASA Astrophysics Data System (ADS)

    Chuang, Chen

    Dilute Nitride GaNP is a promising materials for opto-electronic applications due to its band gap tunability. The efficiency of GaNxP1-x /GaNyP1-y core-shell nanowire solar cell (NWSC) is expected to reach as high as 44% by 1% N and 9% N in the core and shell, respectively. By developing such high efficiency NWSCs on silicon substrate, a further reduction of the cost of solar photovoltaic can be further reduced to 61$/MWh, which is competitive to levelized cost of electricity (LCOE) of fossil fuels. Therefore, a suitable NWSC structure and fabrication process need to be developed to achieve this promising NWSC. This thesis is devoted to the study on the development of fabrication process of GaNxP 1-x/GaNyP1-y core-shell Nanowire solar cell. The thesis is divided into two major parts. In the first parts, previously grown GaP/GaNyP1-y core-shell nanowire samples are used to develop the fabrication process of Gallium Nitride Phosphide nanowire solar cell. The design for nanowire arrays, passivation layer, polymeric filler spacer, transparent col- lecting layer and metal contact are discussed and fabricated. The property of these NWSCs are also characterized to point out the future development of Gal- lium Nitride Phosphide NWSC. In the second part, a nano-hole template made by nanosphere lithography is studied for selective area growth of nanowires to improve the structure of core-shell NWSC. The fabrication process of nano-hole templates and the results are presented. To have a consistent features of nano-hole tem- plate, the Taguchi Method is used to optimize the fabrication process of nano-hole templates.

  15. Phosphorus-Rich Copper Phosphide Nanowires for Field-Effect Transistors and Lithium-Ion Batteries.

    PubMed

    Li, Guo-An; Wang, Chiu-Yen; Chang, Wei-Chung; Tuan, Hsing-Yu

    2016-09-27

    Phosphorus-rich transition metal phosphide CuP2 nanowires were synthesized with high quality and high yield (∼60%) via the supercritical fluid-liquid-solid (SFLS) growth at 410 °C and 10.2 MPa. The obtained CuP2 nanowires have a high aspect ratio and exhibit a single crystal structure of monoclinic CuP2 without any impurity phase. CuP2 nanowires have progressive improvement for semiconductors and energy storages compared with bulk CuP2. Being utilized for back-gate field effect transistor (FET) measurement, CuP2 nanowires possess a p-type behavior intrinsically with an on/off ratio larger than 10(4) and its single nanowire electrical transport property exhibits a hole mobility of 147 cm(2) V(-1) s(-1), representing the example of a CuP2 transistor. In addition, CuP2 nanowires can serve as an appealing anode material for a lithium-ion battery electrode. The discharge capacity remained at 945 mA h g(-1) after 100 cycles, showing a good capacity retention of 88% based on the first discharge capacity. Even at a high rate of 6 C, the electrode still exhibited an outstanding result with a capacity of ∼600 mA h g(-1). Ex-situ transmission electron microscopy and CV tests demonstrate that the stability of capacity retention and remarkable rate capability of the CuP2 nanowires electrode are attributed to the role of the metal phosphide conversion-type lithium storage mechanism. Finally, CuP2 nanowire anodes and LiFePO4 cathodes were assembled into pouch-type lithium batteries offering a capacity over 60 mA h. The full cell shows high capacity and stable capacity retention and can be used as an energy supply to operate electronic devices such as mobile phones and mini 4WD cars.

  16. Materials Development for Boron Phosphide Based Neutron Detectors: Final Technical Report

    SciTech Connect

    Edgar, James Howard

    2014-09-12

    The project goal was to improve the quality of boron phosphide (BP) by optimizing its epitaxial growth on single crystal substrates and by producing bulk BP single crystals with low dislocation densities. BP is potentially a good semiconductor for high efficiency solid state neutron detectors by combining neutron capture and charge creation within the same volume. The project strategy was to use newly available single crystal substrates, silicon carbide and aluminum nitride, engineered to produce the best film properties. Substrate variables included the SiC polytype, crystallographic planes, misorientation of the substrate surface (tilt direction and magnitude) from the major crystallographic plane, and surface polarity (Si and C). The best films were (111)BP on silicon-face (0001) 4H-SiC misoriented 4° in the [1-100] direction, and BP on (100) and (111) 3C-SiC/Si; these substrates resulted in films that were free of in-plane twin defects, as determined by x-ray topography. The impact of the deposition temperature was also assessed: increasing the temperature from 1000 °C to 1200 °C produced films that were more ordered and more uniform, and the size of individual grains increased by more than a factor of twenty. The BP films were free of other compounds such as icosahedral boron phosphide (B12P2) over the entire temperature range, as established by Raman spectroscopy. The roughness of the BP films was reduced by increasing the phosphine to diborane ratio from 50 to 200. Bulk crystals were grown by reacting boron dissolved in nickel with phosphorus vapor to precipitate BP. Crystals with dimensions up to 2 mm were produced.

  17. Striking difference in antiproliferative activity of ruthenium- and osmium-nitrosyl complexes with azole heterocycles.

    PubMed

    Büchel, Gabriel E; Gavriluta, Anatolie; Novak, Maria; Meier, Samuel M; Jakupec, Michael A; Cuzan, Olesea; Turta, Constantin; Tommasino, Jean-Bernard; Jeanneau, Erwann; Novitchi, Ghenadie; Luneau, Dominique; Arion, Vladimir B

    2013-06-01

    Ruthenium nitrosyl complexes of the general formulas (cation)(+)[cis-RuCl4(NO)(Hazole)](-), where (cation)(+) = (H2ind)(+), Hazole = 1H-indazole (Hind) (1c), (cation)(+) = (H2pz)(+), Hazole = 1H-pyrazole (Hpz) (2c), (cation)(+) = (H2bzim)(+), Hazole = 1H-benzimidazole (Hbzim) (3c), (cation)(+) = (H2im)(+), Hazole = 1H-imidazole (Him) (4c) and (cation)(+)[trans-RuCl4(NO)(Hazole)](-), where (cation)(+) = (H2ind)(+), Hazole = 1H-indazole (1t), (cation)(+) = (H2pz)(+), Hazole = 1H-pyrazole (2t), as well as osmium analogues of the general formulas (cation)(+)[cis-OsCl4(NO)(Hazole)](-), where (cation)(+) = (n-Bu4N)(+), Hazole =1H-indazole (5c), 1H-pyrazole (6c), 1H-benzimidazole (7c), 1H-imidazole (8c), (cation)(+) = Na(+); Hazole =1H-indazole (9c), 1H-benzimidazole (10c), (cation)(+) = (H2ind)(+), Hazole = 1H-indazole (11c), (cation)(+) = H2pz(+), Hazole = 1H-pyrazole (12c), (cation)(+) = (H2im)(+), Hazole = 1H-imidazole (13c), and (cation)(+)[trans-OsCl4(NO)(Hazole)](-), where (cation)(+) = n-Bu4N(+), Hazole = 1H-indazole (5t), 1H-pyrazole (6t), (cation)(+) = Na(+), Hazole = 1H-indazole (9t), (cation)(+) = (H2ind)(+), Hazole = 1H-indazole (11t), (cation)(+) = (H2pz)(+), Hazole = 1H-pyrazole (12t), have been synthesized. The compounds have been comprehensively characterized by elemental analysis, ESI mass spectrometry, spectroscopic techniques (IR, UV-vis, 1D and 2D NMR) and X-ray crystallography (1c·CHCl3, 1t·CHCl3, 2t, 3c, 6c, 6t, 8c). The antiproliferative activity of water-soluble compounds (1c, 1t, 3c, 4c and 9c, 9t, 10c, 11c, 11t, 12c, 12t, 13c) in the human cancer cell lines A549 (nonsmall cell lung carcinoma), CH1 (ovarian carcinoma), and SW480 (colon adenocarcinoma) has been assayed. The effects of metal (Ru vs Os), cis/trans isomerism, and azole heterocycle identity on cytotoxic potency and cell line selectivity have been elucidated. Ruthenium complexes (1c, 1t, 3c, and 4c) yielded IC50 values in the low micromolar concentration range. In contrast to most

  18. Polynuclear ruthenium, osmium and gold complexes. The quest for innovative anticancer chemotherapeutics.

    PubMed

    Hartinger, Christian G; Phillips, Andrew D; Nazarov, Alexey A

    2011-01-01

    Polynuclear compounds are a relatively new and successful approach in metal-based cancer chemotherapy as typified by the trinuclear Pt compound BBR3464 which was evaluated in clinical trials. In this review, we discuss newer developments of polynuclear ruthenium, osmium and gold complexes, focusing on their anticancer activity. The compounds presented are often supposed to exert their anticancer activity by different modes of action as compared to established drugs, including newly proposed mechanisms such as enzyme inhibition, crosslinking of biomacromolecules or through photo-activation, though many of the examples are also capable of binding to DNA nucleobases. Important metabolization and chemical characteristics of such compounds are discussed, and if the appropriate data is available, molecular modes of action are highlighted.

  19. A breast cancer stem cell-selective, mammospheres-potent osmium(VI) nitrido complex.

    PubMed

    Suntharalingam, Kogularamanan; Lin, Wei; Johnstone, Timothy C; Bruno, Peter M; Zheng, Yao-Rong; Hemann, Michael T; Lippard, Stephen J

    2014-10-15

    The effect of a newly developed osmium(VI) nitrido complex, 1, on breast cancer stem cells (CSCs) is reported. The complex displays selective toxicity for HMLER breast cancer cells enriched with CD44-positive, CSC-like cells over the same cells having reduced CSC character. Remarkably, 1 also reduces the proportion of CSCs within a heterogeneous breast cancer cell population and irreversibly inhibits the formation of free-floating mammospheres to an extent similar to that of salinomycin, a natural product that targets CSCs. Detailed mechanistic studies reveal that in breast cancer cells 1 induces DNA damage and endoplasmic reticulum stress, the latter being responsible for the CSC selectivity. The anti-CSC properties of 1 provide a strong impetus for the development of new metal-based compounds to target CSCs and to treat chemotherapy-resistant and relapsed tumors.

  20. Osmium isotopes in Ivory Coast tektites: Confirmation of a meteoritic component and rhenium depletion

    NASA Technical Reports Server (NTRS)

    Koeberl, Christian; Shirey, Steven B.

    1993-01-01

    The sensitive negative thermal ionization mass spectrometry method was used for the measurement of concentrations and isotopic ratios of osmium and rhenium in four Ivory Coast tektites. These tektites have crustal major and trace element composition, as well as large negative epsilon(sub Nd)(-20) and positive epsilon(sub Sr)(+260 to +300) which are characteristic for old continental crust. Os concentrations ranging from 0.09 to 0.30 ppb were found, clearly much higher than average crustal values, Os-187/Os-186 ratios of about 1.2-1.7, and low Re-187/Os-186 ratios. These results show unambiguously the existence of a meteoritic component (on the order of 0.06%) in the Ivory Coast tektites. Low Re abundances are the result of fractionation of Re during the impact.

  1. A Crossover from High Stiffness to High Hardness: The Case of Osmium and Its Borides

    NASA Astrophysics Data System (ADS)

    Bian, Yongming; Liu, Xiaomei; Li, Anhu; Liang, Yongcheng

    2016-09-01

    Transition-metal light-element compounds are currently raising great expectations for hard and superhard materials. Using the widely attracting osmium (Os) and its borides (OsB, Os2B3 and OsB2) as prototypes, we demonstrate by first-principles calculations that heavy transition metals, which possess high stiffness but low hardness, can be converted into highly hard materials by incorporating of light elements to form compounds. Such a crossover is a manifestation that the underlying sources of high stiffness and high hardness are fundamentally different. The stiffness is related to elastic deformation that is closely associated with valence electron density, whereas the hardness depends strongly on plastic deformation that is determined by bonding nature. Therefore, the incorporation of light atoms into transition metal should be a valid pathway of designing hard and superhard materials. This strategy is in principle also applicable to other transition-metal borides, carbides, and nitrides.

  2. A metal-bridged tricyclic aromatic system: synthesis of osmium polycyclic aromatic complexes.

    PubMed

    Zhu, Congqing; Zhu, Qin; Fan, Jinglan; Zhu, Jun; He, Xumin; Cao, Xiao-Yu; Xia, Haiping

    2014-06-10

    Aromaticity is one of the most important concepts in organic chemistry. A variety of metalla-aromatic compounds have been recently prepared and in most of those examples, the metal participates only in a monocyclic ring. In contrast, metal-bridged bicyclic aromatic molecules, in which a metal is shared between two aromatic rings, have been less developed. Herein, we report the first metal-bridged tricyclic aromatic system, in which the metal center is shared by three aromatic five-membered rings. These metalla-aromatics are formed by reaction between osmapentalyne and arene nucleophiles. Experimental results and theoretical calculations reveal that the three five-membered rings around the osmium center are aromatic. In addition, the broad absorption bands in the UV/Vis absorption spectra of these novel aromatic systems cover almost the entire visible region. This straightforward synthetic strategy may be extended to the synthesis of other metal-bridged polycyclic aromatics. PMID:24782397

  3. Mechanism and regioselectivity of the osmium-catalyzed aminohydroxylation of olefins.

    PubMed

    Munz, Dominik; Strassner, Thomas

    2010-03-01

    The mechanism and regioselectivity of the osmium-catalyzed aminohydroxylation of olefins was investigated in detail by density functional theory (B3LYP/6-31G(d)) calculations in the gas phase and with the CPCM-solvent model. A systematic variation of the catalyst system (OsO(4) and various nitrogen sources) and the substrate's electronic situation was conducted. Activation barriers could be correlated to Hammett values and linear Gibbs free energy relations could be determined. Experimental results, which indicated an electronic influence on the regioselectivity, could be confirmed and appear to be predictable. The reaction follows a [3+2] mechanism. We additionally report results on the experimentally observed competing dihydroxylation reaction and the ligand-induced reaction rate acceleration. PMID:20128611

  4. THE FINE STRUCTURE OF CHLOROPLAST STROMA FOLLOWING ALDEHYDE OSMIUM-TETROXIDE FIXATION.

    PubMed

    GUNNING, B E

    1965-01-01

    Markedly improved fixation of leaf tissues is obtained by means of a glutaraldehyde (or acrolein)-osmium tetroxide procedure, as compared with the results of potassium permanganate or osmium tetroxide fixation methods. The procedure has proved useful in all species so far examined. Chloroplasts are particularly well preserved. In this paper details of components of the ground-substance of Avena sativa plastids are presented. They include the following:-(i) The "tromacentre" is an area of aggregated fibrils, each 85 A in diameter, and of uncertain length. Individual fibrils may be composed of subunits. The whole aggregate is usually up to 1 micro in diameter, and is visible in thin sections in the light microcope. It is present at all stages of plastid development, and, under conditions of rapid synthesis in the plastid, it may be up to 2 micro in diameter. Evidence that it is proteinaceous is presented. Osmiophilic globules are often associated with it. (ii) Areas which resemble bacterial and blue-green algal nucleoplasms, containing fibrils approximately 30 A wide. These regions are smaller than the stromacentre and, like that structure, they occur in all stages of plastid development. Unlike it, there are several such areas per chloroplast. (iii) Particles which have some of the morphological and staining characteristics of ribosomes. Present at all stages of development, they are approximately two-thirds the size of the cytoplasmic ribosomes. They can occur in groups, thus resembling polyribosomes. (iv) The remaining material is granular, and may include dissociated portions of stromacentre material. The validity of the observations and their significance is discussed. PMID:14286298

  5. Osmium, ruthenium, iridium and uranium in silicates and chromite from the eastern Bushveld Complex, South Africa

    USGS Publications Warehouse

    Gijbels, R.h.; Millard, H.T.; Desborough, G.A.; Bartel, A.J.

    1974-01-01

    Osmium, ruthenium, iridium and uranium contents were determined in eight ortho pyroxene, seven plagioclase, and three chromite mineral separates from the eastern Bushveld Complex. Neutron activation analysis was used to measure the platinum metals, and uranium was determined by a fission track technique. The platinum metals were found to be present within each mine??ral in the proportions Os:Ru:Ir = 1:7:1, while the concentrations of these metals in the minerals are in the ratios orthopyroxene:plagioclase:chromite = 1:16:700. The concentration of uranium was found to range from 11 to 66 ppb (parts per billion) and not to vary significantly from mineral to mineral. The data for the platinum metals are consistent with a model in which the eastern Bushveld Complex was formed by the fractional crystallization of two separately injected magmas. A computer fit of this model to these data indicates that the initial concentrations of Os, Ru and Ir in the first magma were 0.24, 2.0 and 0.21 ppb and in the second magma were 0.16, 1.1 and 0.18 ppb, respectively. The fit also yields the distribution coefficients for the partitioning between the liquid and cumulus orthopyroxene, cumulus plagioclase and cumulus chromite. These coefficients (mineral/liquid) for osmium are 4.5, 66 and 2700; for ruthenium, they are 5, 65 and 2700; and for iridium, they are 4, 60 and 1600. To make this fit, it was necessary to hypothesize the existence of two types of chromite: one type with a large distribution coefficient, presumably formed as a cumulus phase at high temperature, and another, more prevalent type with a smaller distribution coefficient, which may have been formed by postcumulus growth at a lower temperature. This hypothesis is supported by data for coexisting chromite-silicate pairs, which indicate that the chromite grains expelled these platinum metals as they cooled. ?? 1974.

  6. Structure-activity relationships for organometallic osmium arene phenylazopyridine complexes with potent anticancer activity.

    PubMed

    Fu, Ying; Habtemariam, Abraha; Basri, Aida M B H; Braddick, Darren; Clarkson, Guy J; Sadler, Peter J

    2011-10-28

    We report the synthesis and characterisation of 32 half sandwich phenylazopyridine Os(II) arene complexes [Os(η(6)-arene)(phenylazopyridine)X](+) in which X is chloride or iodide, the arene is p-cymene or biphenyl and the pyridine and phenyl rings contain a variety of substituents (F, Cl, Br, I, CF(3), OH or NO(2)). Ten X-ray crystal structures have been determined. Cytotoxicity towards A2780 human ovarian cancer cells ranges from high potency at nanomolar concentrations to inactivity. In general the introduction of an electron-withdrawing group (e.g. F, Cl, Br or I) at specific positions on the pyridine ring significantly increases cytotoxic activity and aqueous solubility. Changing the arene from p-cymene to biphenyl and the monodentate ligand X from chloride to iodide also increases the activity significantly. Activation by hydrolysis and DNA binding appears not to be the major mechanism of action since both the highly active complex [Os(η(6)-bip)(2-F-azpy)I]PF(6) (9) and the moderately active complex [Os(η(6)-bip)(3-Cl-azpy)I]PF(6) (23) are very stable and inert towards aquation. Studies of octanol-water partition coefficients (log P) and subcellular distributions of osmium in A2780 human ovarian cancer cells suggested that cell uptake and targeting to cellular organelles play important roles in determining activity. Although complex 9 induced the production of reactive oxygen species (ROS) in A2780 cells, the ROS level did not appear to play a role in the mechanism of anticancer activity. This class of organometallic osmium complexes has new and unusual features worthy of further exploration for the design of novel anticancer drugs.

  7. Potent organo-osmium compound shifts metabolism in epithelial ovarian cancer cells

    PubMed Central

    Hearn, Jessica M.; Romero-Canelón, Isolda; Munro, Alison F.; Fu, Ying; Pizarro, Ana M.; Garnett, Mathew J.; McDermott, Ultan; Carragher, Neil O.; Sadler, Peter J.

    2015-01-01

    The organometallic “half-sandwich” compound [Os(η6-p-cymene)(4-(2-pyridylazo)-N,N-dimethylaniline)I]PF6 is 49× more potent than the clinical drug cisplatin in the 809 cancer cell lines that we screened and is a candidate drug for cancer therapy. We investigate the mechanism of action of compound 1 in A2780 epithelial ovarian cancer cells. Whole-transcriptome sequencing identified three missense mutations in the mitochondrial genome of this cell line, coding for ND5, a subunit of complex I (NADH dehydrogenase) in the electron transport chain. ND5 is a proton pump, helping to maintain the coupling gradient in mitochondria. The identified mutations correspond to known protein variants (p.I257V, p.N447S, and p.L517P), not reported previously in epithelial ovarian cancer. Time-series RNA sequencing suggested that osmium-exposed A2780 cells undergo a metabolic shunt from glycolysis to oxidative phosphorylation, where defective machinery, associated with mutations in complex I, could enhance activity. Downstream events, measured by time-series reverse-phase protein microarrays, high-content imaging, and flow cytometry, showed a dramatic increase in mitochondrially produced reactive oxygen species (ROS) and subsequent DNA damage with up-regulation of ATM, p53, and p21 proteins. In contrast to platinum drugs, exposure to this organo-osmium compound does not cause significant apoptosis within a 72-h period, highlighting a different mechanism of action. Superoxide production in ovarian, lung, colon, breast, and prostate cancer cells exposed to three other structurally related organo-Os(II) compounds correlated with their antiproliferative activity. DNA damage caused indirectly, through selective ROS generation, may provide a more targeted approach to cancer therapy and a concept for next-generation metal-based anticancer drugs that combat platinum resistance. PMID:26162681

  8. Vibrational characterization of multiply metal-metal bonded osmium, molybdenum, and rhenium porphyrin dimers

    SciTech Connect

    Tait, C.D.; Sattelberger, A.P.; Woodruff, W.H. ); Garner, J.M.; Collman, J.P. )

    1989-12-06

    The resonance Raman (RR) scattering and infrared (IR) absorption spectra of ((M(OEP)){sub 2}){sup n+} complexes (OEP = 2,3,7,8,12,13,17,18-octaethylporphyrin dianion; M = Os (n = 0-2), Re (n = 0-2), and Mo (n=0)) are reported. Resonance Raman studies reveal the Os-Os stretch to increase in frequency upon oxidation (233 cm{sup {minus}1} (n = 0), 254 cm{sup {minus}1} (n = 1), and 266 cm{sup {minus}1} (n = 2)), consistent with the removal of electrons from {pi}* metal-metal antibonding orbitals. The Mo-Mo stretch was also observed spectroscopically, producing a RR peak at 341 cm{sup {minus}1}, while the Re-Re stretch in ((Re(OEP)){sub 2}){sup 1+} was observed at 290 cm{sup {minus}1}. The corresponding metal-metal bond distances estimated from these stretching frequencies are 2.39, 2.31, and 2.27 {angstrom} for the osmium oxidation series, 2.23 {angstrom} for the molybdenum dimer, and 2.20 {angstrom} for the rhenium dimer. The porphyrin-centered vibrational modes (both RR and IR active) for the three osmium complexes are essentially independent of oxidation state, consistent with oxidation of metal-metal antibonding electrons. Little {pi} back-bonding between the metal and porphyrin macrocycle is suggested from porphyrin RR indicator modes, which are sensitive to {pi} electron density. Moreover, the porphyrin core size (center to nitrogen distance) is estimated from core size marker vibrations to be ca. 2.04 {angstrom} for all of the complexes studied. Finally, no vibrational evidence for ground-state intradimer coupling between the {pi} orbitals of the porphyrin rings is found.

  9. Potent organo-osmium compound shifts metabolism in epithelial ovarian cancer cells.

    PubMed

    Hearn, Jessica M; Romero-Canelón, Isolda; Munro, Alison F; Fu, Ying; Pizarro, Ana M; Garnett, Mathew J; McDermott, Ultan; Carragher, Neil O; Sadler, Peter J

    2015-07-21

    The organometallic "half-sandwich" compound [Os(η(6)-p-cymene)(4-(2-pyridylazo)-N,N-dimethylaniline)I]PF6 is 49× more potent than the clinical drug cisplatin in the 809 cancer cell lines that we screened and is a candidate drug for cancer therapy. We investigate the mechanism of action of compound 1 in A2780 epithelial ovarian cancer cells. Whole-transcriptome sequencing identified three missense mutations in the mitochondrial genome of this cell line, coding for ND5, a subunit of complex I (NADH dehydrogenase) in the electron transport chain. ND5 is a proton pump, helping to maintain the coupling gradient in mitochondria. The identified mutations correspond to known protein variants (p.I257V, p.N447S, and p.L517P), not reported previously in epithelial ovarian cancer. Time-series RNA sequencing suggested that osmium-exposed A2780 cells undergo a metabolic shunt from glycolysis to oxidative phosphorylation, where defective machinery, associated with mutations in complex I, could enhance activity. Downstream events, measured by time-series reverse-phase protein microarrays, high-content imaging, and flow cytometry, showed a dramatic increase in mitochondrially produced reactive oxygen species (ROS) and subsequent DNA damage with up-regulation of ATM, p53, and p21 proteins. In contrast to platinum drugs, exposure to this organo-osmium compound does not cause significant apoptosis within a 72-h period, highlighting a different mechanism of action. Superoxide production in ovarian, lung, colon, breast, and prostate cancer cells exposed to three other structurally related organo-Os(II) compounds correlated with their antiproliferative activity. DNA damage caused indirectly, through selective ROS generation, may provide a more targeted approach to cancer therapy and a concept for next-generation metal-based anticancer drugs that combat platinum resistance.

  10. Potent organo-osmium compound shifts metabolism in epithelial ovarian cancer cells.

    PubMed

    Hearn, Jessica M; Romero-Canelón, Isolda; Munro, Alison F; Fu, Ying; Pizarro, Ana M; Garnett, Mathew J; McDermott, Ultan; Carragher, Neil O; Sadler, Peter J

    2015-07-21

    The organometallic "half-sandwich" compound [Os(η(6)-p-cymene)(4-(2-pyridylazo)-N,N-dimethylaniline)I]PF6 is 49× more potent than the clinical drug cisplatin in the 809 cancer cell lines that we screened and is a candidate drug for cancer therapy. We investigate the mechanism of action of compound 1 in A2780 epithelial ovarian cancer cells. Whole-transcriptome sequencing identified three missense mutations in the mitochondrial genome of this cell line, coding for ND5, a subunit of complex I (NADH dehydrogenase) in the electron transport chain. ND5 is a proton pump, helping to maintain the coupling gradient in mitochondria. The identified mutations correspond to known protein variants (p.I257V, p.N447S, and p.L517P), not reported previously in epithelial ovarian cancer. Time-series RNA sequencing suggested that osmium-exposed A2780 cells undergo a metabolic shunt from glycolysis to oxidative phosphorylation, where defective machinery, associated with mutations in complex I, could enhance activity. Downstream events, measured by time-series reverse-phase protein microarrays, high-content imaging, and flow cytometry, showed a dramatic increase in mitochondrially produced reactive oxygen species (ROS) and subsequent DNA damage with up-regulation of ATM, p53, and p21 proteins. In contrast to platinum drugs, exposure to this organo-osmium compound does not cause significant apoptosis within a 72-h period, highlighting a different mechanism of action. Superoxide production in ovarian, lung, colon, breast, and prostate cancer cells exposed to three other structurally related organo-Os(II) compounds correlated with their antiproliferative activity. DNA damage caused indirectly, through selective ROS generation, may provide a more targeted approach to cancer therapy and a concept for next-generation metal-based anticancer drugs that combat platinum resistance. PMID:26162681

  11. Zinc phosphide

    Integrated Risk Information System (IRIS)

    Zinc phoshide ; CASRN 1314 - 84 - 7 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments for Noncarcinogenic Ef

  12. An osmium(III)/osmium(V) redox couple generating Os(V)(O)(OH) center for cis-1,2-dihydroxylation of alkenes with H2O2: Os complex with a nitrogen-based tetradentate ligand.

    PubMed

    Sugimoto, Hideki; Kitayama, Kazuhiro; Mori, Seiji; Itoh, Shinobu

    2012-11-21

    For the synthesis of the 1,2-diols, cis-1,2-dihydroxylation of alkenes catalyzed by osmium(VIII) tetroxide (OsO(4)) is a powerful method. However, OsO(4) is quite toxic due to its highly volatile and sublimable nature. Thus, the development of alternative catalysts for cis-1,2-dihydroxylation of alkenes is highly challenging. Our approach involves the use of a nitrogen-based tetradentate ligand, tris(2-pyridylmethyl)amine (tpa), for an osmium center to develop a new osmium catalyst and hydrogen peroxide (H(2)O(2)) as a cheap and environmentally benign oxidant. The new Os-tpa complex acts as a very efficient turnover catalyst for syn-selective dihydroxylation of various alkenes (turnover number ∼1000) in aqueous media, and H(2)O(2) oxidant is formally incorporated into the products quantitatively (100% atom efficiency). The reaction intermediates involved in the catalytic cycle have been isolated and characterized crystallographically as [Os(III)(OH)(H(2)O)(tpa)](2+) and [Os(V)(O)(OH)(tpa)](2+) complexes. The observed syn-selectivity, structural characteristics of the intermediates, and kinetic studies have suggested a concerted [3 + 2]-cycloaddition mechanism between [Os(V)(O)(OH)(tpa)](2+) and alkenes, which is strongly supported by DFT calculations.

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

    PubMed

    Barry, Nicolas P E; Sadler, Peter J

    2012-04-21

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

  14. Ligand-incorporation site in 5-methylcytosine-detection probe modulating the site of osmium complexation with the target DNA.

    PubMed

    Sugizaki, Kaori; Nakamura, Akiko; Yanagisawa, Hiroyuki; Okamoto, Akimitsu

    2012-09-01

    ICON Probes, short DNA strands containing an adenine linked to a bipyridine ligand, formed an interstrand cross-link with 5-methylcytosine located opposite the modified adenine in the presence of an osmium oxidant. The location of a bipyridine-tethered adenine in the probes varied the selectivity of the reactive base. An ICON probe where the modified adenine was located at the probe center showed a 5-methylcytosine-selective osmium complexation, whereas an ICON probe with the modified adenine at the strand end exhibited high reactivity towards thymine as well as 5-methylcytosine. The modulation of reactive bases by the incorporation of a bipyridine-tethered adenine site made facilitates design of ICON probes for the fluorometric detection of 5-methylcytosine.

  15. Behavior of osmium at the freshwater-saltwater interface based on Ganga derived sediments from the estuarine zone

    NASA Astrophysics Data System (ADS)

    Paul, M.; Reisberg, L.; Vigier, N.; France-Lanord, C.

    2011-12-01

    Leaching experiments performed on several sediments of the Ganga river suggest that between 10 and 20% of the osmium is in an easily exchangeable position. Analyses of sediments from two estuarine rivers (the Pussur and the lower Meghna) reveal no enrichment of Os in the saltwater-freshwater mixing zone relative to Ganga sediments of similar Al2O3/SiO2 ratio, suggesting that osmium is not significantly trapped in this estuary. However, a significant decrease of the 187Os/188Os ratio is observed in the Pussur sediments relative to the Ganga composition. These latter are derived entirely from the Ganga or from erosion of the Ganga paleodelta, and thus would be expected to have similar Os isotopic compositions. Nd isotopic results from the Pussur are indistinguishable from those of the Ganga, while the Sr isotopic results are at the lower end of the Ganga range, confirming the absence of a major source difference between Ganga and Pussur sediments. It thus seems unlikely that the difference in Os isotopic signature can be entirely explained by a change in provenance, suggesting instead that the Os compositions have been modified. Our results show that the less radiogenic Os compositions of the Pussur sediments cannot result simply from desorption of radiogenic Os or from scavenging of river or seawater Os. Instead, the decrease of the 187Os/188Os ratio could imply a complex exchange between dissolved Os, derived partly from seawater, and Os in the leachable fraction of sediments. This mechanism could therefore constitute both a source and a sink for seawater osmium and may significantly influence the osmium marine budget.

  16. Carbon-fluorine bond cleavage in the preparation of Osmium(III) and Osmium(IV) fluorothiolate complexes. Fluorine by fluorine NMR-assignment and fluxional processes.

    PubMed

    Arroyo, Maribel; Bernès, Sylvain; Cerón, Margarita; Cortina, Verónica; Mendoza, Consuelo; Torrens, Hugo

    2007-06-11

    Reactions of OsO4 with HSR (R=C6F5, C6F4H-4,) in refluxing ethanol afford [Os(SC6F5)3(SC6F4(SC6F5)-2)] (1) and [Os(SC6F4H-4)3(SC6F3H-4-(SC6F4H-4)-2)] (2), which involve the rupture of C-F bonds. At room temperature, the compound [Os(SC6F5)3(PMe2Ph)2] or [Os(SC6F5)4(PMe2Ph)] reacts with KOH(aq) in acetone, giving rise to [ Os(SC6F5)(SC6F4(SC6F4O-2)-2)(PMe2Ph)2] (3), through a process involving the rupture of two C-F bonds, while the compound [Os(SC6F4H)4(PPh3)] reacts with KOH(aq) in acetone to afford [Os(SC6F4H-4)2(SC6F3H-4-O-2)(PPh3)] (4), which also implies a C-F bond cleavage. Single-crystal X-ray diffraction studies of 1, 2, and 4 indicate that these compounds include five-coordinated metal ions in essentially trigonal-bipyramidal geometries, whereas these studies on the paramagnetic compound 3 show a six-coordinated osmium center in a distorted octahedral geometry. 19F, 1H, 31P{1H}, and COSY 19F-19F NMR studies for the diamagnetic 1, 2, and 4 compounds, including variable-temperature 19F NMR experiments, showed that these molecules are fluxional. Some of the activation parameters for these dynamic processes have been determined.

  17. Atomically Resolved Site-Isolated Catalyst on MgO: Mononuclear Osmium Dicarbonyls formed from Os3(CO)12

    SciTech Connect

    Aydin, Ceren; kulkarni, Apoorva; Chi, Miaofang; Browning, Nigel D.; Gates, Bruce C.

    2012-01-01

    Supported triosmium clusters, formed from Os{sub 3}(CO){sub 12} on MgO, were treated in helium at 548 K for 2 h, causing fragmentation of the cluster frame and the formation of mononuclear osmium dicarbonyls. The cluster breakup and the resultant fragmented species were characterized by infrared and X-ray absorption spectroscopies, and the fragmented species were imaged by scanning transmission electron microscopy. The spectra identify the surface osmium complexes as Os(CO){sub 2}{l_brace}O{sub support}{r_brace}{sub n} (n = 3 or 4) (where the braces denote support surface atoms). The images show site-isolated Os atoms in mononuclear osmium species on MgO. The intensity analysis on the images of the MgO(110) face showed that the Os atoms were located atop Mg columns. This information led to a model of the Os(CO){sub 2} on MgO(110), with the distances approximated as those determined by EXAFS spectroscopy, which are an average over the whole MgO surface; the results imply that these complexes were located at Mg vacancies.

  18. Wiring microbial biofilms to the electrode by osmium redox polymer for the performance enhancement of microbial fuel cells.

    PubMed

    Yuan, Yong; Shin, Hyosul; Kang, Chan; Kim, Sunghyun

    2016-04-01

    An osmium redox polymer, PAA-PVI-[Os(4,4'-dimethyl-2,2'-bipyridine)2Cl]+/2+ that has been used in enzymatic fuel cells and microbial sensors, was applied for the first time to the anode of single-chamber microbial fuel cells with the mixed culture inoculum aiming at enhancing performance. Functioning as a molecular wire connecting the biofilm to the anode, power density increased from 1479 mW m(-2) without modification to 2355 mW m(-2) after modification of the anode. Evidence from cyclic voltammetry showed that the catalytic activity of an anodic biofilm was greatly enhanced in the presence of an osmium redox polymer, indicating that electrons were more efficiently transferred to the anode via co-immobilized osmium complex tethered to wiring polymer chains at the potential range of -0.3 V-+0.1 V (vs. SCE). The optimum amount of the redox polymer was determined to be 0.163 mg cm(-2).

  19. Sensitive voltammetric detection of DNA damage at carbon electrodes using DNA repair enzymes and an electroactive osmium marker.

    PubMed

    Havran, Ludek; Vacek, Jan; Cahová, Katerina; Fojta, Miroslav

    2008-07-01

    This paper presents a new approach to electrochemical sensing of DNA damage, using osmium DNA markers and voltammetric detection at the pyrolytic graphite electrode. The technique is based on enzymatic digestion of DNA with a DNA repair enzyme exonuclease III (exoIII), followed by single-strand (ss) selective DNA modification by a complex of osmium tetroxide with 2,2'-bipyridine. In double-stranded DNA possessing free 3'-ends, the exoIII creates ss regions that can accommodate the electroactive osmium marker. Intensity of the marker signal measured at the pyrolytic graphite electrode responded well to the extent of DNA damage. The technique was successfully applied for the detection of (1) single-strand breaks (ssb) introduced in plasmid DNA by deoxyribonuclease I, and (2) apurinic sites generated in chromosomal calf thymus DNA upon treatment with the alkylating agent dimethyl sulfate. The apurinic sites were converted into the ssb by DNA repair endonuclease activity of the exoIII enzyme. We show that the presented technique is capable of detection of one lesion per approximately 10(5) nucleotides in supercoiled plasmid DNA.

  20. Characterization of a glucose sensor prepared by electropolymerization of pyrroles containing a tris-bipyridine osmium complex.

    PubMed

    Tsujimoto, Masaki; Yabutani, Tomoki; Sano, Atsushi; Tani, Yuji; Murotani, Hiroki; Mishima, Yuji; Maruyama, Kenichi; Yasuzawa, Mikito; Motonaka, Junko

    2007-01-01

    A glucose sensor was developed by electrocopolymerization using pyrroles containing a tris-bipyridine (bpy) osmium complex (Os-py), pyrrole (py), pyrrole propanoic acid (PPA) and glucose oxidase (GOx) to improve the key performance characteristics, such as the sensitivity, selectivity, and long-term stability. Tris-bipyridine osmium pyrrole complexes with four different methylene moieties were utilized to correlate the methylene length with the glucose sensor performance. The electrocatalytic response of glucose was clearly observed at electrodes modified with Os-py, except for the electrode immobilized with the Os-py complex containing the shortest methylene moiety. The current response to glucose increased up to a concentration of 100 mmol dm(-3). The electrocatalytic response to glucose at the [Os(bpy)(2)(py(6)-bpy)](2+/3+)/py/PPA/GOx electrode was stable for more than 100 days. Dissolved oxygen and potential interference compounds (ascorbic acid, uric acid, and acetaminophen) minimally perturbed the current response to glucose at the [Os(DM-bpy)(2)(py(6)-bpy)](2+/3+)/py/PPA/GOx electrode. Based on these results, a longer methylene moiety appears to improve the performance characteristics of a glucose sensor fabricated via the electropolymerization of tris-bipyridine osmium pyrrole complexes.

  1. Wiring microbial biofilms to the electrode by osmium redox polymer for the performance enhancement of microbial fuel cells.

    PubMed

    Yuan, Yong; Shin, Hyosul; Kang, Chan; Kim, Sunghyun

    2016-04-01

    An osmium redox polymer, PAA-PVI-[Os(4,4'-dimethyl-2,2'-bipyridine)2Cl]+/2+ that has been used in enzymatic fuel cells and microbial sensors, was applied for the first time to the anode of single-chamber microbial fuel cells with the mixed culture inoculum aiming at enhancing performance. Functioning as a molecular wire connecting the biofilm to the anode, power density increased from 1479 mW m(-2) without modification to 2355 mW m(-2) after modification of the anode. Evidence from cyclic voltammetry showed that the catalytic activity of an anodic biofilm was greatly enhanced in the presence of an osmium redox polymer, indicating that electrons were more efficiently transferred to the anode via co-immobilized osmium complex tethered to wiring polymer chains at the potential range of -0.3 V-+0.1 V (vs. SCE). The optimum amount of the redox polymer was determined to be 0.163 mg cm(-2). PMID:26599210

  2. The cyro-thermochromatographic separator (CTS): A new detectionand separation system for highly volatile osmium and hassium (element108) tetroxides

    SciTech Connect

    Kirbach, U.W.; Folden III, C.M.; Ginter, T.N.; Gregorich, K.E.; Lee, D.M.; Ninov, V.; Omtvedt, J.P.; Patin, J.B.; Seward, N.K.; Strellis,D.A.; Sudowe, R.; Wilk, P.A.; Zielinski, P.M.; Hoffman, D.C.; Nitsche, H.

    2002-03-08

    We implemented a new concept for heavy element chemistry research using an ion separator to separate the desired products from the beam, transfer products and other undesirable by-products prior to chemical studies. First, a Recoil product Transfer Chamber (RTC) was designed and attached to the Berkeley Gas-filled Separator (BGS) to collect and transfer the recoiling products to the chemical separation system. The RTC consists of a wire-grid-supported thin mylar foil ({le}) 200 {micro}g/cm{sup 2} that separates the BGS detector chamber, at 1.3 mbar pressure, from the chemistry system at different pressures ranging from 480 mbar to 2000 mbar. The overall transport efficiency ranged between 30% and 15%, compared to the activity measured in the focal plane detector of the BGS. The CTS was designed as a separation and {alpha}-decay detection system for the highly volatile tetroxides of osmium and hassium, element 108. The CTS, shown in figure 1, consists of two rows of 32-{alpha} detectors arranged along a negative temperature gradient. The tetroxides adsorb on the surface of one of the silicone photodiodes at a certain deposition temperature, and the nuclide is then identified by the {alpha}-decay. To test the CTS with the expected hassium homologue osmium, different {alpha}-active osmium isotopes were produced using the nuclear reactions {sup 118}Sn({sup 56}Fe, 4,5n) {sup 170,169}Os and {sup 120}Sn({sup 56}Fe, 4,5n) {sup 172,171}Os. After preseparation in the BGS, a mixture of 90% helium and 10% oxygen was used to transport the osmium to a quartz tube heated to 1225 K, where OsO{sub 4} was formed. The negative temperature gradient in the CTS ranged from 248 K to 173 K. Using a flow rate of 500 mL/min, most of the osmium activity was adsorbed at a temperature of about 203 K. From the measured {alpha}-activity distribution, an adsorption enthalpy of 40 {+-} 1 kJ/mol for OsO{sub 4} on the detector surface was calculated using Monte Carlo simulations. The results show

  3. Backscattered electron image of osmium-impregnated/macerated tissues as a novel technique for identifying the cis-face of the Golgi apparatus by high-resolution scanning electron microscopy.

