Science.gov

Sample records for platinum isotopes

  1. Platinum stable isotopes in ferromanganese crust and nodules

    NASA Astrophysics Data System (ADS)

    Corcoran, Loretta; Seward, Terry; Handler, Monica R.

    2015-04-01

    Hydrogenetic ferromanganese (Fe-Mn) crust and nodules are slow-growing chemical sediments that form by direct precipitation from seawater, resulting in a record of changing seawater chemistry. These sediments are the primary sink for platinum in the modern oxic marine environment, hosting well-documented enrichments over other platinum-group elements (PGEs): the Pt anomaly [1]. Platinum is a non-bio-essential, highly siderophile, transition metal with six stable isotopes (190Pt, 192Pt, 194Pt, 195Pt, 196Pt, and 198Pt) with several oxidation states (Pt0, Pt2+ and Pt4+). Platinum is generally considered to exist in the hydrosphere as Pt2+ although its behaviour in the marine environment is poorly constrained, and Pt4+may also be present. Variations in ocean redox state, together with changes in source fluxes to the oceans, may therefore lead to small variations (< ±1) in the stable isotopic composition of marine platinum, raising the potential of adding platinum to the growing arsenal of paleoceanographic tracers. A method has been developed to measure the platinum isotopic composition using double spike MC-ICPMS analysis [2]and applied to a global suite of modern Fe-Mn crust and nodules. Combining synchrotron XAFS analyses of platinum adsorbed onto Fe-Mn oxide and oxyhydroxide surfaces to determine oxidation state and bonding environment, with platinum stable isotopic measurements allowing us to evaluate both platinum incorporation onto these sediments and the associated degree of platinum isotopic fractionation. Leaching experiments conducted on platinum rich terrestrial materials underwent platinum stable isotopic measurement as an analogue for the Pt isotopic fractionation associated with continental weathering. [1] Hodge, V.F. et al. (1985) Earth and Planetary Science Letters, 72, 158-162. [2] Creech, J. et al. (2013) Journal of Analytical Atomic Spectrometry, 28. 853-865.

  2. Rare isotope studies involving catalytic oxidation of CO over platinum-tin oxide

    NASA Technical Reports Server (NTRS)

    Upchurch, Billy T.; Wood, George M., Jr.; Hess, Robert V.; Hoyt, Ronald F.

    1987-01-01

    Results of studies utilizing normal and rare oxygen isotopes in the catalytic oxidation of carbon monoxide over a platinum-tin oxide catalyst substrate are presented. Chemisorption of labeled carbon monoxide on the catalyst followed by thermal desorption yielded a carbon dioxide product with an oxygen-18 composition consistent with the formation of a carbonate-like intermediate in the chemisorption process. The efficacy of a method developed for the oxygen-18 labeling of the platinum-tin oxide catalyst surface for use in closed cycle pulsed care isotope carbon dioxide lasers is demonstrated for the equivalent of 10 to the 6th power pulses at 10 pulses per second.

  3. Stable platinum isotope measurements in presolar nanodiamonds by TEAMS.

    PubMed

    Wallner, A; Melber, K; Merchel, S; Ott, U; Forstner, O; Golser, R; Kutschera, W; Priller, A; Steier, P

    2013-01-01

    Nanodiamonds are stardust grains commonly found in primitive meteorites. They survived the formation of the solar system and kept their own individuality. Measurements of trace-element isotopic signatures in these grains will help understanding heavy element nucleosynthesis in massive stars and dust formation from their ejecta. We have continued previous attempts to search for stable Pt isotope anomalies in nanodiamonds via trace element accelerator mass spectrometry (TEAMS). The installation of a new injector beam line at the VERA facility allowed studying low traces of stable elements in different materials. Moreover, recent experiments showed that VERA provides the required measurement precision together with a low Pt machine background. Here, we observed for the first time an indication for enhancements of (198)Pt/(195)Pt isotope ratios in two diamond residues prepared by different chemical separation techniques from the Allende meteorite. Variations in other isotopic ratios were within analytical uncertainty, and no anomaly was identified in a third diamond fraction. PMID:23565017

  4. Stable platinum isotope measurements in presolar nanodiamonds by TEAMS

    PubMed Central

    Wallner, A.; Melber, K.; Merchel, S.; Ott, U.; Forstner, O.; Golser, R.; Kutschera, W.; Priller, A.; Steier, P.

    2013-01-01

    Nanodiamonds are stardust grains commonly found in primitive meteorites. They survived the formation of the solar system and kept their own individuality. Measurements of trace-element isotopic signatures in these grains will help understanding heavy element nucleosynthesis in massive stars and dust formation from their ejecta. We have continued previous attempts to search for stable Pt isotope anomalies in nanodiamonds via trace element accelerator mass spectrometry (TEAMS). The installation of a new injector beam line at the VERA facility allowed studying low traces of stable elements in different materials. Moreover, recent experiments showed that VERA provides the required measurement precision together with a low Pt machine background. Here, we observed for the first time an indication for enhancements of 198Pt/195Pt isotope ratios in two diamond residues prepared by different chemical separation techniques from the Allende meteorite. Variations in other isotopic ratios were within analytical uncertainty, and no anomaly was identified in a third diamond fraction. PMID:23565017

  5. Coupled-channels study of fine structure in the {alpha} decay of platinum isotopes

    SciTech Connect

    Ni Dongdong; Ren Zhongzhou

    2011-09-15

    The fine structure observed in the {alpha} decay of deformed platinum isotopes is investigated using the recently developed five-channel formalism, based on the coupled-channel Schroedinger equation with outgoing wave boundary conditions. The internal effect of daughter states is taken into account in dealing with the interaction matrix and the {alpha}-cluster formation. The available experimental data concerning {alpha}-decay half-lives and fine structures are reproduced. Some predictions are made especially for the {alpha} decay of neutron-rich isotopes, which could guide future experiments.

  6. The electrooxidation mechanism of formic acid on platinum and on lead ad-atoms modified platinum studied with the kinetic isotope effect

    NASA Astrophysics Data System (ADS)

    Bełtowska-Brzezinska, M.; Łuczak, T.; Stelmach, J.; Holze, R.

    2014-04-01

    Kinetics and mechanism of formic acid (FA) oxidation on platinum and upd-lead ad-atoms modified platinum electrodes have been studied using unlabelled and deuterated compounds. Poisoning of the electrode surface by CO-like species was prevented by suppression of dissociative chemisorption of FA due to a fast competitive underpotential deposition of lead ad-atoms on the Pt surface from an acidic solution containing Pb2+ cations. Modification of the Pt electrode with upd lead induced a catalytic effect in the direct electrooxidation of physisorbed FA to CO2. With increasing degree of H/D substitution, the rate of this reaction decreased in the order: HCOOH > DCOOH ≥ HCOOD > DCOOD. HCOOH was oxidized 8.5-times faster on a Pt/Pb electrode than DCOOD. This primary kinetic isotope effect proves that the C-H- and O-H-bonds are simultaneously cleaved in the rate determining step. A secondary kinetic isotope effect was found in the dissociative chemisorption of FA in the hydrogen adsorption-desorption range on a bare Pt electrode after H/D exchange in the C-H bond, wherein the influence of deuterium substitution in the O-H group was negligibly small. Thus the C-H bond cleavage is accompanied by the C-OH and not the O-H bond split in the FA decomposition, producing CO-like species on the Pt surface sites.

  7. 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.

  8. Platinum stable isotope analysis of geological standard reference materials by double-spike MC-ICPMS

    PubMed Central

    Creech, J.B.; Baker, J.A.; Handler, M.R.; Bizzarro, M.

    2015-01-01

    We report a method for the chemical purification of Pt from geological materials by ion-exchange chromatography for subsequent Pt stable isotope analysis by multiple-collector inductively coupled plasma mass spectrometry (MC-ICPMS) using a 196Pt-198Pt double-spike to correct for instrumental mass bias. Double-spiking of samples was carried out prior to digestion and chemical separation to correct for any mass-dependent fractionation that may occur due to incomplete recovery of Pt. Samples were digested using a NiS fire assay method, which pre-concentrates Pt into a metallic bead that is readily dissolved in acid in preparation for anion-exchange chemistry. Pt was recovered from anion-exchange resin in concentrated HNO3 acid after elution of matrix elements, including the other platinum group elements (PGE), in dilute HCl and HNO3 acids. The separation method has been calibrated using a precious metal standard solution doped with a range of synthetic matrices and results in Pt yields of ≥90% with purity of ≥95%. Using this chemical separation technique, we have separated Pt from 11 international geological standard reference materials comprising of PGE ores, mantle rocks, igneous rocks and one sample from the Cretaceous–Paleogene boundary layer. Pt concentrations in these samples range from ca. 5 ng g−1 to 4 μg g−1. This analytical method has been shown to have an external reproducibility on δ198Pt (permil difference in the 198Pt/194Pt ratio from the IRMM-010 standard) of ±0.040 (2 sd) on Pt solution standards (Creech et al., 2013, J. Anal. At. Spectrom. 28, 853-865). The reproducibility in natural samples is evaluated by processing multiple replicates of four standard reference materials, and is conservatively taken to be ca. ±0.088 (2 sd). Pt stable isotope data for the full set of reference materials have a range of δ198Pt values with offsets of up to 0.4‰ from the IRMM-010 standard, which are readily resolved with this technique. These results

  9. Separating Continental Mineral Dust from Cosmic Dust using Platinum Group Element Concentrations and Osmium Isotopes in Ancient Polar Ice

    NASA Astrophysics Data System (ADS)

    Seo, J. H.; Jackson, B.; Osterberg, E. C.; Sharma, M.

    2015-12-01

    The platinum group element (PGEs: Pt, Pd, Rh, Ir, Os, and Ru) accumulation in ancient polar archives have been argued to trace cosmic dust and "smoke" from larger meteors but the PGE concentration data lack specificity. For example, the extent to which the terrestrial volcanism/dust has contributed to the PGE inventory of polar ice cannot be readily evaluated. Since the Os isotope compositions (187Os/188Os ratio) of the terrestrial and extraterrestrial sources are distinctly different from each other, the PGE concentrations when combined with Os isotope composition have the potential to untangle contributions from these sources. Platinum group element concentration determinations in polar ice cores are highly challenging due to their extremely low concentrations (down to 10-15 g/g or fg/g). Here, a new procedure is presented that allows PGEs and Os isotope compositions to be determined from a ~50 g sample of polar ice. Decontaminated ice-melt is spiked with 101Ru, 106Pd, 190Os, 191Ir, and 198Pt and frozen at -20 °C in quartz-glass ampoules. A mixture of purified HNO3 and H2O2 is then added and the sample is heated to 300 °C at 128bar using a High Pressure Asher. This allows all spikes to be equilibrated with the sample PGEs and all Os species are oxidized to OsO4. The resulting OsO4 is extracted using distillation, purified, and measured using negative thermal ionization mass spectrometry. PGEs are then separated and purified using two stage column chromatography and their concentrations determined by isotope dilution using a triple quadruople inductively coupled plasma mass spectrometer coupled to an Apex de-solvation nebulizer. The developed method was applied to modern Greenland firn and snow. The PGE concentrations of the firn are 4.0 fg/g for Ir, 20 fg/g for Ru, 590 fg/g for Pt, 38 fg/g for Pd, and 1.3 fg/g for Os, while those of the snow are 3.0 fg/g for Ir, 53 fg/g for Ru, 360 fg/g for Pt, 32 fg/g for Pd, and 0.4 fg/g for Os, respectively. A comparison

  10. 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

  11. Re-Os isotope and platinum group elements of a FOcal ZOne mantle source, Louisville Seamounts Chain, Pacific ocean

    NASA Astrophysics Data System (ADS)

    Tejada, Maria Luisa G.; Hanyu, Takeshi; Ishikawa, Akira; Senda, Ryoko; Suzuki, Katsuhiko; Fitton, Godfrey; Williams, Rebecca

    2015-02-01

    The Louisville Seamount Chain (LSC) is, besides the Hawaiian-Emperor Chain, one of the longest-lived hotspot traces. We report here the first Re-Os isotope and platinum group element (PGE) data for Canopus, Rigil, and Burton Guyots along the chain, which were drilled during IODP Expedition 330. The LSC basalts possess (187Os/188Os)i = 0.1245-0.1314 that are remarkably homogeneous and do not vary with age. A Re-Os isochron age of 64.9 ± 3.2 Ma was obtained for Burton seamount (the youngest of the three seamounts drilled), consistent with 40Ar-39Ar data. Isochron-derived initial 187Os/188Os ratio of 0.1272 ± 0.0008, together with data for olivines (0.1271-0.1275), are within the estimated primitive mantle values. This (187Os/188Os)i range is similar to those of Rarotonga (0.124-0.139) and Samoan shield (0.1276-0.1313) basalts and lower than those of Cook-Austral (0.136-0.155) and Hawaiian shield (0.1283-0.1578) basalts, suggesting little or no recycled component in the LSC mantle source. The PGE data of LSC basalts are distinct from those of oceanic lower crust. Variation in PGE patterns can be largely explained by different low degrees of melting under sulfide-saturated conditions of the same relatively fertile mantle source, consistent with their primitive mantle-like Os and primordial Ne isotope signatures. The PGE patterns and the low 187Os/188Os composition of LSC basalts contrast with those of Ontong Java Plateau (OJP) tholeiites. We conclude that the Re-Os isotope and PGE composition of LSC basalts reflect a relatively pure deep-sourced common mantle sampled by some ocean island basalts but is not discernible in the composition of OJP tholeiites.

  12. Osmium isotopic compositions of Os-rich platinum group element alloys from the Klamath and Siskiyou Mountains

    NASA Astrophysics Data System (ADS)

    Meibom, Anders; Frei, Robert; Sleep, Norman H.

    2004-02-01

    We present new measurements of 186Os/188Os and 187Os/188Os in 10 Os-rich platinum group element (PGE) alloys from placer deposits formed by the mechanical erosion of peridotite-bearing ophiolites in the Klamath and Siskiyou Mountains in northern California and southwestern Oregon. These data nearly double our database of high-precision 186Os/188Os measurements on such samples. Together with previously published data, our new results reinforce the conclusion that the radiogenic 186Os/188Os compositions of these PGE alloys are very difficult to reconcile with a derivation of their Os from the outer core. Such a model requires extremely early growth of the inner core to its present size, within several hundred million years after accretion of the Earth, which is geophysically implausible. Collectively, our data suggest instead that partial melting or metasomatic processes in the upper mantle play a primary role in controlling the Os isotopic systematics of these Os-rich PGE alloys and suggest the existence of upper mantle components characterized by radiogenic 186Os/188Os ratios. Pyroxene-rich lithologies are possible candidates.

  13. 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

  14. Ancient mantle trapped in the Mariana arc-basin system: Insights from the platinum group elements and Os isotopes

    NASA Astrophysics Data System (ADS)

    Savov, I. P.; Shirey, S. B.; Horan, M. F.; Mock, T. D.

    2006-12-01

    Serpentinized harzburgites recently drilled during ODP Leg 195 at South Chamorro Seamount in the Mariana forearc region have been studied for their platinum group element (PGE) concentrations and Os isotopic compositions. The samples allow a look at the slab fluid-modified subarc mantle immediately overlaying the actively subducting Pacific slab at depths of ~ 30 km. The average PGE (Os 2.3 ppb, Ir 1.5 ppb, Ru 5.4 ppb, Pd 1.6 ppb and Pt 16.3 ppb) and Re (60 ppt) abundances are comparable to those measured in other subarc mantle xenolith suites. The PGE and Re abundances are depleted up to 3 orders of magnitude relative to chondrites, with relative order of depletions Ru > Os > Ir> Pt> Re> Pd. The variable Pd contents (0.01-4.5 ppb) and the low Pd/Os (<2) in the Mariana forearc samples differ significantly from that of altered oceanic crust (Pd/Os~ 22), suggesting Os remained relatively unchanged during low temperature subduction-fluid additions. Serpentinitization of the harzburgites occurred in equilibrium with fluids that were both reducing and highly alkaline. Os in its original phases may be stabilized in such an environment, therefore can preserve evidence for ancient melting despite later slab interactions. Finally, the high Pt/Pd (ave. ~ 25) and low Re contents (ave.~ 60 ppt) in the Leg 195 forearc samples are complementary to those measured in boninites from the Izu-Bonin-Mariana arc-basin system, showing a genetic relationship. Our samples reveal an average 187Os/188Os of 0.123 [range = 0.119- 0.127], making them similar to abyssal peridotites from elsewhere. Radiogenic 187Os/188Os ratios would have been imparted to the serpentinites by slab fluids, so the subchondritic Os isotopic compositions implies that peridotite-slab fluid interactions did not alter the Os isotope systematics of the mantle protoliths. Low alumina abundances (<1 %) and trace element signatures (low HFSE; REE with U-shaped chondrite-normalized patterns and 2-3 times lower than

  15. Determination of Ag, Tl, and Pb in few milligrams of platinum nanoclusters by on-line isotope dilution in laser ablation inductively coupled plasma mass spectrometry

    NASA Astrophysics Data System (ADS)

    Becker, J. Sabine; Pickhardt, Carola; Pompe, W.

    2004-09-01

    A new analysis procedure for determination of trace impurities in a few milligram noble metal nanoclusters, using on-line isotope dilution in laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) was developed. During the laser ablation of investigated sample simultaneous the dry aerosol of nebulized enriched isotope spike solution was added and mixed in the laser ablation chamber. The capability of solution-based calibration by a modified isotope dilution analysis in LA-ICP-MS for the determination of selected elements was tested, using platinum reference material NIST SRM 681. A good agreement of measured with certified concentration for Ag and Pb was found. The detection limits for trace element determination of the developed analytical technique, using LA-ICP-MS with quadrupole analyzer varied between 6 ng g-1 for Ag and 90 ng g-1 for Pb. The analytical technique was applied for the determination of Ag, Tl, and Pb in a few milligram of platinum nanoclusters.

  16. Hydrogenation vs. H-D isotope scrambling during the conversion of ethylene with hydrogen/deuterium catalyzed by platinum under single-collision conditions.

    PubMed

    Dong, Yujung; Ebrahimi, Maryam; Tillekaratne, Aashani; Simonovis, Juan Pablo; Zaera, Francisco

    2016-07-28

    The catalytic hydrogenation of olefins promoted by transition metals, represented here by the conversion of ethylene with platinum, was studied under a unique regime representing pressures in the mTorr range and single-collision conditions. Isotope labeling was used to follow the concurrent H-D exchange steps that occur during this conversion. Multiple isotope substitutions were observed in the resulting ethane products, reflecting the operability of the reversible stepwise mechanism proposed a long time ago by Horiuti and Polanyi. In fact, the ethane isotopologue distributions obtained in these experiments reflect a much higher probability for the dehydrogenation of ethyl intermediates back to the olefin, relative to the hydrogenation to ethane, than typically seen in this catalysis. In addition, a second mechanistic pathway was clearly identified, responsible for most of the dideuteroethane produced. Based on the dependence of the rates of formation of each isotopologue on the fluxes of deuterium and ethylene, it is argued that this second route may be a "reverse" Eley-Rideal step between gas-phase ethylene and two deuterium atoms adsorbed on adjacent sites of the platinum surface. The clear identification of this second pathway is new, and was possible thanks to our ability to explore a new single-collision intermediate pressure regime. PMID:27373226

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

    NASA Astrophysics Data System (ADS)

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

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

  18. Far-infrared and resonance Raman spectroscopy and isotopic substitution studies of halogen-bridged platinum chain solids

    SciTech Connect

    Love, S.P.; Worl, L.A.; Donohoe, R.J.; Huckett, S.C.; Johnson, S.R.; Swanson, B.I.

    1992-12-31

    Here we our most recent results on the vibrational spectroscopy of the MX chain solids [Pt(en){sub 2}][Pt(en){sub 2}X{sub 2}](ClO{sub 4}){sub 4}, (X=Cl, Br or I, and en = C{sub 2}H{sub 8}N{sub 2}), referred to as PtX. Isotopic substitutions are used to clarify the nature of various vibrational modes. For Raman spectroscopy, fundamental phonon frequencies are determined, when possible, by excitation far below the band edge using a Ti:Sapphire laser, thus avoiding defect production, while photo-induced defects are studied specifically after intentional production.

  19. Resonance Raman and far-infrared studies of isotopically disordered and mixed-halide halogen-bridged platinum chain solids

    SciTech Connect

    Love, S.P.; Worl, L.A.; Donohoe, R.J.; Huckett, S.C.; Saxena, A.; Huang, X.Z.; Bishop, A.R.; Swanson, B.I.

    1992-12-31

    The MX chain solids [Pt(en){sub 2}][Pt(en){sub 2}X{sub 2}](CIO{sub 4}){sub 4}, (en = C{sub 2}H{sub 8}N{sub 2} and X=Cl, Br), referred to as ``PtX,`` are used to explore some of the surprising spectral consequences of disorder in 1-D systems, first for pure PtCl, where the disorder arises from randomly distributed Cl isotopes, then for the more drastic case of the mixed-halide materials PtCl{sub 1minusx}Br{sub x}. Lattice dynamics and Peierls-Hubbard modelling are used to analyze the observed spectral behavior. In both cases, the complex structure seen in the Raman and IR spectra is found to arise from strongly localized vibrational modes residing on chain segments, defined by sequences of Cl isotopes for PtCl, and by sequences of Cl and Br for PtCl{sub 1minusx}Br{sub x}. 4 figs, 8 refs.

  20. Enantioselective hydrogenation. IV. Hydrogen isotope exchange in 10,11-dihydrocinchonidine and in quinoline catalyzed by platinum group metals

    SciTech Connect

    Bond, G.; Wells, P.B.

    1994-12-01

    Hydrogen isotope (H/D) exchange in the alkaloid 10,11-dihydrocinchonidine has been studied over 6.4% Pt/silica (EUROPT-1), 5% Ru/alumina, 5% Rh/alumina, and 5% Pd/alumina at 293 K using C{sub 2}H{sub 5}OD and D{sub 2} as solvent and deuterium source. Exchange was accompanied by hydrogenation. Over Pt, fast exchange occurred in the hydroxyl group followed by multiple exchange in which alkaloid molecules containing, 2, 3, 4 and 5 deuterium atoms were formed simultaneously. Mass spectrometry and {sup 1}H NMR showed that this multiple exchange occurred in the quinoline ring system and at C{sub 9}, but not in the quinuclidine ring system. The pattern of exchange in Ru was similar. Over Rh extensive hydrogenolysis of the quinuclidine ring system occurred, and over Pd the quinoline ring system was rapidly hydrogenated. Quinoline exchange and hydrogenation were also studied at 293 K; relatively rapid exchange occurred over Pt, Ru, and Rh, particularly at the 2- and 8-positions, whereas hydrogenation without significant exchange occurred over Pd. 10,11-Dihydrocinchonidine is adsorbed on Pt and Ru via the quinoline ring system and the multiple nature of the exchange indicates that the quinoline moiety is adsorbed approximately parallel to the metal surface by multicenter {pi}-bonding. An additional interaction of the alkaloid molecule with the surface occurs at carbon atom C{sub 9}, which may interpret the slower exchange in the alkaloid by comparison with that in quinoline. This study supports and enhances the model proposed to interpret the origin of enantioselectivity in pyruvate hydrogenation over Pt and Ir modified by cinchona alkaloids. The similarities of exchange over Pt and Ru suggest that enantioselective catalysis should be achievable over Ru. 28 refs., 2 figs., 2 tabs.

  1. Rhenium-osmium isotope and platinum-group elements in the Xinjie layered intrusion, SW China: Implications for source mantle composition, mantle evolution, PGE fractionation and mineralization

    NASA Astrophysics Data System (ADS)

    Zhong, Hong; Qi, Liang; Hu, Rui-Zhong; Zhou, Mei-Fu; Gou, Ti-Zhong; Zhu, Wei-Guang; Liu, Bing-Guang; Chu, Zhu-Yin

    2011-03-01

    The Xinjie mafic-ultramafic layered intrusion in the Emeishan large igneous province (ELIP) hosts Cu-Ni-platinum group element (PGE) sulfide ore layers within the lower part and Fe-Ti-V oxide-bearing horizons within the middle part. The major magmatic Cu-Ni-PGE sulfide ores and spatially associated cumulate rocks are examined for their PGE contents and Re-Os isotopic systematics. The samples yielded a Re-Os isochron with an age of 262 ± 27 Ma and an initial 187Os/ 188Os of 0.12460 ± 0.00011 ( γOs( t) = -0.5 ± 0.1). The age is in good agreement with the previously reported U-Pb zircon age, indicating that the Re-Os system remained closed for most samples since the intrusion emplacement. They have near-chondritic γOs( t) values ranging from -0.7 to -0.2, similar to those of the Lijiang picrites and Song Da komatiites. Exceptionally, two samples from the roof zone and one from upper sequence exhibit radiogenic γOs( t) values (+0.6 to +8.6), showing minor contamination by the overlying Emeishan basalts. The PGE-rich ores contain relatively high PGE and small amounts of sulfides (generally less than 2%) and the abundance of Cu and PGE correlate well with S, implying that the distribution of these elements is controlled by the segregation and accumulation of a sulfide liquid. Some ore samples are poor in S (mostly <800 ppm), which may due to late-stage S loss caused by the dissolution of FeS from pre-existing sulfides through their interaction with sulfide-unsaturated flowing magma. The combined study shows that the Xinjie intrusion may be derived from ferropicritic magmas. The sharp reversals in Mg#, Cr/FeO T and Cr/TiO 2 ratios immediately below Units 2-4, together with high Cu/Zr ratios decreasing from each PGE ore layer within these cyclic units, are consistent with multiple magma replenishment episodes. The sulfides in the cumulate rocks show little evidence of PGE depletion with height and thus appear to have segregated from successive inputs of fertile magma

  2. PLATINUM AND FUEL CELLS

    EPA Science Inventory

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

  3. PLATINUM-GROUP METALS

    EPA Science Inventory

    The document assembles, organizes, and evaluates all pertinent information (up to April 1976) about the effects on man and his environment that result either directly or indirectly from pollution by platinum-group metals: iridium (Ir), osmium (Os), palladium (Pd), platinum (Pt), ...

  4. Multiple magma evolution and ore-forming processes of the Hongge layered intrusion, SW China: Insights from Sr-Nd isotopes, trace elements and platinum-group elements

    NASA Astrophysics Data System (ADS)

    Liao, Mingyang; Tao, Yan; Song, Xieyan; Li, Yubang; Xiong, Feng

    2015-12-01

    The Hongge layered intrusion (259 Ma), which is located in the inner zone of the Emeishan large igneous province (ELIP), is one of the most typical Fe-Ti-V ore deposits in the Pan-Xi area. Mafic-ultramafic layered intrusions of the ELIP have attracted a lot of attention lately because these intrusions host world class Fe-Ti-V oxide deposits plus interesting Cu-Ni-(PGE) mineralization which may have economic potential. This paper, reports new whole-rock major and trace element compositions, PGE abundances and Sr-Nd isotopic data for selected cumulate rocks and basalts. We use these data to investigate the nature of parental magmas and the controls on its evolution from the source mantle en route to the surface involving the Hongge ore-bearing intrusion. Two abrupt changes in Mt/Ilm and trace element ratios such as Ba/Th with depths in the Hongge layered intrusion indicate that this intrusion formed by at least two pluses of relatively primitive magma. The whole rock Sr-Nd isotopic data of basaltic and intrusive rocks plot in the region of Emeishan low-Ti basalts and the compositions of residual liquid (at ∼1260 °C and 1155 °C) calculated by MELTS are similar to our actual high-Ti (BFQ-2) and low-Ti (BC-1) basltic samples, indicate they are co-magmatic rather than derivation from a distinct source. Total PGE abundances in the Hongge samples are extremely low, ranging from 0.5 to 10 ppb. Sulfide-bearing rocks in the Hongge intrusion and the nearby coeval Banfangqing and Baicao basalts have similar mantle-like Pd/Pt ratios (2-6) and extremely high Cu/Pd ratios (3 × 104 to 4 × 105), indicating that sulfide segregation took place at depth prior to emplacement at Hongge and eruption in this region. Sulfide saturation in the Hongge magma may have resulted from such crustal contamination event. Crystallization of silicate minerals under the anhydrous magma, magma hydration plus Fe-Ti enrichments in the parental magma are three critical factors for the formation of Fe

  5. Improving Platinum Efficiency:. Nanoformulations

    NASA Astrophysics Data System (ADS)

    Carmona, Rolando; Liang, Xing-Jie

    2013-09-01

    Platinum-based drugs continue being the support of therapy for many different kinds of cancer. Cancer patients often present irreversible resistance to platinum after repeated treatment in clinic. Despite of the great efforts, chemoresistance (intrinsic or acquired) already is a major limitation in the management of this disease. In this review, the last current research on cancer characteristic and cancer chemical resistance is summarized, the major and novel strategies to reverse resistance to platinum- based drugs are discussed and this article mainly emphasizes the contribution of nanotechnology and combination therapies to target sites and reduce the cancer chemoresistance.

  6. Solar abundance of platinum

    PubMed Central

    Burger, Harry; Aller, Lawrence H.

    1975-01-01

    Three lines of neutral platinum, located at λ 2997.98 Å, λ 3064.71 Å, and λ 3301.86 Å have been used to determine the solar platinum abundance by the method of spectral synthesis. On the scale, log A(H) = 12.00, the thus-derived solar platinum abundance is 1.75 ± 0.10, in fair accord with Cameron's value of log A(Pt) = 1.69 derived by Mason from carbonaceous chondrites and calculated on the assumption that log A(Si) = 7.55 in the sun. PMID:16592278

  7. [Platinum antitumor complexes].

    PubMed

    Bonetti, Andrea; Giuliani, Jacopo; Muggia, Franco

    2015-12-01

    In the last 50 years the oncology has experienced remarkable changes resulting in transforming malignant germ-cell testicular tumors from highly fatal to nearly uniformly cured neoplasms. This clinical landmark was justly attributed to the identification of cisplatin by Barnett Rosenberg in his experiments dating to 1965. On this 50th anniversary of this discovery, one is reminded of the following key aspects in cancer therapeutics: 1) the life-story of Barnett Rosenberg and his legacy that included organizing nearly quadrennial "platinum" meetings incorporating advances in cancer biology into evolving therapeutic strategies; 2) the search for less toxic analogs of cisplatin leading to the development of carboplatin; 3) clinical research into attenuation of cisplatin toxicities; 4) oxaliplatin and the expansion of the therapeutic spectrum of platinum compounds; and 5) the ongoing multifaceted investigations into the problem of "platinum resistance". PMID:26780071

  8. Platinum Neurotoxicity Pharmacogenetics

    PubMed Central

    McWhinney, Sarah R.; Goldberg, Richard M.; McLeod, Howard L.

    2009-01-01

    Cisplatin, carboplatin, and oxaliplatin anticancer drugs are commonly used to treat lung, colorectal, ovarian, breast, head/neck, and genitourinary cancers. However, the efficacy of platinum-based drugs is often compromised because of the substantial risk for severe toxicities, including neurotoxicity. Neurotoxicity can result in both acute and chronic debilitation. Moreover, colorectal cancer patients treated with oxaliplatin more often discontinue therapy due to peripheral neuropathy than for tumor progression, potentially compromising patient benefit. Numerous methods to prevent neurotoxicity have so far proven unsuccessful. In order to circumvent this life-altering side effect, while taking advantage of the antitumor activities of the platinum agents, efforts to identify mechanism-based biomarkers are underway. In this review, we detail findings from the current literature for genetic markers associated with neurotoxicity induced by single agent and combination platinum chemotherapy. These data have the potential for broad clinical implications if mechanistic associations lead to the development of toxicity modulators to minimize the noxious sequelae of platinum chemotherapy. PMID:19139108

  9. Growth of platinum nanocrystals

    SciTech Connect

    2009-01-01

    Movie showing the growth of platinum nanocrystals in a liquid cell observed in situ using the JEOL 3010 TEM at the National Center for Electron Microscopy. This is the first ever-real time movie showing nucleation and growth by monomer attachment or by smaller nanocrystals coalescing to form larger nanocrystals. All the nanocrystals end up being roughly the same shape and size. http://newscenter.lbl.gov/feature-stories/2009/08/04/growth-spurts/

  10. Anomalously high retention of radiogenic helium in native platinum

    NASA Astrophysics Data System (ADS)

    Yakubovich, O. V.; Shukolyukov, Yu. A.; Mochalov, A. G.; Kotov, A. B.; Korneev, S. I.

    2012-04-01

    Relatively quick migration of helium from crystal structures has been known for a long time. However there is a group of minerals - native metals - where stability of radiogenic helium is essentially high [1]. Helium, due to its very low solubility in metals, assembles in atomic clusters - "bubbles" of nanometer size. Migration of helium "bubbles" as a whole from the crystal structures needs relatively high temperature near the melting point of metals. On that ground of special interest are platinoids with melting points (and, consequently, temperatures of "explosion-like" release of radiogenic helium) of more than 1550 oC In this respect we believe that the method based on natural radioactivity of platinum is promising. To verify the idea of anomalously high retention of radiogenic helium in native platinum and to check the efficiency of the proposed 190Pt-4He method of isotope geochronology, we studied independent mineral aggregates of native platinum from chromite-bearing dunites of Galmoenan plutonic complex (10 individual samples) (Koryak-Kamchatka belt, Russia) and Konder massif (5 individual samples) (Khabarovsk district,Russia). Because native platinum always has admixture of Fe, Cu etc. for reliable determination of concentration of platinum in the samples in our study we used electron microscope JSM-6510LA with JED 2200 add-on. Amount of 4He in native platinum was determinate on mass-spectrometer complex MSU-G-01-M. Native platinum consists of 6 isotopes. Among them two isotopes are α-radioactive and decay according to following schemes: 190Pt →4He+186Os→4He+182W 192Pt →4He+188Os Presumably, in native platinum there is always a certain amount of uranium and thorium, absorbed in the process of crystallization. However influence of helium generation from uranium becomes more marked at growing of 238U/Pt ratio and beginning with 238U/Pt ≈ 10-5 should be taken into consideration. For the same reason helium produced by the decay of 192Pt and 186Os can

  11. Silicone breast implants and platinum.

    PubMed

    Wixtrom, Roger N

    2007-12-01

    Platinum, in a specific form, is used as a catalyst in the cross-linking reactions of the silicone gel and elastomer in breast implants. After manufacture, it remains in the devices at low-parts-per-million levels. Potential concerns have been raised as to whether this platinum might diffuse from silicone breast implants into the body and result in adverse health effects. The weight of evidence indicates that the platinum present is in its most biocompatible (zero valence) form, and the very minute levels (<0.1 percent) that might diffuse from the implants do not represent a significant health risk to patients. PMID:18090821

  12. Platinum availability for future automotive technologies.

    PubMed

    Alonso, Elisa; Field, Frank R; Kirchain, Randolph E

    2012-12-01

    Platinum is an excellent catalyst, can be used at high temperatures, and is stable in many aggressive chemical environments. Consequently, platinum is used in many current industrial applications, notably automotive catalytic converters, and prospective vehicle fuel cells are expected to rely upon it. Between 2005 and 2010, the automotive industry used approximately 40% of mined platinum. Future automotive industry growth and automotive sales shifts toward new technologies could significantly alter platinum demand. The potential risks for decreased platinum availability are evaluated, using an analysis of platinum market characteristics that describes platinum's geophysical constraints, institutional efficiency, and dynamic responsiveness. Results show that platinum demand for an automotive fleet that meets 450 ppm greenhouse gas stabilization goals would require within 10% of historical growth rates of platinum supply before 2025. However, such a fleet, due largely to sales growth in fuel cell vehicles, will more strongly constrain platinum supply in the 2050 time period. While current platinum reserves are sufficient to satisfy this increased demand, decreasing platinum ore grade and continued concentration of platinum supply in a single geographic area are availability risk factors to platinum end-users. PMID:23088692

  13. Coating Carbon Fibers With Platinum

    NASA Technical Reports Server (NTRS)

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

    2007-01-01

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

  14. Polymorphic transporters and platinum pharmacodynamics

    PubMed Central

    Sprowl, Jason A.; Ness, Rachel A.; Sparreboom, Alex

    2013-01-01

    Summary Several solute carriers and ATP-binding cassette transporters have been implicated in the influx or efflux of platinum-based chemotherapeutic agents such as cisplatin, carboplatin, and oxaliplatin. Given that many of these proteins are highly polymorphic, the genetic status of these proteins could be an important contributor to the extensive interindividual pharmacokinetic variability associated with the clinical use of these agents. In this review article, we provide an updated overview of the various transporters that have shown promise in animal models or patient populations in facilitating the movement of platinum-based agents across cell membranes, and how their function is associated with drug disposition or pharmacodynamic effects. PMID:22986709

  15. Re-Os isotope and platinum-group element geochemistry of the Pobei Ni-Cu sulfide-bearing mafic-ultramafic complex in the northeastern part of the Tarim Craton

    NASA Astrophysics Data System (ADS)

    Yang, Sheng-Hong; Zhou, Mei-Fu; Lightfoot, Peter C.; Xu, Ji-Feng; Wang, Christina Yan; Jiang, Chang-Yi; Qu, Wen-Jun

    2014-03-01

    A number of mafic-ultramafic intrusions that host Ni-Cu sulfide mineralization occur in the northeastern Tarim Craton and the eastern Tianshan Orogenic Belt (NW China). The sulfide-mineralized Pobei mafic-ultramafic complex is located in the northeastern part of the Tarim Craton. The complex is composed of gabbro and olivine gabbro, cut by dunite, wehrlite, and melatroctolite of the Poyi and Poshi intrusions. Disseminated Ni-Cu sulfide mineralization is present towards the base of the ultramafic bodies. The sulfide mineralization is typically low grade (<0.5 wt.% Ni and <2 wt.% S) with low platinum-group element (PGE) concentrations (<24.5 ppb Pt and <69 ppb Pd); the abundance of Cu in 100 % sulfide is 1-8 wt.%, and Ni abundance in 100 % sulfide is typically >4 wt.%. Samples from the Pobei complex have ɛNd (at 280 Ma) values up to +8.1, consistent with the derivation of the magma from an asthenospheric mantle source. Fo 89.5 mol.% olivine from the ultramafic bodies is consistent with a primitive parental magma. Sulfide-bearing dunite and wehrlite have high Cu/Pd ratios ranging from 24,000 to 218,000, indicating a magma that evolved under conditions of sulfide saturation. The grades of Ni, Cu, and PGE in 100 % sulfide show a strong positive correlation. A model for these variations is proposed where the mantle source of the Pobei magma retained ~0.033 wt.% sulfide during the production of a PGE-depleted parental magma. The parental magma migrated from the mantle to the crust and underwent further S saturation to generate the observed mineralization along with its high Cu/Pd ratio at an R-factor varying from 100 to 1,200. The mineralization at Poshi and Poyi has very high γOs (at 280 Ma) values (+30 to +292) that are negatively correlated with the abundance of Os in 100 % sulfide (5.81-271 ppb) and positively correlated with the Re/Os ratios; this indicates that sulfide saturation was triggered by the assimilation of crustal sulfide with both high γOs and Re

  16. Bioavailability of platinum emitted from automobile exhaust.

    PubMed

    Artelt, S; Kock, H; Nachtigall, D; Heinrich, U

    1998-08-01

    A model substance was used which is similar in respect to platinum content of exhaust particles emitted from a three-way-catalytic converter equipped engine. The bioavailability of platinum from such exhaust particles and the kind of platinum species formed in vivo were assessed. An in vitro solubility test showed a solubility of approximately 10 percent of platinum content of the model substance in physiological sodium chloride solution. Two short-term animal studies (8 days) were performed. In all examined rat tissues and body fluids platinum could be detected. In addition, the contribution of the overall bioavailability caused by swallowing a certain amount of the intratracheally applied platinum was evaluated by oral application. It was very low. An analytical method was developed to determine platinum species. Synthetic samples (matrix with a platinum standard solution) were analysed. In rat bronchoalveolar lavage spiked with a platinum standard solution only low molecular complexed platinum was found whereas in rat blood plasma all platinum was bound to proteins. In ongoing studies, the model substance is being tested in a three month rat inhalation study. PMID:9820662

  17. Method for forming porous platinum films

    DOEpatents

    Maya, Leon

    2000-01-01

    A method for forming a platinum film includes providing a substrate, sputtering a crystalline platinum oxide layer over at least a portion of the substrate, and reducing the crystalline platinum oxide layer to form the platinum film. A device includes a non-conductive substrate and a platinum layer having a density of between about 2 and 5 g/cm.sup.3 formed over at least a portion of the non-conductive substrate. The platinum films produced in accordance with the present invention provide porous films suitable for use as electrodes, yet require few processing steps. Thus, such films are less costly. Such films may be formed on both conductive and non-conductive substrates. While the invention has been illustrated with platinum, other metals, such as noble metals, that form a low density oxide when reactively sputtered may also be used.

  18. Nanocarriers for delivery of platinum anticancer drugs☆

    PubMed Central

    Oberoi, Hardeep S.; Nukolova, Natalia V.; Kabanov, Alexander V.; Bronich, Tatiana K.

    2014-01-01

    Platinum based anticancer drugs have revolutionized cancer chemotherapy, and continue to be in widespread clinical use especially for management of tumors of the ovary, testes, and the head and neck. However, several dose limiting toxicities associated with platinum drug use, partial anti-tumor response in most patients, development of drug resistance, tumor relapse, and many other challenges have severely limited the patient quality of life. These limitations have motivated an extensive research effort towards development of new strategies for improving platinum therapy. Nanocarrier-based delivery of platinum compounds is one such area of intense research effort beginning to provide encouraging preclinical and clinical results and may allow the development of the next generation of platinum chemotherapy. This review highlights current understanding on the pharmacology and limitations of platinum compounds in clinical use, and provides a comprehensive analysis of various platinum–polymer complexes, micelles, dendrimers, liposomes and other nanoparticles currently under investigation for delivery of platinum drugs. PMID:24113520

  19. Surface characterization of platinum electrodes.

    PubMed

    Solla-Gullón, José; Rodríguez, Paramaconi; Herrero, Enrique; Aldaz, Antonio; Feliu, Juan M

    2008-03-14

    The quantitative analysis of the different surface sites on platinum samples is attempted from pure voltammetric data. This analysis requires independent knowledge of the fraction of two-dimensional (111) and (100) domains. Specific site-probe reactions are employed to achieve this goal. Irreversibly-adsorbed bismuth and tellurium have been revealed to be sensitive to the presence of (111) terrace domains of different width whereas almost all sites involved in (100) ordered domains have been characterized through germanium adatoms. The experimental protocol follows that used with well-defined single-crystal electrodes and, therefore, requires careful control of the surface cleanliness. Platinum basal planes and their vicinal stepped surfaces have been employed to obtain calibration plots between the charge density measured under the adatom redox peak, specific for the type of surface site, and the corresponding terrace size. The evaluation of the (100) bidimensional domains can also be achieved using the voltammetric profiles, once the fraction of (111) ordered domains present in the polyoriented platinum has been determined and their featureless contribution has been subtracted from the whole voltammetric response. Using that curve, it is possible to perform a deconvolution of the adsorption states of the polycrystalline sample different from those related to (111) domains. The fraction of (100)-related states in the deconvoluted voltammogram can then be compared to that expected from the independent estimation coming from the charge involved in the redox process undergone by the irreversibly-adsorbed germanium and thus check the result of the deconvolution. The information about the surface-site distribution can also be applied to analyze the voltammetric profile of nanocrystalline platinum electrodes. PMID:18309392

  20. Phosphoric acid fuel cell platinum use study

    NASA Technical Reports Server (NTRS)

    Lundblad, H. L.

    1983-01-01

    The U.S. Department of Energy is promoting the private development of phosphoric acid fuel cell (PAFC) power plants for terrestrial applications. Current PAFC technology utilizes platinum as catalysts in the power electrodes. The possible repercussions that the platinum demand of PAFC power plant commercialization will have on the worldwide supply and price of platinum from the outset of commercialization to the year 2000 are investigated. The platinum demand of PAFC commercialization is estimated by developing forecasts of platinum use per unit of generating capacity and penetration of PAFC power plants into the electric generation market. The ability of the platinum supply market to meet future demands is gauged by assessing the size of platinum reserves and the capability of platinum producers to extract, refine and market sufficient quantities of these reserves. The size and timing of platinum price shifts induced by the added demand of PAFC commercialization are investigated by several analytical methods. Estimates of these price shifts are then used to calculate the subsequent effects on PAFC power plant capital costs.

  1. INDUCTION OF TRISOMICS BY PLATINUM DIAMINODINITRODICHLORIDE

    EPA Science Inventory

    Trisomics were produced in the pollen mother cells of Pennisetum americanum (L) K. Schum plants resulting from seeds treated with M to the minus 6th power platinum diaminodinitrodichloride. On the basis of the preliminary study the relative potency of cis-Platinum diaminodinitrod...

  2. Failure mechanism characterization of platinum alloy

    NASA Technical Reports Server (NTRS)

    Rosen, J. M.; Mcfarlen, W. T.

    1986-01-01

    This article describes procedures and results of testing performed on a platinum/10-percent rhodium, thin-wall tubular product. The purpose of the testing was to develop exemplar SEM fractographs to be used to characterize failures under various environmental conditions. Conditions evaluated for the platinum alloys included high temperature, hydrogen environment, braze metal contamination, and cyclic loading.

  3. Platinum electrodes for electrochemical detection of bacteria

    NASA Technical Reports Server (NTRS)

    Wilkins, J. R.

    1979-01-01

    Bacteria is detected electro-chemically by measuring evolution of hydrogen in test system with platinum and reference electrode. Using system, electrodes of platinum are used to detect and enumerate varieties of gram-positive and gram-negative organisms compared in different media.

  4. Platinum metallization for MEMS application

    PubMed Central

    Guarnieri, Vittorio; Biazi, Leonardo; Marchiori, Roberto; Lago, Alexandre

    2014-01-01

    The adherence of Platinum thin film on Si/SiO2 wafer was studies using Chromium, Titanium or Alumina (Cr, Ti, Al2O3) as interlayer. The adhesion of Pt is a fundamental property in different areas, for example in MEMS devices, which operate at high temperature conditions, as well as in biomedical applications, where the problem of adhesion of a Pt film to the substrate is known as a major challenge in several industrial applications health and in biomedical devices, such as for example in the stents.1-4 We investigated the properties of Chromium, Titanium, and Alumina (Cr, Ti, and Al2O3) used as adhesion layers of Platinum (Pt) electrode. Thin films of Chromium, Titanium and Alumina were deposited on Silicon/Silicon dioxide (Si/SiO2) wafer by electron beam. We introduced Al2O3 as a new adhesion layer to test the behavior of the Pt film at higher temperature using a ceramic adhesion thin film. Electric behaviors were measured for different annealing temperatures to know the performance for Cr/Pt, Ti/Pt, and Al2O3/Pt metallic film in the gas sensor application. All these metal layers showed a good adhesion onto Si/SiO2 and also good Au wire bondability at room temperature, but for higher temperature than 400 °C the thin Cr/Pt and Ti/Pt films showed poor adhesion due to the atomic inter-diffusion between Platinum and the metal adhesion layers.5 The proposed Al2O3/Pt ceramic-metal layers confirmed a better adherence for the higher temperatures tested. PMID:24743057

  5. Extended Platinum Nanotubes as Fuel Cell Catalysts

    SciTech Connect

    Alia, S.; Pivovar, B. S.; Yan, Y.

    2012-01-01

    Energy consumption has relied principally on fossil fuels as an energy source; fuel cells, however, can provide a clean and sustainable alternative, an answer to the depletion and climate change concerns of fossil fuels. Within proton exchange membrane fuel cells, high catalyst cost and poor durability limit the commercial viability of the device. Recently, platinum nanotubes (PtNTs) were studied as durable, active catalysts, providing a platform to meet US Department of Energy vehicular activity targets.[1] Porous PtNTs were developed to increase nanotube surface area, improving mass activity for oxygen reduction without sacrificing durability.[2] Subsurface platinum was then replaced with palladium, forming platinum-coated palladium nanotubes.[3] By forming a core shell structure, platinum utilization was increased, reducing catalyst cost. Alternative substrates have also been examined, modifying platinum surface facets and increasing oxygen reduction specific activity. Through modification of the PtNT platform, catalyst limitations can be reduced, ensuring a commercially viable device.

  6. Characterization of electrochemically modified polycrystalline platinum surfaces

    SciTech Connect

    Krebs, L.C.; Ishida, Takanobu.

    1991-12-01

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

  7. [Mechanism of Platinum Derivatives Induced Kidney Injury].

    PubMed

    Yan, Feifei; Duan, Jianchun; Wang, Jie

    2015-09-20

    Platinum derivatives are the most widely used chemotherapeutic agents to treat solid tumors including ovarian, head and neck, and testicular germ cell tumors, lung cancer, and colorectal cancer. Two major problems exist, however, in the clinic use of platinum derivatives. One is the development of tumor resistance to the drug during therapy, leading to treatment failure. The other is the drug's toxicity such as the cisplatin's nephrotoxicity, which limits the dose that can be administered. This paper describes the mechanism of platinum derivatives induced kidney injury. PMID:26383983

  8. Antitumor effect of arabinogalactan and platinum complex.

    PubMed

    Starkov, A K; Zamay, T N; Savchenko, A A; Ingevatkin, E V; Titova, N M; Kolovskaya, O S; Luzan, N A; Silkin, P P; Kuznetsova, S A

    2016-03-01

    The article presents the results of investigation of antitumor properties of platinum-arabinogalactan complex. We showed the ability of the complex to inhibit the growth of Ehrlich ascites tumor cells. It is found that the distribution of the platinum-arabinogalactan complex is not specific only for tumor cells in mice. The complex was found in all tissues and organs examined (ascites cells, embryonic cells, kidney, and liver). The mechanism of action of the arabinogalactan-platinum complex may be similar to cisplatin as the complex is able to accumulate in tumor cells. PMID:27193706

  9. Teaching the Chemistry of Platinum.

    PubMed

    Anderson, Robert G W

    2015-01-01

    Following colonisation of South America by the Spanish, many new naturally occurring substances were sent to Europe. One of these was the silvery, unreactive metal, platinum, discovered in New Grenada in the mid-eighteenth century. It was often found in granular form, associated with gold, and the challenge to chemists was to refine it, produce it as wire or sheet, and determine its chemical properties. This interested the professor of chemistry at the University of Edinburgh, Joseph Black, who was able to obtain samples from London-based Spanish contacts, particularly Ignacio Luzuriaga. This paper examines how Black transmitted his knowledge of the metal to large numbers of students attending his annual course. PMID:26924332

  10. Calibration of platinum resistance thermometers.

    NASA Technical Reports Server (NTRS)

    Sinclair, D. H.; Terbeek, H. G.; Malone, J. H.

    1972-01-01

    Results of five years experience in calibrating about 1000 commercial platinum resistance thermometers (PRT) are reported. These PRT were relatively small and rugged, with ice-point resistances from 200 to 5000 ohms. Calibrations normalized in terms of resistance-difference ratios (Cragoe Z function) were found to be remarkably uniform for five of six different types of PRT tested, and to agree very closely with normalized calibrations of the primary reference standard type PRT. The Z function normalization cancels residual resistances which are not temperature dependent and simplifies interpolation between calibration points when the quality of a given type of PRT has been established in terms of uniform values of the Z function. Measurements at five or six well spaced base-point temperatures with Z interpolation will suffice to calibrate a PRT accurately from 4 to 900 K.

  11. Evaluation of platinum resistance thermometers

    NASA Technical Reports Server (NTRS)

    Daryabeigi, Kamran; Dillon-Townes, Lawrence A.

    1988-01-01

    An evaluation procedure for the characterization of industrial platinum resistance thermometers (PRTs) for use in the temperature range -120 to 160 C was investigated. This evaluation procedure consisted of calibration, thermal stability and hysteresis testing of four surface measuring PRTs. Five different calibration schemes were investigated for these sensors. The IPTS-68 formulation produced the most accurate result, yielding average sensor systematic error of 0.02 C and random error of 0.1 C. The sensors were checked for thermal stability by successive and thermal cycling between room temperature, 160 C, and boiling point of nitrogen. All the PRTs suffered from instability and hysteresis. The applicability of the self-heating technique as an in situ method for checking the calibration of PRTs located inside wind tunnels was investigated.

  12. Platinum-ruthenium-palladium fuel cell electrocatalyst

    DOEpatents

    Gorer, Alexander

    2006-02-07

    A catalyst suitable for use in a fuel cell, especially as an anode catalyst, that contains platinum at a concentration that is between about 20 and about 60 atomic percent, ruthenium at a concentration that is between about 20 and about 60 atomic percent, palladium at a concentration that is between about 5 and about 45 atomic percent, and having an atomic ratio of platinum to ruthenium that is between about 0.7 and about 1.2. Alternatively, the catalyst may contain platinum at a concentration that is between about 25 and about 50 atomic percent, ruthenium at a concentration that is between about 25 and about 55 atomic percent, palladium at a concentration that is between about 5 and about 45 atomic percent, and having a difference between the concentrations of ruthenium and platinum that is no greater than about 20 atomic percent.

  13. Platinum-ruthenium-nickel fuel cell electrocatalyst

    DOEpatents

    Gorer, Alexander

    2005-07-26

    A catalyst suitable for use in a fuel cell, especially as an anode catalyst, that contains platinum, ruthenium, and nickel, wherein the nickel is at a concentration that is less than about 10 atomic percent.

  14. Platinum-Resistor Differential Temperature Sensor

    NASA Technical Reports Server (NTRS)

    Kolbly, R. B.; Britcliffe, M. J.

    1985-01-01

    Platinum resistance elements used in bridge circuit for measuring temperature difference between two flowing liquids. Temperature errors with circuit are less than 0.01 degrees C over range of 100 degrees C.

  15. Stabilizing platinum in phosphoric acid fuel cells

    NASA Technical Reports Server (NTRS)

    Remick, R. J.

    1981-01-01

    The cathode of the phosphoric acid fuel cell uses a high surface area platinum catalyst supported on a carbon substrate. During operation, the small platinum crystallites sinter, causing loss in cell performance. A support was developed that stabilizes platinum in the high surface area condition by retarding or preventing the sintering process. The approach is to form etch pits in the carbon by oxidizing the carbon in the presence of a metal oxide catalyst, remove the metal oxide by an acid wash, and then deposit platinum in these pits. Results confirm the formation of etch pits in each of the three supports chosen for investigation: Vulcan XC-72R, Vulcan XC-72 that was graphized at 2500 C, and Shawinigan Acetylene Black.

  16. Stabilizing platinum in phosphoric acid fuel cells

    NASA Technical Reports Server (NTRS)

    Remick, R. J.

    1982-01-01

    Platinum sintering on phosphoric acid fuel cell cathodes is discussed. The cathode of the phosphoric acid fuel cell uses a high surface area platinum catalyst dispersed on a conductive carbon support to minimize both cathode polarization and fabrication costs. During operation, however, the active surface area of these electrodes decreases, which in turn leads to decreased cell performance. This loss of active surface area is a major factor in the degradation of fuel cell performance over time.

  17. Allergic reaction to platinum in silicone breast implants.

    PubMed

    Arepalli, Sambasiva R; Bezabeh, Shewit; Brown, S Lori

    2002-01-01

    Platinum is used as a catalyst in the manufacture of silicone breast implants. Because platinum is recognized as a potent sensitizer in certain circumstances, some have expressed concern that women with silicone breast implants are exposed to platinum, which is causing allergic reactions. We searched the literature for information on the level of platinum in breast implants and reports of sensitization that clearly related to platinum in women with breast implants. We found no published report with convincing evidence that platinum causes allergic reactions in women with breast implants or that women with breast implants are any more likely to have allergic reactions than women without breast implants. PMID:12627791

  18. Platinum in Earth surface environments

    NASA Astrophysics Data System (ADS)

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

    2014-04-01

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

  19. Studies of n-butane conversion over silica-supported platinum, platinum-silver and platinum-copper catalysts

    SciTech Connect

    Gu, Junhua

    1992-06-09

    The present work was undertaken to elucidate effect of adding silver and copper to silica-supported platinum catalyst on the activity and selectivity in the n-butane reactions. At the conditions of this study n-butane underwent both hydrogenolysis and structural isomerization. The catalytic activity and selectivities between hydrogenolysis and isomerization and within hydrogenolysis were measured at temperature varying from 330 C to 370 C. For platinum-silver catalysts, at lower temperatures studied the catalytic activity per surface platinum atom (turnover frequency) remained constant at lower silver content (between 0 at. % and 30 at. %) and decreased with further increased silver loading, suggesting that low- index planes could be dominant in the hydrogenolysis of n-butane. Moreover, increasing silver content resulted in an enhancement of the selectivity of isomerization products relative to hydrogenolysis products. At the higher temperature studied, no suppression in catalytic activity was observed. It is postulated that surface structure could change due to the mobility of surface silver atoms, leading to surface silver atoms forming islands or going to the bulk, and leaving large portions of basal planes exposed with active platinum atoms. It is also suggested that the presence of inert silver atoms results in weakening of the H-surface bond. This results in increased mobility of hydrogen atoms on the surface and hence, higher reactivity with other adsorbed species. For platinum copper catalysts, the mixed ensembles could play an active role in the hydrogenolysis of n-butane.

  20. Isotopic Biogeochemistry

    NASA Technical Reports Server (NTRS)

    Hayes, J. M.

    1985-01-01

    An overview is provided of the biogeochemical research. The funding, productivity, personnel and facilities are reviewed. Some of the technical areas covered are: carbon isotopic records; isotopic studies of banded iron formations; isotope effects in microbial systems; studies of organic compounds in ancient sediments; and development in isotopic geochemistry and analysis.

  1. Biologically Inspired Phosphino Platinum Complexes

    SciTech Connect

    Jain, Avijita; Helm, Monte L.; Linehan, John C.; DuBois, Daniel L.; Shaw, Wendy J.

    2012-08-01

    Platinum complexes containing phosphino amino acid and amino acid ester ligands, built upon the PPhNR’2 platform, have been synthesized and characterized (PPhNR’2= [1,3-diaza]-5-phenyl phosphacyclohexane, R’=glycine or glycine ester). These complexes were characterized by 31P, 13C, 1H, 195Pt NMR spectroscopy and mass spectrometry. The X-ray crystal structure of one of the complexes, [PtCl2(PPhNGlyester 2)2], is also reported. These biologically inspired ligands have potential use in homogeneous catalysis, with special applications in chiral chemistry and water soluble chemistry. These complexes also provide a foundation upon which larger peptides can be attached, to allow the introduction of enzyme-like features onto small molecule catalysts. This work was supported by the US Department of Energy, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences & Biosciences. Pacific Northwest National Laboratory is operated by Battelle for the US Department of Energy.

  2. Platinum metals magmatic sulfide ores.

    PubMed

    Naldrett, A J; Duke, J M

    1980-06-27

    Platinum-group elements (PGE) are mined predominantly from deposits that have formed by the segregation of molten iron-nickel-copper sulfides from silicate magmas. The absolute concentrations of PGE in sulfides from different deposits vary over a range of five orders of magnitude, whereas those of other chalcophile elements vary by factors of only 2 to 100. However, the relative proportions of the different PGE in a given deposit are systematically related to the nature of the parent magma. The absolute and relative concentrations of PGE in magmatic sulfides are explained in terms of the degree of partial melting of mantle peridotite required to produce the parent magma and the processes of batch equilibration and fractional segregation of sulfides. The Republic of South Africa and the U.S.S.R. together possess more than 97 percent of the world PGE reserves, but significant undeveloped resources occur in North America. The Stillwater complex in Montana is perhaps the most important example. PMID:17796685

  3. Epirubicin, Cisplatin, and Capecitabine for Primary Platinum-Resistant or Platinum-Refractory Epithelial Ovarian Cancer

    PubMed Central

    Sayal, Karen; Gounaris, Ioannis; Basu, Bristi; Freeman, Sue; Moyle, Penny; Hosking, Karen; Iddawela, Mahesh; Jimenez-Linan, Mercedes; Abraham, Jean; Brenton, James; Hatcher, Helen; Earl, Helena; Parkinson, Christine

    2015-01-01

    Objective Primary platinum-resistant epithelial ovarian cancer (EOC) is an area of unmet medical need. There is limited evidence from small studies that platinum-based combinations can overcome “resistance” in a proportion of patients. We investigated the efficacy and toxicity of platinum-based combination chemotherapy in the platinum-resistant and platinum-refractory setting. Methods Epirubicin, cisplatin, and capecitabine (ECX) combination chemotherapy was used at our institution for the treatment of relapsed EOC. From the institutional database, we identified all patients with primary platinum-refractory or platinum-resistant relapse treated with ECX as second-line therapy between 2001 and 2012. We extracted demographic, clinical, treatment, and toxicity data and outcomes. We used logistic and Cox regression models to identify predictors of response and survival respectively. Results Thirty-four 34 patients (8 refractory, 26 resistant) were treated with ECX. Response Evaluation Criteria In Solid Tumors (RECIST) response rate was 45%, median progression-free survival (PFS) was 6.4 months, and overall survival (OS) was 10.6 months. Platinum-resistant patients had better outcomes than did platinum-refractory patients (response rate, 54% vs 0%, P = 0.047; PFS 7.2 vs 1.8 months, P < 0.0001; OS 14.4 vs 3 months, P < 0.001). In regression models, time to progression after first-line treatment and platinum-refractory status were the strongest predictors of response and PFS or OS, respectively. Patients with time to progression after first-line treatment longer than 3 months showed PFS and OS of 7.9 and 14.7 months, respectively. Toxicity was manageable, with only 13% of cycles administered at reduced doses. Conclusions Epirubicin, cisplatin, and capecitabine seems to be active in platinum-resistant relapsed EOC with manageable toxicity. Further prospective investigation of platinum-anthracycline combinations is warranted in patients who relapse 3 to 6 months after

  4. Surface decorated platinum carbonyl clusters

    NASA Astrophysics Data System (ADS)

    Ciabatti, Iacopo; Femoni, Cristina; Iapalucci, Maria Carmela; Longoni, Giuliano; Zacchini, Stefano; Zarra, Salvatore

    2012-06-01

    Four molecular Pt-carbonyl clusters decorated by Cd-Br fragments, i.e., [Pt13(CO)12{Cd5(μ-Br)5Br2(dmf)3}2]2- (1), [Pt19(CO)17{Cd5(μ-Br)5Br3(Me2CO)2}{Cd5(μ-Br)5Br(Me2CO)4}]2- (2), [H2Pt26(CO)20(CdBr)12]8- (3) and [H4Pt26(CO)20(CdBr)12(PtBr)x]6- (4) (x = 0-2), have been obtained from the reactions between [Pt3n(CO)6n]2- (n = 2-6) and CdBr2.H2O in dmf at 120 °C. The structures of these molecular clusters with diameters of 1.5-2 nm have been determined by X-ray crystallography. Both 1 and 2 are composed of icosahedral or bis-icosahedral Pt-CO cores decorated on the surface by Cd-Br motifs, whereas 3 and 4 display a cubic close packed Pt26Cd12 metal frame decorated by CO and Br ligands. An oversimplified and unifying approach to interpret the electron count of these surface decorated platinum carbonyl clusters is suggested, and extended to other low-valent organometallic clusters and Au-thiolate nanoclusters.Four molecular Pt-carbonyl clusters decorated by Cd-Br fragments, i.e., [Pt13(CO)12{Cd5(μ-Br)5Br2(dmf)3}2]2- (1), [Pt19(CO)17{Cd5(μ-Br)5Br3(Me2CO)2}{Cd5(μ-Br)5Br(Me2CO)4}]2- (2), [H2Pt26(CO)20(CdBr)12]8- (3) and [H4Pt26(CO)20(CdBr)12(PtBr)x]6- (4) (x = 0-2), have been obtained from the reactions between [Pt3n(CO)6n]2- (n = 2-6) and CdBr2.H2O in dmf at 120 °C. The structures of these molecular clusters with diameters of 1.5-2 nm have been determined by X-ray crystallography. Both 1 and 2 are composed of icosahedral or bis-icosahedral Pt-CO cores decorated on the surface by Cd-Br motifs, whereas 3 and 4 display a cubic close packed Pt26Cd12 metal frame decorated by CO and Br ligands. An oversimplified and unifying approach to interpret the electron count of these surface decorated platinum carbonyl clusters is suggested, and extended to other low-valent organometallic clusters and Au-thiolate nanoclusters. CCDC 867747 and 867748. For crystallographic data in CIF or other electronic format see DOI: 10.1039/c2nr30400g

  5. Autonomous movement of platinum-loaded stomatocytes.

    PubMed

    Wilson, Daniela A; Nolte, Roeland J M; van Hest, Jan C M

    2012-04-01

    Polymer stomatocytes are bowl-shaped structures of nanosize dimensions formed by the controlled deformation of polymer vesicles. The stable nanocavity and strict control of the opening are ideal for the physical entrapment of nanoparticles which, when catalytically active, can turn the stomatocyte morphology into a nanoreactor. Herein we report an approach to generate autonomous movement of the polymer stomatocytes by selectively entrapping catalytically active platinum nanoparticles within their nanocavities and subsequently using catalysis as a driving force for movement. Hydrogen peroxide is free to access the inner stomatocyte cavity, where it is decomposed by the active catalyst (the entrapped platinum nanoparticles) into oxygen and water. This generates a rapid discharge, which induces thrust and directional movement. The design of the platinum-loaded stomatocytes resembles a miniature monopropellant rocket engine, in which the controlled opening of the stomatocytes directs the expulsion of the decomposition products away from the reaction chamber (inner stomatocyte cavity). PMID:22437710

  6. Further studies on the synthesis of finely divided platinum

    SciTech Connect

    Turkevich, J.; Miner, R.S. Jr.; Babenkova, L.

