Science.gov

Sample records for activated iridium oxide

  1. Highly Active Iridium/Iridium Tin/Tin Oxide Heterogeneous Nanoparticles as Alternative Electrocatalysts for the Ethanol Oxidation Reaction

    SciTech Connect

    Du W.; Su D.; Wang Q.; Saxner D.; Deskins N.A.; Krzanowski J.E.; Frenkel A.I.; Teng X.

    2011-08-03

    Ethanol is a promising fuel for low-temperature direct fuel cell reactions due to its low toxicity, ease of storage and transportation, high-energy density, and availability from biomass. However, the implementation of ethanol fuel cell technology has been hindered by the lack of low-cost, highly active anode catalysts. In this paper, we have studied Iridium (Ir)-based binary catalysts as low-cost alternative electrocatalysts replacing platinum (Pt)-based catalysts for the direct ethanol fuel cell (DEFC) reaction. We report the synthesis of carbon supported Ir{sub 71}Sn{sub 29} catalysts with an average diameter of 2.7 {+-} 0.6 nm through a 'surfactant-free' wet chemistry approach. The complementary characterization techniques, including aberration-corrected scanning transmission electron microscopy equipped with electron energy loss spectroscopy, X-ray diffraction, X-ray photoelectron spectroscopy, and X-ray absorption spectroscopy, are used to identify the 'real' heterogeneous structure of Ir{sub 71}Sn{sub 29}/C particles as Ir/Ir-Sn/SnO{sub 2}, which consists of an Ir-rich core and an Ir-Sn alloy shell with SnO{sub 2} present on the surface. The Ir{sub 71}Sn{sub 29}/C heterogeneous catalyst exhibited high electrochemical activity toward the ethanol oxidation reaction compared to the commercial Pt/C (ETEK), PtRu/C (Johnson Matthey) as well as PtSn/C catalysts. Electrochemical measurements and density functional theory calculations demonstrate that the superior electro-activity is directly related to the high degree of Ir-Sn alloy formation as well as the existence of nonalloyed SnO{sub 2} on surface. Our cross-disciplinary work, from novel 'surfactant-free' synthesis of Ir-Sn catalysts, theoretical simulations, and catalytic measurements to the characterizations of 'real' heterogeneous nanostructures, will not only highlight the intriguing structure-property correlations in nanosized catalysts but also have a transformative impact on the commercialization of DEFC

  2. Synthesis of nanoporous activated iridium oxide films by anodized aluminum oxide templated atomic layer deposition.

    SciTech Connect

    Comstock, D. J.; Christensen, S. T.; Elam, J. W.; Pellin, M. J.; Hersam, M. C.

    2010-08-01

    Iridium oxide (IrOx) has been widely studied due to its applications in electrochromic devices, pH sensing, and neural stimulation. Previous work has demonstrated that both Ir and IrOx films with porous morphologies prepared by sputtering exhibit significantly enhanced charge storage capacities. However, sputtering provides only limited control over film porosity. In this work, we demonstrate an alternative scheme for synthesizing nanoporous Ir and activated IrOx films (AIROFs). This scheme utilizes atomic layer deposition to deposit a thin conformal Ir film within a nanoporous anodized aluminum oxide template. The Ir film is then activated by potential cycling in 0.1 M H{sub 2}SO{sub 4} to form a nanoporous AIROF. The morphologies and electrochemical properties of the films are characterized by scanning electron microscopy and cyclic voltammetry, respectively. The resulting nanoporous AIROFs exhibit a nanoporous morphology and enhanced cathodal charge storage capacities as large as 311 mC/cm{sup 2}.

  3. State and catalytic activity of iridium compounds in the reaction of mercury(I) oxidation by cerium(IV)

    SciTech Connect

    Khomutova, E.G.; Rysev, A.P.; Romanovskaya, L.E.; Malysheva, N.M.

    1995-12-01

    Kinetic methods of determining Ir are insufficiently selective and sensitive as compared to the methods of determining Os and Ru. These characteristics may be improved by increasing the catalytic activity of iridium. All other factors being equal, catalytic activity depends on the state and form of iridium that enters the catalytic process. This is why one of the ways of improving the performance characteristics of a method of determining iridium involves searching for forms of the catalyst with higher catalytic activity. The aim of this work was to study the state and catalytic activity of iridium compounds. The method based on the iridium-catalyzed reaction of mercury(I) oxidation by cerium(IV) was chosen for the investigation. This method is most commonly used for analyzing complex samples. It was found previously that both the catalytic activity and selectivity of iridium determination increase when the reaction is conducted in the medium of perchloric acid or the sample is pretreated with nitric acid.

  4. Effect of the iridium oxide thin film on the electrochemical activity of platinum nanoparticles.

    PubMed

    Chen, Aicheng; La Russa, Daniel J; Miller, Brad

    2004-10-26

    The influence of the iridium oxide thin film on the electrocatalytic properties of platinum nanoparticles was investigated using the electro-oxidation of methanol and CO as a probe. The presence of the IrO(2) thin film leads to the homogeneous dispersion of Pt nanoparticles. For comparison, polycrystalline platinum and Pt nanoparticles dispersed on a Ti substrate in the absence of an IrO(2) layer (Ti/Pt) were also investigated in this study. Inverted and enhanced CO bipolar peaks were observed using an in situ electrochemical Fourier transform infrared technique during the methanol oxidation on the Pt nanoparticles dispersed on a Ti substrate. Electrochemical impedance studies showed that the charge transfer resistance was significantly lower for the Ti/IrO(2)/Pt electrode compared with that of the massive Pt and Ti/Pt nanoparticles. The presence of the IrO(2) thin film not only greatly increases the active surface area but also promotes CO oxidation at a much lower electrode potential, thus, significantly enhancing the electrocatalytic activity of Pt nanoparticles toward methanol electro-oxidation. PMID:15491204

  5. Excimer laser deinsulation of Parylene-C on iridium for use in an activated iridium oxide film-coated Utah electrode array

    PubMed Central

    Yoo, Je-Min; Negi, Sandeep; Tathireddy, Prashant; Solzbacher, Florian; Song, Jong-In; Rieth, Loren W.

    2013-01-01

    Implantable microelectrodes provide a measure to electrically stimulate neurons in the brain and spinal cord and record their electrophysiological activity. A material with a high charge capacity such as activated or sputter-deposited iridium oxide film (AIROF or SIROF) is used as an interface. The Utah electrode array (UEA) uses SIROF for its interface material with neural tissue and oxygen plasma etching (OPE) with an aluminium foil mask to expose the active area, where the interface between the electrode and neural tissue is formed. However, deinsulation of Parylene-C using OPE has limitations, including the lack of uniformity in the exposed area and reproducibility. While the deinsulation of Parylene-C using an excimer laser is proven to be an alternative for overcoming the limitations, the iridium oxide (IrOx) suffers from fracture when high laser fluence (>1000 mJ/cm2) is used. Iridium (Ir), which has a much higher fracture resistance than IrOx, can be deposited before excimer laser deinsulation and then the exposed Ir film area can be activated by electrochemical treatment to acquire the AIROF. Characterisation of the laser-ablated Ir film and AIROF by surface analysis (X-ray photoelectron spectroscopy, scanning electron microscope, and atomic force microscope) and electrochemical analysis (electrochemical impedance spectroscopy, and cyclic voltammetry) shows that the damage on the Ir film induced by laser irradiation is significantly less than that on SIROF, and the AIROF has a high charge storage capacity. The results show the potential of the laser deinsulation technique for use in high performance AIROF-coated UEA fabrication. PMID:23458659

  6. Iridium material for hydrothermal oxidation environments

    DOEpatents

    Hong, Glenn T.; Zilberstein, Vladimir A.

    1996-01-01

    A process for hydrothermal oxidation of combustible materials in which, during at least a part of the oxidation, corrosive material is present and makes contact with at least a portion of the apparatus over a contact area on the apparatus. At least a portion of the contact surface area comprises iridium, iridium oxide, an iridium alloy, or a base metal overlaid with an iridium coating. Iridium has been found to be highly resistant to environments encountered in the process of hydrothermal oxidation. Such environments typically contain greater than 50 mole percent water, together with oxygen, carbon dioxide, and a wide range of acids, bases and salts. Pressures are typically about 27.5 to about 1000 bar while temperatures range as high as 800.degree. C.

  7. Homogeneous and heterogenized iridium water oxidation catalysts

    NASA Astrophysics Data System (ADS)

    Macchioni, Alceo

    2014-10-01

    The development of an efficient catalyst for the oxidative splitting of water into molecular oxygen, protons and electrons is of key importance for producing solar fuels through artificial photosynthesis. We are facing the problem by means of a rational approach aimed at understanding how catalytic performance may be optimized by the knowledge of the reaction mechanism of water oxidation and the fate of the catalytic site under the inevitably harsh oxidative conditions. For the purposes of our study we selected iridium water oxidation catalysts, exhibiting remarkable performance (TOF > 5 s-1 and TON > 20000). In particular, we recently focused our attention on [Cp*Ir(N,O)X] (N,O = 2-pyridincarboxylate; X = Cl or NO3) and [IrCl(Hedta)]Na water oxidation catalysts. The former exhibited a remarkable TOF whereas the latter showed a very high TON. Furthermore, [IrCl(Hedta)]Na was heterogenized onto TiO2 taking advantage of the presence of a dandling -COOH functionality. The heterogenized catalyst maintained approximately the same catalytic activity of the homogeneous analogous with the advantage that could be reused many times. Mechanistic studies were performed in order to shed some light on the rate-determining step and the transformation of catalysts when exposed to "oxidative stress". It was found that the last oxidative step, preceding oxygen liberation, is the rate-determining step when a small excess of sacrificial oxidant is used. In addition, several intermediates of the oxidative transformation of the catalyst were intercepted and characterized by NMR, X-Ray diffractometry and ESI-MS.

  8. Iridium-Tin oxide solid-solution nanocatalysts with enhanced activity and stability for oxygen evolution

    NASA Astrophysics Data System (ADS)

    Li, Guangfu; Yu, Hongmei; Yang, Donglei; Chi, Jun; Wang, Xunying; Sun, Shucheng; Shao, Zhigang; Yi, Baolian

    2016-09-01

    Addressing major challenges from the material cost, efficiency and stability, it is highly desirable to develop high-performance catalysts for oxygen evolution reaction (OER). Herein we explore a facile surfactant-assisted approach for fabricating Irsbnd Sn (Ir/Sn = 0.6/0.4, by mol.) nano-oxide catalysts with good morphology control. Direct proofs from XRD and X-ray photoelectron spectra indicate hydrophilic triblock polymer (TBP, like Pluronic® F108) surfactant can boost the formation of stable solid-solution structure. With the TBP hydrophilic and block-length increase, the fabricated Irsbnd Sn oxides undergoing the rod-to-sphere transition obtain the relatively lower crystallization, decreased crystallite size, Ir-enriched surface and incremental available active sites, all of which can bolster the OER activity and stability. Meanwhile, it is observed that the coupled Ir oxidative etching takes a crucial role in determining the material structure and performance. Compared with commercial Ir black, half-cell tests confirm F108-assistant catalysts with over 40 wt% Ir loading reduction show 2-fold activity enhancement as well as significant stability improvement. The lowest cell voltage using 0.88 mg cm-2 Ir loading is only 1.621 V at 1000 mA cm-2 and 80 °C with a concomitant energy efficiency of 75.8% which is beyond the DOE 2017 efficiency target of 74%.

  9. The influence of electrolyte composition on the in vitro charge-injection limits of activated iridium oxide (AIROF) stimulation electrodes

    NASA Astrophysics Data System (ADS)

    Cogan, Stuart F.; Troyk, Philip R.; Ehrlich, Julia; Gasbarro, Christina M.; Plante, Timothy D.

    2007-06-01

    The effects of ionic conductivity and buffer concentration of electrolytes used for in vitro measurement of the charge-injection limits of activated iridium oxide (AIROF) neural stimulation electrodes have been investigated. Charge-injection limits of AIROF microelectrodes were measured in saline with a range of phosphate buffer concentrations from [PO43-] = 0 to [PO43-] = 103 mM and ionic conductivities from 2-28 mS cm-1. The charge-injection limits were insensitive to the buffer concentration, but varied significantly with ionic conductivity. Using 0.4 ms cathodal current pulses at 50 Hz, the charge-injection limit increased from 0.5 mC cm-2 to 2.1 mC cm-2 as the conductivity was increased from 2 mS cm-1 to 28 mS cm-1. An explanation is proposed in which the observed dependence on ionic conductivity arises from non-uniform reduction and oxidation within the porous AIROF and from uncorrected iR-drops that result in an overestimation of the redox potential during pulsing. Conversely, slow-sweep-rate cyclic voltammograms (CVs) were sensitive to buffer concentration with the potentials of the primary Ir3+/Ir4+ reduction and oxidation reactions shifting ~300 mV as the buffer concentration decreased from [PO43-] = 103 mM to [PO43-] = 0 mM. The CV response was insensitive to ionic conductivity. A comparison of in vitro AIROF charge-injection limits in commonly employed electrolyte models of extracellular fluid revealed a significant dependence on the electrolyte, with more than a factor of 4 difference under some pulsing conditions, emphasizing the need to select an electrolyte model that closely matches the conductivity and ionic composition of the in vivo environment.

  10. Iridium-based double perovskites for efficient water oxidation in acid media

    PubMed Central

    Diaz-Morales, Oscar; Raaijman, Stefan; Kortlever, Ruud; Kooyman, Patricia J.; Wezendonk, Tim; Gascon, Jorge; Fu, W. T.; Koper, Marc T. M.

    2016-01-01

    The development of active, cost-effective and stable oxygen-evolving catalysts is one of the major challenges for solar-to-fuel conversion towards sustainable energy generation. Iridium oxide exhibits the best available compromise between catalytic activity and stability in acid media, but it is prohibitively expensive for large-scale applications. Therefore, preparing oxygen-evolving catalysts with lower amounts of the scarce but active and stable iridium is an attractive avenue to overcome this economical constraint. Here we report on a class of oxygen-evolving catalysts based on iridium double perovskites which contain 32 wt% less iridium than IrO2 and yet exhibit a more than threefold higher activity in acid media. According to recently suggested benchmarking criteria, the iridium double perovskites are the most active catalysts for oxygen evolution in acid media reported until now, to the best of our knowledge, and exhibit similar stability to IrO2. PMID:27498694

  11. Iridium-based double perovskites for efficient water oxidation in acid media

    NASA Astrophysics Data System (ADS)

    Diaz-Morales, Oscar; Raaijman, Stefan; Kortlever, Ruud; Kooyman, Patricia J.; Wezendonk, Tim; Gascon, Jorge; Fu, W. T.; Koper, Marc T. M.

    2016-08-01

    The development of active, cost-effective and stable oxygen-evolving catalysts is one of the major challenges for solar-to-fuel conversion towards sustainable energy generation. Iridium oxide exhibits the best available compromise between catalytic activity and stability in acid media, but it is prohibitively expensive for large-scale applications. Therefore, preparing oxygen-evolving catalysts with lower amounts of the scarce but active and stable iridium is an attractive avenue to overcome this economical constraint. Here we report on a class of oxygen-evolving catalysts based on iridium double perovskites which contain 32 wt% less iridium than IrO2 and yet exhibit a more than threefold higher activity in acid media. According to recently suggested benchmarking criteria, the iridium double perovskites are the most active catalysts for oxygen evolution in acid media reported until now, to the best of our knowledge, and exhibit similar stability to IrO2.

  12. Iridium-based double perovskites for efficient water oxidation in acid media.

    PubMed

    Diaz-Morales, Oscar; Raaijman, Stefan; Kortlever, Ruud; Kooyman, Patricia J; Wezendonk, Tim; Gascon, Jorge; Fu, W T; Koper, Marc T M

    2016-01-01

    The development of active, cost-effective and stable oxygen-evolving catalysts is one of the major challenges for solar-to-fuel conversion towards sustainable energy generation. Iridium oxide exhibits the best available compromise between catalytic activity and stability in acid media, but it is prohibitively expensive for large-scale applications. Therefore, preparing oxygen-evolving catalysts with lower amounts of the scarce but active and stable iridium is an attractive avenue to overcome this economical constraint. Here we report on a class of oxygen-evolving catalysts based on iridium double perovskites which contain 32 wt% less iridium than IrO2 and yet exhibit a more than threefold higher activity in acid media. According to recently suggested benchmarking criteria, the iridium double perovskites are the most active catalysts for oxygen evolution in acid media reported until now, to the best of our knowledge, and exhibit similar stability to IrO2. PMID:27498694

  13. Iridium-mediated Bond Activation and Water Oxidation as an Exemplary Case of CARISMA, A European Network for the Development of Catalytic Routines for Small Molecule Activation.

    PubMed

    Licini, Giulia; Albrecht, Martin

    2015-01-01

    CARISMA is a currently running COST Action that pools leading European experts in computational and experimental chemistry to foster synergies for developing new catalytic processes for the transformation of abundant small molecules such as water, carbon dioxide, or ammonia into high-value chemicals and energy-relevant products. CARISMA promotes new collaborations, exchange of knowledge and skills, frontier training to young as well as established researchers, and a platform for the advancement of theoretical and experimental research in an iterative process, comprised of expertise in various connate domains including synthesis, catalysis, spectroscopy, kinetics, and computational chemistry. These interactions stimulate the discovery of new and efficient catalytic processes, illustrated in the second part of this contribution with the collaborative development of powerful iridium-based complexes for bond activation and water oxidation catalysis. PMID:26507475

  14. Iridium ultrasmall nanoparticles, worm-like chain nanowires, and porous nanodendrites: One-pot solvothermal synthesis and catalytic CO oxidation activity

    NASA Astrophysics Data System (ADS)

    Zhang, Tao; Li, Shuai-Chen; Zhu, Wei; Ke, Jun; Yu, Jing-Wen; Zhang, Zhi-Ping; Dai, Lin-Xiu; Gu, Jun; Zhang, Ya-Wen

    2016-06-01

    We report a facile one-pot solvothermal synthesis of monodisperse iridium (Ir) ultrasmall (1.5-2.5 nm in diameter) nanoparticles (NPs), worm-like chain nanowires (NWs), and porous nanodendrites (NDs), for which CO oxidation reaction has been employed as a probe reaction to investigate the effects of nanoparticle size and surface-capping organics on the catalytic activities. Time-dependent experiments revealed that an oriented attachment mechanism induced by the strong adsorption of halide anions (Br- and I-) on specific facet of Ir nanoclusters or by decreasing the reduction rate of Ir precursors with changing their concentrations during the synthesis was responsible for the formation of Ir NWs and NDs. Annealing tests indicated that an O2-H2 atmosphere treatment turned out to be an effective measure to clean up the surface-capping organics of Ir NPs supported on commercial SiO2. Catalytic CO oxidation reaction illustrated that a significant improvement in the catalytic activity of CO oxidation reaction was achieved together with the changing of activation energies after such atmosphere treatment for the supported catalysts of the ultrasmall Ir NPs. It is noteworthy that this enhancement in catalytic activity could be ascribed to the changes in the surface status (including populations of Ir species in metallic and oxidized states, removal of surface capping organics, the variety of active sites, and total effective active site number) for the supported nanocatalysts during the atmosphere treatment.

  15. Heterogeneous Catalysis for Water Oxidation by an Iridium Complex Immobilized on Bipyridine-Periodic Mesoporous Organosilica.

    PubMed

    Liu, Xiao; Maegawa, Yoshifumi; Goto, Yasutomo; Hara, Kenji; Inagaki, Shinji

    2016-07-01

    Heterogenization of metal-complex catalysts for water oxidation without loss of their catalytic activity is important for the development of devices simulating photosynthesis. In this study, efficient heterogeneous iridium complexes for water oxidation were prepared using bipyridine-bridged periodic mesoporous organosilica (BPy-PMO) as a solid chelating ligand. The BPy-PMO-based iridium catalysts (Ir-BPy-PMO) were prepared by postsynthetic metalation of BPy-PMO and characterized through physicochemical analyses. The Ir-BPy-PMOs showed high catalytic activity for water oxidation. The turnover frequency (TOF) values for Ir-BPy-PMOs were one order of magnitude higher than those of conventional heterogeneous iridium catalysts. The reusability and stability of Ir-BPy-PMO were also examined, and detailed characterization was conducted using powder X-ray diffraction, nitrogen adsorption, (13) C DD MAS NMR spectroscopy, TEM, and XAFS methods. PMID:27168492

  16. Transformation of a Cp*-iridium(III) precatalyst for water oxidation when exposed to oxidative stress.

    PubMed

    Zuccaccia, Cristiano; Bellachioma, Gianfranco; Bortolini, Olga; Bucci, Alberto; Savini, Arianna; Macchioni, Alceo

    2014-03-17

    The reaction of [Cp*Ir(bzpy)NO3 ] (1; bzpy=2-benzoylpyridine, Cp*=pentamethylcyclopentadienyl anion), a competent water-oxidation catalyst, with several oxidants (H2 O2 , NaIO4 , cerium ammonium nitrate (CAN)) was studied to intercept and characterize possible intermediates of the oxidative transformation. NMR spectroscopy and ESI-MS techniques provided evidence for the formation of many species that all had the intact Ir-bzpy moiety and a gradually more oxidized Cp* ligand. Initially, an oxygen atom is trapped in between two carbon atoms of Cp* and iridium, which gives an oxygen-Ir coordinated epoxide, whereas the remaining three carbon atoms of Cp* are involved in a η(3) interaction with iridium (2 a). Formal addition of H2 O to 2 a or H2 O2 to 1 leads to 2 b, in which a double MeCOH functionalization of Cp* is present with one MeCOH engaged in an interaction with iridium. The structure of 2 b was unambiguously determined in the solid state and in solution by X-ray single-crystal diffractometry and advanced NMR spectroscopic techniques, respectively. Further oxidation led to the opening of Cp* and transformation of the diol into a diketone with one carbonyl coordinated at the metal (2 c). A η(3) interaction between the three non-oxygenated carbons of "ex-Cp*" and iridium is also present in both 2 b and 2 c. Isolated 2 b and mixtures of 2 a-c species were tested in water-oxidation catalysis by using CAN as sacrificial oxidant. They showed substantially the same activity than 1 (turnover frequency values ranged from 9 to 14 min(-1) ). PMID:24523138

  17. Donor-Flexible Nitrogen Ligands for Efficient Iridium-Catalyzed Water Oxidation Catalysis.

    PubMed

    Navarro, Miquel; Li, Mo; Müller-Bunz, Helge; Bernhard, Stefan; Albrecht, Martin

    2016-05-10

    A pyridylideneamide ligand with variable donor properties owing to a pronounced zwitterionic and a neutral diene-type resonance structure was used as a dynamic ligand at a Cp* iridium center to facilitate water oxidation catalysis, a reaction that requires the stabilization of a variety of different iridium oxidation states and that is key for developing an efficient solar fuel device. The ligand imparts high activity (nearly three-fold increase of turnover frequency compared to benchmark systems), and exceptionally high turnover numbers, which indicate a robust catalytic cycle and little catalyst degradation. PMID:26919306

  18. Composition-dependent electrocatalytic activity of palladium-iridium binary alloy nanoparticles supported on the multiwalled carbon nanotubes for the electro-oxidation of formic acid.

    PubMed

    Bao, Jianming; Dou, Meiling; Liu, Haijing; Wang, Feng; Liu, Jingjun; Li, Zhilin; Ji, Jing

    2015-07-22

    Surface-functionalized multiwalled carbon nanotubes (MWCNTs) supported Pd100-xIrx binary alloy nanoparticles (Pd100-xIrx/MWCNT) with tunable Pd/Ir atomic ratios were synthesized by a thermolytic process at varied ratios of bis(acetylacetonate) palladium(II) and iridium(III) 2,4-pentanedionate precursors and then applied as the electrocatalyst for the formic acid electro-oxidation. The X-ray diffraction pattern (XRD) and transmission electron microscope (TEM) analysis showed that the Pd100-xIrx alloy nanoparticles with the average size of 6.2 nm were uniformly dispersed on the MWCNTs and exhibited a single solid solution phase with a face-centered cubic structure. The electrocatalytic properties were evaluated through the cyclic voltammetry and chronoamperometry tests, and the results indicated that both the activity and stability of Pd100-xIrx/MWCNT were strongly dependent on the Pd/Ir atomic ratios: the best electrocatalytic performance in terms of onset potential, current density, and stability against CO poisoning was obtained for the Pd79Ir21/MWCNT. Moreover, compared with pure Pd nanoparticles supported on MWCNTs (Pd/MWCNT), the Pd79Ir21/MWCNT exhibited enhanced steady-state current density and higher stability, as well as maintained excellent electrocatalytic activity in high concentrated formic acid solution, which was attributed to the bifunctional effect through alloying Pd with transition metal. PMID:26132867

  19. Iridium-Doped Ruthenium Oxide Catalyst for Oxygen Evolution

    NASA Technical Reports Server (NTRS)

    Valdez, Thomas I.; Narayan, Sri R.; Billings, Keith J.

    2011-01-01

    NASA requires a durable and efficient catalyst for the electrolysis of water in a polymer-electrolyte-membrane (PEM) cell. Ruthenium oxide in a slightly reduced form is known to be a very efficient catalyst for the anodic oxidation of water to oxygen, but it degrades rapidly, reducing efficiency. To combat this tendency of ruthenium oxide to change oxidation states, it is combined with iridium, which has a tendency to stabilize ruthenium oxide at oxygen evolution potentials. The novel oxygen evolution catalyst was fabricated under flowing argon in order to allow the iridium to preferentially react with oxygen from the ruthenium oxide, and not oxygen from the environment. Nanoparticulate iridium black and anhydrous ruthenium oxide are weighed out and mixed to 5 18 atomic percent. They are then heat treated at 300 C under flowing argon (in order to create an inert environment) for a minimum of 14 hours. This temperature was chosen because it is approximately the creep temperature of ruthenium oxide, and is below the sintering temperature of both materials. In general, the temperature should always be below the sintering temperature of both materials. The iridium- doped ruthenium oxide catalyst is then fabricated into a PEM-based membrane- electrode assembly (MEA), and then mounted into test cells. The result is an electrolyzer system that can sustain electrolysis at twice the current density, and at the same efficiency as commercial catalysts in the range of 100-200 mA/sq cm. At 200 mA/sq cm, this new system operates at an efficiency of 85 percent, which is 2 percent greater than commercially available catalysts. Testing has shown that this material is as stable as commercially available oxygen evolution catalysts. This means that this new catalyst can be used to regenerate fuel cell systems in space, and as a hydrogen generator on Earth.

  20. Phase control of iridium and iridium oxide thin films in atomic layer deposition

    SciTech Connect

    Kim, Sung-Wook; Kwon, Se-Hun; Kwak, Dong-Kee; Kang, Sang-Won

    2008-01-15

    The atomic layer deposition of iridium (Ir) and iridium oxide (IrO{sub 2}) films was investigated using an alternating supply of (ethylcyclopentadienyl)(1,5-cyclooctadiene) iridium and oxygen gas at temperatures between 230 and 290 deg. C. The phase transition between Ir and IrO{sub 2} occurred at the critical oxygen partial pressure during the oxygen injection pulse. The oxygen partial pressure was controlled by the O{sub 2}/(Ar+O{sub 2}) ratio or deposition pressures. The resistivity of the deposited Ir and IrO{sub 2} films was about 9 and 120 {mu}{omega} cm, respectively. In addition, the critical oxygen partial pressure for the phase transition between Ir and IrO{sub 2} was increased with increasing the deposition temperature. Thus, the phase of the deposited film, either Ir or IrO{sub 2}, was controlled by the oxygen partial pressure and the deposition temperature. However, the formation of a thin Ir layer was detected between the IrO{sub 2} and SiO{sub 2} substrate. To remove this interfacial layer, the oxygen partial pressure is increased to a severe condition. And the impurity contents were below the detection limit of Auger electron spectroscopy in both Ir and IrO{sub 2} films.

  1. Multi-component nanoporous platinum-ruthenium-copper-osmium-iridium alloy with enhanced electrocatalytic activity towards methanol oxidation and oxygen reduction

    NASA Astrophysics Data System (ADS)

    Chen, Xiaoting; Si, Conghui; Gao, Yulai; Frenzel, Jan; Sun, Junzhe; Eggeler, Gunther; Zhang, Zhonghua

    2015-01-01

    Multi-component nanoporous platinum-ruthenium-copper-osmium-iridium (np-PtRuCuOsIr) electrocatalyst has been facilely fabricated by chemical dealloying of mechanically alloyed AlCuPtRuOsIr precursor. The np-PtRuCuOsIr catalyst exhibits a typical three-dimensional bi-continuous interpenetrating ligament/channel structure with a length scale of ∼2.5 nm. The np-PtRuCuOsIr catalyst reaches a higher level in the mass activity (857.5 mA mgPt-1) and specific activity (3.0 mA cm-2) towards methanol oxidation compared to the commercial PtC catalyst (229.5 mA mgPt-1 and 0.5 mA cm-2 respectively). Moreover, the CO stripping peak of np-PtRuCuOsIr is 0.54 V (vs. SCE), 130 mV negative shift in comparison with the commercial PtC (0.67 V vs. SCE). The half-wave potential of np-PtRuCuOsIr is 0.900 V vs. RHE, 36 mV positive compared with that of the commercial PtC (0.864 V vs. RHE). The np-PtRuCuOsIr catalyst also shows 1.8 and 3.8 times enhancement in the mass and specific activity towards oxygen reduction than the commercial PtC. Moreover, the np-PtRuCuOsIr alloy exhibits superior oxygen reduction activities even after 15 K cycles, indicating its excellent long-term stability. The present np-PtRuCuOsIr can act as a promising candidate for the electrocatalyst in direct methanol fuel cells (DMFCs).

  2. Optimization and electrochemical characterization of RF-sputtered iridium oxide microelectrodes for electrical stimulation

    NASA Astrophysics Data System (ADS)

    Kang, Xiaoyang; Liu, Jingquan; Tian, Hongchang; Yang, Bin; NuLi, Yanna; Yang, Chunsheng

    2014-02-01

    A reactively sputtered iridium oxide (IrOx) thin film has been developed as electrochemical modification material for microelectrodes to obtain high stability and charge storage capacity (CSC) in functional electrical stimulation. The effect of the oxygen flow and oxygen to argon ratio during sputtering process on the microstructure and electrochemical properties of the IrOx film is characterized. After optimization, the activated IrOx microelectrode shows the highest CSC of 36.15 mC cm-2 at oxygen flow of 25 sccm and oxygen to argon ratio of (2.5:1). Because the deposition process of the reactively sputtered iridium oxide is an exothermic reaction, it is difficult to form film patterning by the lift-off process. The lift-off process was focused on the partially carbonized photoresist (PR) and normal PR. The higher of the carbonization degree of PR reaches, the longer the immersion duration. However, the patterning process of the iridium oxide film becomes feasible when the sputtering pressure is increasing. The experimental results show that the iridium oxide films forms the pattern with the lowest duration of ultrasonic agitation when the deposition pressure is 4.2 Pa and pressure ratio between O2 and Ar pressure is 3:4.

  3. Luminescent Iridium(III) Complex Labeled DNA for Graphene Oxide-Based Biosensors.

    PubMed

    Zhao, Qingcheng; Zhou, Yuyang; Li, Yingying; Gu, Wei; Zhang, Qi; Liu, Jian

    2016-02-01

    There has been growing interest in utilizing highly photostable iridium(III) complexes as new luminescent probes for biotechnology and life science. Herein, iridium(III) complex with carboxyl group was synthesized and activated with N-hydroxysuccinimide, followed by tagging to the amino terminate of single-stranded DNA (ssDNA). The Ir-ssDNA probe was further combined with graphene oxide (GO) nanosheets to develop a GO-based biosensor for target ssDNA detection. The quenching efficiency of GO, and the photostability of iridium(III) complex and GO-Ir-ssDNA biosensor, were also investigated. On the basis of the high luminescence quenching efficiency of GO toward iridium(III) complex, the GO-Ir-ssDNA biosensor exhibited minimal background signals, while strong emission was observed when Ir-ssDNA desorbed from GO nanosheets and formed a double helix with the specific target, leading to a high signal-to-background ratio. Moreover, it was found that luminescent intensities of iridium(III) complex and GO-Ir-ssDNA biosensor were around 15 and 3 times higher than those of the traditional carboxyl fluorescein (FAM) dye and the GO-FAM-ssDNA biosensor after UV irradiation, respectively. Our study suggested the sensitive and selective Ir-ssDNA probe was suitable for the development of highly photostable GO-based detection platforms, showing promise for application beyond the OLED (organic light emitting diode) area. PMID:26753824

  4. Determination of surface coverage of catalysts: Temperature programmed experiments on platinum and iridium sponge catalysts after low temperature ammonia oxidation

    SciTech Connect

    Broek, A.C.M. van den; Grondelle, J. van; Santen, R.A. van

    1999-07-25

    The activity of iridium and platinum sponge catalysts was studied in the low temperature gas phase oxidation of ammonia with oxygen. Under the reaction conditions used, iridium was found to be more active and more selective to nitrogen than platinum. Furthermore it was established from activity measurements that both catalysts lose activity as a function of time on stream due to inhibition of the surface by reaction intermediates. The used catalysts were studied by XPS and temperature programmed techniques. It was found that the surface of the catalysts had a high coverage of NH and OH and some additional NH{sub 2}. It seems most likely that the reaction mechanism proceeds through a stepwise dehydrogenation of the ammonia molecule. It appears that the last dehydrogenation step (NH by OH to N and water) is the rate determining step. The high selectivity of iridium to nitrogen can be explained by the higher activity of iridium in dissociating NO.