    PubMed

    Koga, D; Bochimoto, H; Watanabe, T; Ushiki, T

    2016-07-01

    The osmium maceration method with scanning electron microscopy (SEM) enabled to demonstrate directly the three-dimensional (3D) structure of membranous cell organelles. However, the polarity of the Golgi apparatus (that is, the cis-trans axis) can hardly be determined by SEM alone, because there is no appropriate immunocytochemical method for specific labelling of its cis- or trans-faces. In the present study, we used the osmium impregnation method, which forms deposits of reduced osmium exclusively in the cis-Golgi elements, for preparation of specimens for SEM. The newly developed procedure combining osmium impregnation with subsequent osmium maceration specifically visualised the cis-elements of the Golgi apparatus, with osmium deposits that were clearly detected by backscattered electron-mode SEM. Prolonged osmication by osmium impregnation (2% OsO4 solution at 40°C for 40 h) and osmium maceration (0.1% OsO4 solution at 20°C for 24 h) did not significantly impair the 3D ultrastructure of the membranous cell organelles, including the Golgi apparatus. This novel preparation method enabled us to determine the polarity of the Golgi apparatus with enough information about the surrounding 3D ultrastructure by SEM, and will contribute to our understanding of the global organisation of the entire Golgi apparatus in various differentiated cells.

  4. Backscattered electron image of osmium-impregnated/macerated tissues as a novel technique for identifying the cis-face of the Golgi apparatus by high-resolution scanning electron microscopy.

    PubMed

    Koga, D; Bochimoto, H; Watanabe, T; Ushiki, T

    2016-07-01

    The osmium maceration method with scanning electron microscopy (SEM) enabled to demonstrate directly the three-dimensional (3D) structure of membranous cell organelles. However, the polarity of the Golgi apparatus (that is, the cis-trans axis) can hardly be determined by SEM alone, because there is no appropriate immunocytochemical method for specific labelling of its cis- or trans-faces. In the present study, we used the osmium impregnation method, which forms deposits of reduced osmium exclusively in the cis-Golgi elements, for preparation of specimens for SEM. The newly developed procedure combining osmium impregnation with subsequent osmium maceration specifically visualised the cis-elements of the Golgi apparatus, with osmium deposits that were clearly detected by backscattered electron-mode SEM. Prolonged osmication by osmium impregnation (2% OsO4 solution at 40°C for 40 h) and osmium maceration (0.1% OsO4 solution at 20°C for 24 h) did not significantly impair the 3D ultrastructure of the membranous cell organelles, including the Golgi apparatus. This novel preparation method enabled us to determine the polarity of the Golgi apparatus with enough information about the surrounding 3D ultrastructure by SEM, and will contribute to our understanding of the global organisation of the entire Golgi apparatus in various differentiated cells. PMID:26807791

  5. Origin of platinum-group mineral assemblages in a mantle tectonite at Unst deduced from mineral chemistry and osmium isotopes

    NASA Astrophysics Data System (ADS)

    Badanina, Inna Yu.; Lord, Richard A.; Malitch, Kreshimir N.; Meisel, Thomas C.

    2013-04-01

    This study assesses textural and mineral chemistry data, whole-rock and mineral separate Os-isotope compositions for distinct platinum-group mineral (PGM) inclusion assemblages in an isolated chromitite pod at Harold's Grave, which occurrs in a mantle tectonite at Unst in the Shetland Ophiolite Complex, Scotland. The investigation employed a multi-technique approach and utilized a number of analytical techniques, including electron microprobe analysis, ID ICP-MS after high pressure acid digestion, and LA MC-ICP-MS. Two distinct PGM assemblages have been recognized. They comprise a 'primary' euhedrally shaped (up to 15 μm in size) PGM assemblage, which occur as inclusions in chromite, and a modified 'secondary' subeuhedral to anhedral PGM assemblage (up to 100 μm) associated with Ru-rich pentlandite observed in cracks filled by chlorite or serpentine, interstitially to chromite grains. A 'primary' PGM assemblage is represented by solitary grains of laurite or iridian osmium and composite grains that display well defined phase boundaries between two or three distinct PGM. The latter are dominated by laurite and iridian osmium, with subordinate laurite + osmian iridium + iridian osmium and rare laurite + Ir-Rh alloy + Rh-rich sulphide (possibly prassoite). The compositional variability of associated laurite and Os-rich alloys at Harold's Grave fit the predicted compositions of experiment W-1200-0.37 of Andrews and Brenan (2002) providing unequivocal information on conditions of their genesis, with the upper thermal stability of laurite in equilibrium with Os-rich alloys estimated at 1200 - 1250° C and f(S2) of 10-0.39-10-0.07. The inconsistent grouping of different primary PGM grains argues against an origin by subsolidus exsolution from the chromite host, providing useful information on conditions of their genesis. The 'secondary' PGM assemblage is polyphase, with dominant laurite, intimately intergrown with native osmium, irarsite and Ru-rich pentlandite. This

  6. Development of a reliable analytical method for the precise extractive spectrophotometric determination of osmium(VIII) with 2-nitrobenzaldehydethiocarbohydrazone: Analysis of alloys and real sample.

    PubMed

    Zanje, Sunil B; Kokare, Arjun N; Suryavanshi, Vishal J; Waghmode, Duryodhan P; Joshi, Sunil S; Anuse, Mansing A

    2016-12-01

    The proposed method demonstrates that the osmium(VIII) forms complex with 2-NBATCH from 0.8molL(-1) HCl at room temperature. The complex formed was extracted in 10mL of chloroform with a 5min equilibration time. The absorbance of the red colored complex was measured at 440nm against the reagent blank. The Beer's law was obeyed in the range of 5-25μgmL(-1), the optimum concentration range was 10-20μgmL(-1) of osmium(VIII) as evaluated by Ringbom's plot. Molar absorptivity and Sandell's sensitivity of osmium(VIII)-2NBATCH complex in chloroform is 8.94×10(3)Lmol(-1)cm(-1) and 0.021μgcm(-2), respectively. The composition of osmium(VIII)-2NBATCH complex was 1:2 investigated from Job's method of continuous variation, Mole ratio method and slope ratio method. The interference of diverse ions was studied and masking agents were used wherever necessary. The present method was successfully applied for determination of osmium(VIII) from binary, ternary and synthetic mixtures corresponding to alloys and real samples. The validity of the method was confirmed by finding the relative standard deviation for five determinations which was 0.29%.

  7. Development of a reliable analytical method for the precise extractive spectrophotometric determination of osmium(VIII) with 2-nitrobenzaldehydethiocarbohydrazone: Analysis of alloys and real sample.

    PubMed

    Zanje, Sunil B; Kokare, Arjun N; Suryavanshi, Vishal J; Waghmode, Duryodhan P; Joshi, Sunil S; Anuse, Mansing A

    2016-12-01

    The proposed method demonstrates that the osmium(VIII) forms complex with 2-NBATCH from 0.8molL(-1) HCl at room temperature. The complex formed was extracted in 10mL of chloroform with a 5min equilibration time. The absorbance of the red colored complex was measured at 440nm against the reagent blank. The Beer's law was obeyed in the range of 5-25μgmL(-1), the optimum concentration range was 10-20μgmL(-1) of osmium(VIII) as evaluated by Ringbom's plot. Molar absorptivity and Sandell's sensitivity of osmium(VIII)-2NBATCH complex in chloroform is 8.94×10(3)Lmol(-1)cm(-1) and 0.021μgcm(-2), respectively. The composition of osmium(VIII)-2NBATCH complex was 1:2 investigated from Job's method of continuous variation, Mole ratio method and slope ratio method. The interference of diverse ions was studied and masking agents were used wherever necessary. The present method was successfully applied for determination of osmium(VIII) from binary, ternary and synthetic mixtures corresponding to alloys and real samples. The validity of the method was confirmed by finding the relative standard deviation for five determinations which was 0.29%. PMID:27380306

  8. Amide-Directed Formation of Five-Coordinate Osmium Alkylidenes from Alkynes

    PubMed Central

    2015-01-01

    The amide-directed synthesis of five-coordinate osmium alkylidene derivatives from alkynes is reported. These types of complexes, which have been elusive until now because of the tendency of osmium to give hydride alkylidyne species, are prepared by reaction of the dihydride OsH2Cl2(PiPr3)2 (1) with terminal alkynes containing a distal amide group. Complex 1 reacts with N-phenylhex-5-ynamide and N-phenylhepta-6-ynamide to give OsCl2{=C(CH3)(CH2)nNH(CO)Ph}(PiPr3)2 (n = 3 (2), 4 (3)). The relative position of carbonyl and NH groups in the organic substrates has no influence on the reaction. Thus, treatment of 1 with N-(pent-4-yn-1-yl)benzamide leads to OsCl2{=C(CH3)(CH2)3NHC(O)Ph}(PiPr3)2 (4). The new compounds are intermediate species in the cleavage of the C–C triple bond of the alkynes. Under mild conditions, they undergo the rupture of the Cα–CH3 bond of the alkylidene, which comes from the alkyne triple bond, to afford six-coordinate hydride–alkylidyne derivatives. In dichloromethane, complex 2 gives a 10:7 mixture of OsHCl2{≡C(CH2)3C(O)NHPh}(PiPr3)2 (5) and OsHCl2{≡CCH(CH3)(CH2)2C(O)NHPh}(PiPr3)2 (6). The first complex contains a linear separation between the alkylidyne Cα atom and the amide group, whereas the spacer is branched in the second complex. In contrast to the case for 2, complex 4 selectively affords OsHCl2{≡C(CH2)3NHC(O)Ph}(PiPr3)2 (7). In spite of their instability, these compounds give the alkylidene–allene metathesis, being a useful entry to five-coordinate vinylidene complexes, including the dicarbon-disubstituted OsCl2(=C=CMe2)(PiPr3)2 (8) and the monosubstituted OsCl2(=C=CHCy)(PiPr3)2 (9). PMID:26877575

  9. Effect of dislocations on the open-circuit voltage, short-circuit current and efficiency of heteroepitaxial indium phosphide solar cells

    NASA Technical Reports Server (NTRS)

    Jain, Raj K.; Flood, Dennis J.

    1990-01-01

    Excellent radiation resistance of indium phosphide solar cells makes them a promising candidate for space power applications, but the present high cost of starting substrates may inhibit their large scale use. Thin film indium phosphide cells grown on Si or GaAs substrates have exhibited low efficiencies, because of the generation and propagation of large number of dislocations. Dislocation densities were calculated and its influence on the open circuit voltage, short circuit current, and efficiency of heteroepitaxial indium phosphide cells was studied using the PC-1D. Dislocations act as predominant recombination centers and are required to be controlled by proper transition layers and improved growth techniques. It is shown that heteroepitaxial grown cells could achieve efficiencies in excess of 18 percent AMO by controlling the number of dislocations. The effect of emitter thickness and surface recombination velocity on the cell performance parameters vs. dislocation density is also studied.

  10. Recent advances in transition metal phosphide nanomaterials: synthesis and applications in hydrogen evolution reaction.

    PubMed

    Shi, Yanmei; Zhang, Bin

    2016-03-21

    The urgent need of clean and renewable energy drives the exploration of effective strategies to produce molecular hydrogen. With the assistance of highly active non-noble metal electrocatalysts, electrolysis of water is becoming a promising candidate to generate pure hydrogen with low cost and high efficiency. Very recently, transition metal phosphides (TMPs) have been proven to be high performance catalysts with high activity, high stability, and nearly ∼100% Faradic efficiency in not only strong acidic solutions, but also in strong alkaline and neutral media for electrochemical hydrogen evolution. In this tutorial review, an overview of recent development of TMP nanomaterials as catalysts for hydrogen generation with high activity and stability is presented. The effects of phosphorus (P) on HER activity, and their synthetic methods of TMPs are briefly discussed. Then we will demonstrate the specific strategies to further improve the catalytic efficiency and stability of TMPs by structural engineering. Making use of TMPs as cocatalysts and catalysts in photochemical and photoelectrochemical water splitting is also discussed. Finally, some key challenges and issues which should not be ignored during the rapid development of TMPs are pointed out. These strategies and challenges of TMPs are instructive for designing other high-performance non-noble metal catalysts.

  11. Electronic Structures of Free-Standing Nanowires made from Indirect Bandgap Semiconductor Gallium Phosphide

    PubMed Central

    Liao, Gaohua; Luo, Ning; Chen, Ke-Qiu; Xu, H. Q.

    2016-01-01

    We present a theoretical study of the electronic structures of freestanding nanowires made from gallium phosphide (GaP)—a III-V semiconductor with an indirect bulk bandgap. We consider [001]-oriented GaP nanowires with square and rectangular cross sections, and [111]-oriented GaP nanowires with hexagonal cross sections. Based on tight binding models, both the band structures and wave functions of the nanowires are calculated. For the [001]-oriented GaP nanowires, the bands show anti-crossing structures, while the bands of the [111]-oriented nanowires display crossing structures. Two minima are observed in the conduction bands, while the maximum of the valence bands is always at the Γ-point. Using double group theory, we analyze the symmetry properties of the lowest conduction band states and highest valence band states of GaP nanowires with different sizes and directions. The band state wave functions of the lowest conduction bands and the highest valence bands of the nanowires are evaluated by spatial probability distributions. For practical use, we fit the confinement energies of the electrons and holes in the nanowires to obtain an empirical formula. PMID:27307081

  12. Elastic, magnetic and electronic properties of iridium phosphide Ir2P.

    PubMed

    Wang, Pei; Wang, Yonggang; Wang, Liping; Zhang, Xinyu; Yu, Xiaohui; Zhu, Jinlong; Wang, Shanmin; Qin, Jiaqian; Leinenweber, Kurt; Chen, Haihua; He, Duanwei; Zhao, Yusheng

    2016-01-01

    Cubic (space group: Fmm) iridium phosphide, Ir2P, has been synthesized at high pressure and high temperature. Angle-dispersive synchrotron X-ray diffraction measurements on Ir2P powder using a diamond-anvil cell at room temperature and high pressures (up to 40.6 GPa) yielded a bulk modulus of B0 = 306(6) GPa and its pressure derivative B0' = 6.4(5). Such a high bulk modulus attributed to the short and strongly covalent Ir-P bonds as revealed by first - principles calculations and three-dimensionally distributed [IrP4] tetrahedron network. Indentation testing on a well-sintered polycrystalline sample yielded the hardness of 11.8(4) GPa. Relatively low shear modulus of ~64 GPa from theoretical calculations suggests a complicated overall bonding in Ir2P with metallic, ionic, and covalent characteristics. In addition, a spin glass behavior is indicated by magnetic susceptibility measurements. PMID:26905444

  13. Self-catalyzed epitaxial growth of vertical indium phosphide nanowires on silicon.

    PubMed

    Gao, Li; Woo, Robyn L; Liang, Baolai; Pozuelo, Marta; Prikhodko, Sergey; Jackson, Mike; Goel, Niti; Hudait, Mantu K; Huffaker, Diana L; Goorsky, Mark S; Kodambaka, Suneel; Hicks, Robert F

    2009-06-01

    Vertical indium phosphide nanowires have been grown epitaxially on silicon (111) by metalorganic vapor-phase epitaxy. Liquid indium droplets were formed in situ and used to catalyze deposition. For growth at 350 degrees C, about 70% of the wires were vertical, while the remaining ones were distributed in the 3 other <111> directions. The vertical fraction, growth rate, and tapering of the wires increased with temperature and V/III ratio. At 370 degrees C and V/III equal to 200, 100% of the wires were vertical with a density of approximately 1.0 x 10(9) cm(-2) and average dimensions of 3.9 mum in length, 45 nm in base width, and 15 nm in tip width. X-ray diffraction and transmission electron microscopy revealed that the wires were single-crystal zinc blende, although they contained a high density of rotational twins perpendicular to the <111> growth direction. The room temperature photoluminescence spectrum exhibited one peak centered at 912 +/- 10 nm with a FWHM of approximately 60 nm. PMID:19413340

  14. Boron phosphide under pressure: In situ study by Raman scattering and X-ray diffraction

    NASA Astrophysics Data System (ADS)

    Solozhenko, Vladimir L.; Kurakevych, Oleksandr O.; Le Godec, Yann; Kurnosov, Aleksandr V.; Oganov, Artem R.

    2014-07-01

    Cubic boron phosphide, BP, has been studied in situ by X-ray diffraction and Raman scattering up to 55 GPa at 300 K in a diamond anvil cell. The bulk modulus of B0 = 174(2) GPa has been established, which is in excellent agreement with our ab initio calculations. The data on Raman shift as a function of pressure, combined with equation-of-state (EOS) data, allowed us to estimate the Grüneisen parameters of the TO and LO modes of zinc-blende structure, γGTO= 1.26 and γGLO= 1.13, just like in the case of other AIIIBV diamond-like phases, for which γGTO> γGLO≅ 1. We also established that the pressure dependence of the effective electro-optical constant α is responsible for a strong change in relative intensities of the TO and LO modes from ITO/ILO ˜ 0.25 at 0.1 MPa to ITO/ILO ˜ 2.5 at 45 GPa, for which we also find excellent agreement between experiment and theory.

  15. Elastic, magnetic and electronic properties of iridium phosphide Ir2P

    DOE PAGES

    Wang, Pei; Wang, Yonggang; Wang, Liping; Zhang, Xinyu; Yu, Xiaohui; Zhu, Jinlong; Wang, Shanmin; Qin, Jiaqian; Leinenweber, Kurt; Chen, Haihua; et al

    2016-02-24

    Cubic (space group: Fm3¯m) iridium phosphide, Ir2P, has been synthesized at high pressure and high temperature. Angle-dispersive synchrotron X-ray diffraction measurements on Ir2P powder using a diamond-anvil cell at room temperature and high pressures (up to 40.6 GPa) yielded a bulk modulus of B0 = 306(6) GPa and its pressure derivative B0'= 6.4(5). Such a high bulk modulus attributed to the short and strongly covalent Ir-P bonds as revealed by first – principles calculations and three-dimensionally distributed [IrP4] tetrahedron network. Indentation testing on a well–sintered polycrystalline sample yielded the hardness of 11.8(4) GPa. Relatively low shear modulus of ~64 GPamore » from theoretical calculations suggests a complicated overall bonding in Ir2P with metallic, ionic, and covalent characteristics. Additionally, a spin glass behavior is indicated by magnetic susceptibility measurements.« less

  16. Boron phosphide under pressure: In situ study by Raman scattering and X-ray diffraction

    SciTech Connect

    Solozhenko, Vladimir L.; Kurakevych, Oleksandr O.; Le Godec, Yann; Kurnosov, Aleksandr V.; Oganov, Artem R.

    2014-07-21

    Cubic boron phosphide, BP, has been studied in situ by X-ray diffraction and Raman scattering up to 55 GPa at 300 K in a diamond anvil cell. The bulk modulus of B{sub 0} = 174(2) GPa has been established, which is in excellent agreement with our ab initio calculations. The data on Raman shift as a function of pressure, combined with equation-of-state (EOS) data, allowed us to estimate the Grüneisen parameters of the TO and LO modes of zinc-blende structure, γ{sub G}{sup TO }= 1.26 and γ{sub G}{sup LO }= 1.13, just like in the case of other A{sup III}B{sup V} diamond-like phases, for which γ{sub G}{sup TO }> γ{sub G}{sup LO }≅ 1. We also established that the pressure dependence of the effective electro-optical constant α is responsible for a strong change in relative intensities of the TO and LO modes from I{sub TO}/I{sub LO} ∼ 0.25 at 0.1 MPa to I{sub TO}/I{sub LO} ∼ 2.5 at 45 GPa, for which we also find excellent agreement between experiment and theory.

  17. Controlled synthesis and magnetic properties of iron-cobalt-phosphide nanorods.

    PubMed

    Yang, Weiwei; Wu, Xiaoming; Yu, Yongsheng; Yang, Chunhui; Xu, Shichong; Li, Haibo

    2016-09-28

    A simple one-step solution-phase synthesis of iron-cobalt-phosphide ((Fe1-xCox)2P) nanorods (NRs) is reported in this paper. Through the control of the amount of Co in the samples, the crystal structure of (Fe1-xCox)2P NRs changes from a pure Fe-rich hexagonal Fe2P type structure to a mixture of Fe-rich hexagonal Fe2P and Co-rich orthorhombic Co2P type structures. These samples show superparamagnetic behavior at room temperature and ferromagnetic properties at 10 K. When the Co composition is 0.09, the (Fe0.91Co0.09)2P sample has the highest coercivity around 5.74 kOe at 10 K. The current route provides a new and general chemical method for tunable preparation of (Fe1-xCox)2P (x < 0.28) NRs, which are significant for the development of new iron- or cobalt-rich permanent magnet materials without rare-earth or noble metals. PMID:27602987

  18. Planar array antenna with director on indium phosphide substrate for 300GHz wireless link

    NASA Astrophysics Data System (ADS)

    Kanaya, Haruichi; Oda, Tomoki; Iizasa, Naoto; Kato, Kazutoshi

    2016-02-01

    This paper presents a design and fabrication of 1 x 4 one-sided directional slot array antenna with director metal layer on indium phosphide (InP) substrate for 300 GHz wireless link. The floating metal and polyimide dielectric layer are stacked on InP. Antenna is designed on the top metal layer. By optimizing the length of the bottom floating metal layer, one-sided directional radiation can be realized. The branched coplanar wave guide (CPW) transmission line is connected to each antenna element with the same electrical length. The size of the 1 x 4 array antenna is 2,550 µm x 1,217 µm x 18 µm. In order to enhance the gain of forward direction, director metal layer is placed over 83 µm from top metal layer. Simulated realized gain in peak direction of our antenna is 9.23 dBi. The measured center frequency is almost the same as that of the simulation results.

  19. Highly stable two-dimensional silicon phosphides: Different stoichiometries and exotic electronic properties

    SciTech Connect

    Huang, Bing; Zhuang, Houlong L.; Yoon, Mina; Sumpter, Bobby G.; Wei, Su-Huai

    2015-03-03

    We report that the discovery of stable two-dimensional, earth-abundant, semiconducting materials is of great interest and may impact future electronic technologies. By combining global structural prediction and first-principles calculations, we have theoretically discovered several previously unknown semiconducting silicon phosphides (SixPy) monolayers, which could be formed stably at the stoichiometries of y/x ≥1. Unexpectedly, some of these compounds, i.e., P-6m2 Si1P1 and Pm Si1P2, have comparable or even lower formation enthalpies than their previously known bulk allotropes. The band gaps (Eg) of SixPy compounds can be dramatically tuned in an extremely wide range (0< Eg < 3 eV) by simply changing the number of layers or applying an in-plane strain. Furthermore, we find that carrier doping can drive the ground state of C2/m Si1P3 from a nonmagnetic state into a robust half-metallic spin-polarized state, originating from its unique valence band structure, which can extend the use of Si-related compounds for spintronics.

  20. Electronic Structures of Free-Standing Nanowires made from Indirect Bandgap Semiconductor Gallium Phosphide.

    PubMed

    Liao, Gaohua; Luo, Ning; Chen, Ke-Qiu; Xu, H Q

    2016-01-01

    We present a theoretical study of the electronic structures of freestanding nanowires made from gallium phosphide (GaP)-a III-V semiconductor with an indirect bulk bandgap. We consider [001]-oriented GaP nanowires with square and rectangular cross sections, and [111]-oriented GaP nanowires with hexagonal cross sections. Based on tight binding models, both the band structures and wave functions of the nanowires are calculated. For the [001]-oriented GaP nanowires, the bands show anti-crossing structures, while the bands of the [111]-oriented nanowires display crossing structures. Two minima are observed in the conduction bands, while the maximum of the valence bands is always at the Γ-point. Using double group theory, we analyze the symmetry properties of the lowest conduction band states and highest valence band states of GaP nanowires with different sizes and directions. The band state wave functions of the lowest conduction bands and the highest valence bands of the nanowires are evaluated by spatial probability distributions. For practical use, we fit the confinement energies of the electrons and holes in the nanowires to obtain an empirical formula. PMID:27307081

  1. Growth and Photoelectrochemical Energy Conversion of Wurtzite Indium Phosphide Nanowire Arrays.

    PubMed

    Kornienko, Nikolay; Gibson, Natalie A; Zhang, Hao; Eaton, Samuel W; Yu, Yi; Aloni, Shaul; Leone, Stephen R; Yang, Peidong

    2016-05-24

    Photoelectrochemical (PEC) water splitting into hydrogen and oxygen is a promising strategy to absorb solar energy and directly convert it into a dense storage medium in the form of chemical bonds. The continual development and improvement of individual components of PEC systems is critical toward increasing the solar to fuel efficiency of prototype devices. Within this context, we describe a study on the growth of wurtzite indium phosphide (InP) nanowire (NW) arrays on silicon substrates and their subsequent implementation as light-absorbing photocathodes in PEC cells. The high onset potential (0.6 V vs the reversible hydrogen electrode) and photocurrent (18 mA/cm(2)) of the InP photocathodes render them as promising building blocks for high performance PEC cells. As a proof of concept for overall system integration, InP photocathodes were combined with a nanoporous bismuth vanadate (BiVO4) photoanode to generate an unassisted solar water splitting efficiency of 0.5%. PMID:27124203

  2. Growth and Photoelectrochemical Energy Conversion of Wurtzite Indium Phosphide Nanowire Arrays.

    PubMed

    Kornienko, Nikolay; Gibson, Natalie A; Zhang, Hao; Eaton, Samuel W; Yu, Yi; Aloni, Shaul; Leone, Stephen R; Yang, Peidong

    2016-05-24

    Photoelectrochemical (PEC) water splitting into hydrogen and oxygen is a promising strategy to absorb solar energy and directly convert it into a dense storage medium in the form of chemical bonds. The continual development and improvement of individual components of PEC systems is critical toward increasing the solar to fuel efficiency of prototype devices. Within this context, we describe a study on the growth of wurtzite indium phosphide (InP) nanowire (NW) arrays on silicon substrates and their subsequent implementation as light-absorbing photocathodes in PEC cells. The high onset potential (0.6 V vs the reversible hydrogen electrode) and photocurrent (18 mA/cm(2)) of the InP photocathodes render them as promising building blocks for high performance PEC cells. As a proof of concept for overall system integration, InP photocathodes were combined with a nanoporous bismuth vanadate (BiVO4) photoanode to generate an unassisted solar water splitting efficiency of 0.5%.

  3. Electronic Structures of Free-Standing Nanowires made from Indirect Bandgap Semiconductor Gallium Phosphide

    NASA Astrophysics Data System (ADS)

    Liao, Gaohua; Luo, Ning; Chen, Ke-Qiu; Xu, H. Q.

    2016-06-01

    We present a theoretical study of the electronic structures of freestanding nanowires made from gallium phosphide (GaP)—a III-V semiconductor with an indirect bulk bandgap. We consider [001]-oriented GaP nanowires with square and rectangular cross sections, and [111]-oriented GaP nanowires with hexagonal cross sections. Based on tight binding models, both the band structures and wave functions of the nanowires are calculated. For the [001]-oriented GaP nanowires, the bands show anti-crossing structures, while the bands of the [111]-oriented nanowires display crossing structures. Two minima are observed in the conduction bands, while the maximum of the valence bands is always at the Γ-point. Using double group theory, we analyze the symmetry properties of the lowest conduction band states and highest valence band states of GaP nanowires with different sizes and directions. The band state wave functions of the lowest conduction bands and the highest valence bands of the nanowires are evaluated by spatial probability distributions. For practical use, we fit the confinement energies of the electrons and holes in the nanowires to obtain an empirical formula.

  4. Elastic, magnetic and electronic properties of iridium phosphide Ir2P

    PubMed Central

    Wang, Pei; Wang, Yonggang; Wang, Liping; Zhang, Xinyu; Yu, Xiaohui; Zhu, Jinlong; Wang, Shanmin; Qin, Jiaqian; Leinenweber, Kurt; Chen, Haihua; He, Duanwei; Zhao, Yusheng

    2016-01-01

    Cubic (space group: Fmm) iridium phosphide, Ir2P, has been synthesized at high pressure and high temperature. Angle-dispersive synchrotron X-ray diffraction measurements on Ir2P powder using a diamond-anvil cell at room temperature and high pressures (up to 40.6 GPa) yielded a bulk modulus of B0 = 306(6) GPa and its pressure derivative B0′ = 6.4(5). Such a high bulk modulus attributed to the short and strongly covalent Ir-P bonds as revealed by first – principles calculations and three-dimensionally distributed [IrP4] tetrahedron network. Indentation testing on a well–sintered polycrystalline sample yielded the hardness of 11.8(4) GPa. Relatively low shear modulus of ~64 GPa from theoretical calculations suggests a complicated overall bonding in Ir2P with metallic, ionic, and covalent characteristics. In addition, a spin glass behavior is indicated by magnetic susceptibility measurements. PMID:26905444

  5. Direct Band Gap Gallium Antimony Phosphide (GaSbxP1-x) Alloys

    NASA Astrophysics Data System (ADS)

    Russell, H. B.; Andriotis, A. N.; Menon, M.; Jasinski, J. B.; Martinez-Garcia, A.; Sunkara, M. K.

    2016-02-01

    Here, we report direct band gap transition for Gallium Phosphide (GaP) when alloyed with just 1-2 at% antimony (Sb) utilizing both density functional theory based computations and experiments. First principles density functional theory calculations of GaSbxP1-x alloys in a 216 atom supercell configuration indicate that an indirect to direct band gap transition occurs at x = 0.0092 or higher Sb incorporation into GaSbxP1-x. Furthermore, these calculations indicate band edge straddling of the hydrogen evolution and oxygen evolution reactions for compositions ranging from x = 0.0092 Sb up to at least x = 0.065 Sb making it a candidate for use in a Schottky type photoelectrochemical water splitting device. GaSbxP1-x nanowires were synthesized by reactive transport utilizing a microwave plasma discharge with average compositions ranging from x = 0.06 to x = 0.12 Sb and direct band gaps between 2.21 eV and 1.33 eV. Photoelectrochemical experiments show that the material is photoactive with p-type conductivity. This study brings attention to a relatively uninvestigated, tunable band gap semiconductor system with tremendous potential in many fields.

  6. Submillimeter sources for radiometry using high power Indium Phosphide Gunn diode oscillators

    NASA Technical Reports Server (NTRS)

    Deo, Naresh C.

    1990-01-01

    A study aimed at developing high frequency millimeter wave and submillimeter wave local oscillator sources in the 60-600 GHz range was conducted. Sources involved both fundamental and harmonic-extraction type Indium Phosphide Gunn diode oscillators as well as varactor multipliers. In particular, a high power balanced-doubler using varactor diodes was developed for 166 GHz. It is capable of handling 100 mW input power, and typically produced 25 mW output power. A high frequency tripler operating at 500 GHz output frequency was also developed and cascaded with the balanced-doubler. A dual-diode InP Gunn diode combiner was used to pump this cascaded multiplier to produce on the order of 0.5 mW at 500 GHz. In addition, considerable development and characterization work on InP Gunn diode oscillators was carried out. Design data and operating characteristics were documented for a very wide range of oscillators. The reliability of InP devices was examined, and packaging techniques to enhance the performance were analyzed. A theoretical study of a new class of high power multipliers was conducted for future applications. The sources developed here find many commercial applications for radio astronomy and remote sensing.

  7. Electronic Structures of Free-Standing Nanowires made from Indirect Bandgap Semiconductor Gallium Phosphide.

    PubMed

    Liao, Gaohua; Luo, Ning; Chen, Ke-Qiu; Xu, H Q

    2016-06-16

    We present a theoretical study of the electronic structures of freestanding nanowires made from gallium phosphide (GaP)-a III-V semiconductor with an indirect bulk bandgap. We consider [001]-oriented GaP nanowires with square and rectangular cross sections, and [111]-oriented GaP nanowires with hexagonal cross sections. Based on tight binding models, both the band structures and wave functions of the nanowires are calculated. For the [001]-oriented GaP nanowires, the bands show anti-crossing structures, while the bands of the [111]-oriented nanowires display crossing structures. Two minima are observed in the conduction bands, while the maximum of the valence bands is always at the Γ-point. Using double group theory, we analyze the symmetry properties of the lowest conduction band states and highest valence band states of GaP nanowires with different sizes and directions. The band state wave functions of the lowest conduction bands and the highest valence bands of the nanowires are evaluated by spatial probability distributions. For practical use, we fit the confinement energies of the electrons and holes in the nanowires to obtain an empirical formula.

  8. Direct Band Gap Gallium Antimony Phosphide (GaSbxP1−x) Alloys

    PubMed Central

    Russell, H. B.; Andriotis, A. N.; Menon, M.; Jasinski, J. B.; Martinez-Garcia, A.; Sunkara, M. K.

    2016-01-01

    Here, we report direct band gap transition for Gallium Phosphide (GaP) when alloyed with just 1–2 at% antimony (Sb) utilizing both density functional theory based computations and experiments. First principles density functional theory calculations of GaSbxP1−x alloys in a 216 atom supercell configuration indicate that an indirect to direct band gap transition occurs at x = 0.0092 or higher Sb incorporation into GaSbxP1−x. Furthermore, these calculations indicate band edge straddling of the hydrogen evolution and oxygen evolution reactions for compositions ranging from x = 0.0092 Sb up to at least x = 0.065 Sb making it a candidate for use in a Schottky type photoelectrochemical water splitting device. GaSbxP1−x nanowires were synthesized by reactive transport utilizing a microwave plasma discharge with average compositions ranging from x = 0.06 to x = 0.12 Sb and direct band gaps between 2.21 eV and 1.33 eV. Photoelectrochemical experiments show that the material is photoactive with p-type conductivity. This study brings attention to a relatively uninvestigated, tunable band gap semiconductor system with tremendous potential in many fields. PMID:26860470

  9. Elastic, magnetic and electronic properties of iridium phosphide Ir2P.

    PubMed

    Wang, Pei; Wang, Yonggang; Wang, Liping; Zhang, Xinyu; Yu, Xiaohui; Zhu, Jinlong; Wang, Shanmin; Qin, Jiaqian; Leinenweber, Kurt; Chen, Haihua; He, Duanwei; Zhao, Yusheng

    2016-02-24

    Cubic (space group: Fmm) iridium phosphide, Ir2P, has been synthesized at high pressure and high temperature. Angle-dispersive synchrotron X-ray diffraction measurements on Ir2P powder using a diamond-anvil cell at room temperature and high pressures (up to 40.6 GPa) yielded a bulk modulus of B0 = 306(6) GPa and its pressure derivative B0' = 6.4(5). Such a high bulk modulus attributed to the short and strongly covalent Ir-P bonds as revealed by first - principles calculations and three-dimensionally distributed [IrP4] tetrahedron network. Indentation testing on a well-sintered polycrystalline sample yielded the hardness of 11.8(4) GPa. Relatively low shear modulus of ~64 GPa from theoretical calculations suggests a complicated overall bonding in Ir2P with metallic, ionic, and covalent characteristics. In addition, a spin glass behavior is indicated by magnetic susceptibility measurements.

  10. Highly stable two-dimensional silicon phosphides: Different stoichiometries and exotic electronic properties

    DOE PAGES

    Huang, Bing; Zhuang, Houlong L.; Yoon, Mina; Sumpter, Bobby G.; Wei, Su-Huai

    2015-03-03

    We report that the discovery of stable two-dimensional, earth-abundant, semiconducting materials is of great interest and may impact future electronic technologies. By combining global structural prediction and first-principles calculations, we have theoretically discovered several previously unknown semiconducting silicon phosphides (SixPy) monolayers, which could be formed stably at the stoichiometries of y/x ≥1. Unexpectedly, some of these compounds, i.e., P-6m2 Si1P1 and Pm Si1P2, have comparable or even lower formation enthalpies than their previously known bulk allotropes. The band gaps (Eg) of SixPy compounds can be dramatically tuned in an extremely wide range (0< Eg < 3 eV) by simply changingmore » the number of layers or applying an in-plane strain. Furthermore, we find that carrier doping can drive the ground state of C2/m Si1P3 from a nonmagnetic state into a robust half-metallic spin-polarized state, originating from its unique valence band structure, which can extend the use of Si-related compounds for spintronics.« less

  11. Characterization and ultrafiltration of semiconductor indium phosphide (InP) wastewater for recycling.

    PubMed

    Wu, M; Sun, D D; Tay, J H

    2005-01-01

    This research work investigated the physical and chemical properties of a new type of wastewater produced from the semiconductor industry. The wastewater generated from indium phosphide (InP) wafer backgrinding and sawing processes was characterized in term of its particle size distribution (PSD), zeta potential, suspended and dissolved solids, total organic carbon, and turbidity. The wastewater contained high concentration of fine InP dusts with a size ranging from 0.07 - 1.44 mm. In spite of its high concentration of suspended solids resulting in high turbidity up to 371 NTU, the wastewater contained very low organic matters (TOC < 2.2 mg l(-1)) and other inorganic impurities (SO4(2-) < 0.21 mg l(-1) and Na+ < 0.16 mg l(-1)). Based on the experimental data collected, the treatment technologies using chemical precipitation and ultrafiltration were applied to the wastewater. Both processes could effectively remove InP particles from the wastewater, however the coagulants in chemical precipitation introduced other ionic contents into the process resulting in difficulties of water recycling in the later stage. In comparison, ultrafiltration was more promising for InP wastewater treatment and recycling. Based on the results of this study, a full-scale UF system was built in a local semiconductor plant and it has successfully reclaimed water from the InP wastes for the past six months without any quality issue being raised.

  12. Low resistance silver contacts to indium phosphide - Electrical and metallurgical considerations

    NASA Technical Reports Server (NTRS)

    Weizer, Victor G.; Fatemi, Navid S.

    1993-01-01

    The electrical and metallurgical behavior of the Ag-InP contact system has been investigated. Specific contact resistivity (Rc) values in the low 10 exp -6 Ohm sq cm range are readily achieved on n-InP (Si: 1.7 x 10 exp 18/cu cm) after sintering at 400 C for several minutes. The low Rc values, however, are shown to be accompanied by dissolution of InP into the metallization, resulting in device degradation. An analysis of the sinter-induced metallurgical interactions shows this system to be similar to the well-characterized Au-InP system, albeit with fundamental differences. The similarities include the dissociative diffusion of In, the reaction-suppressing effect of SiO2 capping, and especially, the formation of a phosphide layer at the metal-InP interface. The low post-sinter Rc values in the Ag-InP system may be due to the presence of a AgP2 layer at the metal-InP interface; low values of Rc can be achieved without incurring device degrading metallurgical interactions by introducing a thin AgP2 layer between the InP and the current carrying metallization.

  13. Forward-biased current annealing of radiation degraded indium phosphide and gallium arsenide solar cells

    NASA Technical Reports Server (NTRS)

    Michael, Sherif; Cypranowski, Corinne; Anspaugh, Bruce

    1990-01-01

    The preliminary results of a novel approach to low-temperature annealing of previously irradiated indium phosphide and gallium arsenide solar cells are reported. The technique is based on forward-biased current annealing. The two types of III-V solar cells were irradiated with 1-MeV electrons to a fluence level of (1-10) x 10 to the 14th electrons/sq cm. Several annealing attempts were made, varying all conditions. Optimum annealing was achieved when cells were injected with minority currents at a constant 90 C. The current density for each type of cell was also determined. Significant recovery of degraded parameters was achieved in both cases. However, the InP cell recovery notably exceeded the recovery in GaAs cells. The recovery is thought to be caused by current-stimulated reordering of the radiator-induced displacement damage. Both types of cell were then subjected to several cycles of irradiation and annealing. The results were also very promising. The significant recovery of degraded cell parameters at low temperature might play a major role in considerably extending the end of life of future spacecraft.

  14. Highly Efficient and Robust Nickel Phosphides as Bifunctional Electrocatalysts for Overall Water-Splitting.

    PubMed

    Li, Jiayuan; Li, Jing; Zhou, Xuemei; Xia, Zhaoming; Gao, Wei; Ma, Yuanyuan; Qu, Yongquan

    2016-05-01

    To search for the efficient non-noble metal based and/or earth-abundant electrocatalysts for overall water-splitting is critical to promote the clean-energy technologies for hydrogen economy. Herein, we report nickel phosphide (NixPy) catalysts with the controllable phases as the efficient bifunctional catalysts for water electrolysis. The phases of NixPy were determined by the temperatures of the solid-phase reaction between the ultrathin Ni(OH)2 plates and NaH2PO2·H2O. The NixPy with the richest Ni5P4 phase synthesized at 325 °C (NixPy-325) delivered efficient and robust catalytic performance for hydrogen evolution reaction (HER) in the electrolytes with a wide pH range. The NixPy-325 catalysts also exhibited a remarkable performance for oxygen evolution reaction (OER) in a strong alkaline electrolyte (1.0 M KOH) due to the formation of surface NiOOH species. Furthermore, the bifunctional NixPy-325 catalysts enabled a highly performed overall water-splitting with ∼100% Faradaic efficiency in 1.0 M KOH electrolyte, in which a low applied external potential of 1.57 V led to a stabilized catalytic current density of 10 mA/cm(2) over 60 h.

  15. Size-dependent magnetic and electrocatalytic properties of nickel phosphide nanoparticles

    NASA Astrophysics Data System (ADS)

    Pan, Yuan; Lin, Yan; Liu, Yunqi; Liu, Chenguang

    2016-03-01

    Nickel phosphide (Ni2P) nanoparticles (NPs) with different sizes were synthesized via thermal decomposition of bis(triphenylphosphine)nickel dichloride precursor in the presence of oleylamine. The size of the as-synthesized Ni2P NPs could easily be controlled by increasing the reaction temperature from 300 to 340 °C. The structure and morphology were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), N2 adsorption-desorption and X-ray photoelectron spectroscopy (XPS). Then the influences of the size of the Ni2P NPs on the magnetic and electrocatalytic properties were investigated systematically. The results indicate that the as-synthesized Ni2P NPs exhibit ferromagnetic characteristic at 5 K. The Ni2P NPs with small size exhibit superparamagnetism and the larger size exhibit ferromagnetic characteristic at 300 K. The blocking temperature, saturation magnetization, remanent magnetization and coercivity increased significantly with the increase of size of Ni2P NPs, indicating the strong size effect of Ni2P NPs for magnetic properties. Electrochemical tests indicate that the catalytic activity can be enhanced by decreasing the size of Ni2P NPs. Due to the larger electrochemical active surface area and higher electrical conductivity, the Ni2P NPs with small size exhibit higher electrocatalytic activity. This work suggests that the size of Ni2P NPs is an important factor to affect the magnetic and electrocatalytic properties.