    1986-09-25

    An investigation was made of the effect of pH and of starting platinum complexes on the synthesis of monodisperse platinum particles by citrate reduction. The antitumor drug cis-platin does not readily produce colloidal particles, and these lack activity for hydrogen peroxide decomposition. The growth of platinum particles by both citrate reduction and hydrogen gas treatment was also studied.

  7. Platinum Publications, January 1–March 31, 2016 | Poster

    Cancer.gov

    Platinum Publications are selected from articles by NCI at Frederick scientists published in 42 prestigious science journals. This list represents articles published during the time period shown above, as generated from PubMed. Articles designated as Platinum Highlights are noteworthy articles selected by Dr. Craig Reynolds, associate director, National Cancer Institute, from among the most recently published Platinum Publications.

  8. Platinum Publications, October 1–29, 2015 | Poster

    Cancer.gov

    Platinum Publications are selected from articles by NCI at Frederick scientists published in 42 prestigious science journals. This list represents articles published during the time period shown above, as generated from PubMed. Articles designated as Platinum Highlights are noteworthy articles selected by Dr. Craig Reynolds, associate director, National Cancer Institute, from among the most recently published Platinum Publications.

  9. Platinum Publications, July 31–September 30, 2015 | Poster

    Cancer.gov

    Platinum Publications are selected from articles by NCI at Frederick scientists published in 42 prestigious science journals. This list represents articles published during the time period shown above, as generated from PubMed. Articles designated as Platinum Highlights are noteworthy articles selected by Dr. Craig Reynolds, associate director, National Cancer Institute, from among the most recently published Platinum Publications.

  10. Platinum Publications, June 26–July 30, 2015 | Poster

    Cancer.gov

    Platinum Publications are selected from articles by NCI at Frederick scientists published in 42 prestigious science journals. This list represents articles published during the time period shown above, as generated from PubMed. Articles designated as Platinum Highlights are noteworthy articles selected by Dr. Craig Reynolds, associate director, National Cancer Institute, from among the most recently published Platinum Publications.

  11. Platinum Publications, October 30–December 31, 2015 | Poster

    Cancer.gov

    Platinum Publications are selected from articles by NCI at Frederick scientists published in 42 prestigious science journals. This list represents articles published during the time period shown above, as generated from PubMed. Articles designated as Platinum Highlights are noteworthy articles selected by Dr. Craig Reynolds, associate director, National Cancer Institute, from among the most recently published Platinum Publications.

  12. Platinum Publications, November 27, 2014 – February 26, 2015 | Poster

    Cancer.gov

    Platinum Publications are selected from articles by NCI at Frederick scientists published in 42 prestigious science journals. This list represents articles published during the time period shown above, as generated from PubMed. Articles designated as Platinum Highlights are noteworthy articles selected by Dr. Craig Reynolds, associate director, National Cancer Institute, from among the most recently published Platinum Publications.

  13. Platinum Publications, October 30 – November 26, 2014 | Poster

    Cancer.gov

    Platinum Publications are selected from articles by NCI at Frederick scientists published in 42 prestigious science journals. This list represents articles published during the time period shown above, as generated from PubMed. Articles designated as Platinum Highlights are noteworthy articles selected by Dr. Craig Reynolds, associate director, National Cancer Institute, from among the most recently published Platinum Publications.

  14. Platinum Publications, February 27 – March 26, 2015 | Poster

    Cancer.gov

    Platinum Publications are selected from articles by NCI at Frederick scientists published in 42 prestigious science journals. This list represents articles published during the time period shown above, as generated from PubMed. Articles designated as Platinum Highlights are noteworthy articles selected by Dr. Craig Reynolds, associate director, National Cancer Institute, from among the most recently published Platinum Publications.

  15. Platinum Publications as of May 29, 2014 | Poster

    Cancer.gov

    Platinum Publications are selected from articles by NCI at Frederick scientists published in 21 prestigious science journals. This list represents new publications generated from PubMed as of the date shown above. Articles designated as Platinum Highlights are noteworthy articles selected by Dr. Craig Reynolds, associate director, National Cancer Institute, from among the most recently published Platinum Publications.

  16. Platinum Publications as of June 25, 2014 | Poster

    Cancer.gov

    Platinum Publications are selected from articles by NCI at Frederick scientists published in 21 prestigious science journals. This list represents new publications generated from PubMed as of the date shown above. Articles designated as Platinum Highlights are noteworthy articles selected by Dr. Craig Reynolds, associate director, National Cancer Institute, from among the most recently published Platinum Publications.

  17. Platinum Publications as of March 6, 2014 | Poster

    Cancer.gov

    Platinum Publications are selected from articles by NCI at Frederick scientists published in 21 prestigious science journals. This list represents new publications generated from PubMed as of the date shown above. Articles designated as Platinum Highlights are noteworthy articles selected by Dr. Craig Reynolds, associate director, National Cancer Institute, from among the most recently published Platinum Publications.

  18. Platinum Publications as of September 25, 2014 | Poster

    Cancer.gov

    Platinum Publications are selected from articles by NCI at Frederick scientists published in 21 prestigious science journals. This list represents new publications generated from PubMed as of the date shown above. Articles designated as Platinum Highlights are noteworthy articles selected by Dr. Craig Reynolds, associate director, National Cancer Institute, from among the most recently published Platinum Publications.

  19. Platinum Publications, March 27 – April 30, 2015 | Poster

    Cancer.gov

    Platinum Publications are selected from articles by NCI at Frederick scientists published in 42 prestigious science journals. This list represents articles published during the time period shown above, as generated from PubMed. Articles designated as Platinum Highlights are noteworthy articles selected by Dr. Craig Reynolds, associate director, National Cancer Institute, from among the most recently published Platinum Publications.

  20. Platinum Publications, February 27 – March 26, 2015 | Poster

    Cancer.gov

    Platinum Publications are selected from articles by NCI at Frederick scientists published in 42 prestigious science journals. This list represents articles published during the time period shown above, as generated from PubMed. Articles designated as Platinum Highlights are noteworthy articles selected by Dr. Craig Reynolds, associate director, National Cancer Institute, from among the most recently published Platinum Publications.

  1. Platinum Publications, October 30 – November 26, 2014 | Poster

    Cancer.gov

    Platinum Publications are selected from articles by NCI at Frederick scientists published in 42 prestigious science journals. This list represents articles published during the time period shown above, as generated from PubMed. Articles designated as Platinum Highlights are noteworthy articles selected by Dr. Craig Reynolds, associate director, National Cancer Institute, from among the most recently published Platinum Publications.

  2. Platinum Publications, July 31–September 30, 2015 | Poster

    Cancer.gov

    Platinum Publications are selected from articles by NCI at Frederick scientists published in 42 prestigious science journals. This list represents articles published during the time period shown above, as generated from PubMed. Articles designated as Platinum Highlights are noteworthy articles selected by Dr. Craig Reynolds, associate director, National Cancer Institute, from among the most recently published Platinum Publications.

  3. Platinum Publications, June 26–July 30, 2015 | Poster

    Cancer.gov

    Platinum Publications are selected from articles by NCI at Frederick scientists published in 42 prestigious science journals. This list represents articles published during the time period shown above, as generated from PubMed. Articles designated as Platinum Highlights are noteworthy articles selected by Dr. Craig Reynolds, associate director, National Cancer Institute, from among the most recently published Platinum Publications.

  4. Platinum Publications, July 1–July 28, 2016 | Poster

    Cancer.gov

    Platinum Publications are selected from articles by NCI at Frederick scientists published in 42 prestigious science journals. This list represents articles published during the time period shown above, as generated from PubMed. Articles designated as Platinum Highlights are noteworthy articles selected by Dr. Craig Reynolds, associate director, National Cancer Institute, from among the most recently published Platinum Publications.

  5. Platinum Publications, September 26 – October 29, 2014 | Poster

    Cancer.gov

    Platinum Publications are selected from articles by NCI at Frederick scientists published in 42 prestigious science journals. This list represents articles published during the time period shown above, as generated from PubMed. Articles designated as Platinum Highlights are noteworthy articles selected by Dr. Craig Reynolds, associate director, National Cancer Institute, from among the most recently published Platinum Publications.

  6. Platinum Publications as of April 30, 2014 | Poster

    Cancer.gov

    Platinum Publications are selected from articles by NCI at Frederick scientists published in 21 prestigious science journals. This list represents new publications generated from PubMed as of the date shown above. Articles designated as Platinum Highlights are noteworthy articles selected by Dr. Craig Reynolds, associate director, National Cancer Institute, from among the most recently published Platinum Publications.

  7. Platinum Publications, October 30–December 31, 2015 | Poster

    Cancer.gov

    Platinum Publications are selected from articles by NCI at Frederick scientists published in 42 prestigious science journals. This list represents articles published during the time period shown above, as generated from PubMed. Articles designated as Platinum Highlights are noteworthy articles selected by Dr. Craig Reynolds, associate director, National Cancer Institute, from among the most recently published Platinum Publications.

  8. Platinum Publications, September 26 – October 29, 2014 | Poster

    Cancer.gov

    Platinum Publications are selected from articles by NCI at Frederick scientists published in 42 prestigious science journals. This list represents articles published during the time period shown above, as generated from PubMed. Articles designated as Platinum Highlights are noteworthy articles selected by Dr. Craig Reynolds, associate director, National Cancer Institute, from among the most recently published Platinum Publications.

  9. Platinum Publications, April 1–May 27, 2016 | Poster

    Cancer.gov

    Platinum Publications are selected from articles by NCI at Frederick scientists published in 42 prestigious science journals. This list represents articles published during the time period shown above, as generated from PubMed. Articles designated as Platinum Highlights are noteworthy articles selected by Dr. Craig Reynolds, associate director, National Cancer Institute, from among the most recently published Platinum Publications.

  10. Platinum Publications, January 1–March 31, 2016 | Poster

    Cancer.gov

    Platinum Publications are selected from articles by NCI at Frederick scientists published in 42 prestigious science journals. This list represents articles published during the time period shown above, as generated from PubMed. Articles designated as Platinum Highlights are noteworthy articles selected by Dr. Craig Reynolds, associate director, National Cancer Institute, from among the most recently published Platinum Publications.

  11. Platinum Publications as of December 3, 2013 | Poster

    Cancer.gov

    Platinum Publications are selected from articles by NCI at Frederick scientists published in 21 prestigious science journals. This list represents new publications generated from PubMed as of the date shown above. Articles designated as Platinum Highlights are noteworthy articles selected by Dr. Craig Reynolds, associate director, National Cancer Institute, from among the most recently published Platinum Publications.

  12. Mineral resource of the month: platinum-group metals

    USGS Publications Warehouse

    Hilliard, Henry

    2003-01-01

    The precious metals commonly referred to as platinum-group metals (PGM) include iridium, osmium, palladium, platinum, rhodium and ruthenium. PGM are among the rarest of elements, and their market values — particularly for palladium, platinum and rhodium — are the highest of all precious metals.

  13. Platinum Publications, June 1–June 30, 2016 | Poster

    Cancer.gov

    Platinum Publications are selected from articles by NCI at Frederick scientists published in 42 prestigious science journals. This list represents articles published during the time period shown above, as generated from PubMed. Articles designated as Platinum Highlights are noteworthy articles selected by Dr. Craig Reynolds, associate director, National Cancer Institute, from among the most recently published Platinum Publications.

  14. Platinum Publications, May 1 – June 25, 2015 | Poster

    Cancer.gov

    Platinum Publications are selected from articles by NCI at Frederick scientists published in 42 prestigious science journals. This list represents articles published during the time period shown above, as generated from PubMed. Articles designated as Platinum Highlights are noteworthy articles selected by Dr. Craig Reynolds, associate director, National Cancer Institute, from among the most recently published Platinum Publications.

  15. Nonenzymatic glucose detection using mesoporous platinum.

    PubMed

    Park, Sejin; Chung, Taek Dong; Kim, Hee Chan

    2003-07-01

    Roughness of nanoscopic dimensions can be used to selectively enhance the faradaic current of a sluggish reaction. Using this principle, we constructed mesoporous structures on the surfaces of pure platinum electrodes responding even more sensitively to glucose than to common interfering species, such as L-ascorbic acid and 4-acetamidophenol. Good sensitivities, as high as 9.6 microA cm(-2) mM(-1), were reproducibly observed in the presence of high concentration of chloride ion. The selectivities, sensitivities, and stabilities determined experimentally have demonstrated the potential of mesoporous platinum as a novel candidate for nonenzymatic glucose sensors. PMID:12964749

  16. Platinum particle size and support effects in NO(x) mediated carbon oxidation over platinum catalysts.

    PubMed

    Villani, Kenneth; Vermandel, Walter; Smets, Koen; Liang, Duoduo; van Tendeloo, Gustaaf; Martens, Johan A

    2006-04-15

    Platinum metal was dispersed on microporous, mesoporous, and nonporous support materials including the zeolites Na-Y, Ba-Y, Ferrierite, ZSM-22, ETS-10, and AIPO-11, alumina, and titania. The oxidation of carbon black loosely mixed with catalyst powder was monitored gravimetrically in a gas stream containing nitric oxide, oxygen, and water. The carbon oxidation activity of the catalysts was found to be uniquely related to the Pt dispersion and little influenced by support type. The optimum dispersion is around 3-4% corresponding to relatively large Pt particle sizes of 20-40 nm. The carbon oxidation activity reflects the NO oxidation activity of the platinum catalyst, which reaches an optimum in the 20-40 nm Pt particle size range. The lowest carbon oxidation temperatures were achieved with platinum loaded ZSM-22 and AIPO-11 zeolite crystallites bearing platinum of optimum dispersion on their external surfaces. PMID:16683615

  17. Platinum recycling in the United States in 1998

    USGS Publications Warehouse

    Hilliard, Henry E.

    2001-01-01

    In the United States, catalytic converters are the major source of secondary platinum for recycling. Other sources of platinum scrap include reforming and chemical process catalysts. The glass industry is a small but significant source of platinum scrap. In North America, it has been estimated that in 1998 more than 20,000 kilograms per year of platinum-group metals from automobile catalysts were available for recycling. In 1998, an estimated 7,690 kilograms of platinum were recycled in the United States. U.S. recycling efficiency was calculated to have been 76 percent in 1998; the recycling rate was estimated at 16 percent.

  18. Chronology of platinum accumulation in an urban lake

    NASA Astrophysics Data System (ADS)

    Rauch, S.; Hermond, H. F.; Ravizza, G.; Morrison, G. M.

    2003-05-01

    Concern has recently emerged over the release of platinum from automobile catalysts and increasing environmental concentrations. The history of platinum deposition is followed through the natural incorporation of pollutants into the sediment record of the Upper Mystic Lake. Platinum was determined by ICP-MS in dated sediments. Platinum concentration remained relatively constant until the mid-1970s when Pt-containing catalysts were introduced in the US. After the introduction of catalysts, platinum concentration increased significantly, with an average deposition rate of 5.4 μg m^{-2} year^{-1} after 1990.

  19. Use of platinum electrodes for the electrochemical detection of bacteria

    NASA Technical Reports Server (NTRS)

    Wilkins, J. R.

    1978-01-01

    Platinum electrodes with surface area ratios of four to one were used to detect and enumerate a variety of gram-positive and gram-negative organisms. Linear relationships were established between inoculum size and detection time. End points for platinum electrodes were similar to those obtained with a platinum-reference electrode combination. Shape of the overall response curves and length of detection times for gram-positive organisms were markedly different than those for the majority of gram-negative species. Platinum electrodes are better than the platinum-reference electrode combination because of cost, ease of handling, and clearer definition of the end point.

  20. Platinum-based drugs: past, present and future.

    PubMed

    Dilruba, Shahana; Kalayda, Ganna V

    2016-06-01

    Platinum-based drugs cisplatin, carboplatin and oxaliplatin are widely used in the therapy of human neoplasms. Their clinical success is, however, limited due to severe side effects and intrinsic or acquired resistance to the treatment. Much effort has been put into the development of new platinum anticancer complexes, but none of them has reached worldwide clinical application so far. Nedaplatin, lobaplatin and heptaplatin received only regional approval. Some new platinum complexes and platinum drug formulations are undergoing clinical trials. Here, we review the main classes of new platinum drug candidates, such as sterically hindered complexes, monofunctional platinum drugs, complexes with biologically active ligands, trans-configured and polynuclear platinum complexes, platinum(IV) prodrugs and platinum-based drug delivery systems. For each class of compounds, a detailed overview of the mechanism of action is given, the cytotoxicity is compared to that of the clinically used platinum drugs, and the clinical perspectives are discussed. A critical analysis of lessons to be learned is presented. Finally, a general outlook regarding future directions in the field of new platinum drugs is given. PMID:26886018

  1. Fraction of platinum surface covered with carbonaceous species following hydrogenolysis of hexane on platinum alumina catalysts

    SciTech Connect

    Rivera Latas, F.J.

    1986-01-01

    Catalytic naphtha reforming plays a major role in satisfying the demand for unleaded, high octane gasoline. Hydrogen containing carbonaceous deposits (coke) accumulation on the surface of the catalysts during reforming operation. This study investigated the following question: what is the fraction of the platinum surface covered with the deposits following a typical reforming reaction. These observations prompted us to prepare a platinum-alumina catalyst with a high metal content (5%) to enhance the sensitivity of experiments designed to examine the platinum surface following hexane hydrogenolysis. The reaction was selected because it is a good model reaction for catalytic reforming and it was also studied by the Somorjai group in the higher temperature range of their work. Hydrogenolysis of hexane was carried out in a flow system for 3 h at 713 K, at atmospheric pressure, and around 0.1 total conversion. The catalyst was cooled down to room temperature in the reactant mixture, and the fraction of surface platinum atoms exposed was measured in situ by four independent methods: titration of adsorbed oxygen by dihydrogen, chemisorption of carbon monoxide, infra-red spectroscopy of carbon monoxide bonded to platinum, and rate of ethylene hydrogenation. Independent gravimetric studies showed that coke deposits of around 1% by weight were formed on the same catalyst during hydrogenolysis of hexane under similar conditions. Each of the four methods indicate that approximately 50% of the platinum surface remains exposed under the conditions.

  2. Platinum-containing compound platinum pyrithione is stronger and safer than cisplatin in cancer therapy.

    PubMed

    Zhao, Chong; Chen, Xin; Zang, Dan; Lan, Xiaoying; Liao, Siyan; Yang, Changshan; Zhang, Peiquan; Wu, Jinjie; Li, Xiaofen; Liu, Ningning; Liao, Yuning; Huang, Hongbiao; Shi, Xianping; Jiang, Lili; Liu, Xiuhua; He, Zhimin; Wang, Xuejun; Liu, Jinbao

    2016-09-15

    DNA is the well-known molecular target of current platinum-based anticancer drugs; consequently, their clinical use is severely restricted by their systemic toxicities and drug resistance originating from non-selective DNA damage. Various strategies have been developed to circumvent the shortcomings of platinum-based chemotherapy but the inherent problem remains unsolved. Here we report that platinum pyrithione (PtPT), a chemically well-characterized synthetic complex of platinum, inhibits proteasome function and thereby exhibits greater and more selective cytotoxicity to multiple cancer cells than cisplatin, without showing discernible DNA damage both in vitro and in vivo. Moreover, unlike the classical proteasome inhibitor bortezomib/Velcade which inhibits the proteasome via blocking the peptidase activity of 20S proteasomes, PtPT primarily deactivates 26S proteasome-associated deubiquitinases USP14 and UCHL5. Furthermore, PtPT can selectively induce cytotoxicity and proteasome inhibition in cancer cells from leukemia patients but not peripheral blood mononuclear cells from healthy humans. In nude mice, PtPT also remarkably inhibited tumor xenograft growth, without showing the adverse effects that were induced by cisplatin. Hence, we have discovered a new platinum-based anti-tumor agent PtPT which targets 26S proteasome-associated deubiquitinases rather than DNA in the cell and thereby exerts safer and more potent anti-tumor effects, identifying a highly translatable new platinum-based anti-cancer strategy. PMID:27381943

  3. Skin Sensitizing Potency of Halogenated Platinum Salts.

    EPA Science Inventory

    The relationship between occupational exposure to halogenated platinum (Pt) salts and Pt-specific allergic sensitization is well-established. Although human case reports and clinical studies demonstrate that Pt salts are potent skin sensitizers, no studies have been published tha...

  4. Nanoscale platinum printing on insulating substrates.

    PubMed

    O'Connell, C D; Higgins, M J; Sullivan, R P; Jamali, S S; Moulton, S E; Wallace, G G

    2013-12-20

    The deposition of noble metals on soft and/or flexible substrates is vital for several emerging applications including flexible electronics and the fabrication of soft bionic implants. In this paper, we describe a new strategy for the deposition of platinum electrodes on a range of materials, including insulators and flexible polymers. The strategy is enabled by two principle advances: (1) the introduction of a novel, low temperature strategy for reducing chloroplatinic acid to platinum using nitrogen plasma; (2) the development of a chloroplatinic acid based liquid ink formulation, utilizing ethylene glycol as both ink carrier and reducing agent, for versatile printing at nanoscale resolution using dip-pen nanolithography (DPN). The ink formulation has been printed and reduced upon Si, glass, ITO, Ge, PDMS, and Parylene C. The plasma treatment effects reduction of the precursor patterns in situ without subjecting the substrate to destructively high temperatures. Feature size is controlled via dwell time and degree of ink loading, and platinum features with 60 nm dimensions could be routinely achieved on Si. Reduction of the ink to platinum was confirmed by energy dispersive x-ray spectroscopy (EDS) elemental analysis and x-ray diffraction (XRD) measurements. Feature morphology was characterized by optical microscopy, SEM and AFM. The high electrochemical activity of individually printed Pt features was characterized using scanning electrochemical microscopy (SECM). PMID:24270681

  5. Nanoscale platinum printing on insulating substrates

    NASA Astrophysics Data System (ADS)

    O'Connell, C. D.; Higgins, M. J.; Sullivan, R. P.; Jamali, S. S.; Moulton, S. E.; Wallace, G. G.

    2013-12-01

    The deposition of noble metals on soft and/or flexible substrates is vital for several emerging applications including flexible electronics and the fabrication of soft bionic implants. In this paper, we describe a new strategy for the deposition of platinum electrodes on a range of materials, including insulators and flexible polymers. The strategy is enabled by two principle advances: (1) the introduction of a novel, low temperature strategy for reducing chloroplatinic acid to platinum using nitrogen plasma; (2) the development of a chloroplatinic acid based liquid ink formulation, utilizing ethylene glycol as both ink carrier and reducing agent, for versatile printing at nanoscale resolution using dip-pen nanolithography (DPN). The ink formulation has been printed and reduced upon Si, glass, ITO, Ge, PDMS, and Parylene C. The plasma treatment effects reduction of the precursor patterns in situ without subjecting the substrate to destructively high temperatures. Feature size is controlled via dwell time and degree of ink loading, and platinum features with 60 nm dimensions could be routinely achieved on Si. Reduction of the ink to platinum was confirmed by energy dispersive x-ray spectroscopy (EDS) elemental analysis and x-ray diffraction (XRD) measurements. Feature morphology was characterized by optical microscopy, SEM and AFM. The high electrochemical activity of individually printed Pt features was characterized using scanning electrochemical microscopy (SECM).

  6. Evaluation of industrial platinum resistance thermometers

    NASA Technical Reports Server (NTRS)

    Daryabeigi, Kamran; Dillontownes, Lawrence A.; Alderfer, David W.

    1987-01-01

    The calibration and stability of four surface temperature measuring industrial platinum resistance thermometers for use in the temperature range -120 C to 160 C was investigated. It was found that the calibration formulation of the International Practical Temperature Scale of 1968 provided the most accurate calibration. It was also found that all the resistance thermometers suffered from varying degrees of instability and hysteresis.

  7. Cataloging antineoplastic agents according to their effectiveness against platinum-resistant and platinum-sensitive ovarian carcinoma cell lines

    PubMed Central

    Ishiguro, Kimiko; Zhu, Yong-Lian; Lin, Z. Ping; Penketh, Philip G.; Shyam, Krishnamurthy; Zhu, Rui; Baumann, Raymond P.; Sartorelli, Alan C.; Rutherford, Thomas J.; Ratner, Elena S.

    2016-01-01

    Although epithelial ovarian cancers (EOCs) are initially treated with platinum-based chemotherapy, EOCs vary in platinum responsiveness. Cataloging antineoplastic agents according to their effectiveness against platinum-resistant and platinum-sensitive EOC cell lines is valuable for development of therapeutic strategies to avoid platinum inefficacy and to exploit platinum sensitivity. TOV-21G devoid of FANCF expression, OV-90 and SKOV-3 were employed as examples of platinum-sensitive, platinum-intermediate and platinum-resistant cell lines, respectively. Antineoplastic agents examined included mitomycin C, doxorubicin, etoposide, gemcitabine, chlorambucil, paclitaxel, triapine and X-rays. Their effectiveness against cell lines was analyzed by clonogenic assays. Cytotoxic profiles of mitomycin C and carboplatin were similar, with mitomycin C exhibiting greater potency and selectivity against TOV-21G than carboplatin. Cytotoxic profiles of doxorubicin, etoposide and X-rays overlapped with that of carboplatin, while OV-90 overexpressing Rad51 was more resistant to chlorambucil than SKOV-3. The efficacy of paclitaxel and triapine was independent of platinum sensitivity or resistance. Consistent with these cytotoxic profiles, cisplatin/mitomycin C, triapine, and paclitaxel differed in the capacity to induce phosphorylation of H2AX, and produced unique inhibitory patterns of DNA/RNA syntheses in HL-60 human leukemia cells. Paclitaxel and triapine in combination produced additive antitumor effects in M109 murine lung carcinoma. In conclusion, mitomycin C is potentially more effective against Fanconi anemia pathway-deficient EOCs than carboplatin. Doxorubicin and etoposide, because of their overlapping cytotoxic properties with carboplatin, are unlikely to be efficacious against platinum-refractory EOCs. Paclitaxel and triapine are effective regardless of platinum sensitivity status, and promising in combination for both platinum-sensitive and platinum-refractory EOCs

  8. Unsaturated platinum-rhenium cluster complexes. Synthesis, structures and reactivity.

    PubMed

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

    2007-05-01

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

  9. Platinum-conjugated antibodies for application in mass cytometry.

    PubMed

    Mei, Henrik E; Leipold, Michael D; Maecker, Holden T

    2016-03-01

    Mass cytometry has overcome limitations of fluorescent single cell cytometry by allowing for the measurement of up to currently ∼40 different parameters on a single cell level. However, the cellular proteome comprises many more potential analytes, and current mass cytometry instrumentation allows for theoretically up to 121 different mass detection channels. The labeling of specific probes with appropriate metal ions is a significant hurdle for exploiting more of mass cytometry's analytical capacity. To this end, we here describe the labeling of antibody with natural abundance or isotopically purified platinum as formulated in cisplatin and circumventing the use of chelator-loaded polymers. We confirm the utility of cisplatin-antibody-conjugates for surface, intracellular, and phosphoepitope-specific immunophenotyping, as well as for application in cell surface CD45-based barcoding. Cisplatin-labeling of antibody increases the analytical capacity of the CyTOF(®) platform by two channels based on available reagents, and has the potential to add a total of six channels for detection of specific probes, thus helping to better extend the analytical mass range of mass cytometers. PMID:26355391

  10. Synthesis of Bimetallic Platinum Nanoparticles for Biosensors

    PubMed Central

    Leteba, Gerard M.; Lang, Candace I.

    2013-01-01

    The use of magnetic nanomaterials in biosensing applications is growing as a consequence of their remarkable properties; but controlling the composition and shape of metallic nanoalloys is problematic when more than one precursor is required for wet chemistry synthesis. We have developed a successful simultaneous reduction method for preparation of near-spherical platinum-based nanoalloys containing magnetic solutes. We avoided particular difficulties in preparing platinum nanoalloys containing Ni, Co and Fe by the identification of appropriate synthesis temperatures and chemistry. We used transmission electron microscopy (TEM) to show that our particles have a narrow size distribution, uniform size and morphology, and good crystallinity in the as-synthesized condition. Energy dispersive spectroscopy (EDS) and X-ray diffraction (XRD) confirms the coexistence of Pt with the magnetic solute in a face-centered cubic (FCC) solid solution. PMID:23941910

  11. Raman characterization of platinum diselenide thin films

    NASA Astrophysics Data System (ADS)

    O’Brien, Maria; McEvoy, Niall; Motta, Carlo; Zheng, Jian-Yao; Berner, Nina C.; Kotakoski, Jani; Elibol, Kenan; Pennycook, Timothy J.; Meyer, Jannik C.; Yim, Chanyoung; Abid, Mohamed; Hallam, Toby; Donegan, John F.; Sanvito, Stefano; Duesberg, Georg S.

    2016-06-01

    Platinum diselenide (PtSe2) is a newly discovered 2D material which is of great interest for applications in electronics and catalysis. PtSe2 films were synthesized by thermally assisted selenization of predeposited platinum films and scanning transmission electron microscopy revealed the crystal structure of these films to be 1T. Raman scattering of these films was studied as a function of film thickness, laser wavelength and laser polarization. E g and A 1g Raman active modes were identified using polarization measurements in the Raman setup. These modes were found to display a clear position and intensity dependence with film thickness, for multiple excitation wavelengths, and their peak positions agree with simulated phonon dispersion curves for PtSe2. These results highlight the practicality of using Raman spectroscopy as a prime characterization technique for newly synthesized 2D materials.

  12. Isotope separation

    DOEpatents

    Bartlett, Rodney J.; Morrey, John R.

    1978-01-01

    A method and apparatus is described for separating gas molecules containing one isotope of an element from gas molecules containing other isotopes of the same element in which all of the molecules of the gas are at the same electronic state in their ground state. Gas molecules in a gas stream containing one of the isotopes are selectively excited to a different electronic state while leaving the other gas molecules in their original ground state. Gas molecules containing one of the isotopes are then deflected from the other gas molecules in the stream and thus physically separated.

  13. Remarkable NO oxidation on single supported platinum atoms

    SciTech Connect

    Narula, Chaitanya K.; Allard, Lawrence F.; Stocks, G. M.; Moses-DeBusk, Melanie

    2014-11-28

    Our first-principles density functional theoretical modeling suggests that NO oxidation is feasible on fully oxidized single θ-alumina-supported platinum atoms via a modified Langmuir-Hinshelwood pathway. This is in contrast to the known decrease in NO oxidation activity of supported platinum with decreasing Pt particle size believed to be due to increased platinum oxidation. In order to validate our theoretical study, we evaluated single θ-Al2O3-supported platinum atoms and found them to exhibit remarkable NO oxidation activity. A comparison of turnover frequencies (TOF) of single supported Pt atoms with those of platinum particles for NO oxidation shows that single supported Pt atoms are as active as fully formed platinum particles. The overall picture of NO oxidation on supported Pt is that NO oxidation activity decreases with decreasing Pt particle size but accelerates when Pt is present only as single atoms.

  14. Remarkable NO oxidation on single supported platinum atoms

    DOE PAGESBeta

    Narula, Chaitanya K.; Allard, Lawrence F.; Stocks, G. M.; Moses-DeBusk, Melanie

    2014-11-28

    Our first-principles density functional theoretical modeling suggests that NO oxidation is feasible on fully oxidized single θ-alumina-supported platinum atoms via a modified Langmuir-Hinshelwood pathway. This is in contrast to the known decrease in NO oxidation activity of supported platinum with decreasing Pt particle size believed to be due to increased platinum oxidation. In order to validate our theoretical study, we evaluated single θ-Al2O3-supported platinum atoms and found them to exhibit remarkable NO oxidation activity. A comparison of turnover frequencies (TOF) of single supported Pt atoms with those of platinum particles for NO oxidation shows that single supported Pt atoms aremore » as active as fully formed platinum particles. The overall picture of NO oxidation on supported Pt is that NO oxidation activity decreases with decreasing Pt particle size but accelerates when Pt is present only as single atoms.« less

  15. Remarkable NO oxidation on single supported platinum atoms

    PubMed Central

    Narula, Chaitanya K.; Allard, Lawrence F.; Stocks, G. M.; Moses-DeBusk, Melanie

    2014-01-01

    Our first-principles density functional theoretical modeling suggests that NO oxidation is feasible on fully oxidized single θ-Al2O3 supported platinum atoms via a modified Langmuir-Hinshelwood pathway. This is in contrast to the known decrease in NO oxidation activity of supported platinum with decreasing Pt particle size believed to be due to increased platinum oxidation. In order to validate our theoretical study, we evaluated single θ-Al2O3 supported platinum atoms and found them to exhibit remarkable NO oxidation activity. A comparison of turnover frequencies (TOF) of single supported Pt atoms with those of platinum particles for NO oxidation shows that single supported Pt atoms are as active as fully formed platinum particles. Thus, the overall picture of NO oxidation on supported Pt is that NO oxidation activity decreases with decreasing Pt particle size but accelerates when Pt is present only as single atoms. PMID:25429995

  16. Luminescent Platinum Compounds: From Molecules to OLEDs

    NASA Astrophysics Data System (ADS)

    Murphy, Lisa; Williams, J. A. Gareth

    Around 30 years ago, much of the research into platinum coordination chemistry was being driven either by research into one-dimensional, electrically conducting molecular materials exploiting the stacking interactions of planar complexes, or by the unprecedented success of cis-Pt(NH3)2Cl2 (cisplatin) as an anticancer agent. At that time, a number of simple platinum(II) compounds were known to be photoluminescent at low temperature or in the solid state, but almost none in fluid solution at room temperature. Since that time, several families of complexes have been discovered that are brightly luminescent, and a number of investigations have shed light on the factors that govern the luminescence efficiencies of Pt(II) complexes. Over the past decade, such studies have been spurred on by the potential application of triplet-emitting metal complexes as phosphors in organic light-emitting devices (OLEDs), where their ability to trap otherwise wasted triplet states can lead to large gains in efficiency. In this contribution, we take a chemist's perspective of the field, overviewing in the first instance the factors that need to be taken into account in the rational design of highly luminescent platinum(II) complexes, and the background to their use in OLEDs. We then consider in more detail the properties of some individual classes, highlighting work from the past 3 years, and including selected examples of their utility in OLEDs and other applications.

  17. Controlled synthesis of porous platinum nanostructures for catalytic applications.

    PubMed

    Cao, Yanqin; Zhang, Junwei; Yang, Yong; Huang, Zhengren; Long, Nguyen Viet; Nogami, Masayuki

    2014-02-01

    Porous platinum, that has outstanding catalytic and electrical properties and superior resistant characteristics to corrosion, has been widely applied in chemical, petrochemical, pharmaceutical, electronic, and automotive industries. As the catalytic activity and selectivity depend on the size, shape and structure of nanomaterials, the strategies for controlling these factors of platinum nanomaterials to get excellent catalytic properties are discussed. Here, recent advances in the design and preparation of various porous platinum nanostructures are reviewed, including wet-chemical synthesis, electro-deposition, galvanic replacement reaction and de-alloying technology. The applications of various platinum nanostructures are also discussed, especially in fuel cells. PMID:24749422

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

    DOEpatents

    Ragle, Christie Susan; Silver, Ronald G.; Zemskova, Svetlana Mikhailovna; Eckstein, Colleen J.

    2011-12-06

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

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

    DOEpatents

    Ragle, Christie Susan; Silver, Ronald G.; Zemskova, Svetlana Mikhailovna; Eckstein, Colleen J.

    2012-08-07

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

  20. Catalytic activities of platinum nanotubes: a density functional study

    NASA Astrophysics Data System (ADS)

    Mukherjee, Prajna; Gupta, Bikash C.; Jena, Puru

    2015-10-01

    In this work we investigate the catalytic properties of platinum nanotubes using density functional theory based calculations. In particular, we study the dissociation of hydrogen and oxygen molecules as well as oxidation of CO molecules. The results indicate that platinum nanotubes have good catalytic properties and can be effectively used in converting CO molecule to CO2.

  1. Bimetallic alloy electrocatalysts with multilayered platinum-skin surfaces

    DOEpatents

    Stamenkovic, Vojislav R.; Wang, Chao; Markovic, Nenad M.

    2016-01-26

    Compositions and methods of preparing a bimetallic alloy having enhanced electrocatalytic properties are provided. The composition comprises a PtNi substrate having a surface layer, a near-surface layer, and an inner layer, where the surface layer comprises a nickel-depleted composition, such that the surface layer comprises a platinum skin having at least one atomic layer of platinum.

  2. Determination of platinum in blood by adsorptive voltammetry.

    PubMed

    Nygren, O; Vaughan, G T; Florence, T M; Morrison, G M; Warner, I M; Dale, L S

    1990-08-01

    This work describes a sensitive method for the determination of platinum in blood, which can be used for determining the natural levels of platinum in human blood, for monitoring patients treated with platinum cytotoxic drugs, and for monitoring occupational exposure to these drugs and other platinum compounds. The method involves dry ashing of blood samples in a muffle furnace and determination of platinum by adsorptive voltammetric (AV) measurement of the catalytic reduction of protons by the platinum-formazone complex. The detection limit for a 100-microL sample of blood is 0.017 micrograms/L, with a recovery of 94% and a relative standard deviation of 7% at a platinum level of 1 microgram/L. By using this method, the natural levels of platinum in human blood were found to be in the range 0.1-2.8 micrograms/L (median = 0.6 micrograms/L). These results were verified by inductively coupled plasma mass spectrometry (ICP-MS) with blood prepared by wet ashing and using gold as an internal standard. PMID:2400106

  3. 76 FR 8627 - Revision of Class E Airspace; Platinum, AK

    Federal Register 2010, 2011, 2012, 2013, 2014

    2011-02-15

    ... Class E airspace at Platinum AK (75 FR 77572). Interested parties were invited to participate in this... U.S.C. 106(g), 40103, 40113, 40120; E.O. 10854, 24 FR 9565, 3 CFR, 1959-1963 Comp., p. 389. Sec. 71... Federal Aviation Administration 14 CFR Part 71 Revision of Class E Airspace; Platinum, AK AGENCY:...

  4. Vapor-deposited platinum as a fuel-cell catalyst

    NASA Technical Reports Server (NTRS)

    Asher, W. J.; Batzold, J. S.

    1974-01-01

    Electrodes are prepared by vacuum deposition of platinum on nickel substrate with conventional vapor-deposition apparatus. Amount of platinum loaded on substrate can be veried by changing exposure time during deposition. These electrodes are significantly more effective than conventional oxygen electrodes.

  5. Platinum trans-Bis(borirene) complexes displaying coplanarity and communication across a platinum metal center.

    PubMed

    Braunschweig, Holger; Damme, Alexander; Dewhurst, Rian D; Kelch, Hauke; Macha, Bret B; Radacki, Krzysztof; Vargas, Alfredo; Ye, Qing

    2015-02-01

    Ambient-temperature photolysis of the aminoborylene complex [(OC)5 Cr=B=N(SiMe3 )2 ] in the presence of a series of trans-bis(alkynyl)platinum(II) precursors of the type trans-[Pt(CCAr)2 (PEt3 )2 ] (Ar=Ph, p-C6 H4 OMe, and p-C6 H4 CF3 ) successfully leads to twofold transfer of the borylene moiety [:B=N(SiMe3 )2 ] onto the alkyne functionalities. The alkynyl precursors and resultant bis(borirene)platinum(II) complexes formed are of the type trans-[Pt(B{=N(SiMe3 )2 }C=CAr)2 (PEt3 )2 ] (Ar=Ph, p-C6 H4 OMe, and p-C6 H4 CF3 ). These species have all been successfully characterized by NMR, IR, and UV/Vis spectroscopy as well as by elemental analysis. Single-crystal X-ray diffraction has verified that these trans-bis(borirene)platinum(II) complexes display coplanarity between the twin three-membered rings across the platinum core in the solid state and stand as the first examples of coplanar conformations of twin borirene systems. These complexes were modeled using density functional theory (DFT), providing information helpful in determining the ability of the transition metal core to interact with each individual borirene ring system and allowing for the observed coplanarity of these rings in the solid state. This proposed transition metal interaction with the twin borirene systems is manifested in the electronic characterization of these borirene species, which display divergent photophysical UV/Vis spectroscopic profiles compared to a previously published mono(borirene)platinum(II) complex. PMID:25430871

  6. Induction of protein crystallization by platinum nanoparticles

    NASA Astrophysics Data System (ADS)

    Takeda, Yoshihiro; Mafuné, Fumitaka

    2016-03-01

    We have investigated effects of platinum nanoparticles (PtNPs) on protein crystal nucleation. The presence of PtNPs increased the number of crystals in a crystallization solution, indicating that the PtNPs have the ability to promote the crystal nucleation. Dynamic light scattering measurements revealed that the PtNP gathers more than 10 lysozyme molecules around it to form an embryonic complex of PtNP and lysozyme. Zeta potential measurements revealed that the charges of the lysozyme molecules were reduced by delocalization of their charges in the complex. As a result, the energy barrier of association between the complexes is reduced, followed by the nucleation.

  7. Impedance spectra of polypyrrole coated platinum electrodes.

    PubMed

    Onnela, Niina; Savolainen, Virpi; Hiltunen, Maiju; Kellomäki, Minna; Hyttinen, Jari

    2013-01-01

    Polypyrrole (PPy) coated electrodes may provide new solutions to increase the charge injection capacity and biocompatibility of metal electrodes in e.g., neural stimulus applications. In this study, electrical impedance spectra of PPy coated platinum (Pt) electrodes having three different coating thicknesses were measured and modeled. A suitable equivalent electrical circuit providing the material characteristics was chosen and the impedance data was analyzed using the model and data fitting. The modeled parameter values of different coating thicknesses were compared and our results demonstrated the changes in charge transfer properties and mechanisms of thin and thick PPy film coatings. PMID:24109743

  8. Computational Study of Platinum Group Superalloys

    NASA Astrophysics Data System (ADS)

    Popoola, A. I.; Lowther, J. E.

    2014-02-01

    Various properties of substitutional alloys formed from aluminium and the platinum group metals (PGMs) are examined using density functional (D-F) theory and show strong variations depending on metal type. A similar pattern for the binary alloys is observed using molecular dynamics modeling employing Sutton Chen potentials. All results suggest that several of the PGMs could have superior properties to the presently used Ni3Al alloy for high temperature applications. Some phases are predicted to be stable with extremely high melting temperatures (MTs).

  9. Response time correlations for platinum resistance thermometers

    NASA Technical Reports Server (NTRS)

    Pandey, D. K.; Ash, R. L.; Dillon-Townes, L. A.

    1985-01-01

    The 'plunge method' recommended by ASTM has been used to determine the time constant of 100-ohm platinum resistance thermometers (PRT) considered for use in the National Transonic Facility. It is shown that the response time of ventilated PRT can be correlated with the reciprocal of the heat transfer coefficient in a given field. Universal correlations are established for the 100- and 1000-ohm PRT with uncertainties of 20 and 30 percent, respectively. The correlations are found to be consistent with the uncertainty involved in heat transfer correlations available in the literature and are recommended for use in flowing liquids and gases.

  10. Platinum adlayered ruthenium nanoparticles, method for preparing, and uses thereof

    DOEpatents

    Tong, YuYe; Du, Bingchen

    2015-08-11

    A superior, industrially scalable one-pot ethylene glycol-based wet chemistry method to prepare platinum-adlayered ruthenium nanoparticles has been developed that offers an exquisite control of the platinum packing density of the adlayers and effectively prevents sintering of the nanoparticles during the deposition process. The wet chemistry based method for the controlled deposition of submonolayer platinum is advantageous in terms of processing and maximizing the use of platinum and can, in principle, be scaled up straightforwardly to an industrial level. The reactivity of the Pt(31)-Ru sample was about 150% higher than that of the industrial benchmark PtRu (1:1) alloy sample but with 3.5 times less platinum loading. Using the Pt(31)-Ru nanoparticles would lower the electrode material cost compared to using the industrial benchmark alloy nanoparticles for direct methanol fuel cell applications.

  11. EPM Fine-Disperse Platinum Coating on Powder Carriers

    NASA Astrophysics Data System (ADS)

    Serga, V.; Kulikova, L.; Cvetkov, A.; Krumina, A.

    2012-08-01

    In the reported investigation the extractive-pyrolytic method of fine-disperse platinum coating on powder carriers was applied. Nanopowders of Al2O3, γ- AlO(OH), Y2O3, CeO2, SiO2 were used as carriers. Investigations on the effect of synthesis parameters on the mean size of platinum crystallites in the produced composites (metal content 4.8 wt%) have revealed that the increase of the pyrolysis temperature, annealing period, metal concentration in the precursor [(C8H17)3NH]2PtCI6 in toluene as well as the decrease of the specific surface area result in growth of the mean size of platinum crystallites. Microscopic studies show the formation of platinum spherical particles sized 5 to 35 nm as a results of the pyrolysis of the platinum-containing precursor in a water-soluble carrier (fine-disperse NaCl).

  12. Isotopic chirality

    SciTech Connect

    Floss, H.G.

    1994-12-01

    This paper deals with compounds that are chiral-at least in part, due to isotope substitution-and their use in tracing the steric course of enzyme reaction in vitro and in vivo. There are other applications of isotopically chiral compounds (for example, in analyzing the steric course of nonenzymatic reactions and in probing the conformation of biomolecules) that are important but they will not be discussed in this context.

  13. Transuranium isotopes

    SciTech Connect

    Hoffman, D.C.

    1985-12-01

    The needs of the research community for the production of transuranium isotopes, the quantities required, the continuity of production desired, and what a new steady state neutron source would have to provide to satisfy these needs are discussed. Examples of past frontier research which need these isotopes as well as an outline of the proposed Large Einsteinium Activation Program, LEAP, which requires roughly ten times the current production of /sup 254/Es are given. 15 refs., 5 figs., 4 tabs.

  14. 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

  15. 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

  16. Therapeutic gold, silver, and platinum nanoparticles.

    PubMed

    Yamada, Miko; Foote, Matthew; Prow, Tarl W

    2015-01-01

    There are an abundance of nanoparticle technologies being developed for use as part of therapeutic strategies. This review focuses on a narrow class of metal nanoparticles that have therapeutic potential that is a consequence of elemental composition and size. The most widely known of these are gold nanoshells that have been developed over the last two decades for photothermal ablation in superficial cancers. The therapeutic effect is the outcome of the thickness and diameter of the gold shell that enables fine tuning of the plasmon resonance. When these metal nanoparticles are exposed to the relevant wavelength of light, their temperature rapidly increases. This in turn induces a localized photothermal ablation that kills the surrounding tumor tissue. Similarly, gold nanoparticles have been developed to enhance radiotherapy. The high-Z nature of gold dramatically increases the photoelectric cross-section. Thus, the photoelectric effects are significantly increased. The outcome of these interactions is enhanced tumor killing with lower doses of radiation, all while sparing tissue without gold nanoparticles. Silver nanoparticles have been used for their wound healing properties in addition to enhancing the tumor-killing effects of anticancer drugs. Finally, platinum nanoparticles are thought to serve as a reservoir for platinum ions that can induce DNA damage in cancer cells. The future is bright with the path to clinical trials is largely cleared for some of the less complex therapeutic metal nanoparticle systems. PMID:25521618

  17. Platinum group elements in a 3.5 Ga nickel-iron occurrence - Possible evidence of a deep mantle origin

    NASA Technical Reports Server (NTRS)

    Tredoux, Marian; Hart, Rodger J.; Lindsay, Nicholas M.; De Wit, Maarten J.; Armstrong, Richard A.

    1989-01-01

    This paper reports the results of new field observations and the geochemical analyses for the area of the Bon Accord (BA) (the Kaapvaal craton, South Africa) Ni-Fe deposit, with particular consideration given to the trace element, platinum-group element, and isotopic (Pb, Nd, and Os) compositions. On the basis of these data, an interpretation of BA is suggested, according to which the BA deposit is a siderophile-rich heterogeneity remaining in the deep mantle after a process of incomplete core formation. The implications of such a model for the study of core-mantle segregation and the geochemistry of the lowermost mantle are discussed.

  18. Core-Protected Platinum Monolayer Shell High-Stability Electrocatalysts for Fuel-Cell Cathodes

    SciTech Connect

    K Sasaki; H Naohara; Y Cai; Y Choi; P Liu; M Vukmirovic; J Wang; R Adzic

    2011-12-31

    Platinum monolayers can act as shells for palladium nanoparticles to lead to electrocatalysts with high activities and an ultralow platinum content, but high platinum utilization. The stability derives from the core protecting the shell from dissolution. In fuel-cell tests, no loss of platinum was observed in 200,000 potential cycles, whereas loss of palladium was significant.

  19. Core-Protected Platinum Monolayer Shell High-Stability Electrocatalysts for Fuel-Cell Cathodes

    SciTech Connect

    Adzic, R.R.; Sasaki, K.; Naohara, H.; Cai, Y.; Choi, Y.M.; Liu, P.; Vukmirovic, M.B.; Wang, J.X.

    2010-11-08

    More than skin deep: Platinum monolayers can act as shells for palladium nanoparticles to lead to electrocatalysts with high activities and an ultralow platinum content, but high platinum utilization. The stability derives from the core protecting the shell from dissolution. In fuel-cell tests, no loss of platinum was observed in 200?000 potential cycles, whereas loss of palladium was significant.

  20. Monofunctional and Higher-Valent Platinum Anticancer Agents

    PubMed Central

    Johnstone, Timothy C.; Wilson, Justin J.

    2013-01-01

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

  1. Electrochemical platinum coatings for improving performance of implantable microelectrode arrays.

    PubMed

    de Haro, C; Mas, R; Abadal, G; Muñoz, J; Perez-Murano, F; Dominguez, C

    2002-12-01

    The formation and properties of electrochemical platinum films grown on platinum contacts contained in implantable flexible microelectrodes were investigated. The resulting platinum deposits were obtained by applying cyclic voltammetry to baths containing concentrations around 70 mM of chloroplatinic acid. A pre-activation step was necessary before the platinum-electroplating step in order to achieve good adhesive properties. The benefits of this process were ascribed to higher corrosion resistance, lower impedance and improved adhesion to the sputtered platinum. These improvements can make the application of this electrochemical technique highly useful for increasing the lifetime of implantable microelectrode arrays, such as cuff structures (IEEE Trans. Biomed. Eng. 40 (1993) 640). These medical devices, obtained by semiconductor technology could be used for selective stimulation of nerve fascicles, although, poor long-term performance has been achieved with them. The dissolution rate for platinum thin-film microelectrodes under fixed corrosion test conditions was 38.8 ng/C. Lower rates were observed for electroplated microelectrodes, obtaining a dissolution rate of 7.8 ng/C under analogous experimental ageing conditions. The corrosion behaviour of the electroplated platinum during stimulation experimental conditions was estimated by electrochemical impedance spectroscopy. PMID:12322971

  2. Electron Beam Welder Used to Braze Sapphire to Platinum

    NASA Technical Reports Server (NTRS)

    Forsgren, Roger C.; Vannuyen, Thomas

    1998-01-01

    A new use for electron beam brazing was recently developed by NASA Lewis Research Center's Manufacturing Engineering Division. This work was done to fabricate a fiberoptic probe (developed by Sentec Corporation) that could measure high temperatures less than 600 deg C of vibrating machinery, such as in jet engine combustion research. Under normal circumstances, a sapphire fiber would be attached to platinum by a ceramic epoxy. However, no epoxies can adhere ceramic fibers to platinum under such high temperatures and vibration. Also, since sapphire and platinum have different thermal properties, the epoxy bond is subjected to creep over time. Therefore, a new method had to be developed that would permanently and reliably attach a sapphire fiber to platinum. Brazing a sapphire fiber to a platinum shell. The fiber-optic probe assembly consists of a 0.015-in.-diameter sapphire fiber attached to a 0.25-in.-long, 0.059-in.-diameter platinum shell. Because of the small size of this assembly, electron beam brazing was chosen instead of conventional vacuum brazing. The advantage of the electron beam is that it can generate a localized heat source in a vacuum. Gold reactive braze was used to join the sapphire fiber and the platinum. Consequently, the sapphire fiber was not affected by the total heat needed to braze the components together.

  3. Surface Analysis of 4-Aminothiophenol Adsorption at Polycrystalline Platinum Electrodes

    NASA Technical Reports Server (NTRS)

    Rosario-Castro, Belinda I.; Fachini, Estevao R.; Contes, Enid J.; Perez-Davis, Marla E.; Cabrera, Carlos R.

    2008-01-01

    Formation of self-assembled monolayer (SAM) of 4-aminothiophenol (4-ATP) on polycrystalline platinum electrodes has been studied by surface analysis and electrochemistry techniques. The 4-ATP monolayer was characterized by cyclic voltammetry (CV), Raman spectroscopy, reflection absorption infrared (RAIR) spectroscopy, and X-ray photoelectron spectroscopy (XPS). Cyclic voltammetry (CV) experiments give an idea about the packing quality of the monolayer. RAIR and Raman spectra for 4-ATP modified platinum electrodes showed the characteristic adsorption bands for neat 4-ATP indicating the adsorption of 4-ATP molecules on platinum surface. The adsorption on platinum was also evidenced by the presence of sulfur and nitrogen peaks by XPS survey spectra of the modified platinum electrodes. High resolution XPS studies and RAIR spectrum for platinum electrodes modified with 4-ATP indicate that molecules are sulfur-bonded to the platinum surface. The formation of S-Pt bond suggests that ATP adsorption gives up an amino terminated SAM. Thickness of the monolayer was evaluated via angle-resolved XPS (AR-XPS) analyses. Derivatization of 4-ATP SAM was performed using 16-Br hexadecanoic acid.

  4. Osmium and Platinum Decoupling in the Environment: Evidences in Intertidal Sediments (Tagus Estuary, SW Europe).

    PubMed

    Almécija, Clara; Sharma, Mukul; Cobelo-García, Antonio; Santos-Echeandía, Juan; Caetano, Miguel

    2015-06-01

    Catalytic converters in automobiles have significantly increased the input of platinum group elements (PGE) to the environment, and their coupled geochemical behavior has been proposed. To check this hypothesis, Pt and Os concentrations and (187)Os/(188)Os ratios were determined in sediment cores and interstitial waters from the Tagus Estuary (SW Europe) affected by different traffic pressure. Platinum concentration in surface sediments nearby the high traffic zone (up to 40 ng g(-1)) indicated severe contamination. Although lower than Pt, Os enrichment was also observed in surface sediments, with lower (187)Os/(188)Os ratios than in deeper layers. Dissolved Pt and Os in interstitial waters, 0.1-0.7 pg g(-1) and 0.03-0.10 pg g(-1), respectively, were higher than in typical uncontaminated waters. Results indicate two sources of Pt and Os into the Tagus Estuary salt marshes: a regional input associated with industrial activities, fossil fuel combustions, and regional traffic and a local source linked to nearby traffic density emissions. Estimations of Os and Pt released by catalytic converters support this two-source model. Differences in geochemical reactivity and range of dispersion from their sources lead to a decoupled behavior of Os and Pt, questioning the use of Os isotopes as proxies of PGE sources to the environment. PMID:25923357

  5. Preparation of low-sulfur platinum and platinum aluminide layers in thermal barrier coatings

    NASA Technical Reports Server (NTRS)

    Spitsberg, Irene T. (Inventor); Walston, William S. (Inventor); Schaeffer, Jon C. (Inventor)

    2003-01-01

    A method for preparing a coated nickel-base superalloy article reduces the sulfur content of the surface region of the metallic coating layers to low levels, thereby improving the adhesion of the coating layers to the article. The method includes depositing a first layer of platinum overlying the surface of a substrate, depositing a second layer of aluminum over the platinum, and final desulfurizing the article by heating the article to elevated temperature, preferably in hydrogen, and removing a small amount of material from the surface that was exposed during the step of heating. A ceramic layer may be deposited over the desulfurized article. The article may also be similarly desulfurized at other points in the fabrication procedure.

  6. Platinum coat color locus in the deer mouse.

    PubMed

    Dodson, K M; Dawson, W D; Van Ooteghem, S O; Cushing, B S; Haigh, G R

    1987-01-01

    Platinum coat color in the deer mouse, Peromyscus maniculatus, is an autosomal recessive trait marking a locus, pt, distinct from silver (si), albino (c), blonde (bl), brown (b), and agouti (a). Platinum deer mice are conspicuously pale, with light ears and tail stripe. The pewter trait is allelic with and phenotypically identical to platinum, and represents an independent recurrence of this mutant. The rate of recoveries of coat color mutations from wild deer mice is consistent with available data for recurring mutation rates balanced by strong selection against the recessive phenotype. PMID:3611714

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

    SciTech Connect

    Cha, Jennifer N.; Wang, Joseph

    2014-08-31

    The overall objective of the proposed research is to use fundamental advances in bionanotechnology to design powerful platinum nanocrystal electrocatalysts for fuel cell applications. The new economically-viable, environmentally-friendly, bottom-up biochemical synthetic strategy will produce platinum nanocrystals with tailored size, shape and crystal orientation, hence leading to a maximum electrochemical reactivity. There are five specific aims to the proposed bio-inspired strategy for synthesizing efficient electrocatalytic platinum nanocrystals: (1) isolate peptides that both selectively bind particular crystal faces of platinum and promote the nucleation and growth of particular nanocrystal morphologies, (2) pattern nanoscale 2-dimensional arrays of platinum nucleating peptides from DNA scaffolds, (3) investigate the combined use of substrate patterned peptides and soluble peptides on nanocrystal morphology and growth (4) synthesize platinum crystals on planar and large-area carbon electrode supports, and (5) perform detailed characterization of the electrocatalytic behavior as a function of catalyst size, shape and morphology. Project Description and Impact: This bio-inspired collaborative research effort will address key challenges in designing powerful electrocatalysts for fuel cell applications by employing nucleic acid scaffolds in combination with peptides to perform specific, environmentally-friendly, simultaneous bottom-up biochemical synthesis and patterned assembly of highly uniform and efficient platinum nanocrystal catalysts. Bulk synthesis of nanoparticles usually produces a range of sizes, accessible catalytic sites, crystal morphologies, and orientations, all of which lead to inconsistent catalytic activities. In contrast, biological systems routinely demonstrate exquisite control over inorganic syntheses at neutral pH and ambient temperature and pressures. Because the orientation and arrangement of the templating biomolecules can be precisely

  8. Oxidation performance of platinum-clad Mo-47Re alloy

    NASA Technical Reports Server (NTRS)

    Clark, Ronald K.; Wallace, Terryl A.

    1994-01-01

    The alloy Mo-47Re has favorable mechanical properties at temperatures above 1400 C, but it undergoes severe oxidation when used in air with no protective coating. To shield the alloy from oxidation, platinum cladding has been evaluated. The unprotected alloy undergoes catastrophic oxidation under static and dynamic oxidation conditions. The platinum cladding provides good protection from static and dynamic oxidation for moderate times at 1260 C. Samples tested for longer times under static oxidation conditions experienced severe oxidation. The data suggest that oxidation results from the transport of oxygen through the grain boundaries and through the pinhole defects of the platinum cladding.

  9. ISOTOPE SEPARATORS

    DOEpatents

    Bacon, C.G.