  5. Photochemical Oxidative Growth of Iridium Oxide Nanoparticles on CdSe@CdS Nanorods.

    PubMed

    Kalisman, Philip; Nakibli, Yifat; Amirav, Lilac

    2016-01-01

    We demonstrate a procedure for the photochemical oxidative growth of iridium oxide catalysts on the surface of seeded cadmium selenide-cadmium sulfide (CdSe@CdS) nanorod photocatalysts. Seeded rods are grown using a colloidal hot-injection method and then moved to an aqueous medium by ligand exchange. CdSe@CdS nanorods, an iridium precursor and other salts are mixed and illuminated. The deposition process is initiated by absorption of photons by the semiconductor particle, which results with formation of charge carriers that are used to promote redox reactions. To insure photochemical oxidative growth we used an electron scavenger. The photogenerated holes oxidize the iridium precursor, apparently in a mediated oxidative pathway. This results in the growth of high quality crystalline iridium oxide particles, ranging from 0.5 nm to about 3 nm, along the surface of the rod. Iridium oxide grown on CdSe@CdS heterostructures was studied by a variety of characterization methods, in order to evaluate its characteristics and quality. We explored means for control over particle size, crystallinity, deposition location on the CdS rod, and composition. Illumination time and excitation wavelength were found to be key parameters for such control. The influence of different growth conditions and the characterization of these heterostructures are described alongside a detailed description of their synthesis. Of significance is the fact that the addition of iridium oxide afforded the rods astounding photochemical stability under prolonged illumination in pure water (alleviating the requirement for hole scavengers). PMID:26891234

  6. In situ observation of surface species on iridium oxide nanoparticles during the oxygen evolution reaction.

    PubMed

    Sanchez Casalongue, Hernan G; Ng, May Ling; Kaya, Sarp; Friebel, Daniel; Ogasawara, Hirohito; Nilsson, Anders

    2014-07-01

    An iridium oxide nanoparticle electrocatalyst under oxygen evolution reaction conditions was probed in situ by ambient-pressure X-ray photoelectron spectroscopy. Under OER conditions, iridium undergoes a change in oxidation state from Ir(IV) to Ir(V) that takes place predominantly at the surface of the catalyst. The chemical change in iridium is coupled to a decrease in surface hydroxide, providing experimental evidence which strongly suggests that the oxygen evolution reaction on iridium oxide occurs through an OOH-mediated deprotonation mechanism. PMID:24889896

  7. Single step radiolytic synthesis of iridium nanoparticles onto graphene oxide

    NASA Astrophysics Data System (ADS)

    Rojas, J. V.; Molina Higgins, M. C.; Toro Gonzalez, M.; Castano, C. E.

    2015-12-01

    In this work a new approach to synthesize iridium nanoparticles on reduced graphene oxide is presented. The nanoparticles were directly deposited and grown on the surface of the carbon-based support using a single step reduction method through gamma irradiation. In this process, an aqueous isopropanol solution containing the iridium precursor, graphene oxide, and sodium dodecyl sulfate was initially prepared and sonicated thoroughly to obtain a homogeneous dispersion. The samples were irradiated with gamma rays with energies of 1.17 and 1.33 MeV emitted from the spontaneous decay of the 60Co irradiator. The interaction of gamma rays with water in the presence of isopropanol generates highly reducing species homogeneously distributed in the solution that can reduce the Ir precursor down to a zero valence state. An absorbed dose of 60 kGy was used, which according to the yield of reducing species is sufficient to reduce the total amount of precursor present in the solution. This novel approach leads to the formation of 2.3 ± 0.5 nm Ir nanoparticles distributed along the surface of the support. The oxygenated functionalities of graphene oxide served as nucleation sites for the formation of Ir nuclei and their subsequent growth. XPS results revealed that the interaction of Ir with the support occurs through Irsbnd O bonds.

  8. Properties of mixed molybdenum oxide iridium oxide thin films synthesized by spray pyrolysis

    NASA Astrophysics Data System (ADS)

    Patil, P. S.; Kawar, R. K.; Sadale, S. B.; Inamdar, A. I.; Deshmukh, H. P.

    2006-09-01

    Molybdenum-doped iridium oxide thin films have been deposited onto corning glass- and fluorine-doped tin oxide coated corning glass substrates at 350 °C by using a pneumatic spray pyrolysis technique. An aqueous solution of 0.01 M ammonium molybdate was mixed with 0.01 M iridium trichloride solution in different volume proportions and the resultant solution was used as a precursor solution for spraying. The as-deposited samples were annealed at 600 °C in air medium for 1 h. The structural, electrical and optical properties of as-deposited and annealed Mo-doped iridium oxide were studied and values of room temperature electrical resistivity, and thermoelectric power were estimated. The as-deposited samples with 2% Mo doping exhibit more pronounced electrochromism than other samples, including pristine Ir oxide.

  9. Merger of visible light induced oxidation and enantioselective alkylation with a chiral iridium catalyst.

    PubMed

    Wang, Chuanyong; Zheng, Yu; Huo, Haohua; Röse, Philipp; Zhang, Lilu; Harms, Klaus; Hilt, Gerhard; Meggers, Eric

    2015-05-11

    A single chiral octahedral iridium(III) complex is used for visible light activated asymmetric photoredox catalysis. In the presence of a conventional household lamp and under an atmosphere of air, the oxidative coupling of 2-acyl-1-phenylimidazoles with N,N-diaryl-N-(trimethylsilyl)methylamines provides aminoalkylated products in 61-93 % yields with high enantiomeric excess (90-98 % ee). Notably, the iridium center simultaneously serves three distinct functions: as the exclusive source of chirality, as the catalytically active Lewis acid, and as a central part of the photoredox sensitizer. This conceptionally simple reaction Scheme may provide new avenues for the green synthesis of non-racemic chiral molecules. PMID:25832794

  10. Evaluation of oxide-coated iridium-rhenium chambers

    NASA Technical Reports Server (NTRS)

    Reed, Brian D.

    1994-01-01

    Iridium-coated rhenium (Ir-Re) provides long life operation of radiation-cooled rockets at temperatures up to 2200 C. Ceramic oxide coatings could be used to increase Ir-Re rocket lifetimes and allow operation in highly oxidizing environments. Ceramic oxide coatings promise to serve as both thermal and diffusion barriers for the iridium layer. Seven ceramic oxide-coated Ir-Re, 22-N rocket chambers were tested with gaseous hydrogen/gaseous oxygen (GHz/G02) propellants. Five chambers had thick (over 10 mils), monolithic coatings of either hafnia (HfO2) or zirconia (ZrO2). Two chambers had coatings with thicknesses less than 5 mils. One of these chambers had a thin-walled coating of ZrO2 infiltrated with sol gel HfO2. The other chamber had a coating composed of an Ir-oxide composite. The purpose of this test program was to assess the ability of the oxide coatings to withstand the thermal shock of combustion initiation, adhere under repeated thermal cycling, and operate in aggressively oxidizing environments. All of the coatings survived the thermal shock of combustion and demonstrated operation at mixture ratios up to 11. Testing the Ir-oxide composite-coated chamber included over 29 min at mixture ratio 16. The thicker walled coatings provided the larger temperature drops across the oxide layer (up to 570 C), but were susceptible to macrocracking and eventual chipping at a stress concentrator. The cracks apparently resealed during firing, under compression of the oxide layer. The thinner walled coatings did not experience the macrocracking and chipping of the chambers that was seen with the thick, monolithic coatings. However, burn-throughs in the throat region did occur in both of the thin-walled chambers at mixture ratios well above stoichiometric. The burn-throughs were probably the result of oxygen diffusion through the oxide coating that allowed the underlying Ir and Re layers to be oxidized. The results of this test program indicated that the thin-walled oxide

  11. Evaluation of oxide-coated iridium-rhenium chambers

    NASA Astrophysics Data System (ADS)

    Reed, Brian D.

    1994-03-01

    Iridium-coated rhenium (Ir-Re) provides long life operation of radiation-cooled rockets at temperatures up to 2200 C. Ceramic oxide coatings could be used to increase Ir-Re rocket lifetimes and allow operation in highly oxidizing environments. Ceramic oxide coatings promise to serve as both thermal and diffusion barriers for the iridium layer. Seven ceramic oxide-coated Ir-Re, 22-N rocket chambers were tested with gaseous hydrogen/gaseous oxygen (GHz/G02) propellants. Five chambers had thick (over 10 mils), monolithic coatings of either hafnia (HfO2) or zirconia (ZrO2). Two chambers had coatings with thicknesses less than 5 mils. One of these chambers had a thin-walled coating of ZrO2 infiltrated with sol gel HfO2. The other chamber had a coating composed of an Ir-oxide composite. The purpose of this test program was to assess the ability of the oxide coatings to withstand the thermal shock of combustion initiation, adhere under repeated thermal cycling, and operate in aggressively oxidizing environments. All of the coatings survived the thermal shock of combustion and demonstrated operation at mixture ratios up to 11. Testing the Ir-oxide composite-coated chamber included over 29 min at mixture ratio 16. The thicker walled coatings provided the larger temperature drops across the oxide layer (up to 570 C), but were susceptible to macrocracking and eventual chipping at a stress concentrator. The cracks apparently resealed during firing, under compression of the oxide layer. The thinner walled coatings did not experience the macrocracking and chipping of the chambers that was seen with the thick, monolithic coatings. However, burn-throughs in the throat region did occur in both of the thin-walled chambers at mixture ratios well above stoichiometric. The burn-throughs were probably the result of oxygen diffusion through the oxide coating that allowed the underlying Ir and Re layers to be oxidized. The results of this test program indicated that the thin-walled oxide

  12. Microscopic measurement of pH with iridium oxide microelectrodes

    PubMed

    Wipf; Ge; Spaine; Baur

    2000-10-15

    Microscopic pH electrodes were produced by deposition of hydrous iridium oxide onto carbon fiber microelectrodes. The electrodes exhibit two linear regions of potentiometric response between pH 2-6 and pH 6-12. The electrodes respond to pH changes within 50 ms, and an equilibrium value is reached within 30 s. By using these electrodes as probes in the scanning electrochemical microscope, dynamic pH changes occurring at or near a surface can be measured and pH maps of the surface can be generated. Vertical pH profiles and images of pH were obtained at substrates where electrochemical (oxidation and reduction of H2O2, hydrogen evolution) or enzymatic (glucose oxidase) reactions involving proton transfers occur. PMID:11055710

  13. Development and Testing of High Surface Area Iridium Anodes for Molten Oxide Electrolysis

    NASA Technical Reports Server (NTRS)

    Shchetkovskiy, Anatoliy; McKechnie, Timothy; Sadoway, Donald R.; Paramore, James; Melendez, Orlando; Curreri, Peter A.

    2010-01-01

    Processing of lunar regolith into oxygen for habitat and propulsion is needed to support future space missions. Direct electrochemical reduction of molten regolith is an attractive method of processing, because no additional chemical reagents are needed. The electrochemical processing of molten oxides requires high surface area, inert anodes. Such electrodes need to be structurally robust at elevated temperatures (1400-1600 C), be resistant to thermal shock, have good electrical conductivity, be resistant to attack by molten oxide (silicate), be electrochemically stable and support high current density. Iridium with its high melting point, good oxidation resistance, superior high temperature strength and ductility is the most promising candidate for anodes in high temperature electrochemical processes. Several innovative concepts for manufacturing such anodes by electrodeposition of iridium from molten salt electrolyte (EL-Form process) were evaluated. Iridium electrodeposition to form of complex shape components and coating was investigated. Iridium coated graphite, porous iridium structure and solid iridium anodes were fabricated. Testing of electroformed iridium anodes shows no visible degradation. The result of development, manufacturing and testing of high surface, inert iridium anodes will be presented.

  14. Development and Testing of High Surface Area Iridium Anodes for Molten Oxide Electrolysis

    NASA Technical Reports Server (NTRS)

    Shchetkovskiy, Anatoliy; McKechnie, Timothy; Sadoway, Donald R.; Paramore, James; Melendez, Orlando; Curreri, Peter A.

    2010-01-01

    Processing of lunar regolith into oxygen for habitat and propulsion is needed to support future space missions. Direct electrochemical reduction of molten regolith is an attractive method of processing, because no additional chemical reagents are needed. The electrochemical processing of molten oxides requires high surface area, inert anodes. Such electrodes need to be structurally robust at elevated temperatures (1400-1600?C), be resistant to thermal shock, have good electrical conductivity, be resistant to attack by molten oxide (silicate), be electrochemically stable and support high current density. Iridium with its high melting point, good oxidation resistance, superior high temperature strength and ductility is the most promising candidate for anodes in high temperature electrochemical processes. Several innovative concepts for manufacturing such anodes by electrodeposition of iridium from molten salt electrolyte (EL-Form? process) were evaluated. Iridium electrodeposition to form of complex shape components and coating was investigated. Iridium coated graphite, porous iridium structure and solid iridium anodes were fabricated. Testing of electroformed iridium anodes shows no visible degradation. The result of development, manufacturing and testing of high surface, inert iridium anodes will be presented.

  15. High-Temperature Oxidation Behavior of Iridium-Rhenium Alloys

    NASA Technical Reports Server (NTRS)

    Reed, Brian D.

    1995-01-01

    The life-limiting mechanism for radiation-cooled rockets made from iridium-coated rhenium (Ir/Re) is the diffusion of Re into the Ir layer and the subsequent oxidation of the resulting Ir-Re alloy from the inner surface. In a previous study, a life model for Ir/Re rockets was developed. It incorporated Ir-Re diffusion and oxidation data to predict chamber lifetimes as a function of temperature and oxygen partial pressure. Oxidation testing at 1540 deg C suggested that a 20-wt percent Re concentration at the inner wall surface should be established as the failure criterion. The present study was performed to better define Ir-oxidation behavior as a function of Re concentration and to supplement the data base for the life model. Samples ranging from pure Ir to Ir-40 wt percent Re (Ir-40Re) were tested at 1500 deg C, in two different oxygen environments. There were indications that the oxidation rate of the Ir-Re alloy increased significantly when it went from a single-phase solid solution to a two-phase mixture, as was suggested in previous work. However, because of testing anomalies in this study, there were not enough dependable oxidation data to definitively raise the Ir/Re rocket failure criterion from 20-wt percent Re to a Re concentration corresponding to entry into the two-phase region.

  16. Design, analysis, and fabrication of oxide-coated iridium/rhenium combustion chambers

    NASA Technical Reports Server (NTRS)

    Jang, Q.; Tuffias, R. H.; Laferla, R.; Ghoniem, N. M.

    1993-01-01

    Iridium-coated rhenium (Ir/Re) combustion chambers provide high temperature, oxidation-resistant operation for radiation-cooled liquid-fueled rocket engines. A 22-N (5-lb(sub f)) chamber has been operated for 15 hours at 2200 C (4000 F) using nitrogen tetroxide/monomethyl hydrazine (NTO/MMH) propellant, with negligible internal erosion. The oxidation resistance of these chambers could be further increased by the addition of refractory oxide coatings, providing longer life and/or operation in more oxidizing and higher temperature environments. The oxide coatings would serve as a thermal and diffusion barrier for the iridium coating, lowering the temperature of the iridium layer while also preventing the ingress of oxygen and egress of iridium oxides. This would serve to slow the failure mechanisms of Ir/Re chambers, namely the diffusion of rhenium to the inner surface and the oxidation of iridium. Such protection could extend chamber lifetimes by tens or perhaps hundreds of hours, and allow chamber operation on stoichiometric or higher mixture ratio oxygen/hydrogen (O2/H2) propellant. Extensive thermomechanical, thermochemical, and mass transport modeling was performed as a key material/structure design tool. Based on the results of these analyses, several 22-N oxide-coated Ir/Re chambers were fabricated and delivered to NASA Lewis Research Center for hot-fire testing.

  17. Design, analysis, and fabrication of oxide-coated iridium/rhenium combustion chambers

    NASA Astrophysics Data System (ADS)

    Jang, Q.; Tuffias, R. H.; Laferla, R.; Ghoniem, N. M.

    1993-11-01

    Iridium-coated rhenium (Ir/Re) combustion chambers provide high temperature, oxidation-resistant operation for radiation-cooled liquid-fueled rocket engines. A 22-N (5-lb(sub f)) chamber has been operated for 15 hours at 2200 C (4000 F) using nitrogen tetroxide/monomethyl hydrazine (NTO/MMH) propellant, with negligible internal erosion. The oxidation resistance of these chambers could be further increased by the addition of refractory oxide coatings, providing longer life and/or operation in more oxidizing and higher temperature environments. The oxide coatings would serve as a thermal and diffusion barrier for the iridium coating, lowering the temperature of the iridium layer while also preventing the ingress of oxygen and egress of iridium oxides. This would serve to slow the failure mechanisms of Ir/Re chambers, namely the diffusion of rhenium to the inner surface and the oxidation of iridium. Such protection could extend chamber lifetimes by tens or perhaps hundreds of hours, and allow chamber operation on stoichiometric or higher mixture ratio oxygen/hydrogen (O2/H2) propellant. Extensive thermomechanical, thermochemical, and mass transport modeling was performed as a key material/structure design tool. Based on the results of these analyses, several 22-N oxide-coated Ir/Re chambers were fabricated and delivered to NASA Lewis Research Center for hot-fire testing.

  18. Parahydrogen induced polarization and the oxidative addition of hydrogen to iridium tribromostannyl carbonylate anions.

    PubMed

    Permin, Alexei; Eisenberg, Richard

    2002-05-01

    Activation of dihydrogen by a system composed of (Bu(4)N)[IrBr(2)(CO)(2)] (1) and tin dibromide in varying ratios was studied using parahydrogen induced polarization (PHIP) which allows the detection of transient dihydrides not observable in conventional (1)H NMR spectra. While the oxidative addition of dihydrogen to neutral and cationic Ir(I) species is common, there are only a few examples of H(2) addition to anionic complexes. Tin dibromide reacts with iridium(I) complex 1 in acetone forming equilibrium mixtures of cis- and trans-tribromostannyl derivatives [IrBr(n)()(SnBr(3))(2)(-)(n)()(CO)(2)](-), n = 0,1, the existence of which is inferred from the stereochemistries of the dihydrogen addition products determined using PHIP. The sigma-donating effect of the SnBr(3)(-) ligand facilitates the oxidative addition to the iridium center. The structures of the dihydrides formed upon addition of dihydrogen are assigned on the basis of hydride chemical shifts and values of (2)J((1)H-(117,119)Sn). The only dihydride observed in conventional (1)H NMR spectra is cis-trans-cis-[IrH(2)(SnBr(3))(2)(CO)(2)](-), the identity of which was confirmed using the (13)C labeled Ir(I) precursor. Both [IrBr(2)(CO)(2)](-) and its tribromostannyl derivatives catalyze cis-pairwise addition of dihydrogen to phenylacetylene. PMID:11978112

  19. Testing and evaluation of oxide-coated iridium/rhenium chambers

    NASA Technical Reports Server (NTRS)

    Reed, Brian D.

    1993-01-01

    Iridium-coated rhenium provides long life operation of radiation-cooled rockets at temperatures up to 2200 C. Ceramic oxide coatings could be used to increase iridium/rhenium rocket lifetimes and allow operation in highly oxidizing environments. Ceramic oxide coatings promise to serve as both thermal and diffusion barriers for the iridium layer. Seven ceramic oxide-coated iridium/rhenium, 22 N rocket chambers were tested on gaseous hydrogen/gaseous oxygen propellants. Five chambers had thick (over 10 mils), monolithic coatings of either hafnia or zirconia. Two chambers had coatings with thicknesses less than 5 mils. One of these chambers had a thin-walled coating of zirconia infiltrated with sol gel hafnia. The other chamber had a coating composed of an iridium/oxide composite. The purpose of this test program was to assess the ability of the oxide coatings to withstand the thermal shock of combustion initiation, adhere under repeated thermal cycling, and operate in aggressively oxidizing environments. All of the coatings survived the thermal shock of combustion and demonstrated operation at mixture ratios up to 11. The iridium/oxide composite coated chamber included testing for over 29 minutes at mixture ratio 16. The thicker-walled coatings provided the larger temperature drops across the oxide layer (up to 570 C), but were susceptible to macrocracking and eventual chipping at a stress concentrator. The cracks apparently resealed during firing, under compression of the oxide layer. The thinner-walled coatings did not experience the macrocracking and chipping of the chambers seen with the thick, monolithic coatings. However, burnthroughs in the throat region did occur in both of the thin-walled chambers at mixture ratios well above stochiometric. The burn-throughs were probably the result of oxygen-diffusion through the oxide coating that allowed the underlying iridium and rhenium layers to be oxidized. The results of this test program indicated that the thin

  20. Electrochromic Properties of Iridium Oxide Films Prepared by Pulsed Anodic Electrodeposition

    NASA Astrophysics Data System (ADS)

    Jung, Youngwoo; Tak, Yongsug; Lee, Jaeyoung

    2002-12-01

    Thin films of iridium oxide to be used as an electrochromic material were prepared by pulsed anodic current electrodeposition onto indium tin oxide (ITO) coated glass substrates. Before the pulsed electrodeposition, iridium oxide films formed by cyclic voltammetry (CV) played an important role in good adhesion as a seed layer. Iridium oxide films with light-blue color (100 mC/cm2) were deposited when anodic current of 0.07 mA/cm2 for 0.5 sec was superimposed on off-time of 0.5 sec (i.e., zero current) in each cycle. During CV experiment in phosphate buffered saline solution, electrodeposited iridium oxide films exhibited anodic electrochromism of blue and black color at two oxidation potentials (i.e., the ejection of H+) of +0.5 V and +0.9 V (vs. SCE), respectively, while on the cathodic scan, black thin film became colorless due to the injection of H+. When +0.9 V and -0.7 V were applied for coloring and bleaching observation in different pulse voltammetry, minimal times needed for each process are 9 sec and 5 sec, respectively.

  1. Identification of an iridium-containing compound with a formal oxidation state of IX.

    PubMed

    Wang, Guanjun; Zhou, Mingfei; Goettel, James T; Schrobilgen, Gary J; Su, Jing; Li, Jun; Schlöder, Tobias; Riedel, Sebastian

    2014-10-23

    One of the most important classifications in chemistry and within the periodic table is the concept of formal oxidation states. The preparation and characterization of compounds containing elements with unusual oxidation states is of great interest to chemists. The highest experimentally known formal oxidation state of any chemical element is at present VIII, although higher oxidation states have been postulated. Compounds with oxidation state VIII include several xenon compounds (for example XeO4 and XeO3F2) and the well-characterized species RuO4 and OsO4 (refs 2-4). Iridium, which has nine valence electrons, is predicted to have the greatest chance of being oxidized beyond the VIII oxidation state. In recent matrix-isolation experiments, the IrO4 molecule was characterized as an isolated molecule in rare-gas matrices. The valence electron configuration of iridium in IrO4 is 5d(1), with a formal oxidation state of VIII. Removal of the remaining d electron from IrO4 would lead to the iridium tetroxide cation ([IrO4](+)), which was recently predicted to be stable and in which iridium is in a formal oxidation state of IX. There has been some speculation about the formation of [IrO4](+) species, but these experimental observations have not been structurally confirmed. Here we report the formation of [IrO4](+) and its identification by infrared photodissociation spectroscopy. Quantum-chemical calculations were carried out at the highest level of theory that is available today, and predict that the iridium tetroxide cation, with a Td-symmetrical structure and a d(0) electron configuration, is the most stable of all possible [IrO4](+) isomers. PMID:25341786

  2. Identification of an iridium-containing compound with a formal oxidation state of IX

    NASA Astrophysics Data System (ADS)

    Wang, Guanjun; Zhou, Mingfei; Goettel, James T.; Schrobilgen, Gary J.; Su, Jing; Li, Jun; Schlöder, Tobias; Riedel, Sebastian

    2014-10-01

    One of the most important classifications in chemistry and within the periodic table is the concept of formal oxidation states. The preparation and characterization of compounds containing elements with unusual oxidation states is of great interest to chemists. The highest experimentally known formal oxidation state of any chemical element is at present VIII, although higher oxidation states have been postulated. Compounds with oxidation state VIII include several xenon compounds (for example XeO4 and XeO3F2) and the well-characterized species RuO4 and OsO4 (refs 2, 3, 4). Iridium, which has nine valence electrons, is predicted to have the greatest chance of being oxidized beyond the VIII oxidation state. In recent matrix-isolation experiments, the IrO4 molecule was characterized as an isolated molecule in rare-gas matrices. The valence electron configuration of iridium in IrO4 is 5d1, with a formal oxidation state of VIII. Removal of the remaining d electron from IrO4 would lead to the iridium tetroxide cation ([IrO4]+), which was recently predicted to be stable and in which iridium is in a formal oxidation state of IX. There has been some speculation about the formation of [IrO4]+ species, but these experimental observations have not been structurally confirmed. Here we report the formation of [IrO4]+ and its identification by infrared photodissociation spectroscopy. Quantum-chemical calculations were carried out at the highest level of theory that is available today, and predict that the iridium tetroxide cation, with a Td-symmetrical structure and a d0 electron configuration, is the most stable of all possible [IrO4]+ isomers.

  3. Performance of laboratory polymer electrolyte membrane hydrogen generator with sputtered iridium oxide anode

    NASA Astrophysics Data System (ADS)

    Labou, D.; Slavcheva, E.; Schnakenberg, U.; Neophytides, S.

    The continuous improvement of the anode materials constitutes a major challenge for the future commercial use of polymer electrolyte membranes (PEM) electrolyzers for hydrogen production. In accordance to this direction, iridium/titanium films deposited directly on carbon substrates via magnetron sputtering are operated as electrodes for the oxygen evolution reaction interfaced with Nafion 115 electrolyte in a laboratory single cell PEM hydrogen generator. The anode with 0.2 mg cm -2 Ir catalyst loading was electrochemically activated by cycling its potential value between 0 and 1.2 V (vs. RHE). The water electrolysis cell was operated at 90 °C with current density 1 A cm -2 at 1.51 V without the ohmic contribution. The corresponding current density per mgr of Ir catalyst is 5 A mg -1. The achieved high efficiency is combined with sufficient electrode stability since the oxidation of the carbon substrate during the anodic polarization is almost negligible.

  4. A pH Sensor Based on a Stainless Steel Electrode Electrodeposited with Iridium Oxide

    ERIC Educational Resources Information Center

    Martinez, C. C. M.; Madrid, R. E.; Felice, C. J.

    2009-01-01

    A simple procedure to make an iridium oxide (IrO[subscript 2]) electrodeposited pH sensor, that can be used in a chemical, biomedical, or materials laboratory, is presented here. Some exercises, based on this sensor, that can be used to teach important concepts in the field of biomedical, biochemical, tissue, or materials engineering, are also…

  5. C-H activation and C=C double bond formation reactions in iridium ortho-methyl arylphosphane complexes.

    PubMed

    Baratta, Walter; Ballico, Maurizio; Del Zotto, Alessandro; Zangrando, Ennio; Rigo, Pierluigi

    2007-01-01

    The Vaska-type iridium(I) complex [IrCl(CO){PPh(2)(2-MeC(6)H(4))}(2)] (1), characterized by an X-ray diffraction study, was obtained from iridium(III) chloride hydrate and PPh(2)(2,6-MeRC(6)H(3)) with R=H in DMF, whereas for R=Me, activation of two ortho-methyl groups resulted in the biscyclometalated iridium(III) compound [IrCl(CO){PPh(2)(2,6-CH(2)MeC(6)H(3))}(2)] (2). Conversely, for R=Me the iridium(I) compound [IrCl(CO){PPh(2)(2,6-Me(2)C(6)H(3))}(2)] (3) can be obtained by treatment of [IrCl(COE)(2)](2) (COE=cyclooctene) with carbon monoxide and the phosphane in acetonitrile. Compound 3 in CH(2)Cl(2) undergoes intramolecular C-H oxidative addition, affording the cyclometalated hydride iridium(III) species [IrHCl(CO){PPh(2)(2,6-CH(2)MeC(6)H(3))}{PPh(2)(2,6-Me(2)C(6)H(3))}] (4). Treatment of 2 with Na[BAr(f) (4)] (Ar(f)=3,5-C(6)H(3)(CF(3))(2)) gives the fluxional cationic 16-electron complex [Ir(CO){PPh(2)(2,6-CH(2)MeC(6)H(3))}(2)][BAr(f) (4)] (5), which reversibly reacts with dihydrogen to afford the delta-agostic complex [IrH(CO){PPh(2)(2,6-CH(2)MeC(6)H(3))}{PPh(2)(2,6-Me(2)C(6)H(3))}][BAr(f)(4)] (6), through cleavage of an Ir-C bond. This species can also be formed by treatment of 4 with Na[BAr(f)(4)] or of 2 with Na[BAr(f)(4)] through C-H oxidative addition of one ortho-methyl group, via a transient 14-electron iridium(I) complex. Heating of the coordinatively unsaturated biscyclometalated species 5 in toluene gives the trans-dihydride iridium(III) complex [IrH(2)(CO){PPh(2)(2,6-MeC(6)H(3)CH=CHC(6)H(3)Me-2,6)PPh(2)}][BAr(f) (4)] (7), containing a trans-stilbene-type terdentate ligand, as result of a dehydrogenative carbon-carbon double bond coupling reaction, possibly through an iridium carbene species. PMID:17535000

  6. Legitimate intermediates of oxygen evolution on iridium oxide revealed by in situ electrochemical evanescent wave spectroscopy.

    PubMed

    Ooka, Hideshi; Wang, Yuanqing; Yamaguchi, Akira; Hatakeyama, Makoto; Nakamura, Shinichiro; Hashimoto, Kazuhito; Nakamura, Ryuhei

    2016-06-01

    Understanding how the four-electron oxidation of water to dioxygen proceeds in different materials is critical to the rational design of efficient catalysts towards artificial photosynthetic systems. Here, using in situ electrochemical evanescent wave spectroscopy under oxygen-evolving conditions, we report two intermediates of iridium oxide (IrOx), which is the most active and stable catalyst characterized to date in acidic medium. The observed potential dependence of the two intermediates indicated that they were associated with different surface sites, and intermediate scavenging experiments using H2O2 provided insight into their role during catalysis. Notably, an Ir(V) species with an absorption maximum at 450 nm was found to mediate the initial two-electron oxidation of water. Inhibition of the Ir(V) species by H2O2, combined with computational modeling, indicates that the accumulation and concurrent spin-state change of the Ir(V) species is a prerequisite for efficient water oxidation by IrOx electrodes. PMID:27197557

  7. Iridium/Iridium Silicide as an Oxidation Resistant Capping Layer for Soft X-ray Mirrors

    SciTech Connect

    Prisbrey, S; Vernon, S

    2004-04-05

    Rust on a sword, tarnish on the silverware, and a loss in reflectivity for soft x-ray mirrors are all caused by oxidation that changes the desired characteristics of a material. Methods to prevent the oxidation have varied over the centuries with the default method of a protective coating being the most common. The protective coating for x-ray mirrors is usually a self-limiting oxidized layer on the surface of the material that stops further oxidation of the material by limiting the diffusion of oxygen to the material underneath.