  16. Phase-controllable synthesis of nanosized nickel phosphides and comparison of photocatalytic degradation ability.

    PubMed

    Ni, Yonghong; Jin, Lina; Hong, Jianming

    2011-01-01

    In this paper, we employed a facile hydrothermal route to successfully synthesize nanosized nickel phosphide particles with controlled phases via selecting different surfactants at different temperatures and times. The phases of the as-obtained products were determined by X-ray powder diffraction (XRD) patterns and Rietveld refinement of XRD data. The morphologies of the products were characterized by (high resolution) transmission electron microscopy (HR/TEM) and field emission scanning electron microscopy (FESEM). Experiments indicated that pure Ni2P phase could be prepared when nontoxic red phosphorus and nickel dichloride were used as starting materials in the presence of polyvinylpyrrolidone (PVP, 30 K), sodium dodecylbenzene sulfonate (SDBS), cetyltrimethylammonium bromide (CTAB) or polyethylene glycol 10000 (PEG-10000) at 160 °C for 10 h. When acrylamide (AM) was selected as the surfactant, however, pure Ni12P5 phase could be prepared by prolonging the reaction time to 20 h at 160 °C, or enhancing the reaction temperature to 180 °C for 10 h. Furthermore, the experiments indicated that the pure Ni2P phase possessed a stronger photocatalytic degradation ability than the pure Ni12P5 phase. PMID:21049133

  17. Highly Efficient and Robust Nickel Phosphides as Bifunctional Electrocatalysts for Overall Water-Splitting.

    PubMed

    Li, Jiayuan; Li, Jing; Zhou, Xuemei; Xia, Zhaoming; Gao, Wei; Ma, Yuanyuan; Qu, Yongquan

    2016-05-01

    To search for the efficient non-noble metal based and/or earth-abundant electrocatalysts for overall water-splitting is critical to promote the clean-energy technologies for hydrogen economy. Herein, we report nickel phosphide (NixPy) catalysts with the controllable phases as the efficient bifunctional catalysts for water electrolysis. The phases of NixPy were determined by the temperatures of the solid-phase reaction between the ultrathin Ni(OH)2 plates and NaH2PO2·H2O. The NixPy with the richest Ni5P4 phase synthesized at 325 °C (NixPy-325) delivered efficient and robust catalytic performance for hydrogen evolution reaction (HER) in the electrolytes with a wide pH range. The NixPy-325 catalysts also exhibited a remarkable performance for oxygen evolution reaction (OER) in a strong alkaline electrolyte (1.0 M KOH) due to the formation of surface NiOOH species. Furthermore, the bifunctional NixPy-325 catalysts enabled a highly performed overall water-splitting with ∼100% Faradaic efficiency in 1.0 M KOH electrolyte, in which a low applied external potential of 1.57 V led to a stabilized catalytic current density of 10 mA/cm(2) over 60 h. PMID:27064172

  18. Dilute phosphide nitride materials as photocathodes for electrochemical solar energy conversion

    NASA Astrophysics Data System (ADS)

    Parameshwaran, Vijay; Xu, Xiaoqing; Kang, Yangsen; Harris, James; Wong, H.-S. Philip; Clemens, Bruce

    2013-03-01

    Dilute nitride materials have been used in a variety of III-V photonic devices, but have not been significantly explored in photoelectrochemical applications. This work focuses on using dilute phosphide nitride materials of the form (Al,In)P1-xNx as photocathodes for the generation of hydrogen fuel from solar energy. Heteroepitaxial MOCVD growth of AlPN thin films on GaP yields high quality material with a direct bandgap energy of 2.218 eV. Aligned epitaxial growth of InP and GaP nanowires on InP and Si substrates, respectively, provides a template for designing nanostructured photocathodes over a large area. Electrochemical testing of a AlPN/GaP heterostructure electrode yields up to a sixfold increase in photocurrent enhancement under blue light illumination as compared to a GaP electrode. Additionally, the AlPN/GaP electrodes exhibit no degradation in performance after galvanostatic biasing over time. These results show that (Al,In)P1-xNx is a promising materials system for use in nanoscale photocathode structures.

  19. Alkyl Chain Growth on a Transition Metal Center: How Does Iron Compare to Ruthenium and Osmium?

    PubMed Central

    Sainna, Mala A.; de Visser, Sam P.

    2015-01-01

    Industrial Fischer-Tropsch processes involve the synthesis of hydrocarbons usually on metal surface catalysts. On the other hand, very few homogeneous catalysts are known to perform a Fischer-Tropsch style of reaction. In recent work, we established the catalytic properties of a diruthenium-platinum carbene complex, [(CpRu)2(μ2-H)(μ2-NHCH3)(μ3-C)PtCH3(P(CH3)3)2](CO)n+ with n = 0, 2 and Cp = η5-C5(CH3)5, and showed it to react efficiently by initial hydrogen atom transfer followed by methyl transfer to form an alkyl chain on the Ru-center. In particular, the catalytic efficiency was shown to increase after the addition of two CO molecules. As such, this system could be viewed as a potential homogeneous Fischer-Tropsch catalyst. Herein, we have engineered the catalytic center of the catalyst and investigated the reactivity of trimetal carbene complexes of the same type using iron, ruthenium and osmium at the central metal scaffold. The work shows that the reactivity should increase from diosmium to diruthenium to diiron; however, a non-linear trend is observed due to multiple factors contributing to the individual barrier heights. We identified all individual components of these reaction steps in detail and established the difference in reactivity of the various complexes. PMID:26426009

  20. Coronary wall imaging in mice using osmium tetroxide and micro-computed tomography

    NASA Astrophysics Data System (ADS)

    Kozlowski, Megan; Donohue, Danielle; Chen, Marcus; Daniels, Mathew; Connelly, Patricia; Jeffries, Kenneth; Clevenger, Randall; Wen, Han H.; Pai, Vinay M.

    2011-07-01

    Coronary artery disease (CAD) is a major cause of death in the United States and results from the accumulation of atherosclerotic plaques in the arteries of the heart. Plaques accumulate as the result of the retention of low-density lipoprotein (LDL) particles in the sub-endothelium of the arterial wall. In mouse aorta, these lesions form primarily at the branching sites or bifurcations. However, in the coronary system, data has shown that late-stage plaque formation occurs throughout the proximal segments of the arteries. In order to better understand plaque formation in the coronary arteries, we have developed an osmium tetroxide (OsO4) stained coronary wall imaging protocol performed using microcomputed tomography (microCT). OsO4 is a heavy metal contrast agent that readily binds to lipids. Our data in 3- to 25-week old C57BL6 wild-type mice shows that the coronary vessel walls are highlighted by the use of the contrast agent. We expect that this combination of OsO4 and microCT will allow us to investigate the coronary artery wall in atherogenesis models of mice to characterize plaque formation.

  1. Intramolecular excited-state interactions of surfactant-active osmium(II) photosensitizers

    SciTech Connect

    Sasksteder, L.; Demas, J.N. ); DeGraff, B.A. )

    1989-05-17

    A new class of luminescent surfactant-active complexes, cis-OsL{sub 2}(CO)NC(CH{sub 2}){sub n}CH{sub 3}{sup 2+} (n = 0-19; L = 2,2{prime}-bipyridine and 1,10-phenanthroline), were synthesized and characterized. They represent another example of an intramolecular perturbation of excited-state properties by what would normally be considered an electronically passive alkyl ligand. The effect is smaller in the Os(II) case and has a different n dependence than was observed in the fac-ReL(CO){sub 3}NC(CH{sub 2}){sub n}CH{sub 3}{sup +} system. The differences arise from varied geometric constraints on the foldback and the orbital parentage of the emitting state. Foldback must be directly to ligands involved in the emission process in order to perturb the emission. The osmium(II) center highly activates the bound nitrile to thermal nucleophilic attack, and luminescent adducts are formed with alcohols and aliphatic and aromatic amines. Such activation has not been previously observed in complexes with {alpha}-diimine ligands. The complexes also photodecompose by labilization of the nitrile. 37 refs., 5 figs.

  2. Osmium-191/iridium-191m radionuclide generator using an oxalato osmate parent complex

    SciTech Connect

    Packard, A.B.; Treves, S.T.; O'Brien, G.M.; Lim, K.S.

    1987-10-01

    A new osmium-191/iridium-191m (/sup 191/Os//sup 191/mIr) radionuclide generator has been developed that offers high /sup 191/mIr yield (greater than 20%/ml) and low /sup 191/Os breakthrough (less than 5 X 10(-4)%/ml) when eluted with a solution of 0.001 M oxalic acid and 0.9% (normal) saline. This is the first /sup 191/Os//sup 191/mIr generator that combines the advantages of high /sup 191/mIr yield, extremely low /sup 191/Os breakthrough, and an eluate that does not require buffering prior to injection. These improvements in performance were accomplished through use of the chelate transdioxobisoxalatoosmate(VI) as the parent complex on the generator. The clinical result of the combination of higher yield and lower breakthrough is a 100-fold decrease in the estimated patient radiation dose compared with the same study performed with technetium-99m (/sup 99m/Tc), and the injectable eluate makes the generator easier to use. Acute and subacute toxicity studies performed on this generator eluate have shown no adverse effects attributable to the eluate.

  3. Rhenium-osmium and samarium-neodymium isotopic systematics of the stillwater complex

    USGS Publications Warehouse

    Lambert, D.D.; Morgan, J.W.; Walker, R.J.; Shirey, S.B.; Carlson, R.W.; Zientek, M.L.; Koski, M.S.

    1989-01-01

    Isotopic data for the Stillwater Complex, Montana , which formed about 2700 Ma (million years ago), were obtained to evaluate the role of magma mixing in the formation of strategic platinum-group element (PGE) ore deposits. Neodymium and osmium isotopic data indicate that the intrusion formed from at least two geochemically distinct magmas. Ultramafic affinity (U-type) magmas had initial ??Nd of -0.8 to -3.2 and a chondritic initial 187Os/186Os ratio of ???0.88, whereas anorthositic affinity (A-type) magmas had ??Nd of -0.7 to +1.7 and an initial 187Os/186Os ratio of ???1.13. These data suggest that U-type magmas were derived from a lithospheric mantle source containing recycled crustal materials whereas A-type magmas originated either by crustal contamination of basaltic magmas or by partial melting of basalt in the lower crust. The Nd and Os isotopic data also suggest that Os, and probably the other PGEs in ore horizons such as the J-M Reef, was derived from A-type magmas. The Nd and Os isotopic heterogeneity observed in rocks below the J-M Reef also suggests that A-type magmas were injected into the Stillwater U-type magma chamber at several stages during the development of the Ultramafic series.

  4. Rapid and direct determination of fructose in food: a new osmium-polymer mediated biosensor.

    PubMed

    Antiochia, Riccarda; Vinci, Giuliana; Gorton, Lo

    2013-10-15

    This paper describes the development and performance of a new rapid amperometric biosensor for fructose monitoring in food analysis. The biosensor is based on the activity of fructose dehydrogenase (FDH) immobilised into a carbon nanotube paste electrode according to two different procedures. The direct wiring of the FDH in a highly original osmium-polymer hydrogel was found to offer a better enzyme entrapment compared to the immobilisation of the enzyme in an albumin hydrogel. The optimised biosensor required only 5U of FDH and kept the 80% of its initial sensitivity after 4months. During this time, the biosensor showed a detection limit for fructose of 1μM, a large linear range between 0.1 and 5mM, a high sensitivity (1.95μAcm(-2)mM), good reproducibility (RSD=2.1%) and a fast response time (4s). Finally, the biosensor was applied for specific determination of fructose in honey, fruit juices, soft and energy drinks. The results indicated a very good agreement with those obtained with a commercial reference kit. No significant interference was observed with the proposed biosensor.

  5. Emissive osmium(II) complexes with tetradentate bis(pyridylpyrazolate) chelates.

    PubMed

    Chang, Shih-Han; Chang, Chun-Fu; Liao, Jia-Ling; Chi, Yun; Zhou, Dong-Ying; Liao, Liang-Sheng; Jiang, Tzung-Ying; Chou, Tsao-Pei; Li, Elise Y; Lee, Gene-Hsiang; Kuo, Ting-Yi; Chou, Pi-Tai

    2013-05-20

    A tetradentate bis(pyridylpyrazolate) chelate, L, is assembled by connecting two bidentate 3-(trifluoromethyl)-5-(2-pyridyl)pyrazole chelates at the 6 position of the pyridyl fragment with a phenylamido appendage. This chelate was then utilized in the synthesis of three osmium(II) complexes, namely, [Os(L)(CO)2] (4), [Os(L)(PPh2Me)2] (5), and [Os(L)(PPhMe2)2] (6). Single-crystal X-ray structural analyses were executed on 4 and 5 to reveal the bonding arrangement of the L chelate. Phosphine-substituted derivatives 5 and 6 are highly emissive in both solution and the solid state, and their photophysical properties were measured and discussed on the basis of computational approaches. For application, fabrication and analysis of organic light-emitting diodes (OLEDs) were also carried out. The OLEDs using 5 and 6 as dopants exhibit saturated red emission with maximum external quantum efficiencies of 9.8% and 9.4%, respectively, which are higher than that of the device using [Ir(piq)3] as a red-emitting reference sample. Moreover, for documentation, 5 and 6 also achieve a maximum brightness of 19540 cd·m(-2) at 800 mA·cm(-2) (11.6 V) and 12900 cd·m(-2) at 500 mA·cm(-2) (10.5 V), respectively.

  6. Alkyl Chain Growth on a Transition Metal Center: How Does Iron Compare to Ruthenium and Osmium?

    PubMed

    Sainna, Mala A; de Visser, Sam P

    2015-09-28

    Industrial Fischer-Tropsch processes involve the synthesis of hydrocarbons usually on metal surface catalysts. On the other hand, very few homogeneous catalysts are known to perform a Fischer-Tropsch style of reaction. In recent work, we established the catalytic properties of a diruthenium-platinum carbene complex, [(CpRu)₂(μ²-H) (μ²-NHCH₃)(μ³-C)PtCH₃(P(CH₃)₃)₂](CO)n⁺ with n=0, 2 and Cp=η⁵-C₅(CH₃)₅, and showed it to react efficiently by initial hydrogen atom transfer followed by methyl transfer to form an alkyl chain on the Ru-center. In particular, the catalytic efficiency was shown to increase after the addition of two CO molecules. As such, this system could be viewed as a potential homogeneous Fischer-Tropsch catalyst. Herein, we have engineered the catalytic center of the catalyst and investigated the reactivity of trimetal carbene complexes of the same type using iron, ruthenium and osmium at the central metal scaffold. The work shows that the reactivity should increase from diosmium to diruthenium to diiron; however, a non-linear trend is observed due to multiple factors contributing to the individual barrier heights. We identified all individual components of these reaction steps in detail and established the difference in reactivity of the various complexes.

  7. Lattice strain of osmium diboride under high pressure and nonhydrostatic stress

    SciTech Connect

    Kavner, Abby; Weinberger, Michelle B.; Shahar, Anat; Cumberland, Robert W.; Levine, Jonathan B.; Kaner, Richard B.; Tolbert, Sarah H.

    2012-01-01

    The lattice strain behavior of osmium diboride—a member of a group of third-row transition metal borides associated with hard/superhard behavior—has been studied using radial diffraction in a diamond anvil cell under high pressure and non-hydrostatic stress. We interpret the average values of the measured lattice strains as a lower-bound to the lattice-plane dependent yield strengths using existing estimates for the elastic constants of OsB2, with a yield strength of 11 GPa at 27.5 GPa of hydrostaticpressure. The measured differential lattice strains show significant plane-dependent anisotropy, with the (101) lattice plane showing the largest differential strain and the (001) lattice plane showing the least strain. At the highest pressure, the a-axis develops a larger compressive strain and supports a larger differential strain than either the b or c axes. This causes an increase in the c/a ratio and a decrease in the a/b ratio especially in the maximum stress direction. The large strength anisotropy of this material points to possible ways to modulate directional mechanical properties by taking advantage of the interplay between aggregate polycrystalline texture with directional mechanical properties.

  8. Alkyl Chain Growth on a Transition Metal Center: How Does Iron Compare to Ruthenium and Osmium?

    PubMed

    Sainna, Mala A; de Visser, Sam P

    2015-01-01

    Industrial Fischer-Tropsch processes involve the synthesis of hydrocarbons usually on metal surface catalysts. On the other hand, very few homogeneous catalysts are known to perform a Fischer-Tropsch style of reaction. In recent work, we established the catalytic properties of a diruthenium-platinum carbene complex, [(CpRu)₂(μ²-H) (μ²-NHCH₃)(μ³-C)PtCH₃(P(CH₃)₃)₂](CO)n⁺ with n=0, 2 and Cp=η⁵-C₅(CH₃)₅, and showed it to react efficiently by initial hydrogen atom transfer followed by methyl transfer to form an alkyl chain on the Ru-center. In particular, the catalytic efficiency was shown to increase after the addition of two CO molecules. As such, this system could be viewed as a potential homogeneous Fischer-Tropsch catalyst. Herein, we have engineered the catalytic center of the catalyst and investigated the reactivity of trimetal carbene complexes of the same type using iron, ruthenium and osmium at the central metal scaffold. The work shows that the reactivity should increase from diosmium to diruthenium to diiron; however, a non-linear trend is observed due to multiple factors contributing to the individual barrier heights. We identified all individual components of these reaction steps in detail and established the difference in reactivity of the various complexes. PMID:26426009

  9. The most incompressible metal osmium at static pressures above 750 gigapascals.

    PubMed

    Dubrovinsky, L; Dubrovinskaia, N; Bykova, E; Bykov, M; Prakapenka, V; Prescher, C; Glazyrin, K; Liermann, H-P; Hanfland, M; Ekholm, M; Feng, Q; Pourovskii, L V; Katsnelson, M I; Wills, J M; Abrikosov, I A

    2015-09-10

    Metallic osmium (Os) is one of the most exceptional elemental materials, having, at ambient pressure, the highest known density and one of the highest cohesive energies and melting temperatures. It is also very incompressible, but its high-pressure behaviour is not well understood because it has been studied so far only at pressures below 75 gigapascals. Here we report powder X-ray diffraction measurements on Os at multi-megabar pressures using both conventional and double-stage diamond anvil cells, with accurate pressure determination ensured by first obtaining self-consistent equations of state of gold, platinum, and tungsten in static experiments up to 500 gigapascals. These measurements allow us to show that Os retains its hexagonal close-packed structure upon compression to over 770 gigapascals. But although its molar volume monotonically decreases with pressure, the unit cell parameter ratio of Os exhibits anomalies at approximately 150 gigapascals and 440 gigapascals. Dynamical mean-field theory calculations suggest that the former anomaly is a signature of the topological change of the Fermi surface for valence electrons. However, the anomaly at 440 gigapascals might be related to an electronic transition associated with pressure-induced interactions between core electrons. The ability to affect the core electrons under static high-pressure experimental conditions, even for incompressible metals such as Os, opens up opportunities to search for new states of matter under extreme compression. PMID:26302297

  10. The most incompressible metal osmium at static pressures above 750 gigapascals

    NASA Astrophysics Data System (ADS)

    Dubrovinsky, L.; Dubrovinskaia, N.; Bykova, E.; Bykov, M.; Prakapenka, V.; Prescher, C.; Glazyrin, K.; Liermann, H.-P.; Hanfland, M.; Ekholm, M.; Feng, Q.; Pourovskii, L. V.; Katsnelson, M. I.; Wills, J. M.; Abrikosov, I. A.

    2015-09-01

    Metallic osmium (Os) is one of the most exceptional elemental materials, having, at ambient pressure, the highest known density and one of the highest cohesive energies and melting temperatures. It is also very incompressible, but its high-pressure behaviour is not well understood because it has been studied so far only at pressures below 75 gigapascals. Here we report powder X-ray diffraction measurements on Os at multi-megabar pressures using both conventional and double-stage diamond anvil cells, with accurate pressure determination ensured by first obtaining self-consistent equations of state of gold, platinum, and tungsten in static experiments up to 500 gigapascals. These measurements allow us to show that Os retains its hexagonal close-packed structure upon compression to over 770 gigapascals. But although its molar volume monotonically decreases with pressure, the unit cell parameter ratio of Os exhibits anomalies at approximately 150 gigapascals and 440 gigapascals. Dynamical mean-field theory calculations suggest that the former anomaly is a signature of the topological change of the Fermi surface for valence electrons. However, the anomaly at 440 gigapascals might be related to an electronic transition associated with pressure-induced interactions between core electrons. The ability to affect the core electrons under static high-pressure experimental conditions, even for incompressible metals such as Os, opens up opportunities to search for new states of matter under extreme compression.

  11. Mutual effect of ligands in nitrido and nitroso complexes of osmium and ruthenium from NQR data

    SciTech Connect

    Kravchenko. E.A.; Burtsev, M.Yu.; Sinitsyn, M.N.; Svetlov, A.A.; Kokunov, Ya.V.; Buslaev, A.

    1987-11-01

    The purpose of this investigation was to study by NQR the spectral results of the mutual ligand effect in complex compounds having various types of short bonds. The authors obtained the /sup 35/Cl, /sup 81/Br, and /sup 127/I NQR spectra of a large number of halogen complexes of osmium and ruthenium having short Os=N and M in equilibrium NO bonds of the following types: R(OsNHal/sub 4/) (R = (Ph/sub 4/P)/sup +/, (Bu/sub 4/N)/sup +/; Hal = Cl/sup -/, Br/sup -/, I/sup -/), K/sub 2/(OsNCl/sub 5/), Rb/sub 2/(OsNBr/sub 5/), (NH/sub 4/)/sub 2/(OsNBr/sub 5/), K(OsNHal/sub 4/L) (Hal = Cl/sup -/, Br/sup -/; L = H/sub 2/O, CH/sub 3/CN), K/sub 2/(MNOHal/sub 5/) (M = Os, Ru; Hal = Cl/sup -/, Br/sup -/, I/sup -/). The experimental NQR values measured are connected by the Townes and Dailey theory with the chemical bond characteristics i, sigma, ..pi.., the degree of the ionic, the sigma-covalent, and the ..pi..-covalent natures respectively ( i + sigma + ..pi.. = 1).

  12. Rapid adaptation of some phytoplankton species to osmium as a result of spontaneous mutations.

    PubMed

    Marvá, Fernando; García-Balboa, Camino; Baselga-Cervera, Beatriz; Costas, Eduardo

    2014-03-01

    To understand the vulnerability of individual species to anthropogenic contamination, it is important to evaluate the different abilities of phytoplankton to respond to environmental changes induced by pollution. The ability of a species to adapt, rather than its initial tolerance, is the basis for survival under rapidly increasing levels of anthropogenic contamination. High doses of osmium (Os) cause massive destruction of diverse phytoplankton groups. In this study, we found that the coastal chlorophyte Tetraselmis suecica and the continental chlorophyte Dictyosphaerium chlorelloides were able to adapt to a lethal dose of Os. In these species, Os-resistant cells arose as a result of rare spontaneous mutations (at rates of approximately 10(-6) mutants per cell division) that occurred before exposure to Os. The mutants remained in the microalgal populations by means of mutation-selection balance. The huge size of phytoplankton populations ensures that there are always enough Os-resistant mutants to guarantee the survival of the population under Os pollution. In contrast, we observed that neither a haptophyte species from open ocean regions nor a cyanobacterium from continental freshwater were able to adapt to the lethal Os dose. Adaptation of phytoplankton to Os contamination is relevant because industrial activities are leading to a rapid increase in Os pollution worldwide.

  13. ROLE OF C AND P SITES ON THE CHEMICAL ACTIVITY OF METAL CARBIDE AND PHOSPHIDES: FROM CLUSTERS TO SINGLE-CRYSTAL SURFACES

    SciTech Connect

    RODRIGUEZ,J.A.; VINES, F.; LIU, P.; ILLAS, F.

    2007-07-01

    Transition metal carbides and phosphides have shown tremendous potential as highly active catalysts. At a microscopic level, it is not well understood how these new catalysts work. Their high activity is usually attributed to ligand or/and ensemble effects. Here, we review recent studies that examine the chemical activity of metal carbide and phosphides as a function of size, from clusters to extended surfaces, and metal/carbon or metal/phosphorous ratio. These studies reveal that the C and P sites in these compounds cannot be considered as simple spectators. They moderate the reactivity of the metal centers and provide bonding sites for adsorbates.

  14. A comparative field trial, conducted without pre-treatment census baiting, of the rodenticides zinc phosphide, thallium sulphate and gophacide against Rattus norvegicus.

    PubMed Central

    Rennison, B. D.

    1976-01-01

    The effectiveness of the single-dose poison treatments of farm rat infestations, analysed by comparing the weights of the post-treatment census bait takes in covariance with the weights of the prebait takes, showed that treatments with 2-5% zinc phosphide, 0-3% thallium sulphate or 0-3% gophacide were equally effective and significantly better than were treatments with 1% zinc phosphide or 0-1% thallium sulphate. The methodology and sensitivity of different analyses are also considered. PMID:1068192

  15. Diffusion length variation in 0.5- and 3-MeV-proton-irradiated, heteroepitaxial indium phosphide solar cells

    NASA Technical Reports Server (NTRS)

    Jain, Raj K.; Weinberg, Irving; Flood, Dennis J.

    1993-01-01

    Indium phosphide (InP) solar cells are more radiation resistant than gallium arsenide (GaAs) and silicon (Si) solar cells, and their growth by heteroepitaxy offers additional advantages leading to the development of light weight, mechanically strong, and cost-effective cells. Changes in heteroepitaxial InP cell efficiency under 0.5- and 3-MeV proton irradiations have been explained by the variation in the minority-carrier diffusion length. The base diffusion length versus proton fluence was calculated by simulating the cell performance. The diffusion length damage coefficient, K(sub L), was also plotted as a function of proton fluence.

  16. Selectivity control of photosensitive structures based on gallium arsenide phosphide solid solutions by changing the rate of surface recombination

    NASA Astrophysics Data System (ADS)

    Tarasov, S. A.; Andreev, M. Y.; Lamkin, I. A.; Solomonov, A. V.

    2016-08-01

    In this paper, we demonstrate the effect of surface recombination on spectral sensitivity of structures based on gallium arsenide phosphide solid solutions. Simulation of the effect for structures based on a p-n junction and a Schottky barrier was carried out. Photodetectors with different rates of surface recombination were fabricated by using different methods of preliminary treatment of the semiconductor surface. We experimentally demonstrated the possibility to control photodetector selectivity by altering the rate of surface recombination. The full width at half maximum was reduced by almost 4 times, while a relatively small decrease in sensitivity at the maximum was observed.

  17. A Metallacycle Fragmentation Strategy for Vinyl Transfer from Enol Carboxylates to Secondary Alcohol C-H Bonds via Osmium- or Ruthenium-Catalyzed Transfer Hydrogenation.

    PubMed

    Park, Boyoung Y; Luong, Tom; Sato, Hiroki; Krische, Michael J

    2015-06-24

    A strategy for catalytic vinyl transfer from enol carboxylates to activated secondary alcohol C-H bonds is described. Using XPhos-modified ruthenium(0) or osmium(0) complexes, enol carboxylate-carbonyl oxidative coupling forms transient β-acyloxy-oxametallacycles, which eliminate carboxylate to deliver allylic ruthenium(II) or osmium(II) alkoxides. Reduction of the metal(II) salt via hydrogen transfer from the secondary alcohol reactant releases the product of carbinol C-H vinylation and regenerates ketone and zero-valent catalyst.

  18. Mechanism elucidation of the cis-trans isomerization of an azole ruthenium-nitrosyl complex and its osmium counterpart.

    PubMed

    Gavriluta, Anatolie; Büchel, Gabriel E; Freitag, Leon; Novitchi, Ghenadie; Tommasino, Jean Bernard; Jeanneau, Erwann; Kuhn, Paul-Steffen; González, Leticia; Arion, Vladimir B; Luneau, Dominique

    2013-06-01

    Synthesis and X-ray diffraction structures of cis and trans isomers of ruthenium and osmium metal complexes of general formulas (nBu4N)[cis-MCl4(NO)(Hind)], where M = Ru (1) and Os (3), and (nBu4N)[trans-MCl4(NO)(Hind)], where M = Ru (2) and Os (4) and Hind = 1H-indazole are reported. Interconversion between cis and trans isomers at high temperatures (80-130 °C) has been observed and studied by NMR spectroscopy. Kinetic data indicate that isomerizations correspond to reversible first order reactions. The rates of isomerization reactions even at 110 °C are very low with rate constants of 10(-5) s(-1) and 10(-6) s(-1) for ruthenium and osmium complexes, respectively, and the estimated rate constants of isomerization at room temperature are of ca. 10(-10) s(-1). The activation parameters, which have been obtained from fitting the reaction rates at different temperatures to the Eyring equation for ruthenium [ΔH(cis-trans)‡ = 122.8 ± 1.3; ΔH(trans-cis)‡ = 138.8 ± 1.0 kJ/mol; ΔS(cis-trans)‡ = -18.7 ± 3.6; ΔS(trans-cis)‡ = 31.8 ± 2.7 J/(mol·K)] and osmium [ΔH(cis-trans)‡ = 200.7 ± 0.7; ΔH(trans-cis)‡ = 168.2 ± 0.6 kJ/mol; ΔS(cis-trans)‡ = 142.7 ± 8.9; ΔS(trans-cis)‡ = 85.9 ± 3.9 J/(mol·K)] reflect the inertness of these systems. The entropy of activation for the osmium complexes is highly positive and suggests the dissociative mechanism of isomerization. In the case of ruthenium, the activation entropy for the cis to trans isomerization is negative [-18.6 J/(mol·K)], while being positive [31.0 J/(mol·K)] for the trans to cis conversion. The thermodynamic parameters for cis to trans isomerization of [RuCl4(NO)(Hind)]-, viz. ΔH° = 13.5 ± 1.5 kJ/mol and ΔS° = -5.2 ± 3.4 J/(mol·K) indicate the low difference between the energies of cis and trans isomers. The theoretical calculation has been carried out on isomerization of ruthenium complexes with DFT methods. The dissociative, associative, and intramolecular twist isomerization

  19. Mechanism Elucidation of the cis–trans Isomerization of an Azole Ruthenium–Nitrosyl Complex and Its Osmium Counterpart

    PubMed Central

    2013-01-01

    Synthesis and X-ray diffraction structures of cis and trans isomers of ruthenium and osmium metal complexes of general formulas (nBu4N)[cis-MCl4(NO)(Hind)], where M = Ru (1) and Os (3), and (nBu4N)[trans-MCl4(NO)(Hind)], where M = Ru (2) and Os (4) and Hind = 1H-indazole are reported. Interconversion between cis and trans isomers at high temperatures (80–130 °C) has been observed and studied by NMR spectroscopy. Kinetic data indicate that isomerizations correspond to reversible first order reactions. The rates of isomerization reactions even at 110 °C are very low with rate constants of 10–5 s–1 and 10–6 s–1 for ruthenium and osmium complexes, respectively, and the estimated rate constants of isomerization at room temperature are of ca. 10–10 s–1. The activation parameters, which have been obtained from fitting the reaction rates at different temperatures to the Eyring equation for ruthenium [ΔHcis-trans‡= 122.8 ± 1.3; ΔHtrans-cis‡= 138.8 ± 1.0 kJ/mol; ΔScis-trans‡= −18.7 ± 3.6; ΔStrans-cis‡= 31.8 ± 2.7 J/(mol·K)] and osmium [ΔHcis-trans‡= 200.7 ± 0.7; ΔHtrans-cis‡= 168.2 ± 0.6 kJ/mol; ΔScis-trans‡= 142.7 ± 8.9; ΔStrans-cis‡= 85.9 ± 3.9 J/(mol·K)] reflect the inertness of these systems. The entropy of activation for the osmium complexes is highly positive and suggests the dissociative mechanism of isomerization. In the case of ruthenium, the activation entropy for the cis to trans isomerization is negative [−18.6 J/(mol·K)], while being positive [31.0 J/(mol·K)] for the trans to cis conversion. The thermodynamic parameters for cis to trans isomerization of [RuCl4(NO)(Hind)]−, viz. ΔH° = 13.5 ± 1.5 kJ/mol and ΔS° = −5.2 ± 3.4 J/(mol·K) indicate the low difference between the energies of cis and trans isomers. The theoretical calculation has been carried out on isomerization of ruthenium complexes with DFT methods. The dissociative, associative, and intramolecular twist isomerization mechanisms have

  20. Osmium-Isotope and Platinum-Group-Element Systematics of Impact-Melt Rocks, Chesapeake Bay Impact Structure, Virginia, USA

    NASA Technical Reports Server (NTRS)

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

    2005-01-01

    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.

  1. Abundances and isotopic compositions of rhenium and osmium in pyrite samples from the Huaibei coalfield, Anhui, China

    USGS Publications Warehouse

    Liu, Gaisheng; Chou, C.-L.; Peng, Z.; Yang, G.

    2008-01-01

    Two pyrite samples from the Shihezi Formation (Lower Permian), Huaibei coalfield, Anhui, China, have been analyzed for abundances and isotopic compositions of rhenium and osmium using negative thermal ion mass spectrometry. The Re-Os ages of the pyrites are 64.4 and 226 Ma, which are younger than the formation age of the coal seam. The pyrite samples may consist of pyrite formed at various stages during the history of coal formation. The ??Osvalues of the two pyrite samples are +17 and +18, respectively. Such high ??Osvalues are reported for the first time for recycles crustal materials from a sedimentary basin. ?? Springer-Verlag 2007.

  2. A numerical simulation study of gallium-phosphide/silicon heterojunction passivated emitter and rear solar cells

    NASA Astrophysics Data System (ADS)

    Wagner, Hannes; Ohrdes, Tobias; Dastgheib-Shirazi, Amir; Puthen-Veettil, Binesh; König, Dirk; Altermatt, Pietro P.

    2014-01-01

    The performance of passivated emitter and rear (PERC) solar cells made of p-type Si wafers is often limited by recombination in the phosphorus-doped emitter. To overcome this limitation, a realistic PERC solar cell is simulated, whereby the conventional phosphorus-doped emitter is replaced by a thin, crystalline gallium phosphide (GaP) layer. The resulting GaP/Si PERC cell is compared to Si PERC cells, which have (i) a standard POCl3 diffused emitter, (ii) a solid-state diffused emitter, or (iii) a high efficiency ion-implanted emitter. The maximum efficiencies for these realistic PERC cells are between 20.5% and 21.2% for the phosphorus-doped emitters (i)-(iii), and up to 21.6% for the GaP emitter. The major advantage of this GaP hetero-emitter is a significantly reduced recombination loss, resulting in a higher Voc. This is so because the high valence band offset between GaP and Si acts as a nearly ideal minority carrier blocker. This effect is comparable to amorphous Si. However, the GaP layer can be contacted with metal fingers like crystalline Si, so no conductive oxide is necessary. Compared to the conventional PERC structure, the GaP/Si PERC cell requires a lower Si base doping density, which reduces the impact of the boron-oxygen complexes. Despite the lower base doping, fewer rear local contacts are necessary. This is so because the GaP emitter shows reduced recombination, leading to a higher minority electron density in the base and, in turn, to a higher base conductivity.

  3. A numerical simulation study of gallium-phosphide/silicon heterojunction passivated emitter and rear solar cells

    SciTech Connect

    Wagner, Hannes; Ohrdes, Tobias; Dastgheib-Shirazi, Amir; Puthen-Veettil, Binesh; König, Dirk; Altermatt, Pietro P.

    2014-01-28

    The performance of passivated emitter and rear (PERC) solar cells made of p-type Si wafers is often limited by recombination in the phosphorus-doped emitter. To overcome this limitation, a realistic PERC solar cell is simulated, whereby the conventional phosphorus-doped emitter is replaced by a thin, crystalline gallium phosphide (GaP) layer. The resulting GaP/Si PERC cell is compared to Si PERC cells, which have (i) a standard POCl{sub 3} diffused emitter, (ii) a solid-state diffused emitter, or (iii) a high efficiency ion-implanted emitter. The maximum efficiencies for these realistic PERC cells are between 20.5% and 21.2% for the phosphorus-doped emitters (i)–(iii), and up to 21.6% for the GaP emitter. The major advantage of this GaP hetero-emitter is a significantly reduced recombination loss, resulting in a higher V{sub oc}. This is so because the high valence band offset between GaP and Si acts as a nearly ideal minority carrier blocker. This effect is comparable to amorphous Si. However, the GaP layer can be contacted with metal fingers like crystalline Si, so no conductive oxide is necessary. Compared to the conventional PERC structure, the GaP/Si PERC cell requires a lower Si base doping density, which reduces the impact of the boron-oxygen complexes. Despite the lower base doping, fewer rear local contacts are necessary. This is so because the GaP emitter shows reduced recombination, leading to a higher minority electron density in the base and, in turn, to a higher base conductivity.

  4. Hydroxyethyl Starch Could Save a Patient With Acute Aluminum Phosphide Poisoning.

    PubMed

    Marashi, Sayed Mahdi; Nasri Nasrabadi, Zeynab; Jafarzadeh, Mostafa; Mohammadi, Sogand

    2016-07-01

    A 40-year-old male patient with suicidal ingestion of one tablet of aluminium phosphide was referred to the department of toxicology emergency of Baharloo Hospital, Tehran, Iran. The garlic odor was smelled from the patient and abdominal pain and continuous vomiting as well as agitation and heartburn were the first signs and symptoms. Systolic and diastolic blood pressures at the arrival time were 95 and 67 mmHg, respectively. Gastric lavage with potassium permanganate (1:10,000), and 2 vials of sodium bicarbonate through a nasogastric tube was started for the patient and the management was continued with free intravenous infusion of 1 liter of NaCl 0.9% serum plus NaHCO3, hydrocortisone acetate (200 mg), calcium gluconate (1 g) and magnesium sulfate (1 g). Regarding the large intravenous fluid therapy and vasoconstrictor administering (norepinephrine started by 5 µg/min and continued till 15 µg/min), there were no signs of response and the systolic blood pressure was 49 mmHg. At this time, hydroxyethyl starch (HES) (6% hetastarch 600/0.75 in 0.9% sodium chloride) with a dose of 600 cc in 6 hours was started for the patient. At the end of therapy with HES, the patient was stable with systolic and diastolic blood pressure of 110 and 77 mmHg, respectively. He was discharged on the 6th day after the psychological consultation, with normal clinical and paraclinical examinations. This is the first report of using HES in the management of AlP poisoning and its benefit to survive the patient. PMID:27424021

  5. Study of grown-in and radiation-induced defects in indium phosphide

    SciTech Connect

    Shaban, E.H.

    1986-01-01

    This research is focused on (1) conducting detailed theoretical and experimental study of grown-in and radiation-induced defects in liquid encapsulated Czohralski (LEC) grown, Zn-doped P-type indium phosphide (InP), (2) identifying the physical origin of the defects detected using Deep Level Transient Spectroscopy (DLTS) method, and (3) and developing a second-order model to interpret the presence of nonexponential capacitance transients in DLTS method. Analysis of grown-in and radiation-induced defects in P-type InP is undertaken. The main research results are summarized as follows: (1) DLTS analysis of grown-in defects in liquid LEC-grown, Zn-doped, P-type InP is made in this study. A single-hole trap of E/sub v/ + 0.52 eV is detected with a trap density of 1.8 x 10/sup 15/ cm/sup -3/. The physical origin of this hole trap is attributed to a phosphorus vacancy or phosphorus interstitial-related defect. (2) One-MeV electron-irradiated P-type InP introduced two new hole traps, namely E/sub v/ + 0.34 and E/sub v/ + 0.58 eV with introduction rates (dN/sub T/d phi) of 0.4 and 1.2 per electron-cm, respectively. (3) A theoretical model is developed to interpret nonexponential capacitance transients in a deep-level transient spectroscopy method when the capture process competes with the dominant thermal-emission process.

  6. End-coupled optical waveguide MEMS devices in the indium phosphide material system

    NASA Astrophysics Data System (ADS)

    Pruessner, Marcel W.; Siwak, Nathan; Amarnath, Kuldeep; Kanakaraju, S.; Chuang, Wen-Hsien; Ghodssi, Reza

    2006-04-01

    We demonstrate electrostatically actuated end-coupled optical waveguide devices in the indium phosphide (InP) material system. The design of a suitable layer structure and fabrication process for actuated InP-based waveguide micro-electro-mechanical systems (MEMS) is reviewed. Critical issues for optical design, such as coupling losses, are discussed and their effect on device performance is evaluated. Several end-coupled waveguide devices are demonstrated, including 1 × 2 optical switches and resonant sensors with integrated optical readout. The 1 × 2 optical switches exhibit low-voltage operation (<7 V), low crosstalk (-26 dB), reasonable loss (3.2 dB) and switching speed suitable for network restoration applications (140 µs, 2 ms settling time). Experimental characterization of the integrated cantilever waveguide resonant sensors shows high repeatability and accuracy, with a standard deviation as low as σ = 50 Hz (0.027%) for fresonant = 184.969 kHz. By performing focused-ion beam (FIB) milling on a sensor, a mass sensitivity of Δm/Δf = 5.3 × 10-15 g Hz-1 was measured, which is competitive with other sensors. Resonant frequencies as high as f = 1.061 MHz (Qeffective = 159.7) have been measured in air with calculated sensitivity Δm/Δf = 1.1 × 10-16 g Hz-1. Electrostatic tuning of the resonator sensors was also examined. The prospect of developing InP MEMS devices monolithically integrated with active optical components (lasers, LEDs, photodetectors) is discussed.

  7. CVD growth and properties of boron phosphide on 3C-SiC

    NASA Astrophysics Data System (ADS)

    Padavala, Balabalaji; Frye, C. D.; Wang, Xuejing; Raghothamachar, Balaji; Edgar, J. H.