    1958-08-26

    An improvement is presented in the structure of an isotope separation apparatus and, in particular, is concerned with a magnetically operated shutter associated with a window which is provided for the purpose of enabling the operator to view the processes going on within the interior of the apparatus. The shutier is mounted to close under the force of gravity in the absence of any other force. By closing an electrical circuit to a coil mouated on the shutter the magnetic field of the isotope separating apparatus coacts with the magnetic field of the coil to force the shutter to the open position.

  10. Quantum spin fluctuations in quasi-one-dimensional chlorine-bridged platinum complexes

    NASA Astrophysics Data System (ADS)

    Wei, Xing; Donohoe, Robert J.; Wang, Wen Z.; Bishop, Alan R.; Gammel, Jan T.

    1997-12-01

    We report experimental and theoretical studies of spin dynamic process in the quasi-one-dimensional chlorine- bridged platinum complex, [PtII(en)2][PtIV(en)2Cl2](ClO4)4, where en equals ethylenediamine, C2N2H8. The process manifests itself in collapsing of the hyperfine and superhyperfine structures in the electron spin resonance spectrum and non-statistical distribution of spectral weight of the Pt isotopes. More surprisingly, it is activated only at temperatures below 6 K. We interpret the phenomenon in terms of quantum tunneling of the electronic spin in a strong electron-electron and electron-phonon coupling regime. This is modeled using a non-adiabatic many-body approach, in which polarons and solitons represent local spin-Peierls regions in a strongly disproportional charge- density-wave background and display intriguing spin-charge separation in the form of pinned charge and tunneling spin fluctuations.

  11. Cyclotron production of ``very high specific activity'' platinum radiotracers in No Carrier Added form

    NASA Astrophysics Data System (ADS)

    Birattari, C.; Bonardi, M.; Groppi, F.; Gini, L.; Gallorini, M.; Sabbioni, E.; Stroosnijder, M. F.

    2001-12-01

    At the "Radiochemistry Laboratory" of Accelerators and Applied Superconductivity Laboratory, LASA, several production and quality assurance methods for short-lived and high specific activity radionuclides, have been developed. Presently, the irradiations are carried out at the Scanditronix MC40 cyclotron (K=38; p, d, He-4 and He-3) of JRC-Ispra, Italy, of the European Community, while both chemical purity and specific activity determination are carried out at the TRIGA MARK II research reactor of University of Pavia and at LASA itself. In order to optimize the irradiation conditions for platinum radiotracer production, both thin- and thick-target excitation function of natOs(α,xn) nuclear reactions were measured. A very selective radiochemical separation to obtain Pt radiotracers in No Carrier Added form, has been developed. Both real specific activity and chemical purity of radiotracer, have been determined by neutron activation analysis and atomic absorption spectrometry. An Isotopic Dilution Factor (IDF) of the order of 50 is achieved.

  12. Thermodynamic ground states of platinum metal nitrides

    SciTech Connect

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

    2007-10-09

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

  13. Platinum Nickel Nanowires as Methanol Oxidation Electrocatalysts

    SciTech Connect

    Alia, Shaun M.; Pylypenko, Svitlana; Neyerlin, Kenneth C.; Kocha, Shyam S.; Pivovar, Bryan S.

    2015-08-27

    We investigated platinum(Pt) nickel (Ni) nanowires (PtNiNWs) as methanol oxidation reaction (MOR) catalysts in rotating disk electrode (RDE) half-cells under acidic conditions. Pt-ruthenium (Ru) nanoparticles have long been the state of the art MOR catalyst for direct methanol fuel cells (DMFCs) where Ru provides oxophilic sites, lowering the potential for carbon monoxide oxidation and the MOR onset. Ru, however, is a precious metal that has long term durability concerns. Ni/Ni oxide species offer a potential to replace Ru in MOR electrocatalysis. PtNiNWs were investigated for MOR and oxygen annealing was investigated as a route to improve catalyst performance (mass activity 65% greater) and stability to potential cycling. Our results presented show that PtNiNWs offer significant promise in the area, but also result in Ni ion leaching that is a concern requiring further evaluation in fuel cells.

  14. Platinum dendritic nanoparticles with magnetic behavior

    NASA Astrophysics Data System (ADS)

    Li, Wenxian; Sun, Ziqi; Tian, Dongliang; Nevirkovets, Ivan P.; Dou, Shi-Xue

    2014-07-01

    Magnetic nanoparticles have attracted increasing attention for biomedical applications in magnetic resonance imaging, high frequency magnetic field hyperthermia therapies, and magnetic-field-gradient-targeted drug delivery. In this study, three-dimensional (3D) platinum nanostructures with large surface area that features magnetic behavior have been demonstrated. The well-developed 3D nanodendrites consist of plentiful interconnected nano-arms ˜4 nm in size. The magnetic behavior of the 3D dendritic Pt nanoparticles is contributed by the localization of surface electrons due to strongly bonded oxygen/Pluronic F127 and the local magnetic moment induced by oxygen vacancies on the neighboring Pt and O atoms. The magnetization of the nanoparticles exhibits a mixed paramagnetic and ferromagnetic state, originating from the core and surface, respectively. The 3D nanodendrite structure is suitable for surface modification and high amounts of drug loading if the transition temperature was enhanced to room temperature properly.

  15. Superconductivity observed in platinum-silicon interface

    SciTech Connect

    Kuo, Pai-Chia; Chen, Chun-Wei; Lee, Ku-Pin; Shiue, Jessie

    2014-05-26

    We report the discovery of superconductivity with an onset temperature of ∼0.6 K in a platinum-silicon interface. The interface was formed by using a unique focused ion beam sputtering micro-deposition method in which the energies of most sputtered Pt atoms are ∼2.5 eV. Structural and elemental analysis by transmission electron microscopy (TEM) and energy dispersive X-ray spectroscopy reveal a ∼ 7 nm interface layer with abundant Pt, which is the layer likely responsible for the superconducting transport behavior. Similar transport behavior was also observed in a gold-silicon interface prepared by the same technique, indicating the possible generality of this phenomenon.

  16. Role of copper transporters in platinum resistance

    PubMed Central

    Kilari, Deepak; Guancial, Elizabeth; Kim, Eric S

    2016-01-01

    Platinum (Pt)-based antitumor agents are effective in the treatment of many solid malignancies. However, their efficacy is limited by toxicity and drug resistance. Reduced intracellular Pt accumulation has been consistently shown to correlate with resistance in tumors. Proteins involved in copper homeostasis have been identified as Pt transporters. In particular, copper transporter receptor 1 (CTR1), the major copper influx transporter, has been shown to play a significant role in Pt resistance. Clinical studies demonstrated that expression of CTR1 correlated with intratumoral Pt concentration and outcomes following Pt-based therapy. Other CTRs such as CTR2, ATP7A and ATP7B, may also play a role in Pt resistance. Recent clinical studies attempting to modulate CTR1 to overcome Pt resistance may provide novel strategies. This review discusses the role of CTR1 as a potential predictive biomarker of Pt sensitivity and a therapeutic target for overcoming Pt resistance. PMID:26862494

  17. Platinum dendritic nanoparticles with magnetic behavior

    SciTech Connect

    Li, Wenxian; Sun, Ziqi; Nevirkovets, Ivan P.; Dou, Shi-Xue; Tian, Dongliang

    2014-07-21

    Magnetic nanoparticles have attracted increasing attention for biomedical applications in magnetic resonance imaging, high frequency magnetic field hyperthermia therapies, and magnetic-field-gradient-targeted drug delivery. In this study, three-dimensional (3D) platinum nanostructures with large surface area that features magnetic behavior have been demonstrated. The well-developed 3D nanodendrites consist of plentiful interconnected nano-arms ∼4 nm in size. The magnetic behavior of the 3D dendritic Pt nanoparticles is contributed by the localization of surface electrons due to strongly bonded oxygen/Pluronic F127 and the local magnetic moment induced by oxygen vacancies on the neighboring Pt and O atoms. The magnetization of the nanoparticles exhibits a mixed paramagnetic and ferromagnetic state, originating from the core and surface, respectively. The 3D nanodendrite structure is suitable for surface modification and high amounts of drug loading if the transition temperature was enhanced to room temperature properly.

  18. Platinum Nickel Nanowires as Methanol Oxidation Electrocatalysts

    DOE PAGESBeta

    Alia, Shaun M.; Pylypenko, Svitlana; Neyerlin, Kenneth C.; Kocha, Shyam S.; Pivovar, Bryan S.

    2015-08-27

    We investigated platinum(Pt) nickel (Ni) nanowires (PtNiNWs) as methanol oxidation reaction (MOR) catalysts in rotating disk electrode (RDE) half-cells under acidic conditions. Pt-ruthenium (Ru) nanoparticles have long been the state of the art MOR catalyst for direct methanol fuel cells (DMFCs) where Ru provides oxophilic sites, lowering the potential for carbon monoxide oxidation and the MOR onset. Ru, however, is a precious metal that has long term durability concerns. Ni/Ni oxide species offer a potential to replace Ru in MOR electrocatalysis. PtNiNWs were investigated for MOR and oxygen annealing was investigated as a route to improve catalyst performance (mass activitymore » 65% greater) and stability to potential cycling. Our results presented show that PtNiNWs offer significant promise in the area, but also result in Ni ion leaching that is a concern requiring further evaluation in fuel cells.« less

  19. Thermodynamic ground states of platinum metal nitrides.

    PubMed

    Aberg, Daniel; Sadigh, Babak; Crowhurst, Jonathan; Goncharov, Alexander F

    2008-03-01

    The thermodynamic stabilities of various phases of the nitrides of the platinum-metal elements are systematically studied using density functional theory. It is shown that for the nitrides of Rh, Pd, Ir, and Pt two new crystal structures, in which the metal ions occupy simple tetragonal lattice sites, have lower formation enthalpies at ambient conditions than any previously proposed structures. The region of stability with respect to those structures extends to 17 GPa for PtN2. Calculations show that the PtN2 simple tetragonal structures at this pressure are thermodynamically stable also with respect to phase separation. The fact that the local density and generalized gradient approximations predict different values of the absolute formation enthalpies as well different relative stabilities between simple tetragonal and the pyrite or marcasite structures are further discussed. PMID:18352720

  20. Thermodynamic Ground States of Platinum Metal Nitrides

    NASA Astrophysics Data System (ADS)

    Åberg, Daniel; Sadigh, Babak; Crowhurst, Jonathan; Goncharov, Alexander F.

    2008-03-01

    The thermodynamic stabilities of various phases of the nitrides of the platinum-metal elements are systematically studied using density functional theory. It is shown that for the nitrides of Rh, Pd, Ir, and Pt two new crystal structures, in which the metal ions occupy simple tetragonal lattice sites, have lower formation enthalpies at ambient conditions than any previously proposed structures. The region of stability with respect to those structures extends to 17 GPa for PtN2. Calculations show that the PtN2 simple tetragonal structures at this pressure are thermodynamically stable also with respect to phase separation. The fact that the local density and generalized gradient approximations predict different values of the absolute formation enthalpies as well different relative stabilities between simple tetragonal and the pyrite or marcasite structures are further discussed.

  1. Platinum group nuggets in deep sea sediments

    NASA Technical Reports Server (NTRS)

    Brownlee, D. E.; Bates, B. A.; Wheelock, M. M.

    1984-01-01

    The existence of iron meteor oblation spheres in deep sea sediments was known for over a century. These spheres generally were believed to be composed of either pure magnetite and wustite or an oxide shell surrounding a NiFe metal core. A large number of 300 micron to 600 micron spheres found were pure oxide spheres, usually containing a solitary 10 micron platinum group nugget (pgn) composed almost entirely of group VIII metals. Twelve PGN's were analyzed and most had chondritic abundances with some depletions that correlate with element volatility. PGN formation by oxidation of a molten metal sphere entering the atmosphere cannot occur if the oxygen abundance in the atmosphere is less than half of its present value. The first appearance of PGN's in the geological record should mark when, in the Earth's history, oxygen rose to this level.

  2. On the kinetics of platinum silicide formation

    NASA Astrophysics Data System (ADS)

    Faber, Erik J.; Wolters, Rob A. M.; Schmitz, Jurriaan

    2011-02-01

    In this work, the kinetics of platinum silicide formation for thin Pt films (50 nm) on monocrystalline ⟨100⟩ silicon is investigated via in situ resistance measurements under isothermal (197-275 °C) conditions. For Pt2Si diffusion limited growth was observed. For PtSi formation, however, no linear relation between silicide thickness and √t was found. PtSi growth over time could be described using the Avrami relation rendering Avrami exponent n =1.4±0.1. Additionally, an effective activation energy EA=1.7±0.1 eV was derived using the Avrami k values. The findings are important for obtaining well defined silicide films and silicide-to-silicon contacts.

  3. Modeling nuclear volume isotope effects in crystals

    PubMed Central

    Schauble, Edwin A.

    2013-01-01

    Mass-independent isotope fractionations driven by differences in volumes and shapes of nuclei (the field shift effect) are known in several elements and are likely to be found in more. All-electron relativistic electronic structure calculations can predict this effect but at present are computationally intensive and limited to modeling small gas phase molecules and clusters. Density functional theory, using the projector augmented wave method (DFT-PAW), has advantages in greater speed and compatibility with a three-dimensional periodic boundary condition while preserving information about the effects of chemistry on electron densities within nuclei. These electron density variations determine the volume component of the field shift effect. In this study, DFT-PAW calculations are calibrated against all-electron, relativistic Dirac–Hartree–Fock, and coupled-cluster with single, double (triple) excitation methods for estimating nuclear volume isotope effects. DFT-PAW calculations accurately reproduce changes in electron densities within nuclei in typical molecules, when PAW datasets constructed with finite nuclei are used. Nuclear volume contributions to vapor–crystal isotope fractionation are calculated for elemental cadmium and mercury, showing good agreement with experiments. The nuclear-volume component of mercury and cadmium isotope fractionations between atomic vapor and montroydite (HgO), cinnabar (HgS), calomel (Hg2Cl2), monteponite (CdO), and the CdS polymorphs hawleyite and greenockite are calculated, indicating preferential incorporation of neutron-rich isotopes in more oxidized, ionically bonded phases. Finally, field shift energies are related to Mössbauer isomer shifts, and equilibrium mass-independent fractionations for several tin-bearing crystals are calculated from 119Sn spectra. Isomer shift data should simplify calculations of mass-independent isotope fractionations in other elements with Mössbauer isotopes, such as platinum and uranium

  4. Modeling nuclear volume isotope effects in crystals.

    PubMed

    Schauble, Edwin A

    2013-10-29

    Mass-independent isotope fractionations driven by differences in volumes and shapes of nuclei (the field shift effect) are known in several elements and are likely to be found in more. All-electron relativistic electronic structure calculations can predict this effect but at present are computationally intensive and limited to modeling small gas phase molecules and clusters. Density functional theory, using the projector augmented wave method (DFT-PAW), has advantages in greater speed and compatibility with a three-dimensional periodic boundary condition while preserving information about the effects of chemistry on electron densities within nuclei. These electron density variations determine the volume component of the field shift effect. In this study, DFT-PAW calculations are calibrated against all-electron, relativistic Dirac-Hartree-Fock, and coupled-cluster with single, double (triple) excitation methods for estimating nuclear volume isotope effects. DFT-PAW calculations accurately reproduce changes in electron densities within nuclei in typical molecules, when PAW datasets constructed with finite nuclei are used. Nuclear volume contributions to vapor-crystal isotope fractionation are calculated for elemental cadmium and mercury, showing good agreement with experiments. The nuclear-volume component of mercury and cadmium isotope fractionations between atomic vapor and montroydite (HgO), cinnabar (HgS), calomel (Hg2Cl2), monteponite (CdO), and the CdS polymorphs hawleyite and greenockite are calculated, indicating preferential incorporation of neutron-rich isotopes in more oxidized, ionically bonded phases. Finally, field shift energies are related to Mössbauer isomer shifts, and equilibrium mass-independent fractionations for several tin-bearing crystals are calculated from (119)Sn spectra. Isomer shift data should simplify calculations of mass-independent isotope fractionations in other elements with Mössbauer isotopes, such as platinum and uranium. PMID

  5. Modeling nuclear volume isotope effects in crystals

    NASA Astrophysics Data System (ADS)

    Schauble, Edwin A.

    2013-10-01

    Mass-independent isotope fractionations driven by differences in volumes and shapes of nuclei (the field shift effect) are known in several elements and are likely to be found in more. All-electron relativistic electronic structure calculations can predict this effect but at present are computationally intensive and limited to modeling small gas phase molecules and clusters. Density functional theory, using the projector augmented wave method (DFT-PAW), has advantages in greater speed and compatibility with a three-dimensional periodic boundary condition while preserving information about the effects of chemistry on electron densities within nuclei. These electron density variations determine the volume component of the field shift effect. In this study, DFT-PAW calculations are calibrated against all-electron, relativistic Dirac-Hartree-Fock, and coupled-cluster with single, double (triple) excitation methods for estimating nuclear volume isotope effects. DFT-PAW calculations accurately reproduce changes in electron densities within nuclei in typical molecules, when PAW datasets constructed with finite nuclei are used. Nuclear volume contributions to vapor-crystal isotope fractionation are calculated for elemental cadmium and mercury, showing good agreement with experiments. The nuclear-volume component of mercury and cadmium isotope fractionations between atomic vapor and montroydite (HgO), cinnabar (HgS), calomel (Hg2Cl2), monteponite (CdO), and the CdS polymorphs hawleyite and greenockite are calculated, indicating preferential incorporation of neutron-rich isotopes in more oxidized, ionically bonded phases. Finally, field shift energies are related to Mössbauer isomer shifts, and equilibrium mass-independent fractionations for several tin-bearing crystals are calculated from 119Sn spectra. Isomer shift data should simplify calculations of mass-independent isotope fractionations in other elements with Mössbauer isotopes, such as platinum and uranium.

  6. Physical Character and Morphology of Platinum Nanocrystals on Strontium Titanate

    NASA Astrophysics Data System (ADS)

    Gild, Joshua; Pierce, Michael; Komanicky, Vladimir; Barbour, Andi; You, Hoydoo

    2015-03-01

    The physical characteristics of platinum nanocrystals on single crystal strontium titanate, SrTiO3 , can effect the chemical properties of this important model catalyst. The morphology, epitaxy, distribution, and size of the Pt nano-crystals can all be controlled through different growth and processing mechanisms. Nanometer scale platinum thin films are deposited on strontium titanate at ambient temperatures then annealed at range of temperatures and in various oxidizing environments. The process of how these conditions influence the formation of uniformly epitaxial platinum crystals on the sample surface has been investigated using basic materials characterization techniques. Single crystal x-ray diffraction is the primary tool for these experiments, coupled with atomic force microscopy for morphology and x-ray and electron spectroscopy to determine chemical bonding between the particles and gases introduced into the system. These substrate supported nanoparticle samples will then be utilized in experiments to test their catalytic activity compared to an amorphous platinum film.

  7. Defining Therapy for Recurrent Platinum-sensitive Ovarian Cancer

    Cancer.gov

    In this phase III clinical trial, women with platinum-sensitive, recurrent ovarian epithelial, fallopian tube, or primary peritoneal cancer will be randomly assigned to undergo secondary cytoreductive surgery, if they are candidates for such surgery, and

  8. MEIOTIC BEHAVIOR OF PLATINUM-INDUCED ANEUPLOIDS IN PEARL MILLET

    EPA Science Inventory

    Cytotoxicity, measured by seed germination and seedling survival, and the clastogenic potential of platinum diaminodinitrodichloride were evaluated in pear millet (Pennisetum americanum (k) Schum). The study was conducted under controlled climatic conditions. Presoaked seed of pe...

  9. Interfacial electronic effects control the reaction selectivity of platinum catalysts.

    PubMed

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

    2016-05-01

    Tuning the electronic structure of heterogeneous metal catalysts has emerged as an effective strategy to optimize their catalytic activities. By preparing ethylenediamine-coated ultrathin platinum nanowires as a model catalyst, here we demonstrate an interfacial electronic effect induced by simple organic modifications to control the selectivity of metal nanocatalysts during catalytic hydrogenation. This we apply to produce thermodynamically unfavourable but industrially important compounds, with ultrathin platinum nanowires exhibiting an unexpectedly high selectivity for the production of N-hydroxylanilines, through the partial hydrogenation of nitroaromatics. Mechanistic studies reveal that the electron donation from ethylenediamine makes the surface of platinum nanowires highly electron rich. During catalysis, such an interfacial electronic effect makes the catalytic surface favour the adsorption of electron-deficient reactants over electron-rich substrates (that is, N-hydroxylanilines), thus preventing full hydrogenation. More importantly, this interfacial electronic effect, achieved through simple organic modifications, may now be used for the optimization of commercial platinum catalysts. PMID:26808458

  10. Water dissociation on silica in the presence of atomic platinum

    NASA Astrophysics Data System (ADS)

    Klett, Joachim; Elger, Benjamin; Krähling, Stephan; Kaiser, Bernhard; Jaegermann, Wolfram; Schäfer, Rolf

    2016-07-01

    We have investigated the adsorption of water on well-defined silica and silica/Pt interfaces by synchrotron X-Ray Photoelectron Spectroscopy (SXPS). For that purpose silica surfaces grown on Si have been covered with atomic platinum in order to facilitate water dissociation. Water was adsorbed from the gas phase at cryogenic temperatures and its dissociation was observed on clean and platinum coated surfaces. After desorption the adsorbed hydroxides decompose on the blank surface, whereas the hydroxides remain stable if the surface was modified with platinum. The principal reversibility of the hydroxylation process implies the necessity of point defects in order to stabilize hydroxides on well-ordered silica surfaces. Deposited platinum atoms are able to stabilize hydroxides in their proximity and act as an acceptor state on the silica surface.

  11. Interfacial electronic effects control the reaction selectivity of platinum catalysts

    NASA Astrophysics Data System (ADS)

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

    2016-05-01

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

  12. Platinum Publications, April 1–May 27, 2016 | Poster

    Cancer.gov

    Platinum Publications are selected from articles by NCI at Frederick scientists published in 42 prestigious science journals. This list represents articles published during the time period shown above, as generated from PubMed.

  13. Substituent effects in heterogeneous catalysis. VIII. Reactions of 2-methyl- and 2-ethylcyclohexanone with deuterium catalyzed by platinum metals

    SciTech Connect

    Teratani, S.; Tanaka, K.; Ogawa, H.; Taya, K.

    1981-08-01

    2-Methyl and 2-ethyl derivatives of cyclohexanone were allowed to react with deuterium in t-BuOD using platinum group metals as catalysts. The product alcohols and the remaining ketone were examined by mass spectrometry. Over Ru, Os, and Ir, the simple addition of two deuterium atoms to the carbonyl linkage was predominant, accompanied by little isotopic exchange. Over Pt, however, isotopic exchange was significant and over Rh and Pd quite extensive. The samples obtained over Rh and Pd were further analyzed by NMR spectroscopy to determine the loci of the incorporated deuterium atoms. Deuterium exchange over Pd was almost entirely confined to the C(2) and C(6) positions, while that over Rh was smeared beyond these positions. These results can be accounted for by assuming the intermediacy of ..pi..-absorbed ..pi..-oxaallylic species on Pd and of ..beta..-diadsorbed species on Rh.

  14. Platinum nanostructures formed by femtosecond laser irradiation in water

    SciTech Connect

    Huo Haibin; Shen Mengyan

    2012-11-15

    Platinum nanostructures with various morphologies, such as spike-like, ripple-like and array-like structures, have been fabricated by 400 nm and 800 nm femtosecond laser irradiation in water. Different structures can be formed on the surfaces as a function of the laser wavelength, the fluence and scan methods. The reflectance measurements of these structures show much larger absorption on the irradiated surfaces than untreated platinum surfaces.

  15. Mineral resource of the month: platinum group metals

    USGS Publications Warehouse

    Loferski, Patricia J.

    2010-01-01

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

  16. The platinum group metals in Younger Dryas Horizons are terrestrial

    NASA Astrophysics Data System (ADS)

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

    2009-12-01

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

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

    PubMed

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

    2014-12-01

    During platinum group metals (PGMs) refining the possibility exists for dermal exposure to PGM salts. The dermal route has been questioned as an alternative route of exposure that could contribute to employee sensitisation, even though literature has been focused on respiratory exposure. This study aimed to investigate the in vitro permeation of platinum and rhodium through intact Caucasian skin. A donor solution of 0.3mg/ml of metal, K2PtCl4 and RhCl3 respectively, was applied to the vertical Franz diffusion cells with full thickness abdominal skin. The receptor solution was removed at various intervals during the 24h experiment, and analysed with high resolution ICP-MS. Skin was digested and analysed by ICP-OES. Results indicated cumulative permeation with prolonged exposure, with a significantly higher mass of platinum permeating after 24h when compared to rhodium. The mass of platinum retained inside the skin and the flux of platinum across the skin was significantly higher than that of rhodium. Permeated and skin retained platinum and rhodium may therefore contribute to sensitisation and indicates a health risk associated with dermal exposure in the workplace. PMID:25084315

  18. Platinum compounds in children with cancer: toxicity and clinical management.

    PubMed

    Ruggiero, Antonio; Trombatore, Giovanna; Triarico, Silvia; Arena, Roberta; Ferrara, Pietro; Scalzone, Maria; Pierri, Filomena; Riccardi, Riccardo

    2013-11-01

    Platinum compounds are widely used in the treatment of pediatric tumors such as neuroblastoma, germ-cell tumors, osteosarcoma, retinoblastoma, hepatoblastoma, brain tumors (low-grade gliomas and medulloblastoma/PNET), and relapsed and refractory lymphomas. The three major platinum compounds (cisplatin, carboplatin, and oxaliplatin) have a similar pharmacokinetics profile and mechanism of action, but the differences in their chemical structure are responsible for their different antitumor activity and toxicity. In this review, we have described the main characteristics of cisplatin, carboplatin, and oxaliplatin, focusing on their toxic effects and possible strategies to prevent them to improve the clinical outcomes in pediatric cancer patients. The underlying mechanism of each platinum-related toxicity is shown together with the clinical manifestations. Furthermore, possible preventive strategies are suggested to reduce the negative impact of platinum compounds on the quality of life of children with cancer. Cisplatin seems to be mostly ototoxic and nephrotoxic, carboplatin mainly produces myelosuppression, whereas oxaliplatin induces predominantly peripheral sensory neurotoxicity. In contrast, nausea and vomiting can be linked to all platinum compounds, although cisplatin exerts the strongest emetic effect. A correct knowledge of pharmacokinetics and toxicological profile of platinum compounds may aid physicians prevent their toxicity on auditory, nervous, renal, and bone marrow function, improving the quality of life of pediatric cancer patients. PMID:23962902

  19. High-precision gamma-ray spectroscopy for enhancing production and application of medical isotopes

    NASA Astrophysics Data System (ADS)

    McCutchan, E. A.; Sonzogni, A. A.; Smith, S. V.; Muench, L.; Nino, M.; Greene, J. P.; Carpenter, M. P.; Zhu, S.; Chillery, T.; Chowdhury, P.; Harding, R.; Lister, C. J.

    2015-10-01

    Nuclear medicine is a field which requires precise decay data for use in planning radionuclide production and in imaging and therapeutic applications. To address deficiencies in decay data, sources of medical isotopes were produced and purified at the Brookhaven Linear Isotope Producer (BLIP) then shipped to Argonne National Laboratory where high-precision, gamma-ray measurements were performed using Gammasphere. New decay schemes for a number of PET isotopes and the impact on dose calculations will be presented. To investigate the production of next-generation theranostic or radiotherapeutic isotopes, cross section measurements with high energy protons have also been explored at BLIP. The 100-200 MeV proton energy regime is relatively unexplored for isotope production, thus offering high discovery potential but at the same time a challenging analysis due to the large number of open channels at these energies. Results of cross sections deduced from Compton-suppressed, coincidence gamma-ray spectroscopy performed at Lowell will be presented, focusing on the production of platinum isotopes by irradiating natural platinum foils with 100 to 200 MeV protons. DOE Isotope Program is acknowledged for funding ST5001030. Work supported by the US DOE under Grant DE-FG02-94ER40848 and Contracts DE-AC02-98CH10946 and DE-AC02-06CH11357.

  20. Modeling nuclear field shift isotope fractionation in crystals

    NASA Astrophysics Data System (ADS)

    Schauble, E. A.

    2013-12-01

    will be presented for calculations of liquid-vapor fractionation of cadmium and mercury, which indicate an affinity for heavy isotopes in the liquid phase. In the case of mercury the results match well with recent experiments. Mössbauer-calibrated fractionation factors will also be presented for tin and platinum species. Platinum isotope behaviour in metals appears to particularly interesting, with very distinct isotope partitioning behaviour for iron-rich alloys, relative to pure platinum metal. References: 1) Bigeleisen, J. (1996) J. Am. Chem. Soc. 118, 3676-3680. 2) Nomura, M., Higuchi, N., Fujii, Y. (1996) J. Am. Chem. Soc. 118, 9127-9130.

  1. A Single-Site Platinum CO Oxidation Catalyst in Zeolite KLTL: Microscopic and Spectroscopic Determination of the Locations of the Platinum Atoms

    SciTech Connect

    Kistler, Joseph D.; Chotigkrai, Nutchapon; Xu, Pinghong; Enderle, Bryan; Praserthdam, Piyasan; Chen, Cong-Yan; Browning, Nigel D.; Gates, Bruce C.

    2014-07-01

    A stable site-isolated mononuclear platinum catalyst with a well-defined structure is presented. Platinum complexes supported in zeolite KLTL were synthesized from [Pt(NH3)4](NO3)2, oxidized at 633 K, and used to catalyze CO oxidation. Finally, IR and X-ray absorption spectra and electron micrographs determine the structures and locations of the platinum complexes in the zeolite pores, demonstrate the platinum-support bonding, and show that the platinum remained site isolated after oxidation and catalysis.

  2. Platinum- and platinum alloy-coated palladium and palladium alloy particles and uses thereof

    DOEpatents

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

    2010-04-06

    The present invention relates to particle and nanoparticle composites useful as oxygen-reduction electrocatalysts. The particle composites are composed of a palladium or palladium-alloy particle or nanoparticle substrate coated with an atomic submonolayer, monolayer, bilayer, or trilayer of zerovalent platinum atoms. The invention also relates to a catalyst and a fuel cell containing the particle or nanoparticle composites of the invention. The invention additionally includes methods for oxygen reduction and production of electrical energy by using the particle and nanoparticle composites of the invention.

  3. Platinum Nanoparticles Strongly Bonded to Freestanding Graphene

    NASA Astrophysics Data System (ADS)

    Thibado, Paul; Schoelz, J. K.; Ghosh, P. K.; Thompson, J.; Dong, L.; Neek-Amal, M.; Peeters, F. M.

    2015-03-01

    Freestanding graphene membranes were successfully functionalized with platinum nanoparticles (Pt NPs). The membranes were imaged using high-resolution transmission electron microscopy, revealing a homogeneous distribution of uniformly sized, single-crystal Pt NPs that exhibit a preferred orientation and nearest-neighbor distance. The Pt NPs were also found to be partially elevated by the graphene substrate, as deduced from atomic-resolution scanning tunneling microscopy (STM) images. Furthermore, the electrostatic force between the STM tip and sample was utilized to estimate the binding energy of the Pt NPs to the suspended graphene. Local strain accumulation due to strong sp3 bond formation is thought to be the origin of the Pt NP self-organization. Such detailed insight into the atomic nature of this functionalized system was only possible through the cooperation of dual microscopic techniques combined with molecular dynamics simulations. The findings are expected to shape future approaches to develop high-performance electronics based on nanoparticle-functionalized graphene as well as fuel cells using Pt NP catalysts. Financial support provided by the Office of Naval Research under Grant No. N00014-10-1-0181 and the National Science Foundation under Grant No. DMR-0855358.

  4. Superlattices of platinum and palladium nanoparticles

    SciTech Connect

    MARTIN,JAMES E.; WILCOXON,JESS P.; ODINEK,JUDY G.; PROVENCIO,PAULA P.

    2000-04-06

    The authors have used a nonionic inverse micelle synthesis technique to form nanoclusters of platinum and palladium. These nanoclusters can be rendered hydrophobic or hydrophilic by the appropriate choice of capping ligand. Unlike Au nanoclusters, Pt nanoclusters show great stability with thiol ligands in aqueous media. Alkane thiols, with alkane chains ranging from C{sub 6} to C{sub 18} were used as hydrophobic ligands, and with some of these they were able to form 2-D and/or 3-D superlattices of Pt nanoclusters as small as 2.7 nm in diameter. Image processing techniques were developed to reliably extract from transmission electron micrographs (TEMs) the particle size distribution, and information about the superlattice domains and their boundaries. The latter permits one to compute the intradomain vector pair correlation function of the particle centers, from which they can accurately determine the lattice spacing and the coherent domain size. From these data the gap between the particles in the coherent domains can be determined as a function of the thiol chain length. It is found that as the thiol chain length increases, the gaps between particles within superlattice domains increases, but more slowly than one might expect, possibly indicating thiol chain interdigitation.

  5. Guanidine complexes of platinum: a theoretical study.

    PubMed

    Marin-Luna, Marta; Sanchez-Sanz, Goar; O'Sullivan, Patrick; Rozas, Isabel

    2014-07-24

    We have studied theoretically the complexes of model N-phenylguanidine/ium derivatives with PtCl3(-) and PtCl2 in different coordinating modes (mono- and bidentate) with different N atoms of the guanidine/ium moiety using the B3LYP/6-31+G** and LANL2DZ mixed basis set. This will aid the understanding of the complexation between platinum and the guanidine or guanidinium moiety in order to design dual anticancer agents that combine a guanidine-based DNA minor groove binder and a cisplatin-like moiety. Calculated interaction and relative energies, analysis of the electron density, and examination of the orbital interactions indicate that the most stable type of complex is that with a monodentate interaction between PtCl3(-) and guanidinium established through one of the NH2 groups. Next, we optimized the structure of three bis-guanidinium diaromatic systems developed in our group as DNA minor groove binders and their complexation with PtCl3(-), finding that the formation of Pt complexes of these minor groove binders is favorable and would produce stable monodentate coordinated systems. PMID:24988181

  6. Platinum Attachments on Iron Oxide Nanoparticle Surfaces

    SciTech Connect

    Palchoudhury, Soubantika; Xu, Yaolin; An, Wei; Turner, C. H.; Bao, Yuping

    2010-04-30

    Platinum nanoparticles supported on metal oxide surfaces have shown great potential as heterogeneous catalysts to accelerate electrochemical processes, such as the oxygen reduction reaction in fuel cells. Recently, the use of magnetic supports has become a promising research topic for easy separation and recovery of catalysts using magnets, such as Pt nanoparticles supported on iron oxide nanoparticles. The attachment of Pt on iron oxide nanoparticles is limited by the wetting ability of the Pt (metal) on ceramic surfaces. A study of Pt nanoparticle attachment on iron oxide nanoparticle surfaces in an organic solvent is reported, which addresses the factors that promote or inhibit such attachment. It was discovered that the Pt attachment strongly depends on the capping molecules of the iron oxide seeds and the reaction temperature. For example, the attachment of Pt nanoparticles on oleic acid coated iron oxide nanoparticles was very challenging, because of the strong binding between the carboxylic groups and iron oxide surfaces. In contrast, when nanoparticles are coated with oleic acid/tri-n-octylphosphine oxide or oleic acid/oleylamine, a significant increase in Pt attachment was observed. Electronic structure calculations were then applied to estimate the binding energies between the capping molecules and iron ions, and the modeling results strongly support the experimental observations.

  7. Platinum and Gold Complexes for OLEDs.

    PubMed

    Tang, Man-Chung; Chan, Alan Kwun-Wa; Chan, Mei-Yee; Yam, Vivian Wing-Wah

    2016-08-01

    Encouraging efforts on the design of high-performance organic materials and smart architecture during the past two decades have made organic light-emitting device (OLED) technology an important competitor for the existing liquid crystal displays. Particularly, the development of phosphorescent materials based on transition metals plays a crucial role for this success. Apart from the extensively studied iridium(III) complexes with d(6) electronic configuration and octahedral geometry, the coordination-unsaturated nature of d(8) transition metal complexes with square-planar structures has been found to provide intriguing spectroscopic and luminescence properties. This article briefly summarizes the development of d(8) platinum(II) and gold(III) complexes and their application studies in the fabrication of phosphorescent OLEDs. An in-depth understanding of the nature of the excited states has offered a great opportunity to fine-tune the emission colors covering the entire visible spectrum as well as to improve their photophysical properties. With good device engineering, high performance vacuum-deposited OLEDs with external quantum efficiencies (EQEs) of up to 30 % and solution-processable OLEDs with EQEs of up to 10 % have been realized by modifying the cyclometalated or pincer ligands of these metal complexes. These impressive demonstrations reveal that d(8) metal complexes are promising candidates as phosphorescent materials for OLED applications in displays as well as in solid-state lighting in the future. PMID:27573398

  8. Platinum metals in magmatic sulfide ores

    USGS Publications Warehouse

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

    1980-01-01

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

  9. Eribulin mesylate (halichondrin B Analog E7389) in platinum-resistant and platinum-sensitive ovarian cancer: a two-cohort, phase II study

    PubMed Central

    Hensley, Martee L.; Kravetz, Sara; Jia, Xiaoyu; Iasonos, Alexia; Tew, William; Pereira, Lauren; Sabbatini, Paul; Whalen, Christin; Aghajanian, Carol A.; Zarwan, Corinne; Berlin, Suzanne

    2011-01-01

    Background Eribulin mesylate is a tubulin inhibitor with activity superior to paclitaxel in NIH:OVCAR-3 human epithelial ovarian cancer xenograft models. We sought to assess the efficacy of eribulin in platinum-resistant and platinum-sensitive recurrent ovarian cancer. Methods Patients with recurrent measurable epithelial ovarian cancer, ≤2 prior cytotoxic regimens, and adequate organ function were enrolled into two separate cohorts: 1) Platinum resistant (progression-free interval from last platinum-based therapy <6 months); and 2) Platinum sensitive (progression-free interval from last platinum-based therapy ≥6 months). Treatment: Eribulin 1.4 mg/m2 over 15 minutes by vein on days 1 and 8, every 21 days. Efficacy was determined by objective response by computed tomography. Results Platinum-resistant cohort: Thirty-seven patients enrolled. Thirty-six patients were evaluable for response and toxicity. Two patients achieved partial response (PR, 5.5%). Sixteen (44%) had a best response of stable disease. Median progression-free survival was 1.8 months (95% confidence interval, 1.4–2.8 months). Platinum-sensitive cohort: Thirty-seven patients enrolled, and all were evaluable for response. Seven patients achieved partial response (PR, 19%). Median progression-free survival was 4.1 months (95% confidence interval, 2.8–5.8 months). The major toxicity was grade 3 or 4 neutropenia (42% in platinum-resistant patients; 54% in platinum-sensitive patients). Conclusions Eribulin achieved objective response in 5.5% of women with platinum-resistant recurrent ovarian cancer and in 19% of women with platinum-sensitive disease. Median progression-free survival was 1.8 months in the platinum-resistant group and 4.1 months in the platinum-sensitive group. PMID:21935916

  10. Vibrational Recognition of Adsorption Sites for CO on Platinum and Platinum-Ruthenium Surfaces.

    SciTech Connect

    Dabo, Ismaila; Wieckowski, Andrzei; Marzari, Nicola N.

    2007-09-01

    The research described in this product was performed in part in the Environmental Molecular Sciences Laboratory, a national scientific user facility sponsored by the Department of Energy's Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory. We have studied the vibrational properties of CO adsorbed on platinum and platinum-ruthenium surfaces using density-functional perturbation theory within the Perdew-Burke-Ernzerhof generalizedgradient approximation. The calculated C-O stretching frequencies are found to be in excellent agreement with spectroscopic measurements. The frequency shifts that take place when the surface is covered with ruthenium monolayers are also correctly predicted. This agreement for both shifts and absolute vibrational frequencies is made more remarkable by the frequent failure of local and semilocal exchange-correlation functionals in predicting the stability of the different adsorption sites for CO on transition metal surfaces. We have investigated the chemical origin of the C-O frequency shifts introducing an orbital-resolved analysis of the force and frequency density of states, and assessed the effect of donation and backdonation on the CO vibrational frequency using a GGA + molecular U approach. These findings rationalize and establish the accuracy of density-functional calculations in predicting absolute vibrational frequencies, notwithstanding the failure in determining relative adsorption energies, in the strong chemisorption regime.

  11. Characterization of Platinum and Iridium Oxyhydrate Surface Layers from Platinum and Iridium Foils.

    PubMed

    Johnson, Benjamin; Ranjan, Chinmoy; Greiner, Mark; Arrigo, Rosa; Schuster, Manfred Erwin; Höpfner, Britta; Gorgoi, Mihaela; Lauermann, Iver; Willinger, Marc; Knop-Gericke, Axel; Schlögl, Robert

    2016-07-01

    Platinum and iridium polycrystalline foils were oxidized electrochemically through anodization to create thin platinum and iridium hydrous oxide layers, which were analyzed through laboratory photoelectron spectroscopy during heating and time series (temperature-programmed spectroscopy). The films contain oxygen in the form of bound oxides, water, and hydroxides and were investigated by depth profiling with high-energy photoelectron spectroscopy. The Pt films are unstable and begin to degrade immediately after removal from the electrolyte to form core-shell structures with a metallic inner core and a hydrous oxide outer shell almost devoid of Pt. However, evidence was found for metastable intermediate states of degradation; therefore, it may be possible to manufacture PtOx phases with increased stability. Heating the film to even 100 °C causes accelerated degradation, which shows that stoichiometric oxides such as PtO2 or PtO are not the active species in the electrolyte. The Ir films exhibit increased stability and higher surface Ir content, and gentle heating at low temperatures leads to a decrease in defect density. Although both layers are based on noble metals, their surface structures are markedly different. The complexity of such hydrous oxide systems is discussed in detail with the goal of identifying the film composition more precisely. PMID:27226255

  12. BOWIEITE: A NEW RHODIUM-IRIDIUM-PLATINUM SULFIDE IN PLATINUM-ALLOY NUGGETS, GOODNEWS BAY, ALASKA.

    USGS Publications Warehouse

    Desborough, George A.; Criddle, Alan J.

    1984-01-01

    Bowieite (Rh,Ir,Pt)//2S//3, a new mineral species, is found in three nuggets of platinum from Goodnews Bay, Alaska. In linearly polarized reflected light, and compared to the host, higher reflecting white platinum-iridium alloy, bowieite is pale gray to pale gray-brown; neither bireflectance nor reflectance pleochroism is apparent. With polars crossed, its anisotropic rotation tints vary from gray to dark brown. Luminance values (relative to the CIE illuminant C) for R//1 and R//2, computed from full spectral data for the most bireflectant grain, are 45. 8% and 48. 2% in air, and 30. 5% and 33. 0% in oil, respectively. VHN//1//0//0 1288 (858 to 1635). Bowieite is orthorhombic, space group Pnca, with a 8. 454(7) -8. 473(8), b 5. 995(1)-6. 002(7), c 6. 143(1)-6. 121(8) A, Z equals 4. Some grains that are 2. 6 to 3. 8 atomic % metal-deficient occur as an optically coherent rim on bowieite; the rim and the bowieite grain are not optically continuous.

  13. Platinum in the environment: frequency of reactions to platinum-group elements in patients with dermatitis and urticaria.

    PubMed

    Santucci, B; Valenzano, C; de Rocco, M; Cristaudo, A

    2000-12-01

    The aim of the present paper is to evaluate whether increasing environmental exposure increases the frequency of the positive prick and patch test reactions to certain chlorinated platinum salts in patients with dermatitis and urticaria. 800 consecutive subjects with contact dermatitis (n=749) and urticaria (n=51) were variously patch and prick tested with 30 haptens of a standard series, with aqueous solutions of, respectively, hexachloroplatinic acid (H2[PtCl6]), potassium tetrachloroplatinate (K2[PtCl4]), sodium hexachloroplatinate (Na2[PtCl6]), iridium chloride (IrCl3), rhodium chloride (RhCl3) and palladium chloride (PdCl2), and with 16 common inhalants. 153 workers, variably exposed in a platinum refinery, were patch and prick tested only with solutions containing platinum-group elements at various concentrations and with 16 common inhalants. Platinum-group elements did not elicit positive patch or prick test reactions in non-occupationally exposed subjects. In contrast, in exposed workers, positive patch test reactions at day 2 and at 25 min, respectively, were found in 2 subjects with hand dermatitis and in 2 with urticaria and asthma. 22 out of the 153 workers, 18 of whom had rhinitis, asthma, and urticaria, gave positive prick test reactions to 1 or more salts. Furthermore, on patch and prick testing, 4 cross-reactions between platinum, palladium, iridium and rhodium were demonstrated. In conclusion, the test results demonstrate that the present concentration in the environment does not increase the incidence of reactions to platinum salts in patients with dermatitis and/or urticaria. However, if the average level of environmental platinum exposure approaches those existing in industrial settings in the future, we are going to observe more frequent health effects. PMID:11140383

  14. Smoking and occupational allergy in workers in a platinum refinery.

    PubMed Central

    Venables, K. M.; Dally, M. B.; Nunn, A. J.; Stevens, J. F.; Stephens, R.; Farrer, N.; Hunter, J. V.; Stewart, M.; Hughes, E. G.; Newman Taylor, A. J.

    1989-01-01

    OBJECTIVE--To test the hypothesis that smoking increases the risk of sensitisation by occupational allergens. DESIGN--Historical prospective cohort study. SETTING--Platinum refinery. SUBJECTS--91 Workers (86 men) who started work between 1 January 1973 and 31 December 1974 and whose smoking habit and atopic state (on skin prick testing with common allergens) had been noted at joining. MAIN OUTCOME MEASURES--Results of skin prick tests with platinum salts carried out routinely every three to six months and records of any respiratory symptoms noted by the refinery's occupational health service. Follow up was until 1980 or until leaving refinery work, whichever was earlier. RESULTS--57 Workers smoked and 29 were atopic; 22 developed a positive result on skin testing with platinum salts and 49 developed symptoms, including all 22 whose skin test result was positive. Smoking was the only significant predictor of a positive result on skin testing with platinum salts and its effect was greater than that of atopy; the estimated relative risks (95% confidence interval) when both were included in the regression model were: smokers versus non-smokers 5.05 (1.68 to 15.2) and atopic versus non-atopic 2.29 (0.88 to 5.99). Number of cigarettes smoked per day was the only significant predictor of respiratory symptoms. CONCLUSION--Smokers are at increased risk of sensitisation by platinum salts. PMID:2508944

  15. Structures of 38-atom gold-platinum nanoalloy clusters

    SciTech Connect

    Ong, Yee Pin; Yoon, Tiem Leong; Lim, Thong Leng

    2015-04-24

    Bimetallic nanoclusters, such as gold-platinum nanoclusters, are nanomaterials promising wide range of applications. We perform a numerical study of 38-atom gold-platinum nanoalloy clusters, Au{sub n}Pt{sub 38−n} (0 ≤ n ≤ 38), to elucidate the geometrical structures of these clusters. The lowest-energy structures of these bimetallic nanoclusters at the semi-empirical level are obtained via a global-minimum search algorithm known as parallel tempering multi-canonical basin hopping plus genetic algorithm (PTMBHGA), in which empirical Gupta many-body potential is used to describe the inter-atomic interactions among the constituent atoms. The structures of gold-platinum nanoalloy clusters are predicted to be core-shell segregated nanoclusters. Gold atoms are observed to preferentially occupy the surface of the clusters, while platinum atoms tend to occupy the core due to the slightly smaller atomic radius of platinum as compared to gold’s. The evolution of the geometrical structure of 38-atom Au-Pt clusters displays striking similarity with that of 38-atom Au-Cu nanoalloy clusters as reported in the literature.

  16. Oxidation Reaction Induced Structural Changes in Sub-Nanometer Platinum Supported on Alumina

    DOE PAGESBeta

    DeBusk, Melanie Moses; Allard, Jr, Lawrence Frederick; Blom, Douglas Allen; Narula, Chaitanya Kumar

    2015-01-01

    Platinum supported on alumina is an essential component of emission treatment catalysts used in transportation. Theoretical, experimental, and mechanistic aspects of platinum particles supported on a variety of supports have been extensively studied; however, available experimental information on the behavior of single vs. sub-nanometer platinum is extremely limited. To bridge the knowledge gap between single supported platinum and well-formed supported platinum nanoparticles, we have carried out synthesis, characterization, and CO and NO oxidation studies of sub-nanometer platinum supported on α, θ, and γ-Al2O3 and monitored changes in structure upon exposure to CO and NO oxidation conditions. We find that sub-nanometermore » Pt is highly effective for CO oxidation due to high platinum dispersion but is not very efficient as NO oxidation catalyst. Furthermore, sub-nanometer platinum agglomerates rapidly under CO or NO oxidation conditions to form nanoparticles.« less

  17. Oxidation-induced structural changes in sub-nanometer platinum supported on alumina

    SciTech Connect

    DeBusk, Melanie Moses; Allard, Jr, Lawrence Frederick; Blom, Douglas Allen; Narula, Chaitanya Kumar

    2015-06-26

    Platinum supported on alumina is an essential component of emission treatment catalysts used in transportation. Theoretical, experimental, and mechanistic aspects of platinum particles supported on a variety of supports have been extensively studied; however, available experimental information on the behavior of single vs. sub-nanometer platinum is extremely limited. To bridge the knowledge gap between single supported platinum and well-formed supported platinum nanoparticles, we have carried out synthesis, characterization, and CO and NO oxidation studies of sub-nanometer platinum supported on α, θ, and γ-Al2O3 and monitored changes in structure upon exposure to CO and NO oxidation conditions. Furthermore, we find that sub-nanometer Pt is highly effective for CO oxidation due to high platinum dispersion but is not very efficient as NO oxidation catalyst. Lastly, sub-nanometer platinum agglomerates rapidly under CO or NO oxidation conditions to form nanoparticles.

  18. Oxidation-induced structural changes in sub-nanometer platinum supported on alumina

    DOE PAGESBeta

    DeBusk, Melanie Moses; Allard, Jr, Lawrence Frederick; Blom, Douglas Allen; Narula, Chaitanya Kumar

    2015-06-26

    Platinum supported on alumina is an essential component of emission treatment catalysts used in transportation. Theoretical, experimental, and mechanistic aspects of platinum particles supported on a variety of supports have been extensively studied; however, available experimental information on the behavior of single vs. sub-nanometer platinum is extremely limited. To bridge the knowledge gap between single supported platinum and well-formed supported platinum nanoparticles, we have carried out synthesis, characterization, and CO and NO oxidation studies of sub-nanometer platinum supported on α, θ, and γ-Al2O3 and monitored changes in structure upon exposure to CO and NO oxidation conditions. Furthermore, we find thatmore » sub-nanometer Pt is highly effective for CO oxidation due to high platinum dispersion but is not very efficient as NO oxidation catalyst. Lastly, sub-nanometer platinum agglomerates rapidly under CO or NO oxidation conditions to form nanoparticles.« less

  19. PLATINUM HEXAFLUORIDE AND METHOD OF FLUORINATING PLUTONIUM CONTAINING MIXTURES THERE-WITH

    DOEpatents

    Malm, J.G.; Weinstock, B.; Claassen, H.H.

    1959-07-01

    The preparation of platinum hexafluoride and its use as a fluorinating agent in a process for separating plutonium from fission products is presented. According to the invention, platinum is reacted with fluorine gas at from 900 to 1100 deg C to form platinum hexafluoride. The platinum hexafluoride is then contacted with the plutonium containing mixture at room temperature to form plutonium hexafluoride which is more volatile than the fission products fluorides and therefore can be isolated by distillation.

  20. On the system cerium-platinum-silicon

    SciTech Connect

    Gribanov, Alexander Grytsiv, Andriy; Royanian, Esmaeil; Rogl, Peter; Bauer, Ernst; Giester, Gerald; Seropegin, Yurii

    2008-11-15

    Phase relations in the ternary system Ce-Pt-Si have been established for the isothermal section at 800 deg. C based on X-ray powder diffraction, metallography, scanning electron microscopy (SEM) and electron probe microanalysis (EPMA) techniques on about 120 alloys, which were prepared by various methods employing arc-melting under argon or powder reaction sintering. Nineteen ternary compounds were observed. Atom order in the crystal structures of {tau}{sub 18}-Ce{sub 5}(Pt,Si){sub 4} (Pnma; a=0.77223(3) nm, b=1.53279(8) nm c=0.80054(5) nm), {tau}{sub 3}-Ce{sub 2}Pt{sub 7}Si{sub 4} (Pnma; a=1.96335(8) nm, b=0.40361(4) nm, c=1.12240(6) nm) and {tau}{sub 10}-CePtSi{sub 2} (Cmcm; a=0.42943(2) nm, b=1.67357(5) nm, c=0.42372(2) nm) was determined by direct methods from X-ray single-crystal CCD data and found to be isotypic with the Sm{sub 5}Ge{sub 4}-type, the Ce{sub 2}Pt{sub 7}Ge{sub 4}-type and the CeNiSi{sub 2}-type, respectively. Rietveld refinements established the atom arrangement in the structures of Pt{sub 3}Si (Pt{sub 3}Ge-type, C2/m, a=0.7724(2) nm, b=0.7767(2) nm, c=0.5390(2) nm, {beta}=133.86(2){sup o}), {tau}{sub 16}-Ce{sub 3}Pt{sub 5}Si (Ce{sub 3}Pd{sub 5}Si-type, Imma, a=0.74025(8) nm, b=1.2951(2) nm, c=0.7508(1) nm) and {tau}{sub 17}-Ce{sub 3}PtSi{sub 3} (Ba{sub 3}Al{sub 2}Ge{sub 2}-type, Immm, a=0.41065(5) nm, b=0.43221(5) nm, c=1.8375(3) nm). Phase equilibria in Ce-Pt-Si are characterised by the absence of cerium solubility in platinum silicides. Cerium silicides and cerium platinides, however, dissolve significant amounts of the third component, whereby random substitution of the almost equally sized atom species platinum and silicon is reflected in extended homogeneous regions at constant Ce content such as for {tau}{sub 13}-Ce(Pt{sub x}Si{sub 1-x}){sub 2}, {tau}{sub 6}-Ce{sub 2}Pt{sub 3+x}Si{sub 5-x} or {tau}{sub 7}-CePt{sub 2-x}Si{sub 2+x}. - Graphical abstract: Phase relations in the ternary system Ce-Pt-Si have been established for the isothermal

  1. Atomic engineering of platinum alloy surfaces.

    PubMed

    Li, Tong; Bagot, P A J; Marquis, E A; Edman Tsang, S C; Smith, G D W

    2013-09-01

    A major practical challenge in heterogeneous catalysis is to minimize the loading of expensive platinum group metals (PGMs) without degrading the overall catalytic efficiency. Gaining a thorough atomic-scale understanding of the chemical/structural changes occurring during catalyst manufacture/operation could potentially enable the design and production of "nano-engineered" catalysts, optimized for cost, stability and performance. In the present study, the oxidation behavior of a Pt-31 at% Pd alloy between 673-1073 K is investigated using atom probe tomography (APT). Over this range of temperatures, three markedly different chemical structures are observed near the surface of the alloy. At 673 K, the surface oxide formed is enriched with Pd, the concentration of which rises further following oxidation at 773 K. During oxidation at 873 K, a thick, stable oxide layer is formed on the surface with a stoichiometry of PdO, beneath which a Pd-depleted (Pt-rich) layer exists. Above 873 K, the surface composition switches to enrichment in Pt, with the Pt content increasing further with increasing oxidation temperature. This treatment suggests a route for tuning the surfaces of Pt-Pd nanoparticles to be either Pd-rich or Pt-rich, simply by adjusting the oxidation temperatures in order to form two different types of core-shell structures. In addition, comparison of the oxidation behavior of Pt-Pd with Pt-Rh and Pd-Rh alloys demonstrates markedly different trends under the same conditions for these three binary alloys. PMID:23276526

  2. Transport Magnetic Proximity Effects in Platinum

    NASA Astrophysics Data System (ADS)

    Huang, Ssu-Yen

    2013-03-01

    Platinum (Pt) metal, being non-magnetic and having a strong spin-orbit coupling interaction, has been central in detecting pure spin current and establishing most of the recent spin-based phenomena. Thus, it is important to ascertain the transport and magnetic characteristics of thin Pt films in contact with a ferromagnet. In this work, we use both electric and thermal means to conclusively show the transport magnetic proximity effects (MPE) of thin Pt film in contact with ferromagnetic insulator YIG. At thicknesses comparable to, and less than, the spin diffusion length, the strong ferromagnetic characteristics in Pt films on YIG are indistinguishable from those of ferromagnetic permalloy on YIG. The MPE occurs at the interface and decreases exponentially away from the interface, concentrating in only a few monolayers. As a result, the pure spin current detected by a thin Pt is tainted with a spin polarized current. The pure spin current phenomena, such as the inverse spin Hall effect and the spin Seebeck effect, have been contaminated with the anomalous Hall effect and the anomalous Nernst effect respectively. These results raise serious questions about the suitability, and the validity, of using Pt in establishing pure spin current phenomena; on the other hand, a much stronger spin-based effect can be induced by the MPE at the interface. This research is in collaboration with X. Fin, Y. P. Chen, J. Wu, and J. Q. Xiao (University of Delaware), T. Y. Chen (Arizona State University) and D. Qu, W. G. Wang, and C. L. Chien (The Johns Hopkins University).

  3. Design of experimentation with a platinum-magnesium bioelectric battery.

    PubMed

    Fontenier, G; Freschard, R; Mourot, M

    1975-01-01

    The utilization of metal electrodes in the fabrication of a bioelectric battery has been the subject of intensive study for several years. Up to this date, subcutaneous cathodes of black platinum or of silver-silver chloride have been used in conjunction with anodes of aluminum or zinc. The subcutaneous black platinum is not reliable as a function of time due to the growth of overlying heterogeneous tissues. The utilization of a smooth platinum cathode in the right endoauricular position allows good reliability with time, but does not allow using a large surface area. Furthermore we have a reduction of the H-+ ions and not of the oxygen. A pure Domal magnesium anode was utilized with this cathode, which seemed to be a good compromise between to battery's voltage, its lifetime, and its lack of toxicity to body tissues. PMID:1139023

  4. Dissolution of Platinum in the Operational Range of Fuel Cells

    PubMed Central

    Keeley, Gareth P.; Geiger, Simon; Zeradjanin, Aleksandar R.; Hodnik, Nejc; Kulyk, Nadiia

    2015-01-01

    Abstract One of the most important practical issues in low‐temperature fuel‐cell catalyst degradation is platinum dissolution. According to the literature, it initiates at 0.6–0.9 VRHE, whereas previous time‐ and potential‐resolved inductively coupled plasma mass spectrometry (ICP–MS) experiments, however, revealed dissolution onset at only 1.05 VRHE. In this manuscript, the apparent discrepancy is addressed by investigating bulk and nanoparticulated catalysts. It is shown that, given enough time for accumulation, traces of platinum can be detected at potentials as low as 0.85 VRHE. At these low potentials, anodic dissolution is the dominant process, whereas, at more positive potentials, more platinum dissolves during the oxide reduction after accumulation. Interestingly, the potential and time dissolution dependence is similar for both types of electrode. Dissolution processes are discussed with relevance to fuel‐cell operation and plausible dissolution mechanisms are considered. PMID:27525206

  5. Sum frequency generation imaging microscopy of CO on platinum.

    PubMed

    Cimatu, Katherine; Baldelli, Steven

    2006-12-20

    Sum frequency vibrational spectroscopy is utilized as an imaging technique to distinguish and compare the local response of carbon monoxide (CO) covered platinum (Pt) polycrystalline surface versus the average response of the investigated area. The Pt electrode was prepared using the standard method and was exposed to approximately 1 atm of CO(g). SFG images and vibrational spectra were obtained where the contrast is based on the intrinsic nature of each peak in the CO vibrational spectrum. The illustration of the images and the chemical maps of CO on the platinum surface showed the distribution of the CO across the observed area. The results obtained by comparing the local and the average response confirmed the spatial distributions of the CO on the platinum sample which are due to several reasons such as dipole-dipole coupling and surface coverage. This finding has a significant contribution toward recognizing that surfaces usually considered homogeneous may in fact be quite heterogeneous. PMID:17165737

  6. One-dimensional Magnus-type platinum double salts

    PubMed Central

    Hendon, Christopher H.; Walsh, Aron; Akiyama, Norinobu; Konno, Yosuke; Kajiwara, Takashi; Ito, Tasuku; Kitagawa, Hiroshi; Sakai, Ken

    2016-01-01

    Interest in platinum-chain complexes arose from their unusual oxidation states and physical properties. Despite their compositional diversity, isolation of crystalline chains has remained challenging. Here we report a simple crystallization technique that yields a series of dimer-based 1D platinum chains. The colour of the Pt2+ compounds can be switched between yellow, orange and blue. Spontaneous oxidation in air is used to form black Pt2.33+ needles. The loss of one electron per double salt results in a metallic state, as supported by quantum chemical calculations, and displays conductivity of 11 S cm−1 at room temperature. This behaviour may open up a new avenue for controllable platinum chemistry. PMID:27320502

  7. Electron Field Emission Properties of Textured Platinum Surfaces

    NASA Technical Reports Server (NTRS)

    Sovey, James S.

    2002-01-01

    During ground tests of electric microthrusters and space tests of electrodynamic tethers the electron emitters must successfully operate at environmental pressures possibly as high as 1x10(exp -4) Pa. High partial pressures of oxygen, nitrogen, and water vapor are expected in such environments. A textured platinum surface was used in this work for field emission cathode assessments because platinum does not form oxide films at low temperatures. Although a reproducible cathode conditioning process did not evolve from this work, some short term tests for periods of 1 to 4 hours showed no degradation of emission current at an electric field of 8 V/mm and background pressures of about 1x10(exp -6) Pa. Increases of background pressure by air flow to about 3x10(exp -4) Pa yield a hostile environment for the textured platinum field emission cathode.