  8. Iridium-Catalyzed Branch-Selective Hydroarylation of Vinyl Ethers via C-H Bond Activation.

    PubMed

    Ebe, Yusuke; Nishimura, Takahiro

    2015-05-13

    Iridium-catalyzed hydroarylation of vinyl ethers via a directed C-H bond activation of aromatic compounds gave high yields of the corresponding addition products with high branch selectivity. PMID:25928127

  9. Substrate arrays of iridium oxide microelectrodes for in vitro neuronal interfacing.

    PubMed

    Gawad, Shady; Giugliano, Michele; Heuschkel, Marc; Wessling, Börge; Markram, Henry; Schnakenberg, Uwe; Renaud, Philippe; Morgan, Hywel

    2009-01-01

    The design of novel bidirectional interfaces for in vivo and in vitro nervous systems is an important step towards future functional neuroprosthetics. Small electrodes, structures and devices are necessary to achieve high-resolution and target-selectivity during stimulation and recording of neuronal networks, while significant charge transfer and large signal-to-noise ratio are required for accurate time resolution. In addition, the physical properties of the interface should remain stable across time, especially when chronic in vivo applications or in vitro long-term studies are considered, unless a procedure to actively compensate for degradation is provided. In this short report, we describe the use and fabrication of arrays of 120 planar microelectrodes (MEAs) of sputtered Iridium Oxide (IrOx). The effective surface area of individual microelectrodes is significantly increased using electrochemical activation, a procedure that may also be employed to restore the properties of the electrodes as required. The electrode activation results in a very low interface impedance, especially in the lower frequency domain, which was characterized by impedance spectroscopy. The increase in the roughness of the microelectrodes surface was imaged using digital holographic microscopy and electron microscopy. Aging of the activated electrodes was also investigated, comparing storage in saline with storage in air. Demonstration of concept was achieved by recording multiple single-unit spike activity in acute brain slice preparations of rat neocortex. Data suggests that extracellular recording of action potentials can be achieved with planar IrOx MEAs with good signal-to-noise ratios. PMID:19194527

  10. Insights into the oxidative dehydrogenation of amines with nanoparticulate iridium oxide.

    PubMed

    Hammond, Ceri; Schümperli, Martin T; Hermans, Ive

    2013-09-23

    The aerobic oxidation of amines offers a promising route towards many versatile chemical compounds. Within this contribution, we extend our previous investigations of iridium oxide-catalyzed alcohol oxidation to amine substrates. In addition to demonstrating the versatility of this catalyst, particular attention is focused on the mechanisms of the reaction. Herein, we demonstrate that although amines are oxidized slower than the corresponding alcohols, the catalyst has a preference for amine substrates, and oxidizes various amines at turnover frequencies greater than other systems found in the open literature. Furthermore, the competition between double amine dehydrogenation, to yield the corresponding nitrile, and amine-imine coupling, to yield the corresponding coupled imine, has been found to arise from a competitive reaction pathway, and stems from an effect of substrate-to-metal ratio. Finally, the mechanism responsible for the formation of N-benzylidene-1-phenylmethanamine was examined, and attributed to the coupling of free benzyl amine substrate and benzaldehyde, formed in situ through hydrolysis of the primary reaction product, benzyl imine. PMID:23939827

  11. Strongly improved electrochemical cycling durability by adding iridium to electrochromic nickel oxide films.

    PubMed

    Wen, Rui-Tao; Niklasson, Gunnar A; Granqvist, Claes G

    2015-05-13

    Anodically colored nickel oxide (NiO) thin films are of much interest as counter electrodes in tungsten oxide based electrochromic devices such as "smart windows" for energy-efficient buildings. However, NiO films are prone to suffering severe charge density degradation upon prolonged electrochemical cycling, which can lead to insufficient device lifetime. Therefore, a means to improve the durability of NiO-based films is an important challenge at present. Here we report that the incorporation of a modest amount of iridium into NiO films [Ir/(Ir + Ni) = 7.6 atom %] leads to remarkable durability, exceeding 10000 cycles in a lithium-conducting electrolyte, along with significantly improved optical modulation during extended cycling. Structure characterization showed that the face-centered-cubic-type NiO structure remained after iridium addition. Moreover, the crystallinity of these films was enhanced upon electrochemical cycling. PMID:25919917

  12. Flexible Nerve Stimulation Electrode with Iridium Oxide Sputtered on Liquid Crystal Polymer

    PubMed Central

    Wang, Kevin; Liu, Chung-Chiun; Durand, Dominique M.

    2009-01-01

    Current electrode designs require flexible substrates that absorb little moisture and provide large charge injection capability. Sputtered iridium oxide films have superior charge injection capabilities versus noble metals and can adhere to various substrates. Liquid crystal polymers (LCP) have very little water absorption compared to other flexible substrates. Therefore, the combination of sputtered iridium oxide film on liquid crystal polymer substrate was studied using 50Hz, 100μs duration, 10mA biphasic current waveforms for 700 hours at 67°C in bicarbonate buffer saline. Scanning electron micrograph (SEM) analysis showed no delamination and approximately 1% of electrode material was lost to the bicarbonate buffer. The charge injection limit and the cathodic charge storage capacity within the water window were 4.6 +/− 1.0mC/cm2 and 31.5 +/− 6.6mC/cm2 respectively. Additional electrochemical analysis revealed significant charge imbalance attributed to oxygen reduction within the water window. These results, along with the flexible, chemically inert, biocompatible substrate, indicate that sputtered iridium oxide films on liquid crystal polymer could become the method of choice for flexible substrate nerve electrodes. PMID:19224713

  13. The next step in chemical propulsion: Oxide-iridium/rhenium combustion chambers

    NASA Astrophysics Data System (ADS)

    Fortini, Arthur J.; Tuffias, Robert H.

    1999-01-01

    Chemical propulsion systems are currently limited by materials issues. Until recently, the state-of-the-art material for liquid propellant combustion chambers was silicide-coated niobium. However, combustion chamber performance demands have exceeded the capabilities of this material system, requiring development of better materials. The iridium/rhenium combustion chamber, comprising a rhenium structural shell with an iridium inner liner for oxidation protection, represents the current state of the art in high-performance, high temperature, long-life propulsion systems using nitrogen tetroxide/monomethyl hydrazine propellant. However, oxygen/hydrogen (O2/H2) and new ``green'' monopropellants under development to replace hydrazine will be significantly more oxidizing at operating temperature. For these more highly aggressive combustion environments, Ultramet has shown that substantial additional life can be obtained by lining the interior of the combustion chamber with a refractory metal oxide, which functions as a thermal and gas diffusion barrier and provides dramatically increased oxidation resistance. Ultramet has fabricated numerous 22-N (5-lbf) thrust chambers with this oxide-iridium/rhenium architecture that have been hot-fire tested at NASA Lewis Research Center in O2/H2 propellant at mixture ratios of 6 and 16, with steady-state exterior wall temperatures ranging from 2433 to 2899 K, comprising the most severe temperature and oxidizing conditions ever utilized. Of the seven chambers tested to date, three failed due to facility problems, and two never failed. The best-performing chamber was hot-fired for 13,595 seconds (227 minutes; 3.8 hours) and showed no visible signs of degradation. Additional chambers are being fabricated for future testing.

  14. The next step in chemical propulsion: Oxide-iridium/rhenium combustion chambers

    SciTech Connect

    Fortini, Arthur J.; Tuffias, Robert H.

    1999-01-22

    Chemical propulsion systems are currently limited by materials issues. Until recently, the state-of-the-art material for liquid propellant combustion chambers was silicide-coated niobium. However, combustion chamber performance demands have exceeded the capabilities of this material system, requiring development of better materials. The iridium/rhenium combustion chamber, comprising a rhenium structural shell with an iridium inner liner for oxidation protection, represents the current state of the art in high-performance, high temperature, long-life propulsion systems using nitrogen tetroxide/monomethyl hydrazine propellant. However, oxygen/hydrogen (O{sub 2}/H{sub 2}) and new 'green' monopropellants under development to replace hydrazine will be significantly more oxidizing at operating temperature. For these more highly aggressive combustion environments, Ultramet has shown that substantial additional life can be obtained by lining the interior of the combustion chamber with a refractory metal oxide, which functions as a thermal and gas diffusion barrier and provides dramatically increased oxidation resistance. Ultramet has fabricated numerous 22-N (5-lb{sub f}) thrust chambers with this oxide-iridium/rhenium architecture that have been hot-fire tested at NASA Lewis Research Center in O{sub 2}/H{sub 2} propellant at mixture ratios of 6 and 16, with steady-state exterior wall temperatures ranging from 2433 to 2899 K, comprising the most severe temperature and oxidizing conditions ever utilized. Of the seven chambers tested to date, three failed due to facility problems, and two never failed. The best-performing chamber was hot-fired for 13,595 seconds (227 minutes; 3.8 hours) and showed no visible signs of degradation. Additional chambers are being fabricated for future testing.

  15. Iridium in natural waters

    SciTech Connect

    Anbar, A.D.; Wasserburg, G.J.; Papanastassiou, D.A.

    1996-09-13

    Iridium, commonly used as a tracer of extraterrestrial material, was measured in rivers, oceans, and an estuarine environment. The concentration of iridium in the oceans ranges from 3.0 ({+-}1.3) x 10{sup 8} to 5.7 ({+-}0.8) x 10{sup 8} atoms per kilogram. Rivers contain from 17.4 ({+-}0.9) x 10{sup 8} to 92.9 ({+-}2.2) x 10{sup 8} atoms per kilogram and supply more dissolved iridium to the oceans than do extraterrestrial sources. In the Baltic Sea, {approximately}75% of riverine iridium is removed from solution. Iron-manganese oxyhydroxides scavenge iridium under oxidizing conditions, but anoxic environments are not a major sink for iridium. The ocean residence time of iridium is between 2 x 10{sup 3} and 2 x 10{sup 4} years. 32 refs., 3 figs., 1 tab.

  16. Flexible, high-density microphotodiode array with integrated sputtered iridium oxide electrodes for retinal stimulation

    NASA Astrophysics Data System (ADS)

    Yang, Frank; Chang, Mao-Yen; Yang, Chung-Hua; Teng, Chih-Ciao; Fan, Long-Sheng

    2016-01-01

    To assess the charge-injection capacity of the sputtered iridium oxide film (SIROF) electrode on the retinal CMOS image sensor (CIS) chip, a polyimide-based flex device was designed and fabricated to package the retinal CIS chip. The polyimide-flex-based packaging process keeps the surface of photosensors clean, and the measured connection resistance meets the packaging requirement of the low-power retinal CIS chip. The in vitro experimental results show that the small SIROF electrodes can provide a biphasic charge injection per phase of 3.9 nC/ph to achieve the stimulation threshold at a polarization potential of -0.44 V.

  17. Partially oxidized iridium clusters within dendrimers: size-controlled synthesis and selective hydrogenation of 2-nitrobenzaldehyde.

    PubMed

    Higaki, Tatsuya; Kitazawa, Hirokazu; Yamazoe, Seiji; Tsukuda, Tatsuya

    2016-06-01

    Iridium clusters nominally composed of 15, 30 or 60 atoms were size-selectively synthesized within OH-terminated poly(amidoamine) dendrimers of generation 6. Spectroscopic characterization revealed that the Ir clusters were partially oxidized. All the Ir clusters efficiently converted 2-nitrobenzaldehyde to anthranil and 2-aminobenzaldehyde under atmospheric hydrogen at room temperature in toluene via selective hydrogenation of the NO2 group. The selectivity toward 2-aminobenzaldehyde over anthranil was improved with the reduction of the cluster size. The improved selectivity is ascribed to more efficient reduction than intramolecular heterocyclization of a hydroxylamine intermediate on smaller clusters that have a higher Ir(0)-phase population on the surface. PMID:27193739

  18. Identification of an iridium(III) complex with anti-bacterial and anti-cancer activity

    PubMed Central

    Lu, Lihua; Liu, Li-Juan; Chao, Wei-chieh; Zhong, Hai-Jing; Wang, Modi; Chen, Xiu-Ping; Lu, Jin-Jian; Li, Ruei-nian; Ma, Dik-Lung; Leung, Chung-Hang

    2015-01-01

    Group 9 transition metal complexes have been widely explored as therapeutic agents due to their unique geometry, their propensity to undergo ligand exchanges with biomolecules and their diverse steric and electronic properties. These metal complexes can offer distinct modes of action in living organisms compared to carbon-based molecules. In this study, we investigated the antimicrobial and anti-proliferative abilities of a series of cyclometallated iridium(III) complexes. The iridium(III) complex 1 inhibited the growth of S. aureus with MIC and MBC values of 3.60 and 7.19 μM, respectively, indicating its potent bactericidal activity. Moreover, complex 1 also exhibited cytotoxicity against a number of cancer cell lines, with particular potency against ovarian, cervical and melanoma cells. This cyclometallated iridium(III) complex is the first example of a substitutionally-inert, Group 9 organometallic compound utilized as a direct and selective inhibitor of S. aureus. PMID:26416333

  19. C-H activation of ethers by pyridine tethered PCsp3P-type iridium complexes.

    PubMed

    Cui, Peng; Babbini, Dominic C; Iluc, Vlad M

    2016-06-14

    Iridium PCsp3P complexes featuring a novel bis(2-diphenylphosphinophenyl)-2-pyridylmethane ligand (PC(Py)HP) are reported. C-H activation reactions between the dihydride complex [(PC(Py)P)Ir(H)2] and tetrahydrofuran or methyl tert-butyl ether in the presence of a hydrogen acceptor, norbornene (NBE), at ambient temperature led exclusively to the hydrido oxyalkyl complexes, [(PC(Py)P)IrH(C4H7O)] and [(PC(Py)P)IrH(CH2O(t)Bu)], respectively. The internal pyridine donor is important and stabilizes these species by coordination to the iridium center. The coordination of pyridine to the iridium center is labile, however, and its dissociation occurs in the presence of a suitable substrate, as demonstrated by the intramolecular nucleophilic attack of pyridine on a vinylidene intermediate generated from PhC[triple bond, length as m-dash]CH. PMID:27052422

  20. Anodic Deposition of a Robust Iridium-Based Water-Oxidation Catalyst from Organometallic Precursors

    SciTech Connect

    Blakemore, James D; Schley, Nathan D; Olack, G.; Incarvito, Christopher D; Brudvig, Gary W; Crabtree, Robert H

    2011-01-01

    Artificial photosynthesis, modeled on natural light-driven oxidation of water in Photosystem II, holds promise as a sustainable source of reducing equivalents for producing fuels. Few robust water-oxidation catalysts capable of mediating this difficult four-electron, four-proton reaction have yet been described. We report a new method for generating an amorphous electrodeposited material, principally consisting of iridium and oxygen, which is a robust and long-lived catalyst for water oxidation, when driven electrochemically. The catalyst material is generated by a simple anodic deposition from Cp*Ir aqua or hydroxo complexes in aqueous solution. This work suggests that organometallic precursors may be useful in electrodeposition of inorganic heterogeneous catalysts.

  1. Partially oxidized iridium clusters within dendrimers: size-controlled synthesis and selective hydrogenation of 2-nitrobenzaldehyde

    NASA Astrophysics Data System (ADS)

    Higaki, Tatsuya; Kitazawa, Hirokazu; Yamazoe, Seiji; Tsukuda, Tatsuya

    2016-06-01

    Iridium clusters nominally composed of 15, 30 or 60 atoms were size-selectively synthesized within OH-terminated poly(amidoamine) dendrimers of generation 6. Spectroscopic characterization revealed that the Ir clusters were partially oxidized. All the Ir clusters efficiently converted 2-nitrobenzaldehyde to anthranil and 2-aminobenzaldehyde under atmospheric hydrogen at room temperature in toluene via selective hydrogenation of the NO2 group. The selectivity toward 2-aminobenzaldehyde over anthranil was improved with the reduction of the cluster size. The improved selectivity is ascribed to more efficient reduction than intramolecular heterocyclization of a hydroxylamine intermediate on smaller clusters that have a higher Ir(0)-phase population on the surface.Iridium clusters nominally composed of 15, 30 or 60 atoms were size-selectively synthesized within OH-terminated poly(amidoamine) dendrimers of generation 6. Spectroscopic characterization revealed that the Ir clusters were partially oxidized. All the Ir clusters efficiently converted 2-nitrobenzaldehyde to anthranil and 2-aminobenzaldehyde under atmospheric hydrogen at room temperature in toluene via selective hydrogenation of the NO2 group. The selectivity toward 2-aminobenzaldehyde over anthranil was improved with the reduction of the cluster size. The improved selectivity is ascribed to more efficient reduction than intramolecular heterocyclization of a hydroxylamine intermediate on smaller clusters that have a higher Ir(0)-phase population on the surface. Electronic supplementary information (ESI) available. See DOI: 10.1039/c6nr01460g

  2. Synthesis of dendritic iridium nanostructures based on the oriented attachment mechanism and their enhanced CO and ammonia catalytic activities

    NASA Astrophysics Data System (ADS)

    Wang, Chao; Xiao, Guanjun; Sui, Yongming; Yang, Xinyi; Liu, Gang; Jia, Mingjun; Han, Wei; Liu, Bingbing; Zou, Bo

    2014-11-01

    Branched iridium nanodendrites (Ir NDs) have been synthesized by a simple method based on the oriented attachment mechanism. Transmission electron microscopy images reveal the temporal growth process from small particles to NDs. Precursor concentrations and reaction temperatures have a limited effect on the morphology of Ir NDs. Metal oxide and hydroxide-supported Ir NDs exhibit enhanced activity for catalytic CO oxidation. Particularly, the Fe(OH)x-supported Ir NDs catalyst with a 4 wt% Ir loading show superior CO oxidation catalytic activity with a full conversion of CO at 120 °C. Furthermore, compared with Ir NPs and commercial Ir black, Ir NDs exhibit higher activity and stability for ammonia oxidation. The specific activity and mass activity of Ir NDs for ammonia oxidation are 1.7 and 7 times higher than that of Ir NPs. The improved catalytic activities of Ir NDs are attributed not only to their large specific surface area, but also to their considerably high index facets and rich edge and corner atoms. Hence, the obtained Ir NDs provide a promising alternative for direct ammonia fuel cells and proton-exchange membrane fuel cells.Branched iridium nanodendrites (Ir NDs) have been synthesized by a simple method based on the oriented attachment mechanism. Transmission electron microscopy images reveal the temporal growth process from small particles to NDs. Precursor concentrations and reaction temperatures have a limited effect on the morphology of Ir NDs. Metal oxide and hydroxide-supported Ir NDs exhibit enhanced activity for catalytic CO oxidation. Particularly, the Fe(OH)x-supported Ir NDs catalyst with a 4 wt% Ir loading show superior CO oxidation catalytic activity with a full conversion of CO at 120 °C. Furthermore, compared with Ir NPs and commercial Ir black, Ir NDs exhibit higher activity and stability for ammonia oxidation. The specific activity and mass activity of Ir NDs for ammonia oxidation are 1.7 and 7 times higher than that of Ir NPs. The

  3. Characterization of sputtered iridium oxide thin films on planar and laser micro-structured platinum thin film surfaces for neural stimulation applications

    NASA Astrophysics Data System (ADS)

    Thanawala, Sachin

    Electrical stimulation of neurons provides promising results for treatment of a number of diseases and for restoration of lost function. Clinical examples include retinal stimulation for treatment of blindness and cochlear implants for deafness and deep brain stimulation for treatment of Parkinsons disease. A wide variety of materials have been tested for fabrication of electrodes for neural stimulation applications, some of which are platinum and its alloys, titanium nitride, and iridium oxide. In this study iridium oxide thin films were sputtered onto laser micro-structured platinum thin films by pulsed-DC reactive sputtering of iridium metal in oxygen-containing atmosphere, to obtain high charge capacity coatings for neural stimulation applications. The micro-structuring of platinum films was achieved by a pulsed-laser-based technique (KrF excimer laser emitting at lambda=248nm). The surface morphology of the micro-structured films was studied using different surface characterization techniques. In-vitro biocompatibility of these laser micro-structured films coated with iridium oxide thin films was evaluated using cortical neurons isolated from rat embryo brain. Characterization of these laser micro-structured films coated with iridium oxide, by cyclic voltammetry and impedance spectroscopy has revealed a considerable decrease in impedance and increase in charge capacity. A comparison between amorphous and crystalline iridium oxide thin films as electrode materials indicated that amorphous iridium oxide has significantly higher charge capacity and lower impedance making it preferable material for neural stimulation application. Our biocompatibility studies show that neural cells can grow and differentiate successfully on our laser micro-structured films coated with iridium oxide. This indicates that reactively sputtered iridium oxide (SIROF) is biocompatible.

  4. Long Life Testing of Oxide-Coated Iridium/Rhenium Rockets

    NASA Technical Reports Server (NTRS)

    Reed, Brian D.

    1995-01-01

    22-N class rockets, composed of a rhenium (Re) substrate, an iridium (Ir) coating, and an additional composite coating consisting of Ir and a ceramic oxide, were tested on gaseous oxygen/gaseous hydrogen (GO2/GH2) propellants. Two rockets were tested, one for nearly 39 hours at a nominal mixture ratio (MR) of 4.6 and chamber pressure (Pc) of 469 kPa, and the other for over 13 hours at a nominal MR of 5.8 and 621 kPa Pc. Four additional Ir/Re rockets, with a composite Ir-oxide coating fabricated using a modified process, were also tested, including one for 1.3 hours at a nominal MR of 16.7 and Pc of 503 kPa. The long lifetimes demonstrated on low MR GO2/GH2 suggest greatly extended chamber lifetimes (tens of hours) in the relatively low oxidizing combustion environments of Earth storable propellants. The oxide coatings could also serve as a protective coating in the near injector region, where a still-mixing flowfield may cause degradation of the Ir layer. Operation at MR close to 17 suggests that oxide-coated Ir/Re rockets could be used in severely oxidizing combustion environments, such as high MR GO2/GH2, oxygen/hydrocarbon, and liquid gun propellants.

  5. Nd2K2IrO7 and Sm2K2IrO7: Iridium(VI) Oxides Prepared under Ambient Pressure

    SciTech Connect

    Mugavero, III, S.; Smith, M; Yoon, W; zur Loye, H

    2009-01-01

    The most-oxidized iridium oxides known to date are prepared in a hydroxide flux under normal pressure. They contain iridium centers exclusively in the +VI oxidation state and are characterized crystallographically. The picture shows the structure of the Ln2K2IrO7 (Ln=Nd, Sm) and its structural components: IrO6 octahedra (black), KO10 polyhedra (beige), LnO10 polyhedra (blue).

  6. Iridium Oxide Nanotube Electrodes for Highly Sensitive and Prolonged Intracellular Measurement of Action Potentials

    PubMed Central

    Lin, Ziliang Carter; Xie, Chong; Osakada, Yasuko; Cui, Yi; Cui, Bianxiao

    2014-01-01

    Intracellular recording of action potentials is important to understand electrically-excitable cells. Recently, vertical nanoelectrodes have been developed to achieve highly sensitive, minimally invasive, and large scale intracellular recording. It has been demonstrated that the vertical geometry is crucial for the enhanced signal detection. Here we develop nanoelectrodes made up of nanotubes of iridium oxide. When cardiomyocytes are cultured upon those nanotubes, the cell membrane not only wraps around the vertical tubes but also protrudes deep into the hollow center. We show that this geometry enhances cell-electrode coupling and results in measuring much larger intracellular action potentials. The nanotube electrodes afford much longer intracellular access and are minimally invasive, making it possible to achieve stable recording up to an hour in a single session and more than 8 days of consecutive daily recording. This study suggests that the electrode performance can be significantly improved by optimizing the electrode geometry. PMID:24487777

  7. Modulated helical metals at magnetic domain walls of pyrochlore iridium oxides

    NASA Astrophysics Data System (ADS)

    Yamaji, Youhei; Imada, Masatoshi

    2016-05-01

    Spontaneous symmetry breakings, metal-insulator transitions, and transport properties of magnetic-domain-wall states in pyrochlore iridium oxides are studied by employing a symmetry-adapted effective Hamiltonian with a slab perpendicular to the (111) direction of the pyrochlore structure. Emergent metallic domain wall, which has an unconventional topological nature with a controllable and mobile metallic layer, is shown to host Fermi surfaces with modulated helical spin textures resembling Rashba metals. The helical nature of the domain-wall Fermi surfaces is experimentally detectable by anomalous Hall conductivity, circular dichroism, and optical Hall conductivity under external magnetic fields. Possible applications of the domain-wall metals to spin-current generation and "half-metallic" conduction are also discussed.

  8. Noisy CO oxidation on Iridium(111) surfaces. Experiments explained by theory under realistic assumptions

    NASA Astrophysics Data System (ADS)

    Wehner, S.; Cisternas, J.; Descalzi, O.; Küppers, J.

    2014-01-01

    Noise is an everywhere phenomenon. Its influence could be described theoretically quite easily, but is hard to measure in an experiment. Catalytic reactions on surfaces can be described by nonlinear reaction-diffusion equations. For one of such surface reactions - CO oxidation on Iridium(111) surfaces - the probability distribution of CO2 rates around the mean value - showing the influence of noise - could be measured directly in a ultra high vacuum (UHV) experiment. This opens the way to address such a fundamental phenomenon like noise by all three modern methods of physics - experimental, computational and analytical. We show the measured effect of colored noise on a bistable surface reaction and explain all observations directly with the underlying theoretical description - the Langmuir-Hinshelwood reaction scheme - by solving the equations under realistic assumptions. It is a great pleasure to dedicate this work to Prof. Dr. Helmut R. Brand on the occasion of his 60th birthday.

  9. Sol-Gel Deposition of Iridium Oxide for Biomedical Micro-Devices

    PubMed Central

    Nguyen, Cuong M.; Rao, Smitha; Yang, Xuesong; Dubey, Souvik; Mays, Jeffrey; Cao, Hung; Chiao, Jung-Chih

    2015-01-01

    Flexible iridium oxide (IrOx)-based micro-electrodes were fabricated on flexible polyimide substrates using a sol-gel deposition process for utilization as integrated pseudo-reference electrodes for bio-electrochemical sensing applications. The fabrication method yields reliable miniature on-probe IrOx electrodes with long lifetime, high stability and repeatability. Such sensors can be used for long-term measurements. Various dimensions of sol-gel iridium oxide electrodes including 1 mm × 1 mm, 500 μm × 500 μm, and 100 μm × 100 μm were fabricated. Sensor longevity and pH dependence were investigated by immersing the electrodes in hydrochloric acid, fetal bovine serum (FBS), and sodium hydroxide solutions for 30 days. Less pH dependent responses, compared to IrOx electrodes fabricated by electrochemical deposition processes, were measured at 58.8 ± 0.4 mV/pH, 53.8 ± 1.3 mV/pH and 48 ± 0.6 mV/pH, respectively. The on-probe IrOx pseudo-reference electrodes were utilized for dopamine sensing. The baseline responses of the sensors were higher than the one using an external Ag/AgCl reference electrode. Using IrOx reference electrodes integrated on the same probe with working electrodes eliminated the use of cytotoxic Ag/AgCl reference electrode without loss in sensitivity. This enables employing such sensors in long-term recording of concentrations of neurotransmitters in central nervous systems of animals and humans. PMID:25686309

  10. Synthesis of dendritic iridium nanostructures based on the oriented attachment mechanism and their enhanced CO and ammonia catalytic activities.

    PubMed

    Wang, Chao; Xiao, Guanjun; Sui, Yongming; Yang, Xinyi; Liu, Gang; Jia, Mingjun; Han, Wei; Liu, Bingbing; Zou, Bo

    2014-12-21

    Branched iridium nanodendrites (Ir NDs) have been synthesized by a simple method based on the oriented attachment mechanism. Transmission electron microscopy images reveal the temporal growth process from small particles to NDs. Precursor concentrations and reaction temperatures have a limited effect on the morphology of Ir NDs. Metal oxide and hydroxide-supported Ir NDs exhibit enhanced activity for catalytic CO oxidation. Particularly, the Fe(OH)x-supported Ir NDs catalyst with a 4 wt% Ir loading show superior CO oxidation catalytic activity with a full conversion of CO at 120 °C. Furthermore, compared with Ir NPs and commercial Ir black, Ir NDs exhibit higher activity and stability for ammonia oxidation. The specific activity and mass activity of Ir NDs for ammonia oxidation are 1.7 and 7 times higher than that of Ir NPs. The improved catalytic activities of Ir NDs are attributed not only to their large specific surface area, but also to their considerably high index facets and rich edge and corner atoms. Hence, the obtained Ir NDs provide a promising alternative for direct ammonia fuel cells and proton-exchange membrane fuel cells. PMID:25366566

  11. A Rhodium Catalyst Superior to Iridium Congeners for Enantioselective Radical Amination Activated by Visible Light.

    PubMed

    Shen, Xiaodong; Harms, Klaus; Marsch, Michael; Meggers, Eric

    2016-06-27

    A bis-cyclometalated rhodium(III) complex catalyzes a visible-light-activated enantioselective α-amination of 2-acyl imidazoles with up to 99 % yield and 98 % ee. The rhodium catalyst is ascribed a dual function as a chiral Lewis acid and, simultaneously, as a light-activated smart initiator of a radical-chain process through intermediate aminyl radicals. Notably, related iridium-based photoredox catalysts reported before were unsuccessful in this enantioselective radical C-N bond formation. The surprising preference for rhodium over iridium is attributed to much faster ligand-exchange kinetics of the rhodium complexes involved in the catalytic cycle, which is crucial to keep pace with the highly reactive and thus short-lived nitrogen-centered radical intermediate. PMID:27145893

  12. Neutron activation determination of iridium, gold, platinum, and silver in geologic samples

    USGS Publications Warehouse

    Millard, H.T., Jr.

    1987-01-01

    Low-level methods for the determination of iridium and other noble metals have become increasingly important in recent years due to interest in locating abundance anomalies associated with the Cretaceous and Tertiary (K-T) boundary. Typical iridium anomalies are in the range of 1 to 100 ??g/kg (ppb). Thus methods with detection limits near 0.1 ??g/kg should be adequate to detect K-T boundary anomalies. Radiochemical neutron activation analysis methods continue to be required although instrumental neutron activation analysis techniques employing elaborate gamma-counters are under development. In the procedure developed in this study samples irradiated in the epithermal neutron facility of the U. S. Geological Survey TRIGA Reactor (Denver, Colorado) are treated with a mini-fire assay technique. The iridium, gold, and silver are collected in a 1-gram metallic lead button. Primary contaminants at this stage are arsenic and antimony. These can be removed by heating the button with a mixture of sodium perioxide and sodium hydroxide. The resulting 0.2-gram lead bead is counted in a Compton suppression spectrometer. Carrier yields are determined by reirradiation of the lead beads. This procedure has been applied to the U.S.G.S. Standard Rock PCC-1 and samples from K-T boundary sites in the Western Interior of North America. ?? 1987 Akade??miai Kiado??.