    2016-09-01

    Improving the crystalline quality of boron phosphide (BP) is essential for realizing its full potential in semiconductor device applications. In this study, 3C-SiC was tested as a substrate for BP epitaxy. BP films were grown on 3C-SiC(100)/Si, 3C-SiC(111)/Si, and 3C-SiC(111)/4H-SiC(0001) substrates in a horizontal chemical vapor deposition (CVD) system. Films were produced with good crystalline orientation and morphological features in the temperature range of 1000-1200 °C using a PH3+B2H6+H2 mixture. Rotational twinning was absent in the BP due to the crystal symmetry-matching with 3C-SiC. Confocal 3D Raman imaging of BP films revealed primarily uniform peak shift and peak widths across the scanned area, except at defects on the surface. Synchrotron white beam X-ray topography showed the epitaxial relationship between BP and 3C-SiC was (100) < 011 > BP||(100) < 011 > 3C-SiC and (111) < 11 2 ̅ > BP||(111) < 11 2 ̅ > 3C-SiC. Scanning electron microscopy, Raman spectroscopy and X-ray diffraction analysis indicated residual tensile strain in the films and improved crystalline quality at temperatures below 1200 °C. These results indicated that BP properties could be further enhanced by employing high quality bulk 3C-SiC or 3C-SiC epilayers on 4H-SiC substrates.

  8. POP-pincer osmium-polyhydrides: head-to-head (Z)-dimerization of terminal alkynes.

    PubMed

    Alós, Joaquín; Bolaño, Tamara; Esteruelas, Miguel A; Oliván, Montserrat; Oñate, Enrique; Valencia, Marta

    2013-05-20

    A wide range of osmium-polyhydride complexes stabilized by the POP-pincer ligand xant(P(i)Pr2)2 (9,9-dimethyl-4,5-bis(diisopropylphosphino)xanthene) have been synthesized through cis-OsCl2{κ-S-(DMSO)4} (1, DMSO = dimethyl sulfoxide). Treatment of toluene solutions of this adduct with the diphosphine, under reflux, leads to OsCl2{xant(P(i)Pr2)2}(κ-S-DMSO) (2). The reaction of 2 with H2 in the presence of Et3N affords OsH3Cl{xant(P(i)Pr2)2} (3), which can be also prepared by addition of xant(P(i)Pr2)2 to toluene solutions of the unsaturated d(4)-trihydride OsH3Cl(P(i)Pr3)2 (5). Complex 3 reductively eliminates H2 in toluene at 90 °C. In the presence of dimethyl sulfoxide, the resulting monohydride is trapped by the S-donor molecule to give OsHCl{xant(P(i)Pr2)2}(κ-S-DMSO) (6). The reaction of 2 with H2 is sensible to the Brønsted base. Thus, in contrast to Et3N, NaH removes both chloride ligands and the hexahydride OsH6{xant(P(i)Pr2)2} (7), containing a κ(2)-P-binding diphosphine, is formed under 3 atm of hydrogen at 50 °C. Complex 7 releases a H2 molecule to yield the tetrahydride OsH4{xant(P(i)Pr2)2} (8), which can be also prepared by reaction of OsH6(P(i)Pr3)2 (9) with xant(P(i)Pr2)2. Complex 8 reduces H(+) to give, in addition to H2, the oxidized OsH4-species [OsH4(OTf){xant(P(i)Pr2)2}](+) (10, OTf = trifluoromethanesulfonate). The redox process occurs in two stages via the OsH5-cation [OsH5{xant(P(i)Pr2)2}](+) (11). The metal oxidation state four can be recovered. The addition of acetonitrile to 10 leads to [OsH2(η(2)-H2)(CH3CN){xant(P(i)Pr2)2}](2+) (12). The deprotonation of 12 yields the osmium(IV) trihydride [OsH3(CH3CN){xant(P(i)Pr2)2}](+) (13), which is also formed by addition of HOTf to the acetonitrile solutions of 8. The latter is further an efficient catalyst precursor for the head-to-head (Z)-dimerization of phenylacetylene and tert-butylacetylene. During the activation process of the tetrahydride, the bis(alkynyl)vinylidene derivatives Os

  9. Optical properties of beta-iron silicide, ruthenium silicide and osmium silicide: Semiconducting transition metal silicides

    NASA Astrophysics Data System (ADS)

    Birdwell, Anthony Glen

    2001-09-01

    results predicted by group theory. The optical properties of Ru2Si3 single crystals and polycrystalline thin films were explored using spectroscopic ellipsometry, ultraviolet to the near infrared (UV-VIS-NIR) transmission and reflectivity measurements, photothermal deflection spectroscopy, and Raman spectroscopy. We determined that the fundamental transition is direct with a value of 0.85 +/- 0.01 eV. The dielectric function was measured over a large energy range using spectroscopic ellipsometry and compared to theoretical results. A very good agreement was obtained between experiment and theory. Raman spectroscopy was used to study the vibrational properties of both the Ru2Si3 single crystals and polycrystalline thin films. The optical properties of bulk polycrystalline OsSi2 were explored using spectroscopic ellipsometry, UV-VIS-NIR reflectivity measurements, and Raman spectroscopy. We determined the first direct transition to have a value of about 1.88 eV. The dielectric function was measured over a large energy range using spectroscopic ellipsometry and compared to theoretical results. A very good agreement was obtained between experiment and theory. Raman spectroscopy was used to study the vibrational properties of OsSi 2. An electroless metal deposition technique was used to deposit thin films of osmium onto a silicon substrate and a brief summary of the results were given. We suggest that this method of depositing osmium is safer and more economical than conventional techniques such as e-beam evaporation.

  10. Seawater osmium isotope evidence for a middle Miocene flood basalt event in ferromanganese crust records

    USGS Publications Warehouse

    Klemm, V.; Frank, M.; Levasseur, S.; Halliday, A.N.; Hein, J.R.

    2008-01-01

    Three ferromanganese crusts from the northeast, northwest and central Atlantic were re-dated using osmium (Os) isotope stratigraphy and yield ages from middle Miocene to the present. The three Os isotope records do not show evidence for growth hiatuses. The reconstructed Os isotope-based growth rates for the sections older than 10??Ma are higher than those determined previously by the combined beryllium isotope (10Be/9Be) and cobalt (Co) constant-flux methods, which results in a decrease in the maximum age of each crust. This re-dating does not lead to significant changes to the interpretation of previously determined radiogenic isotope neodymium, lead (Nd, Pb) time series because the variability of these isotopes was very small in the records of the three crusts prior to 10??Ma. The Os isotope record of the central Atlantic crust shows a pronounced minimum during the middle Miocene between 15 and 12??Ma, similar to a minimum previously observed in two ferromanganese crusts from the central Pacific. For the other two Atlantic crusts, the Os isotope records and their calibration to the global seawater curve for the middle Miocene are either more uncertain or too short and thus do not allow for a reliable identification of an isotopic minimum. Similar to pronounced minima reported previously for the Cretaceous/Tertiary and Eocene/Oligocene boundaries, possible interpretations for the newly identified middle Miocene Os isotope minimum include changes in weathering intensity and/or a meteorite impact coinciding with the formation of the No??rdlinger Ries Crater. It is suggested that the eruption and weathering of the Columbia River flood basalts provided a significant amount of the unradiogenic Os required to produce the middle Miocene minimum. ?? 2008 Elsevier B.V.

  11. Oxidation does not (always) kill reactivity of transition metals: solution-phase conversion of nanoscale transition metal oxides to phosphides and sulfides.

    PubMed

    Muthuswamy, Elayaraja; Brock, Stephanie L

    2010-11-17

    Unexpected reactivity on the part of oxide nanoparticles that enables their transformation into phosphides or sulfides by solution-phase reaction with trioctylphosphine (TOP) or sulfur, respectively, at temperatures of ≤370 °C is reported. Impressively, single-phase phosphide products are produced, in some cases with controlled anisotropy and narrow polydispersity. The generality of the approach is demonstrated for Ni, Fe, and Co, and while manganese oxides are not sufficiently reactive toward TOP to form phosphides, they do yield MnS upon reaction with sulfur. The reactivity can be attributed to the small size of the precursor particles, since attempts to convert bulk oxides or even particles with sizes approaching 50 nm were unsuccessful. Overall, the use of oxide nanoparticles, which are easily accessed via reaction of inexpensive salts with air, in lieu of organometallic reagents (e.g., metal carbonyls), which may or may not be transformed into metal nanoparticles, greatly simplifies the production of nanoscale phosphides and sulfides. The precursor nanoparticles can easily be produced in large quantities and stored in the solid state without concern that "oxidation" will limit their reactivity.

  12. Electrocatalytic and photocatalytic hydrogen production from acidic and neutral-pH aqueous solutions using iron phosphide nanoparticles.

    PubMed

    Callejas, Juan F; McEnaney, Joshua M; Read, Carlos G; Crompton, J Chance; Biacchi, Adam J; Popczun, Eric J; Gordon, Thomas R; Lewis, Nathan S; Schaak, Raymond E

    2014-11-25

    Nanostructured transition-metal phosphides have recently emerged as Earth-abundant alternatives to platinum for catalyzing the hydrogen-evolution reaction (HER), which is central to several clean energy technologies because it produces molecular hydrogen through the electrochemical reduction of water. Iron-based catalysts are very attractive targets because iron is the most abundant and least expensive transition metal. We report herein that iron phosphide (FeP), synthesized as nanoparticles having a uniform, hollow morphology, exhibits among the highest HER activities reported to date in both acidic and neutral-pH aqueous solutions. As an electrocatalyst operating at a current density of -10 mA cm(-2), FeP nanoparticles deposited at a mass loading of ∼1 mg cm(-2) on Ti substrates exhibited overpotentials of -50 mV in 0.50 M H2SO4 and -102 mV in 1.0 M phosphate buffered saline. The FeP nanoparticles supported sustained hydrogen production with essentially quantitative faradaic yields for extended time periods under galvanostatic control. Under UV illumination in both acidic and neutral-pH solutions, FeP nanoparticles deposited on TiO2 produced H2 at rates and amounts that begin to approach those of Pt/TiO2. FeP therefore is a highly Earth-abundant material for efficiently facilitating the HER both electrocatalytically and photocatalytically.

  13. In vivo tumour and metastasis reduction and in vitro effects on invasion assays of the ruthenium RM175 and osmium AFAP51 organometallics in the mammary cancer model.

    PubMed

    Bergamo, A; Masi, A; Peacock, A F A; Habtemariam, A; Sadler, P J; Sava, G

    2010-01-01

    We have compared the organometallic arene complexes [(eta(6)-biphenyl)M(ethylenediamine)Cl](+) RM175 (M=Ru(II)) and its isostructural osmium(II) analogue AFAP51 (M=Os(II)) for their ability to induce cell detachment resistance from fibronectin, collagen IV and poly-l-lysine, and cell re-adhesion after treatment, their effects on cell migration and cell viability, on matrix metalloproteinases production, and on primary tumour growth of MCa mammary carcinoma, the effect of human serum albumin on their cytotoxicity. There are differences between ruthenium and osmium. The Os complex is up to 6x more potent than RM175 towards highly-invasive breast MDA-MB-231, human breast MCF-7 and human epithelial HBL-100 cancer cells, but whereas RM175 was active against MCa mammary carcinoma in vivo and caused metastasis reduction, AFAP51 was not. Intriguingly the presence of human serum albumin in the growth medium enhanced the cytotoxicity of both compounds. RM175 increased the resistance of MDA-MB-231 cells to detachment from substrates and both compounds inhibited the production of MMP-2. These data confirm the key role of ruthenium itself in anti-metastatic activity. It will be interesting to explore the activity of osmium arene complexes in other tumour models and the possibility of changing the non-arene ligands to tune the anticancer activity of osmium in vivo.

  14. Unexpected higher stabilisation of two classical antiaromatic frameworks with a ruthenium fragment compared to the osmium counterpart: origin probed by DFT calculations.

    PubMed

    Wu, Jingjing; Hao, Yulei; An, Ke; Zhu, Jun

    2016-01-01

    Density functional theory (DFT) calculations were carried out to investigate the stability and aromaticity of metallapentalocyclobutadienes. The results reveal unexpected higher stabilisation achieved with a 4d ruthenium fragment compared to the 5d [corrected] osmium counterpart. Moreover, direct 1-3 metal-carbon bonding in the metallabutadiene unit of these two complexes is negligible. PMID:26505956

  15. Electrochemical Properties of a Thiol Monolayers Coated Gold Electrode Modified with Osmium Gel Membrane as Enzyme Sensor

    NASA Astrophysics Data System (ADS)

    Yabutani, Tomoki; Okada, Nobuyuki; Maruyama, Kenichi; Motonaka, Junko

    The electrochemical behavior of an enzyme sensor for glucose using a gold electrode modified with thiol self-assembled membrane and osmium complex gel as an electron transferring mediator has further been investigated by electrochemical analysis. The gold electrode was initially coated with aminomethanethiol self assembling mono layer membrane(thiol-SAM) and then immobilized with glucose oxidase using poly(vinylpyridine-co-allylamine) (PVP-co-AA), gel coordinated with osmium bipyridine complexes (GOD/Os-PVP-co-AA gel). The cleaning condition of the surface of the Au electrode prior to coating thiol SAM was optimized for reduction of interference caused by concomitant compounds. It was found that interfering influence was most efficiently reduced in the case of use of the Au electrode immersed into nitric acid. The current ratio with a thiol coated gold electrode modified with Os-PVP-co-AA gel in glucose solution in the presence to absence of ascorbic acid, acetaminophen, and uric acid (ID+I/II) was 1.006, 1.014, and 1.018, respectively. The peak current response of glucose in the electrode modified with thiol SAM was dropped to 60 98% as compared with that without thiol SAM.

  16. Use of osmium tetroxide staining with microcomputerized tomography to visualize and quantify bone marrow adipose tissue in vivo.

    PubMed

    Scheller, Erica L; Troiano, Nancy; Vanhoutan, Joshua N; Bouxsein, Mary A; Fretz, Jackie A; Xi, Yougen; Nelson, Tracy; Katz, Griffin; Berry, Ryan; Church, Christopher D; Doucette, Casey R; Rodeheffer, Matthew S; Macdougald, Ormond A; Rosen, Clifford J; Horowitz, Mark C

    2014-01-01

    Adipocytes reside in discrete, well-defined depots throughout the body. In addition to mature adipocytes, white adipose tissue depots are composed of many cell types, including macrophages, endothelial cells, fibroblasts, and stromal cells, which together are referred to as the stromal vascular fraction (SVF). The SVF also contains adipocyte progenitors that give rise to mature adipocytes in those depots. Marrow adipose tissue (MAT) or marrow fat has long been known to be present in bone marrow (BM) but its origin, development, and function remain largely unknown. Clinically, increased MAT is associated with age, metabolic diseases, drug treatment, and marrow recovery in children receiving radiation and chemotherapy. In contrast to the other depots, MAT is unevenly distributed in the BM of long bones. Conventional quantitation relies on sectioning of the bone to overcome issues with distribution but is time-consuming, resource intensive, inconsistent between laboratories and may be unreliable as it may miss changes in MAT volume. Thus, the inability to quantitate MAT in a rapid, systematic, and reproducible manner has hampered a full understanding of its development and function. In this chapter, we describe a new technique that couples histochemical staining of lipid using osmium tetroxide with microcomputerized tomography to visualize and quantitate MAT within the medullary canal in three dimensions. Imaging of osmium staining provides a high-resolution map of existing and developing MAT in the BM. Because this method is simple, reproducible, and quantitative, we expect it will become a useful tool for the precise characterization of MAT.

  17. A SAR study of novel antiproliferative ruthenium and osmium complexes with quinoxalinone ligands in human cancer cell lines.

    PubMed

    Ginzinger, Werner; Mühlgassner, Gerhard; Arion, Vladimir B; Jakupec, Michael A; Roller, Alexander; Galanski, Markus; Reithofer, Michael; Berger, Walter; Keppler, Bernhard K

    2012-04-12

    A series of ruthenium(II) arene complexes with 3-(1H-benzimidazol-2-yl)-1H-quinoxalin-2-one, bearing pharmacophoric groups of known protein kinase inhibitors, and related benzoxazole and benzothiazole derivatives have been synthesized. In addition, the corresponding osmium complexes of the unsubstituted ligands have also been prepared. The compounds have been characterized by NMR, UV-vis, and IR spectroscopy, ESI mass spectrometry, elemental analysis, and by X-ray crystallography. Antiproliferative activity in three human cancer cell lines (A549, CH1, SW480) was determined by MTT assays, yielding IC(50) values of 6-60 μM for three unsubstituted metal-free ligands, whereas values for the metal complexes vary in a broad range from 0.3 to 140 μM. Complexation with osmium of quinoxalinone derivatives with benzimidazole or benzothiazole results in a more consistent increase in cytotoxicity than complexation with ruthenium. For selected compounds, the capacity to induce apoptosis was confirmed by fluorescence microscopy and flow-cytometric analysis, whereas cell cycle effects are only moderate.

  18. Osmium isotopes and silver as tracers of anthropogenic metals in sediments from Massachusetts and Cape Cod bays

    USGS Publications Warehouse

    Ravizza, G.E.; Bothner, Michael H.

    1996-01-01

    High concentrations of osmium (Os) and silver (Ag) and low 187Os/186Os ratios in Boston sewage make these elements sensitive tracers of the influence of sewage on marine sediments in Massachusetts and Cape Cod bays. Pristine marine sediments have Ag concentrations more than 200 times lower than sewage sludge, Os concentrations 10-40 times lower, and 187Os/186Os ratios six times higher. Surface sediments from both Massachusetts and Cape Cod bays exhibit both high Ag concentrations and low 187Os/186Os ratios indicating the influence of sewage particles on marine sediments in this region extends some 70 km from the point of sewage release. In detail, the distribution of Os and Ag do not support a model of simple physical mixing of sewage particles with normal marine sediments. Deviations from the mixing model may be the result of fractionation of Os and Ag in the marine environment, and [or] independent temporal variations in the Os and Ag content of the waste stream. The results of this investigation suggest that osmium isotopes may be widely applicable as tracers of the influence of sewage on sediments in estuarine environments and that subtle variations in the isotopic composition of Os in the waste stream may help constrain the sources of Os and other metals delivered to the environment.

  19. Distribution of coniferin in differentiating normal and compression woods using MALDI mass spectrometric imaging coupled with osmium tetroxide vapor treatment.

    PubMed

    Yoshinaga, Arata; Kamitakahara, Hiroshi; Takabe, Keiji

    2016-05-01

    Matrix-assisted laser desorption/ionization mass spectrometric imaging (MALDI-MSI) was employed to detect monolignol glucosides in differentiating normal and compression woods of two Japanese softwoods, Chamaecyparis obtusa and Cryptomeria japonica Comparison of matrix-assisted laser desorption/ionization time-of-flight mass spectrometry collision-induced dissociation fragmentation analysis and structural time-of-flight (MALDI-TOF CID-FAST) spectra between coniferin and differentiating xylem also confirmed the presence of coniferin in differentiating xylem. However, as matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS) and MALDI-TOF CID-FAST spectra of sucrose were similar to those of coniferin, it was difficult to distinguish the distribution of coniferin and sucrose using MALDI-MSI and collision-induced dissociation measurement only. To solve this problem, osmium tetroxide vapor was applied to sections of differentiating xylem. This vapor treatment caused peak shifts corresponding to the introduction of two hydroxyl groups to the C=C double bond in coniferin. The treatment did not cause a peak shift for sucrose, and therefore was effective in distinguishing coniferin and sucrose. Thus, it was found that MALDI-MSI combined with osmium tetroxide vapor treatment is a useful method to detect coniferin in differentiating xylem. PMID:26507270

  20. Osmium isotope and highly siderophile element systematics of the lunar crust

    USGS Publications Warehouse

    Day, J.M.D.; Walker, R.J.; James, O.B.; Puchtel, I.S.

    2010-01-01

    Coupled 187Os/188Os and highly siderophile element (HSE: Os, Ir, Ru, Pt, Pd, and Re) abundance data are reported for pristine lunar crustal rocks 60025, 62255, 65315 (ferroan anorthosites, FAN) and 76535, 78235, 77215 and a norite clast in 15455 (magnesian-suite rocks, MGS). Osmium isotopes permit more refined discrimination than previously possible of samples that have been contaminated by meteoritic additions and the new results show that some rocks, previously identified as pristine, contain meteorite-derived HSE. Low HSE abundances in FAN and MGS rocks are consistent with derivation from a strongly HSE-depleted lunar mantle. At the time of formation, the lunar floatation crust, represented by FAN, had 1.4 ?? 0.3 pg g- 1 Os, 1.5 ?? 0.6 pg g- 1 Ir, 6.8 ?? 2.7 pg g- 1 Ru, 16 ?? 15 pg g- 1 Pt, 33 ?? 30 pg g- 1 Pd and 0.29 ?? 0.10 pg g- 1 Re (??? 0.00002 ?? CI) and Re/Os ratios that were modestly elevated (187Re/188Os = 0.6 to 1.7) relative to CI chondrites. MGS samples are, on average, characterised by more elevated HSE abundances (??? 0.00007 ?? CI) compared with FAN. This either reflects contrasting mantle-source HSE characteristics of FAN and MGS rocks, or different mantle-crust HSE fractionation behaviour during production of these lithologies. Previous studies of lunar impact-melt rocks have identified possible elevated Ru and Pd in lunar crustal target rocks. The new results provide no supporting evidence for such enrichments. If maximum estimates for HSE in the lunar mantle are compared with FAN and MGS averages, crust-mantle concentration ratios (D-values) must be ??? 0.3. Such D-values are broadly similar to those estimated for partitioning between the terrestrial crust and upper mantle, with the notable exception of Re. Given the presumably completely different mode of origin for the primary lunar floatation crust and tertiary terrestrial continental crust, the potential similarities in crust-mantle HSE partitioning for the Earth and Moon are somewhat

  1. Osmium mass balance in peridotite and the effects of mantle-derived sulphides on basalt petrogenesis

    NASA Astrophysics Data System (ADS)

    Harvey, J.; Dale, C. W.; Gannoun, A.; Burton, K. W.

    2011-10-01

    Analyses of enriched mantle (EM)-basalts, using lithophile element-based isotope systems, have long provided evidence for discrete mantle reservoirs with variable composition. Upon partial melting, the mantle reservoir imparts its isotopic fingerprint upon the partial melt produced. However, it has increasingly been recognised that it may not be simple to delimit these previously well-defined mantle reservoirs; the "mantle zoo" may contain more reservoirs than previously envisaged. Here we demonstrate that a simple model with varying contributions from two populations of compositionally distinct mantle sulphides can readily account for the observed heterogeneities in Os isotope systematics of such basalts without additional mantle reservoirs. Osmium elemental and isotopic analyses of individual sulphide grains separated from spinel lherzolites from Kilbourne Hole, New Mexico, USA demonstrate that two discrete populations of mantle sulphide exist in terms of both Re-Os systematics and textural relationship with co-existing silicates. One population, with a rounded morphology, is preserved in silicate grains and typically possesses high [Os] and low [Re] with unradiogenic, typically sub-chondritic 187Os/ 188Os attributable to long term isolation in a low-Re environment. By contrast, irregular-shaped sulphides, preserved along silicate grain boundaries, possess low [Os], higher [Re] and a wider range of, but generally supra-chondritic 187Os/ 188Os ([Os] typically ⩽ 1-2 ppm, 187Os/ 188Os ⩽ 0.3729; this study). This population is thought to represent metasomatic sulphide. Uncontaminated silicate phases contain negligible Os (<100 ppt) therefore the Os elemental and isotope composition of basalts is dominated by volumetrically insignificant sulphide ([Os] ⩽ 37 ppm; this study). During the early stages of partial melting, supra-chondritic interstitial sulphides are mobilised and incorporated into the melt, adding their radiogenic 187Os/ 188Os signature. Only when

  2. Osmium pyme complexes for fast hydrogenation and asymmetric transfer hydrogenation of ketones.

    PubMed

    Baratta, Walter; Ballico, Maurizio; Del Zotto, Alessandro; Siega, Katia; Magnolia, Santo; Rigo, Pierluigi

    2008-01-01

    The osmium compound trans,cis-[OsCl2(PPh3)2(Pyme)] (1) (Pyme=1-(pyridin-2-yl)methanamine), obtained from [OsCl2(PPh3)3] and Pyme, thermally isomerizes to cis,cis-[OsCl2(PPh3)(2)(Pyme)] (2) in mesitylene at 150 degrees C. Reaction of [OsCl2(PPh3)3] with Ph2P(CH2)(4)PPh2 (dppb) and Pyme in mesitylene (150 degrees C, 4 h) leads to a mixture of trans-[OsCl2(dppb)(Pyme)] (3) and cis-[OsCl2(dppb)(Pyme)] (4) in about an 1:3 molar ratio. The complex trans-[OsCl2(dppb)(Pyet)] (5) (Pyet=2-(pyridin-2-yl)ethanamine) is formed by reaction of [OsCl2(PPh3)3] with dppb and Pyet in toluene at reflux. Compounds 1, 2, 5 and the mixture of isomers 3/4 efficiently catalyze the transfer hydrogenation (TH) of different ketones in refluxing 2-propanol and in the presence of NaOiPr (2.0 mol %). Interestingly, 3/4 has been proven to reduce different ketones (even bulky) by means of TH with a remarkably high turnover frequency (TOF up to 5.7 x 10(5) h(-1)) and at very low loading (0.05-0.001 mol %). The system 3/4 also efficiently catalyzes the hydrogenation of many ketones (H2, 5.0 atm) in ethanol with KOtBu (2.0 mol %) at 70 degrees C (TOF up to 1.5 x 10(4) h(-1)). The in-situ-generated catalysts prepared by the reaction of [OsCl2(PPh3)3] with Josiphos diphosphanes and (+/-)-1-alkyl-substituted Pyme ligands, promote the enantioselective TH of different ketones with 91-96 % ee (ee=enantiomeric excess) and with a TOF of up to 1.9 x 10(4) h(-1) at 60 degrees C.

  3. Osmium isotope variations in the oceans recorded by Fe-Mn crusts

    USGS Publications Warehouse

    Burton, K.W.; Bourdon, B.; Birck, J.-L.; Allegre, C.J.; Hein, J.R.

    1999-01-01

    This study presents osmium (Os) isotope data for recent growth surfaces of hydrogenetic ferromanganese (Fe-Mn) crusts from the Pacific, Atlantic and Indian Oceans. In general, these data indicate a relatively uniform Os isotopic composition for modern seawater, but suggest that North Atlantic seawater is slightly more radiogenic than that of the Pacific and Indian Oceans. The systematic difference in the Os isotopic composition between the major oceans probably reflects a greater input of old continental material with a high Re/Os ratio in the North Atlantic Ocean, consistent with the distribution of Nd and Pb isotopes. This spatial variation in the Os isotope composition in seawater is consistent with a residence time for Os of between 2 and 60 kyr. Indian Ocean samples show no evidence of a local source of radiogenic Os, which suggests that the present-day riverine input from the Himalaya-Tibet region is not a major source for Os. Recently formed Fe-Mn crusts from the TAG hydrothermal field in the North Atlantic yield an Os isotopic composition close to that of modern seawater, which indicates that, in this area, the input of unradiogenic Os from the hydrothermal alteration of oceanic crust is small. However, some samples from the deep Pacific (???4 km) possess a remarkably unradiogenic Os isotope composition (187Os/186Os ratios as low as 4.3). The compositional control of Os incorporation into the crusts and mixing relationships suggest that this unradiogenic composition is most likely due to the direct incorporation of micrometeoritic or abyssal peridotite particles, rather than indicating the presence of an unradiogenic deep-water mass. Moreover, this unradiogenic signal appears to be temporary, and local, and has had little apparent effect on the overall evolution of seawater. These results confirm that input of continental material through erosion is the dominant source of Os in seawater, but it is not clear whether global Os variations are due to the input

  4. Effect of Synthetic Levers on Nickel Phosphide Nanoparticle Formation: Ni5P4 and NiP2.

    PubMed

    Li, Da; Senevirathne, Keerthi; Aquilina, Lance; Brock, Stephanie L

    2015-08-17

    Due to their unique catalytic, electronic, and redox processes, Ni5P4 and NiP2 nanoparticles are of interest for a wide-range of applications from the hydrogen evolution reaction to energy storage (batteries); yet synthetic approaches to these materials are limited. In the present work, a phase-control strategy enabling the arrested-precipitation synthesis of nanoparticles of Ni5P4 and NiP2 as phase-pure samples using different Ni organometallic precursors and trioctylphosphine (TOP) is described. The composition and purity of the product can be tuned by changing key synthetic levers, including the Ni precursor, the oleylamine (OAm) coordinating solvent and TOP concentrations, temperature, time, and the presence or absence of a moderate temperature soak step to facilitate formation of Ni and/or Ni-P amorphous nanoparticle intermediates. Notably, the 230 °C intermediate step favors the ultimate formation of Ni2P and hinders further phosphidation to form Ni5P4 or NiP2 as phase-pure products. In the absence of this step, increasing the P/Ni ratio (13-20), reaction temperature (350-385 °C), and time (10-48 h) favors more P-rich phases, and these parameters can be adjusted to generate either Ni5P4 or NiP2. The phase of the obtained particles can also be tuned between pure Ni2P to Ni5P4 and NiP2 by simply decreasing the OAm/TOP ratio and/or changing the nickel precursor (nickel(II)acetylacetonate, nickel(II)acetate tetrahydrate, or bis(cyclooctadiene)nickel(0)). However, at high concentrations of OAm, the product formed is the same regardless of Ni precursor, suggesting the formation of a uniform Ni intermediate (an Ni-oleylamine complex) under these conditions that is responsible for product distribution. Intriguingly, under the extreme phosphidation conditions required to favor Ni5P4 and NiP2 over Ni2P (large excess of TOP), the 20-30 nm crystallites assemble into supraparticles with diameters of 100-500 nm. These factors are discussed in light of a comprehensive

  5. Antimalarial activity of ruthenium(II) and osmium(II) arene complexes with mono- and bidentate chloroquine analogue ligands.

    PubMed

    Ekengard, Erik; Glans, Lotta; Cassells, Irwin; Fogeron, Thibault; Govender, Preshendren; Stringer, Tameryn; Chellan, Prinessa; Lisensky, George C; Hersh, William H; Doverbratt, Isa; Lidin, Sven; de Kock, Carmen; Smith, Peter J; Smith, Gregory S; Nordlander, Ebbe

    2015-11-28

    Eight new ruthenium and five new osmium p-cymene half-sandwich complexes have been synthesized, characterized and evaluated for antimalarial activity. All complexes contain ligands that are based on a 4-chloroquinoline framework related to the antimalarial drug chloroquine. Ligands HL(1-8) are salicylaldimine derivatives, where HL(1) = N-(2-((2-hydroxyphenyl)methylimino)ethyl)-7-chloroquinolin-4-amine, and HL(2-8) contain non-hydrogen substituents in the 3-position of the salicylaldimine ring, viz. F, Cl, Br, I, NO2, OMe and (t)Bu for HL(2-8), respectively. Ligand HL(9) is also a salicylaldimine-containing ligand with substitutions in both 3- and 5-positions of the salicylaldimine moiety, i.e. N-(2-((2-hydroxy-3,5-di-tert-butylphenyl)methyl-imino)ethyl)-7-chloroquinolin-4-amine, while HL(10) is N-(2-((1-methyl-1H-imidazol-2-yl)methylamino)ethyl)-7-chloroquinolin-4-amine) The half sandwich metal complexes that have been investigated are [Ru(η(6)-cym)(L(1-8))Cl] (Ru-1-Ru-8, cym = p-cymene), [Os(η(6)-cym)(L(1-3,5,7))Cl] (Os-1-Os-3, Os-5, and Os-7), [M(η(6)-cym)(HL(9))Cl2] (M = Ru, Ru-HL(9); M = Os, Os-HL(9)) and [M(η(6)-cym)(L(10))Cl]Cl (M = Ru, Ru-10; M = Os, Os-10). In complexes Ru-1-Ru-8 and Ru-10, Os-1-Os-3, Os-5 and Os-7 and Os-10, the ligands were found to coordinate as bidentate N,O- and N,N-chelates, while in complexes Ru-HL(9) and Os-HL(9), monodentate coordination of the ligands through the quinoline nitrogen was established. The antimalarial activity of the new ligands and complexes was evaluated against chloroquine sensitive (NF54 and D10) and chloroquine resistant (Dd2) Plasmodium falciparum malaria parasite strains. Coordination of ruthenium and osmium arene moieties to the ligands resulted in lower antiplasmodial activities relative to the free ligands, but the resistance index is better for the ruthenium complexes compared to chloroquine. Overall, osmium complexes appeared to be less active than the corresponding ruthenium complexes. PMID:26491831

  6. Simulation of high-efficiency n[sup +]p indium phosphide solar cell results and future improvements

    SciTech Connect

    Jain, R.K.; Flood, D.J. )

    1994-12-01

    A simulation of the highest efficiency (19.1% AM0) n[sup +]p indium phosphide (InP) solar cell was made using a computer code PC-1D in order to understand it and suggest future improvements to it. Available cell design and process data was used in the simulation. Minority carrier diffusion lengths in the emitter and base have been varied to match the experimental cell I-V characteristics with the calculated results. To further understand and improve the InP cell efficiency, simulations were performed using improved values of cell material and process parameters. The authors show that the efficiency of this cell could be increased to more than 23% AM0 by incorporating the suggested cell material, design and process improvements. At these high efficiencies InP cell technology will be very attractive for space use.

  7. Synthesis and x-ray characterization of cobalt phosphide (Co₂P) nanorods for the oxygen reduction reaction

    DOE PAGES

    Doan-Nguyen, Vicky V.T.; Su, Dong; Zhang, Sen; Trigg, Edward B.; Agarwal, Rahul; Li, Jing; Winey, Karen I.; Murray, Christopher B.

    2015-07-14

    Low temperature fuel cells are clean, effective alternative fuel conversion technology. Oxygen reduction reaction (ORR) at the fuel cell cathode has required Pt as the electrocatalyst for high activity and selectivity of the four-electron reaction pathway. Targeting a less expensive, earth abundant alternative, we have developed the synthesis of cobalt phosphide (Co₂P) nanorods for ORR. Characterization techniques that include total X-ray scattering and extended X-ray absorption fine structure revealed a deviation of the nanorods from bulk crystal structure with a contraction along the b orthorhombic lattice parameter. The carbon supported nanorods have comparable activity but are remarkably more stable thanmore » conventional Pt catalysts for the oxygen reduction reaction in alkaline environments.« less

  8. Synthesis and x-ray characterization of cobalt phosphide (Co₂P) nanorods for the oxygen reduction reaction

    SciTech Connect

    Doan-Nguyen, Vicky V.T.; Su, Dong; Zhang, Sen; Trigg, Edward B.; Agarwal, Rahul; Li, Jing; Winey, Karen I.; Murray, Christopher B.

    2015-07-14

    Low temperature fuel cells are clean, effective alternative fuel conversion technology. Oxygen reduction reaction (ORR) at the fuel cell cathode has required Pt as the electrocatalyst for high activity and selectivity of the four-electron reaction pathway. Targeting a less expensive, earth abundant alternative, we have developed the synthesis of cobalt phosphide (Co₂P) nanorods for ORR. Characterization techniques that include total X-ray scattering and extended X-ray absorption fine structure revealed a deviation of the nanorods from bulk crystal structure with a contraction along the b orthorhombic lattice parameter. The carbon supported nanorods have comparable activity but are remarkably more stable than conventional Pt catalysts for the oxygen reduction reaction in alkaline environments.

  9. Recent Progress In The Development Of Boron Phosphide As A Robust Coating Material For Infra-Red Transparencies

    NASA Astrophysics Data System (ADS)

    Lewis, Keith L.; Kelly, Chris J.; Monachan, Brian C.

    1989-09-01

    Boron Phosphide satisfies many of the material requirements for a coating suitable for use on high velocity IR windows. Such coatings have to be robust, resistant to abrasion and to rain erosion, and also capable of surviving thermal shock. Films of BP of several tens of microns in thickness have been produced by plasma assisted chemical vapour deposition on a variety of feedstocks. Growth has been achieved on a wide range of substrate materials, with no apparent limitation in film thickness, suggesting low levels of stress. The degree of optical transparency is high, covering 0.8 μm to 12 μm and beyond, with absorption levels being an order of magnitude lower than found for typical diamond-like carbon (DLC) films. The ability to survive severe erosive conditions is also significantly improved compared with DLC in wiper tests, water jet impact experiments are in whirling arm rain erosion tests.

  10. Characterization of the Absolute Crystal Polarity across Twin Boundaries in Gallium Phosphide Using Convergent-Beam Electron Diffraction.

    PubMed

    Cohen; McKernan; Carter

    1999-05-01

    : The measurement of absolute crystal polarity is crucial to understanding the structural properties of many planar defects in compound semiconductors. Grain boundaries, including twin boundaries, in the sphalerite lattice are uniquely characterized by the crystallographic misorientation of individual grains and the direction of the crystal polarity in domains adjoining the grain boundary. To evaluate crystal polarity in gallium phosphide (GaP), asymmetrical interference contrast in convergent-beam electron-diffraction (CBED) patterns was used to ascertain the nature and direction of polar bonds. The direction of the asymmetry in the electron diffraction reflections was correlated with the crystal polarity of a sample with known polarity. The CBED technique was applied to determine the polar orientation of grains adjoining Sigma = 3 coherent and lateral twin boundaries in polycrystalline GaP. PMID:10383990

  11. Chemical nature of silicon nitride-indium phosphide interface and rapid thermal annealing for InP MISFETs

    NASA Technical Reports Server (NTRS)

    Biedenbender, M. D.; Kapoor, V. J.

    1990-01-01

    A rapid thermal annealing (RTA) process in pure N2 or pure H2 was developed for ion-implanted and encapsulated indium phosphide compound semiconductors, and the chemical nature at the silicon nitride-InP interface before and after RTA was examined using XPS. Results obtained from SIMS on the atomic concentration profiles of the implanted silicon in InP before and after RTA are presented, together with electrical characteristics of the annealed implants. Using the RTA process developed, InP metal-insulator semiconductor FETs (MISFETS) were fabricated. The MISFETS prepared had threshold voltages of +1 V, transconductance of 27 mS/mm, peak channel mobility of 1200 sq cm/V per sec, and drain current drift of only 7 percent.

  12. Probing hydrodesulfurization over bimetallic phosphides using monodisperse Ni2-xMxP nanoparticles encapsulated in mesoporous silica

    NASA Astrophysics Data System (ADS)

    Danforth, Samuel J.; Liyanage, D. Ruchira; Hitihami-Mudiyanselage, Asha; Ilic, Boris; Brock, Stephanie L.; Bussell, Mark E.

    2016-06-01

    Metal phosphide nanoparticles encapsulated in mesoporous silica provide a well-defined system for probing the fundamental chemistry of the hydrodesulfurization (HDS) reaction over this new class of hydrotreating catalysts. To investigate composition effects in bimetallic phosphides, the HDS of dibenzothiophene (DBT) was carried out over a series of Ni-rich Ni2-xMxP@mSiO2 (M = Co, Fe) nanocatalysts (x ≤ 0.50). The Ni2-xMxP nanoparticles (average diameters: 11-13 nm) were prepared by solution-phase arrested precipitation and encapsulated in mesoporous silica, characterized by a range of techniques (XRD, TEM, IR spectroscopy, BET surface area, CO chemisorption) and tested for DBT HDS activity and selectivity. The highest activity was observed for a Ni1.92Co0.08P@mSiO2 nanocatalyst, but the overall trend was a decrease in HDS activity with increasing Co or Fe content. In contrast, the highest turnover frequency (TOF) was observed for the most Co- and Fe-rich compositions based on sites titrated by CO chemisorption. IR spectral studies of adsorbed CO on the Ni2-xMxP@mSiO2 catalysts indicate that an increase in electron density occurs on Ni sites as the Co or Fe content is increased, which may be responsible for the increased TOFs of the catalytic sites. The Ni2-xMxP@mSiO2 nanocatalysts exhibit a strong preference for the direct desulfurization pathway (DDS) for DBT HDS that changes only slightly with increasing Co or Fe content.

  13. Search for a meteoritic component in impact-melt rocks from the Lonar crater, India - Evidence from osmium isotope systematics

    NASA Astrophysics Data System (ADS)

    Schulz, T.; Luguet, A.; Koeberl, C.

    2013-12-01

    Introduction: The Lonar crater in western India (Maharashtra) is a bowl-shaped simple impact structure of 1830 m diameter and a depth of 120 m below the rim crest. The crater formed 0.656 × 0.081 Ma ago on the 65 Ma old basaltic lava flows of the Deccan Traps (Jourdan et al. 2010) and is one of the few terrestrial impact structures to have formed in basaltic host-rocks. In the absence of actual meteorite fragments, the impact origin of this structure was supported by the identification of a variety of shock metamorphic features (e.g. Fredriksson et al. 1973). However, clear indications of an extraterrestrial component in impactites based on geochemical studies are absent or remained ambiguous so far (e.g. Osae et al. 2005). As the Os isotope tool has the potential to provide firm constraints on the presence or absence of even very small (<<1%) contributions of meteoritic matter to impactite lithologies (e.g. Koeberl et al. 2002), we conduct a detailed Os isotope study of a variety of unshocked host-basalts (target rocks) and impactites (impact-melt rocks) from the Lonar crater. Samples and Method: All samples analyzed in this study were collected in 2000 and 2001 and were geochemically characterized by Osae et al. (2005). Osmium (and additional PGE) analyses were performed on about 2 g whole rock powders, which were spiked with a mixed 190Os,185Re,191Ir,194Pt tracer, and digested via high pressure Asher using inverse aqua regia. Osmium solvent extraction and microdistillation were performed as described by Cohen and Waters (1996). Osmium isotopic compositions were measured using a TRITON N-TIMS at the Department of Lithospheric Research in Vienna. Results and Discussion: Osmium data on seven target and nine impact melt rocks reveal 187Os/188Os ratios ranging from ~0.38 to ~2.23 for the target rocks and from ~0.22 to ~0.59 for the nine analyzed impact melt rocks, whereas Os concentrations range from ~7.1 to ~31.6 ppt and ~7.2 to ~134 ppt, respectively. Although in

  14. Osmium(IV) complexes with 1H- and 2H-indazoles: tautomer identity versus spectroscopic properties and antiproliferative activity.