  8. One-dimensional Magnus-type platinum double salts.

    PubMed

    Hendon, Christopher H; Walsh, Aron; Akiyama, Norinobu; Konno, Yosuke; Kajiwara, Takashi; Ito, Tasuku; Kitagawa, Hiroshi; Sakai, Ken

    2016-01-01

    Interest in platinum-chain complexes arose from their unusual oxidation states and physical properties. Despite their compositional diversity, isolation of crystalline chains has remained challenging. Here we report a simple crystallization technique that yields a series of dimer-based 1D platinum chains. The colour of the Pt(2+) compounds can be switched between yellow, orange and blue. Spontaneous oxidation in air is used to form black Pt(2.33+) needles. The loss of one electron per double salt results in a metallic state, as supported by quantum chemical calculations, and displays conductivity of 11 S cm(-1) at room temperature. This behaviour may open up a new avenue for controllable platinum chemistry. PMID:27320502

  9. 40 CFR 440.110 - Applicability; description of the platinum ore subcategory.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... platinum ore subcategory. 440.110 Section 440.110 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) EFFLUENT GUIDELINES AND STANDARDS ORE MINING AND DRESSING POINT SOURCE CATEGORY Platinum Ores Subcategory § 440.110 Applicability; description of the platinum ore subcategory. The provisions of...

  10. 40 CFR 440.110 - Applicability; description of the platinum ore subcategory.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... platinum ore subcategory. 440.110 Section 440.110 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) EFFLUENT GUIDELINES AND STANDARDS (CONTINUED) ORE MINING AND DRESSING POINT SOURCE CATEGORY Platinum Ores Subcategory § 440.110 Applicability; description of the platinum ore subcategory....

  11. 40 CFR 440.110 - Applicability; description of the platinum ore subcategory.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... platinum ore subcategory. 440.110 Section 440.110 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) EFFLUENT GUIDELINES AND STANDARDS (CONTINUED) ORE MINING AND DRESSING POINT SOURCE CATEGORY Platinum Ores Subcategory § 440.110 Applicability; description of the platinum ore subcategory....

  12. 40 CFR 440.110 - Applicability; description of the platinum ore subcategory.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... platinum ore subcategory. 440.110 Section 440.110 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) EFFLUENT GUIDELINES AND STANDARDS ORE MINING AND DRESSING POINT SOURCE CATEGORY Platinum Ores Subcategory § 440.110 Applicability; description of the platinum ore subcategory. The provisions of...

  13. 40 CFR 440.110 - Applicability; description of the platinum ore subcategory.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... platinum ore subcategory. 440.110 Section 440.110 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) EFFLUENT GUIDELINES AND STANDARDS (CONTINUED) ORE MINING AND DRESSING POINT SOURCE CATEGORY Platinum Ores Subcategory § 440.110 Applicability; description of the platinum ore subcategory....

  14. DETERMINATION OF HUMAN BODY BURDEN BASELINE DATA OF PLATINUM THROUGH AUTOPSY TISSUE ANALYSIS

    EPA Science Inventory

    Results of analysis for platinum in 97 autopsy sets are presented. Analysis was performed by a specially developed emission spectrochemical method. Almost half of the individuals studied were found to have detectable platinum in one or more tissue samples. Platinum was found to b...

  15. The effects of platinum on nickel electrodes in the nickel hydrogen cell

    NASA Technical Reports Server (NTRS)

    Zimmerman, Albert H.

    1991-01-01

    Interactions of platinum and platinum compounds with the nickel electrode that are possible in the nickel hydrogen cell, where both the nickel electrode and a platinum catalyst hydrogen electrode are in intimate contact with the alkaline electrolyte, are examined. Additionally, a mechanism of nickel cobalt oxyhydroxide formation in NiH2 cells is presented.

  16. Water-soluble platinum phthalocyanines as potential antitumor agents.

    PubMed

    Bologna, Giuseppina; Lanuti, Paola; D'Ambrosio, Primiano; Tonucci, Lucia; Pierdomenico, Laura; D'Emilio, Carlo; Celli, Nicola; Marchisio, Marco; d'Alessandro, Nicola; Santavenere, Eugenio; Bressan, Mario; Miscia, Sebastiano

    2014-06-01

    Breast cancer represents the second cause of death in the European female population. The lack of specific therapies together with its high invasive potential are the major problems associated to such a tumor. In the last three decades platinum-based drugs have been considered essential constituents of many therapeutic strategies, even though with side effects and frequent generation of drug resistance. These drugs have been the guide for the research, in last years, of novel platinum and ruthenium based compounds, able to overcome these limitations. In this work, ruthenium and platinum based phthalocyanines were synthesized through conventional techniques and their antiproliferative and/or cytotoxic actions were tested. Normal mammary gland (MCF10A) and several models of mammarian carcinoma at different degrees of invasiveness (BT474, MCF-7 and MDA-MB-231) were used. Cells were treated with different concentrations (5-100 μM) of the above reported compounds, to evaluate toxic concentration and to underline possible dose-response effects. The study included growth curves made by trypan blue exclusion test and scratch assay to study cellular motility and its possible negative modulation by phthalocyanine. Moreover, we investigated cell cycle and apoptosis through flow cytometry and AMNIS Image Stream cytometer. Among all the tested drugs, tetrasulfonated phthalocyanine of platinum resulted to be the molecule with the best cytostatic action on neoplastic cell lines at the concentration of 30 μM. Interestingly, platinum tetrasulfophtalocyanine, at low doses, had no antiproliferative effects on normal cells. Therefore, such platinum complex, appears to be a promising drug for mammarian carcinoma treatment. PMID:24699848

  17. Rhenium-osmium and samarium-neodymium isotopic systematics of the Stillwater complex

    NASA Technical Reports Server (NTRS)

    Lambert, David D.; Shirey, Steven B.; Carlson, Richard W.; Morgan, John W.; Walker, Richard J.

    1989-01-01

    The role of magma mixing in the formation of strategic platinum-group element ore deposits is examined using isotopic data from the Stillwater Complex, Montana. Nd and Os isotopic data show that the intrusion formed from at least two distinct magmas: ultramafic (U-type) affinity magmas and anorthositic (A-type) affinity magmas. The U-type magmas formed from a lithospheric mantle source containing recycled crustal materials and the A-type magmas originated either by crustal contamination of basaltic magmas or by partial melting of basalt in the lower crust. The results also suggest that the platinum-group element ore deposits were derived from A-type magmas which were injected into the U-type magma chamber at several stages during the development of the ultramafic series.

  18. Synthesis of platinum nanoparticle electrocatalysts by atomic layer deposition

    NASA Astrophysics Data System (ADS)

    Lubers, Alia Marie

    Demand for energy continues to increase, and without alternatives to fossil fuel combustion the effects on our environment will become increasingly severe. Fuel cells offer a promising improvement on current methods of energy generation; they are able to convert hydrogen fuel into electricity with a theoretical efficiency of up to 83% and interface smoothly with renewable hydrogen production. Fuel cells can replace internal combustion engines in vehicles and are used in stationary applications to power homes and businesses. The efficiency of a fuel cell is maximized by its catalyst, which is often composed of platinum nanoparticles supported on carbon. Economical production of fuel cell catalysts will promote adoption of this technology. Atomic layer deposition (ALD) is a possible method for producing catalysts at a large scale when employed in a fluidized bed. ALD relies on sequential dosing of gas-phase precursors to grow a material layer by layer. We have synthesized platinum nanoparticles on a carbon particle support (Pt/C) by ALD for use in proton exchange membrane fuel cells (PEMFCs) and electrochemical hydrogen pumps. Platinum nanoparticles with different characteristics were deposited by changing two chemistries: the carbon substrate through functionalization; and the deposition process by use of either oxygen or hydrogen as ligand removing reactants. The metal depositing reactant was trimethyl(methylcyclopentadienyl)platinum(IV). Functionalizing the carbon substrate increased nucleation during deposition resulting in smaller and more dispersed nanoparticles. Use of hydrogen produced smaller nanoparticles than oxygen, due to a gentler hydrogenation reaction compared to using oxygen's destructive combustion reaction. Synthesized Pt/C materials were used as catalysts in an electrochemical hydrogen pump, a device used to separate hydrogen fuel from contaminants. Catalysts deposited by ALD on functionalized carbon using a hydrogen chemistry were the most

  19. Temperature dependence of the emissivity of platinum in the IR.

    PubMed

    Deemyad, Shanti; Silvera, Isaac F

    2008-08-01

    The accuracy of temperature determination by fitting the spectral irradiance to a Planck curve depends on knowledge of the emissivity at all temperatures and pressures of interest within a spectral region. Here, the emissivity of platinum is measured in the near infrared as a function of temperature. In the wavelength range of study and the temperature range of 650-1100 K, we find the emissivity to be independent of temperature to within experimental error. This result should lead to improved accuracy of temperature measurement by optical pyrometry where platinum is used as a thermal emitter. PMID:19044386

  20. Determination of palladium and platinum by atomic absorption

    USGS Publications Warehouse

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

    1969-01-01

    Palladium and platinum are determined by atomic absorption after fire-assay concentration into a gold bead. The limit of determination is ~0??06 ppm in a 20-g sample. Serious depressive interelement interferences are removed by buffering the solutions with a mixture of cadmium and copper sulphates with cadmium and copper concentrations each at 0??5%. Substantial amounts of Ag, Al, Au, Bi, Ca, Co, Cr, Fe, Hg, K, La, Mg, Mn, Mo, Na, Ni, Pb, Te, Ti, V, Y, Zn, and the platinum metals do not interfere in the atomic-absorption determination. ?? 1969.

  1. Amphiphilic Cyanine-Platinum Conjugates as Fluorescent Nanodrugs.

    PubMed

    Sun, Tingting; Li, Zhensheng; Xie, Zhigang; Jing, Xiabin

    2016-01-01

    Two fluorescent nanomedicines based on small molecular cyanine-platinum conjugates have been prepared via a nanoprecipitation method and characterized by transmission electron microscopy (TEM) as well as dynamic light scattering (DLS). The conjugates exhibited an enhanced fluorescence in their nanoparticle formulation compared to that in solution. The nanomedicines could be endocytosed by cancer cells as revealed by confocal laser scanning microscopy (CLSM) and showed high cellular proliferation inhibition. Fluorescent platinum nanomedicines prepared directly from small molecules could be an alternative strategy for developing new drugs with simultaneous cellular imaging and cancer therapy functions. PMID:26556434

  2. Evidence for an ancient osmium isotopic reservoir in Earth.

    PubMed

    Meibom, Anders; Frei, Robert

    2002-04-19

    Iridosmine grains from placer deposits associated with peridotite-bearing ophiolites in the Klamath mountains have extremely radiogenic 186Os/188Os ratios and old Re-Os minimum ages, from 256 to 2644 million years. This indicates the existence of an ancient platinum group element reservoir with a supra-chondritic Pt/Os ratio. Such a ratio may be produced in the outer core as a result of inner core crystallization that fractionates Os from Pt. However, if the iridosmine Os isotopic compositions are a signature of the outer core, then the inner core must have formed very early, within several hundred million years after the accretion of Earth. PMID:11964475

  3. 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

  4. Microwave spectroscopy of platinum monofluoride and platinum monochloride in the X 2Π(3/2) states.

    PubMed

    Okabayashi, Toshiaki; Kurahara, Taku; Okabayashi, Emi Y; Tanimoto, Mitsutoshi

    2012-05-01

    Platinum monofluoride (PtF) and platinum monochloride (PtCl) were detected in the gas phase using a source-modulated microwave spectrometer. The PtF and PtCl radicals were generated in a free space cell using the sputtering reaction from a platinum sheet placed on the inner surface of a stainless steel cathode through a dc glow discharge plasma of CF(4) and Cl(2), respectively, diluted with Ar. Rotational transitions were measured in the region between 150 and 313 GHz. Rotational, centrifugal distortion, and several fine- and hyperfine-structure constants were determined by a least-squares analysis. The observed fine-structure spectral patterns indicate that both PtF and PtCl radicals have the (2)Π(3/2) electronic ground states, while the related cyanide PtCN and hydride PtH radicals have the (2)Δ(5/2) electronic ground states. PMID:22583234

  5. Recent strikes in South Africa’s platinum-group metal mines: effects upon world platinum-group metal supplies

    USGS Publications Warehouse

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

    2012-01-01

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

  6. Optimization of carbon-supported platinum cathode catalysts for DMFC operation.

    SciTech Connect

    Zhu, Y.; Brosha, E. L.; Zelenay, P.

    2002-01-01

    In this paper, we describe performance and optimization of carbon-supported cathode catalysts at low platinum loading. We find that at a loading below 0.6 mg cm-2 carbon-supported platinum outperforms platinum black as a DMFC cathode catalyst. A catalyst with a 1:1 volume ratio of the dry NafionTM to the electronically conducting phase (platinum plus carbon support) provides the best performance in oxygen reduction reaction. Thanks to improved catalyst utilization, carbon-supported catalysts with a platinum content varying from 40 wt% to 80 wt% deliver very good DMFC performance, even at relatively modest precious metal loadings investigated in this work.

  7. Method for separating isotopes

    DOEpatents

    Jepson, B.E.

    1975-10-21

    Isotopes are separated by contacting a feed solution containing the isotopes with a cyclic polyether wherein a complex of one isotope is formed with the cyclic polyether, the cyclic polyether complex is extracted from the feed solution, and the isotope is thereafter separated from the cyclic polyether.

  8. Stable isotope studies

    SciTech Connect

    Ishida, T.

    1992-01-01

    The research has been in four general areas: (1) correlation of isotope effects with molecular forces and molecular structures, (2) correlation of zero-point energy and its isotope effects with molecular structure and molecular forces, (3) vapor pressure isotope effects, and (4) fractionation of stable isotopes. 73 refs, 38 figs, 29 tabs.

  9. Hydrogen isotope separation by catalyzed exchange between hydrogen and liquid water

    SciTech Connect

    Butler, J.P.

    1980-04-01

    The discovery, at Chalk River Nuclear Laboratories, of a simple method of wetproofing platinum catalysts so that they retain their activity in liquid water stimulated a concentrated research program for the development of catalysts for the hydrogen-water isotopic exchange reaction. This paper reviews 10 years of study which have resulted in the development of highly active platinum catalysts which remain effective in water for periods greater than a year. The most efficient way to use these catalysts for the separation of hydrogen isotopes is in a trickle bed reactor which effects a continuous separation. The catalyst is packed in a column with hydrogen and water flowing countercurrently through the bed. The overall isotope transfer rate measured for the exchange reaction is influenced by various parameters, such as hydrogen and water flow rates, temperature, hydrogen pressure, and platinum metal loading. The effect of these parameters as well as the improved performance obtained by diluting the hydrophobic catalyst with inert hydrophilic packing are discussed. The hydrophobic catalysts can be effectively used in a variety of applications of particular interest in the nuclear industry. A Combined Electrolysis Catalytic Exchange - Heavy Water Process (CECE-HWP) is being developed at Chalk River with the ultimate aim of producing parasitic heavy water from electrolytic hydrogen streams. Other more immediate applications include the final enrichment of heavy water and the extraction of tritium from light and heavy water. Pilot plant studies on these latter processes are currently in progress.

  10. Oxalato-platinum or 1-OHP, a third-generation platinum complex: an experimental and clinical appraisal and preliminary comparison with cis-platinum and carboplatinum.

    PubMed

    Mathé, G; Kidani, Y; Segiguchi, M; Eriguchi, M; Fredj, G; Peytavin, G; Misset, J L; Brienza, S; de Vassals, F; Chenu, E

    1989-01-01

    A new platinum complex, oxalatoplatin or l-OHP, which, at the same metal dose in experimental tests is as efficient as cisplatin, and is more so at a lower metal dose than carboplatin; which is as efficient in human tumors of the testis and ovary as these other analogs, and more so in melanoma and breast cancer; which is not nephrotoxic, cardiotoxic or mutagenic, and hardly hematotoxic and neurotoxic, is described and compared with the above-mentioned platinum complexes. Combined with 5Fu, it induces a high number of remissions in colorectal cancer, and has brought about cures in inoperable gastric cancers. Combined with carboplatin, it has resulted in a high proportion of cures in L1210-carrying mice, which no other two-by-two combination of these complexes has achieved. PMID:2675999

  11. Biological role in the transformation of platinum-group mineral grains

    NASA Astrophysics Data System (ADS)

    Reith, Frank; Zammit, Carla M.; Shar, Sahar S.; Etschmann, Barbara; Bottrill, Ralph; Southam, Gordon; Ta, Christine; Kilburn, Matthew; Oberthür, Thomas; Ball, Andrew S.; Brugger, Joël

    2016-04-01

    Platinum-group elements are strategically important metals. Finding new deposits is becoming increasingly difficult owing to our limited understanding of the processes that affect their mobility in surface environments. Microorganisms have been shown to promote the mobility of metals around ore deposits. Here we show that microorganisms influence the mobility of platinum-group elements in mineral grains collected from Brazil, Australia and Colombia. Scanning electron microscopy showed biofilms covering the platinum-group mineral grains. The biofilms contained abundant platinum-group element nanoparticles and microcrystalline aggregates, and were dominated by Proteobacteria, many of which were closely related to known metal-resistant species. Some platinum-group mineral grains contained carbon, nitrogen, sulfur, selenium and iodine, suggesting the grains may be biogenic in origin. Molecular analyses show that Brazilian platinum-palladium grains hosted specific bacterial communities, which were different in composition from communities associated with gold grains, or communities in surrounding soils and sediments. Nano-phase metallic platinum accumulated when a metallophillic bacterium was incubated with a percolating platinum-containing medium, suggesting that biofilms can cause the precipitation of mobile platinum complexes. We conclude that biofilms are capable of forming or transforming platinum-group mineral grains, and may play an important role for platinum-group element dispersion and re-concentration in surface environments.

  12. Density Functional Study of the Structure, Stability and Oxygen Reduction Activity of Ultrathin Platinum Nanowires

    SciTech Connect

    Matanovic, Ivana; Kent, Paul; Garzon, Fernando; Henson, Neil J.

    2013-03-14

    We used density functional theory to study the difference in the structure, stability and catalytic reactivity between ultrathin, 0.5–1.0 nm diameter, platinum nanotubes and nanowires. Model nanowires were formed by inserting an inner chain of platinum atoms in small diameter nanotubes. In this way more stable, non-hollow structures were formed. The difference in the electronic structure of platinum nanotubes and nanowires was examined by inspecting the density of surface states and band structure. Furthermore, reactivity toward the oxygen reduction reaction of platinum nanowires was assessed by studying the change in the chemisorption energies of oxygen, hydroxyl, and hydroperoxyl groups, induced by converting the nanotube models to nanowires. Both ultrathin platinum nanotubes and nanowires show distinct properties compared to bulk platinum. Single-wall nanotubes and platinum nanowires with diameters larger than 1 nm show promise for use as oxygen reduction catalysts.

  13. Synthesis, Characterization, and Catalytic Properties of Novel Single-Site and Nanosized Platinum Catalysts

    SciTech Connect

    Bonati, Matteo L.M.; Douglas, Thomas M.; Gaemers, Sander; Guo, Neng

    2013-01-10

    Novel single-site platinum catalysts have been synthesized by reacting platinum(II) organometallics with partially dehydroxylated silica. The resulting materials have been characterized by various methods such as IR, MAS NMR, and EXAFS. Further, the single-site platinum catalysts were calcined in air to remove the ligand and produce nanosized platinum particles, that were characterized by TEM and H{sub 2} chemisorption. All catalysts were tested for the hydrogenation of toluene. The single-site platinum catalysts were less active than a commercial Pt/SiO{sub 2} catalyst with comparable platinum loading, and this has been ascribed to ligand effects. Conversely, the nanosized platinum catalysts were more active than the commercial Pt/SiO{sub 2} catalyst due to their high dispersion and small particle sizes.

  14. Theoretical Study of the Structure, Stability and Oxygen Reduction Activity of Ultrathin Platinum Nanowires

    SciTech Connect

    Matanovic, Ivana; Kent, Paul; Garzon, Fernando; Henson, Neil J.

    2012-10-10

    We use density functional theory to study the difference in the structure, stability and catalytic reactivity between ultrathin, 0.5- 1.0 nm diameter, platinum nanotubes and nanowires. Model nanowires were formed by inserting an inner chain of platinum atoms in small diameter nanotubes. In this way more stable, nonhollow structures were formed. The difference in the electronic structure of platinum nanotubes and nanowires was examined by inspecting the density of surface states and band structure. Furthermore, reactivity towards the oxygen reduction reaction of platinum nanowires was addressed by studying the change in the chemisorption energies of oxygen and hydroxyl groups, induced by inserting the inner chain of platinum atoms into the hollow nanotubes. Both ultrathin platinum nanotubes and nanowires show distinct properties compared to bulk platinum. Nanotubes with diameters larger than 1 nm show promise for use as oxygen reduction catalysts.

  15. Single-Atom Catalyst of Platinum Supported on Titanium Nitride for Selective Electrochemical Reactions.

    PubMed

    Yang, Sungeun; Kim, Jiwhan; Tak, Young Joo; Soon, Aloysius; Lee, Hyunjoo

    2016-02-01

    As a catalyst, single-atom platinum may provide an ideal structure for platinum minimization. Herein, a single-atom catalyst of platinum supported on titanium nitride nanoparticles were successfully prepared with the aid of chlorine ligands. Unlike platinum nanoparticles, the single-atom active sites predominantly produced hydrogen peroxide in the electrochemical oxygen reduction with the highest mass activity reported so far. The electrocatalytic oxidation of small organic molecules, such as formic acid and methanol, also exhibited unique selectivity on the single-atom platinum catalyst. A lack of platinum ensemble sites changed the reaction pathway for the oxygen-reduction reaction toward a two-electron pathway and formic acid oxidation toward direct dehydrogenation, and also induced no activity for the methanol oxidation. This work demonstrates that single-atom platinum can be an efficient electrocatalyst with high mass activity and unique selectivity. PMID:26710326

  16. Enhancement of Platinum Cathode Catalysis by Addition of Transition Metals

    ERIC Educational Resources Information Center

    Duong, Hung Tuan

    2009-01-01

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

  17. Responses of fibroblasts and glial cells to nanostructured platinum surfaces

    NASA Astrophysics Data System (ADS)

    Pennisi, C. P.; Sevcencu, C.; Dolatshahi-Pirouz, A.; Foss, M.; Lundsgaard Hansen, J.; Nylandsted Larsen, A.; Zachar, V.; Besenbacher, F.; Yoshida, K.

    2009-09-01

    The chronic performance of implantable neural prostheses is affected by the growth of encapsulation tissue onto the stimulation electrodes. Encapsulation is associated with activation of connective tissue cells at the electrode's metallic contacts, usually made of platinum. Since surface nanotopography can modulate the cellular responses to materials, the aim of the present work was to evaluate the 'in vitro' responses of connective tissue cells to platinum strictly by modulating its surface nanoroughness. Using molecular beam epitaxy combined with sputtering, we produced platinum nanostructured substrates consisting of irregularly distributed nanopyramids and investigated their effect on the proliferation, cytoskeletal organization and cellular morphology of primary fibroblasts and transformed glial cells. Cells were cultured on these substrates and their responses to surface roughness were studied. After one day in culture, the fibroblasts were more elongated and their cytoskeleton less mature when cultured on rough substrates. This effect increased as the roughness of the surface increased and was associated with reduced cell proliferation throughout the observation period (4 days). Morphological changes also occurred in glial cells, but they were triggered by a different roughness scale and did not affect cellular proliferation. In conclusion, surface nanotopography modulates the responses of fibroblasts and glial cells to platinum, which may be an important factor in optimizing the tissue response to implanted neural electrodes.

  18. Operation of platinum-palladium catalysts with leaded gasoline.

    PubMed Central

    Teague, D M; Clougherty, L B; Speca, A N

    1975-01-01

    The effect of various fuel additives on the ability of platinum-palladium catalytic converters to remove the carbon monoxide and hydrocarbon components of automotive exhaust has been examined. Engine dynamometer studies suggest that these catalysts may be successfully used in conjunction with fuels of relatively high tetraethyllead concentrations, provided the ethylene dibromide portion of the scavenger is excluded. PMID:50929

  19. Operation of platinum-palladium catalysts with leaded gasoline.

    PubMed

    Teague, D M; Clougherty, L B; Speca, A N

    1975-04-01

    The effect of various fuel additives on the ability of platinum-palladium catalytic converters to remove the carbon monoxide and hydrocarbon components of automotive exhaust has been examined. Engine dynamometer studies suggest that these catalysts may be successfully used in conjunction with fuels of relatively high tetraethyllead concentrations, provided the ethylene dibromide portion of the scavenger is excluded. PMID:50929

  20. Do platinum salts fit all triple negative breast cancers?

    PubMed

    Gerratana, L; Fanotto, V; Pelizzari, G; Agostinetto, E; Puglisi, F

    2016-07-01

    Triple-negative breast cancer (TNBC) is an aggressive disease with limited treatment options and poor prognosis once metastatic. Pre-clinical and clinical data suggest that TNBC could be more sensitive to platinum-based chemotherapy, especially among BRCA1/2-mutated patients. In recent years, several randomised trials have been conducted to evaluate platinum efficacy in both early-stage and advanced TNBC, with conflicting results especially for long-term outcomes. Experimental studies are now focusing on identifying biomarkers of response to help selecting patients who may benefit most from platinum-based therapies, including BRCA1/2 mutational status and genomic instability signatures (such as HRD-LOH or HRD-LST scores). A standard therapy for TNBC is still missing and platinum-based regimens represent an emerging therapeutic option for selected patients with a defect in the homologous recombination repair system. The identification of these patients through validated biomarker assays will be crucial to optimize the use of currently approved agents in TNBC. PMID:27343437

  1. Rapid epitaxy-free graphene synthesis on silicidated polycrystalline platinum

    PubMed Central

    Babenko, Vitaliy; Murdock, Adrian T.; Koós, Antal A.; Britton, Jude; Crossley, Alison; Holdway, Philip; Moffat, Jonathan; Huang, Jian; Alexander-Webber, Jack A.; Nicholas, Robin J.; Grobert, Nicole

    2015-01-01

    Large-area synthesis of high-quality graphene by chemical vapour deposition on metallic substrates requires polishing or substrate grain enlargement followed by a lengthy growth period. Here we demonstrate a novel substrate processing method for facile synthesis of mm-sized, single-crystal graphene by coating polycrystalline platinum foils with a silicon-containing film. The film reacts with platinum on heating, resulting in the formation of a liquid platinum silicide layer that screens the platinum lattice and fills topographic defects. This reduces the dependence on the surface properties of the catalytic substrate, improving the crystallinity, uniformity and size of graphene domains. At elevated temperatures growth rates of more than an order of magnitude higher (120 μm min−1) than typically reported are achieved, allowing savings in costs for consumable materials, energy and time. This generic technique paves the way for using a whole new range of eutectic substrates for the large-area synthesis of 2D materials. PMID:26175062

  2. Molybdenum-platinum-oxide electrodes for thermoelectric generators

    DOEpatents

    Schmatz, Duane J.

    1990-01-01

    The invention is directed to a composite article suitable for use in thermoelectric generators. The article comprises a solid electrolyte carrying a thin film comprising molybdenum-platinum-oxide as an electrode deposited by physical deposition techniques. The invention is also directed to the method of making same.

  3. Article having an improved platinum-aluminum-hafnium protective coating

    NASA Technical Reports Server (NTRS)

    Nagaraj, Bangalore Aswatha (Inventor); Williams, Jeffrey Lawrence (Inventor)

    2005-01-01

    An article protected by a protective coating has a substrate and a protective coating having an outer layer deposited upon the substrate surface and a diffusion zone formed by interdiffusion of the outer layer and the substrate. The protective coating includes platinum, aluminum, no more than about 2 weight percent hafnium, and substantially no silicon. The outer layer is substantially a single phase.

  4. Acute and chronic nephrotoxicity of platinum nanoparticles in mice

    NASA Astrophysics Data System (ADS)

    Yamagishi, Yoshiaki; Watari, Akihiro; Hayata, Yuya; Li, Xiangru; Kondoh, Masuo; Yoshioka, Yasuo; Tsutsumi, Yasuo; Yagi, Kiyohito

    2013-09-01

    Platinum nanoparticles are being utilized in various industrial applications, including in catalysis, cosmetics, and dietary supplements. Although reducing the size of the nanoparticles improves the physicochemical properties and provides useful performance characteristics, the safety of the material remains a major concern. The aim of the present study was to evaluate the biological effects of platinum particles less than 1 nm in size (snPt1). In mice administered with a single intravenous dose of snPt1, histological analysis revealed necrosis of tubular epithelial cells and urinary casts in the kidney, without obvious toxic effects in the lung, spleen, and heart. These mice exhibited dose-dependent elevation of blood urea nitrogen, an indicator of kidney damage. Direct application of snPt1 to in vitro cultures of renal cells induced significant cytotoxicity. In mice administered for 4 weeks with twice-weekly intraperitoneal snPt1, histological analysis of the kidney revealed urinary casts, tubular atrophy, and inflammatory cell accumulation. Notably, these toxic effects were not observed in mice injected with 8-nm platinum particles, either by single- or multiple-dose administration. Our findings suggest that exposure to platinum particles of less than 1 nm in size may induce nephrotoxicity and disrupt some kidney functions. However, this toxicity may be reduced by increasing the nanoparticle size.

  5. Platinum Recovery from Synthetic Extreme Environments by Halophilic Bacteria.

    PubMed

    Maes, Synthia; Props, Ruben; Fitts, Jeffrey P; Smet, Rebecca De; Vilchez-Vargas, Ramiro; Vital, Marius; Pieper, Dietmar H; Vanhaecke, Frank; Boon, Nico; Hennebel, Tom

    2016-03-01

    Metal recycling based on urban mining needs to be established to tackle the increasing supply risk of critical metals such as platinum. Presently, efficient strategies are missing for the recovery of platinum from diluted industrial process streams, often characterized by extremely low pHs and high salt concentrations. In this research, halophilic mixed cultures were employed for the biological recovery of platinum (Pt). Halophilic bacteria were enriched from Artemia cysts, living in salt lakes, in different salt matrices (sea salt mixture and NH4Cl; 20-210 g L(-1) salts) and at low to neutral pH (pH 3-7). The main taxonomic families present in the halophilic cultures were Halomonadaceae, Bacillaceae, and Idiomarinaceae. The halophilic cultures were able to recover >98% Pt(II) and >97% Pt(IV) at pH 2 within 3-21 h (4-453 mg Ptrecovered h(-1) g(-1) biomass). X-ray absorption spectroscopy confirmed the reduction to Pt(0) and transmission electron microscopy revealed both intra- and extracellular Pt precipitates, with median diameters of 9-30 nm and 11-13 nm, for Pt(II) and Pt(IV), respectively. Flow cytometric membrane integrity staining demonstrated the preservation of cell viability during platinum recovery. This study demonstrates the Pt recovery potential of halophilic mixed cultures in acidic saline conditions. PMID:26854514

  6. Concentration of some platinum-group metals in coal

    USGS Publications Warehouse

    Finkelman, R.B.; Aruscavage, P. J.

    1981-01-01

    New data on some platinum group metals in coal indicate that the concentration of Pt is generally less than about 5 ppb, that of Pd is generally less than 1 ppb, and that of Rh is generally less than 0.5 ppb. No conclusive evidence was obtained concerning the mode of occurrence of these elements in coal. ?? 1981.

  7. Chitosan sorbents for platinum sorption from dilute solutions

    SciTech Connect

    Guibal, E.; Larkin, A.; Vincent, T.; Tobin, J.M.

    1999-10-01

    Chitosan has proved efficient at removing platinum in dilute effluents. The maximum uptake capacity reaches 300 mg/g (almost 1.5 mmol/g). The optimum pH for sorption is pH 2. A glutaraldehyde cross-linking pretreatment is necessary to stabilize the biopolymer in acidic solutions. Sorption isotherms have been studied as a function of pH, sorbent particle size, and the cross-linking ratio. Surprisingly, the extent of the cross-linking (determined by the concentration of the cross-linking agent in the treatment bath) has no significant influence on uptake capacity. Competitor anions such as chloride or nitrate induce a large decrease in the sorption efficiency. Sorption kinetics show also that uptake rate is not significantly changed by increasing either the cross-linking ratio or the particle size of the sorbent. Mass transfer rates are significantly affected by the initial platinum concentration and by the conditioning of the biopolymer. Gel-bead conditioning appears to reduce the sorption rate. While for molybdate and vanadate ions, mass transfer was governed by intraparticle mass transfer, for platinum, both external and intraparticle diffusion control the uptake rate. In contrast with the former ions, platinum does not form polynuclear hydrolyzed species, which are responsible for steric hindrance of diffusion into the polymer network.

  8. Platinum-group element systematics and petrogenetic processing of the continental upper mantle: A review

    NASA Astrophysics Data System (ADS)

    Lorand, Jean-Pierre; Luguet, Ambre; Alard, Olivier

    2013-04-01

    The platinum-group element (PGE) systematics of continental mantle peridotites show large variability, reflecting petrogenetic processing of the upper mantle during partial melting and melt/fluid percolation inside the lithosphere. By removing Pd-Cu-Ni rich sulfides, partial melting events that have stabilized the sub-continental mantle lithosphere fractionated PPGEs (Palladium-group PGE; Pt, Pd) relative to IPGEs (Iridium-group PGE; Os, Ir, Ru, Rh). Residual base-metal sulfides (BMS) survive as enclosed IPGE-enriched Monosulfide Solid Solutions (Mss), which otherwise decompose into Ru-Os-Ir-rich refractory platinum-group minerals (PGMs) once the partial melts become S-undersaturated. The small-scale heterogeneous distribution of these microphases may cause extreme nugget effects, as seen in the huge variations in absolute PGE concentrations documented in cratonic peridotites. Magmas fluxing through the lithospheric mantle may change the initial PGE budgets inherited from the melting events, resulting in the great diversity of PGE systematics seen in peridotites from the sub-continental lithosphere. For instance, melt-rock reactions at increasing melt/rock ratios operate as open-system melting processes removing residual BMS/PGMs. Highly percolated peridotites are characterized by extreme PGE depletion, coupled with PGE patterns and Os-isotope compositions that gradually evolve toward that of the percolating melt. Reactions at decreasing melt-rock ratios (usually referred to as «mantle metasomatism») precipitate PPGE-enriched BMS that yield suprachondritic Pd/Ir and occasionally affect Pt/Ir and Rh/Ir ratios as well. Moreover, volatile-rich, small volume melts fractionate Os relative to Ir and S relative to Se, thereby producing rocks with supra-chondritic Os/Ir and S/Se coupled with supra-chondritic Pd/Ir and Pt/Ir. Major magmatic inputs at the lithosphere-asthenosphere boundary may rejuvenate the PGE systematics of the depleted mantle. Integrated studies of

  9. Isotope separation by photochromatography

    DOEpatents

    Suslick, Kenneth S.

    1977-01-01

    An isotope separation method which comprises physically adsorbing an isotopically mixed molecular species on an adsorptive surface and irradiating the adsorbed molecules with radiation of a predetermined wavelength which will selectively excite a desired isotopic species. Sufficient energy is transferred to the excited molecules to desorb them from the surface and thereby separate them from the unexcited undesired isotopic species. The method is particularly applicable to the separation of hydrogen isotopes.

  10. Isotope separation by photochromatography

    DOEpatents

    Suslick, K.S.

    1975-10-03

    A photochromatographic method for isotope separation is described. An isotopically mixed molecular species is adsorbed on an adsorptive surface, and the adsorbed molecules are irradiated with radiation of a predetermined wavelength which will selectively excite desired isotopic species. Sufficient energy is transferred to the excited molecules to desorb them from the surface and thus separate them from the undesired isotopic species. The method is particularly applicable to the separation of hydrogen isotopes. (BLM)

  11. Allergy to complex platinum salts: A historical prospective cohort study.

    PubMed Central

    Niezborala, M; Garnier, R

    1996-01-01

    OBJECTIVE: To assess the incidence of allergy to complex platinum salts in a platinum refinery. METHODS: A historical prospective cohort study was carried out on 77 workers (67 men) who started work between 1 January 1979 and 31 December 1991 and who were not atopic on skin prick tests to three common allergens at the time of recruitment. Skin prick tests with complex platinum salts were carried out and diagnosis of allergy to complex platinum salts made by the company's doctor. Skin tests and medical examinations were carried out routinely every six months. Follow up was until 30 September 1992 or until leaving refinery work. RESULTS: 18 workers developed a positive result on skin tests and 23 developed symptoms, including all 18 subjects with positive skin tests; the probability of surviving (95% confidence interval (95% CI)) for 72 months after joining the company, with negative skin test results was 0.67 (0.51-0.79) or with no symptoms was 0.63 (0.49-0.75). The incidence of positive skin tests and symptoms was highest during the first two years of work. Symptoms occurred more frequently in September and October than during the other months of the year. The exclusion of atopic subjects did not seem to have resulted in a lower incidence of sensitisation. Smoking was a significant predictive factor for both positive skin tests (estimated relative risk 5.53) and symptoms (4.70). CONCLUSION: The findings confirm that smoking is and that atopy may not be a high risk factor for the development of allergy to complex platinum salts. The high incidence of sensitisation and the available data on the clinical course of sensitised workers show that sensitised workers must be promptly and completely removed from exposure. PMID:8664963

  12. Radiosensitization of EMT6 cells by four platinum complexes.

    PubMed

    Teicher, B A; Rockwell, S; Lee, J B

    1985-05-01

    The greatest research effort in producing radiation sensitizers has been directed toward organic compounds. However, platinum complexes also have radiosensitizing capabilities, perhaps because they bind to DNA. The compound described here are dichloro complexes of bivalent platinum with one or two potentially radiosensitizing ligands. The radiosensitization of oxygenated and hypoxic exponentially growing EMT6 cells in vitro was measured. The dose modifying factors obtained with 200 microM and 400 microM trans-bis(2-nitroimidazole)dichloroplatinum II (NIPt) in hypoxic cells were 1.5 and 2.1, respectively. For trans-bis(2-amino-5-nitrothiazole)dichloroplatinum II (Plant) under the same conditions, the dose modifying factor was 1.5 at 200 microM and 1.8 at 400 microM. Neither compound sensitized oxygenated cells when tested similar protocols. Unlike the trans complexes, (1,2-diamino-4-nitrobenzene)dichloroplatinum II (Plato) was cytotoxic toward the hypoxic cells in the absence of X rays. The time course of cytotoxicity for 100 microM Plato in exponentially growing cells showed rapid killing of hypoxic cells, and much less toxicity toward oxygenated cells. In radiosensitization studies, dose modifying factors of 1.6 and 2.0 were found with 200 microM and 400 microM Plato in hypoxic cells. The compound did not sensitize aerobic cells. The well-known platinum complex cis-dipyridinedichloroplatinum II (PyPt) represents a cis-platinum heterocyclic aromatic complex that does not have a nitro-functionality. The dose modifying factor obtained with 400 microM PyPt in hypoxic cells was 1.7. On a molar basis, the nitro-functional platinum complexes appear to be more effective as hypoxic cell radiosensitizers than the corresponding free ligands. PMID:4039304

  13. TISSUE ORGAN DISTRIBUTION AND BEHAVIORAL EFFECTS OF PLATINUM FOLLOWING ACUTE AND REPEATED EXPOSURE OF THE MOUSE TO PLATINUM SULFATE

    EPA Science Inventory

    Platinum sulfate was administered intragastrically (IG) to adult male Swiss mice in a single dose at the 7 day LD5 or LD25 level. Control groups received 0.25M H2SO4 (pH 0.85) or 0.14M NaCl. Open field behavior (ambulations, rearings) was measured, and tissue/organ Pt levels dete...

  14. Rapid biological synthesis of platinum nanoparticles using Ocimum sanctum for water electrolysis applications.

    PubMed

    Soundarrajan, C; Sankari, A; Dhandapani, P; Maruthamuthu, S; Ravichandran, S; Sozhan, G; Palaniswamy, N

    2012-06-01

    The leaf extract of Ocimum sanctum was used as a reducing agent for the synthesis of platinum nanoparticles from an aqueous chloroplatinic acid (H(2)PtCl(6)·6H(2)O). A greater conversion of platinum ions to nanoparticles was achieved by employing a tulsi leaf broth with a reaction temperature of 100 °C. Energy-dispersive absorption X-ray spectroscopy confirmed the platinum particles as major constituent in the reduction process. It is evident from scanning electron microscopy that the reduced platinum particles were found as aggregates with irregular shape. Fourier-transform infrared spectroscopy revealed that the compounds such as ascorbic acid, gallic acid, terpenoids, certain proteins and amino acids act as reducing agents for platinum ions reduction. X-ray diffraction spectroscopy suggested the associated forms of platinum with other molecules and the average particle size of platinum nanoparticle was 23 nm, calculated using Scherer equation. The reduced platinum showed similar hydrogen evolution potential and catalytic activity like pure platinum using linear scan voltammetry. This environmentally friendly method of biological platinum nanoparticles production increases the rates of synthesis faster which can potentially be used in water electrolysis applications. PMID:22167464

  15. Atom precise platinum-thiol crowns

    NASA Astrophysics Data System (ADS)

    George, Anu; Asha, K. S.; Reber, Arthur C.; Biltek, Scott R.; Pedicini, Anthony F.; Sen, Ayusman; Khanna, Shiv N.; Mandal, Sukhendu

    2015-11-01

    Ligand stabilized water soluble Pt nanoclusters were synthesized and characterized through electrospray ionization mass spectrometry. Glutathione was used as the ligand, and Pt5(SG)10, and Pt6(SG)12 clusters were synthesized. Theoretical investigations found that these clusters do not possess a metal core, but rather are most stable in a ring structure. The clusters are stabilized through the thiol ligands forming a square planar structure around each Pt atom to form a ring. The structural elucidation was confirmed through UV/Vis and IR spectroscopy.Ligand stabilized water soluble Pt nanoclusters were synthesized and characterized through electrospray ionization mass spectrometry. Glutathione was used as the ligand, and Pt5(SG)10, and Pt6(SG)12 clusters were synthesized. Theoretical investigations found that these clusters do not possess a metal core, but rather are most stable in a ring structure. The clusters are stabilized through the thiol ligands forming a square planar structure around each Pt atom to form a ring. The structural elucidation was confirmed through UV/Vis and IR spectroscopy. Electronic supplementary information (ESI) available: Photograph of the separation of the nanocluster using SEC. Isotopic distribution patterns of the nanocluster overlaid with the simulated one. EDX spectrum and the TEM image of the cluster, time dependent UV-vis spectra, TGA plot, IR spectrum and XPS spectrum and additional figures. See DOI: 10.1039/c5nr05325k

  16. Partitioning of Si and platinum group elements between liquid and solid Fe-Si alloys

    NASA Astrophysics Data System (ADS)

    Morard, G.; Siebert, J.; Badro, J.

    2014-05-01

    Crystallization of the Earth's inner core fractionates major and minor elements between the solid and liquid metal, leaving physical and geochemical imprints on the Earth's core. For example, the density jump observed at the Inner Core Boundary (ICB) is related to the preferential partitioning of lighter elements in the liquid outer core. The fractionation of Os, Re and Pt between liquid and solid during inner core crystallization has been invoked as a process that explains the observed Os isotopic signature of mantle plume-derived lavas (Brandon et al., 1998; Brandon and Walker, 2005) in terms of core-mantle interaction. In this article we measured partitioning of Si, Os, Re and Pt between liquid and solid metal. Isobaric (2 GPa) experiments were conducted in a piston-cylinder press at temperatures between 1250 °C and 1600 °C in which an imposed thermal gradient through the sample provided solid-liquid coexistence in the Fe-Si system. We determined the narrow melting loop in the Fe-Si system using Si partitioning values and showed that order-disorder transition in the Fe-Si solid phases can have a large effect on Si partitioning. We also found constant partition coefficients (DOs, DPt, DRe) between liquid and solid metal, for Si concentrations ranging from 2 to 12 wt%. The compact structure of Fe-Si liquid alloys is compatible with incorporation of Si and platinum group elements (PGEs) elements precluding solid-liquid fractionation. Such phase diagram properties are relevant for other light elements such as S and C at high pressure and is not consistent with inter-elemental fractionation of PGEs during metal crystallization at Earth's inner core conditions. We therefore propose that the peculiar Os isotopic signature observed in plume-derived lavas is more likely explained by mantle source heterogeneity (Meibom et al., 2002; Baker and Krogh Jensen, 2004; Luguet et al., 2008).

  17. Quantum Spin Fluctuations in Quasi-One-Dimensional Chlorine-Bridged Platinum Complexes

    SciTech Connect

    Wei, X.; Donohoe, R. J.; Wang, W. Z.; Bishop, A. R.; Gammel, J. T.

    1997-01-01

    We report experimental and theoretical studies of spin dynamic process in the quasi-one-dimensional chlorine-bridged platinum complex, [Pt{sup II}(en){sub 2}][Pt{sup IV}(en){sub 2}Cl{sub 2}](ClO{sub 4}){sub 4}, where en = ethylenediamine, C{sub 2}N{sub 2}H{sub 8}. The process manifests itself in collapsing of the hyperfine and superhyperfine structures in the electron spin resonance (ESR) spectrum and non-statistical distribution of spectral weight of the Pt isotopes. More surprisingly, it is activated only at temperatures below 6 K. We interpret the phenomenon in terms of quantum tunneling of the electronic spin in a strong electron-electron and electron-phonon coupling regime. This is modeled using a non-adiabatic many-body approach, in which polarons and solitons represent local spin-Peierls regions in a strongly disproportional charge-density-wave background and display intriguing spin-charge separation in the form of pinned charge and tunneling spin fluctuations. 24 refs., 5 figs., 1 tab.

  18. Caution on the use of liquid nitrogen traps in stable hydrogen isotope-ratio mass spectrometry.

    PubMed

    Coplen, Tyler B; Qi, Haiping

    2010-09-15

    An anomalous stable hydrogen isotopic fractionation of 4 ‰ in gaseous hydrogen has been correlated with the process of adding liquid nitrogen (LN(2)) to top off the dewar of a stainless-steel water trap on a gaseous hydrogen-water platinum equilibration system. Although the cause of this isotopic fractionation is unknown, its effect can be mitigated by (1) increasing the capacity of any dewars so that they do not need to be filled during a daily analytic run, (2) interspersing isotopic reference waters among unknowns, and (3) applying a linear drift correction and linear normalization to isotopic results with a program such as Laboratory Information Management System (LIMS) for Light Stable Isotopes. With adoption of the above guidelines, measurement uncertainty can be substantially improved. For example, the long-term (months to years) δ(2)H reproducibility (1σ standard deviation) of nine local isotopic reference waters analyzed daily improved substantially from about 1 ‰ to 0.58 ‰. This isotopically fractionating mechanism might affect other isotope-ratio mass spectrometers in which LN(2) is used as a moisture trap for gaseous hydrogen. PMID:20718408

  19. Caution on the use of liquid nitrogen traps in stable hydrogen isotope-ratio mass spectrometry

    USGS Publications Warehouse

    Coplen, T.B.; Qi, H.

    2010-01-01

    An anomalous stable hydrogen isotopic fractionation of 4 ??? in gaseous hydrogen has been correlated with the process of adding liquid nitrogen (LN2) to top off the dewar of a stainless-steel water trap on a gaseous hydrogen-water platinum equilibration system. Although the cause of this isotopic fractionation is unknown, its effect can be mitigated by (1) increasing the capacity of any dewars so that they do not need to be filled during a daily analytic run, (2) interspersing isotopic reference waters among unknowns, and (3) applying a linear drift correction and linear normalization to isotopic results with a program such as Laboratory Information Management System (LIMS) for Light Stable Isotopes. With adoption of the above guidelines, measurement uncertainty can be substantially improved. For example, the long-term (months to years) ??2H reproducibility (1?? standard deviation) of nine local isotopic reference waters analyzed daily improved substantially from about 1 ??? to 0.58 ???. This isotopically fractionating mechanism might affect other isotope-ratio mass spectrometers in which LN2 is used as a moisture trap for gaseous hydrogen. ?? This article not subject to U.S. Copyright. Published 2010 by the American Chemical Society.

  20. Caution on the use of liquid nitrogen traps in stable hydrogen isotope-ratio mass spectrometry

    USGS Publications Warehouse

    Coplen, Tyler B.; Qi, Haiping

    2010-01-01

    An anomalous stable hydrogen isotopic fractionation of 4 ‰ in gaseous hydrogen has been correlated with the process of adding liquid nitrogen (LN2) to top off the dewar of a stainless-steel water trap on a gaseous hydrogen-water platinum equilibration system. Although the cause of this isotopic fractionation is unknown, its effect can be mitigated by (1) increasing the capacity of any dewars so that they do not need to be filled during a daily analytic run, (2) interspersing isotopic reference waters among unknowns, and (3) applying a linear drift correction and linear normalization to isotopic results with a program such as Laboratory Information Management System (LIMS) for Light Stable Isotopes. With adoption of the above guidelines, measurement uncertainty can be substantially improved. For example, the long-term (months to years) δ2H reproducibility (1& sigma; standard deviation) of nine local isotopic reference waters analyzed daily improved substantially from about 1‰ to 0.58 ‰. This isotopically fractionating mechanism might affect other isotope-ratio mass spectrometers in which LN2 is used as a moisture trap for gaseous hydrogen

  1. Quantitative bioimaging of platinum group elements in tumor spheroids.

    PubMed

    Niehoff, Ann-Christin; Grünebaum, Jonas; Moosmann, Aline; Mulac, Dennis; Söbbing, Judith; Niehaus, Rebecca; Buchholz, Rebecca; Kröger, Sabrina; Wiehe, Arno; Wagner, Sylvia; Sperling, Michael; von Briesen, Hagen; Langer, Klaus; Karst, Uwe

    2016-09-28

    Limited drug penetration into tumor tissue is a significant factor to the effectiveness of cancer therapy. Tumor spheroids, a 3D cell culture model system, can be used to study drug penetration for pharmaceutical development. In this study, a method for quantitative bioimaging of platinum group elements by laser ablation (LA) coupled to inductively coupled plasma mass spectrometry (ICP-MS) is presented. Different matrix-matched standards were used to develop a quantitative LA-ICP-MS method with high spatial resolution. To investigate drug penetration, tumor spheroids were incubated with platinum complexes (Pt(II)acetylacetonate, cisplatin) and the palladium tagged photosensitizer 5,10,15,20-tetrakis(3-hydroxyphenyl)porphyrin (mTHPP). Distribution and accumulation of the pharmaceuticals were determined with the developed method. PMID:27619092

  2. Nanostructured gold and platinum electrodes on silicon structures for biosensing

    NASA Astrophysics Data System (ADS)

    Ogurtsov, V. I.; Sheehan, M. M.

    2005-01-01

    Gold and platinum metal electrodes on Si/SiO2 having undergone anisotropic potassium hydroxide (KOH) etch treatment are considered. This treatment etches at different rates and directions in the material resulting in creation of numerous pyramid shaped holes in the silicon substrate. This surface is used to make metal electrodes with increased electrode efficiency. The electrodes can serve as the sensors or as the sensor substrates (for surface polymer modification) and because both gold and platinum are inert they have applications for food safety biosensing. Wine, an economically significant food product, was chosen as a matrix, and impedance spectroscopy (EIS) was selected as a method of investigation of electrode behaviour. Based on results of EIS, different complexity equivalent circuits were determined by applying fitting mean square root optimisation of sensor complex impedance measurements.

  3. SNMS investigations of platinum-doped nanogranular tin dioxide layers

    NASA Astrophysics Data System (ADS)

    Schneider, T.; Sommer, M.; Goschnick, J.

    2005-09-01

    Thin platinum-doped nanogranular SnO 2 layers are examined because of its high gas sensitivity and fast gas response to be applied in gas sensor microarrays. The nanogranular metal oxide layers were prepared from a colloidal dispersion using spin coating on silicon substrates. Field emission scanning electron microscopy (FE-SEM) investigations showed quite homogeneous layers of 20 nm particles, containing a few holes of some micron width, probably due to bubbles introduced into the layer during wet deposition. Depth resolved analysis with secondary neutral mass spectrometry (SNMS) was employed to characterize the elemental content and depth distribution of the 20 nm particle layers. A platinum content of approx. 1 at.%, homogeneously spread throughout the particles was found, as well as carbon and chlorine residues of a few atomic percent enriched at the surface of the particles.

  4. Platinum(IV)-chlorotoxin (CTX) conjugates for targeting cancer cells.

    PubMed

    Graf, Nora; Mokhtari, Tara E; Papayannopoulos, Ioannis A; Lippard, Stephen J

    2012-05-01

    Cisplatin is one of the most widely used anticancer drugs. Its side effects, however, have motivated researchers to search for equally effective analogs that are better tolerated. Selectively targeting cancer tissue is one promising strategy. For this purpose, a platinum(IV) complex was conjugated to the cancer-targeting peptide chlorotoxin (CTX, TM601) in order to deliver cisplatin selectively to cancer cells. The 1:1 Pt-CTX conjugate was characterized by mass spectrometry and gel electrophoresis. Like most platinum(IV) derivatives, the cytotoxicity of the conjugate was lower in cell culture than that of cisplatin, but greater than those of its Pt(IV) precursor and CTX in several cancer cell lines. PMID:22465700

  5. Extremely fast hydrogen absorption/desorption through platinum overlayers

    NASA Astrophysics Data System (ADS)

    Połczyński, Piotr; Jurczakowski, Rafał

    2016-02-01

    The hydrogen electrosorption in thin palladium films (50-1000 nm) was investigated at palladium electrodes covered with platinum overlayers. The results for this model system show that the rates of the hydrogen sorption/desorption are orders of magnitude higher for platinized samples with respect to pure palladium. The highest absorption kinetics have been observed for Pd electrodes fully covered with 1-3 platinum monolayers. By means of electrochemical impedance spectroscopy (EIS) we have shown that the process is diffusion limited at platinized Pd layers. Diffusion coefficient, DH, determined in EIS, is two orders of magnitude higher than that previously reported for thin palladium films and approaches DH for bulk palladium. The system stability after hydrogen absorption was assessed and the sorption mechanism was discussed. Surprisingly high durability of the platinized palladium enables its use in a variety of applications where fast and selective response in the presence of hydrogen is required.

  6. International strategic minerals inventory summary report: platinum-group metals

    USGS Publications Warehouse

    Sutphin, David M.; Page, Norman J

    1986-01-01

    Major world resources of platinum-group metals are described in this summary report of information in the International Strategic Minerals Inventory {ISMI}. ISMI is a cooperative data-collection effort of earth-science and mineral-resource agencies in Australia, Canada, the Federal Republic of Germany, the Republic of South Africa, and the United States of America. This report, designed to be of benefit to policy analysts, contains two parts. Part I presents an overview of the resources and potential supply of platinum-group metals on the basis of inventory information. Part II contains tables of some of the geologic information and mineral-resource and production data that were collected by ISMI participants.

  7. Joining lead wires to thin platinum alloy films

    NASA Technical Reports Server (NTRS)

    Przybyszewski, J. S.; Claing, R. G. (Inventor)

    1983-01-01

    A two step process of joining a lead wire to .000002 m thick platinum alloy film which rests upon an equally thin alumina insulating layer which is adhered to a metal substrate is described. Typically the platinum alloy film forms part of a thermocouple for measuring the surface temperature of a gas turbine airfoil. In the first step the lead wire is deformed 30 to 60% at room temperature while the characteristic one million ohm resistance of the alumina insulating layer is monitored for degradation. In the second step the cold pressed assembly is heated at 865 to 1025 C for 4 to 75 hr in air. During the heating step any degradation of insulating layer resistance may be reversed, provided the resistance was not decreased below 100 ohm in the cold pressing.

  8. Platinum nanoparticle decorated silicon nanowires for efficient solar energy conversion.

    PubMed

    Peng, Kui-Qing; Wang, Xin; Wu, Xiao-Ling; Lee, Shuit-Tong

    2009-11-01

    High-density aligned n-type silicon nanowire (SiNW) arrays decorated with discrete 5-10 nm platinum nanoparticles (PtNPs) have been fabricated by aqueous electroless Si etching followed by an electroless platinum deposition process. Coating of PtNPs on SiNW sidewalls yielded a substantial enhancement in photoconversion efficiency and an apparent energy conversion efficiency of up to 8.14% for the PtNP-decorated SiNW-based photoelectrochemical solar cell using a liquid electrolyte containing Br(-)/Br(2) redox couple. The results demonstrate PtNP-decorated SiNWs to be a promising hybrid system for solar energy conversion. PMID:19807069

  9. High low-temperature CO oxidation activity of platinum oxide prepared by magnetron sputtering

    NASA Astrophysics Data System (ADS)

    Johánek, V.; Václavů, M.; Matolínová, I.; Khalakhan, I.; Haviar, S.; Matolín, V.

    2015-08-01

    CO oxidation on platinum oxide deposited by magnetron sputtering on flat (Si) and highly porous (multi-walled carbon nanotubes, MWCNT) substrates were examined using X-ray photoelectron spectroscopy, scanning tunneling microscopy, temperature-programmed desorption and temperature-programmed reaction in both UHV and ambient pressure conditions. Platinum in the freshly deposited thin film is present entirely in the 4+ oxidation state. The intrinsic CO oxidation capability of such catalyst proved to be significantly higher under approx. 480 K than that of pure platinum, presumably due to the interplay between metallic and cationic platinum entities, and the reaction yield can be further enhanced by increasing effective surface area when MWCNT is used as a support. The thermo-chemical stability of the platinum oxide, however, has its limitations as the thin film can be gradually thermally reduced to metallic platinum (with small residuum of stable Pt2+ species) and this process is further facilitated in the presence of reducing CO atmosphere.

  10. METHOD OF ISOTOPE CONCENTRATION

    DOEpatents

    Spevack, J.S.

    1957-04-01

    An isotope concentration process is described which consists of exchanging, at two or more different temperature stages, two isotopes of an element between substances that are physically separate from each other and each of which is capable of containing either of the isotopes, and withdrawing from a point between at least two of the temperatare stages one of the substances containing an increased concentration of the desired isotope.

  11. Radiosensitization of EMT6 cells by four platinum complexes

    SciTech Connect

    Teicher, B.A.; Rockwell, S.; Lee, J.B.

    1985-05-01

    The compounds described here are dichloro complexes of bivalent platinum with one or two potentially radiosensitizing ligands. The radiosensitization of oxygenated and hypoxic exponentially growing EMT6 cells in vitro was measured. The dose modifying factors obtained with 200 ..mu..M and 400 ..mu..M trans-bis(2-nitroimidazole)dichloroplatinum II (NIPt) in hypoxic cells were 1.5 and 2.1, respectively. For trans-bis(2-amino-5-nitrothiazole)dichloroplatinum II (Plant) under the same conditions, the dose modifying factor was 1.5 at 200 ..mu..M and 1.8 at 400 ..mu..M. Neither compound sensitized oxygenated cells when tested similar protocols. Unlike the trans complexes (1,2-diamino-4-nitrobenzene)dichloroplatinum II (Plato) was cytotoxic toward the hypoxic cells in the absence of X rays. The time course of cytotoxicity for 100 ..mu..M Plato in exponentially growing cells showed rapid killing of hypoxic cells, and much less toxicity toward oxygenated cells. In radiosensitization studies, dose modifying factors of 1.6 and 2.0 were found with 200 ..mu..M and 400 ..mu..M Plato in hypoxic cells. The compound did not sensitize aerobic cells. The well-known platinum complex cis-dipyridinedichloroplatinum II (PyPt) represents a cis-platinum heterocyclic aromatic complex that does not have a nitro-functionality. The dose modifying factor obtained with 400 ..mu..M PyPt in hypoxic cells was 1.7. On a molar basis, the nitro-functional platinum complexes appear to be more effective as hypoxic cell radiosensitizers than the corresponding free ligands.

  12. Platinum(II) complexes as spectroscopic probes for biomolecules

    SciTech Connect

    Ratilla, E.

    1990-09-21

    The use of platinum(II) complexes as tags and probes for biomolecules is indeed advantageous for their reactivities can be selective for certain purposes through an interplay of mild reaction conditions and of the ligands bound to the platinum. The use of {sup 195}Pt NMR as a method of detecting platinum and its interactions with biomolecules was carried out with the simplest model of platinum(II) tagging to proteins. Variable-temperature {sup 195}Pt NMR spectroscopy proved useful in studying the stereodynamics of complex thioethers like methionine. The complex, Pt(trpy)Cl{sup +}, with its chromophore has a greater potential for probing proteins. It is a noninvasive and selective tag for histidine and cysteine residues on the surface of cytochrome c at pH 5. The protein derivatives obtained are separable, and the tags are easily quantitated and differentiated through the metal-to-ligand charge transfer bands which are sensitive to the environment of the tag. Increasing the pH to 7.0 led to the modification by Pt(trpy)Cl{sup +}of Arg 91 in cytochrome c. Further studies with guanidine-containing ligands as models for arginine modification by Pt(trpy)Cl{sup +} showed that guanidine can act as a terminal ligand and as a bridging ligand. Owing to the potential utility of Pt(trpy)L{sup n+} as electron dense probes of nucleic acid structure, interactions of this bis-Pt(trpy){sup 2+} complex with nucleic acids was evaluated. Indeed, the complex interacts non-covalently with nucleic acids. Its interactions with DNA are not exactly the same as those of its precedents. Most striking is its ability to form highly immobile bands of DNA upon gel electrophoresis. 232 refs.

  13. Double-Stranded Water on Stepped Platinum Surfaces

    NASA Astrophysics Data System (ADS)

    Kolb, Manuel J.; Farber, Rachael G.; Derouin, Jonathan; Badan, Cansin; Calle-Vallejo, Federico; Juurlink, Ludo B. F.; Killelea, Daniel R.; Koper, Marc T. M.

    2016-04-01

    The interaction of platinum with water plays a key role in (electro)catalysis. Herein, we describe a combined theoretical and experimental study that resolves the preferred adsorption structure of water wetting the Pt(111)-step type with adjacent (111) terraces. Double stranded lines wet the step edge forming water tetragons with dissimilar hydrogen bonds within and between the lines. Our results qualitatively explain experimental observations of water desorption and impact our thinking of solvation at the Pt electrochemical interface.

  14. Photochemistry and charge transfer chemistry of the platinum group elements

    SciTech Connect

    Eisenberg, R.

    1991-12-01

    Significant progress has been made on the photochemistry and photophysics of platinum group element dithiolate complexes. The specific systems under investigation are square planar complexes of Pt(II) containing a dithiolate chelate and two other donor groups to complete the coordination sphere. The donor groups may be amines, imines, phosphines, phosphites or olefins, and they can be either monodentate or joined together as part of a chelate ring.