  13. Nanocomposites of iridium oxide and conducting polymers as electroactive phases in biological media.

    PubMed

    Moral-Vico, J; Sánchez-Redondo, S; Lichtenstein, M P; Suñol, C; Casañ-Pastor, N

    2014-05-01

    Much effort is currently devoted to implementing new materials in electrodes that will be used in the central nervous system, either for functional electrostimulation or for tests on nerve regeneration. Their main aim is to improve the charge capacity of the electrodes, while preventing damaging secondary reactions, such as peroxide formation, occurring while applying the electric field. Thus, hybrids may represent a new generation of materials. Two novel hybrid materials are synthesized using three known biocompatible materials tested in the neural system: polypyrrole (PPy), poly(3,4-ethylenedioxythiophene) (PEDOT) and iridium oxide (IrO2). In particular, PPy-IrO2 and PEDOT-IrO2 hybrid nanocomposite materials are prepared by chemical polymerization in hydrothermal conditions, using IrO2 as oxidizing agent. The reaction yields a significant ordered new hybrid where the conducting polymer is formed around the IrO2 nanoparticles, encapsulating them. Scanning electron microscopy and backscattering techniques show the extent of the encapsulation. Both X-ray photoelectron and Fourier transform infrared spectroscopies identify the components of the phases, as well as the absence of impurities. Electrochemical properties of the final phases in powder and pellet form are evaluated by cyclic voltammetry. Biocompatibility is tested with MTT toxicity tests using primary cultures of cortical neurons grown in vitro for 6 and 9days. PMID:24394636

  14. Label-free impedimetric aptasensor for ochratoxin-A detection using iridium oxide nanoparticles.

    PubMed

    Rivas, Lourdes; Mayorga-Martinez, Carmen C; Quesada-González, Daniel; Zamora-Gálvez, Alejandro; de la Escosura-Muñiz, Alfredo; Merkoçi, Arben

    2015-01-01

    In this article, a novel aptasensor for ochratoxin A (OTA) detection based on a screen-printed carbon electrode (SPCE) modified with polythionine (PTH) and iridium oxide nanoparticles (IrO2 NPs) is presented. The electrotransducer surface is modified with an electropolymerized film of PTH followed by the assembly of IrO2 NPs on which the aminated aptamer selective to OTA is exchanged with the citrate ions surrounding IrO2 NPs via electrostatic interactions with the same surface. Electrochemical impedance spectroscopy (EIS) in the presence of the [Fe(CN)6](-3/-4) redox probe is employed to characterize each step in the aptasensor assay and also for label-free detection of OTA in a range between 0.01 and 100 nM, obtaining one of the lowest limits of detection reported so far for label-free impedimetric detection of OTA (14 pM; 5.65 ng/kg). The reported system also exhibits a high reproducibility, a good performance with a white wine sample, and an excellent specificity against another toxin present in such sample. PMID:25901535

  15. Lewis Base Activation of Silyl Acetals: Iridium-Catalyzed Reductive Horner-Wadsworth-Emmons Olefination.

    PubMed

    Dakarapu, Udaya Sree; Bokka, Apparao; Asgari, Parham; Trog, Gabriela; Hua, Yuanda; Nguyen, Hiep H; Rahman, Nawal; Jeon, Junha

    2015-12-01

    A Lewis base promoted deprotonative pronucleophile addition to silyl acetals has been developed and applied to the iridium-catalyzed reductive Horner-Wadsworth-Emmons (HWE) olefination of esters and the chemoselective reduction of the resulting enoates. Lewis base activation of silyl acetals generates putative pentacoordinate silicate acetals, which fragment into aldehydes, silanes, and alkoxides in situ. Subsequent deprotonative metalation of phosphonate esters followed by HWE with aldehydes furnishes enoates. This operationally convenient, mechanistically unique protocol converts the traditionally challenging aryl, alkenyl, and alkynyl esters to homologated enoates at room temperature within a single vessel. PMID:26566189

  16. Iridium complexes containing mesoionic C donors: selective C(sp3)-H versus C(sp2)-H bond activation, reactivity towards acids and bases, and catalytic oxidation of silanes and water.

    PubMed

    Petronilho, Ana; Woods, James A; Mueller-Bunz, Helge; Bernhard, Stefan; Albrecht, Martin

    2014-11-24

    Metalation of a C2-methylated pyridylimidazolium salt with [IrCp*Cl2]2 affords either an ylidic complex, resulting from C(sp(3))-H bond activation of the C2-bound CH3 group if the metalation is performed in the presence of a base, such as AgO2 or Na2CO3, or a mesoionic complex via cyclometalation and thermally induced heterocyclic C(sp(2))-H bond activation, if the reaction is performed in the absence of a base. Similar cyclometalation and complex formation via C(sp(2))-H bond activation is observed when the heterocyclic ligand precursor consists of the analogous pyridyltriazolium salt, that is, when the metal bonding at the C2 position is blocked by a nitrogen rather than a methyl substituent. Despite the strongly mesoionic character of both the imidazolylidene and the triazolylidene, the former reacts rapidly with D(+) and undergoes isotope exchange at the heterocyclic C5 position, whereas the triazolylidene ligand is stable and only undergoes H/D exchange under basic conditions, where the imidazolylidene is essentially unreactive. The high stability of the Ir-C bond in aqueous solution over a broad pH range was exploited in catalytic water oxidation and silane oxidation. The catalytic hydrosilylation of ketones proceeds with turnover frequencies as high as 6,000 h(-1) with both the imidazolylidene and the triazolylidene system, whereas water oxidation is enhanced by the stronger donor properties of the imidazol-4-ylidene ligands and is more than three times faster than with the triazolylidene analogue. PMID:25302630

  17. Si-H activation in an iridium nitrido complex--a mechanistic and theoretical study.

    PubMed

    Sieh, Daniel; Burger, Peter

    2013-03-13

    Si-H activation in triethyl- and triarylsilanes by a square-planar pyridine-diimine iridium complex with a terminal nitrido unit leads to the corresponding silyl amido complexes, which were unambiguously characterized by X-ray crystallography. Based on detailed combined kinetic and theoretical studies (DFT), direct addition of the Si-H bond to the iridium nitrido unit is proposed. The electronic propensities of the transition states for the Si-H activation were probed with a Hammett series of para-substituted triarylsilanes HSi(C6H5)2(4-C6H4-X). Based on the combination of experimental and theoretical studies, two independent pathways for this process are proposed, which point toward an ambiphilic propensity of the nitrido unit. Alternative pathways and the charge transfer in the transition states were also investigated. Furthermore, the barriers for the related H-H and C-H activation processes in dihydrogen and methane were analyzed. PMID:23431955

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

    SciTech Connect

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

    2014-12-08

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

  19. Enhancement of activity of RuSex electrocatalyst by modification with nanostructured iridium towards more efficient reduction of oxygen

    NASA Astrophysics Data System (ADS)

    Dembinska, Beata; Kiliszek, Malgorzata; Elzanowska, Hanna; Pisarek, Marcin; Kulesza, Pawel J.

    2013-12-01

    Electrocatalytic activity of carbon (Vulcan XC-72) supported selenium-modified ruthenium, RuSex/C, nanoparticles for reduction of oxygen was enhanced through intentional decoration with iridium nanostructures (dimensions, 2-3 nm). The catalytic materials were characterized in oxygenated 0.5 mol dm-3 H2SO4 using cyclic and rotating ring disk voltammetric techniques as well as using transmission electron microscopy and scanning electron microscopy equipped with X-ray dispersive analyzer. Experiments utilizing gas diffusion electrode aimed at mimicking conditions existing in the low-temperature fuel cell. Upon application of our composite catalytic system, the reduction of oxygen proceeded at more positive potentials, and higher current densities were observed when compared to the behavior of the simple iridium-free system (RuSex/C) investigated under the analogous conditions. The enhancement effect was more pronounced than that one would expect from simple superposition of voltammetric responses for the oxygen reduction at RuSex/C and iridium nanostructures studied separately. Nanostructured iridium acted here as an example of a powerful catalyst for the reduction of H2O2 (rather than O2) and, when combined with such a moderate catalyst as ruthenium-selenium (for O2 reduction), it produced an integrated system of increased electrocatalytic activity in the oxygen reduction process. The proposed system retained its activity in the presence of methanol that could appear in a cathode compartment of alcohol fuel cell.

  20. Contrasting Anticancer Activity of Half-Sandwich Iridium(III) Complexes Bearing Functionally Diverse 2-Phenylpyridine Ligands

    PubMed Central

    2015-01-01

    We report the synthesis, characterization, and antiproliferative activity of 15 iridium(III) half-sandwich complexes of the type [(η5-Cp*)Ir(2-(R′-phenyl)-R-pyridine)Cl] bearing either an electron-donating (−OH, −CH2OH, −CH3) or electron-withdrawing (−F, −CHO, −NO2) group at various positions on the 2-phenylpyridine (2-PhPy) chelating ligand giving rise to six sets of structural isomers. The X-ray crystal structures of [(η5-Cp*)Ir(2-(2′-fluorophenyl)pyridine)Cl] (1) and [(η5-Cp*)Ir(2-(4′-fluorophenyl)pyridine)Cl] (2) exhibit the expected “piano-stool” configuration. DFT calculations showed that substituents caused only localized effects on the electrostatic potential surface of the chelating 2-PhPy ligand of the complexes. Hydrolysis of all complexes is rapid, but readily reversed by addition of NaCl. The complexes show preferential binding to 9-ethylguanine over 9-methyladenine and are active catalysts for the oxidation of NADH to NAD+. Antiproliferative activity experiments in A2780 ovarian, MCF-7 breast, A549 lung, and HCT116 colon cancer cell lines showed IC50 values ranging from 1 to 89 μM, with the most potent complex, [(η5-Cp*)Ir(2-(2′-methylphenyl)pyridine)Cl] (13) (A2780 IC50 = 1.18 μM), being 10× more active than the parent, [(η5-Cp*)Ir(2-phenylpyridine)Cl], and 2× more active than [(η5-CpxPh)Ir(2-phenylpyridine)Cl]. Intriguingly, contrasting biological activities are observed between structural isomers despite exhibiting similar chemical reactivity. For pairs of structural isomers both the nature and position of the functional group can affect the hydrophobicity of the complex. An increase in hydrophobicity resulted in enhanced cellular-iridium accumulation in A2780 ovarian cells, which generally gave rise to an increase in potency. The structural isomers [(η5-Cp*)Ir(2-(4′-fluorophenyl)pyridine)Cl] (2) and [(η5-Cp*)Ir(2-phenyl-5-fluoropyridine)Cl] (4) preferentially localized in the cytosol > membrane and particulate

  1. Oxidation and β-Alkylation of Alcohols Catalysed by Iridium(I) Complexes with Functionalised N-Heterocyclic Carbene Ligands.

    PubMed

    Jiménez, M Victoria; Fernández-Tornos, Javier; Modrego, F Javier; Pérez-Torrente, Jesús J; Oro, Luis A

    2015-12-01

    The borrowing hydrogen methodology allows for the use of alcohols as alkylating agents for CC bond forming processes offering significant environmental benefits over traditional approaches. Iridium(I)-cyclooctadiene complexes having a NHC ligand with a O- or N-functionalised wingtip efficiently catalysed the oxidation and β-alkylation of secondary alcohols with primary alcohols in the presence of a base. The cationic complex [Ir(NCCH3 )(cod)(MeIm(2- methoxybenzyl))][BF4 ] (cod=1,5-cyclooctadiene, MeIm=1-methylimidazolyl) having a rigid O-functionalised wingtip, shows the best catalyst performance in the dehydrogenation of benzyl alcohol in acetone, with an initial turnover frequency (TOF0 ) of 1283 h(-1) , and also in the β-alkylation of 2-propanol with butan-1-ol, which gives a conversion of 94 % in 10 h with a selectivity of 99 % for heptan-2-ol. We have investigated the full reaction mechanism including the dehydrogenation, the cross-aldol condensation and the hydrogenation step by DFT calculations. Interestingly, these studies revealed the participation of the iridium catalyst in the key step leading to the formation of the new CC bond that involves the reaction of an O-bound enolate generated in the basic medium with the electrophilic aldehyde. PMID:26493780

  2. Impact of metal nano layer thickness on tunneling oxide and memory performance of core-shell iridium-oxide nanocrystals

    SciTech Connect

    Banerjee, W.; Maikap, S.; Tien, T.-C.; Li, W.-C.; Yang, J.-R.

    2011-10-01

    The impact of iridium-oxide (IrO{sub x}) nano layer thickness on the tunneling oxide and memory performance of IrO{sub x} metal nanocrystals in an n-Si/SiO{sub 2}/Al{sub 2}O{sub 3}/IrO{sub x}/Al{sub 2}O{sub 3}/IrO{sub x} structure has been investigated. A thinner (1.5 nm) IrO{sub x} nano layer has shown better memory performance than that of a thicker one (2.5 nm). Core-shell IrO{sub x} nanocrystals with a small average diameter of 2.4 nm and a high density of {approx}2 x 10{sup 12}/cm{sup 2} have been observed by scanning transmission electron microscopy. The IrO{sub x} nanocrystals are confirmed by x-ray photoelectron spectroscopy. A large memory window of 3.0 V at a sweeping gate voltage of {+-}5 V and 7.2 V at a sweeping gate voltage of {+-} 8 V has been observed for the 1.5 nm-thick IrO{sub x} nano layer memory capacitors with a small equivalent oxide thickness of 8 nm. The electrons and holes are trapped in the core and annular regions of the IrO{sub x} nanocrystals, respectively, which is explained by Gibbs free energy. High electron and hole-trapping densities are found to be 1.5 x 10{sup 13}/cm{sup 2} and 2 x 10{sup 13}/cm{sup 2}, respectively, due to the small size and high-density of IrO{sub x} nanocrystals. Excellent program/erase endurance of >10{sup 6} cycles and good retention of 10{sup 4} s with a good memory window of >1.2 V under a small operation voltage of {+-} 5 V are obtained. A large memory size of >10 Tbit/sq. in. can be designed by using the IrO{sub x} nanocrystals. This study is not only important for the IrO{sub x} nanocrystal charge-trapping memory investigation but it will also help to design future metal nanocrystal flash memory.

  3. Control of the iridium oxidation state in the hollandite iridate solid solution K(1-x)Ir4O8.

    PubMed

    Talanov, Artem; Phelan, W Adam; Kelly, Zachary A; Siegler, Maxime A; McQueen, Tyrel M

    2014-05-01

    The synthesis and physical properties of the K(1-x)Ir4O8 (0 ≤ x ≤ 0.7) solid solution are reported. The structure of KIr4O8, solved with single-crystal X-ray diffraction at T = 110 K, is found to be tetragonal, space group I4/m, with a = 10.0492(3) Å and c = 3.14959(13) Å. A highly anisotropic displacement parameter is found for the potassium cation. Density functional theory calculations suggest that this anisotropy is due to a competition between atomic size and bond valence. KIr4O8 has a significant electronic contribution to the specific heat, γ = 13.9 mJ mol-Ir(-1) K(-2), indicating an effective carrier mass of m*/me ≈ 10. Further, there is a magnetic-field-dependent upturn in the specific heat at T < 3 K, suggestive of a magnetically sensitive phase transition below T < 1.8 K. Resistivity and magnetization measurements show that both end-members of the solid solution, KIr4O8 and K(1-x)Ir4O8 (x ≈ 0.7), are metallic, with no significant trends in the temperature-independent contributions to the magnetization. These results are interpreted and discussed in the context of the importance of the variability of the oxidation state of iridium. The differences in physical properties between members of the K(1-x)Ir4O8 (0 ≤ x ≤ 0.7) series are small and appear to be insensitive to the iridium oxidation state. PMID:24739024

  4. The effect of the addition of colloidal iridium oxide into sol-gel obtained titanium and ruthenium oxide coatings on titanium on their electrochemical properties.

    PubMed

    Panić, Vladimir V; Dekanski, Aleksandar B; Mitrić, Miodrag; Milonjić, Slobodan K; Misković-Stanković, Vesna B; Nikolić, Branislav Z

    2010-07-21

    Electrochemical properties of sol-gel processed Ti(0.6)Ir(0.4)O(2) and Ti(0.6)Ru(0.3)Ir(0.1)O(2) coatings on titanium substrate were investigated using cyclic voltammetry, polarization measurements and electrochemical impedance spectroscopy and compared to the properties of Ti(0.6)Ru(0.4)O(2) coating. The role of iridium oxide in the improvement of the electrocatalytic, capacitive and stability properties of titanium anodes activated by a RuO(2)-TiO(2) coating is discussed. The oxide sols were prepared by forced hydrolysis of the metal chlorides. The characterization by dynamic light scattering and X-ray diffraction showed that polydisperse oxide sols were obtained with the particles tending to form agglomerates. The presence of IrO(2) causes a suppression of the X-ray diffraction peaks of TiO(2) and RuO(2) in the sol-gel prepared Ti(0.6)Ir(0.4)O(2) and Ti(0.6)Ru(0.3)Ir(0.1)O(2) coatings. The IrO(2)-containing coatings had an enhanced charge storage ability and activity for the oxygen evolution reaction (OER) in comparison to Ti(0.6)Ru(0.4)O(2) coating. The voltammogram of the Ti(0.6)Ir(0.4)O(2)/Ti electrode showed well-resolved peaks related to Ir redox transitions, which are responsible for the enhanced charge storage ability of IrO(2)-containing coatings. Redox transitions of Ir were also registered in the high-frequency domain of the ac impedance spectra of the coatings as a semicircle with characteristics insensitive to the electrolyte composition and to the electrode potential prior to OER. However, the semicircle characteristics were different for the two IrO(2)-containing coatings, as well as at potentials outside the OER in comparison to those at which the OER occurs. PMID:20544088

  5. Epitaxially stabilized iridium spinel oxide without cations in the tetrahedral site

    NASA Astrophysics Data System (ADS)

    Kuriyama, Hiromichi; Matsuno, Jobu; Niitaka, Seiji; Uchida, Masaya; Hashizume, Daisuke; Nakao, Aiko; Sugimoto, Kunihisa; Ohsumi, Hiroyuki; Takata, Masaki; Takagi, Hidenori

    2010-05-01

    Single-crystalline thin film of an iridium dioxide polymorph Ir2O4 has been fabricated by the pulsed laser deposition of LixIr2O4 precursor and the subsequent Li-deintercalation using soft chemistry. Ir2O4 crystallizes in a spinel (AB2O4) without A cations in the tetrahedral site, which is isostructural to λ-MnO2. Ir ions form a pyrochlore sublattice, which is known to give rise to a strong geometrical frustration. This Ir spinel was found to be a narrow gap insulator, in remarkable contrast to the metallic ground state of rutile-type IrO2. We argue that an interplay of a strong spin-orbit coupling and a Coulomb repulsion gives rise to an insulating ground state as in a layered perovskite Sr2IrO4.

  6. Magnetic symmetries in neutron and resonant x-ray Bragg diffraction patterns of four iridium oxides

    NASA Astrophysics Data System (ADS)

    Lovesey, S. W.; Khalyavin, D. D.; Manuel, P.; Chapon, L. C.; Cao, G.; Qi, T. F.

    2012-12-01

    The magnetic properties of Sr2IrO4, Na2IrO3, Sr3Ir2O7 and CaIrO3 are discussed, principally in the light of experimental data in recent literature for Bragg intensities measured in x-ray diffraction with enhancement at iridium L-absorption edges. The electronic structure factors we report, which incorporate parity-even and acentric entities, serve the immediate purpose of making full use of crystal and magnetic symmetry to refine our knowledge of the magnetic properties of the four iridates from resonant x-ray diffraction data. They also offer a platform on which to interpret future investigations, using dichroic signals, resonant x-ray diffraction and neutron diffraction, for example, as well as ab initio calculations of electronic structure. Unit-cell structure factors, suitable for x-ray Bragg diffraction enhanced by an electric dipole-electric dipole (E1-E1) event, reveal exactly which iridium multipoles are visible, e.g., a magnetic dipole parallel to the crystal c-axis (z-axis) and an electric quadrupole with yz-like symmetry in the specific case of CaIrO3. Magnetic space-groups are assigned to Sr2IrO4, Sr3Ir2O7 and CaIrO3, namely, PIcca, PAban and Cm‧cm‧, respectively, in the Belov-Neronova-Smirnova notation. The assignment for Sr2IrO4 is possible because of our new high-resolution neutron diffraction data, gathered on a powder sample. In addition, the new data are used to show that the ordered magnetic moment of an Ir4+ ion in Sr2IrO4 does not exceed 0.29(4) μB. Na2IrO3 has two candidate magnetic space-groups that are not resolved with currently available resonant x-ray data.

  7. Analysis of diffusion-controlled stochastic events of iridium oxide single nanoparticle collisions by scanning electrochemical microscopy.

    PubMed

    Kwon, Seong Jung; Bard, Allen J

    2012-04-25

    We investigated the electrochemical detection of single iridium oxide nanoparticle (IrO(x) NP) collisions at the NaBH(4)-treated Pt ultramicroelectrode (UME) in a scanning electrochemical microscope (SECM) over an insulating surface. The NP collision events were monitored by observing the electrocatalytic water oxidation reaction at potentials where it does not take place on the Pt UME. These collisions occurred stochastically, resulting in a transient response ("blip") for each collision. The frequency of the collisions is proportional to the flux of NPs to the UME tip, and thus equivalent to the SECM current. A plot of collision frequency versus distance followed the theoretical approach curve behavior for negative feedback for a high concentration of mediator, demonstrating that the collisions were diffusion-controlled and that single-particle measurements of mass transport are equivalent to ensemble ones. When the SECM was operated with a Pt substrate at the same potential as the tip, the behavior followed that expected of the shielding mode. These studies and additional ones result in a model where the IrO(x) NP collision on the Pt UME is adsorptive, with oxygen produced by the catalyzed water oxidation causing a current decay. This results in a blip current response, with the current decay diminished in the presence of the oxygen scavenger, sulfite ion. Random walk and theoretical bulk simulations agreed with the proposed mechanism of IrO(x) NP collision, adsorption, and subsequent deactivation. PMID:22452267

  8. Iridium-catalyzed anti-diastereo- and enantioselective carbonyl (trimethylsilyl)allylation from the alcohol or aldehyde oxidation level.

    PubMed

    Han, Soo Bong; Gao, Xin; Krische, Michael J

    2010-07-01

    Using the ortho-cyclometalated pi-allyl iridium precatalyst (R)-I derived from [Ir(cod)Cl](2), 4-cyano-3-nitrobenzoic acid, (R)-SEGPHOS, and allyl acetate, enantioselective transfer hydrogenation of alpha-(trimethylsilyl)allyl acetate in the presence of aldehydes 2a-i mediated by 2-propanol delivers products of (trimethylsilyl)allylation 4a-i in good isolated yields and with exceptional levels of anti-diastereoselectivity and enantioselectivity (90-99% ee). In the absence of 2-propanol, but under otherwise identical reaction conditions, carbonyl (trimethylsilyl)allylation is achieved directly from the alcohol oxidation level to furnish an equivalent set of adducts 4a-i with roughly equivalent isolated yields and stereoselectivities. To evaluate the synthetic utility of the reaction products 4a-i, adduct 4g was converted to the 1,4-ene-diol 5g via dioxirane-mediated oxidative desilylation with allylic transposition, the allylic alcohol 6g via protodesilylation with allylic transposition, and the gamma-lactam 7g via chlorosulfonyl isocyanate-mediated cycloaddition. PMID:20540509

  9. Anisotropic magnetic interactions in 5d iridium oxides by many-body quantum chemistry calculations

    NASA Astrophysics Data System (ADS)

    Katukuri, Vamshi M.; Nishimoto, Satoshi; Yushankhai, Viktor; Rousochatzakis, Ioannis; Hozoi, Liviu; van den Brink, Jeroen

    2014-03-01

    Ir 5d5 oxides are being actively studied due to the realization of novel spin-orbit coupled jeff ~ 1/2 ground states. One remarkable feature in these compounds is the highly anisotropic magnetic interactions, orders of magnitude stronger than in 3d oxides. We address the nature of the anisotropic exchange in the 2D honeycomb (Na/Li)2IrO3 ((Na/Li)213) and square-lattice (Sr/Ba)2IrO4 ((Sr/Ba)213) iridates, by ab initio multireference configuration-interaction calculations on large embedded clusters. For Na213 we find that the Kitaev term is ferromagnetic and defines the dominant energy scale while the nearest-neighbor Heisenberg contribution is antiferromagnetic. Although Li213 is structurally similar, we predict quite different set of interaction parameters in Li213. We further analyze the magnetic order and the essential differences between these two materials by exact diagonalization and density-matrix renormalization-group calculations that additionally include 2nd and 3rd neighbor couplings. Sizable symmetric anisotropic interactions are also computed for Ba214. From the ab initio data, the relevant in-plane spin model for Ba214 turns out to be a Heisenberg-compass effective model. We finally discuss the Dzyaloshinskii-Moriya exchange in Sr214.

  10. Synthesis, characterization and catalytic activity of saturated and unsaturated N-heterocyclic carbene iridium(i) complexes.

    PubMed

    Chang, Yung-Hung; Fu, Ching-Feng; Liu, Yi-Hong; Peng, Shei-Ming; Chen, Jwu-Ting; Liu, Shiuh-Tzung

    2009-02-01

    Both saturated and unsaturated N-benzyl substituted heterocyclic carbene (NHC) iridum(i) complexes were synthesized. The unsaturated carbene complex [(un-NHC-Bn)Ir(CO)(2)Cl] in the cis form was prepared via the carbene transfer from the corresponding silver complex to [Ir(COD)(2)Cl](2) followed by ligand substitution with CO, whereas the saturated complex was obtained via the transfer from (sat-NHC-Bn)W(CO)(5). The treatment of phosphines with (NHC)Ir(CO)(2)Cl complexes yielded the products with the phosphine ligand trans to the carbene moiety via substitution. X-Ray structural determination shows that distances of Ir-C((carbene)) in both (un-NHC-Bn)Ir(CO)(PR(3))Cl and (un-NHC-Bn)Ir(CO)(PR(3))Cl are essentially the same. Analyses of spectroscopic and crystal structural data of iridium complexes [(NHC)Ir(CO)(PR(3))Cl] and Vaska's complex show similar corresponding data in both types of complexes, suggesting that the studied NHC ligands and phosphines have similar bonding with Ir(i) metal center. All iridium complexes studied in this work illustrated their catalytically activity on N-alkylation of amine with alcohol via hydrogen transfer reduction. It appears no dramatic difference on the catalytic activity among these iridium carbene complexes; but the saturated carbene complex (sat-NHC-Bn)Ir(CO)(PR(3))Cl appears to be slightly more active. For example, the reaction of benzyl alcohol with aniline in the presence of catalyst (1 mol%) under basic conditions at 100 degrees C provided the secondary amine (N-benzylaniline) in 96% yield. PMID:19156280

  11. Metalloporphyrin-sensitized photooxidation of water to oxygen on the surface of colloidal iridium oxides. Photochemical and pulse radiolytic studies

    SciTech Connect

    Nahor, G.S.; Neta, P. ); Hambright, P. ); Thompson, A.N. Jr. ); Harriman, A. )

    1989-08-10

    Derivatives of TSPP (tetrakis(4-sulfonatophenyl)porphyrin) were prepared and tested as photosensitizers for oxidation of water to oxygen on the surface of colloidal iridium oxide. Triplet quantum yields, energies, and lifetimes were measured by laser flash photolysis. Rate constants for quenching the porphyrin triplet state with O{sub 2} and with persulfate ions were also determined. The rates of interaction between the porphyrin radical cations and colloidal IrO{sub x} particles were measured by pulse radiolysis for several of the compounds. The one-electron oxidation potentials of the porphyrins, measured by cyclic voltammetry, were varied between 0.7 and 1.4 V vs. NHE by using different metal centers and by substitution on the phenyl rings. Illumination of a porphyrin in the presence of sodium persulfate and an IrO{sub x} colloid resulted in generation of O{sub 2} in a process that was strongly dependent upon pH and upon the nature of the photosensitizer in the same manner as the kinetics determined by pulse radiolysis. The rate of O{sub 2} production under any conditions could be explained on the basis of thermodynamic criteria relating to either of the individual quenching or water oxidation steps. Zn porphyrins (0.9 < E{sub {1/2}} < 1.02 V) effected O{sub 2} production only in alkaline solution, whereas PdTSPP (E{sub {1/2}} = 1.1 V) gave efficient O{sub 2} evolution even in neutral solution. Further increase in E{sub 1/2}, as achieved with InTSPP (E{sub {1/2}} = 1.16 V), lowers the threshold pH for O{sub 2} evolution, and pulse radiolysis experiments confirmed that the radical cation of this porphyrin is the most reactive toward the catalyst, reacting at diffusion-controlled rates even in acidic solutions. However, the rate of O{sub 2} formation with InTSPP was very low due to the inefficient photochemistry arising from the incomplete quenching of this less-reducing porphyrin triplet state by persulfate ions.

  12. Iridium(I)-catalyzed regioselective C-H activation and hydrogen-isotope exchange of non-aromatic unsaturated functionality.

    PubMed

    Kerr, William J; Mudd, Richard J; Paterson, Laura C; Brown, Jack A

    2014-11-01

    Isotopic labelling is a key technology of increasing importance for the investigation of new CH activation and functionalization techniques, as well as in the construction of labelled molecules for use within both organic synthesis and drug discovery. Herein, we report for the first time selective iridium-catalyzed CH activation and hydrogen-isotope exchange at the β-position of unsaturated organic compounds. The use of our highly active [Ir(cod)(IMes)(PPh3 )][PF6 ] (cod=1,5-cyclooctadiene) catalyst, under mild reaction conditions, allows the regioselective β-activation and labelling of a range of α,β-unsaturated compounds with differing steric and electronic properties. This new process delivers high levels of isotope incorporation over short reaction times by using low levels of catalyst loading. PMID:25283156

  13. Iridium-catalysed ortho-H/D and -H/T exchange under basic conditions: C-H activation of unprotected tetrazoles.

    PubMed

    Kerr, William J; Lindsay, David M; Reid, Marc; Atzrodt, Jens; Derdau, Volker; Rojahn, Patrick; Weck, Remo

    2016-05-10

    The first examples of selective ortho-directed C-H activation with unprotected 2-aryltetrazoles are described. A new base-assisted protocol for iridium(i) hydrogen isotope exchange catalysis allows access to ortho-deuterated and tritiated tetrazoles, including the tetrazole-containing pharmaceutical, Valsartan. Preliminary mechanistic studies are also presented. PMID:27115235

  14. 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

  15. Field emission in air and space-charge-limited currents from iridium-iridium oxide tips with gaps below 100 nm

    NASA Astrophysics Data System (ADS)

    Brimley, Scott; Miller, Mark S.; Hagmann, Mark J.

    2011-05-01

    Field emission diodes made with Ir/IrO2 tips separated by gaps below 100 nm and operating in air gave currents of up to 1 μA just above 10 V and largely survived potentials up to 200 V. The current-voltage characteristics included signatures of Fowler-Nordheim emission and both coherent and incoherent space-charge limited emission, where both behaviors implied molecular-scale effective emission areas. The significant, nanoampere currents that flowed at biases below the expected bulk work functions corroborate the 0.1 eV work functions from Fowler-Nordheim analysis, and are attributed to molecular scale oxide structures and adsorbates shifting the surface Fermi level. Electron transit time analysis indicates that on average only one electron crossed the gap at a time, implying that the space-charge effects are due to self-interactions.

  16. Kinetics of the chemical oxidation of (5,10,15,20-tetraphenyl-21H,23H-porphinato)(chloro)(aqua)iridium(III)

    NASA Astrophysics Data System (ADS)

    Tyulyaeva, E. Yu.; Bichan, N. G.; Mozhzhukhina, E. G.; Lomova, T. N.

    2016-01-01

    The oxidation of (Cl)(H2O)IrTPP with atmospheric oxygen in the presence of concentrated H2SO4 accompanied by coordination of molecular O2 and substitution of axial ligands was studied spectrophotometrically. In 16.785-18.09 MH2SO4 at 298-318 K, (Cl)(H2O)IrTPP experienced two single-electron oxidations in sequence: with an increase in the oxidation state of the iridium cation and with formation of the π-radical cation form (HSO4)IrIVTPP•+ oxidized at the aromatic ligand ( k 298 = 7.2 × 10-6 mol-1 L s-1). Referring to the literature data on the oxidation of (Cl)(H2O)IrTPP in AcOH and CF3COOH, it was shown that the medium acidity and the nature of the axial ligands affect the electron removal site in the chemical oxidation of (Cl)(H2O)IrTPP with atmospheric oxygen in proton-donor solvents.

  17. A luminescence switch-on probe for terminal deoxynucleotidyl transferase (TdT) activity detection by using an iridium(III)-based i-motif probe.

    PubMed

    Lu, Lihua; Wang, Modi; Liu, Li-Juan; Wong, Chun-Yuen; Leung, Chung-Hang; Ma, Dik-Lung

    2015-06-21

    An iridium(III) complex exhibiting higher responce towards i-motif DNA over dsDNA and ssDNA was employed for the construction of a TdT activity detection platform. The assay exhibited a linear signal enhancement for TdT in the concentration range of 0 to 8 U mL(-1), and the limit of detection for TdT was 0.25 U mL(-1). PMID:25999030

  18. Elucidating molecular iridium water oxidation catalysts using metal-organic frameworks: a comprehensive structural, catalytic, spectroscopic, and kinetic study.