    PubMed

    Büchel, Gabriel E; Stepanenko, Iryna N; Hejl, Michaela; Jakupec, Michael A; Keppler, Bernhard K; Heffeter, Petra; Berger, Walter; Arion, Vladimir B

    2012-08-01

    A one-pot synthesis of osmium(IV) complexes with two different tautomers of indazole, 1H-indazole and 2H-indazole, namely (H(2)ind)[Os(IV)Cl(5)(2H-ind)] (1) and (H(2)ind)[Os(IV)Cl(5)(1H-ind)] (2) is reported. Both compounds have been comprehensively characterized by NMR spectroscopy, ESI (electrospray ionization) mass spectrometry, electronic absorption spectroscopy, IR spectroscopy, cyclic voltammetry and tested for antiproliferative activity in vitro in three human cancer cell lines, CH1 (ovarian carcinoma), A549 (non-small cell lung cancer) and SW480 (colon carcinoma), as well as in vivo in a Hep3B SCID mouse xeno-transplantation model. 2H-Indazole tautomer stabilization in 1 has been confirmed by X-ray diffraction.

  15. Transmission electron microscopy staining methods for the cortex of human hair: a modified osmium method and comparison with other stains.

    PubMed

    Harland, D P; Vernon, J A; Walls, R J; Woods, J L

    2011-08-01

    For wool, superior staining of a wide range of ultrastructural components is achieved by en bloc treatment of fibres with a chemical reductant followed by osmium tetroxide. For human scalp hair, although staining quality is similar, the penetration of reagents is poor, resulting in large parts of the fibre cortex remaining unstained. Here we describe a modification to the reduction-osmication method in which reagents penetrate through a cut fibre end, allowing visualization of a wide range of features across the cortex. We compare the staining quality, artefacts and range of structure rendered visible using transmission electron microscopy for en bloc reduction-osmication to other staining alternatives including en bloc silver nitrate and section stains based on uranyl acetate and lead citrate, phosphotungstic acid, potassium permanganate, ammoniacal silver nitrate and some combinations of these stains. The effects of hair-care treatments are briefly examined.

  16. Osmium(IV) complexes with 1H- and 2H-indazoles: Tautomer identity versus spectroscopic properties and antiproliferative activity

    PubMed Central

    Büchel, Gabriel E.; Stepanenko, Iryna N.; Hejl, Michaela; Jakupec, Michael A.; Keppler, Bernhard K.; Heffeter, Petra; Berger, Walter; Arion, Vladimir B.

    2012-01-01

    A one-pot synthesis of osmium(IV) complexes with two different tautomers of indazole, 1H-indazole and 2H-indazole, namely (H2ind)[OsIVCl5(2H-ind)] (1) and (H2ind)[OsIVCl5(1H-ind)] (2) is reported. Both compounds have been comprehensively characterized by NMR spectroscopy, ESI (electrospray ionization) mass spectrometry, electronic absorption spectroscopy, IR spectroscopy, cyclic voltammetry and tested for antiproliferative activity in vitro in three human cancer cell lines, CH1 (ovarian carcinoma), A549 (non-small cell lung cancer) and SW480 (colon carcinoma), as well as in vivo in a Hep3B SCID mouse xeno-transplantation model. 2H-Indazole tautomer stabilization in 1 has been confirmed by X-ray diffraction. PMID:22687494

  17. Theoretical studies of the osmium based perovskites AOsO3 (A=Ca, Sr and Ba)

    NASA Astrophysics Data System (ADS)

    Ali, Zahid; Sattar, Abdul; Asadabadi, S. Jalali; Ahmad, Iftikhar

    2015-11-01

    Osmium based perovskites AOsO3 (A=Ca, Sr and Ba) have been studied theoretically using density functional theory approach. These studies show that CaOsO3 and SrOsO3 are orthorhombic and BaOsO3 is cubic and are consistent with the experiments. The electronic band structures demonstrate that these compounds are metals. The magnetic studies verify the experimental observations at low temperature, where the spin effects are canceled by the orbitals. The stable magnetic phase optimizations and magnetic susceptibilities calculations by the post-DFT treatment confirm that CaOsO3 and SrOsO3 are weak ferromagnetic whereas BaOsO3 is a paramagnetic material. The directional magnetic study shows that these compounds are magnetically anisotropic, and reveals that the easy magnetization axis is [001] direction.

  18. OMVPE synthesis and characterization of heterostructures containing arsenide/phosphide interfaces

    NASA Astrophysics Data System (ADS)

    Emerson, David Todd

    1997-12-01

    The mixed crystal quaternary Gasb{x}Insb{1-x}Assb{y}Psb{1-y} deposited on GaAs and InP substrates is a not only a versatile but also a technologically important materials system. With the group III and group V mole fractions chosen appropriately, the room temperature energy bandgap of the lattice matched alloy can span nearly the entire range from 0.74 to 1.9 eV. In this dissertation, various aspects of the deposition of heterostructures incorporating Gasb{x}Insb{1-x}Assb{y}Psb{1-y} and its constituent binaries and ternaries are discussed. Furthermore, a variety of characterization techniques are used to assess the single layers and heterostructures including double crystal x-ray diffraction, room and low temperature photoluminescence, atomic force and transmission electron microscopy, and Raman scattering. Throughout this dissertation, the importance of using complimentary characterization techniques when assessing complex heterostructures is stressed. In preparation for the study of the GaAs-based structures, strained and partially relaxed GaAsP layers are grown and characterized. New results concerning the application of the Modified Random Element Isodisplacement Model corrected for strain are reported. Then, to investigate the formation of mixed group V (i.e. arsenide to phosphide) interfaces in GaAs-based heterostructures, a series of GaInP/GaAsP single quantum wells are prepared. Various mechanisms leading to layer intermixing and interface degradation are discussed. The effect of adding phosphorous to the wells on the heterostructure energy band alignment is addressed both experimentally and theoretically. In addition, optical methods are used to assess the structural properties of GaInP/GaAsP 80 A period superlattices, and a quantitative technique for determining the layer composition of the thin, strained GaAsP layers in these superlattices is developed. Formation of mixed group V interfaces in GaInAs/InP superlattices deposited on InP substrates is also

  19. The effect of high-temperature heat treatment on the electrical power factor and morphology of silicon germanium-gallium phosphide alloys

    NASA Astrophysics Data System (ADS)

    Min, Gao; Rowe, D. M.

    1991-10-01

    The results of an experimental investigation into the effect of high-temperature heat treatment on the electrical resistivity and Seeback coefficient of silicon germanium-gallium phosphide alloys and the accompanying changes in morphology are reported. Substantial changes in the electrical properties and in morphology were observed after 15 min and 4-h periods of heat treatment, respectively. A less significant decrease in electrical resistivity accompanied further heat treatment. However, the Seeback coefficient remained almost constant which resulted in an increase in the electrical power factor. Prior to heat treatment, the alloy consisted of host matrix and a silicon-rich black phase. Heat treatment was accompanied by the appearance of a white phase which was rich in germanium and gallium phosphide.

  20. Osmium Isotopic Composition of the K/T Boundary Sediments from Sumbar: A Progress Report

    NASA Astrophysics Data System (ADS)

    Meisel, T.; Krahenbuhl, U.; Nazarov, M. A.

    1993-07-01

    Osmium isotope measurements have been performed on the boundary clay at different Cretaceous-Tertiary boundary (KTB) sites [1-5] since [6] suggested that Os isotopes are an indicator of an extraterrestrial component. The debate over "impact vs. volcanic" could not be resolved, but an isotope ratio close to chondritic could be demonstrated. The study of the distribution of iridium in the stratigraphy of the KTB cannot distinguish the contribution of chondritic and/or terrestrial Ir respectively, whereas the Os isotopes allow us to better constrain a mixing model. The ^187Os/^186Os ratio of the continental crust and chondritic reservoirs differ by at least 10-30 times. Assuming certain parameters, we should be able to calculate the proportion of the reservoirs making up the sediments of the KTB section. We studied a complete section of the KTB of Sumbar, Turkmenistan [7], for its Os isotopic composition. In the section 0-30 cm above the boundary clay, the ^187Os/^186Os ratio increases from 1.15 to 1.47, whereas the Ir concentration decreases from 66 to 1.4 ng/g or 66 to 4.7 ng/g on a carbonate-free basis respectively. Calculations show that the chondritic component makes up 9% at the boundary layer and decreases down to 0.6% at +30 cm. The data cannot be simply explained by varying admixtures of a chondritic component to a sediment of constant Os concentration and isotopic signature. To explain the Os ratios completely it is necessary to consider a mixture of four components (extraterrestrial, ejecta material, local terrigeneous, and carbonacous sediments) with certain assumptions: (1) The extraterrestrial source is chondritic in its Os and Re content and has an initial Os isotope ratio of 1.12 at 65 Ma (time of impact), which is above the average for normal chondrites but is within the range measured so far (e.g., Murray). (2) The ejecta material has a higher Os concentration (0.2 ng/g) than the sediments and is only present in the first 5 cm of the sequence above

  1. Electronic structures of ruthenium and osmium complexes of 9,10-phenanthrenequinone.

    PubMed

    Biswas, Manas Kumar; Patra, Sarat Chandra; Maity, Amarendra Nath; Ke, Shyue-Chu; Adhikary, Nirmal Das; Ghosh, Prasanta

    2012-06-18

    The reaction of 9,10-phenanthrenequinone (PQ) with [M(II)(H)(CO)(X)(PPh(3))(3)] in boiling toluene leads to the homolytic cleavage of the M(II)-H bond, affording the paramagnetic trans-[M(PQ)(PPh(3))(2)(CO)X] (M = Ru, X = Cl, 1; M = Os, X = Br, 3) and cis-[M(PQ)(PPh(3))(2)(CO)X] (M = Ru, X = Cl, 2; M = Os, X = Br, 4) complexes. Single-crystal X-ray structure determinations of 1, 2·toluene, and 4·CH(2)Cl(2), EPR spectra, and density functional theory (DFT) calculations have substantiated that 1-4 are 9,10-phenanthrenesemiquinone radical (PQ(•-)) complexes of ruthenium(II) and osmium(II) and are defined as trans-[Ru(II)(PQ(•-))(PPh(3))(2)(CO)Cl] (1), cis-[Ru(II)(PQ(•-))(PPh(3))(2)(CO)Cl] (2), trans-[Os(II)(PQ(•-))(PPh(3))(2)(CO) Br] (3), and cis-[Os(II)(PQ(•-))(PPh(3))(2)(CO)Br] (4). Two comparatively longer C-O [average lengths: 1, 1.291(3) Å; 2·toluene, 1.281(5) Å; 4·CH(2)Cl(2), 1.300(8) Å] and shorter C-C lengths [1, 1.418(5) Å; 2·toluene, 1.439(6) Å; 4·CH(2)Cl(2), 1.434(9) Å] of the OO chelates are consistent with the presence of a reduced PQ(•-) ligand in 1-4. A minor contribution of the alternate resonance form, trans- or cis-[M(I)(PQ)(PPh(3))(2)(CO)X], of 1-4 has been predicted by the anisotropic X- and Q-band electron paramagnetic resonance spectra of the frozen glasses of the complexes at 25 K and unrestricted DFT calculations on 1, trans-[Ru(PQ)(PMe(3))(2)(CO)Cl] (5), cis-[Ru(PQ)(PMe(3))(2)(CO)Cl] (6), and cis-[Os(PQ)(PMe(3))(2)(CO)Br] (7). However, no thermodynamic equilibria between [M(II)(PQ(•-))(PPh(3))(2)(CO)X] and [M(I)(PQ)(PPh(3))(2)(CO)X] tautomers have been detected. 1-4 undergo one-electron oxidation at -0.06, -0.05, 0.03, and -0.03 V versus a ferrocenium/ferrocene, Fc(+)/Fc, couple because of the formation of PQ complexes as trans-[Ru(II)(PQ)(PPh(3))(2)(CO)Cl](+) (1(+)), cis-[Ru(II)(PQ)(PPh(3))(2)(CO)Cl](+) (2(+)), trans-[Os(II)(PQ)(PPh(3))(2)(CO)Br](+) (3(+)), and cis-[Os(II)(PQ)(PPh(3))(2)(CO)Br](+) (4(+)). The trans

  2. Marine osmium isotopic record of cherts across the Triassic-Jurassic boundary: implications for environmental change

    NASA Astrophysics Data System (ADS)

    Suzuki, K.; Kuroda, J.; Hori, R. S.; Ohkouchi, N.; Grocke, D. R.

    2010-12-01

    Attention has long been focused on relationships between massive volcanisms and major environmental change such as large mass extinctions (e.g., Wignall, 2001). The Triassic-Jurassic (T-J) boundary at c.a. 200 Ma has been regarded as one of the five biggest mass extinction events in the Phanerozoic when a substantial proportion of marine and terrestrial species became extinct. This period also marks extensive magmatic activities associated with the emplacement of the Central Atlantic Magmatic Province (CAMP). These magmatic activities are likely to be a possible forcing mechanism for the climatic changes in the T-J transition. However, the mechanism triggering the T-J mass extinction is still under debate, because there are remarkable difficulties in correlating the timing of the widespread CAMP volcanic activity with the environmental events, and in estimating the environmental impact of large-scale igneous activity. Since seawater Os isotopic composition varies in response to change in balance of Os supply from continental, mantle and extraterrestrial sources, Os isotopic record from hydrogenous fraction of marine sediments is useful to reconstruct secular changes in the relative contribution from these sources (Ravizza and Peucker-Ehrenbrink, 2003; Tugeon and Creaser, 2008; Tejada et al., 2009). Such information possibly provides us important constraints on the mechanism of the environmental change and mass extinction. Although Cohen and Coe (2007) have reported Os isotopic records across the T-J boundary from southern England, no data have been reported from the Paleo-Pacific (Panthalassa) pelagic basin that covered approximately half of the Earth’s surface. Here we present a high-resolution isotopic record of osmium extracted from bedded chert successions across the T-J boundary in Kurusu section, central Japan, deposited on a Panthalassa deep basin. Our new dataset show a gradual decrease in seawater 187Os/188Os values through the Rhaetian and subsequent

  3. Electronic structures of ruthenium and osmium complexes of 9,10-phenanthrenequinone.

    PubMed

    Biswas, Manas Kumar; Patra, Sarat Chandra; Maity, Amarendra Nath; Ke, Shyue-Chu; Adhikary, Nirmal Das; Ghosh, Prasanta

    2012-06-18

    The reaction of 9,10-phenanthrenequinone (PQ) with [M(II)(H)(CO)(X)(PPh(3))(3)] in boiling toluene leads to the homolytic cleavage of the M(II)-H bond, affording the paramagnetic trans-[M(PQ)(PPh(3))(2)(CO)X] (M = Ru, X = Cl, 1; M = Os, X = Br, 3) and cis-[M(PQ)(PPh(3))(2)(CO)X] (M = Ru, X = Cl, 2; M = Os, X = Br, 4) complexes. Single-crystal X-ray structure determinations of 1, 2·toluene, and 4·CH(2)Cl(2), EPR spectra, and density functional theory (DFT) calculations have substantiated that 1-4 are 9,10-phenanthrenesemiquinone radical (PQ(•-)) complexes of ruthenium(II) and osmium(II) and are defined as trans-[Ru(II)(PQ(•-))(PPh(3))(2)(CO)Cl] (1), cis-[Ru(II)(PQ(•-))(PPh(3))(2)(CO)Cl] (2), trans-[Os(II)(PQ(•-))(PPh(3))(2)(CO) Br] (3), and cis-[Os(II)(PQ(•-))(PPh(3))(2)(CO)Br] (4). Two comparatively longer C-O [average lengths: 1, 1.291(3) Å; 2·toluene, 1.281(5) Å; 4·CH(2)Cl(2), 1.300(8) Å] and shorter C-C lengths [1, 1.418(5) Å; 2·toluene, 1.439(6) Å; 4·CH(2)Cl(2), 1.434(9) Å] of the OO chelates are consistent with the presence of a reduced PQ(•-) ligand in 1-4. A minor contribution of the alternate resonance form, trans- or cis-[M(I)(PQ)(PPh(3))(2)(CO)X], of 1-4 has been predicted by the anisotropic X- and Q-band electron paramagnetic resonance spectra of the frozen glasses of the complexes at 25 K and unrestricted DFT calculations on 1, trans-[Ru(PQ)(PMe(3))(2)(CO)Cl] (5), cis-[Ru(PQ)(PMe(3))(2)(CO)Cl] (6), and cis-[Os(PQ)(PMe(3))(2)(CO)Br] (7). However, no thermodynamic equilibria between [M(II)(PQ(•-))(PPh(3))(2)(CO)X] and [M(I)(PQ)(PPh(3))(2)(CO)X] tautomers have been detected. 1-4 undergo one-electron oxidation at -0.06, -0.05, 0.03, and -0.03 V versus a ferrocenium/ferrocene, Fc(+)/Fc, couple because of the formation of PQ complexes as trans-[Ru(II)(PQ)(PPh(3))(2)(CO)Cl](+) (1(+)), cis-[Ru(II)(PQ)(PPh(3))(2)(CO)Cl](+) (2(+)), trans-[Os(II)(PQ)(PPh(3))(2)(CO)Br](+) (3(+)), and cis-[Os(II)(PQ)(PPh(3))(2)(CO)Br](+) (4(+)). The trans

  4. Aqueous corrosion of phosphide minerals from iron meteorites: a highly reactive source of prebiotic phosphorus on the surface of the early Earth.

    PubMed

    Pasek, Matthew A; Lauretta, Dante S

    2005-08-01

    We present the results of an experimental study of aqueous corrosion of Fe-phosphide under conditions relevant to the early Earth. The results strongly suggest that iron meteorites were an important source of reactive phosphorus (P), a requirement for the formation of P-based life. We further demonstrate that iron meteorites were an abundant source of phosphide minerals early in Earth history. Phosphide corrosion was studied in five different solutions: deionized water, deionized water buffered with sodium bicarbonate, deionized water with dissolved magnesium and calcium chlorides, deionized water containing ethanol and acetic acid, and deionized water containing the chlorides, ethanol, and acetic acid. Experiments were performed in the presence of both air and pure Ar gas to evaluate the effect of atmospheric chemistry. Phosphide corrosion in deionized water results in a metastable mixture of mixed-valence, P-bearing ions including pyrophosphate and triphosphate, key components for metabolism in modern life. In a pH-buffered solution of NaHCO(3), the condensed and reduced species diphosphonate is an abundant corrosion product. Corrosion in ethanol- and acetic acid-containing solutions yields additional P-bearing organic molecules, including acetyl phosphonate and a cyclic triphosphorus molecule. Phosphonate is a major corrosion product of all experiments and is the only P-bearing molecule that persists in solutions with high concentrations of magnesium and calcium chlorides, which suggests that phosphonate may have been a primitive oceanic source of P. The stability and reactivity of phosphonate and hypophosphite in solution were investigated to elucidate reaction mechanisms and the role of mineral catalysts on P-solution chemistry. Phosphonate oxidation is rapid in the presence of Fe metal but negligible in the presence of magnetite and in the control sample. The rate of hypophosphite oxidation is independent of reaction substrate.

  5. Comparative Study on the Effectiveness of Coumavec® and Zinc Phosphide in Controlling Zoonotic Cutaneous Leishmaniasis in a Hyperendemic Focus in Central Iran

    PubMed Central

    Veysi, A; Vatandoost, H; Yaghoobi-Ershadi, MR; Arandian, MH; Jafari, R; Hosseini, M; abdoli, H; Rassi, Y; Heidari, K; Sadjadi, A; Fadaei, R; Ramazanpour, J; Aminian, K; Shirzadi, MR; Akhavan, AA

    2012-01-01

    Background Zoonotic cutaneous leishmaniasis (ZCL) is an increasing health problems in many rural areas of Iran. The aim of this study was to introduce a new alternative rodenticide to control the reservoirs of ZCL, its effect on the vector density and the incidence of the disease in hyperendemic focus of Esfahan County, central Iran. Methods: The study was carried out from January 2011 to January 2012. In intervention areas, rodent control operation was conducted using zinc phosphide or Coumavec®. Active case findings were done by house-to-house visits once every season during 2011–2012. To evaluate the effect of rodent control operation on the vector density, sand flies were collected twice a month using sticky traps. Results: The reduction rate of rodent holes in intervention areas with Coumavec® and zinc phosphide were 48.46% and 58.15% respectively, whereas in control area results showed 6.66 folds intensification. The Incidence of ZCL significantly reduced in the treated areas. Totally, 3200 adult sand flies were collected and identified in the intervention and control areas. In the treated area with zinc phosphide, the density of Phlebotomus papatasi was higher in outdoors in contrast with the treated area by Coumavec® which the density of the sand fly was higher in indoors. Conclusion: Both rodenticides were effective on the incidence of ZCL and the population of the reservoirs as well. Coumavec® seems to be effective on the outdoor density of the vector. This combination of rodenticide-insecticide could be a suitable alternative for zinc phosphide while bait shyness or behavioral resistance is occurred. PMID:23293775

  6. A simple osmium post-fixation paraffin-embedment technique to identify lipid accumulation in fish liver using medaka (Oryziaslatipes) eggs and eleutheroembryos as lipid rich models.

    PubMed

    Mondon, J A; Howitt, J; Tosiano, M; Kwok, K W H; Hinton, D E

    2011-01-01

    Hepatic lipidosis is a non-specific biomarker of effect from pollution exposure in fish. Fatty liver is often misdiagnosed or overlooked in histological assessments due to the decreasing application of specific fat procedures and stains. For example, ethanol dehydration in standard paraffin processing removes lipids, leaving vacuoles of which the precise nature is unknown. Lipids can be identified using osmium post-fixation in semi-thin resin sections or transmission electron microscopy. However, both are expensive and technically demanding procedures, often not available for routine environmental risk assessment and monitoring programs. The current emphasis to reduce and refine animal toxicity testing, requires refinement of the suite of histopathological techniques currently available to maximize information gained from using fish for toxicity testing and as bio-indicators of environmental quality. This investigation has successfully modified an osmium post-fixation technique to conserve lipids in paraffin-embedded tissues using medaka (Oryzias latipes) eleutheroembryos and eggs (embryos) as lipid rich models.

  7. Electrical Wiring of the Aldehyde Oxidoreductase PaoABC with a Polymer Containing Osmium Redox Centers: Biosensors for Benzaldehyde and GABA

    PubMed Central

    Badalyan, Artavazd; Dierich, Marlen; Stiba, Konstanze; Schwuchow, Viola; Leimkühler, Silke; Wollenberger, Ulla

    2014-01-01

    Biosensors for the detection of benzaldehyde and γ−aminobutyric acid (GABA) are reported using aldehyde oxidoreductase PaoABC from Escherichia coli immobilized in a polymer containing bound low potential osmium redox complexes. The electrically connected enzyme already electrooxidizes benzaldehyde at potentials below −0.15 V (vs. Ag|AgCl, 1 M KCl). The pH-dependence of benzaldehyde oxidation can be strongly influenced by the ionic strength. The effect is similar with the soluble osmium redox complex and therefore indicates a clear electrostatic effect on the bioelectrocatalytic efficiency of PaoABC in the osmium containing redox polymer. At lower ionic strength, the pH-optimum is high and can be switched to low pH-values at high ionic strength. This offers biosensing at high and low pH-values. A “reagentless” biosensor has been formed with enzyme wired onto a screen-printed electrode in a flow cell device. The response time to addition of benzaldehyde is 30 s, and the measuring range is between 10–150 µM and the detection limit of 5 µM (signal to noise ratio 3:1) of benzaldehyde. The relative standard deviation in a series (n = 13) for 200 µM benzaldehyde is 1.9%. For the biosensor, a response to succinic semialdehyde was also identified. Based on this response and the ability to work at high pH a biosensor for GABA is proposed by coimmobilizing GABA-aminotransferase (GABA-T) and PaoABC in the osmium containing redox polymer. PMID:25587431

  8. Electrical Wiring of the Aldehyde Oxidoreductase PaoABC with a Polymer Containing Osmium Redox Centers: Biosensors for Benzaldehyde and GABA.

    PubMed

    Badalyan, Artavazd; Dierich, Marlen; Stiba, Konstanze; Schwuchow, Viola; Leimkühler, Silke; Wollenberger, Ulla

    2014-12-01

    Biosensors for the detection of benzaldehyde and γ-aminobutyric acid (GABA) are reported using aldehyde oxidoreductase PaoABC from Escherichia coli immobilized in a polymer containing bound low potential osmium redox complexes. The electrically connected enzyme already electrooxidizes benzaldehyde at potentials below -0.15 V (vs. Ag|AgCl, 1 M KCl). The pH-dependence of benzaldehyde oxidation can be strongly influenced by the ionic strength. The effect is similar with the soluble osmium redox complex and therefore indicates a clear electrostatic effect on the bioelectrocatalytic efficiency of PaoABC in the osmium containing redox polymer. At lower ionic strength, the pH-optimum is high and can be switched to low pH-values at high ionic strength. This offers biosensing at high and low pH-values. A "reagentless" biosensor has been formed with enzyme wired onto a screen-printed electrode in a flow cell device. The response time to addition of benzaldehyde is 30 s, and the measuring range is between 10-150 µM and the detection limit of 5 µM (signal to noise ratio 3:1) of benzaldehyde. The relative standard deviation in a series (n = 13) for 200 µM benzaldehyde is 1.9%. For the biosensor, a response to succinic semialdehyde was also identified. Based on this response and the ability to work at high pH a biosensor for GABA is proposed by coimmobilizing GABA-aminotransferase (GABA-T) and PaoABC in the osmium containing redox polymer.

  9. Photocatalytic performance of nitrogen, osmium co-doped TiO2 for removal of eosin yellow in water under simulated solar radiation.

    PubMed

    Kuvarega, Alex T; Krause, Rui W M; Mamba, Bhekie B

    2013-07-01

    Nitrogen, osmium co-doped TiO2 photocatalysts were prepared by a modified sol-gel method using ammonia as the nitrogen source and osmium tetroxide as the source of osmium. The role of rutile phase OsO2 in enhancing the photocatalytic activity of rutile TiO2 towards the degradation of Eosin Yellow was investigated. The materials were characterised by various techniques that include FTIR, Raman, XRD, SEM, EDS, TEM, TGA and DRUV-Vis. The amorphous, oven dried sample was transformed to the anatase and then the rutile phase with increasing calcination temperature. DRUV-Vis analysis revealed a red shift in absorption with increasing calcination temperature, confirmed by a decrease in the band gap of the material. The photocatalytic activity of N, Os co-doped TiO2 was evaluated using eosin yellow degradation and activity increased with increase in calcination temperature under simulated solar irradiation. The rutile phase of the co-doped TiO2 was found to be more effective in degrading the dye (k(a) = 1.84 x 10(-2) min(-1)) compared to the anatase co-doped phase (k(a) = 9.90 x 10(-3) min(-1)). The enhanced photocatalytic activity was ascribed to the synergistic effects of rutile TiO2 and rutile OsO2 in the N, Os co-doped TiO2. PMID:23901525

  10. Rhenium and osmium isotopes in black shales and Ni-Mo-PGE-rich sulfide layers, Yukon Territory, Canada, and Hunan and Guizhou provinces, China

    USGS Publications Warehouse

    Horan, M.F.; Morgan, J.W.; Grauch, R.I.; Coveney, R.M.; Murowchick, J.B.; Hulbert, L.J.

    1994-01-01

    Rhenium and osmium abundances and osmium isotopic compositions were determined by negative thermal ionization mass spectrometry for samples of Devonian black shale and an associated Ni-enriched sulfide layer from the Yukon Territory, Canada. The same composition information was also obtained for samples of early Cambrian Ni-Mo-rich sulfide layers hosted in black shale in Guizhou and Hunan provinces, China. This study was undertaken to constrain the origin of the PGE enrichment in the sulfide layers. Samples of the Ni sulfide layer from the Yukon Territory are highly enriched in Re, Os, and other PGE, with distinctly higher Re/192Os but similar Pt/Re, compared to the black shale host. Re-Os isotopic data of the black shale and the sulfide layer are approximately isochronous, and the data plot close to reference isochrons which bracket the depositional age of the enclosing shales. Samples of the Chinese sulfide layers are also highly enriched in Re, Os, and the other PGE. Re/192Os are lower than in the Yukon sulfide layer. Re-Os isotopic data for the sulfide layers lie near a reference isochron with an age of 560 Ma, similar to the depositional age of the black shale host. The osmium isotopic data suggest that Re and PGE enrichment of the brecciated sulfide layers in both the Yukon Territory and in southern China may have occurred near the time of sediment deposition or during early diagenesis, during the middle to late Devonian and early Cambrian, respectively. ?? 1994.

  11. Photocatalytic performance of nitrogen, osmium co-doped TiO2 for removal of eosin yellow in water under simulated solar radiation.

    PubMed

    Kuvarega, Alex T; Krause, Rui W M; Mamba, Bhekie B

    2013-07-01

    Nitrogen, osmium co-doped TiO2 photocatalysts were prepared by a modified sol-gel method using ammonia as the nitrogen source and osmium tetroxide as the source of osmium. The role of rutile phase OsO2 in enhancing the photocatalytic activity of rutile TiO2 towards the degradation of Eosin Yellow was investigated. The materials were characterised by various techniques that include FTIR, Raman, XRD, SEM, EDS, TEM, TGA and DRUV-Vis. The amorphous, oven dried sample was transformed to the anatase and then the rutile phase with increasing calcination temperature. DRUV-Vis analysis revealed a red shift in absorption with increasing calcination temperature, confirmed by a decrease in the band gap of the material. The photocatalytic activity of N, Os co-doped TiO2 was evaluated using eosin yellow degradation and activity increased with increase in calcination temperature under simulated solar irradiation. The rutile phase of the co-doped TiO2 was found to be more effective in degrading the dye (k(a) = 1.84 x 10(-2) min(-1)) compared to the anatase co-doped phase (k(a) = 9.90 x 10(-3) min(-1)). The enhanced photocatalytic activity was ascribed to the synergistic effects of rutile TiO2 and rutile OsO2 in the N, Os co-doped TiO2.

  12. Lifetimes, spectra, and quenching of the excited states of polypyridine complexes of iron(II), ruthenium(II), and osmium(II)

    SciTech Connect

    Creutz, C.; Chou, M.; Netzel, T.L.; Okumura, M.; Sutin, N.

    1980-02-13

    The lifetimes of the excited states formed by 530-nm excitation of polypyridine complexes of iron(II) (FeL/sub 3//sup 2 +/) and osmium(II) (OsL/sub 3//sup 2 +/) have been determined by laser flash-photolysis techniques. The FeL/sub 3//sup 2 +/ lifetimes, measured in water at room temperature using picosecond absorption spectrometry, are as follows (L,tau +- sigma(ns)):2,2',2''-terpyridine (2.54 +- 0.13); 2,2'-bipyridine (0.81 +- 0.07); 4,4'-dimethyl(2,2'-bipyridine) (0.76 +- 0.04); 1,10-phenanthroline (0.80 +- 0.07); 4,7-(diphenyl sulfonate)-1,10-phenanthroline (0.43 +- 0.03). Lifetimes for the analogous complexes of osmium(II) lie in the range 10-100 ns under the same conditions. Unlike the excited states of Ru(bpy)/sub 3//sup 2 +/ and Os(bpy)/sub 3//sup 2 +/ (lambda/sub max/430-460 nm, epsilon approx. 5 x 10/sup 3/ M/sup -1/ cm-/sup 1/), the excited state of Fe(bpy)/sub 3//sup 2 +/ does not luminesce or absorb significantly in the visible (epsilon < 10/sup 3/ M/sup -1/ cm/sup -1/ at lambda greater than or equal to 350 nm) but does exhibit intense absorption below approx. 325 nm. Rate constants for the quenching of the excited states of polypyridine complexes of osmium(II) and ruthenium(II) by ground-state polypyridine complexes of iron(II), ruthenium(II), and osmium(II) are reported and are ascribed to either electron-transfer or energy-transfer processes. The excited states of tris(2,2'-bipyridine)iron(II) and of bis(2,2',2''-terpyridine)iron(II) undergo reaction with Fe/sub aq//sup 3 +/ (0.5 M H/sub 2/SO/sub 4/, 25/sup 0/C) with a rate constant less than or equal to 1 x 10/sup 7/ M-/sup 1/ s/sup -1/. Based on a comparison of its properties with those of the luminescent charge-transfer excited states of ruthenium(II) and osmium(II) polypyridine complexes the excited state of FeL/sub 3//sup 2 +/ is identified as a ligand-field state.

  13. Studies of high temperature ternary phases in mixed-metal-rich early transition metal sulfide and phosphide systems

    SciTech Connect

    Marking, G.A.

    1994-01-04

    Investigations of ternary mixed early transition metal-rich sulfide and phosphide systems resulted in the discovery of new structures and new phases. A new series of Zr and Hf - group V transition metal - sulfur K-phases was synthesized and crystallographically characterized. When the group V transition metal was Nb or Ta, the unit cell volume was larger than any previously reported K-phase. The presence of adventitious oxygen was determined in two K-phases through a combination of neutron scattering and X-ray diffraction experiments. A compound Hf{sub 10}Ta{sub 3}S{sub 3} was found to crystallize in a new-structure type similar to the known gamma brasses. This structure is unique in that it is the only reported {open_quotes}stuffed{close_quotes} gamma-brass type structure. The metal components, Hf and Ta, are larger in size and more electropositive than the metals found in normal gamma brasses (e.g. Cu and Zn) and because of the larger metallic radii, sulfur can be incorporated into the structure where it plays an integral role in stabilizing this phase relative to others. X-ray single-crystal, X-ray powder and neutron powder refinements were performed on this structure. A new structure was found in the ternary Nb-Zr-P system which has characteristics in common with many known early transition metal-rich sulfides, selenides, and phosphides. This structure has the simplest known interconnection of the basic building blocks known for this structural class. Anomalous scattering was a powerful tool for differentiating between Zr and Nb when using Mo K{alpha} X-radiation. The compounds ZrNbP and HfNbP formed in the space group Prima with the simple Co{sub 2}Si structure which is among the most common structures found for crystalline solid materials. Solid solution compounds in the Ta-Nb-P, Ta-Zr-P, Nb-Zr-P, Hf-Nb-P, and Hf-Zr-S systems were crystallographically characterized. The structural information corroborated ideas about bonding in metal-rich compounds.

  14. Sniffing for Clues to the Dinosaurs Demise: Measurement of Osmium Isotope Compositions and Platinum Group Element Abundances in Volcanic Emissions

    NASA Astrophysics Data System (ADS)

    Sims, K. W.; Peucker-Ehrenbrink, B.; Mather, T.; Pyle, D.; Martin, R.; Gauthier, P.; Aiuppa, A.

    2005-12-01

    Platinum Group Elements (PGE: Os, Ir, Rh, Ru, Pt, Pd) and osmium isotopes measured in marine and terrestrial sediment, snow and ice records are important paleo-tracers of riverine, hydrothermal, extraterrestrial, volcanic and anthropogenic inputs into the global surficial environment. For instance, the marine Os isotope record across the Cretaceous-Tertiary Boundary (KTB) indicates that the onset of the main phase of Deccan volcanism and the transient late Maastrichtian warming preceded the large extraterrestrial impact and the related KTB mass extinction by several hundred thousand years [Ravizza and Peucker-Ehrenbrink, 2003]. Distinguishing extraterrestrial from volcanic PGE sources has been difficult due to the similarity in Os isotopic compositions, complex PGE fractionations, and our lack of knowledge of the Os isotopic composition and PGE abundances in volcanic aerosols. These difficulties have fueled vigorous debate about extraterrestrial vs. volcanic triggers of mass extinctions in the geologic record. To assess the volcanic contribution to the global Re-Os-PGE cycle we have initiated a study of Os isotopic compositions and PGE abundances in volcanic emissions from volcanoes around the globe. Here we report preliminary data on PGE abundances and Os isotopes measured in gas and aerosol filter samples from Vulcan Masaya, Nicaragua and Mt Etna, Italy. Samples were analyzed by ID-ICPMS (ThermoFinnigan ELEMENT 2 and NEPTUNE) at the Woods Hole Oceanographic Institution. Osmium isotope compositions of the filters are unradiogenic (0.1272 to 0.187). Osmium concentrations range from 28 to 97 pg/cubic meter and are 3-4 orders of magnitude lower than those measured by Krahenbuhl et al. [1992] during the spring 1984 eruption of Mauna Loa just after the lava fountaining phase. Normalized PGE abundance patterns are fractionated relative to carbonaceous chondrites and two important features distinguish the pattern from other important PGE sources: 1) Os/Ir is much higher

  15. Syntheses and spectroscopic, structural, electrochemical, spectroelectrochemical, and theoretical studies of osmium(II) mono- and bis-alkynyl complexes.

    PubMed

    West, Patrick J; Cifuentes, Marie P; Schwich, Torsten; Randles, Michael D; Morrall, Joseph P; Kulasekera, Erandi; Petrie, Simon; Stranger, Robert; Humphrey, Mark G

    2012-10-15

    The syntheses of trans-[Os(C≡C-4-C(6)H(4)X)Cl(dppe)(2)] [X = Br (3), I (4)], trans-[Os(C≡C-4-C(6)H(4)X)(NH(3))(dppe)(2)](PF(6)) [X = H (5(PF(6))), I (6(PF(6)))], and trans-[Os(C≡C-4-C(6)H(4)X)(C≡C-4-C(6)H(4)Y)(dppe)(2)] [X = Y = H (7), X = I, Y = C≡CSiPr(i)(3) (8)] are reported, together with improved syntheses of cis-[OsCl(2)(dppe)(2)] (cis-1), trans-[Os(C≡CPh)Cl(dppe)(2)] (2), and trans-[Ru(C≡C-4-C(6)H(4)I)(NH(3))(dppe)(2)](PF(6)) (9(PF(6))) (the last-mentioned direct from trans-[Ru(C≡C-4-C(6)H(4)I)Cl(dppe)(2)]), and single-crystal X-ray structural studies of 2-4, 5(PF(6)), 6(PF(6)), and 7. Ammine complexes 5(PF(6))/6(PF(6)) are shown to afford a facile route to both symmetrical (7) and unsymmetrical (8) osmium bis(alkynyl) complexes. A combination of cyclic voltammetry, UV-vis-NIR spectroelectrochemistry, and time-dependent density functional theory (TD-DFT) has permitted identification and assignment of the intense transitions in both the resting state and the oxidized forms of these complexes. Cyclic voltammetric data show fully reversible oxidation processes at 0.32-0.42 V (3, 4, 7, 8) (with respect to ferrocene/ferrocenium 0.56 V), assigned to the (formal) Os(II/III) couple. The osmium(III) complex (di)cations 5(2+) and 7(+) were obtained by in situ oxidation of 5(+) and 7 using an optically transparent thin-layer electrochemical (OTTLE) cell. The UV-vis-NIR optical spectra of 5(2+) and 7(+) reveal low-energy bands in the near IR region, in contrast to 5(+) and 7 which are optically transparent at frequencies below 22,000 cm(-1). TD-DFT calculations on trans-1, 2, 5(+), and 7 and their oxidized forms suggest that the lowest-energy transitions are chloro-to-metal charge transfer (trans-1), chloro-to-phenylethynyl charge transfer (2), and metal-to-phenylethynyl charge transfer (5(+), 7) in the resting state and chloro-to-metal charge transfer (trans-1(+)), phosphorus-to-metal charge transfer (5(2+)), alkynyl-to-metal charge transfer (7(+)), or

  16. cis-1,2-Aminohydroxylation of Alkenes Involving a Catalytic Cycle of Osmium(III) and Osmium(V) Centers: Os(V)(O)(NHTs) Active Oxidant with a Macrocyclic Tetradentate Ligand.

    PubMed

    Sugimoto, Hideki; Mikami, Akine; Kai, Kenichiro; Sajith, P K; Shiota, Yoshihito; Yoshizawa, Kazunari; Asano, Kaori; Suzuki, Takeyuki; Itoh, Shinobu

    2015-07-20

    Catalytic activity of [Os(III)(OH)(H2O)(L-N4Me2)](PF6)2 (1: L-N4Me2 = N,N'-dimethyl-2,11-diaza-[3,3](2,6)pyridinophane) in 1,2-cis-aminohydroxylation of alkenes with sodium N-chloro-4-methylbenzenesulfonamide (chloramine-T) is explored. Simple alkenes as well as those containing several types of substituents are converted to the corresponding 1,2-aminoalcohols in modest to high yields. The aminoalcohol products have exclusively cis conformation with respect to the introduced -OH and -NHTs groups. The spectroscopic measurements including cold mass spectroscopic study of the reaction product of complex 1 and chloromine-T as well as density functional theory (DFT) calculations indicate that an oxido-aminato-osmium(V) species [Os(V)(O)(NHTs)(L-N4Me2)](PF6)2 (2) is an active oxidant for the aminohydroxylation. The DFT calculations further indicate that the reaction involves a [3 + 2] cycloaddition between 2 and alkene, and the regioselectivity in the aminohydroxylation of unsymmetrical alkenes is determined by the orientation that bears less steric hindrance from the tosylamino group, which leads to the energetically more preferred product isomer.

  17. cis-1,2-Aminohydroxylation of Alkenes Involving a Catalytic Cycle of Osmium(III) and Osmium(V) Centers: Os(V)(O)(NHTs) Active Oxidant with a Macrocyclic Tetradentate Ligand.