  15. Nucleolar damage correlates with neurotoxicity induced by different platinum drugs

    PubMed Central

    McKeage, M J; Hsu, T; Screnci, D; Haddad, G; Baguley, B C

    2001-01-01

    Platinum-based drugs are very useful in cancer therapy but are associated with neurotoxicity in the clinic. To investigate the mechanism of neurotoxicity, dorsal root ganglia of rats treated with various platinum drugs were studied. Cell body, nuclear and nucleolar dimensions of dorsal root ganglia sensory nerve cells were measured to determine morphological toxicity. Sensory nerve conduction velocity was measured to determine functional toxicity. After a single dose of oxaliplatin (10 mg kg−1), no significant change in nuclear and cell body diameter was seen but decreased nucleolar size was apparent within a few hours of treatment. Changes in nucleolar size were maximal at 24 hours, recovered very slowly and showed a non-linear dependence on oxaliplatin dose (r2= 0.99). Functional toxicity was delayed in onset until 14 days after a single dose of oxaliplatin but eventually recovered 3 months after treatment. Multiple doses of cisplatin, carboplatin, oxaliplatin, R, R -ormaplatin and S, S -ormaplatin were also associated with time-dependent reduction in nucleolar size. A linear correlation was obtained between the rate of change in nucleolar size during multiple dose treatment with the series of platinum drugs and the time taken for the development of altered sensory nerve conduction velocity (r2= 0.86;P< 0.024). Damage to the nucleolus of ganglionic sensory neurons is therefore linked to the neurotoxicity of platinum-based drugs, possibly through mechanisms resulting in the inhibition of rRNA synthesis. © 2001 Cancer Research Campaign  http://www.bjcancer.com PMID:11710838

  16. [Platinum compounds in cancer therapy--past, present, and future].

    PubMed

    Akaza, H; Saijo, N; Aiba, K; Isonishi, S; Ohashi, Y; Kawai, K; Konishi, T; Saeki, T; Sone, S; Tsukagoshi, S; Tsuruo, T; Noguchi, S; Miki, T; Mikami, O; Smith, M; Hoctin-Boes, G; Stribling, D

    2001-05-01

    Platinum cytotoxics play an important role globally in the management of solid tumours. Cisplatin sets the standard for efficacy in both regions with careful administration to reduce nephrotoxicity. Carboplatin is associated with neurotoxicity, but has become the leading product in the US due largely to the easier to manage toxicity profile. Both agents have been widely used in both registered and non registered indications and are frequently combined with other cytotoxics. In Japan, cisplatin has been used successfully at low doses in combination with 5-FU based regimens and appears to achieve a synergistic effect, but controlled data are not yet available. More recently oxaliplatin (Europe) and nedaplatin (in Japan) have been introduced, but their clinical roles in therapy have yet to be established. One of the limiting features of the first generation of platinum compounds is that a significant proportion of tumours develop cross resistance to platins due to either changes in uptake or excretion, intracellular detoxification or accelerated DNA repair. The forum discussed the possibility for the development of better new platinum compounds, A new platin agent which had lower toxicity and higher efficacy across a wide range of cancers without the development of resistance would be a significant step forward. If the tolerability profile was suitable, an oral formulation may improve the quality of life for patients but this must not be at the expense of efficacy. Even after the introduction of new target based drugs, platinum cytotoxics are likely to be used to reduce the tumour mass and in some cases can be expected to potentiate the effects of the new agents. In preclinical studies, ZD0473 has been shown to by-pass some major mechanisms of resistance and has the potential to achieve these objectives and is now being evaluated in clinical studies in both Japan and the West. PMID:11383210

  17. Cosmic ray isotopes

    NASA Technical Reports Server (NTRS)

    Stone, E. C.

    1973-01-01

    The isotopic composition of cosmic rays is studied in order to develop the relationship between cosmic rays and stellar processes. Cross section and model calculations are reported on isotopes of H, He, Be, Al and Fe. Satellite instrument measuring techniques separate only the isotopes of the lighter elements.

  18. Statistical clumped isotope signatures

    PubMed Central

    Röckmann, T.; Popa, M. E.; Krol, M. C.; Hofmann, M. E. G.

    2016-01-01

    High precision measurements of molecules containing more than one heavy isotope may provide novel constraints on element cycles in nature. These so-called clumped isotope signatures are reported relative to the random (stochastic) distribution of heavy isotopes over all available isotopocules of a molecule, which is the conventional reference. When multiple indistinguishable atoms of the same element are present in a molecule, this reference is calculated from the bulk (≈average) isotopic composition of the involved atoms. We show here that this referencing convention leads to apparent negative clumped isotope anomalies (anti-clumping) when the indistinguishable atoms originate from isotopically different populations. Such statistical clumped isotope anomalies must occur in any system where two or more indistinguishable atoms of the same element, but with different isotopic composition, combine in a molecule. The size of the anti-clumping signal is closely related to the difference of the initial isotope ratios of the indistinguishable atoms that have combined. Therefore, a measured statistical clumped isotope anomaly, relative to an expected (e.g. thermodynamical) clumped isotope composition, may allow assessment of the heterogeneity of the isotopic pools of atoms that are the substrate for formation of molecules. PMID:27535168

  19. Zirconium isotope separation

    SciTech Connect

    Siddall, M.B.

    1984-12-11

    A method of separating zirconium isotopes by converting the zirconium to its iodide salt prior to separation by usual isotope methods is disclosed. After separation the desired isotopes are converted from the salt to the metal by the van Arkel-de Boer iodide process.

  20. Statistical clumped isotope signatures.

    PubMed

    Röckmann, T; Popa, M E; Krol, M C; Hofmann, M E G

    2016-01-01

    High precision measurements of molecules containing more than one heavy isotope may provide novel constraints on element cycles in nature. These so-called clumped isotope signatures are reported relative to the random (stochastic) distribution of heavy isotopes over all available isotopocules of a molecule, which is the conventional reference. When multiple indistinguishable atoms of the same element are present in a molecule, this reference is calculated from the bulk (≈average) isotopic composition of the involved atoms. We show here that this referencing convention leads to apparent negative clumped isotope anomalies (anti-clumping) when the indistinguishable atoms originate from isotopically different populations. Such statistical clumped isotope anomalies must occur in any system where two or more indistinguishable atoms of the same element, but with different isotopic composition, combine in a molecule. The size of the anti-clumping signal is closely related to the difference of the initial isotope ratios of the indistinguishable atoms that have combined. Therefore, a measured statistical clumped isotope anomaly, relative to an expected (e.g. thermodynamical) clumped isotope composition, may allow assessment of the heterogeneity of the isotopic pools of atoms that are the substrate for formation of molecules. PMID:27535168

  1. Platinum-induced structural collapse in layered oxide polycrystalline films

    SciTech Connect

    Wang, Jianlin; Liu, Changhui; Huang, Haoliang; Fu, Zhengping; Peng, Ranran E-mail: yllu@ustc.edu.cn; Zhai, Xiaofang; Lu, Yalin E-mail: yllu@ustc.edu.cn

    2015-03-30

    Effect of a platinum bottom electrode on the SrBi{sub 5}Fe{sub 1−x}Co{sub x}Ti{sub 4}O{sub 18} layered oxide polycrystalline films was systematically studied. The doped cobalt ions react with the platinum to form a secondary phase of PtCoO{sub 2}, which has a typical Delafossite structure with a weak antiferromagnetism and an exceptionally high in-plane electrical conductivity. Formation of PtCoO{sub 2} at the interface partially consumes the cobalt dopant and leads to the structural collapsing from 5 to 4 layers, which was confirmed by X-ray diffraction and high resolution transmission electron microscopy measurements. Considering the weak magnetic contribution from PtCoO{sub 2}, the observed ferromagnetism should be intrinsic of the Aurivillius compounds. Ferroelectric properties were also indicated by the piezoresponse force microscopy. In this work, the platinum induced secondary phase at the interface was observed, which has a strong impact on Aurivillius structural configuration and thus the ferromagnetic and ferroelectric properties.

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

    PubMed

    Tripković, Vladimir; Cerri, Isotta; Nagami, Tetsuo; Bligaard, Thomas; Rossmeisl, Jan

    2013-03-01

    We have analyzed the aptitude of several metal oxide supports (TiO(2), SnO(2), NbO(2), ZrO(2), SiO(2), Ta(2)O(5) and Nb(2)O(5)) to redisperse platinum under electrochemical conditions pertinent to the Proton Exchange Membrane Fuel Cell (PEMFC) cathode. The redispersion on oxide supports in air has been studied in detail; however, due to different operating conditions it is not straightforward to link the chemical and the electrochemical environment. The largest differences reflect in (1) the oxidation state of the surface (the oxygen species coverage), (2) temperature and (3) the possibility of platinum dissolution at high potentials and the interference of redispersion with normal working potential of the PEMFC cathode. We have calculated the PtO(x) (x = 0, 1, 2) adsorption energies on different metal oxides' surface terminations as well as inside the metal oxides' bulk, and we have concluded that NbO(2) might be a good support for platinum redispersion at PEMFC cathodes. PMID:23358311

  3. Heteroleptic Complexes of Cyclometalated Platinum with Triarylformazanate Ligands.

    PubMed

    Kabir, Evanta; Wu, Chia-Hua; Wu, Judy I-Chia; Teets, Thomas S

    2016-01-19

    Formazanates are a ligand class featuring a 1,2,4,5-tetraazapentadienyl core, with variable substitution at the 1, 3, and 5 positions. Here we describe a set of four heteroleptic cylcometalated platinum complexes containing triarylformazanate ligands. The complexes are prepared by metathesis reactions of chloro-bridged dimers [Pt(C∧N)(μ-Cl)]2 (C∧N = 2-phenylpyridine or 2-(2,4-difluorophenyl)pyridine) with triarylformazans in the presence of base. X-ray diffraction studies reveal the molecular structures of three such complexes. Cyclic voltammograms and UV-vis absorption spectra of the complexes show features characteristic of both the cyclometalated platinum fragment and the formazanate, with the latter giving rise to two reversible one-electron reductions in the CV and an intense visible π → π* absorption which is red-shifted by >100 nm relative to the free formazan. The electronic structures and redox properties of the complexes were further investigated by UV-vis spectroelectrochemistry and density functional theory calculations. All of the experimental and theoretical work points to a frontier molecular orbital manifold where the formazanate π and π* orbitals are substantially mixed with d-orbitals derived from the platinum center. PMID:26702999

  4. Porous platinum-based catalysts for oxygen reduction

    DOEpatents

    Erlebacher, Jonah D; Snyder, Joshua D

    2014-11-25

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

  5. Platinum-induced structural collapse in layered oxide polycrystalline films

    NASA Astrophysics Data System (ADS)

    Wang, Jianlin; Huang, Haoliang; Liu, Changhui; Fu, Zhengping; Zhai, Xiaofang; Peng, Ranran; Lu, Yalin

    2015-03-01

    Effect of a platinum bottom electrode on the SrBi5Fe1-xCoxTi4O18 layered oxide polycrystalline films was systematically studied. The doped cobalt ions react with the platinum to form a secondary phase of PtCoO2, which has a typical Delafossite structure with a weak antiferromagnetism and an exceptionally high in-plane electrical conductivity. Formation of PtCoO2 at the interface partially consumes the cobalt dopant and leads to the structural collapsing from 5 to 4 layers, which was confirmed by X-ray diffraction and high resolution transmission electron microscopy measurements. Considering the weak magnetic contribution from PtCoO2, the observed ferromagnetism should be intrinsic of the Aurivillius compounds. Ferroelectric properties were also indicated by the piezoresponse force microscopy. In this work, the platinum induced secondary phase at the interface was observed, which has a strong impact on Aurivillius structural configuration and thus the ferromagnetic and ferroelectric properties.

  6. Reduced hydrogen embrittlement susceptibility in platinum implanted high strength steel

    NASA Astrophysics Data System (ADS)

    Cowie, J. G.; Lowder, L. J.; Culbertson, R. J.; Kosik, W. E.; Brown, R.

    1991-07-01

    High strength steels suffer from a high susceptibility to hydrogen embrittlement in a corrosive atmosphere, a factor which limits their usefulness. A good catalyst, such as platinum, present on the surface of the steel may lead to a low value of hydrogen overvoltage, thereby reducing the accumulation and subsequent diffusion of atomic hydrogen into the metal. In the present study, platinum was implanted into high strength electroslag remelted (ESR) 4340 steel specimens to a dose of 10 16 atoms/cm 2. Both Pt-implanted and unimplanted specimens were rate charged with hydrogen. The relative concentration of diffusible hydrogen was determined using an electrochemical measurement device known as a Barnacle Electrode. The specimens implanted with platinum exhibited less diffusible hydrogen than the unimplanted steel. Slow strain rate notched-tensile tests, in an aqueous solution of 3.5 wt.% NaCI, were performed in order to evaluate the effect of hydrogen on strength and ductility. The Pt-implanted specimens were able to sustain significantly higher loads before fracture than their unimplanted counterparts. Scanning electron microscopy (SEM) verified the presence of brittle cracking typical of hydrogen embrittlement type failures. Degradation of mechanical properties due to hydrogen embrittlement was thus significantly reduced. This suggested that both the electrochemical and catalytic properties of the Pt-implanted surface were responsible for the improvement in properties.

  7. Compatability of dispersion-strengthened platinum with resistojet propellants

    NASA Technical Reports Server (NTRS)

    Whalen, Margaret V.; Nathal, Michael V.

    1987-01-01

    Resistojets for the Space Station require long life and multipropellant capability. The choice of available materials to meet these requirements is limited. Dispersion-strengthened platinum was selected. Past results indicated that it should be suffieiently inert in candidate propellant environments and should be capable of operating at moderate temperatures for extended periods. A series of propellant compatibility tests was done with platinum strengthened with either yttria or zirconia. Data presented included the results of 1000-hr tests in CO2, H2, ammonia (NH3), N2, steam, hydrazine (N2H4), and methane (CH4); and 2000-hr tests in H2 and NH3. The platinum samples were tested at 1400 C in CO2, H2, NH3, N2, steam, and N2H4; at 500 C in CH4; and at 800 C in N2H4. The mass-loss results indicated material life, exptrapolated from experimental mass-loss data, in excess of 100 000 hr in all environments except steam and N2H4, where it was greater than or =45000 hr. Generally, on the basis of mass loss, there were no compatibility concerns in any of the environments considered. Optical and scanning electron microscopy were used to determine the effect of propellants on the material surface and to evaluate material stability.

  8. In vitro free radical scavenging activity of platinum nanoparticles

    NASA Astrophysics Data System (ADS)

    Watanabe, Aki; Kajita, Masashi; Kim, Juewon; Kanayama, Atsuhiro; Takahashi, Kyoko; Mashino, Tadahiko; Miyamoto, Yusei

    2009-11-01

    A polyacrylic acid (PAA)-protected platinum nanoparticle species (PAA-Pt) was prepared by alcohol reduction of hexachloroplatinate. The PAA-Pt nanoparticles were well dispersed and homogeneous in size with an average diameter of 2.0 ± 0.4 nm (n = 200). We used electron spin resonance to quantify the residual peroxyl radical (\\mathrm {AOO}^{\\bullet } ) generated from 2,2-azobis (2-aminopropane) dihydrochloride (AAPH) by thermal decomposition in the presence of O2 and a spectrophotometric method to quantify the residual 1,1-diphenyl-2-picrylhydrazyl (DPPH) radical. PAA-Pt scavenged these two radicals in a dose-dependent manner. Platinum was the functional component. PAA-Pt reduced the rate of oxygen consumption required for linoleic acid peroxidation initiated by \\mathrm {AOO}^{\\bullet } generated from AAPH, indicating inhibition of the propagation of linolate peroxidation. A thiobarbituric acid test also revealed dose-dependent inhibition of the linolate peroxidation by PAA-Pt. Fifty micromolar platinum, as PAA-Pt, completely quenched 250 µM DPPH radical for 5 min. Even when twice diluted in half, the PAA-Pt still quenched 100% of the 250 µM DPPH radical. The scavenging activity of PAA-Pt is durable. These observations suggest that PAA-Pt is an efficient scavenger of free radicals.

  9. Electrocatalyst for oxygen reduction with reduced platinum oxidation and dissolution rates

    SciTech Connect

    Adzic, Radoslav; Zhang, Junliang; Vukmirovic, Miomir

    2012-11-13

    The invention relates to platinum-metal oxide composite particles and their use as electrocatalysts in oxygen-reducing cathodes and fuel cells. The invention particularly relates to methods for preventing the oxidation of the platinum electrocatalyst in the cathodes of fuel cells by use of these platinum-metal oxide composite particles. The invention additionally relates to methods for producing electrical energy by supplying such a fuel cell with an oxidant, such as oxygen, and a fuel source, such as hydrogen.

  10. Cisplatin based chemotherapy in testicular cancer patients: long term platinum excretion and clinical effects.

    PubMed

    Hohnloser, J H; Schierl, R; Hasford, B; Emmerich, B

    1996-09-20

    Patients with advanced testicular cancer (TC) have a very good long-term prognosis owing to cisplatin-based polychemotherapy. Platinum is believed to be excreted at a rapid rate via urine within weeks after chemotherapy. As a new, highly sensitive method has become available detecting even natural background platinum levels in body fluids, this study was set up to analyze urinary and serum platinum levels in long-term survivors of testicular neoplasm after cisplatin based polychemotherapy and to correlate clinical data with urinary and serum platinum levels. Urinary platinum concentrations were measured in 64 healthy controls (C) and 22 male patients (TC) 150 to 3022 days after the last application of i.v. cisplatin using voltammetry after UV-photolysis. In the latter group (TC), serum platinum levels were measured as well. Clinical data were analysed as to long-term organ toxicity. Mean urinary platinum levels were 2700 times higher in the patient group (TC) than natural background noise (p < 0.0001). There was a decline of urinary and serum platinum levels over time, being significantly above normal even 8 years after cisplatin exposure. The only significant variables related to the urine platinum concentration were a) the interval between the last i.v. cisplatin application and time of study and b) the total dose given. Not significant were the number of chemotherapy cycles, pre-therapy renal disease, patient age, tumour resection before/after chemotherapy, site of pre/post therapy resection, clinical staging, histological subtypes or tumour markers. Post-therapy renal disease or peripheral nerve damage were not significantly associated with urinary platinum levels. Our data indicate that even 8 years after cisplatin based chemotherapy 500 times elevated urinary and serum platinum levels can be measured in testicular cancer patients. No organ toxicity related to long-term platinum excretion could be detected. This may be due to our small sample size. PMID

  11. Electrocatalyst for oxygen reduction with reduced platinum oxidation and dissolution rates

    DOEpatents

    Adzic, Radoslav; Zhang, Junliang; Vukmirovic, Miomir

    2011-11-22

    The invention relates to platinum-metal oxide composite particles and their use as electrocatalysts in oxygen-reducing cathodes and fuel cells. The invention particularly relates to methods for preventing the oxidation of the platinum electrocatalyst in the cathodes of fuel cells by use of these platinum-metal oxide composite particles. The invention additionally relates to methods for producing electrical energy by supplying such a fuel cell with an oxidant, such as oxygen, and a fuel source, such as hydrogen.

  12. Platinum-group element resources in podiform chromitites from California and Oregon.

    USGS Publications Warehouse

    Page, N.J.; Singer, D.A.; Moring, B.C.; Carlson, C.A.; McDade, J.M.; Wilson, S.A.

    1986-01-01

    Assays of Pt, Pd, Rh and Ir from approx 280 podiform chromite deposits in Palaeozoic and Mesozoic ophiolites are statistically analysed to estimate their possible by-product value from mining the chromite. The platinum-group elements occur in discrete platinum-group minerals, and in solid solution in Cu-Ni-Fe sulphides. Low grades and small amounts of total platinum-group elements in podiform chromite deposits imply a small resource. -G.J.N.

  13. Optimum Platinum Loading In Pt/SnO2 CO-Oxidizing Catalysts

    NASA Technical Reports Server (NTRS)

    Schryer, David R.; Upchurch, Billy T.; Davis, Patricia P.; Brown, Kenneth G.; Schryer, Jacqueline

    1991-01-01

    Platinum on tin oxide (Pt/SnO2) good catalyst for oxidation of carbon monoxide at or near room temperature. Catalytic activity peaks at about 17 weight percent Pt. Catalysts with platinum loadings as high as 46 percent fabricated by technique developed at Langley Research Center. Work conducted to determine optimum platinum loading for this type of catalyst. Major application is removal of unwanted CO and O2 in CO2 lasers.

  14. Near-UV phosphorescent emitters: N-heterocyclic platinum(ii) tetracarbene complexes.

    PubMed

    Unger, Yvonne; Zeller, Alexander; Taige, Maria A; Strassner, Thomas

    2009-06-28

    Although examples of nickel(ii), palladium(ii) and platinum(ii) N-heterocyclic tetracarbene complexes are known in the literature, particularly platinum(ii) tetracarbene complexes are rare. We developed a new synthetic route via biscarbene acetate complexes, which make homoleptic as well as heteroleptic platinum(ii) tetracarbene complexes accessible. The reported photoluminescence data show that these complexes have good quantum yields and photostability and are a promising class of emitters for PhOLEDs. Characterization of the compounds includes a solid-state structure of the homoleptic complex bis(1,1'-diisopropyl-3,3'-methylenediimidazoline-2,2'-diylidene)platinum(ii) dibromide. PMID:19513490

  15. ISOTOPE CONVERSION DEVICE

    DOEpatents

    Wigner, E.P.; Young, G.J.; Ohlinger, L.A.

    1957-12-01

    This patent relates to nuclear reactors of tbe type utilizing a liquid fuel and designed to convert a non-thermally fissionable isotope to a thermally fissionable isotope by neutron absorption. A tank containing a reactive composition of a thermally fissionable isotope dispersed in a liquid moderator is disposed within an outer tank containing a slurry of a non-thermally fissionable isotope convertible to a thermally fissionable isotope by neutron absorption. A control rod is used to control the chain reaction in the reactive composition and means are provided for circulating and cooling the reactive composition and slurry in separate circuits.

  16. Isotopically controlled semiconductors

    SciTech Connect

    Haller, Eugene E.

    2001-12-21

    Semiconductor bulk crystals and multilayer structures with controlled isotopic composition have attracted much scientific and technical interest in the past few years. Isotopic composition affects a large number of physical properties, including phonon energies and lifetimes, bandgaps, the thermal conductivity and expansion coefficient and spin-related effects. Isotope superlattices are ideal media for self-diffusion studies. In combination with neutron transmutation doping, isotope control offers a novel approach to metal-insulator transition studies. Spintronics, quantum computing and nanoparticle science are emerging fields using isotope control.

  17. Platinum decorated Ru/C: Effects of decorated platinum on catalyst structure and performance for the methanol oxidation reaction

    NASA Astrophysics Data System (ADS)

    Gao, Haili; Liao, Shijun; Zeng, Jianhuang; Xie, Yichun

    Platinum decorated Ru/C catalysts are prepared by successive reduction of a platinum precursor on pre-formed Ru/C. Pt:Ru atomic ratios are varied from 0.13:1 to 0.81:1 to investigate the platinum decoration effects on the catalyst's structure and electrochemical performance towards the methanol oxidation reaction (MOR) at room temperature. The catalysts are extensively characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), and X-ray photoelectron spectroscopy (XPS). Ru@Pt/C catalysts show enhanced mass-normalized activity and specific activity for the MOR relative to Pt/C. For the anodic oxidation of methanol, the ratio of forward to reverse oxidation peak current R (I f/ I b) varies considerably: R decreases from 5.8 to 0.8 when the Pt:Ru ratio increases from 0.13:1 to 0.81:1. When the ratio of Pt:Ru is 0.42:1, R reaches 0.99 (close to that of Pt/C), and further increase of the Pt:Ru ratio leads to almost no decrease in R. Coincidentally, maximum mass-normalized activity is also obtained when Pt:Ru is 0.42:1.

  18. cis-platinum and ovarian carcinoma. In vitro chemosensitivity of cultured tumour cells from patients receiving high dose cis-platinum as first line treatment.

    PubMed Central

    Wilson, A. P.; Ford, C. H.; Newman, C. E.; Howell, A.

    1987-01-01

    A study on the in vitro sensitivity of tumour cells from patients with ovarian cancer has been carried out in parallel with a clinical study designed to evaluate the role of high-dose cis-platinum (CIS) as first-line chemotherapy. A total of 50 samples from 102 patients have been successfully cultured and screened for in vitro chemosensitivity to 7 drugs, including CIS. The malignant nature of cells growing in culture was confirmed using a combination of karyology, morphology and immunohistochemical staining with HMFG2. Tumours were graded as sensitive (less than 40% of control 3H-leucine incorporation), intermediate (41-60% of control) or resistant (greater than 61% of control) to CIS. Correlation of in vitro sensitivity to cis-platinum with clinical response to cis-platinum assessed using CT scan and second-look laparotomy, showed positive correlation in 9/11 (89%) patients (8 = S/S; 1 = R/R); positive correlation between in vitro sensitivity to phosphoramide mustard and clinical response was also found in 4/6 patients receiving cyclophosphamide (3 = S/S; 1 = R/R). All patients with sensitive tumours showed a clinical response to cis-platinum. Comparison of cis-platinum sensitivity with sensitivity to phosphoramide mustard and melphalan showed that some tumours were sensitive only to cis-platinum; resistance to cis-platinum and sensitivity to phosphoramide mustard/melphalan was an infrequent occurrence. Some tumours which were resistant to cis-platinum showed sensitivity to adriamycin and bleomycin, particularly those from untreated patients. Sensitivity to 5-fluorouracil and resistance to cis-platinum was found in approximately equal proportions of tumours in both the treated and untreated groups. PMID:3435704

  19. Structure and Chemistry of Nickel Oxide-Nickel Platinum-Platinum Interfaces

    NASA Astrophysics Data System (ADS)

    Yang, Judith Chun-Hsu

    Recent investigations have demonstrated that interfacial reactions can be used to modify the mechanical strength of metal-ceramic interfaces. To better understand this phenomena, the structure and chemistry of model metal-ceramic interfaces, formed by diffusion bonding single crystals of NiO and Pt together, were studied using electron microscopy techniques. Lattice imaging shows that the interface structure between NiO and Pt may facet depending on the relative twist geometry between them. As suggested by Ni-Pt phase diagrams and previous work, suitable choice of annealing temperature, time and oxygen partial pressure allows the formation of the intermetallic compound NiPt. Conventional transmission electron microscope (CTEM) studies reveal the presence of a 0-20 nm thick NiPt interlayer after heat treatment at low oxygen activities. Electron energy loss spectroscopy (EELS) investigations showed that the nickel diffuses into the platinum for 100nm. Some thermodynamic and kinetic information of the NiPt formation at the NiO -Pt interface, based on the CTEM and EELS studies, is presented. The influence of crystallography, impurities and oxygen activity on the interfacial reactions were investigated. In the (100)_{NiO}//(100)_ {Pt} system, a NiPt layer forms along the interface. Whereas in the (100)_{NiO }//(111)_{Pt} system, NiPt particles appear within the Pt matrix. The growth of the intermetallic interlayer is also sensitive to impurities. The presence of silicon impurities in the heat treatment furnace reduces the thickness of the NiPt interlayer by nearly a factor of ten. The NiPt interlayer may or may not form due to slight changes in the oxygen activity of the heat treatment. A simple bonding model was previously proposed to explain why NiPt improves the interfacial shear strength. That is, the NiPt layer prevents the formation of weak Pt-O bonds. In order to experimentally check this model, NiPt -NiO interface planes, produced by internal oxidation in order

  20. HDAC4-regulated STAT1 activation mediates platinum resistance in ovarian cancer.

    PubMed

    Stronach, Euan A; Alfraidi, Albandri; Rama, Nona; Datler, Christoph; Studd, James B; Agarwal, Roshan; Guney, Tankut G; Gourley, Charlie; Hennessy, Bryan T; Mills, Gordon B; Mai, Antonello; Brown, Robert; Dina, Roberto; Gabra, Hani

    2011-07-01

    Ovarian cancer frequently acquires resistance to platinum chemotherapy, representing a major challenge for improving patient survival. Recent work suggests that resistant clones exist within a larger drug-sensitive cell population prior to chemotherapy, implying that resistance is selected for rather than generated by treatment. We sought to compare clinically derived, intrapatient paired models of initial platinum response and subsequent resistant relapse to define molecular determinants of evolved resistance. Transcriptional analysis of a matched cell line series from three patients with high-grade serous ovarian cancer before and after development of clinical platinum resistance (PEO1/PEO4/PEO6, PEA1/PEA2, PEO14/PEO23) identified 91 up- and 126 downregulated genes common to acquired resistance. Significantly enhanced apoptotic response to platinum treatment in resistant cells was observed following knockdown of histone deacetylase (HDAC) 4, FOLR2, PIK3R1, or STAT1 (P < 0.05). Interestingly, HDAC4 and STAT1 were found to physically interact. Acetyl-STAT1 was detected in platinum-sensitive cells but not in HDAC4 overexpressing platinum-resistant cells from the same patient. In resistant cells, STAT1 phosphorylation/nuclear translocation was seen following platinum exposure, whereas silencing of HDAC4 increased acetyl-STAT1 levels, prevented platinum-induced STAT1 activation, and restored cisplatin sensitivity. Conversely, matched sensitive cells were refractory to STAT1 phosphorylation on platinum treatment. Analysis of 16 paired tumor biopsies taken before and after development of clinical platinum resistance showed significantly increased HDAC4 expression in resistant tumors [n = 7 of 16 (44%); P = 0.04]. Therefore, clinical selection of HDAC4-overexpressing tumor cells upon exposure to chemotherapy promotes STAT1 deacetylation and cancer cell survival. Together, our findings identify HDAC4 as a novel, therapeutically tractable target to counter platinum

  1. HDAC4-regulated STAT1 activation mediates platinum resistance in ovarian cancer

    PubMed Central

    Stronach, Euan A; Alfraidi, Albandri; Rama, Nona; Datler, Christoph; Studd, Jamie; Agarwal, Roshan; Guney, Tankut G; Gourley, Charlie; Hennessy, Bryan T; Mills, Gordon B; Mai, Antonello; Brown, Robert; Dina, Roberto; Gabra, Hani

    2011-01-01

    Ovarian cancer frequently acquires resistance to platinum chemotherapy, representing a major challenge for improving patient survival. Recent work suggests resistant clones exist within a larger drug sensitive cell-population prior to chemotherapy, implying that resistance is selected for rather than generated by treatment. We sought to compare clinically-derived, intra-patient paired models of initial platinum response and subsequent resistant relapse to define molecular determinants of evolved resistance. Transcriptional analysis of a matched cell-line series from three patients with high-grade serous ovarian cancer before and after development of clinical platinum resistance (PEO1/PEO4/PEO6, PEA1/PEA2, PEO14/PEO23) identified 91 up- and 126 down-regulated genes common to acquired resistance. Significantly enhanced apoptotic response to platinum treatment in resistant cells was observed following knockdown of HDAC4, FOLR2, PIK3R1 or STAT1 (p<0.05). Interestingly, HDAC4 and STAT1 were found to physically interact. Acetyl-STAT1 was detected in platinum sensitive but not HDAC4 over-expressing platinum resistant cells from the same patient. In resistant cells, STAT1 phosphorylation/nuclear translocation was seen following platinum exposure, whereas silencing of HDAC4 increased acetyl-STAT1 levels, prevented platinum induced STAT1 activation and restored cisplatin sensitivity. Conversely, matched sensitive cells were refractory to STAT1 phosphorylation on platinum treatment. Analysis of 16 paired tumor biopsies taken before and after development of clinical platinum resistance showed significantly increased HDAC4 expression in resistant tumors (n=7/16[44%]; p=0.04). Therefore, clinical selection of HDAC4 overexpressing tumor cells upon exposure to chemotherapy promotes STAT1 deacetylation and cancer cell survival. Together, our findings identify HDAC4 as a novel, therapeutically tractable target to counter platinum resistance in ovarian cancer. PMID:21571862

  2. Monochloramine-sensitive amperometric microelectrode: optimization of gold, platinum, and carbon fiber sensing materials for removal of dissolved oxygen interference

    EPA Science Inventory

    Amperometric monochloramine detection using newly fabricated gold, platinum, and carbon-fiber microsensors was investigated to optimize sensor operation and eliminate oxygen interference. Gold and platinum microsensors exhibited no oxygen interference during monochloramine measu...

  3. Selective hydrogenation of 1,3-butadiene on platinum-copper alloys at the single-atom limit

    NASA Astrophysics Data System (ADS)

    Lucci, Felicia R.; Liu, Jilei; Marcinkowski, Matthew D.; Yang, Ming; Allard, Lawrence F.; Flytzani-Stephanopoulos, Maria; Sykes, E. Charles H.

    2015-10-01

    Platinum is ubiquitous in the production sectors of chemicals and fuels; however, its scarcity in nature and high price will limit future proliferation of platinum-catalysed reactions. One promising approach to conserve platinum involves understanding the smallest number of platinum atoms needed to catalyse a reaction, then designing catalysts with the minimal platinum ensembles. Here we design and test a new generation of platinum-copper nanoparticle catalysts for the selective hydrogenation of 1,3-butadiene,, an industrially important reaction. Isolated platinum atom geometries enable hydrogen activation and spillover but are incapable of C-C bond scission that leads to loss of selectivity and catalyst deactivation. γ-Alumina-supported single-atom alloy nanoparticle catalysts with <1 platinum atom per 100 copper atoms are found to exhibit high activity and selectivity for butadiene hydrogenation to butenes under mild conditions, demonstrating transferability from the model study to the catalytic reaction under practical conditions.

  4. Selective hydrogenation of 1,3-butadiene on platinum-copper alloys at the single-atom limit.

    PubMed

    Lucci, Felicia R; Liu, Jilei; Marcinkowski, Matthew D; Yang, Ming; Allard, Lawrence F; Flytzani-Stephanopoulos, Maria; Sykes, E Charles H

    2015-01-01

    Platinum is ubiquitous in the production sectors of chemicals and fuels; however, its scarcity in nature and high price will limit future proliferation of platinum-catalysed reactions. One promising approach to conserve platinum involves understanding the smallest number of platinum atoms needed to catalyse a reaction, then designing catalysts with the minimal platinum ensembles. Here we design and test a new generation of platinum-copper nanoparticle catalysts for the selective hydrogenation of 1,3-butadiene,, an industrially important reaction. Isolated platinum atom geometries enable hydrogen activation and spillover but are incapable of C-C bond scission that leads to loss of selectivity and catalyst deactivation. γ-Alumina-supported single-atom alloy nanoparticle catalysts with <1 platinum atom per 100 copper atoms are found to exhibit high activity and selectivity for butadiene hydrogenation to butenes under mild conditions, demonstrating transferability from the model study to the catalytic reaction under practical conditions. PMID:26449766

  5. Measurements of thermoelectric power in annealed and quenched gold-platinum alloys

    NASA Technical Reports Server (NTRS)

    Baarle, C. V.; Huebener, R. P.

    1969-01-01

    Report gives measurements of absolute thermoelectric powers of dilute gold-platinum alloys and influence of quenched-in lattice vacancies on their thermoelectric powers. It investigates phonon-drag component of thermoelectric power as a function of platinum concentration, and change in phonon-drag thermoelectric power by lattice vacancies.

  6. Influence of Dose on Particle Size and Optical Properties of Colloidal Platinum Nanoparticles

    PubMed Central

    Gharibshahi, Elham; Saion, Elias

    2012-01-01

    Attempts to produce colloidal platinum nanoparticles by using steady absorption spectra with various chemical-based reduction methods often resulted in the fast disappearance of the absorption maxima leaving reduced platinum nanoparticles with little information on their optical properties. We synthesized colloidal platinum nanoparticles in an aqueous solution of polyvinyl pyrrolidone by gamma radiolytic reduction method, which produced steady absorption spectra of fully reduced and highly pure platinum nanoparticles free from by-product impurities or reducing agent contamination. The average particle size was found to be in the range of 3.4–5.3 nm and decreased with increasing dose due to the domination of nucleation over ion association in the formation of metal nanoparticles by the gamma radiolytic reduction method. The platinum nanoparticles exhibit optical absorption spectra with two absorption peaks centered at about 216 and 264 nm and the peaks blue shifted to lower wavelengths with decreasing particle size. The absorption spectra of platinum nanoparticles were also calculated using quantum mechanical treatment and coincidently a good agreement was obtained between the calculated and measured absorption peaks at various particle sizes. This indicates that the 216 and 264-nm absorption peaks of platinum nanoparticles conceivably originated from the intra-band transitions of conduction electrons of (n = 5, l = 2) and (n = 6, l = 0) energy states respectively to higher energy states. The absorption energies, i.e., conduction band energies of platinum nanoparticles derived from the absorption peaks increased with increasing dose and decreased with increasing particle size. PMID:23203091

  7. 76 FR 67793 - Notification of Expanded Pricing Grid for Precious Metals Products Containing Platinum and Gold...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2011-11-02

    ... and Gold--Excluding Commemorative Gold Coins AGENCY: United States Mint, Department of the Treasury..., 2009, outlining the new pricing methodology for numismatic products containing platinum and gold. Since that time, the price of platinum and gold has increased considerably, and is approaching the...

  8. 78 FR 11954 - Revised Pricing Grid for Gold and Platinum Products

    Federal Register 2010, 2011, 2012, 2013, 2014

    2013-02-20

    ... From the Federal Register Online via the Government Publishing Office DEPARTMENT OF THE TREASURY United States Mint Revised Pricing Grid for Gold and Platinum Products AGENCY: United States Mint... grid for 2013 gold and platinum products. Please see the grid following signature. DATES: This...

  9. ALLERGIC RESPONSE TO PLATINUM AND PALLADIUM COMPLEXES DETERMINATION OF NO-EFFECT LEVEL

    EPA Science Inventory

    Rabbits, guinea pigs and mice were subcutaneously injected with PtSO4 (with and without NH4Cl) and PdSO4 (with and without NH4Cl) in an attempt to sensitize the animals to platinum or palladium. No allergic induction was found. No allergic induction to platinum or palladium was f...

  10. ENVIRONMENTAL TECHNOLOGY VERIFICATION REPORT, HVLP COATING EQUIPMENT, SHARPE MANUFACTURING COMPANY PLATINUM 2012 HVLP SPRAY GUN

    EPA Science Inventory

    This report presents the results of the verification test of the Sharpe Platinum 2013 high-volume, low-pressure gravity-feed spray gun, hereafter referred to as the Sharpe Platinum, which is designed for use in automotive refinishing. The test coating chosen by Sharpe Manufacturi...

  11. Rumpling phenomenon in platinum modified Ni-Al alloys

    SciTech Connect

    Zimmerman, Benjamin Joseph

    2005-05-01

    Surface undulations known as rumpling have been shown to develop at the surface of bond coats used in advanced thermal barrier coating systems. Rumpling can result in cracking and eventual spallation of the top coat. Many mechanisms to explain rumpling have been proposed, and among them is a martensitic transformation. High-temperature x-ray diffraction, differential scanning calorimetry and potentiometry were used to investigate the nature of the martensitic transformation in bulk platinum-modified nickel aluminides. It was found that the martensitic transformation has strong time dependence and can form over a range of temperatures. Cyclic oxidation experiments were performed on the bulk alloys to investigate the effect of the martensitic transformation on surface rumpling. It was found that the occurrence of rumpling was associated with the martensitic transformation. The degree of rumpling was found to increase with an increasing number of cycles and was independent of the heating and cooling rates used. The thickness of the oxide layer at the surface of the samples had a significant impact on the amplitude of the resulting undulations, with amplitude increasing with increasing oxide-layer thickness. Rumpling was also observed in an alloy based on the {gamma}-{gamma}' region of the nickel-aluminum-platinum phase diagram. Rumpling in this alloy was found to occur during isothermal oxidation and is associated with a subsurface layer containing a platinum-rich phase known as a. Rumpling in both alloy systems may be explained by creep deformation of a weakened subsurface layer in response to the compressive stresses in the thermally grown oxide layer.

  12. Luminescent Cyclometalated Platinum and Palladium Complexes with Novel Photophysical Properties

    NASA Astrophysics Data System (ADS)

    Turner, Eric

    Organic light emitting diodes (OLEDs) is a rapidly emerging technology based on organic thin film semiconductors. Recently, there has been substantial investment in their use in displays. In less than a decade, OLEDs have grown from a promising academic curiosity into a multi-billion dollar global industry. At the heart of an OLED are emissive molecules that generate light in response to electrical stimulation. Ideal emitters are efficient, compatible with existing materials, long lived, and produce light predominantly at useful wavelengths. Developing an understanding of the photophysical processes that dictate the luminescent properties of emissive materials is vital to their continued development. Chapter 1 and Chapter 2 provide an introduction to the topics presented and the laboratory methods used to explore them. Chapter 3 discusses a series of tridentate platinum complexes. A synthetic method utilizing microwave irradiation was explored, as well as a study of the effects ligand structure had on the excited state properties. Results and techniques developed in this endeavor were used as a foundation for the work undertaken in later chapters. Chapter 4 introduces a series of tetradentate platinum complexes that share a phenoxy-pyridyl (popy) motif. The new molecular design improved efficiency through increased rigidity and modification of the excited state properties. This class of platinum complexes were markedly more efficient than those presented in Chapter 3, and devices employing a green emitting complex of the series achieved nearly 100% electron-to-photon conversion efficiency in an OLED device. Chapter 5 adapts the ligand structure developed in Chapter 4 to palladium. The resulting complexes exceed reported efficiencies of palladium complexes by an order of magnitude. This chapter also provides the first report of a palladium complex as an emitter in an OLED device. Chapter 6 discusses the continuation of development efforts to include carbazolyl

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

    USGS Publications Warehouse

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

    2007-01-01

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

  14. Modified electrochromism of tungsten oxide via platinum nanophases

    NASA Astrophysics Data System (ADS)

    Park, Kyung-Won; Shim, Hee-Sang; Seong, Tae-Yeon; Sung, Yung-Eun

    2006-05-01

    We report electrochromic properties of WO3 modified by platinum nanophases. The WO3 incorporated by Pt metallic nanophases (Pt -WO3) showed exactly reverse electrochromic phenomenon compared with that of both pure WO3 and WO3 intercepted and coated by metallic Pt thin-film layer. In addition, to investigate the origin of modified electrochromic properties, electrodes consisting of WO3 and/or Pt layers were designed and observed in optical properties during electrochemical reaction. The change of electrochromic properties in the Pt -WO3 is caused by modified structural and electrochemical properties of the WO3 by Pt metallic nanophases dispersed in the oxide matrix.

  15. Method for determining the presence of platinum in earth formations

    SciTech Connect

    Dion, E.P.

    1984-07-31

    A spectral natural gamma radiation logging tool is calibrated with a material of known potassium content so that the natural gamma radiation measured by such logging tool is related to potassium concentration. The earth formations surrounding a borehole are logged with such logging tool to identify the presence of potassium. A specified concentration of potassium correlates inversely with a magnetic mineral content in the earth formation. The amount of magnetic mineral content is a measure of the presence of the non-magnetic mineral platinum in the earth formation.

  16. Platinum-group element abundance patterns in different mantle environments

    SciTech Connect

    Rehkaemper, M.; Halliday, A.N.; Barfod, D.; Fitton, J.G.; Dawson, J.B.

    1997-11-28

    Mantle-derived xenoliths from the Cameroon Line and northern Tanzania display differences in their platinum-group element (PGE) abundance patterns. The Cameroon Line lherzolites have uniform PGE patterns indicating a homogeneous upper mantle over several hundreds of kilometers, with approximately chondritic PGE ratios. The PGE patterns of the Tanzanian peridotites are similar to the PGE systematics of ultramafic rocks from ophiolites. The differences can be explained if the northern Tanzanian lithosphere developed in a fluid-rich suprasubduction zone environment, whereas the Cameroon Line lithosphere only experienced melt extraction from anhydrous periodotites. 32 refs., 2 figs., 1 tab.

  17. Phosphorescent Organic Light Emitting Diodes Implementing Platinum Complexes

    NASA Astrophysics Data System (ADS)

    Ecton, Jeremy Exton

    Organic light emitting diodes (OLEDs) are a promising approach for display and solid state lighting applications. However, further work is needed in establishing the availability of efficient and stable materials for OLEDs with high external quantum efficiency's (EQE) and high operational lifetimes. Recently, significant improvements in the internal quantum efficiency or ratio of generated photons to injected electrons have been achieved with the advent of phosphorescent complexes with the ability to harvest both singlet and triplet excitons. Since then, a variety of phosphorescent complexes containing heavy metal centers including Os, Ni, Ir, Pd, and Pt have been developed. Thus far, the majority of the work in the field has focused on iridium based complexes. Platinum based complexes, however, have received considerably less attention despite demonstrating efficiency's equal to or better than their iridium analogs. In this study, a series of OLEDs implementing newly developed platinum based complexes were demonstrated with efficiency's or operational lifetimes equal to or better than their iridium analogs for select cases. In addition to demonstrating excellent device performance in OLEDs, platinum based complexes exhibit unique photophysical properties including the ability to form excimer emission capable of generating broad white light emission from a single emitter and the ability to form narrow band emission from a rigid, tetradentate molecular structure for select cases. These unique photophysical properties were exploited and their optical and electrical properties in a device setting were elucidated. Utilizing the unique properties of a tridentate Pt complex, Pt-16, a highly efficient white device employing a single emissive layer exhibited a peak EQE of over 20% and high color quality with a CRI of 80 and color coordinates CIE(x=0.33, y=0.33). Furthermore, by employing a rigid, tetradentate platinum complex, PtN1N, with a narrow band emission into a

  18. Separation of platinum group metal ions by Donnan dialysis

    SciTech Connect

    Brajter, K.; Slonawska, K.; Cox, J.A.

    1985-10-01

    Separations of metal ions on the basis of Donnan dialysis across anion-exchange membranes should be possible if the receiver electrolyte composition favors the formation of selected anionic complexes of the sample metal ions. Moreover, such a separation has the possibility of being better suited from some applications than batch or column experiments with anion-exchange resins. The above hypothesis are tested on the platinum-group metal ions, Pt(IV), Rh(III), Pd(II), Ir(III), and Ir(IV). 13 references, 4 tables.

  19. A branched luminescent multinuclear platinum(II) complex

    NASA Astrophysics Data System (ADS)

    Yang, Hui; Xu, S. J.; Tao, Chi-Hang; Yam, Vivian Wing-Wah; Zhang, Jie

    2011-08-01

    Nonlinear optical properties of luminescent multinuclear platinum(II) complex of branched alkynyls in benzene solution are investigated at room temperature by using two-photon fluorescence (TPF) technique. It is found that the material shows unusual nonlinear optical characteristics under the excitation of near infrared femtosecond laser pulses. The self-focusing of laser beam energy during propagation of the laser pulses in the sample with large nonlinear coefficient for the refractive index is observed. Based on this phenomenon, a new method for measuring the nonlinear coefficient and two-photon absorption cross section of materials is proposed.

  20. Adsorption of xenon on vicinal copper and platinum surfaces

    NASA Astrophysics Data System (ADS)

    Baker, Layton

    The adsorption of xenon was studied on Cu(111), Cu(221), Cu(643) and on Pt(111), Pt(221), and Pt(531) using low energy electron diffraction (LEED), temperature programmed desorption (TPD) of xenon, and ultraviolet photoemission of adsorbed xenon (PAX). These experiments were performed to study the atomic and electronic structure of stepped and step-kinked, chiral metal surfaces. Xenon TPD and PAX were performed on each surface in an attempt to titrate terrace, step edge, and kink adsorption sites by adsorption energetics (TPD) and local work function differences (PAX). Due to the complex behavior of xenon on the vicinal copper and platinum metal surfaces, adsorption sites on these surfaces could not be adequately titrated by xenon TPD. On Cu(221) and Cu(643), xenon desorption from step adsorption sites was not apparent leading to the conclusion that the energy difference between terrace and step adsorption is minuscule. On Pt(221) and Pt(531), xenon TPD indicated that xenon prefers to bond at step edges and that the xenon-xenon interaction at step edges in repulsive but no further indication of step-kink adsorption was observed. The Pt(221) and Pt(531) TPD spectra indicated that the xenon overlayer undergoes strong compression near monolayer coverage on these surfaces due to repulsion between step-edge adsorbed xenon and other encroaching xenon atoms. The PAX experiments on the copper and platinum surfaces demonstrated that the step adsorption sites have lower local work functions than terrace adsorption sites and that higher step density leads to a larger separation in the local work function of terrace and step adsorption sites. The PAX spectra also indicated that, for all surfaces studied at 50--70 K, step adsorption is favored at low coverage but the step sites are not saturated until monolayer coverage is reached; this observation is due to the large entropy difference between terrace and step adsorption states and to repulsive interactions between xenon atoms

  1. Finding Platinum-Coating Gaps On Titanium Anodes

    NASA Technical Reports Server (NTRS)

    Bodemeijer, Ronnald; Flowers, Cecil E.

    1990-01-01

    Simple procedure makes gaps visible to eye. New gap-detection method consists of plating thin layer of non-silver-colored metal like copper or gold on anode. Contrast in color between plated metal and bare anode material makes gaps stand out. If anode passes inspection, copper or gold plate removable by reversal of test-plating current. Remains to be determined whether test plating and removal damages anode. New method simpler and more economical than previous attempts to identify gaps in platinum.

  2. Extraterrestrial platinum group nuggets in deep-sea sediments

    NASA Technical Reports Server (NTRS)

    Brownlee, D. E.; Bates, B. A.; Wheelock, M. M.

    1984-01-01

    A previously unrecognized property of iron cosmic spheres is reported. The most common spheres larger than 300 microns do not, in fact, contain FeNi metal cores, but instead contain a micrometer-sized nugget composed almost entirely of platinum group elements. These elements appear to have been concentrated by the oxidation of molten meteoritic metal during atmospheric entry. This process is critically dependent on the relative abundance of oxygen in the atmosphere, and the first appearance of the nuggets in the geological record may provide a marker indicating when the oxygen abundance attained half of its present level.

  3. Platinum/Tin Oxide/Silica Gel Catalyst Oxidizes CO

    NASA Technical Reports Server (NTRS)

    Upchurch, Billy T.; Davis, Patricia P.; Schryer, David R.; Miller, Irvin M.; Brown, David; Van Norman, John D.; Brown, Kenneth G.

    1991-01-01

    Heterogeneous catalyst of platinum, tin oxide, and silica gel combines small concentrations of laser dissociation products, CO and O2, to form CO22 during long times at ambient temperature. Developed as means to prevent accumulation of these products in sealed CO2 lasers. Effective at ambient operating temperatures and installs directly in laser envelope. Formulated to have very high surface area and to chemisorb controlled quantities of moisture: chemisorbed water contained within and upon its structure, makes it highly active and very longlived so only small quantity needed for long times.

  4. Pretreatment of Platinum/Tin Oxide-Catalyst

    NASA Technical Reports Server (NTRS)

    Hess, Robert V.; Paulin, Patricia A.; Miller, Irvin M.; Schryer, David R.; Sidney, Barry D.; Wood, George M.; Upchurch, Billy T.; Brown, Kenneth G.

    1987-01-01

    Addition of CO to He pretreatment doubles catalytic activity. In sealed, high-energy, pulsed CO2 laser, CO and O2 form as decomposition products of CO2 in laser discharge zone. Products must be recombined, because oxygen concentration of more than few tenths of percent causes rapid deterioration of power, ending in unstable operation. Promising low-temperature catalyst for combining CO and O2 is platinum on tin oxide. New development increases activity of catalyst so less needed for recombination process.

  5. Bulk synthesis of nanoporous palladium and platinum powders

    SciTech Connect

    Robinson, David B; Fares, Stephen J; Tran, Kim L; Langham, Mary E

    2014-04-15

    Disclosed is a method for providing nanoporous palladium and platinum powders. These materials were synthesized on milligram to gram scales by chemical reduction of tetrahalo-complexes with ascorbate in a concentrated aqueous surfactant at temperatures between -20.degree. C. and 30.degree. C. The prepared particles have diameters of approximately 50 nm, wherein each particle is perforated by pores having diameters of approximately 3 nm, as determined by electron tomography. These materials are of potential value for hydrogen and electrical charge storage applications.

  6. Bulk synthesis of nanoporous palladium and platinum powders

    SciTech Connect

    Robinson, David B.; Fares, Stephen J.; Tran, Kim L.; Langham, Mary E.

    2012-04-17

    Disclosed is a method for providing nanoporous palladium and platinum powders. These materials were synthesized on milligram to gram scales by chemical reduction of tetrahalo-complexes with ascorbate in a concentrated aqueous surfactant at temperatures between -20.degree. C. and 30.degree. C. The prepared particles have diameters of approximately 50 nm, wherein each particle is perforated by pores having diameters of approximately 3 nm, as determined by electron tomography. These materials are of potential value for hydrogen and electrical charge storage applications.

  7. Hybrid isotope separation scheme

    DOEpatents

    Maya, Jakob

    1991-01-01

    A method of yielding selectively a desired enrichment in a specific isotope including the steps of inputting into a spinning chamber a gas from which a scavenger, radiating the gas with a wave length or frequency characteristic of the absorption of a particular isotope of the atomic or molecular gas, thereby inducing a photochemical reaction between the scavenger, and collecting the specific isotope-containing chemical by using a recombination surface or by a scooping apparatus.

  8. HYDROGEN ISOTOPE TARGETS

    DOEpatents

    Ashley, R.W.

    1958-08-12

    The design of targets for use in the investigation of nuclear reactions of hydrogen isotopes by bombardment with accelerated particles is described. The target con struction eomprises a backing disc of a metal selected from the group consisting of molybdenunn and tungsten, a eoating of condensed titaniunn on the dise, and a hydrogen isotope selected from the group consisting of deuterium and tritium absorbed in the coatiag. The proeess for preparing these hydrogen isotope targets is described.

  9. Hybrid isotope separation scheme

    DOEpatents

    Maya, J.

    1991-06-18

    A method is described for yielding selectively a desired enrichment in a specific isotope including the steps of inputting into a spinning chamber a gas from which a scavenger, radiating the gas with a wave length or frequency characteristic of the absorption of a particular isotope of the atomic or molecular gas, thereby inducing a photochemical reaction between the scavenger, and collecting the specific isotope-containing chemical by using a recombination surface or by a scooping apparatus. 2 figures.

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

    NASA Astrophysics Data System (ADS)

    Wong, Daniel Yuan Qiang; Ang, Wee Han

    2012-06-01

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

  11. Sn-Ag-Cu and Sn-Cu solders: Interfacial reactions with platinum

    NASA Astrophysics Data System (ADS)

    Kim, Tae Hyun; Kim, Young-Ho

    2004-06-01

    The interfacial reaction and intermetallic formation at the interface between tin solders containing a small amount of copper with platinum were investigated in this study. Sn-0.7Cu and Sn-1.7Cu solders were reacted with platinum by dipping Pt/Ti/Si specimens into the molten solder at 260°C. Sn-3.8Ag-0.7Cu solder was reacted with platinum by reflowing solder paste on a Pt/Ti/Si substrate at 250°C. PtSn4 intermetallic formed in all specimens while Cu6Sn5 interfacial intermetallic was not observed at the solder/platinum interfaces in any specimens. A parabolic relationship existed between the thickness of the Pt-Sn intermetallic and reaction time, which indicates the intermetallic formation in the solder/platinum interface is diffusion controlled.

  12. Palladium–platinum core-shell icosahedra with substantially enhanced activity and durability towards oxygen reduction

    SciTech Connect

    Wang, Xue; Choi, Sang-Il; Roling, Luke T.; Luo, Ming; Ma, Cheng; Zhang, Lei; Chi, Miaofang; Liu, Jingyue; Xie, Zhaoxiong; Herron, Jeffrey A.; Mavrikakis, Manos; Xia, Younan

    2015-07-02

    Conformal deposition of platinum as ultrathin shells on facet-controlled palladium nanocrystals offers a great opportunity to enhance the catalytic performance while reducing its loading. Here we report such a system based on palladium icosahedra. Owing to lateral confinement imposed by twin boundaries and thus vertical relaxation only, the platinum overlayers evolve into a corrugated structure under compressive strain. For the core-shell nanocrystals with an average of 2.7 platinum overlayers, their specific and platinum mass activities towards oxygen reduction are enhanced by eight- and sevenfold, respectively, relative to a commercial catalyst. Density functional theory calculations indicate that the enhancement can be attributed to the weakened binding of hydroxyl to the compressed platinum surface supported on palladium. After 10,000 testing cycles, the mass activity of the core-shell nanocrystals is still four times higher than the commercial catalyst. Ultimately, these results demonstrate an effective approach to the development of electrocatalysts with greatly enhanced activity and durability.

  13. Palladium-platinum core-shell icosahedra with substantially enhanced activity and durability towards oxygen reduction

    NASA Astrophysics Data System (ADS)

    Wang, Xue; Choi, Sang-Il; Roling, Luke T.; Luo, Ming; Ma, Cheng; Zhang, Lei; Chi, Miaofang; Liu, Jingyue; Xie, Zhaoxiong; Herron, Jeffrey A.; Mavrikakis, Manos; Xia, Younan

    2015-07-01

    Conformal deposition of platinum as ultrathin shells on facet-controlled palladium nanocrystals offers a great opportunity to enhance the catalytic performance while reducing its loading. Here we report such a system based on palladium icosahedra. Owing to lateral confinement imposed by twin boundaries and thus vertical relaxation only, the platinum overlayers evolve into a corrugated structure under compressive strain. For the core-shell nanocrystals with an average of 2.7 platinum overlayers, their specific and platinum mass activities towards oxygen reduction are enhanced by eight- and sevenfold, respectively, relative to a commercial catalyst. Density functional theory calculations indicate that the enhancement can be attributed to the weakened binding of hydroxyl to the compressed platinum surface supported on palladium. After 10,000 testing cycles, the mass activity of the core-shell nanocrystals is still four times higher than the commercial catalyst. These results demonstrate an effective approach to the development of electrocatalysts with greatly enhanced activity and durability.

  14. The DOE Isotopes Program

    NASA Astrophysics Data System (ADS)

    Gillo, Jehannes

    2015-10-01

    The DOE Isotope Program is a small federal program with a great deal of impact and is managed by the DOE Office of Nuclear Physics. The Isotope Program has been managed by the Office of Nuclear Physics since 2009, and since that time, has been re-defined in terms of mission, scope and operations. The program produces critical isotopes that are in short supply or simply unavailable from elsewhere to facilitate research and applications. Research is also supported to develop or improve production techniques that will increase availability of isotopes in high demand, such as alpha emitters for cancer therapy.

  15. High surface area platinum-titania aerogels: Preparation, structural properties, and hydrogenation activity

    SciTech Connect

    Schneider, M.; Duff, D.G.; Mallat, T.; Wildberger, M.; Baiker, A. )

    1994-06-01

    High surface area platinum-titania aerogels with marked meso-to macroporosity have been synthesized via the sol-gel-aerogel route. An acid-catalyzed titania gel was prepared from tetrabutoxy-titanium(IV) with methanol as solvent. The platinum precursor solutions added after the redispersion of the titania gel were either PtCl[sub 4], (NH[sub 4])[sub 2]PtCl[sub 6] or Pt(acac)[sub 2] dissolved in protic solvents. Platinum metal particles formed upon high-temperature supercritical drying. The platinum-titania aerogels have a BET surface area of 150 to 190 m[sup 2] g[sup [minus]1] after thermal pretreatments up to 673 K and the titania matrix consists of well-developed anatase crystallites of about 8-9 nm mean size. Depending on the platinum precursor used, the volume-weighted-mean particle size, determined by TEM, varies in the range 3.6 to 68 nm, consistent with XRD results for the platinum component. All aerogel samples showed a pronounced stability of both the titania matrix and the platinum particles towards air or hydrogen at temperatures up to 673 K. Thermal analysis, combined with mass spectroscopy, revealed that the untreated catalysts contain a considerable amount of entrapped organic impurities after the high-temperature supercritical drying. For the characterization of the activity and the accessibility of platinum particles the liquid phase hydrogenations of trans-stilbene and benzophenone were used as test reactions. Compared to a commercial alumina-supported platinum catalyst, the untreated 2-5 wt% platinum-titania catalysts derived from (NH[sub 4])[sub 2]PtCl[sub 6]- and especially PtCl[sub 4]-precursor solutions exhibit a markedly higher catalytic activity. In general, air pretreatments at 573 K or above had either no or promoting influence on activity. In contrast, pretreatments in hydrogen produced either no or detrimental activity change. 50 refs., 9 figs., 3 tabs.

  16. HEPARAN SULFATE PROTEOGLYCAN-MEDIATED ENTRY PATHWAY FOR CHARGED TRI-PLATINUM COMPOUNDS. DIFFERENTIAL CELLULAR ACCUMULATION MECHANISMS FOR PLATINUM

    PubMed Central

    Silva, Heveline; Frézard, Frédéric; Peterson, Erica J.; Kabolizadeh, Peyman; Ryan, John J.; Farrell, Nicholas P.

    2012-01-01

    We examined the mechanism of accumulation of charged polynuclear platinum complexes (PPCs), based on analogy of polyarginine interactions with the cell surface heparan sulfate proteoglycan (HSPG) family of protein-linked glycosoaminoglycan polysaccharides (GAGs). GAGS such as heparan sulfate (HS) and chondroitin sulfate (CS) mediate the cellular entry of many charged molecules. Fluorescence microscopy and flow cytometry showed that PPCs, but not the neutral cisplatin or oxaliplatin, blocked the cellular entry of TAMRA-R9 (a nonarginine peptide, R9) coupled to the TAMRA fluorescent label 5-(and 6-)carboxytetramethylrhodamine) in Chinese Hamster Ovary (CHO), human colon carcinoma (HCT116), and osteosarcoma (SAOS-2) cells. Furthermore, detection of platinum accumulation in wt CHO, mutant CHO-pgsD-677 (lacking HS), and CHO-pgsA (lacking HS/CS) cells confirms that HSPG-mediated interactions are an important mechanism for PPC internalization, but not so for uncharged cisplatin and oxaliplatin. Endocytosis inhibitor studies show that macropinocytosis, a mechanism of cell entry for heparan sulfate GAGs and arginine-rich peptides, is important in the cellular accumulation of “non-covalent” TriplatinNC, and to a lesser degree, the covalently-binding BBR3464. Clathrin-mediated endocytosis, however, was not involved in either case. Overall the results suggest a new proteoglycan-mediated mechanism for cellular accumulation of PPCs not shared by cisplatin or oxaliplatin. The results have significant implications for rational design of platinum antitumor drugs with distinct biological profiles in comparison to the clinically-used agents as well as expanding the chemotypes for HS proteoglycan-dependent receptors. PMID:22494465

  17. NMR of platinum catalysts: Double NMR of chemisorbed carbon monoxide and a model for the platinum NMR line shape

    SciTech Connect

    Makowka, C.D.; Slichter, C.P. ); Sinfelt, J.H. )

    1985-05-01

    The authors report observation of the NMR line of {sup 195}Pt atoms in the surface layer of small platinum-metal particles on which {sup 13}CO has been chemisorbed. The surface {sup 195}Pt atoms are resolved from those of {sup 195}Pt atoms deeper in the particle by spin-echo double resonance between {sup 195}Pt and {sup 13}C. The particles, supported on {eta}-alumina, had dispersions (fraction of the atoms that are on the surface) of 26% and 76%. Comparison with {sup 195}Pt resonance in Pt carbonyls suggests that the magnitude of the Knight shift of the surface Pt is less than 0.2%. Analysis of the {sup 195}Pt spin-lattice relaxation indicates that the small surface Knight shift results from cancellation of 6s and 5d core-polarization contributions as was found theoretically by Weinert and Freeman for clean Pt surfaces. The {sup 13}C-{sup 195}Pt indirect spin coupling is found to be very similar to those in diamagnetic platinum carbonyl molecules. The results show that CO bonds via the C atom and verify that concepts from studies of large single crystals are valid for the small particles. The key features of the {sup 195}Pt line shapes in these small platinum particles are described by a simple phenomenological model of the spatial Knight-shift variation inside these particles. The model successfully describes the major structure seen in the NMR line shapes of samples with dispersions ranging from 5% to 76%.