    PubMed

    Wang, Cheng; Wang, Jin-Liang; Lin, Wenbin

    2012-12-01

    As a new class of porous, crystalline, molecular materials, metal-organic frameworks (MOFs) have shown great promise as recyclable and reusable single-site solid catalysts. Periodic order and site isolation of the catalytic struts in MOFs facilitate the studies of their activities and reaction mechanisms. Herein we report the construction of two highly stable MOFs (1 and 2) using elongated dicarboxylate bridging ligands derived from Cp*Ir(L)Cl complexes (L = dibenzoate-substituted 2,2'-bipyridine, bpy-dc, or dibenzoate-substituted 2-phenylpyridine, ppy-dc) and Zr(6)O(4)(OH)(4)(carboxylate)(12) cuboctahedral secondary building units (SBUs) and the elucidation of water oxidation pathways of the Cp*Ir(L)Cl catalysts using these MOFs. We carried out detailed kinetic studies of Ce(4+)-driven water oxidation reactions (WORs) catalyzed by the MOFs using UV-vis spectroscopy, phosphorescent oxygen detection, and gas chromatographic analysis. These results confirmed not only water oxidation activity of the MOFs but also indicated oxidative degradation of the Cp* rings during the WOR. The (bpy-dc)Ir(H(2)O)(2)XCl (X is likely a formate or acetate group) complex resulted from the oxidative degradation process was identified as a competent catalyst responsible for the water oxidation activity of 1. Further characterization of the MOFs recovered from WORs using X-ray photoelectron, diffuse-reflectance UV-vis absorption, luminescence, and infrared spectroscopies supported the identity of (bpy-dc)Ir(H(2)O)(2)XCl as an active water oxidation catalyst. Kinetics of MOF-catalyzed WORs were monitored by Ce(4+) consumptions and fitted with a reaction-diffusion model, revealing an intricate relationship between reaction and diffusion rates. Our work underscores the opportunity in using MOFs as well-defined single-site solid catalytic systems to reveal mechanistic details that are difficult to obtain for their homogeneous counterparts. PMID:23136923

  19. Iridium-Catalyzed Allylic Substitution

    NASA Astrophysics Data System (ADS)

    Hartwig, John F.; Pouy, Mark J.

    Iridium-catalyzed asymmetric allylic substitution has become a valuable method to prepare products from the addition of nucleophiles at the more substituted carbon of an allyl unit. The most active and selective catalysts contain a phosphoramidite ligand possessing at least one arylethyl substituent on the nitrogen atom of the ligand. In these systems, the active catalyst is generated by a base-induced cyclometalation at the methyl group of this substituent to generate an iridium metalacycle bound by the COD ligand of the [Ir(COD)Cl]2 precursor and one additional labile dative ligand. Such complexes catalyze the reactions of linear allylic esters with alkylamines, arylamines, phenols, alcohols, imides, carbamates, ammonia, enolates and enolate equivalents, as well as typical stabilized carbon nucleophiles generated from malonates and cyanoesters. Iridium catalysts for enantioselective allylic substitution have also been generated from phosphorus ligands with substituents bound by heteroatoms, and an account of the studies of such systems, along with a description of the development of iridium catalysts is included.

  20. Processing of Iridium and Iridium Alloys

    SciTech Connect

    Ohriner, Evan Keith

    2008-01-01

    Iridium and its alloys have been considered to be difficult to fabricate due to their high melting temperatures, limited ductility, sensitivity to impurity content, and chemical properties. The variety of processing methods used for iridium and its alloys are reviewed, including purification, melting, forming, joining, and powder metallurgy techniques. Also included are coating and forming by the methods of electroplating, chemical and physical vapor deposition, and melt particle deposition.

  1. Cp* Iridium Precatalysts for Selective C-H Oxidation via Direct Insertion. A Joint Experimental/Computational Study

    SciTech Connect

    Zhou, Meng; Balcells, David; Parent, Alexander R.; Crabtree, Robert H; Eisenstein, Odile

    2012-01-01

    A series of Cp*Ir complexes are active precatalysts in C–H oxidation of cis-decalin, cyclooctane, 1-acetylpyrrolidine, tetrahydrofurans, and γ-lactones. Moderate to high yields were achieved, and surprisingly, high selectivity for mono-oxidation of cyclooctane to cyclooctanone was observed. Kinetic isotope effect experiments in the C–H oxidation of ethylbenezene to acetophenone yield kH/kD = 15.4 ± 0.8 at 23 °C and 17.8 ± 1.2 at 0 °C, which are consistent with C–H oxidation being the rate-limiting step with a significant tunneling contribution. The nature of the active species was investigated by TEM, UV–vis, microfiltration, and control experiments. DFT calculations showed that the C–H oxidation of cis-decalin by Cp*Ir(ppy)(Cl) (ppy = o-phenylpyridine) follows a direct oxygen insertion mechanism on the singlet potential energy surface, rather than the radical rebound route that would be seen for the triplet, in good agreement with the retention of stereochemistry observed in this reaction.

  2. Electrochemical and chemical routes to hydride loss from an iridium dihydride.

    PubMed

    Walden, A G; Kumar, A; Lease, N; Goldman, A S; Miller, A J M

    2016-06-14

    With a view towards replacing sacrificial hydrogen acceptors in alkane dehydrogenation catalysis, electrochemical methods for oxidative activation of a pincer-ligated iridium hydride intermediate were explored. A 1H(+)/2e(-) oxidation process was observed in THF solvent, with net hydride loss leading to a reactive cationic intermediate that can be trapped by chloride. Analogous reactivity was observed with the concerted hydride transfer reagent Ph3C(+), connecting chemical and electrochemical hydride loss pathways. PMID:26979786

  3. Structure, electrochemical properties and capacitance performance of polypyrrole electrodeposited onto 1-D crystals of iridium complex

    NASA Astrophysics Data System (ADS)

    Wysocka-Żołopa, Monika; Winkler, Krzysztof

    2015-12-01

    Composites of polypyrrole and one-dimensional iridium complex crystals [(C2H5)4N]0.55[IrCl2(CO)2] were prepared by in situ two-step electrodeposition. Initially, iridium complex crystals were formed during [IrCl2(CO)2]- complex oxidation. Next, pyrrole was electropolymerized on the surface of the iridium needles. The morphology of the composite was investigated by scanning and transmission electron microscopy. At positive potentials, the iridium complex crystals and the polypyrrole were oxidized. In aprotic solvents, oxidation of the iridium complex crystals resulted in their dissolution. In water containing tetra(n-butyl)ammonium chlorides, the 1-D iridium complex crystals were reversibly oxidized. The product of the iridium complex oxidation remained on the electrode surface in crystalline form. The iridium complex needles significantly influenced the redox properties of the polymer. The polypyrrole involved electrode processes become more reversible in presence of crystals of iridium complex. The current of polypyrrole oxidation was higher compared to that of pure polypyrrole and the capacitance properties of the polymer were significantly enhanced. A specific capacitance as high as 590 F g-1 was obtained for a composite of polypyrrole and 1-D crystals of the iridium complex in water containing tetra(n-butyl)ammonium chloride. This value is approximately twice as high as the capacitance of the pure polymer deposited onto the electrode surface.

  4. Ultrafast photodriven intramolecular electron transfer from an iridium-based water-oxidation catalyst to perylene diimide derivatives

    PubMed Central

    Vagnini, Michael T.; Smeigh, Amanda L.; Blakemore, James D.; Eaton, Samuel W.; Schley, Nathan D.; D’Souza, Francis; Crabtree, Robert H.; Brudvig, Gary W.; Co, Dick T.; Wasielewski, Michael R.

    2012-01-01

    Photodriving the activity of water-oxidation catalysts is a critical step toward generating fuel from sunlight. The design of a system with optimal energetics and kinetics requires a mechanistic understanding of the single-electron transfer events in catalyst activation. To this end, we report here the synthesis and photophysical characterization of two covalently bound chromophore-catalyst electron transfer dyads, in which the dyes are derivatives of the strong photooxidant perylene-3,4:9,10-bis(dicarboximide) (PDI) and the molecular catalyst is the Cp∗Ir(ppy)Cl metal complex, where ppy = 2-phenylpyridine. Photoexcitation of the PDI in each dyad results in reduction of the chromophore to PDI•- in less than 10 ps, a process that outcompetes any generation of 3∗PDI by spin-orbit-induced intersystem crossing. Biexponential charge recombination largely to the PDI-Ir(III) ground state is suggestive of multiple populations of the PDI•--Ir(IV) ion-pair, whose relative abundance varies with solvent polarity. Electrochemical studies of the dyads show strong irreversible oxidation current similar to that seen for model catalysts, indicating that the catalytic integrity of the metal complex is maintained upon attachment to the high molecular weight photosensitizer. PMID:22586073

  5. Iridium Interfacial Stack (IRIS)

    NASA Technical Reports Server (NTRS)

    Spry, David James (Inventor)

    2015-01-01

    An iridium interfacial stack ("IrIS") and a method for producing the same are provided. The IrIS may include ordered layers of TaSi.sub.2, platinum, iridium, and platinum, and may be placed on top of a titanium layer and a silicon carbide layer. The IrIS may prevent, reduce, or mitigate against diffusion of elements such as oxygen, platinum, and gold through at least some of its layers.

  6. Catalytic Activity of Platinum Monolayer on Iridium and Rhenium Alloy Nanoparticles for the Oxygen Reduction Reaction

    SciTech Connect

    Karan, Hiroko I.; Sasaki, Kotaro; Kuttiyiel, Kurian; Farberow, Carrie A.; Mavrikakis, Manos; Adzic, Radoslav R.

    2012-05-04

    A new type of electrocatalyst with a core–shell structure that consists of a platinum monolayer shell placed on an iridium–rhenium nanoparticle core or platinum and palladium bilayer shell deposited on that core has been prepared and tested for electrocatalytic activity for the oxygen reduction reaction. Carbon-supported iridium–rhenium alloy nanoparticles with several different molar ratios of Ir to Re were prepared by reducing metal chlorides dispersed on Vulcan carbon with hydrogen gas at 400 °C for 1 h. These catalysts showed specific electrocatalytic activity for oxygen reduction reaction comparable to that of platinum. The activities of PtML/PdML/Ir2Re1, PtML/Pd2layers/Ir2Re1, and PtML/Pd2layers/Ir7Re3 catalysts were, in fact, better than that of conventional platinum electrocatalysts, and their mass activities exceeded the 2015 DOE target. Our density functional theory calculations revealed that the molar ratio of Ir to Re affects the binding strength of adsorbed OH and, thereby, the O2 reduction activity of the catalysts. The maximum specific activity was found for an intermediate OH binding energy with the corresponding catalyst on the top of the volcano plot. The monolayer concept facilitates the use of much less platinum than in other approaches. Finally, the results with the PtML/PdML/Ir2Re electrocatalyst indicate that it is a promising alternative to conventional Pt electrocatalysts in low-temperature fuel cells.

  7. Active oxide nanophotonics

    NASA Astrophysics Data System (ADS)

    Dicken, Matthew J.

    Materials that can be manipulated electrically or mechanically to induce a change in their intrinsic properties are highly relevant when suitably integrated with current technologies. These "active" materials, such as oxide-based ferroelectrics or materials with easily accessible changes of phase, find extensive use as mechanical resonators, solid-state memories, and optical modulators. Barium titanate, a tetragonal ferroelectric at room temperature, is a prime example of a material both mechanically and optically active. This thesis deals primarily with the deposition of active, oxide-based materials and their integration into device structures where either the mechanical or optical properties are exploited. The technologically interesting paradigms within which these active oxide materials have been investigated are microelectromechanical systems, plasmonics, and metamaterials. Microelectromechanical systems are devices that have been micromachined and rely on an applied voltage to induce a mechanical response. Mechanically active materials, such as piezoelectrics or ferroelectrics, can increase the response of these devices. Plasmonics deals with electromagnetic waves resonantly coupled into free electron oscillations at a metal-dielectric interface or metal nanoparticle. Coupling to these resonant modes allows surface plasmon polaritons to propagate along the metal with a nonlinear dispersion. Metamaterials are ordered, subwavelength, metal inclusions in a dielectric, which respond collectively to electromagnetic radiation. This response can yield a material permittivity or permeability not found in nature. The optical properties of metamaterials lead to effects such as negative index response and super lensing, and can be used to design optical cloaking structures. Here, devices utilizing these effects are investigated with an eye toward tuning or switching their resonant response using optically active oxide thin films. This manuscript follows the evolution

  8. Iridium-192 Production for Cancer Treatment

    SciTech Connect

    Rostelato, M.E.C.M.; Silva, C.P.G.; Rela, P.R.; Zeituni, C.A.; Lepki, V.; Feher, A.

    2004-10-05

    The purpose of this work is to settle a laboratory for Iridium -192 sources production, that is, to determine a wire activation method and to build a hot cell for the wires manipulation, quality control and packaging. The paper relates, mainly, the wire activation method and its quality control. The wire activation is carried out in our nuclear reactor, IEA- R1m.

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

    PubMed Central

    Mejuto, Carmen; Royo, Beatriz

    2015-01-01

    Summary The coordination versatility of a 1,3,5-triphenylbenzene-tris-mesoionic carbene ligand is illustrated by the preparation of complexes with three different metals: rhodium, iridium and nickel. The rhodium and iridium complexes contained the [MCl(COD)] fragments, while the nickel compound contained [NiCpCl]. The preparation of the tris-MIC (MIC = mesoionic carbene) complex with three [IrCl(CO)2] fragments, allowed the estimation of the Tolman electronic parameter (TEP) for the ligand, which was compared with the TEP value for a related 1,3,5-triphenylbenzene-tris-NHC ligand. The electronic properties of the tris-MIC ligand were studied by cyclic voltammetry measurements. In all cases, the tris-MIC ligand showed a stronger electron-donating character than the corresponding NHC-based ligands. The catalytic activity of the tri-rhodium complex was tested in the addition reaction of arylboronic acids to α,β-unsaturated ketones. PMID:26734104

  10. Iridium: failures & successes

    NASA Astrophysics Data System (ADS)

    Christensen, CarissaBryce; Beard, Suzette

    2001-03-01

    This paper will provide an overview of the Iridium business venture in terms of the challenges faced, the successes achieved, and the causes of the ultimate failure of the venture — bankruptcy and system de-orbit. The paper will address technical, business, and policy issues. The intent of the paper is to provide a balanced and accurate overview of the Iridium experience, to aid future decision-making by policy makers, the business community, and technical experts. Key topics will include the history of the program, the objectives and decision-making of Motorola, the market research and analysis conducted, partnering strategies and their impact, consumer equipment availability, and technical issues — target performance, performance achieved, technical accomplishments, and expected and unexpected technical challenges. The paper will use as sources trade media and business articles on the Iridium program, technical papers and conference presentations, Wall Street analyst's reports, and, where possible, interviews with participants and close observers.

  11. Osmium-191/iridium-191m radionuclide

    DOEpatents

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

    1987-01-01

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

  12. Osmium-191/iridium-191m radionuclide

    DOEpatents

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

    1985-08-26

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

  13. Iridium-coated rhenium thrusters by CVD

    NASA Technical Reports Server (NTRS)

    Harding, J. T.; Kazaroff, J. M.; Appel, M. A.

    1989-01-01

    Operation of spacecraft thrusters at increased temperature reduces propellant requirements. Inasmuch as propellant comprises the bulk of a satellite's mass, even a small percentage reduction makes possible a significant enhancement of the mission in terms of increased payload. Because of its excellent high temperature strength, rhenium is often the structural material of choice. It can be fabricated into free-standing shapes by chemical vapor deposition (CVD) onto an expendable mandrel. What rhenium lacks is oxidation resistance, but this can be provided by a coating of iridium, also by CVD. This paper describes the process used by Ultramet to fabricate 22-N (5-lbf) and, more recently, 445-N (100-lbf) Ir/Re thrusters; characterizes the CVD-deposited materials; and summarizes the materials effects of firing these thrusters. Optimal propellant mixture ratios can be employed because the materials withstand an oxidizing environment up to the melting temperature of iridium, 2400 C (4350 F).

  14. Iridium-coated rhenium thrusters by CVD

    NASA Technical Reports Server (NTRS)

    Harding, John T.; Kazaroff, John M.; Appel, Marshall A.

    1988-01-01

    Operation of spacecraft thrusters at increased temperature reduces propellant requirements. Inasmuch as propellant comprises the bulk of a satellite's mass, even a small percentage reduction makes possible a significant enhancement of the mission in terms of increased payload. Because of its excellent high temperature strength, rhenium is often the structural material of choice. It can be fabricated into free-standing shapes by chemical vapor deposition (CVD) onto an expendable mandrel. What rhenium lacks is oxidation resistance, but this can be provided by a coating of iridium, also by CVD. This paper describes the process used by Ultramet to fabricate 22-N (5-lbf) and, more recently, 445-N (100-lbf) Ir/Re thrusters; characterizes the CVD-deposited materials; and summarizes the materials effects of firing these thrusters. Optimal propellant mixture ratios can be employed because the materials withstand an oxidizing environment up to the meltimg temperature of iridium, 2400 C (4350 F).

  15. Low energy cyclotron production and cyclometalation chemistry of iridium-192.

    PubMed

    Langille, G; Yang, H; Zeisler, S K; Hoehr, C; Storr, T; Andreoiu, C; Schaffer, P

    2016-09-01

    This work demonstrates the labelling of a novel class of iridium lumophore with radioiridium, as proof-of-feasibility for producing and using the medically useful isotope iridium-192. Natural osmium was electroplated onto silver target backings in basic media and irradiated for up to two hours with ≤20μA of 12.8MeV protons. A range of iridium isotopes were generated, characterized and quantified using γ-spectroscopy methods. The target material was removed from the backings via oxidative dissolution with hydrogen peroxide, and the iridium radioisotopes isolated using an anion exchange resin. Both no-carrier-added as well as carrier-added formulations were then used in subsequent cyclometalation reactions. PMID:27344003

  16. Iridium Aluminide Coats For Protection Against Ox idation

    NASA Technical Reports Server (NTRS)

    Kaplan, Richard B.; Tuffias, Robert H.; La Ferla, Raffaele; Jang, Qin

    1996-01-01

    Iridium aluminide coats investigated for use in protecting some metallic substrates against oxidation at high temperatures. Investigation prompted by need for cost-effective anti-oxidation coats for walls of combustion chambers in rocket engines. Also useful in special terrestrial applications like laboratory combustion chambers and some chemical-processing chambers.

  17. Iridium Complexes as a Roadblock for DNA Polymerase during Amplification.

    PubMed

    Chandra, Falguni; Kumar, Prashant; Tripathi, Suman Kumar; Patra, Srikanta; Koner, Apurba L

    2016-07-01

    Iridium-based metal complexes containing polypyridyl-pyrazine ligands show properties of DNA intercalation. They serve as roadblocks to DNA polymerase activity, thereby inhibiting the polymerization process. Upon the addition of increasing concentrations of these iridium complexes, a rapid polymerase chain reaction (PCR)-based assay reveals the selective inhibition of the DNA polymerization process. This label-free approach to study the inhibition of fundamental cellular processes via physical roadblock can offer an alternative route toward cancer therapy. PMID:27240728

  18. pH-Dependent catalytic activity and chemoselectivity in transfer hydrogenation catalyzed by iridium complex with 4,4'-dihydroxy-2,2'-bipyridine.

    PubMed

    Himeda, Yuichiro; Onozawa-Komatsuzaki, Nobuko; Miyazawa, Satoru; Sugihara, Hideki; Hirose, Takuji; Kasuga, Kazuyuki

    2008-01-01

    Transfer hydrogenation catalyzed by an iridium catalyst with 4,4'-dihydroxy-2,2'-bipyridine (DHBP) in an aqueous formate solution exhibits highly pH-dependent catalytic activity and chemoselectivity. The substantial change in the activity is due to the electronic effect based on the acid-base equilibrium of the phenolic hydroxyl group of DHBP. Under basic conditions, high turnover frequency values of the DHBP complex, which can be more than 1000 times the value of the unsubstituted analogue, are obtained (up to 81 000 h(-1) at 80 degrees C). In addition, the DHBP catalyst exhibits pH-dependent chemoselectivity for alpha,beta-unsaturated carbonyl compounds. Selective reduction of the C=C bond of enone with high activity are observed under basic conditions. The ketone moieties can be reduced with satisfactory activity under acidic conditions. In particular, pH-selective chemoselectivity of the C=O versus C=C bond reduction was observed in the transfer hydrogenation of cinnamaldehyde. PMID:18989857

  19. Antiviral activity of oxidized polyamines.

    PubMed

    Bachrach, U

    2007-08-01

    Polyamines, oxidized by serum amine oxidase, yield aminoaldehydes and hydrogen peroxide. Acrolein may be formed from the aminoaldehydes by a spontaneous beta-elimination process. These oxidation products "oxidized polyamines" inhibit bacterial growth and exhibit anticancer activity. The antimicrobial activity of oxidized polyamines is not limited to bacteria; and the inactivation of bacterial viruses, plant viruses and animal viruses, was also reported. Bacteriophages of the T-odd series are permeable and were inactivated by oxidized polyamines. The inactive phages absorb to their bacterial host and injected their DNA, which formed a stable inactive complex with the aminoaldehydes. Aminoaldehydes, synthesized chemically, also inactivated viruses. The growth of the plant viruses: Tobacco mosaic virus, Potato virus X and Alfalfa mosaic virus was also inhibited by oxidized polyamines. The animal viruses, which were inactivated by oxidized polyamines included Myxoviruses (influenza and Newcastle disease viruses), West Nile, vaccinia and Sindbis viruses. These findings may have practical implications. PMID:17429570

  20. Method for refining contaminated iridium

    DOEpatents

    Heshmatpour, B.; Heestand, R.L.

    1982-08-31

    Contaminated iridium is refined by alloying it with an alloying agent selected from the group consisting of manganese and an alloy of manganese and copper, and then dissolving the alloying agent from the formed alloy to provide a purified iridium powder.

  1. Method for refining contaminated iridium

    DOEpatents

    Heshmatpour, Bahman; Heestand, Richard L.

    1983-01-01

    Contaminated iridium is refined by alloying it with an alloying agent selected from the group consisting of manganese and an alloy of manganese and copper, and then dissolving the alloying agent from the formed alloy to provide a purified iridium powder.

  2. Iridium-Catalyzed Hydrogen Transfer Reactions

    NASA Astrophysics Data System (ADS)

    Saidi, Ourida; Williams, Jonathan M. J.

    This chapter describes the application of iridium complexes to catalytic hydrogen transfer reactions. Transfer hydrogenation reactions provide an alternative to direct hydrogenation for the reduction of a range of substrates. A hydrogen donor, typically an alcohol or formic acid, can be used as the source of hydrogen for the reduction of carbonyl compounds, imines, and alkenes. Heteroaromatic compounds and even carbon dioxide have also been reduced by transfer hydrogenation reactions. In the reverse process, the oxidation of alcohols to carbonyl compounds can be achieved by iridium-catalyzed hydrogen transfer reactions, where a ketone or alkene is used as a suitable hydrogen acceptor. The reversible nature of many hydrogen transfer processes has been exploited for the racemization of alcohols, where temporary removal of hydrogen generates an achiral ketone intermediate. In addition, there is a growing body of work where temporary removal of hydrogen provides an opportunity for using alcohols as alkylating agents. In this chemistry, an iridium catalyst "borrows" hydrogen from an alcohol to give an aldehyde or ketone intermediate, which can be transformed into either an imine or alkene under the reaction conditions. Return of the hydrogen from the catalyst provides methodology for the formation of amines or C-C bonds where the only by-product is typically water.

  3. Validation of EXAFS Analysis of Iridium Compounds

    NASA Astrophysics Data System (ADS)

    Feiters, M. C.; Longo, A.; Banerjee, D.; van der Ham, C. J. M.; Hetterscheid, D. G. H.

    2016-05-01

    Results of iridium L3 edge EXAFS measurements of compounds relevant for water oxidation catalysis are compared to those of other structural techniques. The structural results from EXAFS for the Ir compounds investigated here compare well to those of other structural techniques. Multiple scattering contributions are important in the coordinated Cp* and NHC ligands as well as in the IrCl6 unit and the IrO2 rutile structure. NHC is relatively weak compared to Ir, Cl, and even Cp* and O, and often out of phase with the other contributions.

  4. Iridium/Rhenium Parts For Rocket Engines

    NASA Technical Reports Server (NTRS)

    Schneider, Steven J.; Harding, John T.; Wooten, John R.

    1991-01-01

    Oxidation/corrosion of metals at high temperatures primary life-limiting mechanism of parts in rocket engines. Combination of metals greatly increases operating temperature and longevity of these parts. Consists of two transition-element metals - iridium and rhenium - that melt at extremely high temperatures. Maximum operating temperature increased to 2,200 degrees C from 1,400 degrees C. Increases operating lifetimes of small rocket engines by more than factor of 10. Possible to make hotter-operating, longer-lasting components for turbines and other heat engines.

  5. Solar abundance of iridium

    PubMed Central

    Drake, Stephen; Aller, Lawrence H.

    1976-01-01

    By a method of spectrum synthesis, which yields log gfA, where g is the statistical weight of the lower level, f is the oscillator strength, and A is the abundance, an attempt is made to deduce the solar iridium abundance from one relatively unblended, but fairly weak IrI line, λ 3220.78 Å. If the Corliss-Bozman f-value for this line is adopted, we find log A(Ir) = 0.82 on the scale log A(H) = 12.00. The discordance with the value found from carbonaceous chondrites may arise from faulty f-values or from difficulties arising from line blending in this far ultraviolet domain of the solar spectrum. PMID:16578735

  6. Iridium NEXT: A Global access for your sensor needs

    NASA Astrophysics Data System (ADS)

    Gupta, O. P.; Fish, C. S.

    2010-12-01

    The operational Iridium constellation is comprised of 66 satellites, used to primarily provide worldwide voice and data coverage to satellite phones, pagers and integrated transceivers. The satellites are in low Earth orbit at 781 km and inclination of 86.4 deg, resulting in unprecedented 24/7 coverage and real-time visibility of the entire globe. Recently, through funding from the National Science Foundation (NSF), Iridium has been utilized by the Johns Hopkins University Applied Physics Laboratory (APL), with help from The Boeing Company, as an infrastructure for a comprehensive network for space environment measurements. Known as the Active Magnetosphere and Planetary Electrodynamics Response Experiment (AMPERE), the Iridium-based system provides real-time magnetic field measurements using the satellites as part of a new observation network to forecast weather in space. In February 2007, Iridium announced Iridium NEXT, a novel design for a second-generation satellite constellation. Anticipated to begin launching in 2015, Iridium NEXT will maintain the existing Iridium constellation architecture of 66 cross-linked satellite LEO covering 100 percent of the globe. In the spirit of AMPERE, for commercial, government, and scientific organizations Iridium NEXT also plans to offer new earth and space observation opportunities through hosted hosted payloads on the 66 Iridium NEXT satellite network. To provide seamless support and access to this latest innovation in payload transportation, Iridium NEXT has teamed with Space Dynamics Laboratory - Utah State University which has delivered thousands of successful sensors and subsystems for over 400 space borne and aircraf based payloads. One such innovation called SensorPOD will offer unique benefits such as unprecedented spatial and temporal coverage, real-time relay of data to and from up to 5 Kg payloads in space, and access to space at a fraction of the cost of a dedicated missions such as 3U or larger Cubesats. In this

  7. Oxidation preventative capping layer for deep-ultra-violet and soft x-ray multilayers

    DOEpatents

    Prisbrey, Shon T.

    2004-07-06

    The invention uses iridium and iridium compounds as a protective capping layer on multilayers having reflectivity in the deep ultra-violet to soft x-ray regime. The iridium compounds can be formed in one of two ways: by direct deposition of the iridium compound from a prepared target or by depositing a thin layer (e.g., 5-50 angstroms) of iridium directly onto an element. The deposition energy of the incoming iridium is sufficient to activate the formation of the desired iridium compound. The compounds of most interest are iridium silicide (IrSi.sub.x) and iridium molybdenide (IrMo.sub.x).

  8. Grain boundary cavitation and weld underbead cracking in DOP-26 iridium alloy

    SciTech Connect

    Mosley, W.C. Jr.

    1983-01-01

    Plutonium-238 oxide fuel pellets for the General Purpose Heat Source Radioisotopic Thermoelectric Generators to be used on the NASA Galileo Mission to Jupiter and the International Solar Polar Mission are produced and encapsulated in DOP-26 iridium alloy at the Savannah River Plant. DOP-26 iridium alloy was developed at the Oak Ridge National Laboratory (ORNL) and contains nominally 0.3 wt.% tungsten, 60 ppm thorium, and 50 ppm aluminum. Underbead cracks occasionally occur in the girth weld on the iridium alloy cladding in the area where the gas tungsten arc is quenched. Various electron-beam techniques have been used to determine the cause of cracking.

  9. Activating Nonreducible Oxides via Doping.

    PubMed

    Nilius, Niklas; Freund, Hans-Joachim

    2015-05-19

    Nonreducible oxides are characterized by large band gaps and are therefore unable to exchange electrons or to form bonds with surface species, explaining their chemical inertness. The insertion of aliovalent dopants alters this situation, as new electronic states become available in the gap that may be involved in charge-transfer processes. Consequently, the adsorption and reactivity pattern of doped oxides changes with respect to their nondoped counterparts. This Account describes scanning tunneling microscopy (STM) and photoelectron spectroscopy (XPS) experiments that demonstrate the impact of dopants on the physical and chemical properties of well-defined crystalline oxide films. For this purpose, MgO and CaO as archetypical rocksalt oxides have been loaded either with high-valence (Mo, Cr) or low-valence dopants (Li). While the former generate filled states in the oxide band gap and serve as electron donors, the latter produce valence-band holes and give rise to an acceptor response. The dopant-related electronic states and their polarization effect on the surrounding host material are explored with XPS and STM spectroscopy on nonlocal and local scales. Moreover, charge-compensating defects were found to develop in the oxide lattice, such as Ca and O vacancies in Mo- and Li-doped CaO films, respectively. These native defects are able to trap the excess charges of the impurities and therefore diminish the desired doping effect. If noncompensated dopants reside in the host lattice, electron exchange with surface species is observed. Mo ions in CaO, for example, were found to donate electrons to surface Au atoms. The anionic Au strongly binds to the CaO surface and nucleates in the form of monolayer islands, in contrast to the 3D growth prevailing on pristine oxides. Charge transfer is also revealed for surface O2 that traps one Mo electron by forming a superoxo-species. The activated oxygen is characterized by a reinforced binding to the surface, an elongated O

  10. Hydridomethyl iridium complex

    DOEpatents

    Bergman, Robert G.; Buchanan, J. Michael; Stryker, Jeffrey M.; Wax, Michael J.

    1989-01-01

    A process for functionalizing methane comprising: (a) reacting methane with a hydridoalkyl metal complex of the formula: CpIr[P(R.sub.1).sub.3 ]H(R.sub.2) wherein Cp represents a cyclopentadienyl or alkylcyclopentadienyl radical having from 1 to 5 carbon atoms; Ir represents an iridium atom; P represents a phosphorus atom; R.sub.1 represents an alkyl group; R.sub.2 represents an alkyl group having at least two carbon atoms; and H represents a hydrogen atom, in the presence of a liquid alkane R.sub.3 H having at least three carbon atoms to form a hydridomethyl complex of the formula: CpIr[P(R.sub.1).sub.3 ]HMe where Me represents a methyl radical. (b) reacting said hydridomethyl complex with an organic halogenating agent such as a tetrahalomethane or a haloform of the formulas: CX'X"X'"X"" or CHX'X"X'"; wherein X', X", X"', and X"" represent halogens selected from bromine, iodine and chlorine, to halomethyl complex of step (a) having the formula: CpIr[P(R.sub.1).sub.3 ]MeX: (c) reacting said halomethyl complex with a mercuric halide of the formula HgX.sub.2 to form a methyl mercuric halide of the formula HgMeX; and (d) reacting said methyl mercuric halide with a molecular halogen of the formula X.sub.2 to form methyl halide.

  11. Iridium emissions from Hawaiian volcanoes

    NASA Technical Reports Server (NTRS)

    Finnegan, D. L.; Zoller, W. H.; Miller, T. M.

    1988-01-01

    Particle and gas samples were collected at Mauna Loa volcano during and after its eruption in March and April, 1984 and at Kilauea volcano in 1983, 1984, and 1985 during various phases of its ongoing activity. In the last two Kilauea sampling missions, samples were collected during eruptive activity. The samples were collected using a filterpack system consisting of a Teflon particle filter followed by a series of 4 base-treated Whatman filters. The samples were analyzed by INAA for over 40 elements. As previously reported in the literature, Ir was first detected on particle filters at the Mauna Loa Observatory and later from non-erupting high temperature vents at Kilauea. Since that time Ir was found in samples collected at Kilauea and Mauna Loa during fountaining activity as well as after eruptive activity. Enrichment factors for Ir in the volcanic fumes range from 10,000 to 100,000 relative to BHVO. Charcoal impregnated filters following a particle filter were collected to see if a significant amount of the Ir was in the gas phase during sample collection. Iridium was found on charcoal filters collected close to the vent, no Ir was found on the charcoal filters. This indicates that all of the Ir is in particulate form very soon after its release. Ratios of Ir to F and Cl were calculated for the samples from Mauna Loa and Kilauea collected during fountaining activity. The implications for the KT Ir anomaly are still unclear though as Ir was not found at volcanoes other than those at Hawaii. Further investigations are needed at other volcanoes to ascertain if basaltic volcanoes other than hot spots have Ir enrichments in their fumes.