    PubMed

    Sugimoto, Hideki; Mikami, Akine; Kai, Kenichiro; Sajith, P K; Shiota, Yoshihito; Yoshizawa, Kazunari; Asano, Kaori; Suzuki, Takeyuki; Itoh, Shinobu

    2015-07-20

    Catalytic activity of [Os(III)(OH)(H2O)(L-N4Me2)](PF6)2 (1: L-N4Me2 = N,N'-dimethyl-2,11-diaza-[3,3](2,6)pyridinophane) in 1,2-cis-aminohydroxylation of alkenes with sodium N-chloro-4-methylbenzenesulfonamide (chloramine-T) is explored. Simple alkenes as well as those containing several types of substituents are converted to the corresponding 1,2-aminoalcohols in modest to high yields. The aminoalcohol products have exclusively cis conformation with respect to the introduced -OH and -NHTs groups. The spectroscopic measurements including cold mass spectroscopic study of the reaction product of complex 1 and chloromine-T as well as density functional theory (DFT) calculations indicate that an oxido-aminato-osmium(V) species [Os(V)(O)(NHTs)(L-N4Me2)](PF6)2 (2) is an active oxidant for the aminohydroxylation. The DFT calculations further indicate that the reaction involves a [3 + 2] cycloaddition between 2 and alkene, and the regioselectivity in the aminohydroxylation of unsymmetrical alkenes is determined by the orientation that bears less steric hindrance from the tosylamino group, which leads to the energetically more preferred product isomer. PMID:26126185

  18. PLEURAL EFFECTS OF INDIUM PHOSPHIDE IN B6C3F1 MICE: NONFIBROUS PARTICULATE INDUCED PLEURAL FIBROSIS

    PubMed Central

    Kirby, Patrick J.; Shines, Cassandra J.; Taylor, Genie J.; Bousquet, Ronald W.; Price, Herman C.; Everitt, Jeffrey I.; Morgan, Daniel L.

    2010-01-01

    The mechanism(s) by which chronic inhalation of indium phosphide (InP) particles causes pleural fibrosis is not known. Few studies of InP pleural toxicity have been conducted because of the challenges in conducting particulate inhalation exposures, and because the pleural lesions developed slowly over the 2-year inhalation study. The authors investigated whether InP (1 mg/kg) administered by a single oropharyngeal aspiration would cause pleural fibrosis in male B6C3F1 mice. By 28 days after treatment, protein and lactate dehydrogenase (LDH) were significantly increased in bronchoalveolar lavage fluid (BALF), but were unchanged in pleural lavage fluid (PLF). A pronounced pleural effusion characterized by significant increases in cytokines and a 3.7-fold increase in cell number was detected 28 days after InP treatment. Aspiration of soluble InCl3 caused a similar delayed pleural effusion; however, other soluble metals, insoluble particles, and fibers did not. The effusion caused by InP was accompanied by areas of pleural thickening and inflammation at day 28, and by pleural fibrosis at day 98. Aspiration of InP produced pleural fibrosis that was histologically similar to lesions caused by chronic inhalation exposure, and in a shorter time period. This oropharyngeal aspiration model was used to provide an initial characterization of the progression of pleural lesions caused by InP. PMID:19995279

  19. Boron nitride phosphide thin films grown on quartz substrate by hot-filament and plasma-assisted chemical vapor deposition

    NASA Astrophysics Data System (ADS)

    Zhang, X. W.; Xu, S. Y.; Han, G. R.

    2004-10-01

    Boron nitride phosphide films are, for the first time, grown on transparent quartz substrate by hot filament and radio-frequency plasma co-assisted chemical vapor deposition technique. XPS, XRD, SEM, and UV measurements are performed to study the chemical composition, crystallization, microstructure, and optical absorption, respectively. A centipede-like microstructure and undulating ground morphology on the film surface are observed, and their growth mechanism is speculated upon. The chemical composition is determined as BN1-xPx, whose characteristic XRD peak is preliminarily identified. The optical band gap can be modulated between 5.52 eV and 3.74 eV, simply by adjusting the phosphorus content in BN1-xPx through modifying the PH3 flux during the film-deposition process. The merits of the BN1-xPx film, such as high ultraviolet photoelectric sensitivity with negligible sensitivity in the visible region, modifiable wide optical band gap, and good adhesion on transparent substrate, suggest potential applications for ultraviolet photo-electronics.

  20. Epitaxial dysprosium phosphide grown by gas-source and solid-source MBE on gallium arsenide substrates

    NASA Astrophysics Data System (ADS)

    Sadwick, L. P.; Lee, P. P.; Patel, M.; Nikols, M.; Hwu, R. J.; Shield, J. E.; Streit, D. C.; Brehmer, D.; McCormick, K.; Allen, S. J.; Gedridge, R. W.

    1996-07-01

    We report the first known study of the growth of epitaxial dysprosium phosphide (DyP) grown on gallium arsenide (GaAs). DyP is lattice matched to GaAs, with the room-temperature mismatch being less than 0.01%. We have grown DyP on GaAs by gas-source and by solid-source molecular beam epitaxy using custom-designed group V thermal cracker cells and group III high temperature effusion cells. X-ray diffraction results show the DyP epilayer to be (001) single crystal on GaAs(001) substrate. Electrical and optical measurements performed to date are inconclusive as to whether DyP is a semi-metal or a semiconductor with a small band gap. The undoped films are n-type with measured electron concentrations on the order of 5 × 10 19-6 × 10 20cm -3 with mobilities of 1-10 cm 2/V · s. {DyP}/{GaAs} is stable in air with no apparent oxidation taking place, even after months of exposure to ambient untreated air. Material and surface science properties measured for {DyP}/{GaAs} include Hall measurements, 2ϑ and double-crystal X-ray diffraction spectra and photothermal deflection spectroscopy.

  1. Chemical Reaction between Boric Acid and Phosphine Indicates Boric Acid as an Antidote for Aluminium Phosphide Poisoning

    PubMed Central

    Soltani, Motahareh; Shetab-Boushehri, Seyed F.; Shetab-Boushehri, Seyed V.

    2016-01-01

    Objectives: Aluminium phosphide (AlP) is a fumigant pesticide which protects stored grains from insects and rodents. When it comes into contact with moisture, AlP releases phosphine (PH3), a highly toxic gas. No efficient antidote has been found for AlP poisoning so far and most people who are poisoned do not survive. Boric acid is a Lewis acid with an empty p orbital which accepts electrons. This study aimed to investigate the neutralisation of PH3 gas with boric acid. Methods: This study was carried out at the Baharlou Hospital, Tehran University of Medical Sciences, Tehran, Iran, between December 2013 and February 2014. The volume of released gas, rate of gas evolution and changes in pH were measured during reactions of AlP tablets with water, acidified water, saturated boric acid solution, acidified saturated boric acid solution, activated charcoal and acidified activated charcoal. Infrared spectroscopy was used to study the resulting probable adduct between PH3 and boric acid. Results: Activated charcoal significantly reduced the volume of released gas (P <0.01). Although boric acid did not significantly reduce the volume of released gas, it significantly reduced the rate of gas evolution (P <0.01). A gaseous adduct was formed in the reaction between pure AlP and boric acid. Conclusion: These findings indicate that boric acid may be an efficient and non-toxic antidote for PH3 poisoning. PMID:27606109

  2. Chemical Reaction between Boric Acid and Phosphine Indicates Boric Acid as an Antidote for Aluminium Phosphide Poisoning

    PubMed Central

    Soltani, Motahareh; Shetab-Boushehri, Seyed F.; Shetab-Boushehri, Seyed V.

    2016-01-01

    Objectives: Aluminium phosphide (AlP) is a fumigant pesticide which protects stored grains from insects and rodents. When it comes into contact with moisture, AlP releases phosphine (PH3), a highly toxic gas. No efficient antidote has been found for AlP poisoning so far and most people who are poisoned do not survive. Boric acid is a Lewis acid with an empty p orbital which accepts electrons. This study aimed to investigate the neutralisation of PH3 gas with boric acid. Methods: This study was carried out at the Baharlou Hospital, Tehran University of Medical Sciences, Tehran, Iran, between December 2013 and February 2014. The volume of released gas, rate of gas evolution and changes in pH were measured during reactions of AlP tablets with water, acidified water, saturated boric acid solution, acidified saturated boric acid solution, activated charcoal and acidified activated charcoal. Infrared spectroscopy was used to study the resulting probable adduct between PH3 and boric acid. Results: Activated charcoal significantly reduced the volume of released gas (P <0.01). Although boric acid did not significantly reduce the volume of released gas, it significantly reduced the rate of gas evolution (P <0.01). A gaseous adduct was formed in the reaction between pure AlP and boric acid. Conclusion: These findings indicate that boric acid may be an efficient and non-toxic antidote for PH3 poisoning.

  3. A review of episodes of zinc phosphide toxicosis in wild geese (Branta spp.) in Oregon (2004−2011)

    USGS Publications Warehouse

    Bildfell, Rob J.; Rumbeiha, Wilson K.; Schuler, Krysten L.; Meteyer, Carol U.; Wolff, Peregrine L.; Gillin, Colin M.

    2013-01-01

    Epizootic mortality in several geese species, including cackling geese (Branta hutchinsii) and Canada geese (Branta canadensis), has been recognized in the Willamette Valley of Oregon for over a decade. Birds are generally found dead on a body of water or are occasionally observed displaying neurologic clinical signs such as an inability to raise or control the head prior to death. Investigation of these epizootic mortality events has revealed the etiology to be accidental poisoning with the rodenticide zinc phosphide (Zn3P2). Gross and histologic changes are restricted to acute pulmonary congestion and edema, sometimes accompanied by distension of the upper alimentary tract by fresh grass. Geese are unusually susceptible to this pesticide; when combined with an epidemiologic confluence of depredation of specific agricultural crops by rodents and seasonal avian migration pathways, epizootic toxicosis may occur. Diagnosis requires a high index of suspicion, appropriate sample collection and handling, plus specific test calibration for this toxicant. Interagency cooperation, education of farmers regarding pesticide use, and enforcement of regulations has been successful in greatly decreasing these mortality events since 2009.

  4. Lattice-mismatched In(0.40)Al(0.60)As window layers for indium phosphide solar cells

    NASA Technical Reports Server (NTRS)

    Jain, Raj K.; Landis, Geoffrey A.; Wilt, David M.; Flood, Dennis J.

    1993-01-01

    The efficiency of indium phosphide (InP) solar cells is limited by its high surface recombination velocity (approximately 10(exp 7) cm/s). This might be reduced by a wide-bandgap window layer. The performance of InP solar cells with wide-bandgap (1.8 eV) lattice-mismatched In(0.40)Al(0.60)As as a window layer was calculated. Because the required window layer thickness is less than the critical layer thickness, growth of strained (pseudomorphic) layers without interfacial misfit dislocations should be possible. Calculations using the PC-lD numerical code showed that the efficiencies of baseline and optimized p(+)n (p-on-n) cells are increased to more than 22 and 24 percent, (air mass zero (AMO), 25 C), respectively for a lattice-mismatched In(0.40)Al(0.60)As window layer of 10-nm thickness. Currently, most cell development work has been focused on n(+)p (n-on-p) structures although comparatively little improvement has been found for n(+)p cells.

  5. The achievement of low contact resistance to indium phosphide: The roles of Ni, Au, Ge, and combinations thereof

    NASA Technical Reports Server (NTRS)

    Fatemi, Navid S.; Weizer, Victor G.

    1992-01-01

    We have investigated the electrical and metallurgical behavior of Ni, Au-Ni, and Au-Ge-Ni contacts on n-InP. We have found that very low values of contact resistivity rho(sub c) in the E-7 omega-sq cm range are obtained with Ni-only contacts. We show that the addition of Au to Ni contact metallization effects an additional order of magnitude reduction in rho(sub c). Ultra-low contact resistivities in the E-8 omega-sq cm range are obtained with both the Au-Ni and the Au-Ge-Ni systems, effectively eliminating the need for the presence of Ge in the Au-Ge-Ni system. The formation of various nickel phosphides at the metal-InP interface is shown to be responsible for the observed rho(sub c) values in the Ni and Au-Ni systems. We show, finally, that the order in which the constituents of Au-Ni and Au-Ge-Ni contacts are deposited has a significant bearing on the composition of the reaction products formed at the metal-InP interface and therefore on the contact resistivity at that interface.

  6. Indium phosphide all air-gap Fabry-Pérot filters for near-infrared spectroscopic applications

    NASA Astrophysics Data System (ADS)

    Ullah, A.; Butt, M. A.; Fomchenkov, S. A.; Khonina, S. N.

    2016-08-01

    Food quality can be characterized by noninvasive techniques such as spectroscopy in the Near Infrared wavelength range. For example, 930 -1450 nm wavelength range can be used to detect diseases and differentiate between meat samples. Miniaturization of such NIR spectrometers is useful for quick and mobile characterization of food samples. Spectrometers can be miniaturized, without compromising the spectral resolution, using Fabry-Pérot (FP) filters consisting of two highly reflecting mirrors with a central cavity in between. The most commonly used mirrors in the design of FP filters are Distributed Bragg Reflections (DBRs) consisting of alternating high and low refractive index material pairs, due to their high reflectivity compared to metal mirrors. However, DBRs have high reflectivity for a selected range of wavelengths known as the stopband of the DBR. This range is usually much smaller than the sensitivity range of the spectrometer detector. Therefore, a bandpass filter is usually required to restrict wavelengths outside the stopband of the FP DBRs. Such bandpass filters are difficult to design and implement. Alternatively, high index contrast materials must be can be used to broaden the stopband width of the FP DBRs. In this work, Indium phosphide all air-gap filters are proposed in conjunction with InGaAs based detectors. The designed filter has a wide stopband covering the entire InGaAs detector sensitivity range. The filter can be tuned in the 950-1450 nm with single mode operation. The designed filter can hence be used for noninvasive meat quality control.

  7. Solar Hydrogen Production Using Molecular Catalysts Immobilized on Gallium Phosphide (111)A and (111)B Polymer-Modified Photocathodes.

    PubMed

    Beiler, Anna M; Khusnutdinova, Diana; Jacob, Samuel I; Moore, Gary F

    2016-04-20

    We report the immobilization of hydrogen-producing cobaloxime catalysts onto p-type gallium phosphide (111)A and (111)B substrates via coordination to a surface-grafted polyvinylimidazole brush. Successful grafting of the polymeric interface and subsequent assembly of cobalt-containing catalysts are confirmed using grazing angle attenuated total reflection Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy. Photoelectrochemical testing in aqueous conditions at neutral pH shows that cobaloxime modification of either crystal face yields a similar enhancement of photoperformance, achieving a greater than 4-fold increase in current density and associated rates of hydrogen production as compared to results obtained using unfunctionalized electrodes tested under otherwise identical conditions. Under simulated solar illumination (100 mW cm(-2)), the catalyst-modified photocathodes achieve a current density ≈ 1 mA cm(-2) when polarized at 0 V vs the reversible hydrogen electrode reference and show near-unity Faradaic efficiency for hydrogen production as determined by gas chromatography analysis of the headspace. This work illustrates the modularity and versatility of the catalyst-polymer-semiconductor approach for directly coupling light harvesting to fuel production and the ability to export this chemistry across distinct crystal face orientations. PMID:26998554

  8. Tracking millennial-scale Holocene glacial advance and retreat using Osmium isotopes: Insights from the Greenland Ice Sheet

    NASA Astrophysics Data System (ADS)

    Rooney, Alan; Selby, David; Lloyd, Jeremy; Roberts, David; Lückge, Andreas; Sageman, Bradley; Prouty, Nancy

    2016-04-01

    Using new high-resolution osmium (Os) isotope stratigraphy from cores adjacent to the Greenland ice sheet we highlight the potential for chemostratigraphy to contribute to our understanding of ice sheet dynamics. This study utilizes sediment cores that have excellent chronological controls and demonstrates the role of local and regional weathering fluxes on the marine Os residence time. Distal to the Greenland ice streams core MSM-520 displays a steady lowering of the Os isotope composition during the Holocene. In contrast, proximal to the calving front of Jakobshavn Isbræ (core DA00-06), the Os isotope stratigraphy highlights four stages of ice stream retreat and advance. Our chemostratigraphic records provide vital benchmarks as we attempt to better constrain the future response of major ice sheets to climate change. Variations in Os isotope composition from sediment and macro-algae (seaweed) sourced from both near-field and far-field settings emphasize the overwhelming effect local weathering sources have on seawater Os isotope composition.

  9. A novel Osmium-based compound targets the mitochondria and triggers ROS-dependent apoptosis in colon carcinoma.

    PubMed

    Maillet, A; Yadav, S; Loo, Y L; Sachaphibulkij, K; Pervaiz, S

    2013-06-06

    Engagement of the mitochondrial-death amplification pathway is an essential component in chemotherapeutic execution of cancer cells. Therefore, identification of mitochondria-targeting agents has become an attractive avenue for novel drug discovery. Here, we report the anticancer activity of a novel Osmium-based organometallic compound (hereafter named Os) on different colorectal carcinoma cell lines. HCT116 cell line was highly sensitive to Os and displayed characteristic features of autophagy and apoptosis; however, inhibition of autophagy did not rescue cell death unlike the pan-caspase inhibitor z-VAD-fmk. Furthermore, Os significantly altered mitochondrial morphology, disrupted electron transport flux, decreased mitochondrial transmembrane potential and ATP levels, and triggered a significant increase in reactive oxygen species (ROS) production. Interestingly, the sensitivity of cell lines to Os was linked to its ability to induce mitochondrial ROS production (HCT116 and RKO) as HT29 and SW620 cell lines that failed to show an increase in ROS were resistant to the death-inducing activity of Os. Finally, intra-peritoneal injections of Os significantly inhibited tumor formation in a murine model of HCT116 carcinogenesis, and pretreatment with Os significantly enhanced tumor cell sensitivity to cisplatin and doxorubicin. These data highlight the mitochondria-targeting activity of this novel compound with potent anticancer effect in vitro and in vivo, which could have potential implications for strategic therapeutic drug design.

  10. Mediated glucose enzyme electrodes by cross-linking films of osmium redox complexes and glucose oxidase on electrodes.

    PubMed

    Ó Conghaile, Peter; Kamireddy, Sirisha; MacAodha, Domhnall; Kavanagh, Paul; Leech, Dónal

    2013-04-01

    Here, we report on a novel, versatile approach for the preparation of mediated enzyme electrodes, demonstrated using cross-linked films of glucose oxidase and a range of functionalised osmium complexes on graphite electrodes. Response of enzyme electrodes are optimised by evaluation of glucose response as a function of variation in ratios of [Os(2,2'-bipyridine)2(4-aminomethyl pyridine)Cl](+) redox mediator, polyallylamine support and glucose oxidase enzyme cross-linked using a di-epoxide reagent in films on graphite. Lowering of the redox potential required to mediate glucose oxidation is achieved by synthesis of complexes using (4,4'-dimethyl-2,2'-bipyridine) or (4,4'-dimethoxy-2,2'-bipyridine) as a ligand instead of (2,2'-bipyridine). Enzyme electrodes prepared using the complexes based on dimethoxy- or dimethyl-substituted bipyridines provide glucose oxidation current densities of 30 and 70 μA cm(-2) at 0.2 and 0.35 V applied potential compared to 120 μA cm(-2) at 0.45 V for the initial enzyme electrode, under pseudo-physiological conditions in 5 mM glucose, with stability of signals proving inadequate for long-term operation. Current output and stability may be improved by selection of alternate anchoring and cross-linking methodology, to provide enzyme electrodes capable for application to long-term glucose biosensors and anodes in enzymatic fuel cells.

  11. Matrix infrared spectroscopic and computational studies on the reactions of osmium and iron atoms with carbon monoxide and dinitrogen mixtures.

    PubMed

    Lu, Zhang-Hui; Xu, Qiang

    2011-10-01

    Reactions of laser-ablated osmium and iron atoms with CO and N(2) mixtures in excess neon have been investigated using matrix isolation infrared spectroscopy. The (NN)(x)MCO (M = Os, Fe; x = 1, 2) complexes are formed as reaction products during sample deposition and on annealing. These reaction products are characterized on the basis of the results of isotopic substitution, mixed isotopic splitting patterns, stepwise annealing, broad-band irradiation, and change of reagent concentration and laser energy. Density functional theory calculations have been performed on these products. Overall agreement between the experimental and calculated results supports the identification of these species from the matrix infrared spectra. The bonding characteristics and reaction mechanisms have been discussed. The M-C bonds are stronger than the M-N bonds in the same molecules. The formation of metal carbonyl dinitrogen complexes from the addition of CO to metal dinitrogen complexes is found to be more energetically favorable than that from the reactions of N(2) with metal carbonyls.

  12. Matrix infrared spectroscopic and computational studies on the reactions of osmium and iron atoms with carbon monoxide and dinitrogen mixtures.

    PubMed

    Lu, Zhang-Hui; Xu, Qiang

    2011-10-01

    Reactions of laser-ablated osmium and iron atoms with CO and N(2) mixtures in excess neon have been investigated using matrix isolation infrared spectroscopy. The (NN)(x)MCO (M = Os, Fe; x = 1, 2) complexes are formed as reaction products during sample deposition and on annealing. These reaction products are characterized on the basis of the results of isotopic substitution, mixed isotopic splitting patterns, stepwise annealing, broad-band irradiation, and change of reagent concentration and laser energy. Density functional theory calculations have been performed on these products. Overall agreement between the experimental and calculated results supports the identification of these species from the matrix infrared spectra. The bonding characteristics and reaction mechanisms have been discussed. The M-C bonds are stronger than the M-N bonds in the same molecules. The formation of metal carbonyl dinitrogen complexes from the addition of CO to metal dinitrogen complexes is found to be more energetically favorable than that from the reactions of N(2) with metal carbonyls. PMID:21877714

  13. Electrochemical proton-coupled electron transfer of an osmium aquo complex: theoretical analysis of asymmetric tafel plots and transfer coefficients.

    PubMed

    Ludlow, Michelle K; Soudackov, Alexander V; Hammes-Schiffer, Sharon

    2010-02-01

    Electrochemical proton-coupled electron transfer of an osmium aquo complex attached to a self-assembled monolayer on a gold electrode is studied with a recently developed theoretical formulation. The calculated hydrogen/deuterium kinetic isotope effect for the standard rate constant, the cathodic transfer coefficient at zero overpotential, and the Tafel plot are in excellent agreement with experimental data. The input quantities to the heterogeneous rate constant expressions were calculated with density functional theory in conjunction with dielectric continuum models, and no parameters were fit to experimental data. The theoretical calculations indicate that the asymmetry of the Tafel plot and the deviation of the transfer coefficient at zero overpotential from the standard value of one-half arise from the change in the equilibrium proton donor-acceptor distance upon electron transfer. The direction of the asymmetry and deviation from one-half is determined by the sign of this distance change, and the magnitude of these effects is determined by the magnitude of this distance change, as well as the reorganization energy and the distance dependence of the overlap between the initial and final proton vibrational wave functions. This theory provides experimentally testable predictions for the impact of specific system properties on the qualitative behavior of the Tafel plots. PMID:20067257

  14. Molecular fingerprint-region spectroscopy from 5 to 12  μm using an orientation-patterned gallium phosphide optical parametric oscillator.

    PubMed

    Maidment, Luke; Schunemann, Peter G; Reid, Derryck T

    2016-09-15

    We report a femtosecond optical parametric oscillator (OPO) based on the new semiconductor gain material orientation-patterned gallium phosphide (OP-GaP), which enables the production of high-repetition-rate femtosecond pulses spanning 5-12 μm with average powers in the few to tens of milliwatts range. This is the first example of a broadband OPO operating across the molecular fingerprint region, and we demonstrate its potential by conducting broadband Fourier-transform spectroscopy using water vapor and a polystyrene reference standard.

  15. Molecular fingerprint-region spectroscopy from 5 to 12  μm using an orientation-patterned gallium phosphide optical parametric oscillator.

    PubMed

    Maidment, Luke; Schunemann, Peter G; Reid, Derryck T

    2016-09-15

    We report a femtosecond optical parametric oscillator (OPO) based on the new semiconductor gain material orientation-patterned gallium phosphide (OP-GaP), which enables the production of high-repetition-rate femtosecond pulses spanning 5-12 μm with average powers in the few to tens of milliwatts range. This is the first example of a broadband OPO operating across the molecular fingerprint region, and we demonstrate its potential by conducting broadband Fourier-transform spectroscopy using water vapor and a polystyrene reference standard. PMID:27628372

  16. Theoretical modeling, near-optimum design and predicted performance of n(+)pp(+) and p(+)nn(+) indium phosphide homojunction solar cells

    NASA Technical Reports Server (NTRS)

    Goradia, Chandra; Thesling, William; Weinberg, Irving

    1991-01-01

    Using a detailed simulation model of p(+)nn(+) and n(+)pp(+) indium phosphide (InP) homojunction solar cells, extensive parametric variation computer simulation runs are conducted to help arrive at near-optimum designs of these two solar cell configurations. Values of all the geometrical and material parameters corresponding to the near-optimal designs of both these configurations are presented. For each configuration, results are given for parametric variation runs showing how the performance parameters JSC, VOC, and eta vary with each of the cell parameters for the near-optimally designed cell.

  17. Molecular fingerprint-region spectroscopy from 5 to 12 μm using an orientation-patterned gallium phosphide optical parametric oscillator

    NASA Astrophysics Data System (ADS)

    Maidment, Luke; Schunemann, Peter G.; Reid, Derryck T.

    2016-09-01

    We report a femtosecond optical parametric oscillator (OPO) based on the new semiconductor gain material orientation patterned gallium phosphide (OP-GaP), which enables the production of high-repetition-rate femtosecond pulses spanning 5-12 \\mu m with average powers in the few to tens of milliwatts range. This is the first example of a broadband OPO operating across the molecular fingerprint region, and we demonstrate its potential by conducting broadband Fourier-transform spectroscopy using water vapor and a polystyrene reference standard.

  18. The osmium tetroxide-p-phenylenediamine procedure reveals the chromatid cores and kinetochores of meiotic chromosomes by light and electron microscopy.

    PubMed

    Antonio, C; González-García, J M; Page, J; Suja, J A; Stockert, J C; Rufas, J S

    1996-11-01

    We analyzed first-metaphase meiotic chromosomes of the grasshopper Chorthippus jucundus by two different methods, i.e., a silver impregnation technique and the osmium tetroxide-p-phenylenediamine (Os-PPD) procedure. The former was applied on squashed testes previously fixed in ethanol-acetic acid, whereas for Os-PPD the material was not subjected to any previous extraction treatment but was fixed in OsO4, treated with PPD, and embedded in Epon 812. Both techniques revealed chromatid cores and kinetochores regardless of the processing of the material (squashed or sectioned). Unstained Os-PPD sections were analyzed by light microscopy and transmission electron microscopy (TEM). The Os-PPD technique provided a high contrast of chromatid cores and kinetochores in relation to the chromatin, which revealed a low electron density. To determine the Os-PPD reaction mechanism, the PAS procedure, as well as scanning electron microscopy (SEM) backscattering and SEM X-ray microanalysis, was performed on sections. By use of the Os-PPD-PAS procedure, glycol groups formed by oxidation of osmium bound to aromatic substrates were detected in chromatid cores and kinetochores by brightfield and fluorescence microscopy. A high Z contrast was detected in these structures by backscattered electron imaging. SEM X-ray microanalysis showed osmium and phosphorus to be the main elements present on the chromatid cores. Taking into account the known reactivity of OsO4 and the present results, the possible participation of nucleic acids as well as proteins in the Os-PPD reaction mechanism and in the composition of chromatid cores and kinetochores is discussed.

  19. Potent organometallic osmium compounds induce mitochondria-mediated apoptosis and S-phase cell cycle arrest in A549 non-small cell lung cancer cells.

    PubMed

    van Rijt, Sabine H; Romero-Canelón, Isolda; Fu, Ying; Shnyder, Steve D; Sadler, Peter J

    2014-05-01

    The problems of acquired resistance associated with platinum drugs may be addressed by chemotherapeutics based on other transition metals as they offer the possibility of novel mechanisms of action. In this study, the cellular uptake and induction of apoptosis in A549 human non-small cell lung cancer cells of three promising osmium(II) arene complexes containing azopyridine ligands, [Os(η(6)-arene)(p-R-phenylazopyridine)X]PF6, where arene is p-cymene or biphenyl, R is OH or NMe2, and X is Cl or I, were investigated. These complexes showed time-dependent (4–48 h) potent anticancer activity with highest potency after 24 h (IC50 values ranging from 0.1 to 3.6 μM). Cellular uptake of the three compounds as quantified by ICP-MS, was independent of their logP values (hydrophobicity). Furthermore, maximum cell uptake was observed after 24 h, with evident cell efflux of the osmium after 48 and 72 h of exposure, which correlated with the corresponding IC50 values. The most active compound 2, [Os(η(6)-p-cymene)(NMe2-phenylazopyridine)I]PF6, was taken up by lung cancer cells predominately in a temperature-dependent manner indicating that energy-dependent mechanisms are important in the uptake of 2. Cell fractionation studies showed that all three compounds accumulated mainly in cellular membranes. Furthermore, compound 2 induced apoptosis and caused accumulation in the S-phase of the cell cycle. In addition, 2 induced cytochrome c release and alterations in mitochondrial membrane potential even after short exposure times, indicating that mitochondrial apoptotic pathways are involved. This study represents the first steps towards understanding the mode of action of this promising class of new osmium-based chemotherapeutics.

  20. Confirmation of a meteoritic component in impact-melt rocks of the Chesapeake Bay impact structure, Virginia, USA - Evidence from osmium isotopic and PGE systematics

    USGS Publications Warehouse

    Lee, S.R.; Horton, J.W.; Walker, R.J.

    2006-01-01

    The osmium isotope ratios and platinum-group element (PGE) concentrations of impact-melt rocks in the Chesapeake Bay impact structure were determined. The impact-melt rocks come from the cored part of a lower-crater section of suevitic crystalline-clast breccia in an 823 m scientific test hole over the central uplift at Cape Charles, Virginia. The 187Os/188Os ratios of impact-melt rocks range from 0.151 to 0.518. The rhenium and platinum-group element (PGE) concentrations of these rocks are 30-270?? higher than concentrations in basement gneiss, and together with the osmium isotopes indicate a substantial meteoritic component in some impact-melt rocks. Because the PGE abundances in the impact-melt rocks are dominated by the target materials, interelemental ratios of the impact-melt rocks are highly variable and nonchondritic. The chemical nature of the projectile for the Chesapeake Bay impact structure cannot be constrained at this time. Model mixing calculations between chondritic and crustal components suggest that most impact-melt rocks include a bulk meteoritic component of 0.01-0.1% by mass. Several impact-melt rocks with lowest initial 187Os/188Os ratios and the highest osmium concentrations could have been produced by additions of 0.1%-0.2% of a meteoritic component. In these samples, as much as 70% of the total Os may be of meteoritic origin. At the calculated proportions of a meteoritic component (0.01-0.1% by mass), no mixtures of the investigated target rocks and sediments can reproduce the observed PGE abundances of the impact-melt rocks, suggesting that other PGE enrichment processes operated along with the meteoritic contamination. Possible explanations are 1) participation of unsampled target materials with high PGE abundances in the impact-melt rocks, and 2) variable fractionations of PGE during syn- to post-impact events. ?? The Meteoritical Society, 2006.

  1. Enhancement of Near-IR Photoelectric Conversion in Dye-Sensitized Solar Cells Using an Osmium Sensitizer with Strong Spin-Forbidden Transition.

    PubMed

    Kinoshita, Takumi; Fujisawa, Jun-Ichi; Nakazaki, Jotaro; Uchida, Satoshi; Kubo, Takaya; Segawa, Hiroshi

    2012-02-01

    A new osmium (Os) complex of the [Os(tcterpy)-(4,4'-bis(p-butoxystyryl)-2,2'-bipyridine)Cl]PF6 (Os-stbpy) has been synthesized and characterized for dye-sensitized solar cells (DSSCs). The Os-stbpy dye shows enhanced spin-forbidden absorptions around 900 nm. The DSSCs with Os-stbpy show a wide-band spectral response up to 1100 nm with high overall conversion efficiency of 6.1% under standard solar illumination.

  2. Catalytic oxidation of alkanes by a (salen)osmium(VI) nitrido complex using H2O2 as the terminal oxidant.

    PubMed

    Chen, Man; Pan, Yi; Kwong, Hoi-Ki; Zeng, Raymond J; Lau, Kai-Chung; Lau, Tai-Chu

    2015-09-14

    The osmium(VI) nitrido complex, [Os(VI)(N)(L)(CH3OH)](+) (1, L = N,N'-bis(salicylidene)-o-cyclohexyldiamine dianion) is an efficient catalyst for the oxidation of alkanes under ambient conditions using H2O2 as the oxidant. Alkanes are oxidized to the corresponding alcohols and ketones, with yields up to 75% and turnover numbers up to 2230. Experimental and computational studies are consistent with a mechanism that involves O-atom transfer from H2O2 to [Os(VI)(N)(L)](+) to generate an [Os(VIII)(N)(O)(L)](+) active intermediate.

  3. Electron-phonon superconductivity in the ternary phosphides Ba M2P2 (M =Ni,Rh,and Ir)

    NASA Astrophysics Data System (ADS)

    Karaca, Ertuǧrul; Tütüncü, H. M.; Srivastava, G. P.; Uǧur, S.

    2016-08-01

    Ab initio plane-wave pseudopotential calculations of electronic and vibrational properties have been carried out for the ternary phosphides Ba M2P2 (M =Ni,Rh and Ir) with a ThCr2Si2 -type structure. The calculated electronic results show the metallic character of Ba M2P2 , and the plots of total and partial density of states of Ba M2P2 exhibit strong hybridization between the d states of the M atom and the p states of the P atom below the Fermi energy. Differences in the phonon spectrum and density of states both in the acoustical and optical ranges for these compounds are presented and discussed. The Eliashberg spectral function for these compounds has been calculated by using a linear response approach based on the density functional theory. By integrating the Eliashberg spectral function, the average electron-phonon coupling parameter (λ ) is determined to be 0.61 for BaNi2P2 , 0.55 for BaIr2P2 , and 0.43 for BaRh2P2 . Using the calculated values of λ and the logarithmically averaged phonon frequency ωln the superconducting critical temperature (Tc) values for BaNi2P2,BaIr2P2 , and BaRh2P2 are obtained to be 2.80, 1.97, and 0.70 K, respectively, which compare very well with their experimental values of 3.0, 2.1, and 1.0 K.

  4. Solvothermal preparation of tin phosphide as a long-life anode for advanced lithium and sodium ion batteries

    NASA Astrophysics Data System (ADS)

    Liu, Shuling; Zhang, Hongzhe; Xu, Liqiang; Ma, Lanbing; Chen, Xiaoxia

    2016-02-01

    Tin phosphide (Sn4P3) nanoparticles with different sizes are synthesized via a facile solvothermal method at 180 °C for 10 h. The as-prepared Sn4P3 nanoparticles have an average size of about 15 nm. Meanwhile, their size could be easily controlled by the solvent ratio. The long cycle stability and rate performance of the as-obtained Sn4P3 nanoparticles have been tested as an anode material for lithium ion batteries for the first time. Electrochemical measurements show that the Sn4P3 nanoparticles with a smallest size give the best cycling and rate performances. They deliver a discharge capacity of 612 mAh g-1 after 10 cycles and could still maintain 442 mAh g-1 after 320 cycles at the current density of 100 mA g-1 within voltage limit of 0.01-3.0 V. Even after 200 cycles at a current density of 200 mA g-1, the specific capacity still could be remained at 315 mAh g-1. The improved electrochemical performances of Sn4P3 electrode might be largely attributed to their small-size. Furthermore, the as-prepared Sn4P3 nanoparticles have also been tested as an anode material for Na-ion batteries, this Sn4P3 anode can deliver a reversible capacity of 305 mAh g-1 after 10 cycles at the current density of 50 mA g-1.

  5. N-acetylcysteine, Ascorbic Acid, and Methylene Blue for the Treatment of Aluminium Phosphide Poisoning: Still Beneficial?

    PubMed Central

    Gheshlaghi, Farzad; Lavasanijou, Mohamad Reza; Moghaddam, Noushin Afshar; Khazaei, Majid; Behjati, Mohaddeseh; Farajzadegan, Ziba; Sabzghabaee, Ali Mohammad

    2015-01-01

    Objectives: Intentional and accidental intoxication with aluminium phosphide (ALP) remains a clinical problem, especially in the Middle East region. Considering the high mortality rate besides lack of any recommended first option drug for its treatment, this study was aimed to compare the therapeutic effects of N-acetylcysteine (NAC), vitamin C (Vit C), and methylene blue; both in isolate and also in combination, for the treatment of ALP intoxication in a rat model. Materials and Methods: In this experimental animal study, 80 male Wistar rats in eight groups were intoxicated with ALP (12.5 mg/kg) and treated with a single dose of NAC (100 mg/kg) or Vit C (500–1,000 mg/kg) or methylene blue (1 mg/kg/5 min, 0.1%) or two of these agents or all three of them (controls were not treated). Rats were monitored regarding the parameters of drug efficacy as increased survival time and reduced morbidity and mortality rate for 3 consecutive days to ensure toxin neutralization. Macroscopic changes were recorded and biopsy sections were taken from brain, cerebellum, kidney, liver, and heart for microscopic evaluation regarding cellular hypoxia. Results: The mean survival times of rats exposed to ALP and treated with VitC + NAC was 210.55±236.22 minutes. In analysis of survival times, there was a significant difference between Group 5 which received VitC + NAC and the other groups (P < 0.01). Serum magnesium levels after death were higher than normal (P = 0.01). Conclusions: Despite the higher survival rate of antioxidant-treated rats compared with controls, this difference was not statistically significant. PMID:26862259

  6. Osmium isotope perturbations during the Pliensbachian-Toarcian (Early Jurassic): Relationships between volcanism, weathering, and climate change

    NASA Astrophysics Data System (ADS)

    Percival, Lawrence; Cohen, Anthony; Davies, Marc; Dickson, Alexander; Jenkyns, Hugh; Hesselbo, Stephen; Mather, Tamsin; Xu, Weimu; Storm, Marisa

    2016-04-01

    The Mesozoic Era marked a time of greenhouse conditions on Earth, punctuated by a number of abrupt perturbations to the carbon cycle, such as Ocean Anoxic Events (OAEs). OAEs are typically marked in the stratigraphic record by the appearance of organic-rich shales, and excursions in carbon-isotope ratios registered in carbonates and organic matter. A range of geochemical evidence indicates changes to global temperatures, typically featuring abrupt warming possibly caused by CO2 emissions resulting from Large Igneous Province (LIP) volcanism. A warmer atmosphere is thought to have led to changes in the global hydrological cycle, which would likely have enhanced global weathering rates. The Toarcian OAE (T-OAE) is inferred, from osmium isotope ratios in organic-rich mudrocks from Yorkshire and western North America, to have been a time of such increased weathering rates. However, it is likely that the sediments at these locations were deposited in relatively hydrographically restricted environments, potentially more susceptible to the influence of local input; consequently, they may not offer the best representation of the global seawater Os-isotope composition at that time. In this study, we have measured the osmium isotope composition of siciliclastic mudrocks in a core from the Mochras borehole (Llanbedr Farm, Cardigan Bay Basin, Wales), which constitutes a sedimentary record for a fully open-marine seaway that connected Tethys to the Boreal ocean during the Toarcian. We analysed samples from strata including both the T-OAE and preceding Pliensbachian-Toarcian boundary (Pl-To), both of which record multiple geochemical excursions and records of elevated extinction amongst benthic fauna. We find that the latest Pliensbachian records seawater 187Os/188Os of ~0.35-0.4, rising to ~0.5 at the Pl-To boundary, before a further rise to ~0.7 during the T-OAE. We conclude that such increases in radiogenic Os flux to the ocean system resulted from enhanced continental

  7. Coronary artery wall imaging in mice using osmium tetroxide and micro-computed tomography (micro-CT)

    SciTech Connect

    Pai, Vinay M.; Kozlowski, Megan; Donahue, Danielle; Miller, Elishiah; Xiao, Xianghui; Chen, Marcus Y.; Yu, Zu-Xi; Connelly, Patricia; Jeffries, Kenneth; Wen, Han

    2012-05-10

    The high spatial resolution of micro-computed tomography (micro-CT) is ideal for 3D imaging of coronary arteries in intact mouse heart specimens. Previously, micro-CT of mouse heart specimens utilized intravascular contrast agents that hardened within the vessel lumen and allowed a vascular cast to be made. However, for mouse coronary artery disease models, it is highly desirable to image coronary artery walls and highlight plaques. For this purpose, we describe an ex vivo contrast-enhanced micro-CT imaging technique based on tissue staining with osmium tetroxide (OsO{sub 4}) solution. As a tissue-staining contrast agent, OsO{sub 4} is retained in the vessel wall and surrounding tissue during the fixation process and cleared from the vessel lumens. Its high X-ray attenuation makes the artery wall visible in CT. Additionally, since OsO{sub 4} preferentially binds to lipids, it highlights lipid deposition in the artery wall. We performed micro-CT of heart specimens of 5- to 25-week-old C57BL/6 wild-type mice and 5- to 13-week-old apolipoprotein E knockout (apoE{sup -/-}) mice at 10 {mu}m resolution. The results show that walls of coronary arteries as small as 45 {mu}m in diameter are visible using a table-top micro-CT scanner. Similar image clarity was achieved with 1/2000th the scan time using a synchrotron CT scanner. In 13-week-old apoE mice, lipid-rich plaques are visible in the aorta. Our study shows that the combination of OsO{sub 4} and micro-CT permits the visualization of the coronary artery wall in intact mouse hearts.