  18. Isotopically engineered semiconductors

    NASA Astrophysics Data System (ADS)

    Haller, E. E.

    1995-04-01

    Scientific interest, technological promise, and increased availability of highly enriched isotopes have led to a sharp rise in the number of experimental and theoretical studies with isotopically controlled semiconductor crystals. This review of mostly recent activities begins with an introduction to some past classical experiments which have been performed on isotopically controlled semiconductors. A review of the natural isotopic composition of the relevant elements follows. Some materials aspects resulting in part from the high costs of enriched isotopes are discussed next. Raman spectroscopy studies with a number of isotopically pure and deliberately mixed Ge bulk crystals show that the Brillouin-zone-center optical phonons are not localized. Their lifetime is almost independent of isotopic disorder, leading to homogeneous Raman line broadening. Studies with short period isotope superlattices consisting of alternating layers of n atomic planes of 70Ge and 74Ge reveal a host of zone-center phonons due to Brillouin-zone folding. At n≳40 one observes two phonon lines at frequencies corresponding to the bulk values of the two isotopes. In natural diamond, isotope scattering of the low-energy phonons, which are responsible for the thermal conductivity, is very strongly affected by small isotope disorder. Isotopically pure 12C diamond crystals exhibit thermal conductivities as high as 410 W cm-1 K-1 at 104 K, leading to projected values of over 2000 W cm-1 K-1 near 80 K. The changes in phonon properties with isotopic composition also weakly affect the electronic band structures and the lattice constants. The latter isotope dependence is most relevant for future standards of length based on crystal lattice constants. Capture of thermal neutrons by isotope nuclei followed by nuclear decay produces new elements, resulting in a very large number of possibilities for isotope selective doping of semiconductors. This neutron transmutation of isotope nuclei, already used

  19. Intracellular Cadmium Isotope Fractionation

    NASA Astrophysics Data System (ADS)

    Horner, T. J.; Lee, R. B.; Henderson, G. M.; Rickaby, R. E.

    2011-12-01

    Recent stable isotope studies into the biological utilization of transition metals (e.g. Cu, Fe, Zn, Cd) suggest several stepwise cellular processes can fractionate isotopes in both culture and nature. However, the determination of fractionation factors is often unsatisfactory, as significant variability can exist - even between different organisms with the same cellular functions. Thus, it has not been possible to adequately understand the source and mechanisms of metal isotopic fractionation. In order to address this problem, we investigated the biological fractionation of Cd isotopes within genetically-modified bacteria (E. coli). There is currently only one known biological use or requirement of Cd, a Cd/Zn carbonic anhydrase (CdCA, from the marine diatom T. weissfloggii), which we introduce into the E. coli genome. We have also developed a cleaning procedure that allows for the treating of bacteria so as to study the isotopic composition of different cellular components. We find that whole cells always exhibit a preference for uptake of the lighter isotopes of Cd. Notably, whole cells appear to have a similar Cd isotopic composition regardless of the expression of CdCA within the E. coli. However, isotopic fractionation can occur within the genetically modified E. coli during Cd use, such that Cd bound in CdCA can display a distinct isotopic composition compared to the cell as a whole. Thus, the externally observed fractionation is independent of the internal uses of Cd, with the largest Cd isotope fractionation occurring during cross-membrane transport. A general implication of these experiments is that trace metal isotopic fractionation most likely reflects metal transport into biological cells (either actively or passively), rather than relating to expression of specific physiological function and genetic expression of different metalloenzymes.

  20. Discovery of the krypton isotopes

    SciTech Connect

    Heim, M.; Fritsch, A.; Schuh, A.; Shore, A.; Thoennessen, M.

    2010-07-15

    Thirty-two krypton isotopes have been observed so far and the discovery of these isotopes is discussed here. For each isotope a brief summary of the first refereed publication, including the production and identification method, is presented.

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

    SciTech Connect

    Selig, W.S.

    1991-02-04

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

  2. Surface segregations in platinum-based alloy nanoparticles

    NASA Astrophysics Data System (ADS)

    Yamakawa, Shunsuke; Asahi, Ryoji; Koyama, Toshiyuki

    2014-04-01

    A phase-field model that describes the radial distributions of the ordered-disordered phase and surface segregation in a single-alloy nanoparticle is introduced to clarify the overall behavior of surface segregation of various Pt-based alloy nanoparticles. One of the obstacles to apply a platinum-transition metal alloy as a cathode electro-catalyst of a polymer electrolyte fuel cell is the need to ensure the retention of the designed surface composition in an alloy nanoparticle against the alloy combinations, a particle size, and heat treatment. From the results of calculations for CrPt, FePt, CoPt, NiPt, CuPt, PdPt, IrPt, and AuPt binary nanoparticles with diameters below 10 nm at 973.15 K, the compositional variation within a single particle was found to depend on the balance between the atomic interaction within particles and the surface free energy. In addition, the obtained specific steady-state composition of the surface varied significantly with alloy combination and particle diameter. Based on the general tendencies of a binary system to exhibit segregation, attempts to control the amount of platinum segregation on the surface using a ternary-alloy system were examined.

  3. Structural Preferences in Phosphanylthiolato Platinum(II) Complexes

    PubMed Central

    Duran, Josep; Real, Julio; Benet‐Buchholz, Jordi; Solà, Miquel

    2016-01-01

    Abstract Invited for this month's cover picture are the groups of Prof. Alfonso Polo and Dr. Albert Poater at the Universitat de Girona, as well as their collaborators from the Universitat Autònoma de Barcelona and the Institute of Chemical Research of Catalonia. The cover picture shows phosphanylthiolate ligand coordination on a platinum(II) center to give only the bischelate cis ‐P,P isomer when the ligand/Pt ratio is 2, whereas a trinuclear unexpected complex is achieved with a ligand/Pt ratio of 1. Here, the synthesis and structural determination is combined with density functional theory (DFT) calculations to rationalize the reaction mechanistically and through conceptual DFT. The exciting point of this study is that it opens the door to test new experimental pathways to monitor the preferred cis or trans arrangement of bidentate ligands to platinum. (Legend: H‐white, C‐black, P‐purple, S‐yellow, Cl‐green, Pt‐blue.) For more details, see the Full Paper on p. 51 ff. PMID:27308218

  4. Platinum group elements in the environment and their health risk.

    PubMed

    Ravindra, Khaiwal; Bencs, László; Van Grieken, René

    2004-01-01

    Accumulation of platinum group elements (PGEs) in the environment has been increased over the time. Catalytic converters of modern vehicles are considered to be the main sources of PGE pollution, since the correlation is between the Pt:Rh ratios in various environmental compartments and in converter units. The present literature survey shows that the concentration of these metals has increased significantly in the last decades in diverse environmental matrices; like airborne particulate matter, soil, roadside dust and vegetation, river, coastal and oceanic environment. Generally, PGEs are referred to behave in an inert manner and to be immobile. However, there is an evidence of spread and bioaccumulation of these elements in the environment. Platinum content of road dusts can be soluble, consequently, it enters the waters, sediments, soil and finally, the food chain. The effect of chronic occupational exposure to Pt compounds is well-documented, and certain Pt species are known to exhibit allergenic potential. However, the toxicity of biologically available anthropogenic Pt is not clear. Hence, there is a need to study the effect on human health of long-term chronic exposure to low levels of Pt compounds. PMID:14654273

  5. Platinum-group elements: so many excellent properties

    USGS Publications Warehouse

    Zientek, Michael L.; Loferski, Patricia J.

    2014-01-01

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

  6. A new capsule platinum resistance thermometer for cryogenic use

    NASA Astrophysics Data System (ADS)

    Courts, S. S.; Krause, J. K.

    2013-09-01

    Standards grade platinum resistance thermometers (SPRTs) obtain their high stability in part due to the strain-free mounting of the sensing wire. The space required for this strain-free mounting normally results in thermometers on the order of 6 mm diameter by 40 mm length in size. While these SPRTs are acceptable in many applications, it is desirable to reduce the size as much as possible for cryogenic use where space is of major concern. For over 40 years Minco Products, Inc. provided a smaller alternative with their model S1059, a high-stability cryogenic capsule platinum resistance thermometer (PRT) packaged in a copper canister sized only 3.2 mm diameter by 9.7 mm length. The packaging was compatible for use over the 13 K to 533 K temperature range. Unfortunately, this product was discontinued in 2009. In its absence, Lake Shore Cryotronics, Inc., has worked with Advanced Sensing Products to develop a similarly sized replacement sensor for cryogenic use. The replacement capsule PRT is manufactured using the model S1059 design, but with modifications to reduce the chance of lead breakage at the epoxy-lead interface. Test devices have been fabricated and tested for temperature response and stability upon repeated calibration from 13 K to 330 K. The new sensor design features and performance data are presented in this work.

  7. Nonuniformity effects in a hybrid platinum silicide imaging device

    NASA Astrophysics Data System (ADS)

    Dereniak, Eustace L.; Perry, David L.

    1992-05-01

    The objective of this project was twofold. The first objective was to characterize the Hughes Aircraft Company CRC-365 platinum silicide imaging device in a starting infrared sensor system. The CRC-365 is a hybrid 256 x 256 IR focal plane array that operates in the 3-5 micrometer thermal infrared band. A complete sensor and computer interface were built for these tests, using, plans provided by the Rome Laboratory at Hanscom AFB. Testing of the device revealed largely satisfactory performance, with notable exception in the areas of temporal response, temporal noise, and electrical crosstalk. The second objective of this research was to advance the understanding of how detector nonuniformity effects reduce the performance of sensors of this type. Notable accomplishments in this area included a complete linear analysis of corrected thermal imaging in platinum silicide sensors, a nonlinear analysis of the CRC-365's expected performance, analysis of its actual performance when operated with nonuniformity correction, and the development of a new figure of merit. It was demonstrated that the CRC-365 is capable of maintaining background-noise-limited performance over at least a 40 K target temperature range, when operated with two-point nonuniformity correction.

  8. (Carbon isotope fractionation inplants)

    SciTech Connect

    O'Leary, M.H.

    1990-01-01

    The objectives of this research are: To develop a theoretical and experimental framework for understanding isotope fractionations in plants; and to develop methods for using this isotope fractionation for understanding the dynamics of CO{sub 2} fixation in plants. Progress is described.

  9. Detecting isotopic ratio outliers

    SciTech Connect

    Bayne, C.K.; Smith, D.H.

    1985-01-01

    An alternative method is proposed for improving isotopic ratio estimates. This method mathematically models pulse-count data and uses iterative reweighted Poisson regression to estimate model parameters to calculate the isotopic ratios. This computer-oriented approach provides theoretically better methods than conventional techniques to establish error limits and to identify outliers. 6 refs., 3 figs., 3 tabs.

  10. Laser isotope separation

    DOEpatents

    Robinson, C. Paul; Jensen, Reed J.; Cotter, Theodore P.; Boyer, Keith; Greiner, Norman R.

    1988-01-01

    A process and apparatus for separating isotopes by selective excitation of isotopic species of a volatile compound by tuned laser light. A highly cooled gas of the volatile compound is produced in which the isotopic shift is sharpened and defined. Before substantial condensation occurs, the cooled gas is irradiated with laser light precisely tuned to a desired wavelength to selectively excite a particular isotopic species in the cooled gas. The laser light may impart sufficient energy to the excited species to cause it to undergo photolysis, photochemical reaction or even to photoionize. Alternatively, a two-photon irradiation may be applied to the cooled gas to induce photolysis, photochemical reaction or photoionization. The process is particularly applicable to the separation of isotopes of uranium.

  11. Photochemical isotope separation

    DOEpatents

    Robinson, C. Paul; Jensen, Reed J.; Cotter, Theodore P.; Greiner, Norman R.; Boyer, Keith

    1987-01-01

    A process for separating isotopes by selective excitation of isotopic species of a volatile compound by tuned laser light. A highly cooled gas of the volatile compound is produced in which the isotopic shift is sharpened and defined. Before substantial condensation occurs, the cooled gas is irradiated with laser light precisely tuned to a desired wavelength to selectively excite a particular isotopic species in the cooled gas. The laser light may impart sufficient energy to the excited species to cause it to undergo photochemical reaction or even to photoionize. Alternatively, a two-photon irradiation may be applied to the cooled gas to induce photochemical reaction or photoionization. The process is particularly applicable to the separation of isotopes of uranium and plutonium.

  12. Discovery of Isotopes

    NASA Astrophysics Data System (ADS)

    May, Erin; Thoennessen, Michael

    2011-10-01

    To date, no comprehensive study has been undertaken regarding the initial detection and identification of isotopes. At NSCL, a project has been initiated to catalog and report the initial observation of every isotope. The conditions characterizing the successful discovery of an isotope include a clear and unambiguous mass and element identification through decay curves, mass spectroscopy, gamma-ray spectra, and/or relationships to other isotopes, as well as the publication of such findings in a refereed journal. I will present the documentation for eight elements: cesium, lanthanum, praseodymium, promethium, samarium, europium, gadolinium, and terbium. The year and author of each initial publication along with the location and methods of production and identification will be shown. A summary and overview of all ~3000 isotopes documented so far as a function of discovery year, method and place will also be presented.

  13. Photochemical isotope separation

    DOEpatents

    Robinson, C.P.; Jensen, R.J.; Cotter, T.P.; Greiner, N.R.; Boyer, K.

    1987-04-28

    A process is described for separating isotopes by selective excitation of isotopic species of a volatile compound by tuned laser light. A highly cooled gas of the volatile compound is produced in which the isotopic shift is sharpened and defined. Before substantial condensation occurs, the cooled gas is irradiated with laser light precisely tuned to a desired wavelength to selectively excite a particular isotopic species in the cooled gas. The laser light may impart sufficient energy to the excited species to cause it to undergo photochemical reaction or even to photoionize. Alternatively, a two-photon irradiation may be applied to the cooled gas to induce photochemical reaction or photoionization. The process is particularly applicable to the separation of isotopes of uranium and plutonium. 8 figs.

  14. Laser isotope separation

    DOEpatents

    Robinson, C.P.; Reed, J.J.; Cotter, T.P.; Boyer, K.; Greiner, N.R.

    1975-11-26

    A process and apparatus for separating isotopes by selective excitation of isotopic species of a volatile compound by tuned laser light is described. A highly cooled gas of the volatile compound is produced in which the isotopic shift is sharpened and defined. Before substantial condensation occurs, the cooled gas is irradiated with laser light precisely tuned to a desired wavelength to selectively excite a particular isotopic species in the cooled gas. The laser light may impart sufficient energy to the excited species to cause it to undergo photolysis, photochemical reaction or even to photoionize. Alternatively, a two-photon irradiation may be applied to the cooled gas to induce photolysis, photochemical reaction or photoionization. The process is particularly applicable to the separation of isotopes of uranium.

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

    NASA Astrophysics Data System (ADS)

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

    1995-09-01

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

  16. Concealed configuration mixing and shape coexistence in the platinum nuclei

    SciTech Connect

    Garcia-Ramos, J. E.; Hellemans, V.; Heyde, K.

    2012-10-20

    The role of configuration mixing in the Pt region is investigated. The nature of the ground state changes smoothly, being spherical around mass A{approx} 174 and A{approx} 192 and deformed around the mid-shell N= 104 region. Interacting Boson Model with configuration mixing calculations are presented for deformations and isotope shifts. The assumption of the existence of two configurations with very different deformation provides a simple framework to explain the observed isotope shifts systematics.

  17. Evolving concepts in the management of drug resistant ovarian cancer: dose dense chemotherapy and the reversal of clinical platinum resistance.

    PubMed

    Pinato, David J; Graham, Janet; Gabra, Hani; Sharma, Rohini

    2013-04-01

    Despite the initially high response rate to standard front-line debulking surgery followed by platinum-based chemotherapy, the relapse rate in ovarian cancer is high and many patients will recur within 6 months of completing platinum based treatment. These patients may still require further chemotherapy despite being considered "platinum resistant". In this setting, response rates to conventionally scheduled second line platinum and non-platinum agents is low, ranging between 5% and 15%. There is an emerging body of evidence that in this scenario, chemotherapeutic activity can be enhanced using unconventionally scheduled "dose-dense" platinum and non-platinum based regimens with improved response rates of up to 65%. Randomised studies to evaluate the impact of this approach on survival in recurrent, platinum resistant disease are urgently required to confirm the promising phase II findings if there is to be a change in the standard of care of patients with platinum resistant disease. In this review we discuss the evolving strategies to overcome resistance in patients with platinum resistant ovarian cancer with a particular focus on alterations in dose schedule as a means of reversing platinum resistance. PMID:22595680

  18. Predicting Ovarian Cancer Patients' Clinical Response to Platinum-Based Chemotherapy by Their Tumor Proteomic Signatures.

    PubMed

    Yu, Kun-Hsing; Levine, Douglas A; Zhang, Hui; Chan, Daniel W; Zhang, Zhen; Snyder, Michael

    2016-08-01

    Ovarian cancer is the deadliest gynecologic malignancy in the United States with most patients diagnosed in the advanced stage of the disease. Platinum-based antineoplastic therapeutics is indispensable to treating advanced ovarian serous carcinoma. However, patients have heterogeneous responses to platinum drugs, and it is difficult to predict these interindividual differences before administering medication. In this study, we investigated the tumor proteomic profiles and clinical characteristics of 130 ovarian serous carcinoma patients analyzed by the Clinical Proteomic Tumor Analysis Consortium (CPTAC), predicted the platinum drug response using supervised machine learning methods, and evaluated our prediction models through leave-one-out cross-validation. Our data-driven feature selection approach indicated that tumor proteomics profiles contain information for predicting binarized platinum response (P < 0.0001). We further built a least absolute shrinkage and selection operator (LASSO)-Cox proportional hazards model that stratified patients into early relapse and late relapse groups (P = 0.00013). The top proteomic features indicative of platinum response were involved in ATP synthesis pathways and Ran GTPase binding. Overall, we demonstrated that proteomic profiles of ovarian serous carcinoma patients predicted platinum drug responses as well as provided insights into the biological processes influencing the efficacy of platinum-based therapeutics. Our analytical approach is also extensible to predicting response to other antineoplastic agents or treatment modalities for both ovarian and other cancers. PMID:27312948

  19. Hierarchical Nanoporous Gold-Platinum with Heterogeneous Interfaces for Methanol Electrooxidation

    PubMed Central

    Xiao, Shuang; Xiao, Fei; Hu, Yuan; Yuan, Songliu; Wang, Shuai; Qian, Lihua; Liu, Yunqi

    2014-01-01

    The electrocatalysts utilized as the prospective electrodes in fuel cells and high efficient energy conversion devices require both the interconnected channels for efficient electrolyte transportation and the superior catalytic activity with long service life. In this work, nanoporous gold with the rigid skeletons in three dimensions is partially decorated by porous platinum shell containing nanoscale interstitials, aiming to create the heterogeneous gold-platinum interfaces and facilitate the electrolyte transportation as well. In comparison with no catalytic activity of bare nanoporous gold, the catalytic activity of hierarchical nanoporous gold-platinum towards electrochemical oxidation of methanol increases with the loading level of platinum shells, resulting in the highest electrochemical area of 70.4 m2·g−1 after the normalization by the mass of platinum. Heterogeneous gold-platinum interfaces affect the tolerance of the absorbed intermediate species because of the oxidization by the oxygenated species absorbed on the gold surface and the enhanced ion transportation within the porous platinum shell. PMID:24621809

  20. DNA-PK mediates AKT activation and apoptosis inhibition in clinically acquired platinum resistance.

    PubMed

    Stronach, Euan A; Chen, Michelle; Maginn, Elaina N; Agarwal, Roshan; Mills, Gordon B; Wasan, Harpreet; Gabra, Hani

    2011-11-01

    Clinical resistance to chemotherapy is a frequent event in cancer treatment and is closely linked to poor outcome. High-grade serous (HGS) ovarian cancer is characterized by p53 mutation and high levels of genomic instability. Treatment includes platinum-based chemotherapy and initial response rates are high; however, resistance is frequently acquired, at which point treatment options are largely palliative. Recent data indicate that platinum-resistant clones exist within the sensitive primary tumor at presentation, implying resistant cell selection after treatment with platinum chemotherapy. The AKT pathway is central to cell survival and has been implicated in platinum resistance. Here, we show that platinum exposure induces an AKT-dependent, prosurvival, DNA damage response in clinically platinum-resistant but not platinum-sensitive cells. AKT relocates to the nucleus of resistant cells where it is phosphorylated specifically on S473 by DNA-dependent protein kinase (DNA-PK), and this activation inhibits cisplatin-mediated apoptosis. Inhibition of DNA-PK or AKT, but not mTORC2, restores platinum sensitivity in a panel of clinically resistant HGS ovarian cancer cell lines: we also demonstrate these effects in other tumor types. Resensitization is associated with prevention of AKT-mediated BAD phosphorylation. Strikingly, in patient-matched sensitive cells, we do not see enhanced apoptosis on combining cisplatin with AKT or DNA-PK inhibition. Insulin-mediated activation of AKT is unaffected by DNA-PK inhibitor treatment, suggesting that this effect is restricted to DNA damage-mediated activation of AKT and that, clinically, DNA-PK inhibition might prevent platinum-induced AKT activation without interfering with normal glucose homeostasis, an unwanted toxicity of direct AKT inhibitors. PMID:22131882

  1. DNA-PK Mediates AKT Activation and Apoptosis Inhibition in Clinically Acquired Platinum Resistance12

    PubMed Central

    Stronach, Euan A; Chen, Michelle; Maginn, Elaina N; Agarwal, Roshan; Mills, Gordon B; Wasan, Harpreet; Gabra, Hani

    2011-01-01

    Clinical resistance to chemotherapy is a frequent event in cancer treatment and is closely linked to poor outcome. High-grade serous (HGS) ovarian cancer is characterized by p53 mutation and high levels of genomic instability. Treatment includes platinum-based chemotherapy and initial response rates are high; however, resistance is frequently acquired, at which point treatment options are largely palliative. Recent data indicate that platinum-resistant clones exist within the sensitive primary tumor at presentation, implying resistant cell selection after treatment with platinum chemotherapy. The AKT pathway is central to cell survival and has been implicated in platinum resistance. Here, we show that platinum exposure induces an AKT-dependent, prosurvival, DNA damage response in clinically platinum-resistant but not platinum-sensitive cells. AKT relocates to the nucleus of resistant cells where it is phosphorylated specifically on S473 by DNA-dependent protein kinase (DNA-PK), and this activation inhibits cisplatin-mediated apoptosis. Inhibition of DNA-PK or AKT, but not mTORC2, restores platinum sensitivity in a panel of clinically resistant HGS ovarian cancer cell lines: we also demonstrate these effects in other tumor types. Resensitization is associated with prevention of AKT-mediated BAD phosphorylation. Strikingly, in patient-matched sensitive cells, we do not see enhanced apoptosis on combining cisplatin with AKT or DNA-PK inhibition. Insulin-mediated activation of AKT is unaffected by DNA-PK inhibitor treatment, suggesting that this effect is restricted to DNA damage-mediated activation of AKT and that, clinically, DNA-PK inhibition might prevent platinum-induced AKT activation without interfering with normal glucose homeostasis, an unwanted toxicity of direct AKT inhibitors. PMID:22131882

  2. Characterization of the mechanical properties of freestanding platinum thin films

    NASA Astrophysics Data System (ADS)

    Abbas, Khawar

    Many MEMS devices utilize nanocrystalline thin metallic films as mechanical structures, in particular, micro switching devices where these films are used as Ohmic contacts. But the elastic and plastic properties of these thin films (thickness < 1mum) are significantly different from those of the bulk material. At these scales the volume fraction of material defects such as: grain boundaries, dislocations and interstitials become quite significant and become a chief contributor to the physical and mechanical material properties. In order to effectively design MEMS devices it is important that these material properties are explored and mechanical behavior of the structure they form be characterized. Popular thin film materials used in MEMS devices are Aluminum (Al), Copper (Cu), Nickel (Ni) and Gold (Au). Platinum has traditionally gained acceptance into the MEMS industry because of its chemical inertness and high temperature stability. However the mechanical properties of platinum remains the least exploited. Platinum has a high Young's Modulus (164 GPa, for bulk) and high melting temperature (1768 °C) and therefore can be used as a 'thin film' structure (cantilever, a bridge or a membrane) in high temperature environments with high resistance to mechanical failure. The physical size of these thin film structure make it very difficult to handle them and employ traditional mechanical testing methodologies and techniques and therefore require custom test platforms. One such recently developed platform is presented in this dissertation. The test platform is comprised of a microfabricated cascaded thermal actuator system and test specimen. The cascaded thermal actuator system is capable of providing tens of microns of displacement and tens of milli-Newton forces simultaneously while applying a relatively low temperature gradient across the test specimen. The dimensions of the platform make its use possible in both the SEM/TEM environments and on a probe station under

  3. Platinum anticancer drugs. From serendipity to rational design.

    PubMed

    Monneret, C

    2011-11-01

    The discovery of cis-platin was serendipitous. In 1965, Rosenberg was looking into the effects of an electric field on the growth of Escherichia coli bacteria. He noticed that bacteria ceased to divide when placed in an electric field but what Rosenberg also observed was a 300-fold increase in the size of the bacteria. He attributed this to the fact that somehow the platinum-conducting plates were inducing cell growth but inhibiting cell division. It was later deduced that the platinum species responsible for this was cis-platin. Rosenberg hypothesized that if cis-platin could inhibit bacterial cell division it could also stop tumor cell growth. This conjecture has proven correct and has led to the introduction of cis-platin in cancer therapy. Indeed, in 1978, six years after clinical trials conducted by the NCI and Bristol-Myers-Squibb, the U.S. Food and Drug Administration (FDA) approved cis-platin under the name of Platinol(®) for treating patients with metastatic testicular or ovarian cancer in combination with other drugs but also for treating bladder cancer. Bristol-Myers Squibb also licensed carboplatin, a second-generation platinum drug with fewer side effects, in 1979. Carboplatin entered the U.S. market as Paraplatin(®) in 1989 for initial treatment of advanced ovarian cancer in established combination with other approved chemotherapeutic agents. Numerous platin derivatives have been further developed with more or less success and the third derivative to be approved in 1994 was oxaliplatin under the name of Eloxatin(®). It was the first platin-based drug to be active against metastatic colorectal cancer in combination with fluorouracil and folinic acid. The two others platin-based drugs to be approved were nedaplatin (Aqupla(®)) in Japan and lobaplatin in China, respectively. More recently, a strategy to overcome resistance due to interaction with thiol-containing molecules led to the synthesis of picoplatin in which one of the amines linked to Pt

  4. Biotinylated Platinum(II) Ferrocenylterpyridine Complexes for Targeted Photoinduced Cytotoxicity.

    PubMed

    Mitra, Koushambi; Shettar, Abhijith; Kondaiah, Paturu; Chakravarty, Akhil R

    2016-06-01

    Biotinylated platinum(II) ferrocenylterpyridine (Fc-tpy) complexes [Pt(Fc-tpy)(L(1))]Cl (1) and [Pt(Fc-tpy)(L(2))]Cl (2), where HL(1) and HL(2) are biotin-containing ligands, were prepared, and their targeted photoinduced cytotoxic effect in cancer cells over normal cells was studied. A nonbiotinylated complex, [Pt(Fc-tpy)(L(3))]Cl (3), was prepared as a control to study the role of the biotin moiety in cellular uptake properties of the complexes. Three platinum(II) phenylterpyridine (Ph-tpy) complexes, viz., [Pt(Ph-tpy)(L(1))]Cl (4), [Pt(Ph-tpy)(L(2))]Cl (5), and [Pt(Ph-tpy)(L(3))]Cl (6), were synthesized and explored to understand the role of a metal-bound Fc-tpy ligand over Ph-tpy as a photoinitiator. The Fc-tpy complexes displayed an intense absorption band near 640 nm, which was absent in their Ph-tpy analogues. The Fc-tpy complexes (1 mM in 0.1 M TBAP) showed an irreversible cyclic voltammetric anodic response of the Fc/Fc(+) couple near 0.25 V. The Fc-tpy complexes displayed photodegradation in red light of 647 nm involving the formation of a ferrocenium ion (Fc(+)) and reactive oxygen species (ROS). Photoinduced release of the biotinylated ligands was observed from spectral measurements, and this possibly led to the controlled generation of an active platinum(II) species, which binds to the calf-thymus DNA used for this study. The biotinylated photoactive Fc-tpy complexes showed significant photoinduced cytotoxicity, giving a IC50 value of ∼7 μM in visible light of 400-700 nm with selective uptake in BT474 cancer cells over HBL-100 normal cells. Furthermore, ferrocenyl complexes resulted in light-induced ROS-mediated apoptosis, as indicated by DCFDA, annexin V/FITC staining, and sub-G1 DNA content determined by fluorescent activated cell sorting analysis. The phenyl analogues 4 and 5 were photostable, served as DNA intercalators, and demonstrated selective cytotoxicity in the cancer cells, giving IC50 values of ∼4 μM. PMID:27171926

  5. Synthesis and reactivity of dichloroboryl complexes of platinum(II).

    PubMed

    Charmant, Jonathan P H; Fan, Cheng; Norman, Nicholas C; Pringle, Paul G

    2007-01-01

    The reaction between [Pt(nbe)3] (nbe=norbornene), two equivalents of the phosphines PPh3, PMePh2 or PMe2Ph and 1 equivalent of BCl3 affords the platinum dichloroboryl species [PtCl(BCl2)(PPh3)2], [PtCl(BCl2)(PMePh2)2] and [PtCl(BCl2)(PMe2Ph)2]. All three complexes were characterised by X-ray crystallography and reveal that the boryl group lies trans to the chloride. With PMe3 as the phosphine, the complex [PtCl(BCl2)(PMe3)2] is isolated in high yield as a white crystalline powder although crystals suitable for X-ray crystallography were not obtained. Crystals were obtained of a product shown by X-ray crystallography to be the unusual dinuclear species [Pt2(BCl2)2(PMe3)4(micro-Cl)][BCl4] which reveals an arrangement in which two square planar platinum(II) centres are linked by a single bridging chloride which is trans to a BCl2 group on each platinum centre. The reaction of [PtCl(BCl2)(PMe3)2] with NEt3 or pyridine (py) affords the adducts [PtCl{BCl2(NEt3)}(PMe3)2] and [PtCl{BCl2(py)}(PMe3)2], respectively, both characterised spectroscopically. The reaction between [PtCl(BCl2)(PMe3)2] and either 4 equivalents of NHEt2 or piperidine (pipH) results in the mono-substituted boryl species [PtCl{BCl(NEt2)}(PMe3)2] and [PtCl{BCl(pip)}(PMe3)2], respectively, the former characterised by X-ray crystallography. Treatment of either [PtCl(BCl2)(PMe3)2] (in the presence of excess NEt3) or [PtCl{BCl(NEt2)}(PMe3)2] with catechol affords the B(cat) (cat=catecholate) derivative [PtCl{B(cat)}(PMe3)2] which is also formed in the reaction between [Pt(PMe3)4] and ClB(cat) and also from the slow decomposition of [Pt{B(cat)}2(PMe3)2] in dichloromethane over a period of months. The compound [Pt{B(cat)}2(PMe3)2] was prepared from the reaction between [Pt(PMe3)4] and B2(cat)2. PMID:17160181

  6. Rare-isotope and kinetic studies of Pt/SnO2 catalysts

    NASA Technical Reports Server (NTRS)

    Upchurch, Billy T.; Wood, George M.; Schryer, David R.; Hess, Robert V.; Miller, Irvin M.; Kielin, Erik J.

    1990-01-01

    Closed-cycle pulsed CO2 laser operation requires the use of an efficient CO-O2 recombination catalyst for these dissociation products which otherwise would degrade the laser operation. The catalyst must not only operate at low temperatures but also must operate efficiently for long periods. In the case of the Laser Atmospheric Wind Sounder (LAWS) laser, an operational lifetime of 3 years is required. Additionally, in order to minimize atmospheric absorption and enhance aerosol scatter of laser radiation, the LAWS system will operate at 9.1 micrometers with an oxygen-18 isotope CO2 lasing medium. Consequently, the catalyst must not only operate at low temperatures but must also preserve the isotopic integrity of the rare-isotope composition in the recombination mode. Several years ago an investigation of commercially available and newly synthesized recombination catalysts for use in closed-cycle pulsed common and rare-isotope CO2 lasers was implemented at the NASA Langley Research Center. Since that time, mechanistic efforts utilizing both common and rare oxygen isotopes have been implemented and continue. Rare-isotope studies utilizing commercially available platinum-tin oxide catalyst have demonstrated that the catalyst contributes oxygen-16 to the product carbon dioxide thus rendering it unusable for rare-isotope applications. A technique has been developed for modification of the surface of the common-isotope catalyst to render it usable. Results of kinetic and isotope label studies using plug flow, recycle plug flow, and closed internal recycle plug flow reactor configuration modes are discussed.

  7. Antimicrobial Properties of Diamondlike Carbon-Silver-Platinum Nanocomposite Thin Films

    SciTech Connect

    CHRISTOPHER, BERRY

    2005-03-07

    Silver and platinum were incorporated within diamondlike carbon (DLC) thin films using a multicomponent target pulsed laser deposition process. Transmission electron microscopy of the DLC-silver and DLC-platinum composite films reveals that the metals self-assemble into particulate nanocomposite structures. Nanoindentation testing has shown that diamondlike carbon-silver films exhibit hardness and Young's modulus values of approximately 37 GPa and 333 GPa, respectively. DLC-silver-platinum films exhibited antimicrobial properties against Staphylococcus bacteria. Diamondlike carbon-biofunctional metal nanocomposite films have a variety of potential medical and antimicrobial applications.

  8. Dielectric loss peak due to platinum electrode porosity in lead zirconate titanate thin-film capacitors

    NASA Astrophysics Data System (ADS)

    Jung, D. J.; Dawber, M.; Ruediger, A.; Scott, J. F.; Kim, H. H.; Kim, Kinam

    2002-09-01

    Impedance spectroscopy measurements were carried out in situ on lead zirconate titanate capacitors 1.2×1.2 μm2 in size on a Samsung 4 Mbit 6 in, wafer. We show here that large dielectric loss appears at low frequencies, which is a constriction effect due to the porosity of the platinum electrode. Porous platinum electrodes facilitate an oxygen electrode reaction. The effect may be removed by annealing the platinum electrode at moderate temperature (300 °C). Such an anneal should thus be considered an essential step in the fabrication of a ferroelectric thin-film capacitor on Pt.

  9. Surface free energy of platinum nanoparticles at zero pressure: A molecular dynamic study

    NASA Astrophysics Data System (ADS)

    Akbarzadeh, Hamed; Abroshan, Hadi; Parsafar, Gholam Abbas

    2010-02-01

    Metallic nanoparticles are interesting because of their use in catalysis and sensors. The surface energy of the FCC platinum nanoparticles are investigated via molecular dynamics simulation using Quantum Sutton-Chen (QSC) potential. We have calculated the Gibbs free energy for the FCC platinum bulk and also for its nanoparticle. All calculations have been carried out at zero pressure. We have used the thermodynamic integration method to obtain the Gibbs free energy. The total Gibbs free energy is taken as the sum of its central bulk and its surface free energy. We have calculated the free energy of a platinum nanoparticle as a function of temperature.

  10. Evaluation of novel trans-sulfonamide platinum complexes against tumor cell lines.

    PubMed

    Pérez, Carlos; Díaz-García, C Vanesa; Agudo-López, Alba; del Solar, Virginia; Cabrera, Silvia; Agulló-Ortuño, M Teresa; Navarro-Ranninger, Carmen; Alemán, José; López-Martín, José A

    2014-04-01

    Platinum-based drugs, mainly cisplatin, are employed for the treatment of solid malignancies. However, cisplatin treatment often results in the development of chemoresistance, leading to therapeutic failure. Here, the antitumor activity of different trans-sulfonamide platinum complexes in a panel of human cell lines is presented. The cytotoxicity profiles and cell cycle analyses of these platinum sulfonamide complexes were different from those of cisplatin. These studies showed that complex 2b with cyclohexyldiamine and dansyl moieties had the best antitumoral activities. PMID:24589491

  11. Chemisorptive properties of platinum supported on zeolite Y studied by infrared emission spectroscopy

    SciTech Connect

    Primet, M.; Fouilloux, P.; Imelik, B.

    1980-02-01

    IR emission spectra obtained with a Fourier transform spectrometer at 110/sup 0/C revealed that pyridine adsorbed on platinum Y zeolite by coordination to the Na ion and by formation of pyridinium ions with bands at 755 and 685 cm/sup -//sup 1/; the formation of pyridinium ions suggested the presence of acidic OH groups formed during platinum reduction with hydrogen. Bands observed at 465 and 2070 cm/sup -//sup 1/ in the spectra of adsorbed carbon monoxide were attributed to linearly adsorbed species, and a band at 1850 cm/sup -//sup 1/ to carbon monoxide bonded to two platinum atoms. The experimental technique and its scope are discussed.

  12. Concentrations of platinum group elements in 122 U.S. coal samples

    USGS Publications Warehouse

    Oman, C.L.; Finkelman, R.B.; Tewalt, S.J.

    1997-01-01

    Analysis of more than 13,000 coal samples by semi-quantitative optical emission spectroscopy (OES) indicates that concentrations of the platinum group elements (iridium, palladium, platinum, osmium, rhodium, and ruthenium) are less than 1 ppm in the ash, the limit of detection for this method of analysis. In order to accurately determine the concentration of the platinum group elements (PGE) in coal, additional data were obtained by inductively coupled plasma mass spectroscopy, an analytical method having part-per-billion (ppb) detection limits for these elements. These data indicate that the PGE in coal occur in concentrations on the order of 1 ppb or less.

  13. Isotopically controlled semiconductors

    SciTech Connect

    Haller, Eugene E.

    2006-06-19

    The following article is an edited transcript based on the Turnbull Lecture given by Eugene E. Haller at the 2005 Materials Research Society Fall Meeting in Boston on November 29, 2005. The David Turnbull Lectureship is awarded to recognize the career of a scientist who has made outstanding contributions to understanding materials phenomena and properties through research, writing, and lecturing, as exemplified by the life work of David Turnbull. Haller was named the 2005 David Turnbull Lecturer for his 'pioneering achievements and leadership in establishing the field of isotopically engineered semiconductors; for outstanding contributions to materials growth, doping and diffusion; and for excellence in lecturing, writing, and fostering international collaborations'. The scientific interest, increased availability, and technological promise of highly enriched isotopes have led to a sharp rise in the number of experimental and theoretical studies with isotopically controlled semiconductor crystals. This article reviews results obtained with isotopically controlled semiconductor bulk and thin-film heterostructures. Isotopic composition affects several properties such as phonon energies, band structure, and lattice constant in subtle, but, for their physical understanding, significant ways. Large isotope-related effects are observed for thermal conductivity in local vibrational modes of impurities and after neutron transmutation doping. Spectacularly sharp photoluminescence lines have been observed in ultrapure, isotopically enriched silicon crystals. Isotope multilayer structures are especially well suited for simultaneous self- and dopant-diffusion studies. The absence of any chemical, mechanical, or electrical driving forces makes possible the study of an ideal random-walk problem. Isotopically controlled semiconductors may find applications in quantum computing, nanoscience, and spintronics.

  14. ISOTOPE SEPARATING APPARATUS

    DOEpatents

    Kudravetz, M.K.; Greene, H.B.

    1958-09-16

    This patent relates to control systems for a calutron and, in particular, describes an electro-mechanical system for interrupting the collection of charged particles when the ratio between the two isotopes being receivcd deviates from a predetermined value. One embodiment of the invention includes means responsive to the ratio between two isotopes being received for opening a normally closed shutter over the receiver entrance when the isotope ratio is the desired value. In another form of the invention the collection operation is interrupted by changing the beam accelerating voltage to deflect the ion beam away from the receiver.

  15. Carbon isotope techniques

    SciTech Connect

    Coleman, D.C. ); Fry, B. )

    1991-01-01

    This book is a hands-on introduction to using carbon isotope tracers in experimental biology and ecology. It is a bench-top reference with protocols for the study of plants, animals, and soils. The {sup 11}C, {sup 12}C, {sup 13}C, and {sup 14}C carbon isotopes are considered and standard techniques are described by established authors. The compilation includes the following features: specific, well-established, user-oriented techniques; carbon cycles in plants, animals, soils, air, and water; isotopes in ecological research; examples and sample calculations.

  16. Trapping five-coordinate platinum(iv) intermediates.

    PubMed

    Shaw, Paul A; Phillips, Jessica M; Clarkson, Guy J; Rourke, Jonathan P

    2016-07-28

    The oxidation of three different complexes of the doubly cycloplatinated 2,6-di(4-fluorophenyl)pyridine ligand (namely DMSO, PPh3 and PPr3 derivatives, 1a, 1b and 1c, respectively) with the electrophilic oxidant iodobenzenedichloride was studied. In each case oxidation can yield a simple trans-dichloro platinum(iv) complex (2(t)), which subsequently isomerises to the cis isomer (2(c)). However, by changing the solvent, or performing the reaction in the presence of an additional ligating species, a five-coordinate intermediate can be trapped out and isolated. Thus, cationic species with additional DMSO or pyridine coordinated could be collected for the DMSO and PPh3 derivatives. The PPr3 derivative traps out the reactive five-coordinate species with an agostic interaction that subsequently induces a transcyclometallation reaction to give a complex with a singly cyclometallated pyridine and a cyclometallated phosphine, which was characterised crystallographically, (6c PMID:27335216

  17. On the high-pressure superconducting phase in platinum hydride

    NASA Astrophysics Data System (ADS)

    Szczȩśniak, D.; Zemła, T. P.

    2015-08-01

    Motivated by the ambiguous experimental data for the superconducting phase in silane (SiH4), which may originate from platinum hydride (PtH), we provide a theoretical study of the superconducting state in the latter alloy. The quantitative estimates of the thermodynamics of PtH at 100 GPa are given for a wide range of Coulomb pseudopotential values ({μ }*) within the Eliashberg formalism. The obtained critical temperature value ({T}{{C}}\\in < 12.94,20.01> for {μ }*\\in < 0.05,0.15> ) agrees well with the experimental TC for SiH4, which may be ascribed to PtH. Moreover, the calculated characteristic thermodynamic ratios exceed the predictions of the Bardeen-Cooper-Schrieffer theory, implying the occurrence of strong-coupling and retardation effects in PtH. We note that our results may be of high relevance for future theoretical and experimental studies on hydrides.

  18. RF magnetron sputtering of thick platinum coatings on glass microspheres

    SciTech Connect

    Meyer, S.F.; Hsieh, E.J.; Burt, R.J.

    1980-05-28

    Thick platinum coatings on glass microspheres are needed for proposed Laser Fusion targets. The spherical nature of these substrates coupled with the small dimensions (approx. 100 ..mu..m OD) make it difficult to achieve a smooth and uniform coating. Coating problems encountered include a rough surface and porous microstructure from the oblique incidence and lack of temperature and bias control, clumping of the microspheres causing non-uniformities, and particle accumulation causing cone defects. Sputtering parameters significantly affecting the coatings include total pressure, DC substrate bias, and the addition of doping gases. Using an ultrasonic vibrating screened cage and RF magnetron Sputtergun, we have successfully batch coated microspheres with up to 6 ..mu..m of Pt, with a surface roughness of 200 nm, thickness non-concentricity of 300 nm, and density greater than 98% of bulk Pt.

  19. Mitochondria-Localized Fluorescent BODIPY-Platinum Conjugate

    PubMed Central

    2015-01-01

    A convenient synthesis of a BODIPY (1,3,5,7-tetramethyl-8-(4-pyridyl)-4,4′-difluoroboradiazaindacene) labeled platinum compound (BODIPY-Pt) was developed by direct conjugation of cisplatin with the pyridine group of BODIPY. The membrane permeability and selective uptake of BODIPY-Pt in the mitochondria was studied using confocal laser scanning microscopy (CLSM). The fluorescent BODIPY-Pt conjugate showed high cellular proliferation inhibition against human cervical carcinoma (HeLa) and human breast cancer (MCF-7) cells, with half maximal inhibitory concentrations (IC50) of 27.37 and 12.14 μM, respectively. This work highlights the potential of using BODIPY labeled Pt compounds to realize the visualization of Pt distribution in living cells. PMID:25941554

  20. Observation of Single Colloidal Platinum Nanocrystal Growth Trajectories

    SciTech Connect

    Zheng, Haimei; Smith, Rachel; Jun, Young-wook; Kisielowski, Christian; Dahmen, Ulrich; Alivisatos, A. Paul

    2009-02-09

    It is conventionally assumed that the growth of monodisperse colloidal nanocrystals requires a temporally discrete nucleation followed by monomer attachment onto the existing nuclei. However, recent studies have reported violations of this classical growth model, and have suggested that inter-particle interactions are also involved during the growth. Mechanisms of nanocrystal growth still remain controversial. Using in situ transmission electron microscopy, we show that platinum nanocrystals can grow either by monomer attachment from solution onto the existing particles or by coalescence between the particles. Surprisingly, an initially broad size distribution of the nanocrystals can spontaneously narrow. We suggest that nanocrystals take different pathways of growth based on their size- and morphology-dependent internal energies. These observations are expected to be highly relevant for other nanocrystal systems.

  1. Platinum Group Metal Recycling Technology Development - Final Report

    SciTech Connect

    Lawrence Shore

    2009-08-19

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

  2. Potentiometric sensors with carbon black supporting platinum nanoparticles.

    PubMed

    Paczosa-Bator, Beata; Cabaj, Leszek; Piech, Robert; Skupień, Krzysztof

    2013-11-01

    For the first time, a single-piece, all-solid-state ion-selective electrode was fabricated with carbon black supporting platinum nanoparticles (PtNPs-CB) and a polymeric membrane. The PtNPs-CB, as an intermediate layer, was drop-casted directly on the solid substrate, and then an ionophore-doped solvent polymeric membrane was added in order to form a sensor. The performance of the newly developed electrodes was evaluated on the basis of potassium and nitrate ions. The stability of the electrical potential for the electrodes was examined by performing current-reversal chronopotentiometry, and the influence of the interfacial water film was assessed by the potentiometric aqueous-layer test. Fabricated potassium- and nitrate-selective electrodes displayed a Nernstian slope and several outstanding properties such as high long-term potential stability, potential repeatability, and reproducibility. PMID:24094044

  3. Emerging magnetic order in platinum atomic contacts and chains

    PubMed Central

    Strigl, Florian; Espy, Christopher; Bückle, Maximilian; Scheer, Elke; Pietsch, Torsten

    2015-01-01

    The development of atomic-scale structures revealing novel transport phenomena is a major goal of nanotechnology. Examples include chains of atoms that form while stretching a transition metal contact or the predicted formation of magnetic order in these chains, the existence of which is still debated. Here we report an experimental study of the magneto-conductance (MC) and anisotropic MC with atomic-size contacts and mono-atomic chains of the nonmagnetic metal platinum. We find a pronounced and diverse MC behaviour, the amplitude and functional dependence change when stretching the contact by subatomic distances. These findings can be interpreted as a signature of local magnetic order in the chain, which may be of particular importance for the application of atomic-sized contacts in spintronic devices of the smallest possible size. PMID:25649440

  4. Aqueous synthesis of near-infrared highly fluorescent platinum nanoclusters

    NASA Astrophysics Data System (ADS)

    García Fernández, Jenifer; Trapiella-Alfonso, Laura; Costa-Fernández, José M.; Pereiro, Rosario; Sanz-Medel, Alfredo

    2015-05-01

    A one-step synthesis of near infrared fluorescent platinum nanoclusters (PtNCs) in aqueous medium is described. The proposed optimized procedure for PtNC synthesis is rather simple, fast and it is based on the direct metal reduction with NaBH4. Bidentated thiol ligands (lipoic acid) were selected as nanoclusters stabilizers in water media. The structural characterization revealed attractive features of the PtNCs, including small size, high water solubility, near-infrared luminescence centered at 680 nm, long-term stability and the highest quantum yield in water reported so far (47%) for PtNCs. Moreover, their stability in different pH media and an ionic strength of 0.2 M NaCl was studied and no significant changes in fluorescence emission were detected. In brief, they offer a new type of fluorescent noble metal nanoprobe with a great potential to be applied in several fields, including biolabeling and imaging experiments.

  5. Platinum(iv) anticancer prodrugs - hypotheses and facts.

    PubMed

    Gibson, Dan

    2016-08-16

    In this manuscript we focus on Pt(iv) anticancer prodrugs. We explore the main working hypotheses for the design of effective Pt(iv) prodrugs and note the exceptions to the common assumptions that are prevalent in the field. Special attention was devoted to the emerging class of "dual action" Pt(iv) prodrugs, where bioactive ligands are conjugated to the axial positions of platinum in order to obtain orthogonal or complementary effects that will increase the efficacy of killing the cancer cells. We discuss the rationale behind the design of the "dual action" prodrugs and the results of the pharmacological studies obtained. Simultaneous release of two bioactive moieties inside the cancer cells often triggers several processes that together determine the fate of the cell. Pt(iv) complexes provide many opportunities for applying new concepts in targeting, synergistic cell killing and exploiting novel nanodelivery systems. PMID:27214873

  6. Coulometric study of ethanol adsorption at a polycrystalline platinum electrode

    NASA Astrophysics Data System (ADS)

    Gilman, Sol

    2012-01-01

    For the first time, use of a novel pre-conditioning sequence and measurements of hydrogen blockage during fast cathodic scans has enabled the determination of rates of accumulation of ethanolic species on the surface of a platinum electrode under well-controlled conditions of surface cleanliness/activity and mass transport. For dilute solutions of ethanol in 1 N perchloric acid (HClO4), oxidative adsorption rates maximize at 0.3 V, drop off at more cathodic potentials due to competition with adsorbed hydrogen and drop off at more anodic potentials due to oxidative processes that produce products released to the electrolyte. The time and concentration dependence of adsorption follows relationships that are common for adsorption on a heterogeneous surface. Some evidence are presented supporting a mechanism for production of soluble products that does not involve the adsorbed species that are detected through the measurement of blockage of hydrogen adsorption sites.

  7. Preparation of platinum nanoparticles in liquids by laser ablation method

    NASA Astrophysics Data System (ADS)

    Binh Nguyen, The; Dinh Nguyen, Thanh; Nguyen, Quang Dong; Trinh Nguyen, Thi

    2014-09-01

    Platinum (Pt) nanoparticles were prepared in solutions of ethanol and TSC (trisodium citrate—Na3C6H5O7.nH2O) in water by laser ablation method using Nd:YAG laser. The role of laser fluence, laser wavelength and concentration of surfactant liquids in laser ablation process were investigated. The morphology, size distribution and optical properties of the Pt nanoparticles (NPs) were observed by transmission electron microscopy (TEM), UV-vis spectrometer and x-ray diffraction measurements. The average diameter of Pt NPs prepared in ethanol and TSC solutions ranges around 7-9 nm and 10-12 nm, respectively. The results showed advantages of the laser ablation method.

  8. Monolayer graphene growth on sputtered thin film platinum

    SciTech Connect

    Kang, Byung Jin; Mun, Jeong Hun; Cho, Byung Jin; Hwang, Chan Yong

    2009-11-15

    It is demonstrated that sputtered thin film platinum (Pt) can be used as a catalytic metal for graphene growth on metal. During the crystallization annealing, the sputtered Pt is crystallized mostly into Pt (111) orientation, maintaining excellent surface roughness with no sign of agglomeration. The relatively lower carbon solubility in Pt and the good surface roughness of the thin film Pt enable us to form a uniform monolayer graphene on Pt over the entire region of the thin film Pt/SiO{sub 2}/Si substrate by carbon dissolution and segregation method processed in a methane ambient. The monolayer graphene grown on Pt has been successfully transferred to SiO{sub 2}/Si substrate by simple wet etching of Pt. The results of Raman spectroscopic and scanning tunneling microscopic measurements of the synthesized graphene layer are presented.

  9. Nanoparticle growth. Facet development during platinum nanocube growth.

    PubMed

    Liao, Hong-Gang; Zherebetskyy, Danylo; Xin, Huolin; Czarnik, Cory; Ercius, Peter; Elmlund, Hans; Pan, Ming; Wang, Lin-Wang; Zheng, Haimei

    2014-08-22

    An understanding of how facets of a nanocrystal develop is critical for controlling nanocrystal shape and designing novel functional materials. However, the atomic pathways of nanocrystal facet development are mostly unknown because of the lack of direct observation. We report the imaging of platinum nanocube growth in a liquid cell using transmission electron microscopy with high spatial and temporal resolution. The growth rates of all low index facets are similar until the {100} facets stop growth. The continuous growth of the rest facets leads to a nanocube. Our calculation shows that the much lower ligand mobility on the {100} facets is responsible for the arresting of {100} growing facets. These findings shed light on nanocrystal shape-control mechanisms and future design of nanomaterials. PMID:25146287

  10. Sum Frequency Generation Studies of Hydrogenation Reactions on Platinum Nanoparticles

    SciTech Connect

    Krier, James M.

    2013-08-31

    Sum Frequency Generation (SFG) vibrational spectroscopy is used to characterize intermediate species of hydrogenation reactions on the surface of platinum nanoparticle catalysts. In contrast to other spectroscopy techniques which operate in ultra-high vacuum or probe surface species after reaction, SFG collects information under normal conditions as the reaction is taking place. Several systems have been studied previously using SFG on single crystals, notably alkene hydrogenation on Pt(111). In this thesis, many aspects of SFG experiments on colloidal nanoparticles are explored for the first time. To address spectral interference by the capping agent (PVP), three procedures are proposed: UV cleaning, H2 induced disordering and calcination (core-shell nanoparticles). UV cleaning and calcination physically destroy organic capping while disordering reduces SFG signal through a reversible structural change by PVP.

  11. Solid-state dewetting of continuous thin platinum coatings

    NASA Astrophysics Data System (ADS)

    Hanief, N.; Topić, M.; Pineda-Vargas, C.

    2015-11-01

    Thermal stability of coatings is of crucial importance for reliability of electronic devices operating at high temperature. Thus, we investigated the Cr-Pt system where a thin platinum coating of 0.1 μm was deposited on chromium substrate and annealed at 1000 °C for 8 h. The scanning electron microscope (SEM) showed that a continuous and uniformly deposited Pt coating experienced the formation of "islands" after annealing. The grain-boundary grooving, dewetting and agglomeration were the main mechanisms of degradation of thermally annealed coatings. Results by μ-PIXE (particle-induced X-ray emission) and transmission electron microscope (TEM) showed the presence of Cr3Pt phase in "islands" and the coating thickness was approximately 0.5 μm. The surrounding regions were left uncovered due to coating agglomeration at the expense of initially deposited coating.

  12. Platinum electrodeposition on unsupported carbon nano-onions.

    PubMed

    Santiago, Diana; Rodríguez-Calero, Gabriel G; Palkar, Amit; Barraza-Jimenez, Diana; Galvan, D H; Casillas, Gilberto; Mayoral, Alvaro; Jose-Yacamán, Miguel; Echegoyen, Luis; Cabrera, Carlos R

    2012-12-11

    An effort to develop smaller, well-dispersed catalytic materials electrochemically on high-surface-area carbon supports is required for improved fuel cell performance. A high-surface-area carbon material of interest is carbon nano-onions (CNOs), also known as multilayer fullerenes. The most convenient synthesis method for CNOs is annealing nanodiamond particles, thus retaining the size of the precursors and providing the possibility to prepare very small nanocatalysts using electrochemical techniques. In terms of pure metal catalysts, platinum is the most common catalyst used in fuel cells. The combination of Pt nanoparticles with CNOs could lead to new catalytic nanomaterials. In this work, this was accomplished by using a rotating disk-slurry electrode (RoDSE) technique. The Pt/CNO catalysts were prepared from slurries that contained functionalized CNOs and K(2)PtCl(6) as the platinum precursor in aqueous 0.1 M H(2)SO(4) solution. X-ray photoelectron spectroscopy results showed that 37% of the Pt on the CNOs is metallic Pt whereas 63% had higher binding energies, which is evidence of higher oxidation states or the presence of Pt atoms and clusters on CNOs. However, aberration-corrected scanning transmission electron microscopy of the Pt/CNOs confirmed the presence of Pt atoms and clusters on CNOs. Thermal gravimetric analysis showed the excellent thermal stability of the Pt/CNOs and a lower onset potential for the electrochemical oxidation of methanol compared to that of commercial Pt/Vulcan catalyst material. The computational method confirmed the Pt atoms' location at CNOs surface sites. Geometric parameters for distances between Pt atoms in the 3Pt/CNOs molecular system from our theoretical calculations are in agreement with the respective parameters obtained experimentally. The combination of CNO with RoDSE presents a new highly dispersed catalyst nanomaterial. PMID:23145813

  13. Ozone enhancement of platinum asthma in a primate model

    SciTech Connect

    Biagini, R.E.; Moorman, W.J.; Lewis, T.R.; Bernstein, I.L.

    1986-10-01

    Three groups of adult male cynomolgus monkeys (Macaca fascicularis) were exposed to either 200 micrograms/m/sup 3/ ammonium hexachloroplatinate ((NH/sub 4/)2PtCl/sub 6/), 200 micrograms (NH/sub 4/)2PtCl/sub 6/ concurrently with 1 ppm ozone (O/sub 3/), or to 1 ppm O/sub 3/ only. The animals were exposed by inhalation for 6 h per day, 5 days per week for 12 wk. The experimental design included methacholine preexposure and Na2PtCl/sub 6/ bronchoprovocation challenge evaluations, Na2PtCl/sub 6/ threshold skin tests, and sera for analyses of antibodies. Two weeks after the 12-wk exposures, these same indices were reevaluated. Baseline pulmonary function was not significantly affected by the exposure regimens; however, the combination of exposure to O/sub 3/ and (NH/sub 4/)2PtCl/sub 6/ significantly reduced the concentration of platinum (Pt) salt and methacholine necessary to increase average pulmonary flow resistance (RL) 200% (EC200 RL). Ozone or Pt exposure alone had no significant effect on these parameters. Platinum and methacholine EC200 RL values were highly correlated for both Pt-exposed groups after exposure. These data indicated that combined O/sub 3/ and Pt exposure significantly increased specific (Pt) and nonspecific (methacholine) bronchial hyperreactivity more often than did exposure to either O/sub 3/ or the Pt salt alone. Combined O/sub 3/ plus Pt exposure also significantly increases the incidence of positive Pt skin tests when compared with the other exposure groups. Similar to the human experience, radioallergosorbent testing (RAST) for Pt-specific antibodies was not as sensitive as direct skin testing in identifying allergic persons.

  14. Tissue cell assisted fabrication of tubular catalytic platinum microengines

    NASA Astrophysics Data System (ADS)

    Wang, Hong; Moo, James Guo Sheng; Pumera, Martin

    2014-09-01

    We report a facile platform for mass production of robust self-propelled tubular microengines. Tissue cells extracted from fruits of banana and apple, Musa acuminata and Malus domestica, are used as the support on which a thin platinum film is deposited by means of physical vapor deposition. Upon sonication of the cells/Pt-coated substrate in water, microscrolls of highly uniform sizes are spontaneously formed. Tubular microengines fabricated with the fruit cell assisted method exhibit a fast motion of ~100 bodylengths per s (~1 mm s-1). An extremely simple and affordable platform for mass production of the micromotors is crucial for the envisioned swarms of thousands and millions of autonomous micromotors performing biomedical and environmental remediation tasks.We report a facile platform for mass production of robust self-propelled tubular microengines. Tissue cells extracted from fruits of banana and apple, Musa acuminata and Malus domestica, are used as the support on which a thin platinum film is deposited by means of physical vapor deposition. Upon sonication of the cells/Pt-coated substrate in water, microscrolls of highly uniform sizes are spontaneously formed. Tubular microengines fabricated with the fruit cell assisted method exhibit a fast motion of ~100 bodylengths per s (~1 mm s-1). An extremely simple and affordable platform for mass production of the micromotors is crucial for the envisioned swarms of thousands and millions of autonomous micromotors performing biomedical and environmental remediation tasks. Electronic supplementary information (ESI) available: Related video. See DOI: 10.1039/c4nr03720k

  15. The "missing link": the gas-phase generation of platinum-methylidyne clusters Pt(n)CH+ (n=1, 2) and their reactions with hydrocarbons and ammonia.