  12. Iridium(iii)-catalyzed regioselective C7-sulfonamidation of indoles.

    PubMed

    Song, Zengqiang; Antonchick, Andrey P

    2016-06-01

    Iridium(iii)-catalyzed direct C7-sulfonamidation of indoles with sulfonyl azides is described. The developed method has good compatibility with diverse functional groups, providing various 7-amino-substituted indoles with good to excellent yields in a short time under mild reaction conditions. The key feature of the developed method is the regioselective functionalization at the C7-position of 2,3-unsubstituted indoles. Biologically active compounds can be obtained using this protocol. The application of the iridium(iii) catalyst and directing group plays a crucial role in the regioselectivity of the developed reaction. PMID:27173668

  13. Positional effects of hydroxy groups on catalytic activity of proton-responsive half-sandwich Cp*Iridium(III) complexes

    SciTech Connect

    Suna, Yuki; Fujita, Etsuko; Ertem, Mehmed Z.; Wang, Wan-Hui; Kambayashi, Hide; Manaka, Yuichi; Muckerman, James T.; Himeda, Yuichiro

    2014-11-12

    Proton-responsive half-sandwich Cp*Ir(III) complexes possessing a bipyridine ligand with two hydroxy groups at the 3,3'-, 4,4'-, 5,5'- or 6,6'-positions (3DHBP, 4DHBP, 5DHBP, or 6DHBP) were systematically investigated. UV-vis titration data provided average pK a values of the hydroxy groups on the ligands. Both hydroxy groups were found to deprotonate in the pH 4.6–5.6 range for the 4–6DHBP complexes. One of the hydroxy groups of the 3DHBP complex exhibited the low pKa value of < 0.4 because the deprotonation is facilitated by the strong intramolecular hydrogen bond formed between the generated oxyanion and the remaining hydroxy group, which in turn leads to an elevated pKa value of ~13.6 for the second deprotonation step. The crystal structures of the 4– and 6DHBP complexes obtained from basic aqueous solutions revealed their deprotonated forms. The intramolecular hydrogen bond in the 3DHBP complex was also observed in the crystal structures. The catalytic activities of these complexes in aqueous phase reactions, at appropriate pH, for hydrogenation of carbon dioxide (pH 8.5), dehydrogenation of formic acid (pH 1.8), transfer hydrogenation reactions using formic acid/formate as a hydrogen source (pH 7.2 and 2.6) were investigated to compare the positional effects of the hydroxy groups. The 4– and 6DHBP complexes exhibited remarkably enhanced catalytic activities under basic conditions because of the resonance effect of the strong electrondonating oxyanions, whereas the 5DHBP complex exhibited negligible activity despite the presence of electron-donating groups. The 3DHBP complex exhibited relatively high catalytic activity at low pH owing to the one strong electron-donating oxyanion group stabilized by the intramolecular hydrogen bond. DFT calculations were employed to study the mechanism of CO₂ hydrogenation by the 4DHBP and 6DHBP complexes, and comparison of the activation free energies of the H₂ heterolysis and CO

  14. Positional effects of hydroxy groups on catalytic activity of proton-responsive half-sandwich Cp*Iridium(III) complexes

    DOE PAGESBeta

    Suna, Yuki; Fujita, Etsuko; Ertem, Mehmed Z.; Wang, Wan-Hui; Kambayashi, Hide; Manaka, Yuichi; Muckerman, James T.; Himeda, Yuichiro

    2014-11-12

    Proton-responsive half-sandwich Cp*Ir(III) complexes possessing a bipyridine ligand with two hydroxy groups at the 3,3'-, 4,4'-, 5,5'- or 6,6'-positions (3DHBP, 4DHBP, 5DHBP, or 6DHBP) were systematically investigated. UV-vis titration data provided average pK a values of the hydroxy groups on the ligands. Both hydroxy groups were found to deprotonate in the pH 4.6–5.6 range for the 4–6DHBP complexes. One of the hydroxy groups of the 3DHBP complex exhibited the low pKa value of < 0.4 because the deprotonation is facilitated by the strong intramolecular hydrogen bond formed between the generated oxyanion and the remaining hydroxy group, which in turn leadsmore » to an elevated pKa value of ~13.6 for the second deprotonation step. The crystal structures of the 4– and 6DHBP complexes obtained from basic aqueous solutions revealed their deprotonated forms. The intramolecular hydrogen bond in the 3DHBP complex was also observed in the crystal structures. The catalytic activities of these complexes in aqueous phase reactions, at appropriate pH, for hydrogenation of carbon dioxide (pH 8.5), dehydrogenation of formic acid (pH 1.8), transfer hydrogenation reactions using formic acid/formate as a hydrogen source (pH 7.2 and 2.6) were investigated to compare the positional effects of the hydroxy groups. The 4– and 6DHBP complexes exhibited remarkably enhanced catalytic activities under basic conditions because of the resonance effect of the strong electrondonating oxyanions, whereas the 5DHBP complex exhibited negligible activity despite the presence of electron-donating groups. The 3DHBP complex exhibited relatively high catalytic activity at low pH owing to the one strong electron-donating oxyanion group stabilized by the intramolecular hydrogen bond. DFT calculations were employed to study the mechanism of CO₂ hydrogenation by the 4DHBP and 6DHBP complexes, and comparison of the activation free energies of the H₂ heterolysis and CO₂ insertion steps

  15. Homolytic N–H Activation of Ammonia: Hydrogen Transfer of Parent Iridium Ammine, Amide, Imide, and Nitride Species

    PubMed Central

    2015-01-01

    The redox series [Irn(NHx)(PNP)] (n = II–IV, x = 3–0; PNP = N(CHCHPtBu2)2) was examined with respect to electron, proton, and hydrogen atom transfer steps. The experimental and computational results suggest that the IrIII imido species [Ir(NH)(PNP)] is not stable but undergoes disproportionation to the respective IrII amido and IrIV nitrido species. N–H bond strengths are estimated upon reaction with hydrogen atom transfer reagents to rationalize this observation and are used to discuss the reactivity of these compounds toward E–H bond activation. PMID:26192601

  16. Iridium-catalyzed enantioselective hydrogenation of unsaturated heterocyclic acids.

    PubMed

    Song, Song; Zhu, Shou-Fei; Pu, Liu-Yang; Zhou, Qi-Lin

    2013-06-01

    Spiral binding: A highly enantioselective hydrogenation of unsaturated heterocyclic acids has been developed by using chiral iridium/spirophosphino oxazoline catalysts (see scheme; BArF(-) =tetrakis[3,5-bis(trifluoromethyl)phenyl]borate, Boc=tert-butoxycarbonyl). This reaction provided an efficient method for the preparation of optically active heterocyclic acids with excellent enantioselectivities. PMID:23610004

  17. Processing and properties of iridium alloys for space power applications

    SciTech Connect

    Ohriner, E.K.

    1994-12-31

    Iridium alloys are used as fuel cladding in radioisotope thermoelectric generators due to their high-melting point, high- temperature strength, and oxidation and corrosion resistance. Although iridium has a face-centered cubic crystal structure, it undergoes a distinct ductile-to-brittle transition characteristic of many body-centered cubic metals. Improved ductility in the alloys is achieved through material purification and controlled alloy additions at the parts per million (ppm) level. A vacuum arc remelt operation produces a nearly defect-free casting, which is further processed to sheet products. A change in processing from drop castings of small arc-melted buttons to large arc-remelted ingots has substantially improved product yields. The effects of processing changes on alloy microstructure, sheet textures, oxidation effects, high-strain-rate ductility, and fabricability are discussed.

  18. Iridium-catalyst-based autonomous bubble-propelled graphene micromotors with ultralow catalyst loading.

    PubMed

    Wang, Hong; Sofer, Zdeněk; Eng, Alex Yong Sheng; Pumera, Martin

    2014-11-10

    A novel concept of an iridium-based bubble-propelled Janus-particle-type graphene micromotor with very high surface area and with very low catalyst loading is described. The low loading of Ir catalyst (0.54 at %) allows for fast motion of graphene microparticles with high surface area of 316.2 m(2)  g(-1). The micromotor was prepared with a simple and scalable method by thermal exfoliation of iridium-doped graphite oxide precursor composite in hydrogen atmosphere. Oxygen bubbles generated from the decomposition of hydrogen peroxide at the iridium catalytic sites provide robust propulsion thrust for the graphene micromotor. The high surface area and low iridium catalyst loading of the bubble-propelled graphene motors offer great possibilities for dramatically enhanced cargo delivery. PMID:25293511

  19. IRIDIUM LINER FOR NASA 5 LBF CLASS MATERIAL TEST CHAMBER IRIDIUM LINER FOR ATLANTIC RESEARCH CORPORA

    NASA Technical Reports Server (NTRS)

    1995-01-01

    IRIDIUM LINER FOR NASA 5 LBF CLASS MATERIAL TEST CHAMBER IRIDIUM LINER FOR ATLANTIC RESEARCH CORPORATION 5 LBF CLASS ROCKET CHAMBER 25 LBF CLASS 75 HFC 25 TAC CERAMIC COMPOSITE ROCKET CHAMBER FROM REFRACTURY COMPOSITES INC. PURCHASE ORDER C-551941-

  20. Identification of an Iridium(III)-Based Inhibitor of Tumor Necrosis Factor-α.

    PubMed

    Kang, Tian-Shu; Mao, Zhifeng; Ng, Chan-Tat; Wang, Modi; Wang, Wanhe; Wang, Chunming; Lee, Simon Ming-Yuen; Wang, Yitao; Leung, Chung-Hang; Ma, Dik-Lung

    2016-04-28

    The novel iridium(III) complex 1 was verified as a potent inhibitor of the TNF-α-TNFR protein-protein interaction in vitro and in cellulo. The iridium(III) center plays a critical role in organizing the structure of the bioactive metal complex, as the isolated ligands were found to be completely inactive. Both iridium enantiomers inhibited TNF-α-induced NF-κB activity and TNF-α-TNFR binding. 1 represents a promising scaffold for the further development of more potent organometallic TNF-α inhibitors. PMID:27054262

  1. A molecular catalyst for water oxidation that binds to metal oxide surfaces

    PubMed Central

    Sheehan, Stafford W.; Thomsen, Julianne M.; Hintermair, Ulrich; Crabtree, Robert H.; Brudvig, Gary W.; Schmuttenmaer, Charles A.

    2015-01-01

    Molecular catalysts are known for their high activity and tunability, but their solubility and limited stability often restrict their use in practical applications. Here we describe how a molecular iridium catalyst for water oxidation directly and robustly binds to oxide surfaces without the need for any external stimulus or additional linking groups. On conductive electrode surfaces, this heterogenized molecular catalyst oxidizes water with low overpotential, high turnover frequency and minimal degradation. Spectroscopic and electrochemical studies show that it does not decompose into iridium oxide, thus preserving its molecular identity, and that it is capable of sustaining high activity towards water oxidation with stability comparable to state-of-the-art bulk metal oxide catalysts. PMID:25757425

  2. Toward the Digital Electrochemical Recognition of Cobalt, Iridium, Nickel, and Iron Ion Collisions by Catalytic Amplification.

    PubMed

    Dick, Jeffrey E; Bard, Allen J

    2016-07-13

    We report the electrochemical detection of femtomolar amounts of cobalt, iridium, nickel, and iron ions in solution by electrocatalyst formation and amplification. The metal oxides of these ions can be formed electrochemically and can catalyze the oxidation of water. Alternatively, the reduction of metal ions to metals, such as the reduction of IrCl6(3-) to iridium, is capable of electrocatalytically reducing protons to molecular hydrogen, as shown previously with Pt. These events, which manifest themselves in amperometry, correspond to the formation of electrocatalytic nuclei on the electrode surface, capable of electrocatalytically oxidizing water or reducing protons. An analysis of the frequency of anodic blips compared to theory implies that the requirement for water oxidation is 10 ± 1 ions of cobalt, 13 ± 4 ions of iridium, and 11 ± 3 ions of nickel. A similar analysis for iridium reduction and the corresponding catalytic reduction of protons implies that 6 ± 2 ions of iridium are required for proton reduction. These numbers are confirmed in an analysis of the time of first nucleation event, i.e. the time at which the first blip on the amperometric i-t experiment occurs. We further show that the anodic blips in detecting nickel increase in intensity upon increasing amounts of iron ions in solution to a ratio of Ni/Fe of ∼5, surprisingly close to that for bulk electrocatalysts of Ni-Fe. PMID:27295309

  3. Rhenium and iridium

    SciTech Connect

    Ohriner, E.K.

    1997-02-01

    Re is used together with Ir in a number of metallurgical applications. Ir has been used as coating for Re rocket thrusters and as an oxidation-resistant coating in a number of other applications. The high strength of Re at elevated temperature is combined with the oxidation resistance and high melting point of Ir. The use of the two metals together is advantageous due to absence of stable intermetallic compounds. Both Re and Ir alloying additions improve the ductility of W. The high solubility of Re in Ir is also taken advantage of to produce Ir-based alloys for structural applications. Uses of Re in conjunction with Ir are discussed.

  4. Electronic Structure of Iridium Clusters on Graphene

    NASA Astrophysics Data System (ADS)

    Barker, Bradford A.; Bradley, Aaron J.; Ugeda, Miguel M.; Coh, Sinisa; Zettl, Alex; Crommie, Michael F.; Cohen, Marvin L.; Louie, Steven G.

    2015-03-01

    Graphene was predicted to exhibit non-trivial Z2 topology, but its exceedingly weak spin-orbit coupling prevented this from being observed. Previous theoretical work has proposed enhancing the spin-orbit coupling strength by depositing individual adatoms adsorbed onto the surface of graphene. We show experimental evidence that the iridium adatoms cluster, with a cluster size of at least two atoms. We investigate through theoretical calculations the orientation of the iridium dimers on graphene, contrast the electronic structure of iridium dimers with iridium monomers, and compare the theoretical iridium dimer electronic structure calculations with the experimental results determined via scanning tunneling spectroscopy. This work was supported by NSF Grant No. DMR10-1006184 and U.S. DOE under Contract No. DE-AC02-05CH11231. Computational resources have been provided by DOE at LBNL's NERSC facility.

  5. PURIFICATION OF IRIDIUM BY ELECTRON BEAM MELTING

    SciTech Connect

    Ohriner, Evan Keith

    2008-01-01

    The purification of iridium metal by electron beam melting has been characterized for 48 impurity elements. Chemical analysis was performed by glow discharge mass spectrographic (GDMS) analysis for all elements except carbon, which was analyzed by combustion. The average levels of individual elemental impurities in the starting powder varied from 37 g/g to 0.02 g/g. The impurity elements Li, Na, Mg, P, S, Cl, K, Ca, Mn, Co, Ni, Cu, Zn, As, Pd, Ag, Cd, Sn, Sb, Te, Ba, Ce, Tl, Pb, and Bi were not detectable following the purification. No significant change in concentration of the elements Ti, V, Zr, Nb, Mo, and Re was found. The elements B, C, Al, Si, Cr, Fe, Ru, Rh, and Pt were partially removed by vaporization during electron beam melting. Langmuir's equation for ideal vaporization into a vacuum was used to calculate for each impurity element the expected ratio of impurity content after melting to that before melting. Equilibrium vapor pressures were calculated using Henry's law, with activity coefficients obtained from published data for the elements Fe, Ti, and Pt. Activity coefficients were estimated from enthalpy data for Al, Si, V, Cr, Mn, Co, Ni, Zr, Nb, Mo, and Hf and an ideal solution model was used for the remaining elements. The melt temperature was determined from measured iridium weight loss. Excellent agreement was found between measured and calculated impurity ratios for all impurity elements. The results are consistent with some localized heating of the melt pool due to rastering of the electron beam, with an average vaporization temperature of 3100 K as compared to a temperature of 2965 K calculated for uniform heating of the melt pool. The results are also consistent with ideal mixing in the melt pool.

  6. Study of degradation intermediates formed during electrochemical oxidation of pesticide residue 2,6-dichlorobenzamide (BAM) at boron doped diamond (BDD) and platinum-iridium anodes.

    PubMed

    Madsen, Henrik Tækker; Søgaard, Erik Gydesen; Muff, Jens

    2014-08-01

    Electrochemical oxidation is a promising technique for degradation of otherwise recalcitrant organic micropollutants in waters. In this study, the applicability of electrochemical oxidation was investigated concerning the degradation of the groundwater pollutant 2,6-dichlorobenzamide (BAM) through the electrochemical oxygen transfer process with two anode materials: Ti/Pt90-Ir10 and boron doped diamond (Si/BDD). Besides the efficiency of the degradation of the main pollutant, it is also of outmost importance to control the formation and fate of stable degradation intermediates. These were investigated quantitatively with HPLC-MS and TOC measurements and qualitatively with a combined HPLC-UV and HPLC-MS protocol. 2,6-Dichlorobenzamide was found to be degraded most efficiently by the BDD cell, which also resulted in significantly lower amounts of intermediates formed during the process. The anodic degradation pathway was found to occur via substitution of hydroxyl groups until ring cleavage leading to carboxylic acids. For the BDD cell, there was a parallel cathodic degradation pathway that occurred via dechlorination. The combination of TOC with the combined HPLC-UV/MS was found to be a powerful method for determining the amount and nature of degradation intermediates. PMID:24873711

  7. TCP Performance Enhancement Over Iridium

    NASA Technical Reports Server (NTRS)

    Torgerson, Leigh; Hutcherson, Joseph; McKelvey, James

    2007-01-01

    In support of iNET maturation, NASA-JPL has collaborated with NASA-Dryden to develop, test and demonstrate an over-the-horizon vehicle-to-ground networking capability, using Iridium as the vehicle-to-ground communications link for relaying critical vehicle telemetry. To ensure reliability concerns are met, the Space Communications Protocol Standards (SCPS) transport protocol was investigated for its performance characteristics in this environment. In particular, the SCPS-TP software performance was compared to that of the standard Transmission Control Protocol (TCP) over the Internet Protocol (IP). This paper will report on the results of this work.

  8. Isomerization of Internal Alkynes to Iridium(III) Allene Complexes via C-H Bond Activation: Expanded Substrate Scope, and Progress towards a Catalytic Methodology.

    PubMed

    Phadke, Neha; Findlater, Michael

    2015-01-01

    The synthesis of a series of allene complexes (POCOP)Ir(η²-RC=(.)=CR') 1b-4b (POCOP = 2,6-bis(di-tert-butylphosphonito)benzene) via isomerization of internal alkynes is reported. We have demonstrated that the application of this methodology is viable for the isomerization of a wide variety of alkyne substrates. Deuterium labeling experiments support our proposed mechanism. The structures of the allene complexes 1b-4b were determined using spectroscopic data analysis. Additionally, the solid-state molecular structure of complex 2b was determined using single crystal X-ray diffraction studies and it confirmed the assignment of an iridium-bound allene isomerization product. The rates of isomerization were measured using NMR techniques over a range of temperatures to allow determination of thermodynamic parameters. Finally, we report a preliminary step towards developing a catalytic methodology; the allene may be liberated from the metal center by exposure of the complex to an atmosphere of carbon monoxide. PMID:26569203

  9. On the dissolution of iridium by aluminum.

    SciTech Connect

    Hewson, John C.

    2009-08-01

    The potential for liquid aluminum to dissolve an iridium solid is examined. Substantial uncertainties exist in material properties, and the available data for the iridium solubility and iridium diffusivity are discussed. The dissolution rate is expressed in terms of the regression velocity of the solid iridium when exposed to the solvent (aluminum). The temperature has the strongest influence in the dissolution rate. This dependence comes primarily from the solubility of iridium in aluminum and secondarily from the temperature dependence of the diffusion coefficient. This dissolution mass flux is geometry dependent and results are provided for simplified geometries at constant temperatures. For situations where there is negligible convective flow, simple time-dependent diffusion solutions are provided. Correlations for mass transfer are also given for natural convection and forced convection. These estimates suggest that dissolution of iridium can be significant for temperatures well below the melting temperature of iridium, but the uncertainties in actual rates are large because of uncertainties in the physical parameters and in the details of the relevant geometries.

  10. Circularly polarised phosphorescent photoluminescence and electroluminescence of iridium complexes

    PubMed Central

    Li, Tian-Yi; Jing, Yi-Ming; Liu, Xuan; Zhao, Yue; Shi, Lin; Tang, Zhiyong; Zheng, You-Xuan; Zuo, Jing-Lin

    2015-01-01

    Nearly all the neutral iridium complexes widely used as dopants in PhOLEDs are racemic mixtures; however, this study observed that these complexes can be separated into stable optically active Λ and ∆ isomers and that their chirality is an intrinsic property. The circularly polarised phosphorescent photoluminescence (CPPPL) signals of Λ/Δ isomers are perfect mirror images with opposite polarisation and equal intensity exhibiting a “handedness” for the polarisation. For the first time, we applied the Λ/Δ iridium isomers as emitters in OLEDs, and the circularly polarised phosphorescent electroluminescence (CPPEL) spectra reveal completely positive or negative broad peaks consistent with the CPPPL spectra. The results demonstrate that the Λ/Δ isomers have potential application for 3D OLEDs because they can exhibit high efficiency and luminance, and 3D display technology based on circularly polarised light is the most comfortable for the eyes. PMID:26446521

  11. Determining the Altitude of Iridium Flares

    NASA Technical Reports Server (NTRS)

    Foster, James; Owe, Manfred

    1999-01-01

    Iridium flares have nothing to do with the element iridium. Iridium is also the name of a telecommunications company that has been launching satellites into low orbits around the Earth. These satellites are being used for a new type of wireless phone and paging service. Flares have been observed coming from these satellites. These flares have the potential, especially when the full fleet of satellites is in orbit, to disrupt astronomical observations. The paper reviews using simple trigonometry how to calculate the altitude of one of these satellites.

  12. Synergistic effects of Ir-Au/TiO₂ catalysts in the total oxidation of propene: influence of the activation conditions.

    PubMed

    Aguilar-Tapia, Antonio; Zanella, Rodolfo; Calers, Christophe; Louis, Catherine; Delannoy, Laurent

    2015-11-14

    Iridium was added to the Au/TiO2 system to try to enhance its catalytic activity in the reaction of propene oxidation, performed under conditions close to those used in the studies of decomposition of volatile organic compounds (1200 ppm propene and 9 vol% O2 in He). Titania supported Ir-Au (Ir/Au = 1) was prepared by sequential deposition-precipitation with urea (DPU) of Ir then Au. The effect of the activation conditions (hydrogen or air at 400 °C) was investigated. The study of the activation conditions of Ir-Au/TiO2 showed that activation under hydrogen at 400 °C generated a catalyst more active than the monometallic ones, while Ir-Au/TiO2 activated in air remained as poorly active as Au/TiO2. TEM characterization showed the formation of metallic particles of similar size (2-3 nm) in both monometallic Au/TiO2 and bimetallic Ir-Au/TiO2. Characterization especially by DRIFTS using CO as a probe molecule suggests the presence of Ir-Au interaction, IrO2-Au(0) interaction when the sample is calcined and Ir(0)-Au(0) bimetallic particles when it is reduced. XPS and TPR characterization techniques showed that gold hinders to some extent the reoxidation of iridium in the reduced bimetallic Ir-Au/TiO2 catalyst. The enhanced catalytic activity of the reduced bimetallic Ir-Au/TiO2 catalyst is attributed to a surface Ir(0)-Au(0) synergism. PMID:25785784

  13. Active Oxidation of SiC

    NASA Technical Reports Server (NTRS)

    Jacobson, Nathan S.; Myers,Dwight L.; Harder, Bryan J.

    2011-01-01

    The high temperature oxidation of silicon carbide occurs in either a passive or active mode, depending on temperature and oxygen potential. Passive oxidation forms a protective oxide film which limits attack of the SiC:SiC(s) + 3/2 O2(g) = SiO2(s) + CO(g.) Active oxidation forms a volatile oxide and leads to extensive attack of the SiC: SiC(s) + O2(g) = SiO(g) + CO(g). The transition points and rates of active oxidation are a major issue. Previous studies are reviewed and the leading theories of passive/active transitions summarized. Comparisons are made to the active/passive transitions in pure Si, which are relatively well-understood. Critical questions remain about the difference between the active-to-passive transition and passive-to-active transition. For Si, Wagner [2] points out that the active-to-passive transition is governed by the criterion for a stable Si/SiO2 equilibria and the passive-to-active transition is governed by the decomposition of the SiO2 film. This suggests a significant oxygen potential difference between these two transitions and our experiments confirm this. For Si, the initial stages of active oxidation are characterized by the formation of SiO(g) and further oxidation to SiO2(s) as micron-sized rods, with a distinctive morphology. SiC shows significant differences. The active-to-passive and the passive-to-active transitions are close. The SiO2 rods only appear as the passive film breaks down. These differences are explained in terms of the reactions at the SiC/SiO2 interface. In order to understand the breakdown of the passive film, pre-oxidation experiments are conducted. These involve forming dense protective scales of 0.5, 1, and 2 microns and then subjecting the samples with these scales to a known active oxidation environment. Microstructural studies show that SiC/SiO2 interfacial reactions lead to a breakdown of the scale with a distinct morphology.

  14. 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

  15. Grain-boundary cavitation and weld-underbead cracking in DOP-26 iridium alloy

    SciTech Connect

    Mosley, W.C. Jr.

    1983-01-01

    Plutonium-238 oxide fuel pellets for the General Purpose Heat Source Radioisotopic thermoelectric generators to be used on the NASA Galileo Mission to Jupiter and the International Solar Polar Mission are produced and encapsulated in DOP-26 iridium alloy at the Savannah River Plant. DOP-26 iridium alloy was developed at the Oak Ridge National Laboratory and contains nominally 0.3 weight-percent tungsten, 60-ppM thorium and 50-ppM aluminum. Underbead cracks occasionally occur in the girth weld on the iridium alloy cladding in the area where the gas tungsten arc is quenched. A variety of electron beam techniques have been used to determine the cause of cracking. Results are discussed. (WHK)

  16. Thermal stability of sputtered iridium oxide films

    SciTech Connect

    Sanjines, R.; Aruchamy, A.; Levy, F. )

    1989-06-01

    Dry and partially hydrated films of IrO/sub 2/ were prepared by reactive sputtering. The authors discuss their thermal stability investigated by means of XPS, x-ray diffraction, and resistivity measurements. Dry films decomposed at about 400{sup 0}C iin air and at 200{sup 0}C in vacuum (10/sup -2/ Pa), whereas partially hydrated films decomposed at 350{sup 0} and 150{sup 0}C, respectively. After electrochemical treatments of the films mounted as electrochromic electrodes in an electrolytic cell, the decomposition occurred at different temperatures. In particular, the bleached state was found to have the relatively low decomposition temperature of about 100{sup 0}C in air.

  17. Leukocytic oxygen activation and microbicidal oxidative toxins.

    PubMed

    Hurst, J K; Barrette, W C

    1989-01-01

    Following a brief introduction of cellular response to stimulation comprising leukocyte activation, three major areas are discussed: (1) the neutrophil oxidase; (2) myeloperoxidase (MPO)-dependent oxidative microbicidal reactions; and (3) MPO-independent oxidative reactions. Topics included in section (A) are current views on the activation mechanism, redox composition, structural and topographic organization of the oxidase, and its respiratory products. In section (B), emphasis is placed on recent research on cidal mechanisms of HOCl, including the oxidative biochemistry of active chlorine compounds, identification of sites of lesions in bacteria, and attendant metabolic consequences. In section (C), we review the (bio)chemistry of H2O2 and .OH microbicidal reactions, with particular attention being given to addressing the controversial issue of probe methods to identify .OH radical and critical assessment of the recent proposal that MPO-independent killing arises from site-specific metal-catalyzed Fenton-type chemistry. PMID:2548810

  18. The Active Oxidation of Silicon Carbide

    NASA Technical Reports Server (NTRS)

    Jacobson, Nathan S.; Myers, Dwight L.

    2009-01-01

    The high temperature oxidation of silicon carbide occurs in two very different modes. Passive oxidation forms a protective oxide film which limits further attack of the SiC: SiC(s) + 3/2 O2(g) = SiO2(s) + CO(g) Active oxidation forms a volatile oxide and may lead to extensive attack of the SiC: SiC(s) + O2(g) = SiO(g) + CO(g) Generally passive oxidation occurs at higher oxidant pressures and active oxidation occurs at lower oxidant pressures and elevated temperatures. Active oxidation is a concern for reentry, where the flight trajectory involves the latter conditions. Thus the transition points and rates of active oxidation are a major concern. Passive/active transitions have been studied by a number of investigators. An examination of the literature indicates many questions remain regarding the effect of impurity, the hysteresis of the transition (i.e. the difference between active-to-passive and passive-toactive), and the effect of total pressure. In this study we systematically investigate each of these effects. Experiments were done in both an alumina furnace tube and a quartz furnace tube. It is known that alumina tubes release impurities such as sodium and increase the kinetics in the passive region [1]. We have observed that the active-to-passive transition occurs at a lower oxygen pressure when the experiment is conducted in alumina tubes and the resultant passive silica scale contains sodium. Thus the tests in this study are conducted in quartz tubes. The hysteresis of the transition has been discussed in the detail in the original theoretical treatise of this problem for pure silicon by Wagner [2], yet there is little mention of it in subsequent literature. Essentially Wagner points out that the active-to-passive transition is governed by the criterion for a stable Si/SiO2 equilibria and the passive-to-active transition is governed by the decomposition of the SiO2 film. A series of experiments were conducted for active-to-passive and passive-to-active

  19. Effect of ultrasound sonication on electroplating of iridium.

    PubMed

    Ohsaka, Takashi; Isaka, Motohiro; Hirano, Katsuhiko; Ohishi, Tomoji

    2008-04-01

    Effect of ultrasound sonication was examined on the electroplating of iridium in aqueous hexabromoiridate(III) solution. The electrodeposits were evaluated by observing the defects of the iridium deposits by means of voltammetry, in which the current-potential curves of the iridium deposits on copper were measured. Applying ultrasound sonication to the electroplating of iridium decreased the defects including the cracks in the deposit whenever the glycerol as the additives was contained or not in the electrolyte. PMID:18164231

  20. Process for preparing active oxide powders

    DOEpatents

    Berard, Michael F.; Hunter, Jr., Orville; Shiers, Loren E.; Dole, Stephen L.; Scheidecker, Ralph W.

    1979-02-20

    An improved process for preparing active oxide powders in which cation hydroxide gels, prepared in the conventional manner are chemically dried by alternately washing the gels with a liquid organic compound having polar characteristics and a liquid organic compound having nonpolar characteristics until the mechanical water is removed from the gel. The water-free cation hydroxide is then contacted with a final liquid organic wash to remove the previous organic wash and speed drying. The dried hydroxide treated in the conventional manner will form a highly sinterable active oxide powder.

  1. Methanol dehydrogenation by iridium N-heterocyclic carbene complexes.

    PubMed

    Campos, Jesús; Sharninghausen, Liam S; Manas, Michael G; Crabtree, Robert H

    2015-06-01

    A series of homogeneous iridium bis(N-heterocyclic carbene) catalysts are active for three transformations involving dehydrogenative methanol activation: acceptorless dehydrogenation, transfer hydrogenation, and amine monoalkylation. The acceptorless dehydrogenation reaction requires base, yielding formate and carbonate, as well as 2-3 equivalents of H2. Of the few homogeneous systems known for this reaction, our catalysts tolerate air and employ simple ligands. Transfer hydrogenation of ketones and imines from methanol is also possible. Finally, N-monomethylation of anilines occurs through a "borrowing hydrogen" reaction. Notably, this reaction is highly selective for the monomethylated product. PMID:25615426

  2. IRIDIUM (R): A Lockheed transition to commercial space

    NASA Technical Reports Server (NTRS)

    Tadano, Thomas N.

    1995-01-01

    At Lockheed Missiles & Space Company, the IRIDIUM commercial space program is dramatically revolutionizing spacecraft development and manufacturing processes to reduce cost while maintaining quality and reliability. This report includes the following sections: an overview of the IRIDIUM system, the Lockheed IRIDIUM project and challenges; cycle-time reduction through production reorganization; and design for manufacturing and quality.