  8. Complex Förster energy transfer interactions between semiconductor quantum dots and a redox-active osmium assembly.

    PubMed

    Stewart, Michael H; Huston, Alan L; Scott, Amy M; Efros, Alexander L; Melinger, Joseph S; Gemmill, Kelly Boeneman; Trammell, Scott A; Blanco-Canosa, Juan B; Dawson, Philip E; Medintz, Igor L

    2012-06-26

    The ability of luminescent semiconductor quantum dots (QDs) to engage in diverse energy transfer processes with organic dyes, light-harvesting proteins, metal complexes, and redox-active labels continues to stimulate interest in developing them for biosensing and light-harvesting applications. Within biosensing configurations, changes in the rate of energy transfer between the QD and the proximal donor, or acceptor, based upon some external (biological) event form the principle basis for signal transduction. However, designing QD sensors to function optimally is predicated on a full understanding of all relevant energy transfer mechanisms. In this report, we examine energy transfer between a range of CdSe-ZnS core-shell QDs and a redox-active osmium(II) polypyridyl complex. To facilitate this, the Os complex was synthesized as a reactive isothiocyanate and used to label a hexahistidine-terminated peptide. The Os-labeled peptide was ratiometrically self-assembled to the QDs via metal affinity coordination, bringing the Os complex into close proximity of the nanocrystal surface. QDs displaying different emission maxima were assembled with increasing ratios of Os-peptide complex and subjected to detailed steady-state, ultrafast transient absorption, and luminescence lifetime decay analyses. Although the possibility exists for charge transfer quenching interactions, we find that the QD donors engage in relatively efficient Förster resonance energy transfer with the Os complex acceptor despite relatively low overall spectral overlap. These results are in contrast to other similar QD donor-redox-active acceptor systems with similar separation distances, but displaying far higher spectral overlap, where charge transfer processes were reported to be the dominant QD quenching mechanism.

  9. Subsurface modifications in indium phosphide induced by single and multiple femtosecond laser pulses: A study on the formation of periodic ripples

    SciTech Connect

    Couillard, M.; Borowiec, A.; Haugen, H. K.; Preston, J. S.; Griswold, E. M.; Botton, G. A.

    2007-02-01

    We use cross-sectional transmission electron microscopy to study the damage induced below the surface of indium phosphide (InP) samples by single and multiple femtosecond laser pulses with a photon energy lower than the InP band gap. Single-pulse irradiation creates a {approx}100 nm deep crater with a resolidified surface layer consisting of quasiamorphous indium phosphide. The resolidified layer has a thickness of {approx}60 nm at the center and extends laterally beyond the edge of the crater rim. Exposure to multiple femtosecond pulses of 2050 nm center wavelength results in the formation of laser-induced periodic surface structures (LIPSS) with two different periods, one ({approx}1730 nm) less than but close to the laser wavelength and one ({approx}470 nm) four times smaller. Segregation beneath both types of ripples leads to the formation of In-rich particles embedded in the resolidified surface layer. Extended defects are detected only below the center of the multiple-pulse crater and their distribution appears to be correlated with the LIPSS modulation. Finally, LIPSS formation is discussed in terms of the observed subsurface microstructures.

  10. Antiferromagnetic transitions of osmium-containing rare earth double perovskites Ba{sub 2}LnOsO{sub 6} (Ln=rare earths)

    SciTech Connect

    Hinatsu, Yukio Doi, Yoshihiro; Wakeshima, Makoto

    2013-10-15

    The perovskite-type compounds containing both rare earth and osmium Ba{sub 2}LnOsO{sub 6} (Ln=Pr, Nd, Sm–Lu) have been prepared. Powder X-ray diffraction measurements and Rietveld analysis show that Ln{sup 3+} and Os{sup 5+} ions are structurally ordered at the M site of the perovskite BaMO{sub 3}. Magnetic susceptibility and specific heat measurements show that an antiferromagnetic ordering of Os{sup 5+} ions has been observed for Ba{sub 2}LnOsO{sub 6} (Ln=Pr, Nd, Sm, Eu, Gd, Lu) at 65–71 K. Magnetic ordering of Ln{sup 3+} moments occurs when the temperature is furthermore decreased. - Graphical abstract: The perovskite-type compounds containing both rare earth and osmium Ba{sub 2}LnOsO{sub 6} (Ln=Pr, Nd, Sm–Lu) have been prepared. An antiferromagnetic ordering of Os{sup 5+} ions has been observed for Ba{sub 2}LnOsO{sub 6} (Ln=Pr, Nd, Sm, Eu, Gd, Lu) at 65–71 K. Measurements and analysis of the specific heat for Ba{sub 2}PrOsO{sub 6} show that magnetic ordering of the Pr{sup 3+} moments should have occurred at ∼20 K. Display Omitted.

  11. En route to osmium analogues of KP1019: synthesis, structure, spectroscopic properties and antiproliferative activity of trans-[Os(IV)Cl4(Hazole)2].

    PubMed

    Büchel, Gabriel E; Stepanenko, Iryna N; Hejl, Michaela; Jakupec, Michael A; Keppler, Bernhard K; Arion, Vladimir B

    2011-08-15

    By controlled Anderson type rearrangement reactions complexes of the general formula trans-[Os(IV)Cl(4)(Hazole)(2)], where Hazole = 1H-pyrazole, 2H-indazole, 1H-imidazole, and 1H-benzimidazole, have been synthesized. Note that 2H-indazole tautomer stabilization in trans-[Os(IV)Cl(4)(2H-indazole)(2)] is unprecedented in coordination chemistry of indazole. The metal ion in these compounds possesses the same coordination environment as ruthenium(III) in (H(2)ind)[Ru(III)Cl(4)(Hind)(2)], where Hind = 1H-indazole, (KP1019), an investigational anticancer drug in phase I clinical trials. These osmium(IV) complexes are appropriate precursors for the synthesis of osmium(III) analogues of KP1019. In addition the formation of an adduct of trans-[Os(IV)Cl(4)(Hpz)(2)] with cucurbit[7]uril is described. The compounds have been comprehensively characterized by elemental analysis, EI and ESI mass spectrometry, spectroscopy (IR, UV-vis, 1D and 2D NMR), cyclic voltammetry, and X-ray crystallography. Their antiproliferative acitivity in the human cancer cell lines CH1 (ovarian carcinoma), A549 (nonsmall cell lung carcinoma), and SW480 (colon carcinoma) is reported.

  12. Luminescence response of an osmium(II) complex to macromolecular polyanions for the detection of heparin and chondroitin sulfate in biomedical preparations.

    PubMed

    Wu, Hao; Wu, Jain; Saez, Christopher; Campana, Maria; Megehee, Elise G; Wang, Enju

    2013-12-01

    Heparin, dextran sulfate (DS), chondroitin sulfate (CS), and carrageenan are found to enhance the luminescence intensity of an osmium(II) carbonyl complex with phenanthroline (phen) and 4-phenylpyridine (4-phpy) ligands in aqueous and ethanol solutions. The enhancing effect of the polyanions on the luminescence of the complex is heavily dependent on the sulfate content and other factors such as structure, solubility, and counter ions of the polyanion. The highly sulfated dextran and ι-carrageenan have the most profound effect, while the low charged κ-carrageenan and CS have the least response in aqueous solution. All polyanions exhibited enhanced luminescence intensity of the complex in ethanol solutions, and even the low charged CS and κ-carrageenan enhanced the luminescence more than 4 times. DS contamination of the sodium heparin at 5% can show a significant increase in luminescence response. The osmium complex is found to be highly successful in the fast and sensitive detection of heparin in commercial injectable samples with various backgrounds as well as the detection of CS in over the counter food supplement tablets.

  13. MRT letter: high resolution SEM imaging of nano-architecture of cured urea-formaldehyde resin using plasma coating of osmium.

    PubMed

    Park, Byung-Dae; Singh, Adya P; Nuryawan, Arif; Hwang, Kiju

    2013-11-01

    Nanoarchitecture of cured urea-formaldehyde (UF) resins was examined with a field-emission scanning electron microscope (FE-SEM) after coating samples with osmium, which is considered to produce particles of considerably smaller size compared to other metal coatings used in SEM studies. This method enabled comparison of the nanoarchitecture of UF resins of low (1.0) and high (1.6) formaldehyde/urea (F/U) mole ratios to be made, based on imaging of extremely small size particles as part of UF resin architecture, not described before. Imaging revealed presence of relatively large globular particles (148.084-703.983 nm size range) as well as smaller substructures (28.004-39.604 nm size range) as part of the architecture of 1.0-mole UF resin. Globular particles were also present in 1.6 mole UF resin, but of considerably smaller size (14.760-50.269 nm). The work presented demonstrates usefulness of osmium coating in unraveling the intricacies of the nanostructural organization of cured UF resins, prompting wider application of this immensely useful but grossly underutilized metal coating type in high resolution SEM examination of biological and materials samples.

  14. Defect Analysis of Boron Phosphide Thin Films and Sapphire Single Crystal Using Synchrotron X-ray Topography

    NASA Astrophysics Data System (ADS)

    Ding, Zihao

    Boron phosphide is an ideal semiconductor material used for neutron detectors because of its superior material properties, such as wide band gap and large thermal neutron capture cross-section of 10B. Since bulk BP is not readily available for neutron detector application, BP thin films are mainly synthesized by chemical vapor deposition (CVD). Among all the feasible substrates for BP deposition, SiC stands out due to its small lattice mismatch (4.5%) with BP, however it is necessary to optimize the growth condition to synthesize high quality BP thin films on SiC. In chapter III, BP thin film samples deposited on 4H-SiC and 6H-SiC under different growth conditions are characterized, mainly using synchrotron X-ray topography and other techniques such as optical microscopy and scanning electron microscopy. The relationship between BP thin film crystal quality and substrate material and orientation and other growth conditions is investigated. It can be concluded from the experimental data that the crystal quality of BP thin films on 4H-SiC substrate is much better than that on 6H-SiC substrate. Besides, poor crystalline quality of substrate will likely degrade the crystalline quality of epitaxial thin films. Sapphire single crystal has been widely used in high-technology industry because of its excellent combination between optical, electrical and mechanical properties. In this thesis, a-plane sapphire ribbon grown by Edge-defined Film-fed Growth method (EFG) is analyzed by characterizing the seed crystals used and the quality of as-grown ribbon, by reflection X-ray topography. Distributions and formation mechanisms of defects inside both the sapphire seed crystal and ribbon crystal are studied. Transmission topographs reveal the presence of two sets of slip bands that are nucleated from either edge, the distribution of which is symmetric in the used seed crystal and asymmetric in the pristine seed crystal. This phenomenon could be caused by the unstable growth

  15. Hessian Fly (Diptera: Cecidomyiidae) Mortality in Export Bale Compressors and Response to a Hydrogen Phosphide and Carbon Dioxide Gas Mixture.

    PubMed

    Yokoyama, Victoria Y; Cambron, Sue E; Muhareb, Jeannette

    2015-02-01

    Hessian fly, Mayetiola destructor (Say), puparial mortality was evaluated in three modern hay compressors that produce compressed standard and large-size bales for export to Asia-Pacific countries. Pressure on bales ranged from 93.4 to 139.4 kg/cm2, causing 90.0-99.9% mortality of 10,891-23,164 puparia. Puparial response to a cylinderized hydrogen phosphide (1.8-2%) and carbon dioxide (97.8-98%) gas mixture was evaluated as a potential quarantine treatment using 2-4 d-exposures to low, medium, and high doses of 0.73-0.86, 1.05-1.26, and 1.39-1.56 mg/liter, and temperatures of 5.87±1.14, 9.84±0.05, 16.14±0.14, and 20.35±0.11°C. Accumulative concentration multiplied by time products (mg h/liter) at all fumigation temperatures for low, medium, and high fumigant doses were 34.9-37.7, 52.2-54.3, and 67.9-73.1 for 2 d; 52.7-60.6, 77.9-89.2, and 102.1-110.7 for 3 d; and 69.9-82.0, 99.4-118.2, and 132.3-146.8 for 4 d, respectively. An increase in mortality was significantly related to an increase in fumigation duration at 5, 10, and 15°C, and an increase in fumigant dose at 10 and 15°C. Puparial mortality ranged from 97.2 to 100% at all doses and durations at 20°C with no survivors at the highest dose for 3 d and the mid- and highest dose for 4 d. Bale compression is currently used in the first phase of a multiple quarantine treatment to control potential Hessian fly contaminants in exported hay. The novel fumigant may have application as a single quarantine treatment for noncompressed, standard exported bales.

  16. Hessian Fly (Diptera: Cecidomyiidae) Mortality in Export Bale Compressors and Response to a Hydrogen Phosphide and Carbon Dioxide Gas Mixture.

    PubMed

    Yokoyama, Victoria Y; Cambron, Sue E; Muhareb, Jeannette

    2015-02-01

    Hessian fly, Mayetiola destructor (Say), puparial mortality was evaluated in three modern hay compressors that produce compressed standard and large-size bales for export to Asia-Pacific countries. Pressure on bales ranged from 93.4 to 139.4 kg/cm2, causing 90.0-99.9% mortality of 10,891-23,164 puparia. Puparial response to a cylinderized hydrogen phosphide (1.8-2%) and carbon dioxide (97.8-98%) gas mixture was evaluated as a potential quarantine treatment using 2-4 d-exposures to low, medium, and high doses of 0.73-0.86, 1.05-1.26, and 1.39-1.56 mg/liter, and temperatures of 5.87±1.14, 9.84±0.05, 16.14±0.14, and 20.35±0.11°C. Accumulative concentration multiplied by time products (mg h/liter) at all fumigation temperatures for low, medium, and high fumigant doses were 34.9-37.7, 52.2-54.3, and 67.9-73.1 for 2 d; 52.7-60.6, 77.9-89.2, and 102.1-110.7 for 3 d; and 69.9-82.0, 99.4-118.2, and 132.3-146.8 for 4 d, respectively. An increase in mortality was significantly related to an increase in fumigation duration at 5, 10, and 15°C, and an increase in fumigant dose at 10 and 15°C. Puparial mortality ranged from 97.2 to 100% at all doses and durations at 20°C with no survivors at the highest dose for 3 d and the mid- and highest dose for 4 d. Bale compression is currently used in the first phase of a multiple quarantine treatment to control potential Hessian fly contaminants in exported hay. The novel fumigant may have application as a single quarantine treatment for noncompressed, standard exported bales. PMID:26470109

  17. Substituent directed selectivity in anion recognition by a new class of simple osmium-pyrazole derived receptors.

    PubMed

    Das, Ankita; Mondal, Prasenjit; Dasgupta, Moumita; Kishore, Nand; Lahiri, Goutam Kumar

    2016-02-14

    The present article deals with the structurally, spectroscopically and electrochemically characterised osmium-bipyridyl derived complexes [(bpy)2Os(II)(HL1)Cl]ClO4 [1]ClO4 and [(bpy)2Os(II)(HL2)Cl]ClO4 [2]ClO4 incorporating neutral and monodentate pyrazole derivatives (HL) with one free NH function (bpy = 2,2'-bipyridine, HL1 = pyrazole, HL2 = 3,5-dimethylpyrazole). The crystal structures of [1]ClO4 and [2]ClO4 reveal intramolecular hydrogen bonding interactions between the free NH proton of HL and the equatorially placed Cl(-) ligand (N-HCl) with donor-acceptor distances of 3.114(7) Å and 3.153(6) Å as well as intermolecular hydrogen bonding interactions between the NH proton and one of the oxygen atoms of ClO4(-) (N-HO) with donor-acceptor distances of 2.870(10) Å and 3.024(8) Å, respectively. The effect of hydrogen bonding interactions has translated into the less acidic nature of the NH proton of the coordinated HL with estimated pKa > 12. 1(+) and 2(+) exhibit reversible Os(II)/(III) and irreversible Os(III)/(IV) processes in CH3CN within ± 2.0 V versus SCE. The effect of 3,5-dimethyl substituted HL2 on 2(+) has been reflected in the appreciable lowering (40 mV) of the Os(II/III) potential, along with the further decrease in the acidity of the NH proton (pKa > 13.0) with regard to HL1 coordinated 1(+) (pKa: ∼ 12.3). The electronic spectral features of Os(ii) (1(+)/2(+)) and electrochemically generated Os(III) (1(2+)/2(2+)) derived complexes have been analysed by TD-DFT calculations. The efficacy of the 1(+) and 2(+) encompassing free NH proton towards the anion recognition process has been evaluated by different experimental investigations using a wide variety of anions. It however establishes that receptor 1(+) can recognise both F(-) and OAc(-) in acetonitrile solution, while 2(+) is exclusively selective for the F(-) ion. PMID:26733437

  18. Accretion rate of extraterrestrial particles determined from osmium isotope systematics of pacific pelagic clay and manganese nodules

    SciTech Connect

    Esser, B.K.; Turekian, K.K. )

    1988-06-01

    Pelagic clay and Mn nodules from DOMES sites in the North Pacific and a varved glacial lake deposit from Connecticut were analyzed for Os concentration and isotopic composition by isotope-dilution secondary ion mass spectrometry after treatment by NiS fusion of oxalic acid leaching. Bulk pelagic clay from DOMES site C has {sup 187}Os/{sup 186}Os = 6.5 and Os = 0.14 ng/g. Oxalic acid leaches of this same sediment and of Mn nodules for DOMES sites A and C have more radiogenic {sup 187}Os/{sup 186}Os ratios which average 8.3. Bulk glacial Lake Hitchcock sediment has {sup 187}Os/{sup 186}Os = 12.5 and Os = 0.06 ng/g. The total Os flux to North Pacific pelagic clay is 7 to 10 ng Os/cm{sup 2}/10{sup 6} y. Lake Hitchcock sediment provides an integrated value for the local crustal {sup 187}Os/{sup 186}Os ratio. The oxalic acid leaches are assumed to attack hydrogenous phases selectively. A simple model in which the only sources of Os to the ocean are continental crust with the isotopic composition of Lake Hitchcock and extraterrestrial particles with {sup 187}Os/{sup 186}Os = 1.1 results in a cosmic flux of osmium to the sediment of 4.9 ng Os/cm{sup 2}/10{sub 6} y of which 20% is hydrogenous. A model in which the sources of Os to the ocean are continental crust with an {sup 187}Os/{sup 186}Os ratio of 30, oceanic mantle or crust with {sup 187}Os/{sup 186}Os = 1.04 and extraterrestrial particles with {sup 187}Os/{sup 186}Os = 1.1 results in a cosmic flux of Os to the sediment of 5.7 ng Os/cm{sup 2}/10{sup 6} y of which none is hydrogenous. These extraterrestrial Os fluxes correspond to maximum C-1 chondrite accretion rates of between 4.9 {times} 10{sub 4} and 5.6 {times}10{sub 4} tonnes/y.

  19. Monometallic osmium(II) complexes with bis(N-methylbenzimidazolyl)benzene or -pyridine: a comparison study with ruthenium(II) analogues.

    PubMed

    Shao, Jiang-Yang; Zhong, Yu-Wu

    2013-06-01

    Seven bis-tridentate osmium complexes with Mebib or Mebip (Mebib is the 2-deprotonated form of 1,3-bis(N-methylbenzimidazolyl)benzene and Mebip is bis(N-methylbenzimidazolyl)pyridine) have been prepared, and their electrochemical and spectroscopic properties are compared with ruthenium structural analogues. Among them, four complexes have the [Os(NCN)(NNN)]-type coordination, including [Os(Mebib)(Mebip)](PF6)2 (1(PF6)2), [Os(dpb)(Mebip)](PF6) (2(PF6), dpb is the 2-deprotonated form of 1,3-di(pyrid-2-yl)benzene), [Os(Mebib)(ttpy)](PF6) (3(PF6), ttpy = 4'-tolyl-2,2':6',2"-terpyridine), and [Os(dpb)(ttpy)](PF6) (4(PF6)). The other three complexes are [Os(Mebip)2](PF6)2 (5(PF6)2), [Os(Mebip)(tpy)](PF6)2 (6(PF6)2, tpy = 2,2':6',2"-terpyridine), and [Os(ttpy)2](PF6)2 (7(PF6)2) with the [Os(NNN)(NNN)]-type coordination. Single crystals of 2(PF6) and 6(PF6)2 have been obtained, and their structures are studied by X-ray crystallographic analysis. The Os(II/III) redox potentials of 1(PF6)2 to 7(PF6)2 progressively increase from +0.04, +0.23, +0.24, +0.36, +0.56, +0.79 to +0.94 V vs Ag/AgCl, which are 200-300 mV less positive relative to the Ru(II/III) potentials of their ruthenium counterparts. The highest occupied molecular orbital energy levels of 1(+)-7(2+) are calculated to vary in a descending order. The ruthenium and osmium complexes have singlet metal-to-ligand charge-transfer (MLCT) transitions of similar energies and band shapes, while the osmium complexes display additional (3)MLCT transitions in the lower-energy region. Complexes 6(PF6)2 and 7(PF6)2 emit weakly at 780 and 740 nm, respectively. Complex 1(PF6)2 was synthesized as the oxidized Os(III) salt because of the low Os(II/III) potential. The transformation of 1(2+) to 1(+) by chemical reduction or electrolysis led to the emergence of the (1)MLCT transitions in the visible region.

  20. Escape of unradiogenic osmium during sub-aerial lava degassing: Evidence from fumarolic deposits, Piton de la Fournaise, Réunion Island

    NASA Astrophysics Data System (ADS)

    Gannoun, Abdelmouhcine; Vlastélic, Ivan; Schiano, Pierre

    2015-10-01

    This study presents new Re-Os isotope and elemental data in gas condensates and corresponding lavas in order to examine the geochemical behavior of these two elements during magma degassing at Piton de la Fournaise, Réunion Island. Gas sublimates formed between 2007 and 2011 at temperature ranging from 400 to ca. 100 °C include Na-K sulfate (aphthitalite), Na sulfate (thenardite), Ca-Cu sulfate (e.g. gypsum), Ca-Mg-Al-Fe fluoride (e.g. ralstonite) and native sulfur. The high temperature deposits show trace element typical of volcanic gas with high enrichment in Re (24 to 79 ppb), almost two order of magnitude higher than the corresponding lavas but with Os abundances similar to those of the lavas (14-132 ppt). In contrast the Os contents of the low temperature fluoride deposits (13-77 ppb) are higher than any of the other condensates. The fluorides are also enriched in Re, albeit to lesser extent than Os (2.9-15.3 ppb). Based on high-temperature samples, the fluid/melt partition coefficients estimated for Re and Os are 100 ± 80 and 1 ± 2, respectively. Considering 1% of fluid loss, these partition coefficients translate into emanation coefficients of 0.50 (0.17-0.65) for Re and 0.01 (0-0.03) for Os. These results indicate that Re, unlike Os, is highly volatile at Piton de la Fournaise. Osmium isotopic compositions of samples collected at medium and low temperature (<350 °C) are very uniform and unfractionated (187Os/188Os between 0.130-0.135) and plot within the range of the April 2007 lava flow and the historical lavas of Piton de la Fournaise (i.e. 0.130-0.137). However the highest temperature condensates (Na-K sulfates with T of 384-400°C) yield lower 187Os/188Os ratios (i.e. 0.124-0.129) within the field of mantle signal. Such unradiogenic compositions are best explained if old mantle sulfides occur in lavas and contribute to volcanic gases. Within the general frame of osmium mantle geochemistry, loss of unradiogenic Os during magmas degassing could help

  1. Results from Coupled Optical and Electrical Sentaurus TCAD Models of a Gallium Phosphide on Silicon Electron Carrier Selective Contact Solar Cell

    SciTech Connect

    Limpert, Steven; Ghosh, Kunal; Wagner, Hannes; Bowden, Stuart; Honsberg, Christiana; Goodnick, Stephen; Bremner, Stephen; Green, Martin

    2014-06-09

    We report results from coupled optical and electrical Sentaurus TCAD models of a gallium phosphide (GaP) on silicon electron carrier selective contact (CSC) solar cell. Detailed analyses of current and voltage performance are presented for devices having substrate thicknesses of 10 μm, 50 μm, 100 μm and 150 μm, and with GaP/Si interfacial quality ranging from very poor to excellent. Ultimate potential performance was investigated using optical absorption profiles consistent with light trapping schemes of random pyramids with attached and detached rear reflector, and planar with an attached rear reflector. Results indicate Auger-limited open-circuit voltages up to 787 mV and efficiencies up to 26.7% may be possible for front-contacted devices.

  2. A theoretical comparison of the near-optimum design and predicted performance of n/p and p/n indium phosphide homojunction solar cells

    NASA Technical Reports Server (NTRS)

    Goradia, Chandra; Thesling, William; Weinberg, Irving

    1991-01-01

    Using a detailed simulation model of p(+)nn(+) and n(+)pp(+) indium phosphide (InP) homojunction solar cells, extensive parametric variation computer simulation runs were performed to aid in making near-optimum designs for these two solar cell configurations. The values of all the geometrical and material parameters corresponding to the near-optimal designs of both these configurations are presented. The results of parametric variation runs are presented for each configuration showing how the performance parameters J(sub sc), V(sub oc), and eta vary with each of the cell design parameters for the near-optimally designed cell. Finally, the theoretically obtained results are discussed, and the relative merits and drawbacks of the two configurations are compared.

  3. Oxyfunctionalization of unactivated C-H bonds in triterpenoids with tert-butylhydroperoxide catalyzed by meso-5,10,15,20-tetramesitylporphyrinate osmium(II) carbonyl complex.

    PubMed

    Ogawa, Shoujiro; Wakatsuki, Yasuo; Makino, Mitsuko; Fujimoto, Yasuo; Yasukawa, Ken; Kikuchi, Takashi; Ukiya, Motohiko; Akihisa, Toshihiro; Iida, Takashi

    2010-02-01

    A system consisting of meso-5,10,15,20-tetramesitylporphyrinate osmium(II) carbonyl complex [Os(TMP)CO] as a precatalyst and tert-butylhydroperoxide (TBHP) as an oxygen donor is shown to be an efficient, regioselective oxidant system for the allylic oxidation, ketonization and hydroxylation of unactivated C-H bonds in a series of the peracetate derivatives of penta- and tetracyclic triterpenoids. Treatment of the substrates with this oxidant system afforded a variety of novel or scarce oxygenated derivatives in one-step. Structures of the isolated components, after chromatographic separation, were determined by spectroscopic methods including GC-MS and shift-correlated 2D-NMR techniques. Factors governing the regioselectivity and the possible mechanism for the oxyfunctionalization of the unactivated carbons are also discussed.

  4. Oxidative Cyclization of 1,5-Dienes with Hydrogen Peroxide Catalyzed by an Osmium(III) Complex: Synthesis of cis-Tetrahydrofurans.

    PubMed

    Sugimoto, Hideki; Kanetake, Takayuki; Maeda, Kazuki; Itoh, Shinobu

    2016-03-18

    Stereoselective oxidative cyclization of 1,5-dienes with hydrogen peroxide catalyzed by [Os(III)(OH)(H2O)(L-N4Me2)](PF6)2 (1: L-N4Me2 = N,N'-dimethyl-2,11-diaza-[3,3](2,6)pyridinophane) is explored. 1,5-Dienes involving geraniol derivatives are converted to the corresponding tetrahydrofurans in modest to high yields. The products exclusively have the cis-conformation with respect to the substituents at the 2- and 5-positions of the tetrahydrofuran ring. The products also have a syn-conformation with respect to the furan oxygen atom and the hydroxyl groups. Mechanistic studies including a direct reaction of the oxo-hydroxo-osmium(V) complex, 2, with a dihydroxylated geraniol derivative are performed.

  5. Oxidative Cyclization of 1,5-Dienes with Hydrogen Peroxide Catalyzed by an Osmium(III) Complex: Synthesis of cis-Tetrahydrofurans.

    PubMed

    Sugimoto, Hideki; Kanetake, Takayuki; Maeda, Kazuki; Itoh, Shinobu

    2016-03-18

    Stereoselective oxidative cyclization of 1,5-dienes with hydrogen peroxide catalyzed by [Os(III)(OH)(H2O)(L-N4Me2)](PF6)2 (1: L-N4Me2 = N,N'-dimethyl-2,11-diaza-[3,3](2,6)pyridinophane) is explored. 1,5-Dienes involving geraniol derivatives are converted to the corresponding tetrahydrofurans in modest to high yields. The products exclusively have the cis-conformation with respect to the substituents at the 2- and 5-positions of the tetrahydrofuran ring. The products also have a syn-conformation with respect to the furan oxygen atom and the hydroxyl groups. Mechanistic studies including a direct reaction of the oxo-hydroxo-osmium(V) complex, 2, with a dihydroxylated geraniol derivative are performed. PMID:26950609

  6. Osmium(III) analogues of KP1019: electrochemical and chemical synthesis, spectroscopic characterization, X-ray crystallography, hydrolytic stability, and antiproliferative activity.

    PubMed

    Kuhn, Paul-Steffen; Büchel, Gabriel E; Jovanović, Katarina K; Filipović, Lana; Radulović, Siniša; Rapta, Peter; Arion, Vladimir B

    2014-10-20

    A one-electron reduction of osmium(IV) complexes trans-[Os(IV)Cl4(Hazole)2], where Hazole = 1H-pyrazole ([1](0)), 2H-indazole ([2](0)), 1H-imidazole ([3](0)), and 1H-benzimidazole ([4](0)), afforded a series of eight new complexes as osmium analogues of KP1019, a lead anticancer drug in clinical trials, with the general formula (cation)[trans-Os(III)Cl4(Hazole)2], where cation = H2pz(+) (H2pz[1]), H2ind(+) (H2ind[2]), H2im(+) (H2im[3]), Ph4P(+) (Ph4P[3]), nBu4N(+) (nBu4N[3]), H2bzim(+) (H2bzim[4]), Ph4P(+) (Ph4P[4]), and nBu4N(+) (nBu4N[4]). All complexes were characterized by elemental analysis, (1)H NMR spectroscopy, electrospray ionization mass spectrometry, UV-vis spectroscopy, cyclic voltammetry, while H2pz[1], H2ind[2], and nBu4[3], in addition, by X-ray diffraction. The reduced species [1](-) and [4](-) are stable in aqueous media in the absence of air oxygen and do not react with small biomolecules such as amino acids and the nucleotide 5'-dGMP. Cell culture experiments in five different human cancer cell lines (HeLa, A549, FemX, MDA-MB-453, and LS-174) and one noncancerous cell line (MRC-5) were performed, and the results were discussed and compared to those for KP1019 and cisplatin. Benzannulation in complexes with similar structure enhances antitumor activity by several orders of magnitude, implicating different mechanisms of action of the tested compounds. In particular, complexes H2ind[2] and H2bzim[4] exhibited significant antiproliferative activity in vitro when compared to H2pz[1] and H2im[3].

  7. Growth of Zinc Phosphide (Zn3P2) and Iron Disulfide (FeS2) using pulsed laser deposition

    NASA Astrophysics Data System (ADS)

    Vaddi, Rajesh

    The growing energy needs of society have triggered tremendous interest in the development of photovoltaics formed from earth abundant materials. Zinc Phosphide (Zn3P2) and Iron Pyrite (FeS2) are two materials formed from elements with large Earth crustal abundances that have nearly ideal band gap energies (1.5eV and 0.96 eV, respectively) and optical absorption coefficients (~104 /cm) for use as absorber layers in solar cells. In this work, the structural, optical, and electronic properties of these materials produced in thin film form using pulsed laser deposition have been explored. Stoichiometric Zn3P2 thin films were obtained at a laser energy density of 3 J/cm2. However, these films were found to be amorphous. Crystallization of these highly resistive amorphous thin films was possible after rapid thermal annealing (RTA). A near optimal band gap of 1.6 eV and a high absorption coefficient of >104/cm were observed for samples annealed at 500 C for 60 seconds when high ramp rates of 150 °C/sec were used for annealing. XPS studies showed the presence of a trace amount of oxygen in the samples upon depth profiling. Schottky barrier heights were extracted for samples annealed at 350 °C and 500 °C with different metals. Al and Mg showed higher barrier heights with good diode rectification behavior. Fermi level pinning was shown to be a significant concern in both cases due to the large values of interface states observed (> 1013/cm2-eV). A Schottky barrier solar cell was fabricated using these films and showed low efficiency with a low Voc of 410 mV that was impacted by Fermi level pinning. Growth of Iron pyrite thin films from an FeS target was demonstrated for the first time using pulsed laser deposition. For the different laser energy densities and substrate temperatures explored, amorphous FeS (Pyrrhotite) was mainly produced. Conversion of FeS to FeS2 was obtained by sulfurization of thin films at 350 °C for times of 30 minutes at a N2 flow rates of 200

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

    PubMed

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

    2014-03-01

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

  9. Evaluation of the rhenium-osmium geochronometer in the Phosphoria petroleum system, Bighorn Basin of Wyoming and Montana, USA

    USGS Publications Warehouse

    Lillis, Paul G.; Selby, David

    2013-01-01

    Rhenium-osmium (Re-Os) geochronometry is applied to crude oils derived from the Permian Phosphoria Formation of the Bighorn Basin in Wyoming and Montana to determine whether the radiogenic age reflects the timing of petroleum generation, timing of migration, age of the source rock, or the timing of thermochemical sulfate reduction (TSR). The oils selected for this study are interpreted to be derived from the Meade Peak Phosphatic Shale and Retort Phosphatic Shale Members of the Phosphoria Formation based on oil-oil and oil-source rock correlations utilizing bulk properties, elemental composition, δ13C and δ34S values, and biomarker distributions. The δ34S values of the oils range from -6.2‰ to +5.7‰, with oils heavier than -2‰ interpreted to be indicative of TSR. The Re and Os isotope data of the Phosphoria oils plot in two general trends: (1) the main trend (n = 15 oils) yielding a Triassic age (239 ± 43 Ma) with an initial 187Os/188Os value of 0.85 ± 0.42 and a mean square weighted deviation (MSWD) of 1596, and (2) the Torchlight trend (n = 4 oils) yielding a Miocene age (9.24 ± 0.39 Ma) with an initial 187Os/188Os value of 1.88 ± 0.01 and a MSWD of 0.05. The scatter (high MSWD) in the main-trend regression is due, in part, to TSR in reservoirs along the eastern margin of the basin. Excluding oils that have experienced TSR, the regression is significantly improved, yielding an age of 211 ± 21 Ma with a MSWD of 148. This revised age is consistent with some studies that have proposed Late Triassic as the beginning of Phosphoria oil generation and migration, and does not seem to reflect the source rock age (Permian) or the timing of re-migration (Late Cretaceous to Eocene) associated with the Laramide orogeny. The low precision of the revised regression (±21 Ma) is not unexpected for this oil family given the long duration of generation from a large geographic area of mature Phosphoria source rock, and the possible range in the initial 187Os/188Os

  10. Rhenium - osmium heterogeneity of enriched mantle basalts explained by composition and behaviour of mantle-derived sulfides

    NASA Astrophysics Data System (ADS)

    Harvey, J.; Dale, C. W.; Gannoun, A.; Burton, K. W.

    2010-12-01

    Analyses of enriched mantle (EM) -basalts, using lithophile element-based isotope systems have long provided evidence for discrete, but variable mantle reservoirs [1]. Upon partial melting, the isotopic fingerprint of each reservoir is imparted upon the partial melt produced. However, recent work involving the Re-Os isotope systematics of EM-basalts [2] suggests that it may not be so simple to delimit these previously well defined mantle reservoirs; the “mantle zoo” [3] may contain more reservoirs than previously envisaged. However, a simple model, with varying contributions from two populations of compositionally distinct mantle sulfides can readily account for the observed heterogeneities in Re-Os isotope systematics of such basalts without additional mantle reservoirs. Rhenium-osmium elemental and isotopic analyses of individual sulfide grains separated from spinel lherzolites from Kilbourne Hole, NM, USA demonstrate that two discrete populations of mantle sulfide exist in terms of both Re-Os systematics and textural relationship with co-existing silicates. One population, with a rounded morphology, is preserved in silicate grains and typically possesses high [Os], low [Re] with unradiogenic, typically sub-chondritic, 187Os/188Os attributable to long term isolation in a low-Re environment. By contrast, irregular-shaped sulfides, preserved along silicate grain boundaries, possess low [Os], higher [Re] and a wider range of, but generally supra-chondritic, 187Os/188Os ([Os] typically ≤ 1-2 ppm, 187Os/188Os ≤ 0.3729; this study). This population is thought to represent metasomatic sulfide (e.g. [4,5]). Uncontaminated silicate phases contain negligible Os (<100 ppt) therefore the Os elemental and isotope composition of basalts is dominated by volumetrically insignificant sulfide ([Os] ≤ 37 ppm, this study). During the early stages of partial melting, supra-chondritic interstitial sulfides are mobilized and incorporated into the melt, adding their radiogenic

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

    PubMed

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

    2014-09-28

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

  12. Indium phosphide solar cells

    NASA Technical Reports Server (NTRS)

    Weinberg, Irving

    1991-01-01

    The direction for InP solar cell research; reduction of cell cost; increase of cell efficiency; measurements needed to better understand cell performance; n/p versus p/n; radiation effects; major problems in cell contacting; and whether the present level of InP solar cell research in the USA should be maintained, decreased, or increased were considered.

  13. Cross sections for (n, 2n), (n, p) and (n, ) reactions on osmium isotopes in the neutron energy range of 13.5-14.8 MeV.

    PubMed

    Zhao, Liangyong; Yuan, Jilong; Tuo, Fei; Zhang, Yanbin; Kong, Xiangzhong; Liu, Rong; Jiang, Li

    2008-10-01

    Cross sections for (n, 2n), (n, p) and (n, alpha) reactions on the osmium isotopes were measured in the neutron energies 13.5-14.8 MeV by the activation technique with the monitor reaction (93)Nb(n, 2n)(92 m)Nb. Our measurements were carried out by gamma-detection using a coaxial high-purity germanium (HPGe) detector. Natural high-purity osmium powder (99.9%) was fabricated as the samples. The neutron energies were determined by the cross-section ratios for (93)Nb(n, 2n)(92 m)Nb and (90)Zr(n, 2n)(89 m+g)Zr reactions. The fast neutrons were produced by the T(d, n)(4)He reaction. The results obtained were compared with previous data.

  14. Anthropogenic Osmium in Precipitation

    NASA Astrophysics Data System (ADS)

    Chen, C.; Sedwick, P. N.; Sharma, M.

    2007-12-01

    Here we report the Os isotopic composition for precipitation from Hanover (NH), Soda Springs (CA) and the Ross Sea (Antarctica) as determined by negative thermal ionization mass spectrometry. All samples yielded non- radiogenic Os isotopic compositions. Snow and rain samples from Hanover, NH had Os concentrations of 0.8 - 12.2 fg/g (1 fg/g = 1E-15 g/g) and 187Os/188Os from 0.16 - 0.24. Snowpack from the high Sierra Nevada (Central Sierra Snow Laboratory, Soda Springs, CA) yielded Os concentration and isotopic composition of 3.6 fg/g and 0.21, respectively; Antarctic snow deposited above first year pack ice had [Os] = 0.8 fg/g and 187Os/188Os = 0.42. The isotopic ratios indicate that potential natural sources of Os to the atmosphere, such as continental mineral aerosols (187Os/188Os = 1.26) and seawater (187Os/188Os = 1.05) do not contribute bulk of Os to the precipitation. Instead, the isotopic ratios are identical to the platinum ores from the Merensky Reef in the Bushveld Igneous Complex, South Africa and Noril'sk Ni-Cu sulfide deposit associated with the Siberian Flood Basalts, Russia. These two deposits produce greater than 95 percent of the total Pt, Pd and Rh consumed annually primarily by the automotive industry. We infer that anthropogenic Os contribution dominates the isotopic composition of precipitation. The similar and non-radiogenic Os isotopic compositions observed in precipitation from disparate locations suggest that contamination of the troposphere with anthropogenic Os may be global in scale. We think that processing of ore to extract Pt, Pd, and Rh from PGE ores (PGE: group of six closely related elements Os, Ir, Pt, Pd, Rh, and Ru), which involves smelting and converting at high temperature and in the presence of oxygen, releases the volatile, toxic compound OsO4 into the troposphere, where it is mixed and then scavenged by precipitation, thus explaining both the non-radiogenic isotopic composition and the high and variable Os concentrations of Os in the precipitation. The magnitude of this contamination is likely sufficient to alter the global Os cycle and impact the isotopic composition of Os in the surface ocean.

  15. Metal–Arene Complexes with Indolo[3,2-c]-quinolines: Effects of Ruthenium vs Osmium and Modifications of the Lactam Unit on Intermolecular Interactions, Anticancer Activity, Cell Cycle, and Cellular Accumulation

    PubMed Central

    2013-01-01

    Six novel ruthenium(II)– and osmium(II)–arene complexes with three modified indolo[3,2-c]quinolines have been synthesized in situ starting from 2-aminoindoloquinolines and 2-pyridinecarboxaldehyde in the presence of [M(p-cymene)Cl2]2 (M = Ru, Os) in ethanol. All complexes have been characterized by elemental analysis, spectroscopic techniques (1H, 13C NMR, IR, UV–vis), and ESI mass spectrometry, while four complexes were investigated by X-ray diffraction. The complexes have been tested for antiproliferative activity in vitro in A549 (non-small cell lung), SW480 (colon), and CH1 (ovarian) human cancer cell lines and showed IC50 values between 1.3 and >80 μM. The effects of Ru vs Os and modifications of the lactam unit on intermolecular interactions, antiproliferative activity, and cell cycle are reported. One ruthenium complex and its osmium analogue have been studied for anticancer activity in vivo applied both intraperitoneally and orally against the murine colon carcinoma model CT-26. Interestingly, the osmium(II) complex displayed significant growth-inhibitory activity in contrast to its ruthenium counterpart, providing stimuli for further investigation of this class of compounds as potential antitumor drugs. PMID:23431223

  16. Binding of an organo-osmium(II) anticancer complex to guanine and cytosine on DNA revealed by electron-based dissociations in high resolution Top-Down FT-ICR mass spectrometry.