    PubMed

    Butschke, Burkhard; Schwarz, Helmut

    2011-10-10

    Electrospray ionization (ESI) of tetrameric platinum(II) acetate, [Pt(4)(CH(3)COO)(8)], in methanol generates the formal platinum(III) dimeric cation [Pt(2)(CH(3)COO)(3)(CH(2)COO)(MeOH)(2)](+), which, upon harsher ionization conditions, sequentially loses the two methanol ligands, CO(2), and CH(2)COO to form the platinum(II) dimer [Pt(2)(CH(3)COO)(2)(CH(3))](+). Next, intramolecular sequential double hydrogen-atom transfer from the methyl group concomitant with the elimination of two acetic acid molecules produces Pt(2)CH(+) from which, upon even harsher conditions, PtCH(+) is eventually generated. This degradation sequence is supported by collision-induced dissociation (CID) experiments, extensive isotope-labeling studies, and DFT calculations. Both PtCH(+) and Pt(2)CH(+) react under thermal conditions with the hydrocarbons C(2)H(n) (n=2, 4, 6) and C(3)H(n) (n=6, 8). While, in ion-molecule reactions of PtCH(+) with C(2) hydrocarbons, the relative rates decrease with increasing n, the opposite trend holds true for Pt(2)CH(+). The Pt(2)CH(+) cluster only sluggishly reacts with C(2)H(2), but with C(2)H(4) and C(2)H(6) dihydrogen loss dominates. The reactions with the latter two substrates were preceded by a complete exchange of all of the hydrogen atoms present in the adduct complex. The PtCH(+) ion is much less selective. In the reactions with C(2)H(2) and C(2)H(4), elimination of H(2) occurs; however, CH(4) formation prevails in the decomposition of the adduct complex that is formed with C(2)H(6). In the reaction with C(2)H(2), in addition to H(2) loss, C(3)H(3)(+) is produced, and this process formally corresponds to the transfer of the cationic methylidyne unit CH(+) to C(2)H(2), accompanied by the release of neutral Pt. In the ion-molecule reactions with the C(3) hydrocarbons C(3)H(6) and C(3)H(8), dihydrogen loss occurs with high selectivity for Pt(2)CH(+), but in the reactions of these substrates with PtCH(+) several reaction routes compete. Finally, in the

  16. Uptake of platinum by zebrafish (Danio rerio) and ramshorn snail (Marisa cornuarietis) and resulting effects on early embryogenesis.

    PubMed

    Osterauer, Raphaela; Haus, Nadine; Sures, Bernd; Köhler, Heinz-R

    2009-11-01

    Platinum group elements (PGEs), platinum, palladium and rhodium are widely used in automobile catalytic converters. PGEs are emitted into the environment and enter the aquatic ecosystem via runoff rainwater. The present study investigated the bioavailability of platinum chloride for the zebrafish (Danio rerio) and the ramshorn snail (Marisa cornuarietis) and determined the bioaccumulation rate of platinum. Applying the fish early life stage assay for D. rerio (DarT) and the Marisa embryo toxicity test ("Mariett") for M. cornuarietis, effects of platinum chloride on the embryonic development were investigated. Platinum concentrations tested in this study ranged from environmentally relevant concentrations of 38 ng L(-1) up to a concentration of 74.2 microg L(-1) for D. rerio and of 200 ngL(-1) up to 98.7 microg L(-1) for M. cornuarietis. Platinum was found to be accumulated in both organisms. Bioaccumulation factors (BAFs) were in the range of 5-55 for D. rerio and of 218.4-723.9 for M. cornuarietis, depending on the tested Pt concentrations. During the embryonic development, platinum was shown to alter the heart rate of both organisms already at the lowest tested concentration. At higher concentrations, platinum decelerated the hatching rate of the embryos of both species. Additionally, a retardation of the general development and a loss of weight due to platinum exposure was observed in M. cornuarietis. Results of this study contribute important data on the ecotoxicity of a rarely studied element. PMID:19796790

  17. Stable isotopes in mineralogy

    USGS Publications Warehouse

    O'Neil, J.R.

    1977-01-01

    Stable isotope fractionations between minerals are functions of the fundamental vibrational frequencies of the minerals and therefore bear on several topics of mineralogical interest. Isotopic compositions of the elements H, C, O, Si, and S can now be determined routinely in almost any mineral. A summary has been made of both published and new results of laboratory investigations, analyses of natural materials, and theoretical considerations which bear on the importance of temperature, pressure, chemical composition and crystal structure to the isotopic properties of minerals. It is shown that stable isotope studies can sometimes provide evidence for elucidating details of crystal structure and can be a powerful tool for use in tracing the reaction paths of mineralogical reactions. ?? 1977 Springer-Verlag.

  18. Perchlorate isotope forensics

    USGS Publications Warehouse

    Böhlke, J.K.; Sturchio, N.C.; Gu, B.; Horita, J.; Brown, G.M.; Jackson, W.A.; Batista, J.; Hatzinger, P.B.

    2005-01-01

    Perchlorate has been detected recently in a variety of soils, waters, plants, and food products at levels that may be detrimental to human health. These discoveries have generated considerable interest in perchlorate source identification. In this study, comprehensive stable isotope analyses ( 37Cl/35Cl and 18O/17O/ 16O) of perchlorate from known synthetic and natural sources reveal systematic differences in isotopic characteristics that are related to the formation mechanisms. In addition, isotopic analyses of perchlorate extracted from groundwater and surface water demonstrate the feasibility of identifying perchlorate sources in contaminated environments on the basis of this technique. Both natural and synthetic sources of perchlorate have been identified in water samples from some perchlorate occurrences in the United States by the isotopic method. ?? 2005 American Chemical Society.

  19. Rare Isotope Accelerators

    NASA Astrophysics Data System (ADS)

    Savard, Guy

    2002-04-01

    The next frontier for low-energy nuclear physics involves experimentation with accelerated beams of short-lived radioactive isotopes. A new facility, the Rare Isotope Accelerator (RIA), is proposed to produce large amount of these rare isotopes and post-accelerate them to energies relevant for studies in nuclear physics, astrophysics and the study of fundamental interactions at low energy. The basic science motivation for this facility will be introduced. The general facility layout, from the 400 kW heavy-ion superconducting linac used for production of the required isotopes to the novel production and extraction schemes and the highly efficient post-accelerator, will be presented. Special emphasis will be put on a number of technical breakthroughs and recent R&D results that enable this new facility.

  20. Isotopically controlled semiconductors

    SciTech Connect

    Haller, E.E.

    2004-11-15

    A review of recent research involving isotopically controlled semiconductors is presented. Studies with isotopically enriched semiconductor structures experienced a dramatic expansion at the end of the Cold War when significant quantities of enriched isotopes of elements forming semiconductors became available for worldwide collaborations. Isotopes of an element differ in nuclear mass, may have different nuclear spins and undergo different nuclear reactions. Among the latter, the capture of thermal neutrons which can lead to neutron transmutation doping, can be considered the most important one for semiconductors. Experimental and theoretical research exploiting the differences in all the properties has been conducted and will be illustrated with selected examples. Manuel Cardona, the longtime editor-in-chief of Solid State Communications has been and continues to be one of the major contributors to this field of solid state physics and it is a great pleasure to dedicate this review to him.

  1. Oxygen isotope cosmothermometer.

    NASA Technical Reports Server (NTRS)

    Onuma, N.; Clayton, R. N.; Mayeda, T. K.

    1972-01-01

    Variations in oxygen isotopic abundances of meteoritic minerals, chondrules, whole meteorites, and planets are discussed in terms of a model involving isotopic exchange between primordial dust and a cooling solar nebular gas. From the temperature-dependence of the isotopic fractionation factors, temperatures have been assigned to the processes of initial condensation, chondrule formation, and planetary accretion. Separated phases from carbonaceous chondrites fall into three isotopic groups representing widely differing conditions of formation: (1) low-iron olivine and pyroxene, and calcium-aluminum silicates condensed at temperatures above 1000 K; (2) high-iron olivine and pyroxene melted to form chondrules after prior cooling and exchange to temperatures of 530-620 K; and (3) hydrous silicates condensed at temperatures below 400 K.

  2. The Next Generation of Platinum Drugs: Targeted Pt(II) Agents, Nanoparticle Delivery, and Pt(IV) Prodrugs

    PubMed Central

    Johnstone, Timothy C.; Suntharalingam, Kogularamanan; Lippard, Stephen J.

    2016-01-01

    The platinum drugs, cisplatin, carboplatin, and oxaliplatin, prevail in the treatment of cancer,, but new platinum agents have been very slow to enter the clinic. Recently, however, there has been a surge of activity, based on a great deal of mechanistic information, aimed at developing non-classical platinum complexes that operate via mechanisms of action distinct from those of the approved drugs. The use of nanodelivery devices has also grown and many different strategies have been explored to incorporate platinum warheads into nanomedicine constructs. In this review, we discuss these efforts to create the next generation of platinum anticancer drugs. The introduction provides the reader with a brief overview of the use, development, and mechanism of action of the approved platinum drugs to provide the context in which more recent research has flourished. We then describe approaches that explore non-classical platinum(II) complexes with trans geometry and with a monofunctional coordination mode, polynuclear platinum(II) compounds, platinum(IV) prodrugs, dual-treat agents, and photoactivatable platinum(IV) complexes. Nanodelivery particles designed to deliver platinum(IV) complexes will also be discussed, including carbon nanotubes, carbon nanoparticles, gold nanoparticles, quantum dots, upconversion nanoparticles, and polymeric micelles. Additional nanoformulations including supramolecular self-assembled structures, proteins, peptides, metal-organic frameworks, and coordination polymers will then be described. Finally, the significant clinical progress made by nanoparticle formulations of platinum(II) agents will be reviewed. We anticipate that such a synthesis of disparate research efforts will not only help to generate new drug development ideas and strategies, but also reflect our optimism that the next generation of platinum cancer drugs is about to arrive. PMID:26865551

  3. The Next Generation of Platinum Drugs: Targeted Pt(II) Agents, Nanoparticle Delivery, and Pt(IV) Prodrugs.

    PubMed

    Johnstone, Timothy C; Suntharalingam, Kogularamanan; Lippard, Stephen J

    2016-03-01

    The platinum drugs, cisplatin, carboplatin, and oxaliplatin, prevail in the treatment of cancer, but new platinum agents have been very slow to enter the clinic. Recently, however, there has been a surge of activity, based on a great deal of mechanistic information, aimed at developing nonclassical platinum complexes that operate via mechanisms of action distinct from those of the approved drugs. The use of nanodelivery devices has also grown, and many different strategies have been explored to incorporate platinum warheads into nanomedicine constructs. In this Review, we discuss these efforts to create the next generation of platinum anticancer drugs. The introduction provides the reader with a brief overview of the use, development, and mechanism of action of the approved platinum drugs to provide the context in which more recent research has flourished. We then describe approaches that explore nonclassical platinum(II) complexes with trans geometry or with a monofunctional coordination mode, polynuclear platinum(II) compounds, platinum(IV) prodrugs, dual-threat agents, and photoactivatable platinum(IV) complexes. Nanoparticles designed to deliver platinum(IV) complexes will also be discussed, including carbon nanotubes, carbon nanoparticles, gold nanoparticles, quantum dots, upconversion nanoparticles, and polymeric micelles. Additional nanoformulations, including supramolecular self-assembled structures, proteins, peptides, metal-organic frameworks, and coordination polymers, will then be described. Finally, the significant clinical progress made by nanoparticle formulations of platinum(II) agents will be reviewed. We anticipate that such a synthesis of disparate research efforts will not only help to generate new drug development ideas and strategies, but also will reflect our optimism that the next generation of approved platinum cancer drugs is about to arrive. PMID:26865551

  4. Platinum-ruthenium-palladium alloys for use as a fuel cell catalyst

    DOEpatents

    Gorer, Alexander

    2002-01-01

    A noble metal alloy composition for a fuel cell catalyst, a ternary alloy composition containing platinum, ruthenium and palladium. The alloy shows increased activity as compared to well-known catalysts.

  5. Investigating the performance of catalyst layer micro-structures with different platinum loadings

    SciTech Connect

    Khakaz-Baboli, Moben; Harvey, David; Pharoah, Jon

    2012-07-01

    In this study a four-phase micro-structure of a PEFC catalyst layer was reconstructed by randomly placing overlapping spheres for each solid catalyst phase. The micro-structure was mirrored to make a micro-structure. A body-fit computational mesh was produced for the reconstructed micro-structure in OpenFOAM. Associated conservation equations were solved within all the phases with electrochemical reaction as the boundary condition at the interface between ionomer and platinum phases. The study is focused on the platinum loading of CL. The polarization curves of the micro-structure performance have been compared for different platinum loadings. This paper gives increased insight into the relatively greater losses at decreased platinum loadings.

  6. Fluoropyrimidine and platinum toxicity pharmacogenetics: an umbrella review of systematic reviews and meta-analyses.

    PubMed

    Campbell, Jared M; Bateman, Emma; Peters, Micah Dj; Bowen, Joanne M; Keefe, Dorothy M; Stephenson, Matthew D

    2016-03-01

    Fluoropyrimidine (FU) and platinum-based chemotherapies are greatly complicated by their associated toxicities. This umbrella systematic review synthesized all systematic reviews that investigated associations between germline variations and toxicity, with the aim of informing personalized medicine. Systematic reviews are important in pharmacogenetics where false positives are common. Four systematic reviews were identified for FU-induced toxicity and three for platinum. Polymorphisms of DPYD and TYMS, but not MTHFR, were statistically significantly associated with FU-induced toxicity (although only DPYD had clinical significance). For platinum, GSTP1 was found to not be associated with toxicity. This umbrella systematic review has synthesized the best available evidence on the pharmacogenetics of FU and platinum toxicity. It provides a useful reference for clinicians and identifies important research gaps. PMID:26894782

  7. Platinum monolayer electrocatalyst on gold nanostructures on silicon for photoelectrochemical hydrogen evolution.

    PubMed

    Kye, Joohong; Shin, Muncheol; Lim, Bora; Jang, Jae-Won; Oh, Ilwhan; Hwang, Seongpil

    2013-07-23

    Pt monolayer decorated gold nanostructured film on planar p-type silicon is utilized for photoelectrochemical H2 generation in this work. First, gold nanostructured film on silicon was spontaneously produced by galvanic displacement of the reduction of gold ion and the oxidation of silicon in the presence of fluoride anion. Second, underpotential deposition (UPD) of copper under illumination produced Cu monolayer on gold nanostructured film followed by galvanic exchange of less-noble Cu monolayer with more-noble PtCl6(2-). Pt(shell)/Au(core) on p-type silicon showed the similar activity with platinum nanoparticle on silicon for photoelectrochemical hydrogen evolution reaction in spite of low platinum loading. From Tafel analysis, Pt(shell)/Au(core) electrocatalyst shows the higher area-specific activity than platinum nanoparticle on silicon demonstrating the significant role of underlying gold for charge transfer reaction from silicon to H(+) through platinum catalyst. PMID:23750804

  8. Advances in drug delivery system for platinum agents based combination therapy

    PubMed Central

    Kang, Xiang; Xiao, Hai-Hua; Song, Hai-Qin; Jing, Xia-Bin; Yan, Le-San; Qi, Ruo-Gu

    2015-01-01

    Platinum-based anticancer agents are widely used as first-line drugs in cancer chemotherapy for various solid tumors. However, great side effects and occurrence of resistance remain as the major drawbacks for almost all the platinum drugs developed. To conquer these problems, new strategies should be adopted for platinum drug based chemotherapy. Modern nanotechnology has been widely employed in the delivery of various therapeutics and diagnostic. It provides the possibility of targeted delivery of a certain anticancer drug to the tumor site, which could minimize toxicity and optimize the drug efficacy. Here, in this review, we focused on the recent progress in polymer based drug delivery systems for platinum-based combination therapy. PMID:26779373

  9. Corrosion-resistant iridium-platinum anode material for high polarization application in corrosive acids

    SciTech Connect

    Farmer, J.; Summers, L.; Lewis, P.

    1993-09-08

    The present invention relates to highly corrosion resistant components for use in an electrochemical cell. Specifically, these components are resistant to corrosion under very extreme conditions such as exposure to aqua regia in the presence of a constant current density of 100mA/m{sup 2}. The components are comprised of an iridium-platinum alloy that comprises less than 30% iridium. In a preferred embodiment of the present invention, the iridium-platinum alloy comprises 15-20% iridium. In another preferred embodiment of the present invention, the iridium-platinum alloy is deposited on the surface of an electrochemical cell component by magnetron sputtering. The present invention also relates to a method for conducting an electrochemical reaction in the presence of highly corrosive acids under a high degree of polarization wherein the electrochemical cell comprises a component, preferably the anode, containing an iridium-platinum alloy that comprises less than 30% iridium.

  10. Synthesis and characterisation of platinum (II) salphen complex and its interaction with calf thymus DNA

    NASA Astrophysics Data System (ADS)

    Sukri, Shahratul Ain Mohd; Heng, Lee Yook; Karim, Nurul Huda Abd

    2014-09-01

    A platinum (II) salphen complex was synthesised by condensation reaction of 2,4-dihydroxylbenzaldehyde and o-phenylenediamine with potassium tetrachloroplatinate to obtain N,N'-Bis-4-(hydroxysalicylidene)-phenylenediamine-platinum (II). The structure of the complex was confirmed by 1H and 13C NMR spectroscopy, FTIR spectroscopy, CHN elemental analyses and ESI-MS spectrometry. The platinum (II) salphen complex with four donor atoms N2O2 from its salphen ligand coordinated to platinum (II) metal centre were determined. The binding mode and interaction of this complex with calf thymus DNA was determined by UV/Vis DNA titration and emission titration. The intercalation between the DNA bases by π-π stacking due to its square planar geometry and aromatic rings structures was proposed.

  11. CVD aluminiding process for producing a modified platinum aluminide bond coat for improved high temperature performance

    NASA Technical Reports Server (NTRS)

    Nagaraj, Bangalore A. (Inventor); Williams, Jeffrey L. (Inventor)

    2003-01-01

    A method of depositing by chemical vapor deposition a modified platinum aluminide diffusion coating onto a superalloy substrate comprising the steps of applying a layer of a platinum group metal to the superalloy substrate; passing an externally generated aluminum halide gas through an internal gas generator which is integral with a retort, the internal gas generator generating a modified halide gas; and co-depositing aluminum and modifier onto the superalloy substrate. In one form, the modified halide gas is hafnium chloride and the modifier is hafnium with the modified platinum aluminum bond coat comprising a single phase additive layer of platinum aluminide with at least about 0.5 percent hafnium by weight percent and about 1 to about 15 weight percent of hafnium in the boundary between a diffusion layer and the additive layer. The bond coat produced by this method is also claimed.

  12. NREL Team Creates High-Activity, Durable Platinum Extended Surface Catalyst for Fuel Cells (Fact Sheet)

    SciTech Connect

    Not Available

    2011-02-01

    Researchers with NREL's Fuel Cell team showed that platinum can replace copper nanowires in such a way that high-surface-area and high-specific-activity catalysts are produced, potentially allowing for lower-cost catalysts.

  13. Synthesis and characterisation of platinum (II) salphen complex and its interaction with calf thymus DNA

    SciTech Connect

    Sukri, Shahratul Ain Mohd; Heng, Lee Yook; Karim, Nurul Huda Abd

    2014-09-03

    A platinum (II) salphen complex was synthesised by condensation reaction of 2,4-dihydroxylbenzaldehyde and o-phenylenediamine with potassium tetrachloroplatinate to obtain N,N′-Bis-4-(hydroxysalicylidene)-phenylenediamine-platinum (II). The structure of the complex was confirmed by {sup 1}H and {sup 13}C NMR spectroscopy, FTIR spectroscopy, CHN elemental analyses and ESI-MS spectrometry. The platinum (II) salphen complex with four donor atoms N{sub 2}O{sub 2} from its salphen ligand coordinated to platinum (II) metal centre were determined. The binding mode and interaction of this complex with calf thymus DNA was determined by UV/Vis DNA titration and emission titration. The intercalation between the DNA bases by π-π stacking due to its square planar geometry and aromatic rings structures was proposed.

  14. Diffusion of hydrogen through platinum membranes at high pressures and temperatures

    NASA Technical Reports Server (NTRS)

    Chou, I.-M.; Eugster, H. P.; Berens, P.; Weare, J. H.

    1978-01-01

    The diffusion of hydrogen through platinum membranes has been measured at 450, 500, 550 and 600 C at 2000 bar pressure, using the hydrogen sensor technique. Ag + AgCl + 3M HCl was the starting solution inside the platinum tube. Hydrogen diffuses out of the platinum tube into a system containing Fe2O3 + Fe3O4 + H2O; that is, a solution with a fixed hydrogen fugacity. After quench, the drop in hydrogen fugacity inside the platinum tube was calculated from measurements of pH and chloride molality. The hydrogen fugacity is initially roughly proportional to the square root of time. Diffusion constants were calculated from these data by numerical integration.

  15. Precocious puberty in rats induced by hypothalamic lesions: a comparison of platinum and stainless steel electrodes.

    PubMed

    Ruf, K B; YoungLai, E V; Kitchen, J H; Vuillet, M

    1976-05-15

    Precocious sexual maturation was induced in immature female rats by 2 types of unilateral hypothalamic lesions. Stainless steel electrodes produced smaller tissue defects but proved more efficient than platinum electrodes. PMID:1278327

  16. Undoped and boron doped diamond nanoparticles as platinum and platinum-ruthenium catalyst support for direct methanol fuel cell application

    NASA Astrophysics Data System (ADS)

    La Torre Riveros, Lyda

    Nanoparticular diamond is a promising material that can be used as a robust and chemically stable catalytic support. It has been studied and characterized physically and electrochemically, in its powder and thin film forms. This thesis work intends to demonstrate that undoped diamond nanoparticles (DNPs) and boron-doped diamond nanoparticles (BDDNPs) can be used as an electrode and a catalytic support material for platinum and ruthenium catalysts. The electrochemical properties of diamond nanoparticle electrodes, fabricated using the ink paste method, were investigated. As an initial step, we carried out chemical purification of commercially available undoped DNPs by refluxing in aqueous HNO3 as well as of BDDNPs which were doped through a collaborative work with the University of Missouri. The purified material was characterized by spectroscopic and surface science techniques. The reversibility of reactions such as ferricyanide/ferrocyanide (Fe(CN) 63-/Fe(CN)64-) and hexaamineruthenium (III) chloride complexes as redox probes were evaluated by cyclic voltammetry at the undoped DNPs and BDDNPs surface. These redox probes showed limited peak currents and presented linear relationships between current (i) and the square root of the potential scan rate (v1/2). However, compared to conventional electrodes, the peak currents were smaller. BDDNPs show an improvement in charge transfer currents when compared to undoped DNPs. Platinum and ruthenium nanoparticles were chemically deposited on undoped DNPs and BDDNPs through the use of the excess of a mild reducing agent such NaBH4. In order to improve the nanoparticle dispersion sodium dodecyl benzene sulfonate (SDBS), a surfactant agent, was used. Percentages of platinum and ruthenium metals were varied as well as the stoichiometric amount of the reducing agent to determine adequate parameters for optimum performance in methanol oxidation. Both before and after the reducing process the samples were characterized by scanning

  17. A platinum shell for ultraslow ligand exchange: unmodified DNA adsorbing more stably on platinum than thiol and dithiol on gold.

    PubMed

    Zhou, Wenhu; Ding, Jinsong; Liu, Juewen

    2015-08-01

    Due to the ultraslow ligand exchange rate on Pt, non-thiolated DNA is adsorbed on platinum nanoparticles (PtNPs) more stably than thiolated and even dithiolated DNA on AuNPs. Adsorption kinetics, capacity and stability are systematically compared as a function of DNA sequence. The Pt conjugates can tolerate extreme pH, salt, and thiol molecules. Taking advantage of the optical properties of AuNPs and the extreme stability of DNA on PtNPs, DNA-functionalized Au@Pt NPs are prepared using a cost-effective and more stable bioconjugation method. The DNA-directed assembly of non-thiolated DNA conjugates is also demonstrated. PMID:26121333

  18. Aberrant DNA Damage Response Pathways May Predict the Outcome of Platinum Chemotherapy in Ovarian Cancer

    PubMed Central

    Stefanou, Dimitra T.; Bamias, Aristotelis; Episkopou, Hara; Kyrtopoulos, Soterios A.; Likka, Maria; Kalampokas, Theodore; Photiou, Stylianos; Gavalas, Nikos; Sfikakis, Petros P.; Dimopoulos, Meletios A.; Souliotis, Vassilis L.

    2015-01-01

    Ovarian carcinoma (OC) is the most lethal gynecological malignancy. Despite the advances in the treatment of OC with combinatorial regimens, including surgery and platinum-based chemotherapy, patients generally exhibit poor prognosis due to high chemotherapy resistance. Herein, we tested the hypothesis that DNA damage response (DDR) pathways are involved in resistance of OC patients to platinum chemotherapy. Selected DDR signals were evaluated in two human ovarian carcinoma cell lines, one sensitive (A2780) and one resistant (A2780/C30) to platinum treatment as well as in peripheral blood mononuclear cells (PBMCs) from OC patients, sensitive (n = 7) or resistant (n = 4) to subsequent chemotherapy. PBMCs from healthy volunteers (n = 9) were studied in parallel. DNA damage was evaluated by immunofluorescence γH2AX staining and comet assay. Higher levels of intrinsic DNA damage were found in A2780 than in A2780/C30 cells. Moreover, the intrinsic DNA damage levels were significantly higher in OC patients relative to healthy volunteers, as well as in platinum-sensitive patients relative to platinum-resistant ones (all P<0.05). Following carboplatin treatment, A2780 cells showed lower DNA repair efficiency than A2780/C30 cells. Also, following carboplatin treatment of PBMCs ex vivo, the DNA repair efficiency was significantly higher in healthy volunteers than in platinum-resistant patients and lowest in platinum-sensitive ones (t1/2 for loss of γH2AX foci: 2.7±0.5h, 8.8±1.9h and 15.4±3.2h, respectively; using comet assay, t1/2 of platinum-induced damage repair: 4.8±1.4h, 12.9±1.9h and 21.4±2.6h, respectively; all P<0.03). Additionally, the carboplatin-induced apoptosis rate was higher in A2780 than in A2780/C30 cells. In PBMCs, apoptosis rates were inversely correlated with DNA repair efficiencies of these cells, being significantly higher in platinum-sensitive than in platinum-resistant patients and lowest in healthy volunteers (all P<0.05). We conclude that

  19. Oxygen Isotopes in Meteorites

    NASA Astrophysics Data System (ADS)

    Clayton, R. N.

    2003-12-01

    Oxygen isotope abundance variations in meteorites are very useful in elucidating chemical and physical processes that occurred during the formation of the solar system (Clayton, 1993). On Earth, the mean abundances of the three stable isotopes are 16O: 99.76%, 17O: 0.039%, and 18O: 0.202%. It is conventional to express variations in abundances of the isotopes in terms of isotopic ratios, relative to an arbitrary standard, called SMOW (for standard mean ocean water), as follows:The isotopic composition of any sample can then be represented by one point on a "three-isotope plot," a graph of δ17O versus δ18O. It will be seen that such plots are invaluable in interpreting meteoritic data. Figure 1 shows schematically the effect of various processes on an initial composition at the center of the diagram. Almost all terrestrial materials lie along a "fractionation" trend; most meteoritic materials lie near a line of "16O addition" (or subtraction). (4K)Figure 1. Schematic representation of various isotopic processes shown on an oxygen three-isotope plot. Almost all terrestrial materials plot along a line of "fractionation"; most primitive meteoritic materials plot near a line of "16O addition." The three isotopes of oxygen are produced by nucleosynthesis in stars, but by different nuclear processes in different stellar environments. The principal isotope, 16O, is a primary isotope (capable of being produced from hydrogen and helium alone), formed in massive stars (>10 solar masses), and ejected by supernova explosions. The two rare isotopes are secondary nuclei (produced in stars from nuclei formed in an earlier generation of stars), with 17O coming primarily from low- and intermediate-mass stars (<8 solar masses), and 18O coming primarily from high-mass stars (Prantzos et al., 1996). These differences in type of stellar source result in large observable variations in stellar isotopic abundances as functions of age, size, metallicity, and galactic location ( Prantzos

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

    SciTech Connect

    Benavides, Pahola T.; Dai, Qiang; Sullivan, John L.; Kelly, Jarod C.; Dunn, Jennifer B.

    2015-09-01

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

  1. Identification of genes associated with platinum drug sensitivity and resistance in human ovarian cancer cells

    PubMed Central

    Roberts, D; Schick, J; Conway, S; Biade, S; Laub, P B; Stevenson, J P; Hamilton, T C; O'Dwyer, P J; Johnson, S W

    2005-01-01

    Platinum-based chemotherapeutic regimens are ultimately unsuccessful due to intrinsic or acquired drug resistance. Understanding the molecular basis for platinum drug sensitivity/resistance is necessary for the development of new drugs and therapeutic regimens. In an effort to identify such determinants, we evaluated the expression of approximately 4000 genes using cDNA microarray screening in a panel of 14 unrelated human ovarian cancer cell lines derived from patients who were either untreated or treated with platinum-based chemotherapy. These data were analysed relative to the sensitivities of the cells to four platinum drugs (cis-diamminedichloroplatinum (cisplatin), carboplatin, DACH-(oxalato)platinum (II) (oxaliplatin) and cis-diamminedichloro (2-methylpyridine) platinum (II) (AMD473)) as well as the proliferation rate of the cells. Correlation analysis of the microarray data with respect to drug sensitivity and resistance revealed a significant association of Stat1 expression with decreased sensitivity to cisplatin (r=0.65) and AMD473 (r=0.76). These results were confirmed by quantitative RT–PCR and Western blot analyses. To study the functional significance of these findings, the full-length Stat1 cDNA was transfected into drug-sensitive A2780 human ovarian cancer cells. The resulting clones that exhibited increased Stat1 expression were three- to five-fold resistant to cisplatin and AMD473 as compared to the parental cells. The effect of inhibiting Jak/Stat signalling on platinum drug sensitivity was investigated using the Janus kinase inhibitor, AG490. Pretreatment of platinum-resistant cells with AG490 resulted in significant increased sensitivity to AMD473, but not to cisplatin or oxaliplatin. Overall, the results indicate that cDNA microarray analysis may be used successfully to identify determinants of drug sensitivity/resistance and future functional studies of other candidate genes from this database may lead to an increased understanding of the

  2. Electrocatalysts having gold monolayers on platinum nanoparticle cores, and uses thereof

    DOEpatents

    Adzic, Radoslav; Zhang, Junliang

    2010-04-27

    The invention relates to gold-coated particles useful as fuel cell electrocatalysts. The particles are composed of an electrocatalytically active core at least partially encapsulated by an outer shell of gold or gold alloy. The invention more particularly relates to such particles having a noble metal-containing core, and more particularly, a platinum or platinum alloy core. In other embodiments, the invention relates to fuel cells containing these electrocatalysts and methods for generating electrical energy therefrom.

  3. Platinum(iv) N-heterocyclic carbene complexes: their synthesis, characterisation and cytotoxic activity.

    PubMed

    Bouché, M; Dahm, G; Wantz, M; Fournel, S; Achard, T; Bellemin-Laponnaz, S

    2016-07-28

    Platinum(ii) N-heterocyclic carbene complexes have been oxidized by bromine or iodobenzene dichloride to provide the fully characterised corresponding platinum(iv) NHC complexes. Antiproliferative activities of Pt(iv) NHC complexes were assayed against several cancer cell lines and the results were correlated with respect to their stability. Mechanistic investigations revealed that mitochondrial dysfunction and ROS production were associated with the cytotoxic process induced by these compounds. PMID:27331604

  4. The isotopic distribution conundrum.

    PubMed

    Valkenborg, Dirk; Mertens, Inge; Lemière, Filip; Witters, Erwin; Burzykowski, Tomasz

    2012-01-01

    Although access to high-resolution mass spectrometry (MS), especially in the field of biomolecular MS, is becoming readily available due to recent advances in MS technology, the accompanied information on isotopic distribution in high-resolution spectra is not used at its full potential, mainly because of lack of knowledge and/or awareness. In this review, we give an insight into the practical problems related to calculating the isotopic distribution for large biomolecules, and present an overview of methods for the calculation of the isotopic distribution. We discuss the key events that triggered the development of various algorithms and explain the rationale of how and why the various isotopic-distribution calculations were performed. The review is focused around the developmental stages as briefly outlined below, starting with the first observation of an isotopic distribution. The observations of Beynon in the field of organic MS that chlorine appeared in a mass spectrum as two variants with odds 3:1 lie at the basis of the first wave of algorithms for the calculation of the isotopic distribution, based on the atomic composition of a molecule. From here on, we explain why more complex biomolecules such as peptides exhibit a highly complex isotope pattern when assayed by MS, and we discuss how combinatorial difficulties complicate the calculation of the isotopic distribution on computers. For this purpose, we highlight three methods, which were introduced in the 1980s. These are the stepwise procedure introduced by Kubinyi, the polynomial expansion from Brownawell and Fillippo, and the multinomial expansion from Yergey. The next development was instigated by Rockwood, who suggested to decompose the isotopic distribution in terms of their nucleon count instead of the exact mass. In this respect, we could claim that the term "aggregated" isotopic distribution is more appropriate. Due to the simplification of the isotopic distribution to its aggregated counterpart

  5. Platinum group elements provide no indication of a meteoritic component in ICDP cores from the Bosumtwi crater, Ghana

    NASA Astrophysics Data System (ADS)

    Goderis, S.; Tagle, R.; Schmitt, R. T.; Erzinger, J.; Claeys, P. H.

    In an attempt to identify the type of projectile, 14 samples from the Bosumtwi crater in Ghana were analyzed for platinum group element (PGE) concentrations by nickel sulfide fire assay inductively coupled plasma-mass spectrometry (ICP-MS). The majority of the samples come from the impactite material recovered by cores LB-07A and LB-08A, which were drilled by the International Continental Scientific Drilling program (ICDP). One sample originates from the fallback material found at the contact between the impactite and the overlying lake sediment in core LB-05B. No clear signature of a meteoritic contamination was identified in the 13 impactite samples. The target rock apparently dominates the PGE contribution in the impactites. These results agree with the PGE concentrations reported for the suevites collected at the crater rim and in other parts of the Bosumtwi ICDP cores. However, based on Cr and Os isotopic signatures, a meteoritic component could be present in the sample of fallback material, supporting the reports of the existence of meteoritic material in the Ivory Coast tektites. Further analyses of the fallback material from the Bosumtwi drill cores should confirm (or not) this first result.

  6. A unique subset of epithelial ovarian cancers with platinum sensitivity and PARP inhibitor resistance.

    PubMed

    Ceccaldi, Raphael; O'Connor, Kevin W; Mouw, Kent W; Li, Adam Y; Matulonis, Ursula A; D'Andrea, Alan D; Konstantinopoulos, Panagiotis A

    2015-02-15

    Platinum and PARP inhibitor (PARPi) sensitivity commonly coexist in epithelial ovarian cancer (EOC) due to the high prevalence of alterations in the homologous recombination (HR) DNA repair pathway that confer sensitivity to both drugs. In this report, we describe a unique subset of EOC with alterations in another DNA repair pathway, the nucleotide excision repair (NER) pathway, which may exhibit a discordance in sensitivities to these drugs. Specifically, 8% of high-grade serous EOC from The Cancer Genome Atlas dataset exhibited NER alterations, including nonsynonymous or splice site mutations and homozygous deletions of NER genes. Tumors with NER alterations were associated with improved overall survival (OS) and progression-free survival (PFS), compared with patients without NER alterations or BRCA1/2 mutations. Furthermore, patients with tumors with NER alterations had similar OS and PFS as BRCA1/2-mutated patients, suggesting that NER pathway inactivation in EOC conferred enhanced platinum sensitivity, similar to BRCA1/2-mutated tumors. Moreover, two NER mutations (ERCC6-Q524* and ERCC4-A583T), identified in the two most platinum-sensitive tumors, were functionally associated with platinum sensitivity in vitro. Importantly, neither NER alteration affected HR or conferred sensitivity to PARPi or other double-strand break-inducing agents. Overall, our findings reveal a new mechanism of platinum sensitivity in EOC that, unlike defective HR, may lead to a discordance in sensitivity to platinum and PARPi, with potential implications for previously reported and ongoing PARPi trials in this disease. PMID:25634215

  7. Synthesis and characterization of potential iron–platinum drugs and supplements by laser liquid photolysis

    PubMed Central

    Nkosi, Steven S; Mwakikunga, Bonex W; Sideras-Haddad, Elias; Forbes, Andrew

    2012-01-01

    Highly crystalline nanospherical iron–platinum systems were produced by 248 nm laser irradiation of a liquid precursor at different laser fluences, ranging from 100–375 mJ/cm2. The influence of laser intensity on particle size, iron composition, and structure was systematically investigated. Different nanostructures of iron–platinum alloy and chemically disordered iron–platinum L10 phase were obtained without annealing. The prepared precursor solution underwent deep photolysis to polycrystalline iron–platinum nanoalloys through Fe(III) acetylacetonate and Pt(II) acetylacetonate. Fe(II) and Pt(I) acetylacetone decomposed into Fe0 and Pt0 nanoparticles. We found that the (001) diffraction peak shifted linearly to a lower angle, with the last peak shifting in opposition to the others. This caused the face-centered cubic L10 structure to change its composition according to laser fluence. The nanostructures were shown to contain iron and platinum only by energy-dispersive spectroscopy at several spots. The response of these iron–platinum nanoparticles to infrared depends on their stoichiometric composition, which is controlled by laser fluence. PMID:24198494

  8. Profile of bevacizumab in the treatment of platinum-resistant ovarian cancer: current perspectives

    PubMed Central

    McClung, E Clair; Wenham, Robert M

    2016-01-01

    Patients with platinum-resistant ovarian cancer have progression of disease within 6 months of completing platinum-based chemotherapy. While several chemotherapeutic options exist for the treatment of platinum-resistant ovarian cancer, the overall response to any of these therapies is ~10%, with a median progression-free survival of 3–4 months and a median overall survival of 9–12 months. Bevacizumab (Avastin), a humanized, monoclonal antivascular endothelial growth factor antibody, has demonstrated antitumor activity in the platinum-resistant setting and was recently approved by US Food and Drug Administration for combination therapy with weekly paclitaxel, pegylated liposomal doxorubicin, or topotecan. This review summarizes key clinical trials investigating bevacizumab for recurrent, platinum-resistant ovarian cancer and provides an overview of efficacy, safety, and quality of life data relevant in this setting. While bevacizumab is currently the most studied and clinically available antiangiogenic therapy, we summarize recent studies highlighting novel alternatives, including vascular endothelial growth factor-trap, tyrosine kinase inhibitors, and angiopoietin inhibitor trebananib, and discuss their application for the treatment of platinum-resistant ovarian cancer. PMID:27051317

  9. Electrodeposition of platinum-iridium alloy nanowires for hermetic packaging of microelectronics.

    PubMed

    Petrossians, Artin; Whalen, John J; Weiland, James D; Mansfeld, Florian

    2012-01-01

    An electrodeposition technique was applied for fabrication of dense platinum-iridium alloy nanowires as interconnect structures in hermetic microelectronic packaging to be used in implantable devices. Vertically aligned arrays of platinum-iridium alloy nanowires with controllable length and a diameter of about 200 nm were fabricated using a cyclic potential technique from a novel electrodeposition bath in nanoporous aluminum oxide templates. Ti/Au thin films were sputter deposited on one side of the alumina membranes to form a base material for electrodeposition. Scanning Electron Microscopy (SEM) and Energy Dispersive Spectroscopy (EDS) were used to characterize the morphology and the chemical composition of the nanowires, respectively. SEM micrographs revealed that the electrodeposited nanowires have dense and compact structures. EDS analysis showed a 60:40% platinum-iridium nanowire composition. Deposition rates were estimated by determining nanowire length as a function of deposition time. High Resolution Transmission Electron Microscopy (HRTEM) images revealed that the nanowires have a nanocrystalline structure with grain sizes ranging from 3 nm to 5 nm. Helium leak tests performed using a helium leak detector showed leak rates as low as 1 × 10(-11) mbar L s(-1) indicating that dense nanowires were electrodeposited inside the nanoporous membranes. Comparison of electrical measurements on platinum and platinum-iridium nanowires revealed that platinum-iridium nanowires have improved electrical conductivity. PMID:23365995

  10. Innovative use of platinum compounds to selectively detect live microorganisms by polymerase chain reaction.

    PubMed

    Soejima, Takashi; Minami, Jun-Ichi; Xiao, Jin-Zhong; Abe, Fumiaki

    2016-02-01

    PCR cannot distinguish live microorganisms from dead ones. To circumvent this disadvantage, ethidium/propidium-monoazide (EMA/PMA) and psoralen to discriminate live from dead bacteria have been used for 2 decades. These methods require the use of numerous laborious procedures. We introduce an innovative method that uses platinum compounds, which are primarily used as catalysts in organic chemistry and partly used as anti-cancer drugs. Microorganisms are briefly exposed to platinum compounds in vivo, and these compounds penetrate dead (compromised) microorganisms but not live ones and are chelated by chromosomal DNA. The use of platinum compounds permits clear discrimination between live and dead microorganisms in water and milk (including Cronobacter sakazakii and Escherichia coli) via PCR compared with typically used PMA. This platinum-PCR method could enable the specific detection of viable coliforms in milk at a concentration of 5-10 CFU mL(-1) specified by EU/USA regulations after a 4-h process. For sample components, environmental water contains lower levels of PCR inhibitors than milk does, and milk is similar to infant formula, skim milk and blood; thus, the use of the platinum-PCR method could also prevent food poisoning due to the presence of C. sakazakii in dairy products. This method could provide outstanding rapidity for use in environmental/food/clinical tests. Platinum-PCR could also be a substitute for the typical culture-based methods currently used. PMID:26192088

  11. Amorphous nickel boride membrane on a platinum-nickel alloy surface for enhanced oxygen reduction reaction

    NASA Astrophysics Data System (ADS)

    He, Daping; Zhang, Libo; He, Dongsheng; Zhou, Gang; Lin, Yue; Deng, Zhaoxiang; Hong, Xun; Wu, Yuen; Chen, Chen; Li, Yadong

    2016-08-01

    The low activity of the oxygen reduction reaction in polymer electrolyte membrane fuel cells is a major barrier for electrocatalysis, and hence needs to be optimized. Tuning the surface electronic structure of platinum-based bimetallic alloys, a promising oxygen reduction reaction catalyst, plays a key role in controlling its interaction with reactants, and thus affects the efficiency. Here we report that a dealloying process can be utilized to experimentally fabricate the interface between dealloyed platinum-nickel alloy and amorphous nickel boride membrane. The coating membrane works as an electron acceptor to tune the surface electronic structure of the platinum-nickel catalyst, and this composite catalyst composed of crystalline platinum-nickel covered by amorphous nickel boride achieves a 27-times enhancement in mass activity relative to commercial platinum/carbon at 0.9 V for the oxygen reduction reaction performance. Moreover, this interactional effect between a crystalline surface and amorphous membrane can be readily generalized to facilitate the 3-times higher catalytic activity of commercial platinum/carbon.

  12. Stable platinum nanoclusters on genomic DNA–graphene oxide with a high oxygen reduction reaction activity

    PubMed Central

    Tiwari, Jitendra N.; Nath, Krishna; Kumar, Susheel; Tiwari, Rajanish N.; Kemp, K. Christian; Le, Nhien H.; Youn, Duck Hyun; Lee, Jae Sung; Kim, Kwang S.

    2013-01-01

    Nanosize platinum clusters with small diameters of 2–4 nm are known to be excellent catalysts for the oxygen reduction reaction. The inherent catalytic activity of smaller platinum clusters has not yet been reported due to a lack of preparation methods to control their size (<2 nm). Here we report the synthesis of platinum clusters (diameter ≤1.4 nm) deposited on genomic double-stranded DNA–graphene oxide composites, and their high-performance electrocatalysis of the oxygen reduction reaction. The electrochemical behaviour, characterized by oxygen reduction reaction onset potential, half-wave potential, specific activity, mass activity, accelerated durability test (10,000 cycles) and cyclic voltammetry stability (10,000 cycles) is attributed to the strong interaction between the nanosize platinum clusters and the DNA–graphene oxide composite, which induces modulation in the electronic structure of the platinum clusters. Furthermore, we show that the platinum cluster/DNA–graphene oxide composite possesses notable environmental durability and stability, vital for high-performance fuel cells and batteries. PMID:23900456

  13. Profile of bevacizumab in the treatment of platinum-resistant ovarian cancer: current perspectives.

    PubMed

    McClung, E Clair; Wenham, Robert M

    2016-01-01

    Patients with platinum-resistant ovarian cancer have progression of disease within 6 months of completing platinum-based chemotherapy. While several chemotherapeutic options exist for the treatment of platinum-resistant ovarian cancer, the overall response to any of these therapies is ~10%, with a median progression-free survival of 3-4 months and a median overall survival of 9-12 months. Bevacizumab (Avastin), a humanized, monoclonal antivascular endothelial growth factor antibody, has demonstrated antitumor activity in the platinum-resistant setting and was recently approved by US Food and Drug Administration for combination therapy with weekly paclitaxel, pegylated liposomal doxorubicin, or topotecan. This review summarizes key clinical trials investigating bevacizumab for recurrent, platinum-resistant ovarian cancer and provides an overview of efficacy, safety, and quality of life data relevant in this setting. While bevacizumab is currently the most studied and clinically available antiangiogenic therapy, we summarize recent studies highlighting novel alternatives, including vascular endothelial growth factor-trap, tyrosine kinase inhibitors, and angiopoietin inhibitor trebananib, and discuss their application for the treatment of platinum-resistant ovarian cancer. PMID:27051317

  14. Production of Platinum Atom Nanoclusters at One End of Helical Plant Viruses

    PubMed Central

    2013-01-01

    Platinum atom clusters (Pt nanoparticles, Pt-NPs) were produced selectively at one end of helical plant viruses, tobacco mosaic virus (TMV) and potato virus X (PVX), when platinum coordinate compounds were reduced chemically by borohydrides. Size of the platinum NPs depends on conditions of the electroless deposition of platinum atoms on the virus. Results suggest that the Pt-NPs are bound concurrently to the terminal protein subunits and the 5′ end of encapsidated TMV RNA. Thus, a special structure of tobacco mosaic virus and potato X virus particles with nanoparticles of platinum, which looks like a push-pin with platinum head and virus needle, was obtained. Similar results were obtained with ultrasonically fragmented TMV particles. By contrast, the Pt-NPs fully filled the central axial hole of in vitro assembled RNA-free TMV-like particles. We believe that the results presented here will be valuable in the fundamental understanding of interaction of viral platforms with ionic metals and in a mechanism of nanoparticles formation. PMID:24187551

  15. Amorphous nickel boride membrane on a platinum-nickel alloy surface for enhanced oxygen reduction reaction.

    PubMed

    He, Daping; Zhang, Libo; He, Dongsheng; Zhou, Gang; Lin, Yue; Deng, Zhaoxiang; Hong, Xun; Wu, Yuen; Chen, Chen; Li, Yadong

    2016-01-01

    The low activity of the oxygen reduction reaction in polymer electrolyte membrane fuel cells is a major barrier for electrocatalysis, and hence needs to be optimized. Tuning the surface electronic structure of platinum-based bimetallic alloys, a promising oxygen reduction reaction catalyst, plays a key role in controlling its interaction with reactants, and thus affects the efficiency. Here we report that a dealloying process can be utilized to experimentally fabricate the interface between dealloyed platinum-nickel alloy and amorphous nickel boride membrane. The coating membrane works as an electron acceptor to tune the surface electronic structure of the platinum-nickel catalyst, and this composite catalyst composed of crystalline platinum-nickel covered by amorphous nickel boride achieves a 27-times enhancement in mass activity relative to commercial platinum/carbon at 0.9 V for the oxygen reduction reaction performance. Moreover, this interactional effect between a crystalline surface and amorphous membrane can be readily generalized to facilitate the 3-times higher catalytic activity of commercial platinum/carbon. PMID:27503412

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

    NASA Technical Reports Server (NTRS)

    Glawe, George E; Shepard, Charles E

    1954-01-01

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

  17. Preparation of Carbon-Platinum-Ceria and Carbon-Platinum-Cerium catalysts and its application in Polymer Electrolyte Fuel Cell: Hydrogen, Methanol, and Ethanol

    NASA Astrophysics Data System (ADS)

    Guzman Blas, Rolando Pedro

    This thesis is focused on fuel cells using hydrogen, methanol and ethanol as fuel. Also, in the method of preparation of catalytic material for the anode: Supercritical Fluid Deposition (SFD) and impregnation method using ethylenediaminetetraacetic acid (EDTA) as a chelating agent. The first part of the thesis describes the general knowledge about Hydrogen Polymer Exchange Membrane Fuel Cell (HPEMFC),Direct Methanol Fuel Cell (DMFC) and Direct Ethanol Fuel Cell (DEFC), as well as the properties of Cerium and CeO2 (Ceria). The second part of the thesis describes the preparation of catalytic material by Supercritical Fluid Deposition (SFD). SFD was utilized to deposit Pt and ceria simultaneously onto gas diffusion layers. The Pt-ceria catalyst deposited by SFD exhibited higher methanol oxidation activity compared to the platinum catalyst alone. The linear sweep traces of the cathode made for the methanol cross over study indicate that Pt-Ceria/C as the anode catalyst, due to its better activity for methanol, improves the fuel utilization, minimizing the methanol permeation from anode to cathode compartment. The third and fourth parts of the thesis describe the preparation of material catalytic material Carbon-Platinum-Cerium by a simple and cheap impregnation method using EDTA as a chelating agent to form a complex with cerium (III). This preparation method allows the mass production of the material catalysts without additional significant cost. Fuel cell polarization and power curves experiments showed that the Carbon-Platinum-Cerium anode materials exhibited better catalytic activity than the only Vulcan-Pt catalysts for DMFC, DEFC and HPEMFC. In the case of Vulcan-20%Pt-5%w Cerium, this material exhibits better catalytic activity than the Vulcan-20%Pt in DMFC. In the case of Vulcan-40% Pt-doped Cerium, this material exhibits better catalytic activity than the Vulcan-40% Pt in DMFC, DEFC and HPEMFC. Finally, I propose a theory that explains the reason why the

  18. The age of Kondyor massif dunites (Aldan Province, Russia): First U-Pb isotopic data

    NASA Astrophysics Data System (ADS)

    Malitch, K. N.; Efimov, A. A.; Badanina, I. Yu.

    2012-09-01

    The material and isotope-geochemical peculiarities of zircons from dunites of the Kondyor massif (Aldan Province, Southeast Siberian Craton) have been described for the first time. This massif is associated with an economic platinum placer deposit. On the basis of detailed study of the morphology, internal structure, and geochemical characteristics, zircons have been subdivided into two types. The first type is represented by crystals of oval and rounded shapes, characterized by a bimodal distribution of "ancient" (2477 ± 18 and 1885 ± 52 Ma) U-Pb (SHRIMP-II) ages. The second type of zircons forms idiomorphic crystals and aggregates of prismatic habitus, forming two "young" age clusters (176 ± 1.2 and 143 ± 2.0 Ma). The obtained results allow us to make a conclusion about the long evolution of platinum-bearing dunites. The first type of zircons formed by metamictic cores and homogeneous peripheral rims indicates the time of metamorphism at the Archean-Proterozoic boundary (˜2.5 Ga), implying an older age of porous zircon cores. Such zircons characterize the minimal age of the initial mantle substance or a close time when the platinum-bearing dunite was generated. Based on their formation time, the second type of zircons can be referred to the epoch of tectonic-magmatic activation of the Aldan Shield. The new geochronological data, along with the material identity of dunites from the Urals and the Aldan Province, argue for a common genetic origin of platinum-bearing dunites of the fold belts and ancient cratons.

  19. Novel Anticancer Platinum(IV) Complexes with Adamantylamine: Their Efficiency and Innovative Chemotherapy Strategies Modifying Lipid Metabolism.

    PubMed

    Kozubík, Alois; Vaculová, Alena; Soucek, Karel; Vondrácek, Jan; Turánek, Jaroslav; Hofmanová, Jirina

    2008-01-01

    The impressive impact of cisplatin on cancer on one side and severe side effects, as well as the development of drug resistance during treatment on the other side, were the factors motivating scientists to design and synthesize new more potent analogues lacking disadvantages of cisplatin. Platinum(IV) complexes represent one of the perspective groups of platinum-based drugs. In this review, we summarize recent findings on both in vitro and in vivo effects of platinum(IV) complexes with adamantylamine. Based on a literary overview of the mechanisms of activity of platinum-based cytostatics, we discuss opportunities for modulating the effects of novel platinum complexes through interactions with apoptotic signaling pathways and with cellular lipids, including modulations of the mitochondrial cell death pathway, oxidative stress, signaling of death ligands, lipid metabolism/signaling, or intercellular communication. These approaches might significantly enhance the efficacy of both novel and established platinum-based cytostatics. PMID:18414587

  20. Physicochemical isotope anomalies

    SciTech Connect

    Esat, T.M.

    1988-06-01

    Isotopic composition of refractory elements can be modified, by physical processes such as distillation and sputtering, in unexpected patterns. Distillation enriches the heavy isotopes in the residue and the light isotopes in the vapor. However, current models appear to be inadequate to describe the detailed mass dependence, in particular for large fractionations. Coarse- and fine-grained inclusions from the Allende meteorite exhibit correlated isotope effects in Mg both as mass-dependent fractionation and residual anomalies. This isotope pattern can be duplicated by high temperature distillation in the laboratory. A ubiquitous property of meteoritic inclusions for Mg as well as for most of the other elements, where measurements exist, is mass-dependent fractionation. In contrast, terrestrial materials such as microtektites, tektite buttons as well as lunar orange and green glass spheres have normal Mg isotopic composition. A subset of interplanetary dust particles labelled as chondritic aggregates exhibit excesses in {sup 26}Mg and deuterium anomalies. Sputtering is expected to be a dominant mechanism in the destruction of grains within interstellar dust clouds. An active proto-sun as well as the present solar-wind and solar-flare flux are of sufficient intensity to sputter significant amounts of material. Laboratory experiments in Mg show widespread isotope effects including residual {sup 26}Mg excesses and mass dependent fractionation. It is possible that the {sup 26}Mg excesses in interplanetary dust is related to sputtering by energetic solar-wind particles. The implication if the laboratory distillation and sputtering effects are discussed and contrasted with the anomalies in meteoritic inclusions the other extraterrestrial materials the authors have access to.

  1. Enriched Pt-Re-Os isotope systematics in plume lavas explained by metasomatic sulfides.

    PubMed

    Luguet, Ambre; Graham Pearson, D; Nowell, Geoff M; Dreher, Scott T; Coggon, Judith A; Spetsius, Zdislav V; Parman, Stephen W

    2008-01-25

    To explain the elevated osmium isotope (186Os-187Os) signatures in oceanic basalts, the possibility of material flux from the metallic core into the crust has been invoked. This hypothesis conflicts with theoretical constraints on Earth's thermal and dynamic history. To test the veracity and uniqueness of elevated 186Os-187Os in tracing core-mantle exchange, we present highly siderophile element analyses of pyroxenites, eclogites plus their sulfides, and new 186Os/188Os measurements on pyroxenites and platinum-rich alloys. Modeling shows that involvement in the mantle source of either bulk pyroxenite or, more likely, metasomatic sulfides derived from either pyroxenite or peridotite melts can explain the 186Os-187Os signatures of oceanic basalts. This removes the requirement for core-mantle exchange and provides an effective mechanism for generating Os isotope diversity in basalt source regions. PMID:18218894

  2. Platinum(II) 1,5-COD oxo complexes

    SciTech Connect

    Shan, H.; James, A.; Sharp, P.R.

    1998-11-02

    Three new types of platinum(II) oxo complexes--[(1,5-COD)Pt({mu}{sup 3}-O)(AuL)]{sub 2}(BF{sub 4}){sub 2} [1, L = PPh{sub 3}, PPh{sub 2}Et, PPh{sub 2}-i-Pr, P(o-tol){sub 3}, P(p-tol){sub 3}, P(p-MeOC{sub 6}H{sub 4}){sub 3}, P(p-CF{sub 3}C{sub 6}H{sub 4}){sub 3}], [(1,5-COD)Pt{l_brace}{mu}{sup 3}-O(AuL){sub 2}{r_brace}{sub 2}](BF{sub 4}){sub 2} (2), and [(1,5-COD){sub 4}Pt{sub 4}({mu}{sup 3}-O){sub 2}Cl{sub 2}]X{sub 2} (3, X = BF{sub 4}; 3a, X = CF{sub 3}SO{sub 3})--are obtained from oxo/chloro exchange reactions between (1,5-COD)PtCl{sub 2} and [(LAu){sub 3}({mu}{sup 3}-O)]BF{sub 4}. Crystals of 1 (L = PPh{sub 3}) from CDCl{sub 3} are triclinic. Crystals of 3a from CH{sub 2}Cl{sub 2}/toluene are trigonal. The structure of the cationic portion of 1 shows a planar (COD)-Pt({mu}-O){sub 2}Pt(COD) unit with slightly out-of-plane LAu{sup +} groups linearly coordinated to the oxo ligands. The structure of the cationic portion of 3a is similar and shows a slightly folded (COD)Pt({mu}-O){sub 2}Pt(COD) unit with out-of-plane [(COD)PtCl]{sup +} groups coordinated to the oxo ligands. Solutions of 3 in untreated CH{sub 2}Cl{sub 2} or CD{sub 2}Cl{sup 2} deposit crystals of [(1,5-COD){sub 4}Pt{sub 4}({mu}{sup 3}-O){sub 2}({mu}{sup 2}-OH)](BF{sub 4}){sub 3} (4) which are monoclinic. The core structure of the cationic portion of 4 shows a tetranuclear platinum cation in which the metal atoms occupy the corners of a distorted tetrahedron and two {mu}{sup 3}-oxo ligands and one {mu}{sup 2}-hydroxo ligand bridge the four platinum atoms. Reaction of 1 (L = PPh{sub 3}) with PPh{sub 3} gives OPPh{sub 3} and [(Ph{sub 3}P){sub 3}PtAuPPh{sub 3}]BF{sub 4} (5) which is also obtained from (Ph{sub 3}P){sub 4}Pt and Ph{sub 3}-PAuBF{sub 4}. Crystals of 5 from THF are monoclinic. The structure of 5 consists of an L{sub 3}Pt-AuL cation where the Au atom is linear 2-coordinate and the Pt atom is distorted square-planar 4-coordinate.

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

    NASA Astrophysics Data System (ADS)

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

    2012-06-01

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

  4. Determination of platinum and palladium in geological materials by neutron-activation analysis after fire-assay preconcentration

    USGS Publications Warehouse

    Rowe, J.J.; Simon, F.O.

    1971-01-01

    Fire-asay preconcentration followed by neutron-activation analysis permits the determination of as little as 0.5 ppM of platinum and 0.5 ppM of palladium on a 20-g sample. Platinum and palladium are separated with carriers and beta-counted. Results for the platinum and palladium content of seven U.S.G.S. standard rocks are presented. ?? 1971.

  5. Isotopic geochemistry and cosmochemistry

    NASA Astrophysics Data System (ADS)

    Shchukoliukov, Iu. A.

    The book includes recent information on isotope geology, geochemistry, and cosmochemistry, discussed at a recent Soviet-Japanese symposium (at Irkutsk, USSR). Attention is given to numerical modeling of geochronometric systems, a classification of noble-gas components in the earth's interior, the feasibility of using ion microprobe for local isotope analysis of zircons for the purpose of deriving the early history of the earth (on the example of the Novopavlovsk complex from the Ukranian shield), a geological and geochronological study of the Ganalski complex of Kamchatka, and strontium isotopes as a criterion of the nature of acid melts (i.e., mantle- or crust-related). Other papers are on the geochronology and geology of Siberian kimberlites, the nature of sulfur from effusive rocks of the Kamchatka-Kuril-Japan island arc, mass-spectrometric studies of volatile components in exocontact rocks of alkaline-basic intrusions, and an analytical method for stable-isotope analysis in ultrasmall amounts of CO2 and its application to studies of the microscale isotopic zoning in calcite and graphite crystals in marble.

  6. Separation of sulfur isotopes

    DOEpatents

    DeWitt, Robert; Jepson, Bernhart E.; Schwind, Roger A.

    1976-06-22

    Sulfur isotopes are continuously separated and enriched using a closed loop reflux system wherein sulfur dioxide (SO.sub.2) is reacted with sodium hydroxide (NaOH) or the like to form sodium hydrogen sulfite (NaHSO.sub.3). Heavier sulfur isotopes are preferentially attracted to the NaHSO.sub.3, and subsequently reacted with sulfuric acid (H.sub.2 SO.sub.4) forming sodium hydrogen sulfate (NaHSO.sub.4) and SO.sub.2 gas which contains increased concentrations of the heavier sulfur isotopes. This heavy isotope enriched SO.sub.2 gas is subsequently separated and the NaHSO.sub.4 is reacted with NaOH to form sodium sulfate (Na.sub.2 SO.sub.4) which is subsequently decomposed in an electrodialysis unit to form the NaOH and H.sub.2 SO.sub.4 components which are used in the aforesaid reactions thereby effecting sulfur isotope separation and enrichment without objectionable loss of feed materials.

  7. Transportation of medical isotopes

    SciTech Connect

    Nielsen, D.L.

    1997-11-19

    A Draft Technical Information Document (HNF-1855) is being prepared to evaluate proposed interim tritium and medical isotope production at the Fast Flux Test Facility (FFTF). This assessment examines the potential health and safety impacts of transportation operations associated with the production of medical isotopes. Incident-free and accidental impacts are assessed using bounding source terms for the shipment of nonradiological target materials to the Hanford Site, the shipment of irradiated targets from the FFTF to the 325 Building, and the shipment of medical isotope products from the 325 Building to medical distributors. The health and safety consequences to workers and the public from the incident-free transportation of targets and isotope products would be within acceptable levels. For transportation accidents, risks to works and the public also would be within acceptable levels. This assessment is based on best information available at this time. As the medical isotope program matures, this analysis will be revised, if necessary, to support development of a final revision to the Technical Information Document.

  8. Can the state of platinum species be unambiguously determined by the stretching frequency of an adsorbed CO probe molecule?

    PubMed

    Aleksandrov, Hristiyan A; Neyman, Konstantin M; Hadjiivanov, Konstantin I; Vayssilov, Georgi N

    2016-08-10

    The paper addresses possible ambiguities in the determination of the state of platinum species by the stretching frequency of a CO probe, which is a common technique for characterization of platinum-containing catalytic systems. We present a comprehensive comparison of the available experimental data with our theoretical modeling (density functional) results of pertinent systems - platinum surfaces, nanoparticles and clusters as well as reduced or oxidized platinum moieties on a ceria support. Our results for CO adsorbed on-top on metallic Pt(0), with C-O vibrational frequencies in the region 2018-2077 cm(-1), suggest that a decrease of the coordination number of the platinum atom, to which CO is bound, by one lowers the CO frequency by about 7 cm(-1). This trend corroborates the Kappers-van der Maas correlation derived from the analysis of the experimental stretching frequency of CO adsorbed on platinum-containing samples on different supports. We also analyzed the effect of the charge of platinum species on the CO frequency. Based on the calculated vibrational frequencies of CO in various model systems, we concluded that the actual state of the platinum species may be mistaken based only on the measured value of the C-O vibrational frequency due to overlapping regions of frequencies corresponding to different types of species. In order to identify the actual state of platinum species one has to combine this powerful technique with other approaches. PMID:27444400

  9. Isotope separation apparatus

    DOEpatents

    Arnush, Donald; MacKenzie, Kenneth R.; Wuerker, Ralph F.