  3. Iridium nanoparticles supported on hierarchical porous N-doped carbon: an efficient water-tolerant catalyst for bio-alcohol condensation in water

    NASA Astrophysics Data System (ADS)

    Liu, Di; Chen, Xiufang; Xu, Guoqiang; Guan, Jing; Cao, Quan; Dong, Bo; Qi, Yunfei; Li, Chunhu; Mu, Xindong

    2016-02-01

    Nitrogen-doped hierarchical porous carbons were synthesized successfully by a controllable one-pot method using glucose and dicyandiamide as carbon source and nitrogen source via hydrothermal carbonization process. The nitrogen-doped materials, possessing high nitrogen content (up to 7 wt%), large surface area (>320 m2 g-1) and excellent hierarchical nanostructure, were employed as catalyst supports for immobilization of iridium nanoparticles for bio-alcohol condensation in water. The introduction of nitrogen atoms into the carbon framework significantly improved iridium nanoparticles dispersion and stabilization. The novel iridium catalysts exhibited superior catalytic activity in the aqueous phase condensation of butanol, offering high butanol conversion of 45% with impressive 2-ethylhexanol selectivity of 97%. The heterogeneous catalysts had great advantages of easy recovery and high catalytic stability. The outstanding catalytic performance could be attributed to excellent dispersion of iridium nanoparticles, stronger iridium-support interactions and interaction of nitrogen species with alcohol substrates.

  4. Iridium nanoparticles supported on hierarchical porous N-doped carbon: an efficient water-tolerant catalyst for bio-alcohol condensation in water

    PubMed Central

    Liu, Di; Chen, Xiufang; Xu, Guoqiang; Guan, Jing; Cao, Quan; Dong, Bo; Qi, Yunfei; Li, Chunhu; Mu, Xindong

    2016-01-01

    Nitrogen-doped hierarchical porous carbons were synthesized successfully by a controllable one-pot method using glucose and dicyandiamide as carbon source and nitrogen source via hydrothermal carbonization process. The nitrogen-doped materials, possessing high nitrogen content (up to 7 wt%), large surface area (>320 m2 g−1) and excellent hierarchical nanostructure, were employed as catalyst supports for immobilization of iridium nanoparticles for bio-alcohol condensation in water. The introduction of nitrogen atoms into the carbon framework significantly improved iridium nanoparticles dispersion and stabilization. The novel iridium catalysts exhibited superior catalytic activity in the aqueous phase condensation of butanol, offering high butanol conversion of 45% with impressive 2-ethylhexanol selectivity of 97%. The heterogeneous catalysts had great advantages of easy recovery and high catalytic stability. The outstanding catalytic performance could be attributed to excellent dispersion of iridium nanoparticles, stronger iridium-support interactions and interaction of nitrogen species with alcohol substrates. PMID:26912370

  5. Iridium nanoparticles supported on hierarchical porous N-doped carbon: an efficient water-tolerant catalyst for bio-alcohol condensation in water.

    PubMed

    Liu, Di; Chen, Xiufang; Xu, Guoqiang; Guan, Jing; Cao, Quan; Dong, Bo; Qi, Yunfei; Li, Chunhu; Mu, Xindong

    2016-01-01

    Nitrogen-doped hierarchical porous carbons were synthesized successfully by a controllable one-pot method using glucose and dicyandiamide as carbon source and nitrogen source via hydrothermal carbonization process. The nitrogen-doped materials, possessing high nitrogen content (up to 7 wt%), large surface area (>320 m(2) g(-1)) and excellent hierarchical nanostructure, were employed as catalyst supports for immobilization of iridium nanoparticles for bio-alcohol condensation in water. The introduction of nitrogen atoms into the carbon framework significantly improved iridium nanoparticles dispersion and stabilization. The novel iridium catalysts exhibited superior catalytic activity in the aqueous phase condensation of butanol, offering high butanol conversion of 45% with impressive 2-ethylhexanol selectivity of 97%. The heterogeneous catalysts had great advantages of easy recovery and high catalytic stability. The outstanding catalytic performance could be attributed to excellent dispersion of iridium nanoparticles, stronger iridium-support interactions and interaction of nitrogen species with alcohol substrates. PMID:26912370

  6. Mechanistically Driven Development of Iridium Catalysts for Asymmetric Allylic Substitution

    PubMed Central

    Hartwig, John F.; Stanley, Levi M.

    2010-01-01

    Conspectus Enantioselective allylic substitution reactions comprise some of the most versatile methods for preparing enantiomerically enriched materials. These reactions form products that contain multiple functionalities by creating carbon–nitrogen, carbon–oxygen, carbon–carbon, and carbon–sulfur bonds. For many years, the development of catalysts for allylic substitution focused on palladium complexes. However, studies of complexes of other metals have revealed selectivities that often complement those of palladium systems. Most striking is the observation that reactions with unsymmetrical allylic electrophiles that typically occur with palladium catalysts at the less hindered site of an allylic electrophile occur at the more hindered site with catalysts based on other metals. In this Account, we describe an iridium precursor and a phosphoramidite ligand that catalyze reactions with a particularly broad scope of nucleophiles. The active form of this iridium catalyst is not generated by the simple binding of the phosphoramidite ligand to the metal precursor. Instead, the initial phosphoramidite and iridium precursor react in the presence of base to form a metallacyclic species that is the active catalyst. This species is generated either in situ or separately in isolated form by reactions with added base. The identification of the structure of the active catalyst led to the development of simplified catalysts as well as the most active form of the catalyst now available, which is stabilized by a loosely bound ethylene. Most recently, this structure was used to prepare intermediates containing allyl ligands, the structures of which provide a model for the enantioselectivities discussed here. Initial studies from our laboratory on the scope of iridium-catalyzed allylic substitution showed that reactions of primary and secondary amines, including alkylamines, benzylamines, and allylamines, and reactions of phenoxides and alkoxides occurred in high yields

  7. Characterization of Iridium Coated Rhenium Used in High-Temperature, Radiation-Cooled Rocket Thrusters

    NASA Technical Reports Server (NTRS)

    Stulen, R. H.; Boehme, D. R.; Clift, W. M.; McCarty, K. F.

    1990-01-01

    Materials used for radiation-cooled rocket thrusters must be capable of surviving under extreme conditions of high-temperatures and oxidizing environments. While combustion efficiency is optimized at high temperatures, many refractory metals are unsuitable for thruster applications due to rapid material loss from the formation of volatile oxides. This process occurs during thruster operation by reaction of the combustion products with the material surface. Aerojet Technical Systems has developed a thruster cone chamber constructed of Re coated with Ir on the inside surface where exposure to the rocket exhaust occurs. Re maintains its structural integrity at high temperature and the Ir coating is applied as an oxidation barrier. Ir also forms volatile oxide species (IrO2 and IrO3) but at a considerably slower rate than Re. In order to understand the performance limits of Ir-coated Re thrusters, we are investigating the interdiffusion and oxidation kinetics of Ir/Re. The formation of iridium and rhenium oxides has been monitored in situ by Raman spectroscopy during high temperature exposure to oxygen. For pure Ir, the growth of oxide films as thin as approximately 200 A could be easily detected and the formation of IrO2 was observed at temperatures as low as 600 C. Ir/Re diffusion test specimens were prepared by magnetron sputtering of Ir on Re substrates. Concentration profiles were determined by sputter Auger depth profiles of the heat treated specimens. Significant interdiffusion was observed at temperatures as low as 1000 C. Measurements of the activation energy suggest that below 1350 C, the dominant diffusion path is along defects, most likely grain boundaries, rather than bulk diffusion through the grains. The phases that form during interdiffusion have been examined by x ray diffraction. Analysis of heated test specimens indicates that the Ir-Re reaction produces a solid solution phase of Ir dissolved in the HCP structure of Re.

  8. Iridium satellites light up the sky

    NASA Astrophysics Data System (ADS)

    James, N. D.

    1998-08-01

    Motorola's Iridium satellite system is the largest and most ambitious of a set of competing satellite-based mobile phone systems. Motorola's objective is to allow handheld mobiles to be used from anywhere on the planet, with the call being routed directly from handset to handset via one or several of the satellites. After a bad start when the first Delta launch failed, Iridium spacecraft have been launched up to five at a time and the system is due to go operational late this year.

  9. Origin of brittle cleavage in iridium.

    PubMed

    Cawkwell, Marc J; Nguyen-Manh, Duc; Woodward, Christopher; Pettifor, David G; Vitek, Vaclav

    2005-08-12

    Iridium is unique among the face-centered cubic metals in that it undergoes brittle cleavage after a period of plastic deformation under tensile stress. Atomistic simulation using a quantum-mechanically derived bond-order potential shows that in iridium, two core structures for the screw dislocation are possible: a glissile planar core and a metastable nonplanar core. Transformation between the two core structures is athermal and leads to exceptionally high rates of cross slip during plastic deformation. Associated with this athermal cross slip is an exponential increase in the dislocation density and strong work hardening from which brittle cleavage is a natural consequence. PMID:16099981

  10. Annealing Increases Stability Of Iridium Thermocouples

    NASA Technical Reports Server (NTRS)

    Germain, Edward F.; Daryabeigi, Kamran; Alderfer, David W.; Wright, Robert E.; Ahmed, Shaffiq

    1989-01-01

    Metallurgical studies carried out on samples of iridium versus iridium/40-percent rhodium thermocouples in condition received from manufacturer. Metallurgical studies included x-ray, macroscopic, resistance, and metallographic studies. Revealed large amount of internal stress caused by cold-working during manufacturing, and large number of segregations and inhomogeneities. Samples annealed in furnace at temperatures from 1,000 to 2,000 degree C for intervals up to 1 h to study effects of heat treatment. Wire annealed by this procedure found to be ductile.

  11. Electrocatalytic reduction of dioxygen to water by iridium porphyrins adsorbed on edge plane graphite electrodes

    SciTech Connect

    Collman, J.P.; Chng, Leng Leng; Tyvoll, D.A.

    1995-03-15

    Electrocatalytic effects of adsorbed iridium porphyrin complexes for the reduction of oxygen to water was studied. The Ir(II) metal center is proposed as the active catalytic center and catalytic effects can be attributed to transformation to Ir(II) centers.

  12. Iridium-Coated Rhenium Combustion Chamber

    NASA Technical Reports Server (NTRS)

    Schneider, Steven J.; Tuffias, Robert H.; Rosenberg, Sanders D.

    1994-01-01

    Iridium-coated rhenium combustion chamber withstands operating temperatures up to 2,200 degrees C. Chamber designed to replace older silicide-coated combustion chamber in small rocket engine. Modified versions of newer chamber could be designed for use on Earth in gas turbines, ramjets, and scramjets.

  13. Iridium and tantalum foils for spaceflight neutron dosimetry.

    NASA Technical Reports Server (NTRS)

    English, R. A.; Liles, E. D.

    1972-01-01

    Description of a two-foil system of iridium and tantalum which can measure thermal and intermediate energy neutrons at flux densities of 1 neutron/sq cm-sec over a ten-day lunar mission (1,000,000 neutrons/sq cm). The foils are chemically inert and nontoxic, weigh less than 1 g each, and require only routine gamma pulse height analysis for activation measurement. Detection of fluences below 1,000,000 neutrons/sq cm are achieved for counts of foil activity made as late as two months following neutron exposure. Tantalum foils flown in Apollo 11 indicated a mean dose equivalent to the astronauts of less than 16 mrem from thermal plus intermediate energy neutrons, while nuclear emulsion track analysis indicated approximately 17 mrem from neutrons of energy greater than 0.6 MeV. Iridium foils flown on Apollo 12 indicated dose equivalents of 1.8 to 2.8 mrem from thermal neutrons, excluding tissue thermalized SNAP-27 neutrons.

  14. One-Pot Catalysis Using a Chiral Iridium Complex/Brønsted Base: Catalytic Asymmetric Synthesis of Catalponol.

    PubMed

    Suzuki, Takeyuki; Ismiyarto; Ishizaka, Yuka; Zhou, Da-Yang; Asano, Kaori; Sasai, Hiroaki

    2015-11-01

    Tandem asymmetric hydrogen transfer oxidation/aldol condensation under relay catalysis of a chiral iridium complex/achiral Brønsted base binary system is described for the synthesis of α-benzylidene-γ-hydroxytetralones with high ee's. A two-step synthesis of catalponol was achieved using this sequential methodology together with regio- and stereoselective hydroboration. PMID:26496409

  15. The Potent Oxidant Anticancer Activity of Organoiridium Catalysts**

    PubMed Central

    Liu, Zhe; Romero-Canelón, Isolda; Qamar, Bushra; Hearn, Jessica M; Habtemariam, Abraha; Barry, Nicolas P E; Pizarro, Ana M; Clarkson, Guy J; Sadler, Peter J

    2014-01-01

    Platinum complexes are the most widely used anticancer drugs; however, new generations of agents are needed. The organoiridium(III) complex [(η5-Cpxbiph)Ir(phpy)(Cl)] (1-Cl), which contains π-bonded biphenyltetramethylcyclopentadienyl (Cpxbiph) and C∧N-chelated phenylpyridine (phpy) ligands, undergoes rapid hydrolysis of the chlorido ligand. In contrast, the pyridine complex [(η5-Cpxbiph)Ir(phpy)(py)]+ (1-py) aquates slowly, and is more potent (in nanomolar amounts) than both 1-Cl and cisplatin towards a wide range of cancer cells. The pyridine ligand protects 1-py from rapid reaction with intracellular glutathione. The high potency of 1-py correlates with its ability to increase substantially the level of reactive oxygen species (ROS) in cancer cells. The unprecedented ability of these iridium complexes to generate H2O2 by catalytic hydride transfer from the coenzyme NADH to oxygen is demonstrated. Such organoiridium complexes are promising as a new generation of anticancer drugs for effective oxidant therapy. PMID:24616129

  16. Particulate oxidative burden associated with firework activity.

    PubMed

    Godri, Krystal J; Green, David C; Fuller, Gary W; Dall'Osto, Manuel; Beddows, David C; Kelly, Frank J; Harrison, Roy M; Mudway, Ian S

    2010-11-01

    Firework events are capable of inducing particulate matter (PM) episodes that lead to exceedances of regulatory limit values. As short-term peaks in ambient PM concentration have been associated with negative impacts on respiratory and cardiovascular health, we performed a detailed study of the consequences of firework events in London on ambient air quality and PM composition. These changes were further related to the oxidative activity of daily PM samples by assessing their capacity to drive the oxidation of physiologically important lung antioxidants including ascorbate, glutathione and urate (oxidative potential, OP). Twenty-four hour ambient PM samples were collected at the Marylebone Road sampling site in Central London over a three week period, including two major festivals celebrated with pyrotechnic events: Guy Fawkes Night and Diwali. Pyrotechnic combustion events were characterized by increased gas phase pollutants levels (NO(x) and SO(2)), elevated PM mass concentrations, and trace metal concentrations (specifically Sr, Mg, K, Ba, and Pb). Relationships between NO(x), benzene, and PM(10) were used to apportion firework and traffic source fractions. A positive significant relationship was found between PM oxidative burden and individual trace metals associated with each of these apportioned source fractions. The level of exposure to each source fraction was significantly associated with the total OP. The firework contribution to PM total OP, on a unit mass basis, was greater than that associated with traffic sources: a 1 μg elevation in firework and traffic PM fraction concentration was associated with a 6.5 ± 1.5 OP(T) μg(-1) and 5.2 ± 1.4 OP(T) μg(-1) increase, respectively. In the case of glutathione depletion, firework particulate OP (3.5 ± 0.8 OP(GSH) μg(-1)) considerably exceeded that due to traffic particles (2.2 ± 0.8 OP(GSH) μg(-1)). Therefore, in light of the elevated PM concentrations caused by firework activity and the increased

  17. Application of the Iridium Satellite System to Aeronautical Communications

    NASA Technical Reports Server (NTRS)

    Kerczewski, Robert J.; Meza, Mike; Gupta, Om

    2008-01-01

    The next generation air transportation system will require greater air-ground communications capacity to accommodate more air traffic with increased safety and efficiency. Communications will remain primarily terrestrially based, but satellite communications will have an increased role. Inmarsat s aeronautical services have been approved and are in use for aeronautical safety communications provided by geostationary satellites. More recently the approval process for the Iridium low earth orbit constellation is nearing completion. The current Iridium system will be able to provide basic air traffic services communications suitable for oceanic, remote and polar regions. The planned second generation of the Iridium system, called Iridium NEXT, will provide enhanced capabilities and enable a greater role in the future of aeronautical communications. This paper will review the potential role of satellite communications in the future of air transportation, the Iridium approval process and relevant system testing, and the potential role of Iridium NEXT.

  18. Analysis and Consequences of the Iridium 33-Cosmos 2251 Collision

    NASA Technical Reports Server (NTRS)

    Anz-Meador, P. D.; Liou, Jer-Chi

    2010-01-01

    The collision of Iridium 33 and Cosmos 2251, on 10 February 2009, was the first known unintentional hypervelocity collision in space of intact satellites. Iridium 33 was an active commercial telecommunications satellite, while Cosmos 2251 was a derelict communication satellite of the Strela-2M class. The collision occurred at a relative velocity of 11.6 km/s at an altitude of approximately 790 km over the Great Siberian Plain and near the northern apex of Cosmos 2251 s orbit. This paper describes the physical and orbital characteristics of the relevant spacecraft classes and reports upon our analysis of the resulting debris clouds size, mass, area-to-mass ratio, and relative velocity/directionality distributions. We compare these distributions to those predicted by the NASA breakup model and notable recent fragmentation events; in particular, we compare the area-to-mass ratio distribution for each spacecraft to that exhibited by the FY-1C debris cloud for the purpose of assessing the relative contribution of modern aerospace materials to debris clouds resulting from energetic collisions. In addition, we examine the long-term consequences of this event for the low Earth orbit (LEO) environment. Finally, we discuss "lessons learned", which may be incorporated into NASA s environmental models.

  19. Asymmetric Hydrogenation of Isoxazolium Triflates with a Chiral Iridium Catalyst.

    PubMed

    Ikeda, Ryuhei; Kuwano, Ryoichi

    2016-06-13

    The iridium catalyst [IrCl(cod)]2 -phosphine-I2 (cod=1,5-cyclooctadiene) selectively reduced isoxazolium triflates to isoxazolines or isoxazolidines in the presence of H2 . The iridium-catalyzed hydrogenation proceeded in high-to-good enantioselectivity when an optically active phosphine-oxazoline ligand was used. The 3-substituted 5-arylisoxazolium salts were transformed into 4-isoxazolines with up to 95:5 enantiomeric ratio (e.r.). Chiral cis-isoxazolidines were obtained in up to 89:11 e.r., with no formation of their trans isomers, when the substrates had a primary alkyl substituent at the 5-position. The mechanistic studies indicate that the hydridoiridium(III) species prefers to deliver its hydride to the C5 atom of the isoxazole ring. The hydride attack leads to the formation of the chiral isoxazolidine via a 3-isoxazoline intermediate. Meanwhile, in the selective formation of 4-isoxazolines, hydride attack at the C5 atom may be obstructed by steric hindrance from the 5-aryl substituent. PMID:27105605

  20. Cardioprotective activity of iron oxide nanoparticles

    PubMed Central

    Xiong, Fei; Wang, Hao; Feng, Yidong; Li, Yunman; Hua, Xiaoqing; Pang, Xingyun; Zhang, Song; Song, Lina; Zhang, Yu; Gu, Ning

    2015-01-01

    Iron oxide nanoparticles (IONPs) are chemically inert materials and have been mainly used for imaging applications and drug deliveries. However, the possibility whether they can be used as therapeutic drugs themselves has not yet been explored. We reported here that Fe2O3 nanoparticles (NPs) can protect hearts from ischemic damage at the animal, tissue and cell level. The cardioprotective activity of Fe2O3 NPs requires the integrity of nanoparticles and is not dependent upon their surface charges and molecules that were integrated into nanoparticles. Also, Fe2O3 NPs showed no significant toxicity towards normal cardiomyocytes, indicative of their potential to treat cardiovascular diseases. PMID:25716309

  1. Handling System for Iridium-192 Seeds

    NASA Technical Reports Server (NTRS)

    Carpenter, W.; Wodicka, D.

    1973-01-01

    A complete system is proposed for safe handling of iridium-192 seeds used to internally irradiate malignant growths. A vibratory hopper feeds the seeds onto a transport system for deposit in a magazine or storage area. A circular magazine consisting of segmented plastic tubing with holes in the walls to accommodate the seeds seems feasible. The magazine is indexed to stop and release a seed for calibration and deposition.

  2. Advances in iridium alloy processing in 1987

    SciTech Connect

    Heestand, R.L.; Ohriner, E.K.; Roche, T.K.

    1988-08-01

    A new process for the production of DOP-26 iridium alloy blanks is being evaluated and optimized. The alloy is prepared by electron-beam (EB) melting of Ir-0.3% W powder compacts followed by doping with aluminum and thorium by arc melting. Drop-cast alloy rod segments are EB welded to produce an electrode that is consumable arc melted to produce an ingot for extrusion and subsequent rolling. Initial results showed rejections for ultrasonic indications of alloy blanks produced by this process to be very low. Subsequently, some ingots have exhibited delaminations in the sheet, leading to rejection rates similar to that obtained in the standard process. The increase in delaminations is related to near-surface porosity in the consumable arc-melted ingot. A number of modifications to the arc-melting process and plans for further experimental work are described. In addition, the tensile properties of the DOP-26 iridium alloys have been measured over a range of test temperatures and strain rates. A laboratory evaluation of alternative cleaning procedures indicates that electrolytic dissolution of DOP-26 iridium alloy in an HCl solution is a potential substitute to the KCN process now in use. 7 refs., 13 figs., 6 tabs.

  3. REPEATED REDUCTIVE AND OXIDATIVE TREATMENTS ON GRANULAR ACTIVATED CARBON

    EPA Science Inventory

    Fenton oxidation and Fenton oxidation preceded by reduction solutions were applied to granular activated carbon (GAC) to chemically regenerate the adsorbent. No adsorbate was present on the GAC so physicochemical effects from chemically aggressive regeneration of the carbon coul...

  4. Surface studies of iridium-alloy grain boundaries associated with weld cracking

    SciTech Connect

    Mosley, W.C.

    1982-01-01

    Plutonium-238 oxide fuel pellets for the General Purpose Heat Source (GPHS) Radioisotopic Thermoelectric Generators to be used on the NASA Galileo Mission to Jupiter and the International Solar Polar Mission are produced and encapsulated in iridium alloy at the Savannah River Plant (SRP). Underbead cracks occasionally occur in the girth weld on the iridium-alloy-clad vent sets in the region where the gas tungsten arc is quenched. Grain-boundary structures and compositions were characterized by scanning electron microscopy/x-ray energy spectroscopy, electron microprobe analysis and scanning Auger microprobe analysis to determine the cause of weld quench area cracking. Results suggest that weld quench area cracking may be caused by gas porosity or liquation in the grain boundaries.

  5. Selective Aromatic C–H Hydroxylation Enabled by η6-Coordination to Iridium(III)

    PubMed Central

    D'Amato, Erica M.; Neumann, Constanze N.; Ritter, Tobias

    2016-01-01

    We report an aromatic C–H hydroxylation protocol in which the arene is activated through η6-coordination to an iridium(III) complex. η6-Coordination of the arene increases its electrophilicity and allows for high positional selectivity of hydroxylation at the site of least electron density. Through investigation of intermediate η5-cyclohexadienyl adducts and arene exchange reactions, we evaluate incorporation of arene π-activation into a catalytic cycle for C–H functionalization. PMID:26877574

  6. Iridium complexes of new NCP pincer ligands: catalytic alkane dehydrogenation and alkene isomerization.

    PubMed

    Jia, Xiangqing; Zhang, Lei; Qin, Chuan; Leng, Xuebing; Huang, Zheng

    2014-09-28

    Iridium complexes of novel NCP pincer ligands containing pyridine and phosphinite arms have been synthesized. One Ir complex shows good catalytic activity for alkane dehydrogenation, and all complexes are highly active for olefin isomerization. A combination of the Ir complex and a (PNN)Fe pincer complex catalyzes the formation of linear alkylboronates selectively from internal olefins via sequential olefin isomerization-hydroboration. PMID:25101950

  7. Iridium-Catalyzed Selective Isomerization of Primary Allylic Alcohols.

    PubMed

    Li, Houhua; Mazet, Clément

    2016-06-21

    This Account presents the development of the iridium-catalyzed isomerization of primary allylic alcohols in our laboratory over the past 8 years. Our initial interest was driven by the long-standing challenge associated with the development of a general catalyst even for the nonasymmetric version of this seemingly simple chemical transformation. The added value of the aldehyde products and the possibility to rapidly generate molecular complexity from readily accessible allylic alcohols upon a redox-economical isomerization reaction were additional sources of motivation. Certainly influenced by the success story of the related isomerization of allylic amines, most catalysts developed for the selective isomerization of allylic alcohols were focused on rhodium as a transition metal of choice. Our approach has been based on the commonly accepted precept that hydrogenation and isomerization are often competing processes, with the latter being usually suppressed in favor of the former. The cationic iridium complexes [(Cy3P)(pyridine)Ir(cod)]X developed by Crabtree (X = PF6) and Pfaltz (X = BArF) are usually considered as the most versatile catalysts for the hydrogenation of allylic alcohols. Using molecular hydrogen to generate controlled amounts of the active form of these complexes but performing the reaction in the absence of molecular hydrogen enabled deviation from the typical hydrogenation manifold and favored exclusively the isomerization of allylic alcohols into aldehydes. Isotopic labeling and crossover experiments revealed the intermolecular nature of the process. Systematic variation of the ligand on the iridium center allowed us to identify the structural features beneficial for catalytic activity. Subsequently, three generations of chiral catalysts have been investigated and enabled us to reach excellent levels of enantioselectivity for a wide range of 3,3-disubstituted aryl/alkyl and alkyl/alkyl primary allylic alcohols leading to β-chiral aldehydes. The

  8. Variation of iridium in a differentiated tholeiitic dolerite

    USGS Publications Warehouse

    Greenland, L.P.

    1971-01-01

    Iridium has been determined in a drill core from the Great Lake (Tasmania) dolerite sheet. Iridium decreases systematically from the mafic dolerites (0.25 ppb) to the granophyres (0.006 ppb). The trend with differentiation closely parallels that of chromium. ?? 1971.

  9. Enzymatic Determination of Diglyceride Using an Iridium Nano-Particle Based Single Use, Disposable Biosensor

    PubMed Central

    Hsu, Shu-Yi; Bartling, Brandon; Wang, Christina; Shieu, Fuh-Sheng; Liu, Chung-Chiun

    2010-01-01

    A single use, disposable iridium-nano particle contained biosensor had been developed for the determination of diglyceride (DG). In this study hydrogen peroxide, formed through the enzymatic breakdown of DG via lipase, glycerol kinase and glycerol 3-phosphate oxidase, was electrochemically oxidized at an applied potential of +0.5 V versus the Ag/AgCl reference electrode. The oxidation current was then used to quantify the diglyceride concentration. Optimum enzyme concentrations and the surfactant loading used were established for successful sensor response. Good linear performance was observed over a DG concentration range of 0 to 25 μM in phosphate buffer and bovine serum media. PMID:22219685

  10. Oxidative stress-mediated antibacterial activity of graphene oxide and reduced graphene oxide in Pseudomonas aeruginosa

    PubMed Central

    Gurunathan, Sangiliyandi; Han, Jae Woong; Dayem, Ahmed Abdal; Eppakayala, Vasuki; Kim, Jin-Hoi

    2012-01-01

    Background Graphene holds great promise for potential use in next-generation electronic and photonic devices due to its unique high carrier mobility, good optical transparency, large surface area, and biocompatibility. The aim of this study was to investigate the antibacterial effects of graphene oxide (GO) and reduced graphene oxide (rGO) in Pseudomonas aeruginosa. In this work, we used a novel reducing agent, betamercaptoethanol (BME), for synthesis of graphene to avoid the use of toxic materials. To uncover the impacts of GO and rGO on human health, the antibacterial activity of two types of graphene-based material toward a bacterial model P. aeruginosa was studied and compared. Methods The synthesized GO and rGO was characterized by ultraviolet-visible absorption spectroscopy, particle-size analyzer, X-ray diffraction, scanning electron microscopy and Raman spectroscopy. Further, to explain the antimicrobial activity of graphene oxide and reduced graphene oxide, we employed various assays, such as cell growth, cell viability, reactive oxygen species generation, and DNA fragmentation. Results Ultraviolet-visible spectra of the samples confirmed the transition of GO into graphene. Dynamic light-scattering analyses showed the average size among the two types of graphene materials. X-ray diffraction data validated the structure of graphene sheets, and high-resolution scanning electron microscopy was employed to investigate the morphologies of prepared graphene. Raman spectroscopy data indicated the removal of oxygen-containing functional groups from the surface of GO and the formation of graphene. The exposure of cells to GO and rGO induced the production of superoxide radical anion and loss of cell viability. Results suggest that the antibacterial activities are contributed to by loss of cell viability, induced oxidative stress, and DNA fragmentation. Conclusion The antibacterial activities of GO and rGO against P. aeruginosa were compared. The loss of P

  11. Iridium enrichment in airborne particles from kilauea volcano: january 1983.

    PubMed

    Zoller, W H; Parrington, J R; Kotra, J M

    1983-12-01

    Airborne particulate matter from the January 1983 eruption of Kilauea volcano was inadvertently collected on air filters at Mauna Loa Observatory at a sampling station used to observe particles in global circulation. Analyses of affected samples revealed unusually large concentrations of selenium, arsenic, indium, gold, and sulfur, as expected for volcanic emissions. Strikingly large concentrations of iridium were also observed, the ratio of iridium to aluminum being 17,000 times its value in Hawaiian basalt. Since iridium enrichments have not previously been observed in volcanic emissions, the results for Kilauea suggest that it is part of an unusual volcanic system which may be fed by magma from the mantle. The iridium enrichment appears to be linked with the high fluorine content of the volcanic gases, which suggests that the iridium is released as a volatile IrF(6). PMID:17747384

  12. Iridium(I) Compounds as Prospective Anticancer Agents: Solution Chemistry, Antiproliferative Profiles and Protein Interactions for a Series of Iridium(I) N-Heterocyclic Carbene Complexes.

    PubMed

    Gothe, Yvonne; Marzo, Tiziano; Messori, Luigi; Metzler-Nolte, Nils

    2016-08-22

    A series of structurally related mono- and bis-NHC-iridium(I) (NHC: N-heterocyclic carbene) complexes have been investigated for their suitability as potential anticancer drugs. Their spectral behaviour in aqueous buffers under physiological-like conditions and their cytotoxicity against the cancer cell lines MCF-7 and HT-29 are reported. Notably, almost all complexes exhibit significant cytotoxic effects towards both cancer cell lines. In general, the cationic bis-carbene complexes show higher stability and greater anticancer activity than their neutral mono-carbene analogues with IC50 values in the high nanomolar range. Furthermore, to gain initial mechanistic insight, the interactions of these iridium(I)-NHC complexes with two model proteins, namely lysozyme and cytochrome c, were explored by HR-ESI-MS analyses. The different protein metalation patterns of the complexes can be roughly classified into two distinct groups. Those interactions give us a first idea about the possible mechanism of action of this class of compounds. Overall, our findings show that iridium(I)-NHC complexes represent very interesting candidates for further development as new metal-based anticancer drugs. PMID:27443984

  13. Formation of Chlorination Byproducts and Their Emission Pathways in Chlorine Mediated Electro-Oxidation of Urine on Active and Nonactive Type Anodes.

    PubMed

    Zöllig, Hanspeter; Remmele, Annette; Fritzsche, Cristina; Morgenroth, Eberhard; Udert, Kai M

    2015-09-15

    Chlorination byproducts (CBPs) are harmful to human health and the environment. Their formation in chlorine mediated electro-oxidation is a concern for electrochemical urine treatment. We investigated the formation of chlorate, perchlorate, and organic chlorination byproducts (OCBPs) during galvanostatic (10, 15, 20 mA · cm(-2)) electro-oxidation of urine on boron-doped diamond (BDD) and thermally decomposed iridium oxide film (TDIROF) anodes. In the beginning of the batch experiments, the production of perchlorate was prevented by competing active chlorine and chlorate formation as well as by direct oxidation of organic substances. Perchlorate was only formed at higher specific charges (>17 Ah · L(-1) on BDD and >29 Ah · L(-1) on TDIROF) resulting in chlorate and perchlorate being the dominant CBPs (>90% of initial chloride). BDD produced mainly short chained OCBPs (dichloromethane, trichloromethane, and tetrachloromethane), whereas longer chained OCBPs (1,2-dichloropropane and 1,2-dichloroethane) were more frequently found on TDIROF. The OCBPs were primarily eliminated by electrochemical stripping: On BDD, this pathway accounted for 40% (dichloromethane) to 100% (tetrachloromethane) and on TDIROF for 90% (1,2-dichloroethane) to 100% (trichloromethane) of what was produced. A post-treatment of the liquid as well as the gas phase should be foreseen if CBP formation cannot be prevented by eliminating chloride or organic substances in a pretreatment. PMID:26214011

  14. Synthesis and Electroluminescent Property of New Orange Iridium Compounds for Flexible White Organic Light Emitting Diodes.