    PubMed

    Wootton, Christopher A; Sanchez-Cano, Carlos; Liu, Hong-Ke; Barrow, Mark P; Sadler, Peter J; O'Connor, Peter B

    2015-02-28

    The Os(II) arene anticancer complex [(η(6)-bip)Os(en)Cl](+) (Os1-Cl; where bip = biphenyl, and en = ethylenediamine) binds strongly to DNA. Here we investigate reactions between Os1-Cl and the self-complementary 12-mer oligonucleotide 5'-TAGTAATTACTA-3' (DNA12) using ultra high resolution Fourier Transform-Ion Cyclotron Resonance Mass Spectrometry (FT-ICR MS). Identification of the specific sites of DNA osmiation with {(η(6)-bip)Os(en)}(2+) was made possible by the use of Electron Detachment Dissociation (EDD) which produced a wide range of assignable osmiated MS/MS fragments. In contrast, the more commonly used CAD and IRMPD techniques produced fragments which lose the bound osmium. These studies reveal that not only is guanine G3 a strong binding site for {(η(6)-bip)Os(en)}(2+) but, unexpectedly, so too is cytosine C10. Interestingly, the G3/C10 di-osmiated adduct of DNA12 also formed readily but did not undergo such facile fragmentation by EDD, perhaps due to folding induced by van der Waal's interactions of the bound osmium arene species. These new insights into osmium arene DNA adducts should prove valuable for the design of new organometallic drugs and contribute to understanding the lack of cross resistance of this organometallic anticancer complex with cisplatin.

  17. Laser ablation synthesis of new gold phosphides using red phosphorus and nanogold as precursors. Laser desorption ionisation time-of-flight mass spectrometry.

    PubMed

    Panyala, Nagender Reddy; Peña-Méndez, Eladia María; Havel, Josef

    2012-05-15

    Gold phosphides show unique optical or semiconductor properties and there are extensive high technology applications, e.g. in laser diodes, etc. In spite of the various AuP structures known, the search for new materials is wide. Laser ablation synthesis is a promising screening and synthetic method. Generation of gold phosphides via laser ablation of red phosphorus and nanogold mixtures was studied using laser desorption ionisation time-of-flight mass spectrometry (LDI TOFMS). Gold clusters Au(m)(+) (m = 1 to ~35) were observed with a difference of one gold atom and their intensities were in decreasing order with respect to m. For P(n)(+) (n = 2 to ~111) clusters, the intensities of odd-numbered phosphorus clusters are much higher than those for even-numbered phosphorus clusters. During ablation of P-nanogold mixtures, clusters Au(m)(+) (m = 1-12), P(n)(+) (n = 2-7, 9, 11, 13-33, 35-95 (odd numbers)), AuP(n)(+) (n = 1, 2-88 (even numbers)), Au(2)P(n)(+) (n = 1-7, 14-16, 21-51 (odd numbers)), Au(3)P(n)(+) (n = 1-6, 8, 9, 14), Au(4)P(n)(+) (n = 1-9, 14-16), Au(5)P(n)(+) (n = 1-6, 14, 16), Au(6)P(n)(+) (n = 1-6), Au(7)P(n)(+) (n = 1-7), Au(8)P(n)(+) (n = 1-6, 8), Au(9)P(n)(+) (n = 1-10), Au(10)P(n)(+) (n = 1-8, 15), Au(11)P(n)(+) (n = 1-6), and Au(12)P(n)(+) (n = 1, 2, 4) were detected in positive ion mode. In negative ion mode, Au(m)(-) (m = 1-5), P(n)(-) (n = 2, 3, 5-11, 13-19, 21-35, 39, 41, 47, 49, 55 (odd numbers)), AuP(n)(-) (n = 4-6, 8-26, 30-36 (even numbers), 48), Au(2)P(n)(-) (n = 2-5, 8, 11, 13, 15, 17), A(3) P(n)(-) (n = 6-11, 32), Au(4)P(n)(-) (n = 1, 2, 4, 6, 10), Au(6)P(5)(-), and Au(7)P(8)(-) clusters were observed. In both modes, phosphorus-rich Au(m)P(n) clusters prevailed. The first experimental evidence for formation of AuP(60) and gold-covered phosphorus Au(12)P(n) (n = 1, 2, 4) clusters is given. The new gold phosphides generated might inspire synthesis of

  18. Reactivity of nitrido complexes of ruthenium(VI), osmium(VI), and manganese(V) bearing Schiff base and simple anionic ligands.

    PubMed

    Man, Wai-Lun; Lam, William W Y; Lau, Tai-Chu

    2014-02-18

    Nitrido complexes (M≡N) may be key intermediates in chemical and biological nitrogen fixation and serve as useful reagents for nitrogenation of organic compounds. Osmium(VI) nitrido complexes bearing 2,2':6',2″-terpyridine (terpy), 2,2'-bipyridine (bpy), or hydrotris(1-pyrazolyl)borate anion (Tp) ligands are highly electrophilic: they can react with a variety of nucleophiles to generate novel osmium(IV)/(V) complexes. This Account describes our recent results studying the reactivity of nitridocomplexes of ruthenium(VI), osmium(VI), and manganese(V) that bear Schiff bases and other simple anionic ligands. We demonstrate that these nitrido complexes exhibit rich chemical reactivity. They react with various nucleophiles, activate C-H bonds, undergo N···N coupling, catalyze the oxidation of organic compounds, and show anticancer activities. Ruthenium(VI) nitrido complexes bearing Schiff base ligands, such as [Ru(VI)(N)(salchda)(CH3OH)](+) (salchda = N,N'-bis(salicylidene)o-cyclohexyldiamine dianion), are highly electrophilic. This complex reacts readily at ambient conditions with a variety of nucleophiles at rates that are much faster than similar reactions using Os(VI)≡N. This complex also carries out unique reactions, including the direct aziridination of alkenes, C-H bond activation of alkanes and C-N bond cleavage of anilines. The addition of ligands such as pyridine can enhance the reactivity of [Ru(VI)(N)(salchda)(CH3OH)](+). Therefore researchers can tune the reactivity of Ru≡N by adding a ligand L trans to nitride: L-Ru≡N. Moreover, the addition of various nucleophiles (Nu) to Ru(VI)≡N initially generate the ruthenium(IV) imido species Ru(IV)-N(Nu), a new class of hydrogen-atom transfer (HAT) reagents. Nucleophiles also readily add to coordinated Schiff base ligands in Os(VI)≡N and Ru(VI)≡N complexes. These additions are often stereospecific, suggesting that the nitrido ligand has a directing effect on the incoming nucleophile. M≡N is also

  19. INFLUENCE OF GLUTARALDEHYDE AND/OR OSMIUM TETROXIDE ON CELL VOLUME, ION CONTENT, MECHANICAL STABILITY, AND MEMBRANE PERMEABILITY OF EHRLICH ASCITES TUMOR CELLS

    PubMed Central

    Penttila, Antti; Kalimo, Hannu; Trump, Benjamin F.

    1974-01-01

    Effects of fixation with glutaraldehyde (GA), glutaraldehyde-osmium tetroxide (GA-OsO4), and osmium tetroxide (OsO4) on ion and ATP content, cell volume, vital dye staining, and stability to mechanical and thermal stress were studied in Ehrlich ascites tumor cells (EATC). Among variables investigated were fixation time, fixative concentration, temperature, osmolality of the fixative agent and buffer, total osmolality of the fixative solution, osmolality of the postfixation buffer, and time of postfixation treatment in buffer (Sutherland, R. M., et al. 1967. J. Cell Physiol. 69:185.). Rapid loss of potassium, exchangeable magnesium, and ATP, and increase of vital dye uptake and electrical conductivity occurred with all fixatives studied. These changes were virtually immediate with GA-OsO4 or OsO4 but slower with GA (in the latter case they were dependent on fixative temperature and concentration) (Foot, N. C. 1950. In McClung's Handbook of Microscopical Technique. 3rd edition. 564.). Total fixative osmolality had a marked effect on cell volume with OsO4 but little or no effect with GA or GA-OsO4. Osmolality of the buffer had a marked effect on cell volume with OsO4, whereas with GA or GA-OsO4 it was only significant at very hypotonic buffer osmolalities. Concentration of GA had no effect on cell volume. Osmolality of the postfixation buffer had little effect on cell volume, and duration of fixation or postfixation treatment had no effect with all fixatives. Freezing and thawing or centrifugal stress (up to 100,000 g) had little or no effect on cell volume after all fixatives studied. Mechanical stress obtained by sonication showed that OsO4 alone produced poor stabilization and that GA fixation alone produced the greatest stabilization. The results indicate that rapid membrane permeability changes of EATC follow fixative action. The results are consistent with known greater stabilizing effects of GA on model protein systems since cells were also rendered relatively

  20. Phosphorus K β X-Ray Emission Spectra and Valence-Band Structures of Transition-Metal Phosphides and GaAs 1-xPx

    NASA Astrophysics Data System (ADS)

    Sugiura, Chikara

    1996-07-01

    The P Kβ emission spectra in fluorescence from ZrP, NbP, MoP,HfP, TaP, WP, AgP2, CdP2, Mn3P2, Cd3P2 and GaAs1-xPxfor 0.2 ≤ x ≤ 1 are measured with a high-resolutiontwo-crystal vacuum spectrometer equipped with Ge(111) crystals. Theinfluence of metal atoms appears distinctly in the P Kβemission spectra of transition-metal phosphides. The effect ofarsenic atoms appears slightly in the P Kβ emission spectraof GaAs1-xPx. The P Kβ emission spectra of AgP2,CdP2, Cd3P2 and GaAs0.6 P0.4 are compared withavailable P L2,3 emission and XPS valence-band spectra ona common energy scale. It is shown that the P 3p electronsinteract fairly with the metal d electrons in the upper partof the valence band for MP ( M = Zr, Nb, Mo, Hf, Ta, W) and Mn3P2;considerable p-d, s mixing occurs in the middle part for AgP2and in the lower part for CdP2 and Cd3P2; and the Ga 3dstates mix fairly with the P 3s states in GaAs0.6P0.4.

  1. A Mechanistic Study of CO2 Reduction at the Interface of a Gallium Phosphide (GaP) Surface using Core-level Spectroscopy

    SciTech Connect

    Flynn, Kristen

    2015-08-18

    Carbon dioxide (CO2) emission into the atmosphere has increased tremendously through burning of fossil fuels, forestry, etc.. The increased concentration has made CO2 reductions very attractive though the reaction is considered uphill. Utilizing the sun as a potential energy source, CO2 has the possibility to undergo six electron and four proton transfers to produce methanol, a useable resource. This reaction has been shown to occur selectively in an aqueous pyridinium solution with a gallium phosphide (GaP) electrode. Though this reaction has a high faradaic efficiency, it was unclear as to what role the GaP surface played during the reaction. In this work, we aim to address the fundamental role of GaP during the catalytic conversion, by investigating the interaction between a clean GaP surface with the reactants, products, and intermediates of this reaction using X-ray photoelectron spectroscopy. We have determined a procedure to prepare atomically clean GaP and our initial CO2 adsorption studies have shown that there is evidence of chemisorption and reaction to form carbonate on the clean surface at LN2 temperatures (80K), in contrast to previous theoretical calculations. These findings will enable future studies on CO2 catalysis.

  2. A Mechanistic Study of CO2 Reduction at the Interface of a Gallium Phosphide (GaP) Surface using Core-level Spectroscopy - Oral Presentation

    SciTech Connect

    Flynn, Kristen

    2015-08-19

    Carbon dioxide (CO2) emission into the atmosphere has increased tremendously through burning of fossil fuels, forestry, etc.. The increased concentration has made CO2 reductions very attractive though the reaction is considered uphill. Utilizing the sun as a potential energy source, CO2 has the possibility to undergo six electron and four proton transfers to produce methanol, a useable resource. This reaction has been shown to occur selectively in an aqueous pyridinium solution with a gallium phosphide (GaP) electrode. Though this reaction has a high faradaic efficiency, it was unclear as to what role the GaP surface played during the reaction. In this work, we aim to address the fundamental role of GaP during the catalytic conversion, by investigating the interaction between a clean GaP surface with the reactants, products, and intermediates of this reaction using X-ray photoelectron spectroscopy. We have determined a procedure to prepare atomically clean GaP and our initial CO2 adsorption studies have shown that there is evidence of chemisorption and reaction to form carbonate on the clean surface at LN2 temperatures (80K), in contrast to previous theoretical calculations. These findings will enable future studies on CO2 catalysis.

  3. Power recovery of radiation damaged MOCVD grown indium phosphide on silicon solar cells through argon-ion laser annealing. Master`s thesis

    SciTech Connect

    Boyer, L.L.

    1996-06-01

    This thesis reports the results of a laser annealing technique used to remove defect sites from radiation damaged indium phosphide on silicon MOCVD grown solar cells. This involves the illumination of damaged solar cells with a continuous wave laser to produce a large forward-biased current. The InP/Si cells were irradiated with 1 MeV electrons to a given fluence, and tested for degradation. Light from an argon laser was used to illuminate four cells with an irradiance of 2.5 W/sq cm, producing a current density 3 to 5 times larger than AMO conditions. Cells were annealed at 19 deg C with the laser and at 25 deg C under AMO conditions. Annealing under laser illumination of n/p-type cells resulted in recovery of 48%. P/n type cells lost 4 to 12% of the assumed degradaton. Annealing under AMO conditions resulted in power recovery of 70% in n/p type cells. P/n-type cells recovered approximately 16% of lost power. Results indicate that significant power recovery results from the annealing of defects within n/p type InP/Si solar cells.

  4. New Intermetallic Ternary Phosphide Chalcogenide AP2-xXx (A = Zr, Hf; X = S, Se) Superconductors with PbFCl-Type Crystal Structure

    NASA Astrophysics Data System (ADS)

    Kitô, Hijiri; Yanagi, Yousuke; Ishida, Shigeyuki; Oka, Kunihiko; Gotoh, Yoshito; Fujihisa, Hiroshi; Yoshida, Yoshiyuki; Iyo, Akira; Eisaki, Hiroshi

    2014-07-01

    We have synthesized a series of intermetallic ternary phosphide chalcogenide superconductors, AP2-xXx (A = Zr, Hf; X = S, Se), using the high-pressure synthesis technique. These materials have a PbFCl-type crystal structure (space group P4/nmm) when x is greater than 0.3. The superconducting transition temperature Tc changes systematically with x, yielding dome-like phase diagrams. The maximum Tc is achieved at approximately x = 0.7, at which point the Tc is 6.3 K for ZrP2-xSex (x = 0.75), 5.5 K for HfP2-xSex (x = 0.7), 5.0 K for ZrP2-xSx (x = 0.675), and 4.6 K for Hfp2-xSx (x = 0.5). They are typical type-II superconductors and the upper and lower critical fields are estimated to be 2.92 T at 0 K and 0.021 T at 2 K for ZrP2-xSex (x = 0.75), respectively.

  5. Voltammetry and in situ scanning tunnelling spectroscopy of osmium, iron, and ruthenium complexes of 2,2':6',2''-terpyridine covalently linked to Au(111)-electrodes.

    PubMed

    Salvatore, Princia; Hansen, Allan Glargaard; Moth-Poulsen, Kasper; Bjørnholm, Thomas; Nichols, Richard John; Ulstrup, Jens

    2011-08-28

    We have studied self-assembled molecular monolayers (SAMs) of complexes between Os(II)/(III), Fe(II)/(III), and Ru(II)/(III) and a 2,2',6',2''-terpyridine (terpy) derivative linked to Au(111)-electrode surfaces via a 6-acetylthiohexyloxy substituent at the 4'-position of terpy. The complexes were prepared in situ by first linking the terpy ligand to the surface via the S-atom, followed by addition of suitable metal compounds. The metal-terpy SAMs were studied by cyclic voltammetry (CV), and in situ scanning tunnelling microscopy with full electrochemical potential control of substrate and tip (in situ STM). Sharp CV peaks were observed for the Os- and Fe complexes, with interfacial electrochemical electron transfer rate constants of 6-50 s(-1). Well-defined but significantly broader peaks (up to 300 mV) were observed for the Ru-complex. Addition of 2,2'-bipyridine (bipy) towards completion of the metal coordination spheres induced voltammetric sharpening. In situ STM images of single molecular scale strong structural features were observed for the osmium and iron complexes. As expected from the voltammetric patterns, the surface coverage was by far the highest for the Ru-complex which was therefore selected for scanning tunnelling spectroscopy. These correlations displayed a strong peak around the equilibrium potential with systematic shifts with increasing bias voltage, as expected for a sequential two-step in situ ET mechanism.

  6. Electrochemical detection of DNA binding by tumor suppressor p53 protein using osmium-labeled oligonucleotide probes and catalytic hydrogen evolution at the mercury electrode.

    PubMed

    Němcová, Kateřina; Sebest, Peter; Havran, Luděk; Orság, Petr; Fojta, Miroslav; Pivoňková, Hana

    2014-09-01

    In this paper, we present an electrochemical DNA-protein interaction assay based on a combination of protein-specific immunoprecipitation at magnetic beads (MBIP) with application of oligonucleotide (ON) probes labeled with an electroactive oxoosmium complex (Os,bipy). We show that double-stranded ONs bearing a dT20 tail labeled with Os,bipy are specifically recognized by the tumor suppressor p53 protein according to the presence or absence of a specific binding site (p53CON) in the double-stranded segment. We demonstrate the applicability of the Os,bipy-labeled probes in titration as well as competition MBIP assays to evaluate p53 relative affinity to various sequence-specific or structurally distinct unlabeled DNA substrates upon modulation of the p53-DNA binding by monoclonal antibodies used for the immunoprecipitation. To detect the p53-bound osmium-labeled probes, we took advantage of a catalytic peak yielded by Os,bipy-modified DNA at the mercury-based electrodes, allowing facile determination of subnanogram quantities of the labeled oligonucleotides. Versatility of the electrochemical MBIP technique and its general applicability in studies of any DNA-binding protein is discussed.

  7. Layer-by-layer self-assembled osmium polymer-mediated laccase oxygen cathodes for biofuel cells: the role of hydrogen peroxide.

    PubMed

    Scodeller, Pablo; Carballo, Romina; Szamocki, Rafael; Levin, Laura; Forchiassin, Flavia; Calvo, Ernesto J

    2010-08-18

    High potential purified Trametes trogii laccase has been studied as a biocatalyst for oxygen cathodes composed of layer-by-layer self-assembled thin films by sequential immersion of mercaptopropane sulfonate-modified Au electrode surfaces in solutions containing laccase and osmium-complex bound to poly(allylamine), (PAH-Os). The polycation backbone carries the Os redox relay, and the polyanion is the enzyme adsorbed from a solution of a suitable pH so that the protein carries a net negative charge. Enzyme thin films were characterized by quartz crystal microbalance, ellipsometry, cyclic voltammetry, and oxygen reduction electrocatalysis under variable oxygen partial pressures with a rotating disk electrode. New kinetic evidence relevant to biofuel cells is presented on the detection of traces of H(2)O(2), intermediate in the O(2) reduction, with scanning electrochemical microscopy (SECM). Furthermore the inhibitory effect of peroxide on the biocatalytic current resulted in abnormal current dependence on the O(2) partial pressure and peak shape with hysteresis in the polarization curves under stagnant conditions, which is offset upon stirring with the RDE. The new kinetic evidence reported in the present work is very relevant for the operation of biofuel cells under stagnant conditions of O(2) mass transport.

  8. Electron transfer from Proteus vulgaris to a covalently assembled, single walled carbon nanotube electrode functionalised with osmium bipyridine complex: application to a whole cell biosensor.

    PubMed

    Rawson, Frankie J; Garrett, David J; Leech, Donal; Downard, Alison J; Baronian, Keith H R

    2011-01-15

    We report the fabrication and use of electrodes constructed from single walled carbon nanotubes (SWCNTs) chemically assembled on a carbon surface and functionalised with an osmium(II) bipyridine complex (Osbpy). The ability of the electrodes to transduce biologically generated currents from Proteus vulgaris has been established. Our investigations show that there are two contributions to the current: one from electroactive species secreted into solution and another from cell redox sites. The modified electrode can be used to monitor cell metabolism, thereby acting as a whole cell biosensor. The biosensor was used in a 1-h assay to investigate the toxicity of ethanol, sodium azide and the antibiotic ampicillin and gave quantitative data that were closely correlated with standard cell plate viability assays. The results provide proof of principle that the whole cell biosensor could be used for high throughput screening of antimicrobial activity. One of the modified electrodes was used for approximately 1000 measurements over four months demonstrating the robustness of the system.

  9. Reversible Redox-Based Optical Sensing of Parts per Million Levels of Nitrosyl Cation in Organic Solvents by Osmium Chromophore-Based Monolayers

    SciTech Connect

    Gupta,T.; Cohen, R.; Evmenenko, G.; Dutta, P.; van der Boom, M.

    2007-01-01

    Exposure of an osmium(II)-based monolayer on glass to organic solvents containing 0.36-116 ppm of NOBF{sub 4} results in one-electron transfer from the covalently immobilized complexes to the inorganic analyte with concurrent optical changes. The NO{sup +} induced oxidation of the monolayer can be detected optically with an off-the-self-UV/vis spectrophotometer (260-800 nm). The redox-based NO{sup +} detection and quantification system can be reset with water within {approx}20 s for at least 40 times. The reaction of the monolayer with a THF solution containing 5 ppm of NOBF{sub 4} follows pseudo first-order kinetics in the monolayer with {Delta}G{sup {double_dagger}}{sub 298K} = 21.5 {+-} 0.7 kcal/mol, {Delta}H{sup {double_dagger}} = 9.5 {+-} 0.3 kcal/mol, and {Delta}S{sup {double_dagger}} = -40.6 {+-} 1.1 eu. The monolayer structure and properties have been resolved by electrochemical measurements and synchrotron X-ray reflectivity measurements in combination with density functional theory calculations (B3LYP/SDD level of theory).

  10. Three-dimensional shape of the Golgi apparatus in different cell types: serial section scanning electron microscopy of the osmium-impregnated Golgi apparatus.

    PubMed

    Koga, Daisuke; Kusumi, Satoshi; Ushiki, Tatsuo

    2016-04-01

    Although many studies of the Golgi apparatus structure have been performed by light and electron microscopy, the full shape of the Golgi apparatus remained unclear due to the technical limitations of the previously applied microscopy techniques. In this study, we used serial section scanning electron microscopy (SEM) for the morphological study of the Golgi apparatus. This method is useful for three-dimensional (3D) reconstruction of cellular structures without requiring specialized instruments, unlike focused ion beam SEM (FIB-SEM) and serial block face SEM (SBF-SEM). Using the serial section SEM method developed by our laboratory, we investigate the 3D shape of the osmium-impregnated Golgi apparatus in rat epididymal cells, pancreatic acinar cells and gonadotropes. The combination of serial section SEM and a 3D reconstruction technique enabled us to elucidate the entire shape of the Golgi apparatus in these cells. The full shape of the Golgi apparatus in epididymal cells formed a basket-like structure with oval-shaped cisterns, while the Golgi apparatus in an acinar cell from the pancreas was composed of elongated ribbon-like structures that were connected to each other, making a coarse network. The overall image of the Golgi apparatus cisterns from a gonadotrope looked like a spherical cage. This study has clearly shown that entire 3D shape of the Golgi apparatus varies depending on the cell type and that the Golgi cisterns network appears as a single mass located in the large region of the cytoplasm. PMID:26609075

  11. Investigations of thermal and photochemical arene displacement reactions from ruthenium and osmium arene complexes. 2. Photochemical carbon-hydrogen bond activation via the photolysis of iridium(III) azide and oxalate complexes

    SciTech Connect

    Freedman, D.A.

    1992-01-01

    The syntheses of several new bis-arene Ru(II) complexes are described. Complexes where one arene is naphthalene, anthracene or tetracene react thermally with acetonitrile resulting in arene displacement. Thermally inert complexes will react photochemically with acetonitrile. Kinetic data were collected for the chemical reactions and reaction mechanism are proposed. Electrochemical and spectroelectrochemical data are reported for the new hexacoordinate osmium complexes. Two methods of catalyzing the photochemical displacement of benzene from [CpOsBz][sup +] in acetonitrile to give [CpOs(CH[sub 3]CN)[sub 3

  12. P2 addition to terminal phosphide M[triple bond]P triple bonds: a rational synthesis of cyclo-P3 complexes.

    PubMed

    Piro, Nicholas A; Cummins, Christopher C

    2008-07-23

    The diphosphaazide complex (Mes*NPP)Nb(N[Np]Ar)3 (Mes* = 2,4,6-tri-tert-butylphenyl, Np = neopentyl, Ar = 3,5-Me2C6H3), 1, has previously been reported to lose the P2 unit upon gentle heating, to form (Mes*N)Nb(N[Np]Ar)3, 2. The first-order activation parameters for this process have been estimated here using an Eyring analysis to have the values Delta H(double dagger) = 19.6(2) kcal/mol and Delta S(double dagger) = -14.2(5) eu. The eliminated P2 unit can be transferred to the terminal phosphide complexes P[triple bond]M(N[(i)Pr]Ar)3, 3-M (M = Mo, W), and [P[triple bond]Nb(N[Np]Ar)3](-), 3-Nb, to give the cyclo-P3 complexes (P3)M(N[(i)Pr]Ar)3 and [(P3)Nb(N[Np]Ar)3](-). These reactions represent the formal addition of a P[triple bond]P triple bond across a M[triple bond]P triple bond and are the first efficient transfers of the P2 unit to substrates present in stoichiometric quantities. The related complex (OC)5W(Mes*NPP)Nb(N[Np]Ar)3, 1-W(CO)5, was used to transfer the (P2)W(CO)5 unit in an analogous manner to the substrates 3-M (M = Mo, W, Nb) as well as to [(OC)5WP[triple bond]Nb(N[Np]Ar)3](-). The rate constants for the fragmentation of 1 and 1-W(CO)5 were unchanged in the presence of the terminal phosphide 3-Mo, supporting the hypothesis that molecular P2 and (P2)W(CO)5, respectively, are reactive intermediates. In a reaction related to the combination of P[triple bond]P and M[triple bond]P triple bonds, the phosphaalkyne AdC[triple bond]P (Ad = 1-adamantyl) was observed to react with 3-Mo to generate the cyclo-CP2 complex (AdCP2)Mo(N[(i)Pr]Ar)3. Reactions of the electrophiles Ph3SnCl, Mes*NPCl, and AdC(O)Cl with the anionic, nucleophilic complexes [(OC)5W(P3)Nb(N[Np]Ar)3](-) and [{(OC)5W}2(P3)Nb(N[Np]Ar)3](-) yielded coordinated eta(2)-triphosphirene ligands. The Mes*NPW(CO)5 group of one such product engages in a fluxional ring-migration process, according to NMR spectroscopic data. The structures of (OC)5W(P3)W(N[(i)Pr]Ar)3, [(Et2O)Na][{(OC)5W}2(P3)Nb

  13. Silicon dioxide with a silicon interfacial layer as an insulating gate for highly stable indium phosphide metal-insulator-semiconductor field effect transistors

    NASA Technical Reports Server (NTRS)

    Kapoor, V. J.; Shokrani, M.

    1991-01-01

    A novel gate insulator consisting of silicon dioxide (SiO2) with a thin silicon (Si) interfacial layer has been investigated for high-power microwave indium phosphide (InP) metal-insulator-semiconductor field effect transistors (MISFETs). The role of the silicon interfacial layer on the chemical nature of the SiO2/Si/InP interface was studied by high-resolution X-ray photoelectron spectroscopy. The results indicated that the silicon interfacial layer reacted with the native oxide at the InP surface, thus producing silicon dioxide, while reducing the native oxide which has been shown to be responsible for the instabilities in InP MISFETs. While a 1.2-V hysteresis was present in the capacitance-voltage (C-V) curve of the MIS capacitors with silicon dioxide, less than 0.1 V hysteresis was observed in the C-V curve of the capacitors with the silicon interfacial layer incorporated in the insulator. InP MISFETs fabricated with the silicon dioxide in combination with the silicon interfacial layer exhibited excellent stability with drain current drift of less than 3 percent in 10,000 sec, as compared to 15-18 percent drift in 10,000 sec for devices without the silicon interfacial layer. High-power microwave InP MISFETs with Si/SiO2 gate insulators resulted in an output power density of 1.75 W/mm gate width at 9.7 GHz, with an associated power gain of 2.5 dB and 24 percent power added efficiency.

  14. Responses to Rapid Climate Change: Osmium Isotopic Evidence for Changing Weathering Fluxes in Response to the Paleocene-Eocene Hyperthermal Event

    NASA Astrophysics Data System (ADS)

    Wieczorek, R.; Fantle, M. S.; Kump, L. R.; Ravizza, G. E.

    2009-12-01

    Physical and chemical weathering responses to changes in temperature at the Earth’s surface are strongly debated, yet are critical to understanding the long-term effects of global climate change. One manner of studying such relationships is to use geochemical proxies of weathering (such as osmium isotopes) to examine periods of climate change in the past. Here we report a new high-resolution marine osmium isotope record from Svalbard core BH 9/05 in the North Atlantic over the Paleocene-Eocene Thermal Maximum (PETM). The PETM (55 Ma) is a ~170 ka period of warming characterized by negative excursions in oxygen (about 1-1.5‰) and carbon isotopes (2-2.5‰ in marine foraminifera and 4-6 ‰ in terrestrial records). The measured PETM section of BH 9/05 (> 70 m) consists of carbonate-poor gray shale with total organic carbon contents of 2-3%, deposited in a foreland basin/pro-delta environment. The gray shale record shows a clear increase in bulk 187Os/188Os and Os concentrations (ppt: pg Os/g rock) during the PETM, with increases of > 40 ppt in total Os and at least 0.2 in 187Os/188Os. Re concentrations (0.7 -10.5 ng/g) display a local maximum close to the Os concentration maximum. Age corrections to the measured 187Os/188Os for in situ decay of 187Re are modest (5-30%) with the largest corrections coinciding with the most negative carbon isotope values. The change in 187Os/188Os may be as high as 0.47 at our study site, suggesting a peak seawater 187Os/188Os value around 0.8. This peak value, nearly twice the pre-event value, is substantially more radiogenic than previous estimates for seawater 187Os/188Os during the PETM, though still well below the 187Os/188Os of modern seawater. Previous studies, which also document a 187Os/188Os increase during the PETM, saw changes that were nearly five times smaller than the shift we report here. Preliminary bulk rock 187Os/188Os (age-corrected) show a pre-event 187Os/188Os ratio between 0.36 and 0.45, similar to the steady

  15. 4,4'-dithiodipyridine as a bridging ligand in osmium and ruthenium complexes: the electron conductor ability of the -S-S- bridge.

    PubMed

    Silva, Welter C; Lima, Joacy B; Moreira, Icaro S; Neto, Antônio M; Gandra, Flávio C G; Ferreira, Antônio G; McGarvey, Bruce R; Franco, Douglas W

    2003-10-20

    The compounds [Ru(NH(3))(5)(dtdp)](TFMS)(3), [Os(NH(3))(5)(dtdp)](TFMS)(3), [(NH(3))(5)Os(dtdp)Os(NH(3))(5)](TFMS)(6), [(NH(3))(5)Os(dtdp)Ru(NH(3))(5)](TFMS)(3)(PF(6))(2), and [(NH(3))(5)Os(dtdp)Fe(CN)(5)] (dtdp = 4,4'-dithiodipyridine, TFMS = trifluoromethanesulfonate) have been synthesized and characterized by elemental analysis, cyclic voltammetry, electronic, vibrational, EPR, and (1)H NMR spectroscopies. Changes in the electronic and voltammetric spectra of the ion complex [Os(NH(3))(5)(dtdp)](3+) as a function of the solution pH enable us to calculate the pK(a) for the [Os(NH(3))(5)(dtdpH)](4+) and [Os(NH(3))(5)(dtdpH)](3+) acids as 3.5 and 5.5, respectively. The comparison of the above pK(a) data with that for the free ligand (pK(1) = 4.8) provides evidence for the -S-S- bridge efficiency as an electron conductor between the two pyridine rings. The symmetric complex, [(NH(3))(5)Os(dtdp)Os(NH(3))(5)](6+), is found to exist in two geometric forms, and the most abundant form (most probably trans) has a strong conductivity through the -S-S- bridge, as is shown by EPR, which finds it to have an S = 1 spin state with a spin-spin interaction parameter of 150-200 G both in the solid sate and in frozen solution. Further the NMR of the same complex shows a large displacement of unpaired spin into the pi orbitals of the dttp ligand relative to that found in [Os(NH(3))(5)(dtdp)](3+). The comproportionation constant, K(c) = 2.0 x 10(5), for the equilibrium equation [Os(II)Os(II)] + [Os(III)Os(III)] right harpoon over left harpoon 2[Os(II)Os(III)] and the near-infrared band energy for the mixed-valence species (MMCT), [(NH(3))(5)Os(dtdp)Os(NH(3))(5)](5+) (lambda(MMCT) = 1665 nm, epsilon = 3.5 x 10(3) M(-)(1) cm(-)(1), deltanu(1/2) = 3.7 x 10(3) cm(-)(1), alpha = 0.13, and H(AB) = 7.8 x 10(2) cm(-)(1)), are quite indicative of strong electron delocalization between the two osmium centers. The electrochemical and spectroscopic data for the unsymmetrical binuclear complexes

  16. Multi-component nanoporous platinum-ruthenium-copper-osmium-iridium alloy with enhanced electrocatalytic activity towards methanol oxidation and oxygen reduction

    NASA Astrophysics Data System (ADS)

    Chen, Xiaoting; Si, Conghui; Gao, Yulai; Frenzel, Jan; Sun, Junzhe; Eggeler, Gunther; Zhang, Zhonghua

    2015-01-01

    Multi-component nanoporous platinum-ruthenium-copper-osmium-iridium (np-PtRuCuOsIr) electrocatalyst has been facilely fabricated by chemical dealloying of mechanically alloyed AlCuPtRuOsIr precursor. The np-PtRuCuOsIr catalyst exhibits a typical three-dimensional bi-continuous interpenetrating ligament/channel structure with a length scale of ∼2.5 nm. The np-PtRuCuOsIr catalyst reaches a higher level in the mass activity (857.5 mA mgPt-1) and specific activity (3.0 mA cm-2) towards methanol oxidation compared to the commercial PtC catalyst (229.5 mA mgPt-1 and 0.5 mA cm-2 respectively). Moreover, the CO stripping peak of np-PtRuCuOsIr is 0.54 V (vs. SCE), 130 mV negative shift in comparison with the commercial PtC (0.67 V vs. SCE). The half-wave potential of np-PtRuCuOsIr is 0.900 V vs. RHE, 36 mV positive compared with that of the commercial PtC (0.864 V vs. RHE). The np-PtRuCuOsIr catalyst also shows 1.8 and 3.8 times enhancement in the mass and specific activity towards oxygen reduction than the commercial PtC. Moreover, the np-PtRuCuOsIr alloy exhibits superior oxygen reduction activities even after 15 K cycles, indicating its excellent long-term stability. The present np-PtRuCuOsIr can act as a promising candidate for the electrocatalyst in direct methanol fuel cells (DMFCs).

  17. Ruthenium(II) and osmium(II) vinyl complexes as highly sensitive and selective chromogenic and fluorogenic probes for the sensing of carbon monoxide in air.

    PubMed

    Toscani, Anita; Marín-Hernández, Cristina; Moragues, María E; Sancenón, Félix; Dingwall, Paul; Brown, Neil J; Martínez-Máñez, Ramón; White, Andrew J P; Wilton-Ely, James D E T

    2015-10-01

    The detection of carbon monoxide in solution and air has been achieved using simple, inexpensive systems based on the vinyl complexes [M(CHCHR)Cl(CO)(BTD)(PPh3 )2 ] (R=aryl, BTD=2,1,3-benzothiadiazole). Depending on the nature of the vinyl group, chromogenic and fluorogenic responses signalled the presence of this odourless, tasteless, invisible, and toxic gas. Solutions of the complexes in CHCl3 underwent rapid change between easily differentiated colours when exposed to air samples containing CO. More significantly, the adsorption of the complexes on silica produced colorimetric probes for the naked-eye detection of CO in the gas phase. Structural data for key species before and after the addition of CO were obtained by means of single X-ray diffraction studies. In all cases, the ruthenium and osmium vinyl complexes studied showed a highly selective response to CO with exceptionally low detection limits. Naked-eye detection of CO at concentrations as low as 5 ppb in air was achieved with the onset of toxic levels (i.e., 100 ppm), thus resulting in a remarkably clear colour change. Moreover, complexes bearing pyrenyl, naphthyl, and phenanthrenyl moieties were fluorescent, and greater sensitivities were achieved (through turn-on emission fluorescence) in the presence of CO both in solution and air. This behaviour was explored computationally using time-dependent density functional theory (TDDFT) experiments. In addition, the systems were shown to be selective for CO over all other gases tested, including water vapour and common organic solvents. Supporting the metal complexes on cellulose strips for use in an existing optoelectronic device allows numerical readings for the CO concentration to be obtained and provision of an alarm system.

  18. Ruthenium(II) and osmium(II) mixed chelates based on pyrenyl-pyridylimidazole and 2,2'-bipyridine ligands as efficient DNA intercalators and anion sensors.

    PubMed

    Mardanya, Sourav; Karmakar, Srikanta; Maity, Dinesh; Baitalik, Sujoy

    2015-01-20

    We report herein the synthesis and characterization of two monometallic ruthenium(II) and osmium(II) complexes of composition [(bpy)2M(HImzPPy)] (ClO4)2 derived from pyrenylimidazole-10-pyridin-2-yl-9H-9,11-diazacyclopenta[e]pyrene (HImzPPy) and 2,2'-bipyridine (bpy) ligands. X-ray crystallographic study shows that both crystals belong to the triclinic system having space group P1̅. The photophysical properties of 1 and 2 in acetonitrile indicate that the metal-to-ligand charge-transfer excited state is mainly centered in the [M(bpy)2](2+) moiety of the complexes and slightly affected by the extended conjugation of the pyrenylimidazole moiety. Both complexes display one-electron reversible metal-centered oxidative processes and a number of quasi-reversible reductive processes. The binding affinities of the complexes toward calf-thymus DNA (CT-DNA) were thoroughly studied through different methods such as absorption, emission, excited-state lifetime, circular dichroism, and thermal denaturation of DNA and a relative DNA binding study using ethidium bromide. All of these experiments account for the intercalative nature of both 1 and 2 toward CT-DNA as well as their light-switch behavior. The anion recognition study through different spectroscopic techniques reveals that both complexes act as "turn-on" luminescence sensors for H2PO4(-) and "turn-off" sensors toward F(-) and AcO(-). The imidazole N-H proton of the receptors gets deprotonated with the excessive addition of F(-) and AcO(-), while it interacts with H2PO4(-) through hydrogen-bonding interaction. Theoretical calculations (DFT and TD-DFT) were also performed to understand the photophysical properties of the metalloreceptors.

  19. DNA/nickel oxide nanoparticles/osmium(III)-complex modified electrode toward selective oxidation of l-cysteine and simultaneous detection of l-cysteine and homocysteine.

    PubMed

    Sharifi, Ensiyeh; Salimi, Abdollah; Shams, Esmaeil

    2012-08-01

    The modification of glassy carbon (GC) electrode with electrodeposited nickel oxide nanoparticles (NiOxNPs) and deoxyribonucleic acid (DNA) is utilized as a new efficient platform for entrapment of osmium (III) complex. Surface morphology and electrochemical properties of the prepared nanocomposite modified electrode (GC/DNA/NiOxNPs/Os(III)-complex) were investigated by FESEM, cyclic voltammetry and electrochemical impedance spectroscopy techniques. Cyclic voltammetric results indicated the excellent electrocatalytic activity of the resulting electrode toward oxidation of l-cysteine (CySH) at reduced overpotential (0.1 V vs. Ag/AgCl). Using chronoamperometry to CySH detection, the sensitivity and detection limit of the biosensor are obtained as 44 μA mM(-1) and 0.07 μM with a concentration range up to 1000 μM. The electrocatalytic activity of the modified electrode not only for oxidation of low molecular-mass biothiols derivatives such as, glutathione, l-cystine, l-methionine and electroactive biological species ( dopamine, uric acid, glucose) is negligible but also for very similar biothiol compound (homocysteine) no recognizable response is observed at the applied potential window. Furthermore, the simultaneous voltammetric determination of l-cysteine and homocysteine compounds without any separation or pretreatment process was reported for the first time in this work. Finally, the applicability of sensor for the analysis of CySH concentration in complex serum samples was successfully demonstrated. Highly selectivity, excellent electrocatalytic activity and stability, remarkable antifouling property toward thiols and their oxidation products, as well as the ability for simultaneous detection of l-cysteine and homocysteine are remarkably advantageous of the proposed DNA based biosensor.

  20. Osmium(0)-Catalyzed C-C Coupling of Ethylene and α-Olefins with Diols, Ketols, or Hydroxy Esters via Transfer Hydrogenation.

    PubMed

    Park, Boyoung Y; Luong, Tom; Sato, Hiroki; Krische, Michael J

    2016-09-16

    Osmium(0) complexes derived from Os3(CO)12 and XPhos (2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl) catalyze the C-C coupling of α-hydroxy esters 1a-1i, α-ketols 1j-1o, or 1,2-diols dihydro-1j-1o with ethylene 2a to form ethylated tertiary alcohols 3a-3o. As illustrated in couplings of 1-octene 2b with vicinally dioxygenated reactants 1a, 1b, 1i, 1j, 1k, 1m, higher α-olefins are converted to adducts 4a, 4b, 4i, 4j, 4k, 4m with complete levels of branched regioselectivity. Oxidation level independent C-C coupling is demonstrated by the reaction of 1-octene 2b with diol dihydro-1k, α-ketol 1k, and dione dehydro-1k. Functionalized olefins 2c-2f react with ethyl mandelate 1a to furnish adducts 5a-8a as single regioisomers. The collective data, including deuterium labeling studies, are consistent with a catalytic mechanism involving olefin-dione oxidative coupling to form an oxa-osmacyclopentane, which upon reductive cleavage via hydrogen transfer from the secondary alcohol reactant releases the product of carbinol C-alkylation with regeneration of the ketone. Single-crystal X-ray diffraction data of the dinuclear complex Os2(CO)4(O2CR)2(XPhos)2 and the trinuclear complex Os3(CO)11(XPhos) are reported. These studies suggest increased π-backbonding at the stage of the metal-olefin π-complex plays a critical role in facilitating alkene-carbonyl oxidative coupling, as isostructural ruthenium(0) complexes, which are weaker π-donors, do not catalyze the transformations reported herein. PMID:27580269