    1980-01-01

    Isotope separation apparatus consisting of a plurality of cells disposed adjacent to each other in an evacuated container. A common magnetic field is established extending through all of the cells. A source of energetic electrons at one end of the container generates electrons which pass through the cells along the magnetic field lines. Each cell includes an array of collector plates arranged in parallel or in tandem within a common magnetic field. Sets of collector plates are disposed adjacent to each other in each cell. Means are provided for differentially energizing ions of a desired isotope by applying energy at the cyclotron resonant frequency of the desired isotope. As a result, the energized desired ions are preferentially collected by the collector plates.

  10. [Simultaneous determination of platinum (IV) and palladium (II) using spectrophotometry method].

    PubMed

    Ma, Dong-Lan; Wang, Yun; Ma, Kuang-Biao; Wang, Jin-Ye

    2009-10-01

    The N-(m-methylphenyl)-N'-(sodium p-aminobenzenesulfonate)-thiourea (MMPT) was good reagent of water solubility. In the medium of an HAc-NaAc buffer solution and hexadecyltrimethylammonium bromide (CTMAB), MMPT can react with platinum (IV) and palladium (II) to form green and brown soluble complex. The maximum absorbance of the complex was at lambdaPt(max) = 754.4 nm and lambdaPD(max) = 304.6 nm. Beer's law was obeyed with the concentration in the range of 0-32.0 microg Pt(IV)/25 mL and 0-25.0 microg Pd(II)/25 mL for platinum (IV) and palladium(II) respectively. The correlated coefficient was r754.4 = 0.999 5 for platinum (IV); and r304.6 = 0.999 9 for palladium (II). Their molar absorption coefficients were epsilonPT(754.4 = 8.6 x 10(4) L x mol(-1) x cm(-1) and epsilonPd(304.6) = 7.4 x 10(4) L x mol(-1) x cm(-1) respectively. The contents of platinum (IV) and palladium (II) were converted by determination of the absorbency of mix solution of platinum (IV) and palladium (II) at 754.4 and 304.6 nm. Only Cu2+ and Co2+ interfered with the determination of palladium (II) among 50 coexistent ions, so the selectivity was good. It can be used for the determination of content of synthesis samples. The relative standard deviation (RSD) was less than 2.0%, and the recovery (%) was in the range of 96%-104%. The results are satisfactory. Because the reagent reacts with platinum (IV) and palladium (II) to form water soluble complex and does not require pre-separation for simultaneous determination of platinum (IV) and palladium (II), the method is easy to operate, rapid and environment-friendly. PMID:20038071

  11. Combinations of platinums and selected phytochemicals as a means of overcoming resistance in ovarian cancer.

    PubMed

    Huq, Fazlul; Yu, Jun Q; Beale, Philip; Chan, Charles; Arzuman, Lalia; Nessa, Meher U; Mazumder, Mohammed E H

    2014-01-01

    Cancer sufferers are often found to use herbal products along with targeted therapy although not much information (whether beneficial or harmful) is available about the effects of such combinations. In this study, we investigated synergism from the combination of platinum drugs and a number of tumour-active phytochemicals including curcumin, epigallocatechin-3-gallate, thymoquinone, genistein, resveratrol, betulinic acid and ursolic acid in three human ovarian cancer cell lines A2780, A2780(cisR) and A2780(ZD0473R), as a function of concentration and the sequence of administration. Both the dose-effect curves and combination indices show that the binary combinations of platinum drugs with the phytochemicals exert concentration- and sequence-dependent synergism in the cell lines. Generally the degree of synergism is found to be greater in sequenced administration such as 0/2 h, 2/0 h, 0/4 h and 4/0 h than the bolus. The variation in the nature of the combined drug action from being highly synergistic to antagonistic with the change in sequence of administration clearly indicates that the action of one drug modulates that of the other (towards the induction or inhibition of apoptosis). We have also used sequenced combinations of platinum drugs and bortezomib (a proteasome inhibitor that prevents cisplatin-induced proteasomal degration of copper transporter CTR1) to enhance cellular platinum accumulation and the level of platinum-DNA binding especially in the resistant human ovarian tumour models. Proteomic studies to identify the key proteins associated with platinum resistance are ongoing. We have identified 59 proteins associated with platinum resistance in ovarian tumor models. PMID:24403514

  12. Applying Isotopic Effect in ITS-90 SPRT Calibrations

    NASA Astrophysics Data System (ADS)

    Pavese, F.

    2014-07-01

    The International Temperature Scale of 1990 (ITS-90) defines exact values for all fixed-point temperatures. For example, for the standard platinum resistance thermometers (SPRT), at each fixed point, the measured SPRT resistance and the temperature defined in the ITS-90 are used as input data into the correction equations of the ITS-90. Starting from 2006, formal equations were added to the Technical Annex for the ITS-90 for computing the fixed-point temperatures of the substances of different isotopic compositions, presently the triple and vapor-pressure points, Ne triple point, and triple point. This paper addresses the issue of the method required to apply the procedure defined in the ITS-90 for the calibration of a SPRT, according to the new requirements. The required procedure does not involve a "correction" of the fixed-point temperatures, since they are defined exactly by the ITS-90, but requires instead, the re-computing of the measured resistances at the relevant fixed points. In those cases where resistance ratios with respect to the triple point of water are required, the re-computation must be first applied separately to the specific fixed points and to the triple point of water. In case the re-computation is not possible because of insufficient information on the isotopic composition of the sample used, an additional component must be added to the total uncertainty budget.

  13. Partitioning of Sulfur and Platinum at Core Formation Conditions.

    NASA Astrophysics Data System (ADS)

    Suer, T. A.; Siebert, J.; Fiquet, G.; Remusat, L.

    2015-12-01

    Measuring the partitioning behavior of highly siderophile elements (HSE) at high pressures and temperatures is important for understanding the mantle's elemental reservoir and the core mantle differentiation process. Low solubility of HSEs in silicate melts and the small size of samples obtained from diamond anvil cell (DAC) experiments have prevented the experimental study of the partitioning of these elements at realistic deep magma ocean conditions. In this study, we present results for metal-silicate partitioning experiments of sulfur and platinum conducted at pressures between 45 and 80 GPa and at temperatures from 3500 to 4200 K. With the nanoSIMS as our main tool for measuring trace element concentrations, we have developed a protocol for studying the partitioning behavior of these elements from samples that underwent equilibration at high pressure and temperatures in a Laser-Heated DAC. The nanoSIMS has the spatial resolution and the required sensitivity to measure the low concentration of some HSEs in the quenched silicate glass. The results of this study will help to refine current core-mantle differentiation models. Furthermore they add constraints to the contribution of the late veneer to the mantle's elemental abundances.

  14. Tuning selectivity of electrochemical reactions by atomically dispersed platinum catalyst

    NASA Astrophysics Data System (ADS)

    Choi, Chang Hyuck; Kim, Minho; Kwon, Han Chang; Cho, Sung June; Yun, Seongho; Kim, Hee-Tak; Mayrhofer, Karl J. J.; Kim, Hyungjun; Choi, Minkee

    2016-03-01

    Maximum atom efficiency as well as distinct chemoselectivity is expected for electrocatalysis on atomically dispersed (or single site) metal centres, but its realization remains challenging so far, because carbon, as the most widely used electrocatalyst support, cannot effectively stabilize them. Here we report that a sulfur-doped zeolite-templated carbon, simultaneously exhibiting large sulfur content (17 wt% S), as well as a unique carbon structure (that is, highly curved three-dimensional networks of graphene nanoribbons), can stabilize a relatively high loading of platinum (5 wt%) in the form of highly dispersed species including site isolated atoms. In the oxygen reduction reaction, this catalyst does not follow a conventional four-electron pathway producing H2O, but selectively produces H2O2 even over extended times without significant degradation of the activity. Thus, this approach constitutes a potentially promising route for producing important fine chemical H2O2, and also offers opportunities for tuning the selectivity of other electrochemical reactions on various metal catalysts.

  15. Self-Organized Platinum Nanoparticles Elevated on Freestanding Graphene

    NASA Astrophysics Data System (ADS)

    Ackerman, Matthew; Xu, Peng; Barber, Steven; Schoelz, James; Qi, Dejun; Thibado, Paul; Dong, Lifeng; Yu, Jianhua; Xu, Fangfang; Neek-Amal, Mehdi; Peeters, Francois

    2014-03-01

    Freestanding graphene membranes were successfully functionalized with platinum nanoparticles (Pt NPs) using a single-step sputtering deposition process. The membranes were imaged using high-resolution transmission electron microscopy, revealing a homogeneous distribution of uniformly sized, single-crystal Pt NPs that exhibit a preferred orientation and nearest-neighbor distance. The NPs were also found to be partially elevated by the graphene substrate, as deduced from atomic-resolution scanning tunneling microscopy (STM) images. Furthermore, the electrostatic force between the STM tip and sample was utilized to estimate the binding energy of the NPs to the suspended graphene. Local strain accumulation due to elevation during the growth process is thought to be the origin of the NP self-organization. Such detailed insight into the atomic nature of this functionalized system was only possible through the cooperation of dual microscopic techniques combined with molecular dynamics simulations. The findings are expected to shape future approaches to develop high-performance electronics based on nanoparticle-functionalized graphene as well as fuel cells using Pt NP catalysts. ONR Grant No. N00014-10-1-0181, NSF Grant No. DMR-0855358 and DMR-0821159, National Natural Science Foundation of China (51172113), Shandong Natural Science Foundation (JQ201118), Qingdao Municipal Science and Technology Commission (12-1-4-136-hz).

  16. Dynamics of Single Hydrogen Bubbles at a Platinum Microelectrode.

    PubMed

    Yang, Xuegeng; Karnbach, Franziska; Uhlemann, Margitta; Odenbach, Stefan; Eckert, Kerstin

    2015-07-28

    Bubble dynamics, including the formation, growth, and detachment, of single H2 bubbles was studied at a platinum microelectrode during the electrolysis of 1 M H2SO4 electrolyte. The bubbles were visualized through a microscope by a high-speed camera. Electrochemical measurements were conducted in parallel to measure the transient current. The periodic current oscillations, resulting from the periodic formation and detachment of single bubbles, allow the bubble lifetime and size to be predicted from the transient current. A comparison of the bubble volume calculated from the current and from the recorded bubble image shows a gas evolution efficiency increasing continuously with the growth of the bubble until it reaches 100%. Two different substrates, glass and epoxy, were used to embed the Pt wire. While nearly no difference was found with respect to the growth law for the bubble radius, the contact angle differs strongly for the two types of cell. Data provided for the contact point evolution further complete the image of single hydrogen bubble growth. Finally, the velocity field driven by the detached bubble was measured by means of PIV, and the effects of the convection on the subsequent bubble were evaluated. PMID:26133052

  17. Platinum Nanoparticles: Efficient and Stable Catechol Oxidase Mimetics.

    PubMed

    Liu, Yi; Wu, Haohao; Chong, Yu; Wamer, Wayne G; Xia, Qingsu; Cai, Lining; Nie, Zhihong; Fu, Peter P; Yin, Jun-Jie

    2015-09-01

    Although enzyme-like nanomaterials have been extensively investigated over the past decade, most research has focused on the peroxidase-like, catalase-like, or SOD-like activity of these nanomaterials. Identifying nanomaterials having oxidase-like activities has received less attention. In this study, we demonstrate that platinum nanoparticles (Pt NPs) exhibit catechol oxidase-like activity, oxidizing polyphenols into the corresponding o-quinones. Four unique approaches are employed to demonstrate the catechol oxidase-like activity exerted by Pt NPs. First, UV-vis spectroscopy is used to monitor the oxidation of polyphenols catalyzed by Pt NPs. Second, the oxidized products of polyphenols are identified by ultrahigh-performance liquid chromatography (UHPLC) separation followed by high-resolution mass spectrometry (HRMS) identification. Third, electron spin resonance (ESR) oximetry techniques are used to confirm the O2 consumption during the oxidation reaction. Fourth, the intermediate products of semiquinone radicals formed during the oxidation of polyphenols are determined by ESR using spin stabilization. These results indicate Pt NPs possess catechol oxidase-like activity. Because polyphenols and related bioactive substances have been explored as potent antioxidants that could be useful for the prevention of cancer and cardiovascular diseases, and Pt NPs have been widely used in the chemical industry and medical science, it is essential to understand the potential effects of Pt NPs for altering or influencing the antioxidant activity of polyphenols. PMID:26305170

  18. Single-wall carbon nanotube chemical attachment at platinum electrodes

    NASA Astrophysics Data System (ADS)

    Rosario-Castro, Belinda I.; Contés-de-Jesús, Enid J.; Lebrón-Colón, Marisabel; Meador, Michael A.; Scibioh, M. Aulice; Cabrera, Carlos R.

    2010-11-01

    Self-assembled monolayer (SAM) techniques were used to adsorb 4-aminothiophenol (4-ATP) on platinum electrodes in order to obtain an amino-terminated SAM as the base for the chemical attachment of single-wall carbon nanotubes (SWCNTs). A physico-chemical, morphological and electrochemical characterizations of SWCNTs attached onto the modified Pt electrodes was done by using reflection-absorption infrared spectroscopy (RAIR), X-ray photoelectron spectroscopy (XPS), Raman spectroscopy, scanning electron microscopy (SEM), atomic force microscopy (AFM), and cyclic voltammetry (CV) techniques. The SWNTs/4-ATP/Pt surface had regions of small, medium, and large thickness of carbon nanotubes with heights of 100-200 nm, 700 nm to 1.5 μm, and 1.0-3.0 μm, respectively. Cyclic voltammetries (CVs) in sulfuric acid demonstrated that attachment of SWNTs on 4-ATP/Pt is markedly stable, even after 30 potential cycles. CV in ruthenium hexamine was similar to bare Pt electrodes, suggesting that SWNTs assembly is similar to a closely packed microelectrode array.

  19. Monodisperse Platinum and Rhodium Nanoparticles as Model Heterogeneous Catalysts

    SciTech Connect

    Grass, Michael Edward

    2008-09-01

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

  20. EPR characterisation of platinum nanoparticle functionalised carbon nanotube hybrid materials.

    PubMed

    Dennany, Lynn; Sherrell, Peter; Chen, Jun; Innis, Peter C; Wallace, Gordon G; Minett, Andrew I

    2010-04-28

    The use of nanostructured carbon materials as electrodes for energy storage and conversion is an expanding area of research in recent years. Herein, platinum nanoparticles have been deposited onto both multi-walled and single-walled carbon nanotubes (CNTs) via a microwave assisted polyol reduction method. This interaction has been probed with electron paramagnetic resonance (EPR) and Raman spectroscopies to elucidate the charge/electron transfer interactions between the Pt nanoparticles and the CNTs. Observed shifts in the g factors of the CNTs are indicative of such an electronic interaction, strongly suggesting the covalent attachment of the nanoparticles to the carboxylic groups on the CNTs, formed during the microwave-assisted reduction process. The Pt decorated CNTs show a dramatic increase in electrochemical behaviour in terms of high reversible capacity and relatively stable cycle performance compared to unmodified CNTs increasing their applicability in energy storage devices. For instance, significant increases in the electrochemical double layer capacitance are observed for the CNT-NP composite electrode. PMID:20379504

  1. Distortions induced in DNA by cis-platinum interstrand adducts

    SciTech Connect

    Sip, M.; Schwartz, A.; Vovelle, F.; Ptak, M.; Leng, M. )

    1992-03-10

    A 22 base pair double-stranded oligonucleotide containing a unique interstrand adduct resulting from chelation of the two guanine residues within the central sequence d(TGCT/AGCA) by a cis-platinum residue has been studied by means of gel electrophoresis, chemical probes, and molecular mechanics. The anomalously slow electrophoretic mobility of the multimers of the platinated and ligated oligomers suggests that the platinated oligonucleotide is bent. The two cytosine residues (complementary to the platinated guanines) are hyperreactive to hydroxylamine, indicating a large exposure of the two bases to the solvent. The adduct does not induce a local denaturation within the flanking sequences since the adenine residues are not reactive with diethyl pyrocarbonate. This is confirmed by the nonreactivity of the complementary T residues with osmium tetraoxide. These results and the molecular mechanics modeling suggest that the interstrand adduct bends the double helix by approximately 55{degree} toward the major groove, that the double helix conserves its average twist angle, and that the distortion induced by the adduct is localized at the platinated sequence d(GC/CG).

  2. Hydrogenotitanates nanotubes supported platinum anode for direct methanol fuel cell

    NASA Astrophysics Data System (ADS)

    Abida, Bochra; Chirchi, Lotfi; Baranton, Stève; Napporn, Teko Wilhelmin; Morais, Cláudia; Léger, Jean-Michel; Ghorbel, Abdelhamid

    2013-11-01

    Hydrogenotitanates nanotubes (HTNs) are prepared from TiO2 powder via hydrothermal processing in 11.25 M NaOH aq. The reaction temperature is 130 °C for 20 h. Afterward a heat treatment is done during 2 h at 500 °C in air, to obtain calcined HTNs (HTNs-cal). The structural change on the molecular TiO2 during the hydrothermal treatment is investigated in detail by various analytic techniques such as XRD and TEM, which reveal that the crystal structure of the HTNs materials is similar to that of H2Ti2O5·H2O nanotubes with 160 nm in length and 10 nm in diameter. Nitrogen adsorption-desorption isotherms indicate that synthesized solids are mesoporous materials with a multiwalled nanotubular structure and high specific surface area. Platinum nanoparticles are deposited on the HTNs by the impregnation method for a total noble metal loading of 10 wt%. The electrocatalytic activity of these electrocatalysts is evaluated by cyclic voltammetry in acid medium. Typical CO stripping voltammetry in acidic solutions is investigated. The results demonstrate that the HTNs can greatly enhance the catalytic activity of Pt for methanol oxidation. The CO stripping test shows that the Pt/HTNs can shift the CO oxidation potential to lower direction than Pt/C (XC72) and Pt/HTNs-cal catalysts.

  3. Oxidation of a platinum microwire surface applied in glucose detection

    NASA Astrophysics Data System (ADS)

    Pham Xuan, Thanh Tung; Thanh Tuyen Le, Thi; Duy Tran, Phu; Van Pham, Binh; Hien Tong, Duy; Chien Dang, Mau

    2010-06-01

    In this paper, we report the results of the surface oxidation of platinum (Pt) microwires in aqueous sulfuric acid (H2SO4) solutions by using a cyclic voltammetry technique. The Pt microwire chips were scanned and applied with voltage potentials ranging from 0 to 1.4 V in the H2SO4 solution with concentrations from 0.0003 to 0.0018 M to find out the optimized concentration of sulfuric acid for the oxidation process. The cyclic voltammetry (CV) measurements show the oxidation peak at a potential range from 1.1 to 1.2 V. This is the peak of the interfacial place exchange of chemisorbed O (Ochem) and surface Pt atoms, resulting in the formation of a quasi-3D surface PtO lattice comprising Pt2+ and O2‑. The oxidized surface Pt microwires were then functionalized with a 3-aminopropyl triethoxy silane (APTES) and glucose oxidase (GOD) was immobilized onto the functionalized chips for further application in glucose detection. By using this process, Pt microwires have been used for the successful detection of glucose in solution with concentrations in the range of 4–20 mM.

  4. Tuning selectivity of electrochemical reactions by atomically dispersed platinum catalyst

    PubMed Central

    Choi, Chang Hyuck; Kim, Minho; Kwon, Han Chang; Cho, Sung June; Yun, Seongho; Kim, Hee-Tak; Mayrhofer, Karl J. J.; Kim, Hyungjun; Choi, Minkee

    2016-01-01

    Maximum atom efficiency as well as distinct chemoselectivity is expected for electrocatalysis on atomically dispersed (or single site) metal centres, but its realization remains challenging so far, because carbon, as the most widely used electrocatalyst support, cannot effectively stabilize them. Here we report that a sulfur-doped zeolite-templated carbon, simultaneously exhibiting large sulfur content (17 wt% S), as well as a unique carbon structure (that is, highly curved three-dimensional networks of graphene nanoribbons), can stabilize a relatively high loading of platinum (5 wt%) in the form of highly dispersed species including site isolated atoms. In the oxygen reduction reaction, this catalyst does not follow a conventional four-electron pathway producing H2O, but selectively produces H2O2 even over extended times without significant degradation of the activity. Thus, this approach constitutes a potentially promising route for producing important fine chemical H2O2, and also offers opportunities for tuning the selectivity of other electrochemical reactions on various metal catalysts. PMID:26952517

  5. Aqueous synthesis of near-infrared highly fluorescent platinum nanoclusters.

    PubMed

    García Fernández, Jenifer; Trapiella-Alfonso, Laura; Costa-Fernández, José M; Pereiro, Rosario; Sanz-Medel, Alfredo

    2015-05-29

    A one-step synthesis of near infrared fluorescent platinum nanoclusters (PtNCs) in aqueous medium is described. The proposed optimized procedure for PtNC synthesis is rather simple, fast and it is based on the direct metal reduction with NaBH4. Bidentated thiol ligands (lipoic acid) were selected as nanoclusters stabilizers in water media. The structural characterization revealed attractive features of the PtNCs, including small size, high water solubility, near-infrared luminescence centered at 680 nm, long-term stability and the highest quantum yield in water reported so far (47%) for PtNCs. Moreover, their stability in different pH media and an ionic strength of 0.2 M NaCl was studied and no significant changes in fluorescence emission were detected. In brief, they offer a new type of fluorescent noble metal nanoprobe with a great potential to be applied in several fields, including biolabeling and imaging experiments. PMID:25944823

  6. Oxygen reduction reaction on stepped platinum surfaces in alkaline media.

    PubMed

    Rizo, Ruben; Herrero, Enrique; Feliu, Juan M

    2013-10-01

    The oxygen reduction reaction (ORR) in 0.1 M NaOH on platinum single crystal electrodes has been studied using hanging meniscus rotating disk electrode configuration. Basal planes and stepped surfaces with (111) and (100) terraces have been employed. The results indicate that the Pt(111) electrode has the highest electrocatalytic activity among all the studied surfaces. The addition of steps on this electrode surface significantly diminishes the reactivity of the surface towards the ORR. In fact, the reactivity of the steps on the surfaces with wide terraces can be considered negligible with respect to that measured for the terrace. On the other hand, Pt(100) and Pt(110) electrodes have much lower activity than the Pt(111) electrode. These results have been compared with those obtained in acid media to understand the effect of the pH and the adsorbed OH on the mechanism. It is proposed that the surface covered by adsorbed OH is active for the reduction of the oxygen molecules. PMID:23936903

  7. Kinetics of Platinum-Catalyzed Decomposition of Hydrogen Peroxide

    NASA Astrophysics Data System (ADS)

    Vetter, Tiffany A.; Colombo, D. Philip, Jr.

    2003-07-01

    CIBA Vision Corporation markets a contact lens cleaning system that consists of an AOSEPT disinfectant solution and an AOSEPT lens cup. The disinfectant is a buffered 3.0% m/v hydrogen peroxide solution and the cup includes a platinum-coated AOSEPT disc. The hydrogen peroxide disinfects by killing bacteria, fungi, and viruses found on the contact lenses. Because the concentration of hydrogen peroxide needed to disinfect is irritating to eyes, the hydrogen peroxide needs to be neutralized, or decomposed, before the contact lenses can be used again. A general chemistry experiment is described where the kinetics of the catalyzed decomposition of the hydrogen peroxide are studied by measuring the amount of oxygen generated as a function of time. The order of the reaction with respect to the hydrogen peroxide, the rate constant, and the energy of activation are determined. The integrated rate law is used to determine the time required to decompose the hydrogen peroxide to a concentration that is safe for eyes.

  8. The mechanisms of platinum-catalyzed silicon nanowire growth

    NASA Astrophysics Data System (ADS)

    Hibst, N.; Knittel, P.; Biskupek, J.; Kranz, C.; Mizaikoff, B.; Strehle, S.

    2016-02-01

    Platinum (Pt) has been known as a catalyst material for vapor-liquid-solid (VLS) synthesis since the mid 1960s with the potential to grow electronic grade silicon nanowires (SiNWs). In contrast to gold-based growth, Pt-catalyzed SiNW synthesis has rarely been studied, most likely due to higher synthesis temperatures and the formation of multiple Pt silicide phases. Here we present the growth of SiNWs from a Pt catalyst deposited by a focused ion or electron beam, which opens new strategies for the assembly of Pt-catalyzed SiNW-based devices, as well as SiNW growth from Pt nanoparticles and thin films. We show that single-crystalline SiNWs exhibit either the well-known catalyst tip or a polycrystalline silicon tip so far not reported. The local Pt concentration was found to be one key parameter triggering the growth mode. The proposed growth model for both types of SiNWs is based on a solid-state silicide-mediated crystallization rather than VLS. The discussion of the growth modes is supported by a variation of several growth parameters and SiNW synthesis using the substrate materials silicon nitride, single-crystalline silicon, fused silica, and sapphire.

  9. Mobility and Reactivity of Oxygen Adspecies on Platinum Surface.

    PubMed

    Wang, Wei; Zhang, Jie; Wang, Fangfang; Mao, Bing-Wei; Zhan, Dongping; Tian, Zhong-Qun

    2016-07-27

    The adsorption and mobility of oxygen adspecies on platinum (Pt) surface are crucial for the oxidation of surface-absorbed carbon monoxide (CO), which causes the deactivation of Pt catalyst in fuel cells. By employing nanoelectrode and ultramicroelectrode techniques, we have observed the surface mobility of oxygen adspecies produced by the dissociative adsorption of H2O and the surface reaction between the oxygen adspecies and the preadsorbed CO on the Pt surface. The desorption charge of oxygen adspecies on a Pt nanoelectrode has been found to be in proportion to the reciprocal of the square root of scan rate. Using this information, the apparent surface diffusion coefficient of oxygen adspecies has been determined to be (5.61 ± 0.84) × 10(-10) cm(2)/s at 25 °C. During the surface oxidation of CO, two current peaks are observed, which are attributed to CO oxidation at the Pt/electrolyte interface and the surface mobility of the oxygen adspecies on the adjacent Pt surface, respectively. These results demonstrate that the surface mobility of oxygen adspecies plays an important role in the antipoisoning and reactivation of Pt catalyst. PMID:27400155

  10. Study of carbon monoxide oxidation on mesoporous platinum.

    PubMed

    Esterle, Thomas F; Russell, Andrea E; Bartlett, Philip N

    2010-09-10

    H(1) mesoporous platinum surfaces formed by electrodeposition from lyotropic liquid crystalline templates have high electroactive surface areas (up to 60 m(2) g(-1)) provided by the concave surface within their narrow (≈2 nm diameter) pores. In this respect, they are fundamentally different from the flat surfaces of ordinary Pt electrodes or the convex surfaces of high-surface-area Pt nanoparticles. Cyclic voltammetry of H(1) mesoporous Pt films in acid solution is identical to that for polycrystalline Pt, suggesting that the surfaces of the pores are made up of low-index Pt faces. In contrast, CO stripping voltammetry on H(1) mesoporous Pt is significantly different from the corresponding voltammetry on polycrystalline Pt and shows a clear prewave for CO oxidation and the oxidation CO at lower overpotential. These differences in CO stripping are related to the presence of trough sites where the low-index Pt faces that make up the concave surface of the pore walls meet. PMID:20578119

  11. Structural Preferences in Phosphanylthiolato Platinum(II) Complexes

    PubMed Central

    Duran, Josep; Real, Julio; Benet‐Buchholz, Jordi; Solà, Miquel

    2015-01-01

    Abstract The transition‐metal complexes of heterotopic phosphanylthiolato ligands are useful in various reactions which depend on the stereochemistry of the complexes. Bis‐chelate complex [Pt(SCH2CH2PPh2‐κ2 P,S)2] (1) was obtained in good yields by direct base‐free substitution reaction of the corresponding phosphanylthiol (HSCH2CH2PPh2) with K2PtCl4 or by oxidative addition of the same phosphanylthiol to Pt(PPh3)4. In agreement with the antisymbiosis rule, complex 1 shows a cis‐P,P arrangement in solid state crystallizing in the monoclinic system (C2/c). Density functional theory (DFT) calculations on 1 reveal the right characteristics for the preferred cis‐P,P arrangement, rationalizing its formation. Direct base‐free reaction of [PtCl2(1,5‐cyclooctadiene)] with one equivalent of the same phosphanylthiol produce the trinuclear complex [PtCl(μ‐SCH2CH2PPh2‐κ2 P,S)]3 (2) instead of the binuclear structure common in palladium and nickel derivatives. Crystals of 2 are triclinic (P 1‾ ) showing a sulfur‐bridging edge‐sharing cyclic trinuclear complex with square‐planar coordination geometry around the platinum atoms and a Pt3S3 cycle in skew‐boat conformation. This preference for the trinuclear structure was rationalized mechanistically and through conceptual DFT. PMID:27308212

  12. Bioaccessibility of palladium and platinum in urban aerosol particulates

    NASA Astrophysics Data System (ADS)

    Puls, Christoph; Limbeck, Andreas; Hann, Stephan

    2012-08-01

    To evaluate potential health hazards caused by environmental Platinum Group Elements (PGEs), bioaccessibility of the metals in question needs to be assessed. To gain appropriate data, airborne particulate matter samples of different size fractions (total suspended particles as well as PM10 and PM2.5) were taken in downtown Vienna, an urban site primarily polluted by traffic. Total PGE concentrations in these samples were in the low picogram per cubic meter range, as determined by ID-ICP-MS after microwave digestion. For elimination of elements interfering with the accurate quantification, the digested samples were subjected to a cleaning procedure involving cation exchange. For determination of the bioaccessible fraction, it was assumed that inhaled particles are removed from the respiratory system by mucociliary clearance and subsequently ingested. Accordingly, the solubility of PGE in synthetic gastric juice was investigated by batch extraction of particulate matter samples followed by microwave assisted UV-digestion, cation exchange cleanup and ID-ICP-MS. The acquired data was used to calculate the bioaccessible fraction of Pd and Pt in airborne particulate matter. Average GIT-extractable fractions for Pd and Pt in TSP were 41% and 27%, in PM10 34% and 26%, respectively, thus exceeding previously determined values for bioaccessibility of PGE from ground catalyst materials by up to an order of magnitude.

  13. Donnan dialysis of bromocomplexes of some platinum group metal ions

    SciTech Connect

    Brajter, K.; Slonawska, K. ); Cox, J.A. )

    1989-03-01

    The separation of bromocomplexes of platinum group metals by Donnan dialysis is demonstrated with both anion and cation exchange membranes. The inclusion of ethylenediamine (en) in the sample improves the separation of Pd(II) from Pt(IV) with experiments performed with an anion exchange membrane and decreases the amount of metal retained on the membrane phase. With a cation exchange membrane, the addition of a ligand such as en is required for transport. With 5.6 mM en in the sample at pH 10, 74% of Pd(II) is transported across an anion exchange membrane into 0.5 M NH{sub 4} Br after 6 hours while only 8% of the Pt(IV) is dialyzed. Rhodium(III) and iridium(III) behave like Pt(IV). Using a cation exchange membrane under the same conditions except with a 1 hour dialysis results in a 30-fold preferential preconcentration of Pd(II) relative to Pt(IV), and, based on the amount retained in the membrane, a preconcentration of Ir(III) which exceeds that of Pd(II) and Pt(IV) by factors of 40 and 20, respectively.

  14. Anticancer activity assessment of two novel binuclear platinum (II) complexes.

    PubMed

    Shahsavani, Mohammad Bagher; Ahmadi, Shamseddin; Aseman, Marzieh Dadkhah; Nabavizadeh, S Masoud; Rashidi, Mehdi; Asadi, Zahra; Erfani, Nasrollah; Ghasemi, Atiyeh; Saboury, Ali Akbar; Niazi, Ali; Bahaoddini, Aminollah; Yousefi, Reza

    2016-08-01

    In the current study, two binuclear Pt (II) complexes, containing cis, cis-[Me2Pt (μ-NN) (μ-dppm) PtMe2] (1), and cis,cis-[Me2Pt(μ-NN)(μ dppm) Pt((CH2)4)] (2) in which NN=phthalazine and dppm=bis (diphenylphosphino) methane were evaluated for their anticancer activities and DNA/purine nucleotide binding properties. These Pt (II) complexes, with the non-classical structures, demonstrated a significant anticancer activity against Jurkat and MCF-7 cancer cell lines. The results of ethidium bromide/acridine orange staining and Caspase-III activity suggest that these complexes were capable to stimulate an apoptotic mechanism of cell death in the cancer cells. Using different biophysical techniques and docking simulation analysis, we indicated that these complexes were also capable to interact efficiently with DNA via a non-intercalative mechanism. According to our results, substitution of cyclopentane (in complex 2) with two methyl groups (in complex 1) results in significant improvement of the complex ability to interact with DNA and subsequently to induce the anticancer activity. Overall, these binuclear Pt (II) complexes are promising group of the non-classical potential anticancer agents which can be considered as molecular templates in designing of highly efficient platinum anticancer drugs. PMID:27289447

  15. Catalytic Combustion of Propane/Air Mixtures on Platinum

    NASA Technical Reports Server (NTRS)

    Bruno, C.; Walsh, P. M.; Santavicca, D. A.; Sinha, N.; Bracco, F. V.; Yaw, Y.

    1983-01-01

    A honeycomb catalyst of platinum (4.2 kg/cu m loading) over cordierite, with gamma-alumina washcoat, a cross section of 2.4 x 2.4 sq cm, a length of 7.6 cm, and a characteristic channel diameter of 1.4 mm is used as a steady flow reactor. Measurements are made with C3H8/air mixtures at 650 to 800 K inlet temperatures, 110 KPa pressure, 10 to 40 m/s inlet velocity, 0.19 to 0.32 equivalence ratios, and approximately 1.5 mole percent water content. The measured quantities are the substrate tempeature at ten axial locations, the exhaust gas temperature, the exhaust concentrations of CO, CO2, O2, and total hydrocarbons, and the pressure drop across the monolith. The measured quantities are compared with those computed with a two-dimensional steady-state model for axial and radial convection and diffusion of mass, momentum, energy and homogeneous (three overall reactions) and heterogeneous (infinitely fast) reactions. It is found that, under the tested conditions, most of the fuel is converted to CO2 and H2O at the surface. Gas-phase reactions tend rapidly to become more important as the temperature and equivalence ratio are increased and the flow velocity is decreased. Surface fuel conversion is much more rapid than fuel diffusion, resulting in diffusion-controlled oxidation.

  16. Response time correlations for platinum resistance thermometers in flowing fluids

    NASA Technical Reports Server (NTRS)

    Pandey, D. K.; Ash, R. L.

    1985-01-01

    The thermal response of two types of Platinum Resistance Thermometers (PRT's), which are being considered for use in the National Transonic Wind Tunnel Facility, were studied. Response time correlations for each PRT, in flowing water, oil and air, were established separately. A universal correlation, tau WOA = 2.0 + 1264, 9/h, for a Hy-Cal Sensor (with a reference resistance of 100 ohm) within an error of 20% was established while the universal correlation for the Rosemount Sensor (with a reference resistance of 1000 ohm), tau OA = 0.122 + 1105.6/h, was found with a maximum percentage error of 30%. The correlation for the Rosemount Sensor was based on air and oil data only which is certainly not sufficient to make a correlation applicable to every condition. Therefore, the correlation needs more data to be gathered in different fluids. Also, it is necessary to state that the calculation of the parameter, h, was based on the available heat transfer correlations, whose accuracies are already reported in literature uncertain within 20-30%. Therefore, the universal response constant correlations established here for the Hy-Cal and Rosemount sensors are consistent with the uncertainty in the input data and are recommended for future use in flowing liquids and gases.

  17. Synthesis of ultrasmall platinum nanoparticles and structural relaxation.

    PubMed

    Liu, Chao; Li, Gao; Kauffman, Douglas R; Pang, Guangsheng; Jin, Rongchao

    2014-06-01

    We report the synthesis of ligand-protected, ultrasmall Pt nanoparticles of ∼1 nm size via a one-phase wet chemical method. Using matrix-assisted laser desorption ionization mass spectrometry (MALDI-MS), we determined the mass of the nanoparticles to be ∼8 kDa. Characterization of the Pt nanoparticles was further carried out by powder X-ray diffraction (XRD), transmission electron microscopy (TEM), thermogravimetric analysis (TGA), optical absorption spectroscopy, and X-ray photoelectron spectroscopy (XPS). Interestingly, we observed a large structural relaxation in the 8kDa nanoparticles (i.e. lattice parameter elongation by +10%) compared to bulk platinum. XPS analysis revealed a positive shift of Pt 4f core level energy by approximately +1 eV compared with bulk Pt, indicating charge transfer from Pt to S atom of the thiolate ligand on the particle. Compared to bulk Pt, the 5d band of Pt nanoparticles is narrower and shifts to higher binding energy. Overall, the ∼1 nm ultrasmall Pt nanoparticles exhibit quite distinct differences in electronic and structural properties compared to their larger counterparts and bulk Pt. PMID:24703677

  18. Modeling platinum group metal complexes in aqueous solution.

    PubMed

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

    2001-05-01

    We construct force fields suited for the study of three platinum group metals (PGM) as chloranions in aqueous solution from quantum chemical computations and report experimental data. Density functional theory (DFT) using the local density approximation (LDA), as well as extended basis sets that incorporate relativistic corrections for the transition metal atoms, has been used to obtain equilibrium geometries, harmonic vibrational frequencies, and atomic charges for the complexes. We found that DFT calculations of [PtCl(6)](2-).3H(2)O, [PdCl(4)](2-).2H(2)O, and [RhCl(6)](3-).3H(2)O water clusters compared well with molecular mechanics (MM) calculations using the specific force field developed here. The force field performed equally well in condensed phase simulations. A 500 ps molecular dynamics (MD) simulation of [PtCl(6)](2-) in water was used to study the structure of the solvation shell around the anion. The resulting data were compared to an experimental radial distribution function derived from X-ray diffraction experiments. We found the calculated pair correlation functions (PCF) for hexachloroplatinate to be in good agreement with experiment and were able to use the simulation results to identify and resolve two water-anion peaks in the experimental spectrum. PMID:11327912

  19. Catalytic ignition of fuel/oxygen/nitrogen mixtures over platinum

    SciTech Connect

    Cho, P.; Law, C.K.

    1986-11-01

    Ignition of fuel/oxygen/nitrogen mixtures over platinum wire is experimentally studied by using microcalorimetry and by restricting the flow to the low Reynolds number range so that axisymmetry prevails. The fuels studied are propane, butane, propylene, ethylene, carbon monoxide, and hydrogen. Parameters investigated include flow velocity, fuel type and concentration, and oxygen concentration. The catalytic ignition temperatures of the various fuels are accurately determined over extensive ranges of fuel/oxygen/nitrogen concentrations. Results show two distinctly opposite ignition trends depending on the nature of the fuel. That is, the ignition temperature of lean propane/air and butane/air mixtures decreases as their fuel concentration is increased, while the reverse trend is observed for lean mixtures of propylene, ethylene, carbon monoxide, and hydrogen with air. Furthermore, the ignition of propane depends primarily on fuel concentration, while the ignition of carbon monoxide depends on fuel and oxygen concentrations to a comparable extent. These results are explained on the basis of hierarchical surface adsorption strengths of the different reactants in effecting catalytic ignition. Additional phenomena of interest are observed and discussed.

  20. Interaction of low energy electrons with platinum surface

    NASA Astrophysics Data System (ADS)

    Borka, D.; Tőkési, K.

    2015-07-01

    We present Monte Carlo simulation of low energy electrons backscattered from platinum (Pt) surface. We take into account both elastic and inelastic collisions during the simulation. For the case of the elastic scattering of electrons by Pt atoms we use the static field approximation with non-relativistic Schrödinger partial wave analysis. For the case of inelastic scattering we use the dielectric response formalism. In our simulations the primary electron energy is 250 eV and the incidence angle of the electron beam with respect to the surface is varied between 1° and 90°. The backscattered electron energy loss distributions for primary and as well for secondary electrons and the distribution of maximum electron penetration depths in the Pt sample were calculated using only the bulk and also the surface dielectric function. We found that the maximum attained depth of the electrons is around 20 Å, i.e. the electrons are at the vicinity of the surface. Therefore we expect that the experimental data will be close to our simulation using surface-excitations modes.

  1. Urinary excretion of platinum, arsenic and selenium of cancer patients from the Antofagasta region in Chile treated with platinum-based drugs

    PubMed Central

    2012-01-01

    Background Arsenic exposure increases the risk of non-cancerous and cancerous diseases. In the Antofagasta region in Chile, an established relationship exists between arsenic exposure and the risk of cancer of the bladder, lung and skin. Platinum-based drugs are first-line treatments, and many works recognise selenium as a cancer-fighting nutrient. We characterised the short-term urinary excretion amounts of arsenic, selenium and platinum in 24-h urine samples from patients with lung cancer and those with cancer other than lung treated with cisplatin or/and carboplatin. As - Se - Pt inter-element relationships were also investigated. Results The amounts of platinum excreted in urine were not significantly different between patients with lung cancer and those with other cancers treated with cisplatin, despite the significant variation in platinum amounts supplied from platinum-based drugs. In general, the analytical amounts of excreted selenium were greater than those for arsenic, which could imply that platinum favours the excretion of selenium. For other types of cancers treated with drugs without platinum, excretion of selenium was also greater than that of arsenic, suggesting an antagonist selenium-anti-cancer drug relationship. Conclusions Regards the baseline status of patients, the analytical amounts of excreted Se is greater than those for As, particularly, for cisplatin chemotherapy. This finding could imply that for over the As displacement Pt favours the excretion of Se. The analytical amounts of excreted Se were greater than those for As, either with and without Pt-containing drugs, suggesting an antagonist Se-anti-cancer drug relationship. However, it seemed that differences existed between As - Se - Pt inter-element associations in patients treated for lung cancer in comparison with those treated for cancer other than lung. Therefore, knowledge obtained in this work, can contribute to understanding the arsenic cancer mechanism and the As - Se - Pt

  2. Comparison of two stable hydrogen isotope-ratio measurement techniques on Antarctic surface-water and ice samples

    USGS Publications Warehouse

    Hopple, J.A.; Hannon, J.E.; Coplen, T.B.

    1998-01-01

    A comparison of the new hydrogen isotope-ratio technique of Vaughn et al. ([Vaughn, B.H., White, J.W.C., Delmotte, M., Trolier, M., Cattani, O., Stievenard, M., 1998. An automated system for hydrogen isotope analysis of water. Chem. Geol. (Isot. Geosci. Sect.), 152, 309-319]; the article immediately preceding this article) for the analysis of water samples utilizing automated on-line reduction by elemental uranium showed that 94% of 165 samples of Antarctic snow, ice, and stream water agreed with the ??2H values determined by H2-H2O platinum equilibration, exhibiting a bias of +0.5??? and a 2 - ?? variation of 1.9???. The isotopic results of 10 reduction technique samples, however, gave ??2H values that differed by 3.5??? or more, and were too negative by as much as 5.4??? and too positive by as much as 4.9??? with respect to those determined using the platinum equilibration technique.

  3. Platinum-group element abundance and distribution in chromite deposits of the Acoje Block, Zambales Ophiolite Complex, Philippines

    USGS Publications Warehouse

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

    1990-01-01

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

  4. Atomic Weights and Isotopic Compositions

    National Institute of Standards and Technology Data Gateway

    SRD 144 Atomic Weights and Isotopic Compositions (Web, free access)   The atomic weights are available for elements 1 through 111, and isotopic compositions or abundances are given when appropriate.

  5. Nonbiological fractionation of iron isotopes

    NASA Technical Reports Server (NTRS)

    Anbar, A. D.; Roe, J. E.; Barling, J.; Nealson, K. H.

    2000-01-01

    Laboratory experiments demonstrate that iron isotopes can be chemically fractionated in the absence of biology. Isotopic variations comparable to those seen during microbially mediated reduction of ferrihydrite are observed. Fractionation may occur in aqueous solution during equilibration between inorganic iron complexes. These findings provide insight into the mechanisms of iron isotope fractionation and suggest that nonbiological processes may contribute to iron isotope variations observed in sediments.

  6. DEEP WATER ISOTOPIC CURRENT ANALYZER

    DOEpatents

    Johnston, W.H.

    1964-04-21

    A deepwater isotopic current analyzer, which employs radioactive isotopes for measurement of ocean currents at various levels beneath the sea, is described. The apparatus, which can determine the direction and velocity of liquid currents, comprises a shaft having a plurality of radiation detectors extending equidistant radially therefrom, means for releasing radioactive isotopes from the shaft, and means for determining the time required for the isotope to reach a particular detector. (AEC)

  7. Os Isotope Heterogeneity of the Convecting Upper Mantle: The Mayari-Baracoa Ophiolitic Belt (Eastern Cuba)

    NASA Astrophysics Data System (ADS)

    Frei, R.; Gervilla, F.; Meibom, A.; Proenza, J. A.

    2005-12-01

    Chromite separates from a set of historically important chromite deposits from the 90 Ma old Mayarí-Baracoa Ophiolitic Belt in eastern Cuba were inspected for Re-Os isotopic systematics in an attempt to quantify the extent of Os isotopic heterogeneities within a restricted upper mantle portion represented by a single ophiolite. Compositional variations of chromites indicate their crystallization from hydrous melts varying in composition from back-arc basin basalts (Al-rich chromites; Cr# = 0.43-0.55; low Pd/Ir) to boninites (Cr-rich chromites; Cr# = 0.60-0.83; high Pd/Ir) in a supra-subduction zone setting. Initial Os isotopic compositions of the studied chromites can be grouped according to their distribution in 3 regional districts. Results indicate systematically negative calculated initial γOs values varying from -1.06 ± 0.79 (Moa-Baracoa district), -1.77 ± 0.80 (Sagua de Tanamo district) and -2.79 ± 0.31 (Mayari district). These suprachondritic values are distinctly (3.5-5.2%) less radiogenic than the estimated minimum 187Os/188Os composition of the primitive upper mantle of 0.1296 ± 8 and can be explained by Re depletion during ancient partial melting and melt percolation events. Old Os isotope model ages (<2100 Ma)of some of the chromites (or platinum-group minerals included in them) show and confirm previous findings that ancient Os isotopic signatures can survive in the Earth's upper mantle. Our systematically negative initial γOs values do not improve the definition of an already statistically poorly defined present-day Os isotopic composition of the convecting upper mantle, but instead indicate a complex history for the convecting upper mantle which precludes the calculation of a uniform regional Os isotopic signature for this reservoir.

  8. Method for separating boron isotopes

    DOEpatents

    Rockwood, Stephen D.

    1978-01-01

    A method of separating boron isotopes .sup.10 B and .sup.11 B by laser-induced selective excitation and photodissociation of BCl.sub.3 molecules containing a particular boron isotope. The photodissociation products react with an appropriate chemical scavenger and the reaction products may readily be separated from undissociated BCl.sub.3, thus effecting the desired separation of the boron isotopes.

  9. Uranium Isotopic Analysis with the FRAM Isotopic Analysis Code

    SciTech Connect

    Duc T. Vo; Thomas E. Sampson

    1999-05-01

    FRAM is the acronym for Fixed-energy Response-function Analysis with Multiple efficiency. This software was developed at Los Alamos National Laboratory originally for plutonium isotopic analysis. Later, it was adapted for uranium isotopic analysis in addition to plutonium. It is a code based on a self-calibration using several gamma-ray peaks for determining the isotopic ratios. The versatile-parameter database structure governs all facets of the data analysis. User editing of the parameter sets allows great flexibility in handling data with different isotopic distributions, interfering isotopes, and different acquisition parameters such as energy calibration and detector type.

  10. Surface engineering of hierarchical platinum-cobalt nanowires for efficient electrocatalysis

    DOE PAGESBeta

    Bu, Lingzheng; Guo, Shaojun; Zhang, Xu; Shen, Xuan; Su, Dong; Lu, Gang; Zhu, Xing; Yao, Jianlin; Guo, Jun; Huang, Xiaoqing

    2016-06-29

    Despite intense research in past decades, the lack of high-performance catalysts for fuel cell reactions remains a challenge in realizing fuel cell technologies for transportation applications. Here we report a facile strategy for synthesizing hierarchical platinum-cobalt nanowires with high-index, platinum-rich facets and ordered intermetallic structure. These structural features enable unprecedented performance for the oxygen reduction and alcohol oxidation reactions. The specific/mass activities of the platinum-cobalt nanowires for oxygen reduction reaction are 39.6/33.7 times higher than commercial Pt/C catalyst, respectively. Density functional theory simulations reveal that the active threefold hollow sites on the platinum-rich high-index facets provide an additional factor inmore » enhancing oxygen reduction reaction activities. The nanowires are stable in the electrochemical conditions and also thermally stable. Furthermore, this work may represent a key step towards scalable production of high performance platinum-based nanowires for applications in catalysis and energy conversion.« less

  11. Surface engineering of hierarchical platinum-cobalt nanowires for efficient electrocatalysis

    PubMed Central

    Bu, Lingzheng; Guo, Shaojun; Zhang, Xu; Shen, Xuan; Su, Dong; Lu, Gang; Zhu, Xing; Yao, Jianlin; Guo, Jun; Huang, Xiaoqing

    2016-01-01

    Despite intense research in past decades, the lack of high-performance catalysts for fuel cell reactions remains a challenge in realizing fuel cell technologies for transportation applications. Here we report a facile strategy for synthesizing hierarchical platinum-cobalt nanowires with high-index, platinum-rich facets and ordered intermetallic structure. These structural features enable unprecedented performance for the oxygen reduction and alcohol oxidation reactions. The specific/mass activities of the platinum-cobalt nanowires for oxygen reduction reaction are 39.6/33.7 times higher than commercial Pt/C catalyst, respectively. Density functional theory simulations reveal that the active threefold hollow sites on the platinum-rich high-index facets provide an additional factor in enhancing oxygen reduction reaction activities. The nanowires are stable in the electrochemical conditions and also thermally stable. This work may represent a key step towards scalable production of high-performance platinum-based nanowires for applications in catalysis and energy conversion. PMID:27353725

  12. Evidence of High Electrocatalytic Activity of Molybdenum Carbide Supported Platinum Nanorafts

    SciTech Connect

    Elbaz, Lior; Phillips, Jonathan; Artyushkova, Kateryna; More, Karren Leslie; Brosha, Eric

    2015-01-01

    A remarkable new supported metal catalyst structure on Mo2C substrates, ‘rafts’ of platinum consisting of less than 6 atoms, was synthesized and found to be catalytically active electrocatalyst for oxygen reduction. A novel catalytic synthesis method: Reduction-Expansion-Synthesis of Catalysts (RES-C), from rapid heating of dry mixture of solid precursors of molybdenum, platinum and urea in an inert gas environment, led to the creation of unique platinum Nanorafts on Mo2C. The Pt Nanorafts offer a complete utilization of the Pt atoms for electrocatalysis with no “hidden” atoms. This structure is strongly affected by its interaction with the substrate as was observed by XPS. In this work, we show for the first time, evidence of electrocatalytic activity with such small clusters of non-crystalline Pt atoms as catalysts for oxygen reduction. Electrochemical half-cell characterization shows that this structure permit more efficient utilization of platinum, with mass activity conservatively measured to be 50% that of platinum particles generated using traditional approaches. These novel material may dramatically enhance stability relative to the commercial Pt/carbon catalysts.

  13. Surface engineering of hierarchical platinum-cobalt nanowires for efficient electrocatalysis.

    PubMed

    Bu, Lingzheng; Guo, Shaojun; Zhang, Xu; Shen, Xuan; Su, Dong; Lu, Gang; Zhu, Xing; Yao, Jianlin; Guo, Jun; Huang, Xiaoqing

    2016-01-01

    Despite intense research in past decades, the lack of high-performance catalysts for fuel cell reactions remains a challenge in realizing fuel cell technologies for transportation applications. Here we report a facile strategy for synthesizing hierarchical platinum-cobalt nanowires with high-index, platinum-rich facets and ordered intermetallic structure. These structural features enable unprecedented performance for the oxygen reduction and alcohol oxidation reactions. The specific/mass activities of the platinum-cobalt nanowires for oxygen reduction reaction are 39.6/33.7 times higher than commercial Pt/C catalyst, respectively. Density functional theory simulations reveal that the active threefold hollow sites on the platinum-rich high-index facets provide an additional factor in enhancing oxygen reduction reaction activities. The nanowires are stable in the electrochemical conditions and also thermally stable. This work may represent a key step towards scalable production of high-performance platinum-based nanowires for applications in catalysis and energy conversion. PMID:27353725

  14. Laser ablation of a platinum target in water. III. Laser-induced reactions

    SciTech Connect

    Nichols, William T.; Sasaki, Takeshi; Koshizaki, Naoto

    2006-12-01

    This is the third paper in our series studying the laser-target-liquid interactions occurring in laser ablation in liquids (LAL). Here, laser ablation of a platinum target in pure water at 355 nm wavelength is studied as a function of laser energy. We describe three distinct reaction regimes between the ablated target species and water at different laser focusing conditions. At low laser fluence (<10 J/cm{sup 2}), material removal is caused by laser heating of the platinum surface and the primary products are small clusters with a large percentage of platinum atoms in a nonzero oxidation state. At intermediate fluences (10-70 J/cm{sup 2}), platinum nanoparticles are the primary products. Our previous studies demonstrated that in this fluence regime ablation occurs through both thermal vaporization and explosive ejection of molten droplets. In both cases reactivity is small due to the low reactivity of platinum with water. At high fluences (>70 J/cm{sup 2}), we find large, faceted particles that are attributed to the drying of PtO{sub x} gels formed by reactive plasma etching of the target. Taken together these results demonstrate that significant tunability in the target-liquid interaction is possible during nanomaterial synthesis by LAL.

  15. Trastuzumab-mediated selective delivery for platinum drug to HER2-positive breast cancer cells.

    PubMed

    Huang, Rong; Sun, Yu; Gao, Qihe; Wang, Qiucui; Sun, Baiwang

    2015-10-01

    Oxaliplatin is used widely as an anticancer drug for clinical treatment. However, its applications are limited because of its poor selectivity. In this work, we described the design, synthesis, and characterization of conjugates combining trastuzumab with a platinum (IV) analog of oxaliplatin, in which the trastuzumab acted as an active targeting agent for HER2-positive cancer cells. Indirect enzyme-linked immunosorbent assay and immunofluorescence study indicated the platinum (IV)-trastuzumab conjugates retained specific binding activity to HER2 overexpressed SK-BR-3 cells. In the presence of ascorbic acid, platinum (IV)-trastuzumab conjugates were reduced to platinum (II) analogs, which could bind to and unwind PUC19 DNA in a manner similar to oxaliplatin. The cytotoxic study was tested on three breast cell lines: SK-BR-3, MCF-7, and MDA-MB-231. Platinum (IV)-trastuzumab conjugates showed promising antiproliferative activity against SK-BR-3 cells, but significantly decreased the inhibition to MDA-MB-231 and MCF-7 cells. The flow cytometric analysis showed that the conjugates arrested the cell cycle mainly at the G2/M phase and killed the cells through an apoptotic pathway. PMID:26186063

  16. Surface engineering of hierarchical platinum-cobalt nanowires for efficient electrocatalysis

    NASA Astrophysics Data System (ADS)

    Bu, Lingzheng; Guo, Shaojun; Zhang, Xu; Shen, Xuan; Su, Dong; Lu, Gang; Zhu, Xing; Yao, Jianlin; Guo, Jun; Huang, Xiaoqing

    2016-06-01

    Despite intense research in past decades, the lack of high-performance catalysts for fuel cell reactions remains a challenge in realizing fuel cell technologies for transportation applications. Here we report a facile strategy for synthesizing hierarchical platinum-cobalt nanowires with high-index, platinum-rich facets and ordered intermetallic structure. These structural features enable unprecedented performance for the oxygen reduction and alcohol oxidation reactions. The specific/mass activities of the platinum-cobalt nanowires for oxygen reduction reaction are 39.6/33.7 times higher than commercial Pt/C catalyst, respectively. Density functional theory simulations reveal that the active threefold hollow sites on the platinum-rich high-index facets provide an additional factor in enhancing oxygen reduction reaction activities. The nanowires are stable in the electrochemical conditions and also thermally stable. This work may represent a key step towards scalable production of high-performance platinum-based nanowires for applications in catalysis and energy conversion.

  17. Microstructural Study on Oxidation Resistance of Nonmodified and Platinum Modified Aluminide Coating

    NASA Astrophysics Data System (ADS)

    Zagula-Yavorska, Maryana; Sieniawski, Jan

    2014-03-01

    Platinum electroplating layers (3 and 7 μm thick) were deposited on the surface of the Inconel 713 LC, CMSX 4, and Inconel 625 Ni-base superalloys. Diffusion treatment at 1050°C for 2 h under argon atmosphere was performed after electroplating. Diffusion treated samples were aluminized according to the low activity CVD process at 1050°C for 8 h. The nonmodified aluminide coatings consist of NiAl phase. Platinum modification let to obtain the (Ni,Pt)Al phase in coatings. The coated samples were subjected to cyclic oxidation testing at 1100°C. It was discovered that increase of the platinum electroplating thickness from 3 to 7 μm provides the improvement of oxidation resistance of aluminide coatings. Increase of the platinum thickness causes decreases in weight change and decreases in parabolic constant during oxidation. The platinum provides the pure Al2O3 oxide formation, slow growth oxide layer, and delay the oxide spalling during heating-cooling thermal cycles.

  18. Amrubicin Monotherapy for Patients with Platinum-Refractory Gastroenteropancreatic Neuroendocrine Carcinoma.

    PubMed

    Ando, Takayuki; Hosokawa, Ayumu; Yoshita, Hiroki; Ueda, Akira; Kajiura, Shinya; Mihara, Hiroshi; Nanjo, Sohachi; Fujinami, Haruka; Nishikawa, Jun; Ogawa, Kohei; Nakajima, Takahiko; Imura, Johji; Sugiyama, Toshiro

    2015-01-01

    Objective. Patients with gastroenteropancreatic neuroendocrine carcinoma (NEC) have a poor prognosis. Platinum-based combination chemotherapy is commonly used as first-line treatment; however, the role of salvage chemotherapy remains unknown. This study aimed to analyze the efficacy and safety of amrubicin monotherapy in patients with platinum-refractory gastroenteropancreatic NEC. Methods. Among 22 patients with advanced gastroenteropancreatic NEC, 10 received amrubicin monotherapy between September 2007 and May 2014 after failure of platinum-based chemotherapy. The efficacy and toxicity of the treatment were analyzed retrospectively. Results. Eight males and two females (median age, 67 years (range, 52-78)) received platinum-based chemotherapy, including cisplatin plus irinotecan (n = 7, 70%), cisplatin plus etoposide (n = 2, 20%), and carboplatin plus etoposide (n = 1, 10%) before amrubicin therapy. Median progression-free survival and overall survival after amrubicin therapy were 2.6 and 5.0 months, respectively. Two patients had partial response (20% response rate), and their PFS were 6.2 months and 6.3 months, respectively. Furthermore, NEC with response for amrubicin had characteristics with a high Ki-67 index and receipt of prior chemotherapy with cisplatin and irinotecan. Grade 3-4 neutropenia and anemia were observed in four and five patients, respectively. Conclusion. Amrubicin monotherapy appears to be potentially active and well-tolerated for platinum-refractory gastroenteropancreatic NEC. PMID:26199623

  19. Evidence of High Electrocatalytic Activity of Molybdenum Carbide Supported Platinum Nanorafts

    DOE PAGESBeta

    Elbaz, Lior; Phillips, Jonathan; Artyushkova, Kateryna; More, Karren Leslie; Brosha, Eric

    2015-01-01

    A remarkable new supported metal catalyst structure on Mo2C substrates, ‘rafts’ of platinum consisting of less than 6 atoms, was synthesized and found to be catalytically active electrocatalyst for oxygen reduction. A novel catalytic synthesis method: Reduction-Expansion-Synthesis of Catalysts (RES-C), from rapid heating of dry mixture of solid precursors of molybdenum, platinum and urea in an inert gas environment, led to the creation of unique platinum Nanorafts on Mo2C. The Pt Nanorafts offer a complete utilization of the Pt atoms for electrocatalysis with no “hidden” atoms. This structure is strongly affected by its interaction with the substrate as was observedmore » by XPS. In this work, we show for the first time, evidence of electrocatalytic activity with such small clusters of non-crystalline Pt atoms as catalysts for oxygen reduction. Electrochemical half-cell characterization shows that this structure permit more efficient utilization of platinum, with mass activity conservatively measured to be 50% that of platinum particles generated using traditional approaches. These novel material may dramatically enhance stability relative to the commercial Pt/carbon catalysts.« less

  20. Fabrication of highly porous platinum electrodes for micro-scale applications by pulsed electrodeposition and dealloying

    NASA Astrophysics Data System (ADS)

    Köhler, Christian; Kloke, Arne; Drzyzga, Anna; Zengerle, Roland; Kerzenmacher, Sven

    2013-11-01

    We present the implementation and optimization of a novel electrodeposition method for the fabrication of highly porous platinum electrodes. It is based on the co-deposition of platinum and copper and the selective dealloying of copper in a pulsed manner. The new process yields mechanically stable platinum electrodes with roughness factors of up to RF = 6500 ± 700, compared to the state-of-the-art cyclic electrodeposition method this corresponds to an improvement in RF by 111%. Furthermore the time demand for fabrication is reduced by 59%, whereas the platinum utilization is increased by 53%. The method is particularly advantageous for applications such as micro fuel cells since it enables the precise deposition of catalytically active electrodes on micro-structured conductive areas. In this context the novel platinum electrodes show higher current densities for the oxidation of formic acid and glucose than state-of-the-art electrodes. In terms of methanol oxidation their catalytic activity is comparable to commercial direct methanol fuel cell (DMFC) electrodes, fabricated from Pt-Ru nanoparticles dispersed on carbon black.