    PubMed

    Lee, Ho Won; Jeong, Hyunjin; Kim, Young Kwan; Ha, Yunkyoung

    2015-10-01

    Recently, white organic light-emitting diodes (OLEDs) have aroused considerable attention because they have the potential of next-generation flexible displays and white illuminated applications. White OLED applications are particularly heading to the industry but they have still many problems both materials and manufacturing. Therefore, we proposed that the new iridium compounds of orange emitters could be demonstrated and also applied to flexible white OLEDs for verification of potential. First, we demonstrated the chemical properties of new orange iridium compounds. Secondly, conventional two kinds of white phosphorescent OLEDs were fabricated by following devices; indium-tin oxide coated glass substrate/4,4'-bis[N-(napthyl)-N-phenylamino]biphenyl/N,N'-dicarbazolyl-3,5-benzene doped with blue and new iridium compounds for orange emitting 8 wt%/1,3,5-tris[N-phenylbenzimidazole-2-yl]benzene/lithium quinolate/aluminum. In addition, we fabricated white OLEDs using these emitters to verify the potential on flexible substrate. Therefore, this work could be proposed that white light applications can be applied and could be extended to additional research on flexible applications. PMID:26726407

  15. Iridium Interfacial Stack - IrIS

    NASA Technical Reports Server (NTRS)

    Spry, David

    2012-01-01

    Iridium Interfacial Stack (IrIS) is the sputter deposition of high-purity tantalum silicide (TaSi2-400 nm)/platinum (Pt-200 nm)/iridium (Ir-200 nm)/platinum (Pt-200 nm) in an ultra-high vacuum system followed by a 600 C anneal in nitrogen for 30 minutes. IrIS simultaneously acts as both a bond metal and a diffusion barrier. This bondable metallization that also acts as a diffusion barrier can prevent oxygen from air and gold from the wire-bond from infiltrating silicon carbide (SiC) monolithically integrated circuits (ICs) operating above 500 C in air for over 1,000 hours. This TaSi2/Pt/Ir/Pt metallization is easily bonded for electrical connection to off-chip circuitry and does not require extra anneals or masking steps. There are two ways that IrIS can be used in SiC ICs for applications above 500 C: it can be put directly on a SiC ohmic contact metal, such as Ti, or be used as a bond metal residing on top of an interconnect metal. For simplicity, only the use as a bond metal is discussed. The layer thickness ratio of TaSi2 to the first Pt layer deposited thereon should be 2:1. This will allow Si from the TaSi2 to react with the Pt to form Pt2Si during the 600 C anneal carried out after all layers have been deposited. The Ir layer does not readily form a silicide at 600 C, and thereby prevents the Si from migrating into the top-most Pt layer during future anneals and high-temperature IC operation. The second (i.e., top-most) deposited Pt layer needs to be about 200 nm to enable easy wire bonding. The thickness of 200 nm for Ir was chosen for initial experiments; further optimization of the Ir layer thickness may be possible via further experimentation. Ir itself is not easily wire-bonded because of its hardness and much higher melting point than Pt. Below the iridium layer, the TaSi2 and Pt react and form desired Pt2Si during the post-deposition anneal while above the iridium layer remains pure Pt as desired to facilitate easy and strong wire-bonding to the Si

  16. Iridium Film For Charge-Coupled Device

    NASA Technical Reports Server (NTRS)

    Hecht, Michael H.

    1990-01-01

    Usability extended to different environments. Application of thin film of iridium to back surface of back-surface-illuminated charge-coupled device expected to increase and stabilize quantum efficiency at wavelengths less than 4,500 Angstrom. Enhances quantum efficiency according to principle discussed in "Metal Film Increases CCD Output" (NPO-16815). Does not react with hydrogen, so device need not be kept in oxygen: Advantage where high absorption of ultraviolet light by oxygen undesirable; for example, when device used to make astronomical observations from high altitudes.

  17. Iridium(III)-Catalyzed Tandem [3 + 2] Annulation: Synthesis of Spirocyclic Phosphoramide Derivatives.

    PubMed

    Li, Shuai-Shuai; Wu, Lin; Qin, Liu; Zhu, Yu-Qin; Su, Fu; Xu, Yan-Jun; Dong, Lin

    2016-09-01

    A highly efficient iridium(III)-catalyzed C-H activation/tandem Grignard-type [3 + 2] annulation process was developed for the synthesis of novel spirocyclic phosphoramide derivatives. Compared with other transition-metal catalysts, [Cp*IrCl2]2 exhibited favorite efficiency and best selectivity in this cascade reaction. The strategy could be applied to further construct more complex heterocyclic compounds. PMID:27553969

  18. Iridium Catalysts with f-Amphox Ligands: Asymmetric Hydrogenation of Simple Ketones.

    PubMed

    Wu, Weilong; Liu, Shaodong; Duan, Meng; Tan, Xuefeng; Chen, Caiyou; Xie, Yun; Lan, Yu; Dong, Xiu-Qin; Zhang, Xumu

    2016-06-17

    A series of modular and rich electronic tridentate ferrocene aminophosphoxazoline ligands (f-amphox) have been successfully developed and used in iridium-catalytic asymmetric hydrogenation of simple ketones to afford corresponding enantiomerically enriched alcohols under mild conditions with superb activities and excellent enantioselectivities (up to 1 000 000 TON, almost all products up to >99% ee, full conversion). The resulting chiral alcohols and their derivatives are important intermediates in pharmaceuticals. PMID:27257935

  19. An Iridium(I) N-Heterocyclic Carbene Complex Catalyzes Asymmetric Intramolecular Allylic Amination Reactions.

    PubMed

    Ye, Ke-Yin; Cheng, Qiang; Zhuo, Chun-Xiang; Dai, Li-Xin; You, Shu-Li

    2016-07-01

    A chiral iridium(I) N-heterocyclic carbene complex was reported for the first time as the catalyst in the highly enantioselective intramolecular allylic amination reaction. The current method provides facile access to biologically important enantioenriched indolopiperazinones and piperazinones in good yields (74-91 %) and excellent enantioselectivities (92-99 % ee). Preliminary mechanistic investigations reveal that the C-H activation occurs at the position ortho to the N-aryl group of the ligand. PMID:27162135

  20. Light activated nitric oxide releasing materials

    NASA Astrophysics Data System (ADS)

    Muizzi Casanas, Dayana Andreina

    The ability to control the location and dosage of biologically active molecules inside the human body can be critical to maximizing effective treatment of cardiovascular diseases like angina. The current standard of treatment relies on the metabolism of organonitrate drugs into nitric oxide (NO), which are not specific, and also show problems with densitization with long-term use. There is a need then to create a treatment method that gives targeted release of NO. Metal-nitrosyl (M-NO) complexes can be used for delivery of NO since the release of NO can be controlled with light. However, the NO-releasing drug must be activated with red light to ensure maximum penetration of light through tissue. However, the release of NO from M-NO complexes with red-light activation is a significant challenge since the energy required to break the metal-NO bond is usually larger than the energy provided by red light. The goal of this project was to create red- sensitive, NO-releasing materials based on Ru-salen-nitrosyl compounds. Our approach was to first modify Ru salen complexes to sensitize the photochemistry for release of NO after red light irradiation. Next, we pursued polymerization of the Ru-salen complexes. We report the synthesis and quantitative photochemical characterization of a series of ruthenium salen nitrosyl complexes. These complexes were modified by incorporating electron donating groups in the salen ligand structure at key locations to increase electron density on the Ru. Complexes with either an --OH or --OCH3 substituent showed an improvement in the quantum yield of release of NO upon blue light irradiation compared to the unmodified salen. These --OH and --OCH3 complexes were also sensitized for NO release after red light activation, however the red-sensitive complexes were unstable and showed ligand substitution on the order of minutes. The substituted complexes remained sensitive for NO release, but only after blue light irradiation. The Ru

  1. Diminiode thermionic conversion with 111-iridium electrodes

    NASA Technical Reports Server (NTRS)

    Koeger, E. W.; Bair, V. L.; Morris, J. F.

    1976-01-01

    Preliminary data indicating thermionic-conversion potentialities for a 111-iridium emitter and collector spaced 0.2 mm apart are presented. These results comprise output densities of current and of power as functions of voltage for three sets of emitter, collector, and reservoir temperatures: 1553, 944, 561 K; 1605, 898, 533 K; and 1656, 1028, 586 K. For the 1605 K evaluation, estimates produced work-function values of 2.22 eV for the emitter and 1.63 eV for the collector with a 2.0-eV barrier index (collector work function plus interelectrode voltage drop) corresponding to the maximum output of 5.5 W/sq cm at 0.24 volt. The current, voltage curve for the 1656 K 111-iridium diminiode yields a 6.2 W/sq cm maximum at 0.25 volt and is comparable with the 1700 K envelope for a diode with an etched-rhenium emitter and a 0.025-mm electrode gap made by TECO and evaluated by NASA.

  2. An Analysis of the FY-1C, Iridium 33, and Cosmos 2251 Fragments

    NASA Technical Reports Server (NTRS)

    Liou, J.-C.

    2014-01-01

    The beginning of the year 2013 marks the sixth anniversary of the destruction of the Fengyun-1C (FY-1C) weather satellite as the result of an anti-satellite test conducted by China in January 2007 and the fourth anniversary of the accidental collision between Cosmos 2251 and the operational Iridium 33 in February 2009. These two events represent the worst satellite breakups in history. A total of 5579 fragments have been cataloged by the U.S. Space Surveillance Network (SSN), and almost 5000 of them were still in orbit in January 2013. In addition to these cataloged objects, hundreds of thousands (or more) of fragments down to the millimeter size regime were also generated during the breakups. These fragments are too small to be tracked by the SSN, but are large enough to be a safety concern for human space activities and robotic missions in low Earth orbit (LEO, the region below 2000 km altitude). Like their cataloged siblings, many of them remain in orbit today. These two breakup events dramatically changed the landscape of the orbital debris environment in LEO. The spatial density of the cataloged population in January 2013 is shown as the top blue curve. The combined FY-1C, Iridium 33, and Cosmos 2251 fragments (black curve) account for about 50 percent of the cataloged population below an altitude of 1000 km. They are also responsible for the concentrations at 770 km and 850 km, altitudes at which the collisions occurred. The effects of the FY-1C, Iridium 33, and Cosmos 2251 fragments will continue to be felt for decades to come. For example, approximately half of the generated FY-1C fragments will remain in orbit 20 years from now. In general, the Iridium 33 and Cosmos 2251 fragments will decay faster than the FY-1C fragments because of their lower altitudes. Of the Iridium 33 and Cosmos 2251 fragments, the former have much shorter orbital lifetimes than the latter, because lightweight composite materials were heavily used in the construction of the Iridium

  3. Iridium-bearing sublimates at a hot-spot volcano (Piton de la Fournaise, Indian Ocean)

    SciTech Connect

    Toutain, J.P. ); Meyer, G.

    1989-12-01

    Sublimates and incrustations derived upon the cooling of volcanic gases have been collected on various sites (Piton de la Fournaise, Poas, Momotombo, Etna, Ardoukoba and Erta-Ale). They have been analyzed for Ir and other volatile elements (Se, As, Cu, Au, Ag, Pb, Tl) by means of instrumental neutron activation analysis (INAA) and proton induced X-Ray emission (PIXE). Among the investigated volcanoes, only Piton de la Fournaise is found to release detectable amounts of iridium. Ir in Piton de la Fournaise sublimates is associated with F-minerals. This confirms its gaseous transport as a volatile fluoride compound. Iridium seems to be preferentialy released by hot-spot type volcanoes, and its detection in Piton de la Fournaise sublimates provides a positive argument in favor of a volcanic hypothesis to explain the KTB events.

  4. Catalytic activity of metal oxides in hydrogen sulfide oxidation by oxygen and sulfur dioxide

    SciTech Connect

    Marshneva, V.I.; Mokrinskii, V.V.

    1989-02-01

    Separate investigations have been made of the catalytic activities of a wide range of oxides by groups I-VIII metals in the Claus reaction and oxidation of H/sub 2/S by oxygen. Only 9 of 21 oxides used in the Claus reaction exhibit stable activity. The remaining oxides are deactivated, mainly by absorbing H/sub 2/S and being converted into sulfides. There are similar tendencies in the changes of sulfur formation specific velocities in both processes in the series of stable oxides V/sub 2/O/sub 5/, TiO/sub 2/, Mn/sub 2/O/sub 3/, Al/sub 2/O/sub 3/, MgO, Cr/sub 2/O/sub 3/. Vanadium pentoxide is the most active catalyst in the total and partial oxidations of H/sub 2/S and the Claus reaction.

  5. Active Oxidation of a UHTC-Based CMC

    NASA Technical Reports Server (NTRS)

    Glass, David E.; Splinter, Scott C.

    2012-01-01

    The active oxidation of ceramic matrix composites (CMC) is a severe problem that must be avoided for multi-use hypersonic vehicles. Much work has been performed studying the active oxidation of silicon-based CMCs such as C/SiC and SiC-coated carbon/carbon (C/C). Ultra high temperature ceramics (UTHC) have been proposed as a possible material solution for high-temperature applications on hypersonic vehicles. However, little work has been performed studying the active oxidation of UHTCs. The intent of this paper is to present test data indicating an active oxidation process for a UHTC-based CMC similar to the active oxidation observed with Si-based CMCs. A UHTC-based CMC was tested in the HyMETS arc-jet facility (or plasma wind tunnel, PWT) at NASA Langley Research Center, Hampton, VA. The coupon was tested at a nominal surface temperature of 3000 F (1650 C), with a stagnation pressure of 0.026 atm. A sudden and large increase in surface temperature was noticed with negligible increase in the heat flux, indicative of the onset of active oxidation. It is shown that the surface conditions, both temperature and pressure, fall within the region for a passive to active transition (PAT) of the oxidation.

  6. Superconductivity in Ca10(Ir4As8)(Fe2As2)5 with Square-Planar Coordination of Iridium

    PubMed Central

    Kudo, Kazutaka; Mitsuoka, Daisuke; Takasuga, Masaya; Sugiyama, Yuki; Sugawara, Kento; Katayama, Naoyuki; Sawa, Hiroshi; Kubo, Hiroaki S.; Takamori, Kenta; Ichioka, Masanori; Fujii, Tatsuo; Mizokawa, Takashi; Nohara, Minoru

    2013-01-01

    We report the unprecedented square-planar coordination of iridium in the iron iridium arsenide Ca10(Ir4As8)(Fe2As2)5. This material experiences superconductivity at 16 K. X-ray photoemission spectroscopy and first-principles band calculation suggest Ir(II) oxidation state, which yields electrically conductive Ir4As8 layers. Such metallic spacer layers are thought to enhance the interlayer coupling of Fe2As2, in which superconductivity emerges, thus offering a way to control the superconducting transition temperature. PMID:24173038

  7. Rhodium- and iridium-catalyzed dehydrogenative cyclization through double C-H bond cleavages to produce fluorene derivatives.

    PubMed

    Itoh, Masaki; Hirano, Koji; Satoh, Tetsuya; Shibata, Yu; Tanaka, Ken; Miura, Masahiro

    2013-02-15

    The rhodium-catalyzed cyclization of a series of 2,2-diarylalkanoic acids in the presence of copper acetate as an oxidant smoothly proceeded through double C-H bond cleavages and subsequent decarboxylation to produce the corresponding fluorene derivatives. The direct cyclization of triarylmethanols also took place efficiently by using an iridium catalyst in place of the rhodium, while the hydroxy function was still intact. PMID:23360206

  8. Mechanism of iridium-catalysed branched-selective hydroarylation of vinyl ethers: a computational study.

    PubMed

    Zhang, Mei; Huang, Genping

    2016-02-16

    The iridium-catalysed branched-selective hydroarylation of vinyl ethers represents a rare example of the branched-selective hydroarylation involving the non-styrene-type alkenes. Herein, we report our DFT calculations on the mechanism of this reaction. The results show that after C-H oxidative addition, instead of the widely accepted Chalk-Harrod type mechanism, the branched-selective hydroarylation may proceed through an unconventional modified Chalk-Harrod type mechanism, involving the migratory insertion into the Ir-C bond and C-H reductive elimination. Both steric and electronic effects of the alkoxy group were found to account for the complete branched selectivity. PMID:26804666

  9. Iridium anomaly approximately synchronous with terminal eocene extinctions

    SciTech Connect

    Alvarez, W.; Asaro, F.; Michel, H.V.; Alvarez, L.W.

    1982-05-21

    An iridium anomaly has been found in coincidence with the known microtektite level in cores from Deep Sea Drilling Project site 149 in the Caribbean Sea. The iridium was probably not in the microtektites but deposited simultaneously with them; this could occur if the iridium was deposited from a dust cloud resulting from a bolide impact, as suggested for the anomaly associated with the Cretaceous-Tertiary boundary. Other workers have deduced that the microtektites are part of the North American strewn tektite field, which is dated at about 34 million years before present, and that the microtektite horizon in deep-sea cores is synchronous with the extinction of five radiolarian species. Mass extinctions also occur in terrestrial mammals within 4 million years of this time. The iridium anomaly and the tektites and microtektites are supportive of a major bolide impact about 34 million years ago.

  10. Iridium anomaly approximately synchronous with terminal eocene extinctions.

    PubMed

    Alvarez, W; Asaro, F; Michel, H V; Alvarez, L W

    1982-05-21

    An iridium anomaly has been found in coincidence with the known microtektite level in cores from Deep Sea Drilling Project site 149 in the Caribbean Sea. The iridium was probably not in the microtektites but deposited simultaneously with them; this could occur if the iridium was deposited from a dust cloud resulting from a bolide impact, as suggested for the anomaly associated with the Cretaceous-Tertiary boundary. Other workers have deduced that the microtektites are part of the North American strewn tektite field, which is dated at about 34 million years before present, and that the microtektite horizon in deep-sea cores is synchronous with the extinction of five radiolarian species. Mass extinctions also occur in terrestrial mammals within 4 million years of this time. The iridium anomaly and the tektites and microtektites are supportive of a major bolide impact about 34 million years ago. PMID:17819180

  11. Acute radiodermatitis from occupational exposure to iridium 192

    SciTech Connect

    Becker, J.; Rosen, T. )

    1989-12-01

    Industrial radiography using the man-made radioisotope iridium 192 is commonplace in the southern states. Despite established procedures and safeguards, accidental exposure may result in typical acute radiodermatitis. We have presented a clinical example of this phenomenon.9 references.

  12. Cysteine redox sensor in PKGIa enables oxidant-induced activation.

    PubMed

    Burgoyne, Joseph R; Madhani, Melanie; Cuello, Friederike; Charles, Rebecca L; Brennan, Jonathan P; Schröder, Ewald; Browning, Darren D; Eaton, Philip

    2007-09-01

    Changes in the concentration of oxidants in cells can regulate biochemical signaling mechanisms that control cell function. We have found that guanosine 3',5'-monophosphate (cGMP)-dependent protein kinase (PKG) functions directly as a redox sensor. The Ialpha isoform, PKGIalpha, formed an interprotein disulfide linking its two subunits in cells exposed to exogenous hydrogen peroxide. This oxidation directly activated the kinase in vitro, and in rat cells and tissues. The affinity of the kinase for substrates it phosphorylates was enhanced by disulfide formation. This oxidation-induced activation represents an alternate mechanism for regulation along with the classical activation involving nitric oxide and cGMP. This mechanism underlies cGMP-independent vasorelaxation in response to oxidants in the cardiovascular system and provides a molecular explantion for how hydrogen peroxide can operate as an endothelium-derived hyperpolarizing factor. PMID:17717153

  13. GPS/GNSS Interference from Iridium Data Transmitters

    NASA Astrophysics Data System (ADS)

    Berglund, H. T.; Blume, F.; Estey, L.; White, S.

    2011-12-01

    The Iridium satellite communication system broadcasts in the 1610 to 1626.5 MHz band. The L1 frequencies broadcast by GPS, Galileo and GLONASS satellites are 1575.42 MHz, 1575.42 MHz and 1602 MHz + n × 0.5625 MHz, respectively (each GLONASS satellite uses a unique frequency). The proximity of the Iridium frequency band with the L1 frequencies of the GPS, Galileo and GLONASS systems leaves GNSS receivers susceptible to interference from Iridium data transmissions. Interference from Iridium transmissions can cause cycle slips and loss of lock on the carrier and code phases, thereby degrading the quality of GNSS observations and position estimates. In 2008, UNAVCO staff members observed that the percent of slips vs. the number of observations increased as the distance between a GPS choke ring antenna (TRM29659.00) and an Iridium antenna decreased. From those observations they suggested that Iridium antennas and GPS antennas should be separated by >30 m to minimize cycle slips caused by the interference from Iridium data transmissions. A second test conducted in 2009 using a newer Trimble GNSS choke ring antenna (TRM59800.00) showed similar results to the previous test despite the wider frequency range of the newer antenna. More recent testing conducted to investigate the response of new receiver models to iridium transmissions has shown that many GNSS enabled models, when combined with GNSS enabled antennas, have increased sensitivity to interference when compared to older GPS-only models. The broader frequency spectrum of the Low Noise Amplifiers (LNA) installed in many newer GNSS antennas can increase the impact of near-band RF interference on tracking performance. Our testing has shown that the quality of data collected at sites collocated with iridium communications is highly degraded for antenna separations exceeding 100m. Using older GPS antenna models (e.g. TRM29659.00) with newer GNSS enabled receivers can reduce this effect. To mitigate the effects that

  14. The fourth spectrum of iridium (Ir IV)

    NASA Astrophysics Data System (ADS)

    Azarov, Vladimir I.; Gayasov, Robert R.

    2016-03-01

    The spectrum of three times ionized iridium, Ir IV, was investigated in the 650-2045 Å wavelength region. The analysis has led to the determination of the 5d6, 5d5 6 s and 5d5 6 p configurations. Twenty-nine of 34 theoretically possible 5d6 levels, 44 of 74 possible 5d5 6 s levels and 150 of 214 possible 5d5 6 p levels have been established. The levels are based on 1348 classified spectral lines. The level structure and transition probabilities were calculated using the orthogonal operators technique. The energy parameters have been determined by the least squares fit to the observed levels. Calculated energy values and LS-compositions obtained from the fitted parameter values are given. The level optimization procedure and the determination of uncertainties of the obtained energy level values are discussed.

  15. Synthesis and characterization of nitrides of iridium and palladiums

    SciTech Connect

    Crowhurst, Jonathan C.; Goncharov, Alexander F.; Sadigh, B.; Zaug, J.M.; Aberg, D.; Meng, Yue; Prakapenka, Vitali B.

    2008-08-14

    We describe the synthesis of nitrides of iridium and palladium using the laser-heated diamond anvil cell. We have used the in situ techniques of x-ray powder diffraction and Raman scattering to characterize these compounds and have compared our experimental findings where possible to the results of first-principles theoretical calculations. We suggest that palladium nitride is isostructural with pyrite, while iridium nitride has a monoclinic symmetry and is isostructural with baddeleyite.

  16. Iridium{reg_sign} worldwide personal communication system

    SciTech Connect

    Helm, J.

    1997-01-01

    The IRIDIUM system is a personal worldwide communication system designed to support portable, low power subscriber units through the use of a constellation of satellites in low earth polar orbit. The satellites are networked together to form a system which provides continuous line-of-sight communications between the IRIDIUM system and any point within 30 km of the earth{close_quote}s surface. The system architecture and operation are described. {copyright} {ital 1997 American Institute of Physics.}

  17. Supported Molecular Iridium Catalysts: Resolving Effects of Metal Nuclearity and Supports as Ligands

    SciTech Connect

    Lu, Jing; Serna, Pedro; Aydin, Cerem; Browning, Nigel D.; Gates, Bruce C.

    2012-02-07

    The performance of a supported catalyst is influenced by the size and structure of the metal species, the ligands bonded to the metal, and the support. Resolution of these effects has been lacking because of the lack of investigations of catalysts with uniform and systematically varied catalytic sites. We now demonstrate that the performance for ethene hydrogenation of isostructural iridium species on supports with contrasting properties as ligands (electron-donating MgO and electron-withdrawing HY zeolite) can be elucidated on the basis of molecular concepts. Spectra of the working catalysts show that the catalytic reaction rate is determined by the dissociation of H{sub 2} when the iridium, either as mono- or tetra-nuclear species, is supported on MgO and is not when the support is the zeolite. The neighboring iridium sites in clusters are crucial for activation of both H{sub 2} and C{sub 2}H{sub 4} when the support is MgO but not when it is the zeolite, because the electron-withdrawing properties of the zeolite support enable even single site-isolated Ir atoms to bond to both C{sub 2}H{sub 4} and H{sub 2} and facilitate the catalysis.

  18. Organometallic Iridium Complex Containing a Dianionic, Tridentate, Mixed Organic-Inorganic Ligand.

    PubMed

    Bloomfield, Aaron J; Matula, Adam J; Mercado, Brandon Q; Batista, Victor S; Crabtree, Robert H

    2016-08-15

    A pentamethylcyclopentadienyl-iridium complex containing a tricyclic, dianionic, tridentate, scorpionate (facial binding), mixed organic-inorganic ligand was synthesized and characterized by single-crystal X-ray crystallography, as well as polynuclear NMR, UV-vis, and IR spectroscopies. The central cycle of the tridentate ligand consists of a modified boroxine in which two of the boron centers are tetrahedral, anionic borates. The complex is stable to hydrolysis in aqueous solution for >9 weeks at 25 °C but reacts with a 50 mM solution of sodium periodate within 12 s to form a periodate-driven oxygen evolution catalyst that has a turnover frquency of >15 s(-1). However, the catalyst is almost completely deactivated within 5 min, achieving an average turnover number of ca. 2500 molecules of oxygen per atom of iridium. Nanoparticles were not observed on this time scale but did form within 4 h of catalyst activation under these experimental conditions. The parent complex was modeled using density functional theory, which accurately reflected the geometry of the complex and indicated significant interaction of iridium- and boracycle-centered orbitals. PMID:27462911

  19. Oxidative Regulation of Large Conductance Calcium-Activated Potassium Channels

    PubMed Central

    Tang, Xiang D.; Daggett, Heather; Hanner, Markus; Garcia, Maria L.; McManus, Owen B.; Brot, Nathan; Weissbach, Herbert; Heinemann, Stefan H.; Hoshi, Toshinori

    2001-01-01

    Reactive oxygen/nitrogen species are readily generated in vivo, playing roles in many physiological and pathological conditions, such as Alzheimer's disease and Parkinson's disease, by oxidatively modifying various proteins. Previous studies indicate that large conductance Ca2+-activated K+ channels (BKCa or Slo) are subject to redox regulation. However, conflicting results exist whether oxidation increases or decreases the channel activity. We used chloramine-T, which preferentially oxidizes methionine, to examine the functional consequences of methionine oxidation in the cloned human Slo (hSlo) channel expressed in mammalian cells. In the virtual absence of Ca2+, the oxidant shifted the steady-state macroscopic conductance to a more negative direction and slowed deactivation. The results obtained suggest that oxidation enhances specific voltage-dependent opening transitions and slows the rate-limiting closing transition. Enhancement of the hSlo activity was partially reversed by the enzyme peptide methionine sulfoxide reductase, suggesting that the upregulation is mediated by methionine oxidation. In contrast, hydrogen peroxide and cysteine-specific reagents, DTNB, MTSEA, and PCMB, decreased the channel activity. Chloramine-T was much less effective when concurrently applied with the K+ channel blocker TEA, which is consistent with the possibility that the target methionine lies within the channel pore. Regulation of the Slo channel by methionine oxidation may represent an important link between cellular electrical excitability and metabolism. PMID:11222629

  20. Mitochondrial oxidant stress in locus coeruleus is regulated by activity and nitric oxide synthase.

    PubMed

    Sanchez-Padilla, Javier; Guzman, Jaime N; Ilijic, Ema; Kondapalli, Jyothisri; Galtieri, Daniel J; Yang, Ben; Schieber, Simon; Oertel, Wolfgang; Wokosin, David; Schumacker, Paul T; Surmeier, D James

    2014-06-01

    Loss of noradrenergic locus coeruleus (LC) neurons is a prominent feature of aging-related neurodegenerative diseases, such as Parkinson's disease (PD). The basis of this vulnerability is not understood. To explore possible physiological determinants, we studied LC neurons using electrophysiological and optical approaches in ex vivo mouse brain slices. We found that autonomous activity in LC neurons was accompanied by oscillations in dendritic Ca(2+) concentration that were attributable to the opening of L-type Ca(2+) channels. This oscillation elevated mitochondrial oxidant stress and was attenuated by inhibition of nitric oxide synthase. The relationship between activity and stress was malleable, as arousal and carbon dioxide increased the spike rate but differentially affected mitochondrial oxidant stress. Oxidant stress was also increased in an animal model of PD. Thus, our results point to activity-dependent Ca(2+) entry and a resulting mitochondrial oxidant stress as factors contributing to the vulnerability of LC neurons. PMID:24816140

  1. Oxidative esterification via photocatalytic C-H activation

    EPA Science Inventory

    Direct oxidative esterification of alcohol via photocatalytic C-H activation has been developed using VO@g-C3N4 catalyst; an expeditious esterification of alcohols occurs under neutral conditions using visible light as the source of energy.

  2. Energetic basis of catalytic activity of layered nanophase calcium manganese oxides for water oxidation

    PubMed Central

    Birkner, Nancy; Nayeri, Sara; Pashaei, Babak; Najafpour, Mohammad Mahdi; Casey, William H.; Navrotsky, Alexandra

    2013-01-01

    Previous measurements show that calcium manganese oxide nanoparticles are better water oxidation catalysts than binary manganese oxides (Mn3O4, Mn2O3, and MnO2). The probable reasons for such enhancement involve a combination of factors: The calcium manganese oxide materials have a layered structure with considerable thermodynamic stability and a high surface area, their low surface energy suggests relatively loose binding of H2O on the internal and external surfaces, and they possess mixed-valent manganese with internal oxidation enthalpy independent of the Mn3+/Mn4+ ratio and much smaller in magnitude than the Mn2O3-MnO2 couple. These factors enhance catalytic ability by providing easy access for solutes and water to active sites and facile electron transfer between manganese in different oxidation states. PMID:23667149

  3. Mitochondrial oxidant stress in locus coeruleus is regulated by activity and nitric oxide synthase

    PubMed Central

    Sanchez–Padilla, J.; Guzman, J.N.; Ilijic, E.; Kondapalli, J.; Galtieri, D.J.; Yang, B.; Schieber, S.; Oertel, W.; Wokosin, D.; Schumacker, P. T.; Surmeier, D. J.

    2014-01-01

    Summary Loss of noradrenergic locus coeruleus (LC) neurons is a prominent feature of aging–related neurodegenerative diseases, like Parkinson’s disease (PD). The basis of this vulnerability is not understood. To explore possible physiological determinants, LC neurons were studied using electrophysiological and optical approaches in ex vivo mouse brain slices. These studies revealed that autonomous activity in LC neurons was accompanied by oscillations in dendritic Ca2+ concentration attributable to opening of L–type Ca2+ channels. This oscillation elevated mitochondrial oxidant stress and was attenuated by inhibition of nitric oxide synthase. The relationship between activity and stress was malleable, as arousal and carbon dioxide, each increased the spike rate, but differentially affected mitochondrial oxidant stress. Oxidant stress also was increased in an animal model of PD. Thus, our results point to activity–dependent Ca2+ entry and a resulting mitochondrial oxidant stress as factors contributing to the vulnerability of LC neurons. PMID:24816140

  4. Mobility of iridium in terrestrial environments: Implications for the interpretation of impact-related mass-extinctions

    NASA Astrophysics Data System (ADS)

    Martín-Peinado, F. J.; Rodríguez-Tovar, F. J.

    2010-08-01

    Traditionally, iridium has been considered an element of low mobility, but its behavior is still debated. Ir concentration in a soil affected by a catastrophic mining spill in 1998 that covered the soil with a layer of tailings offers the opportunity to analyse an exceptional Ir-bearing horizon 10 years after deposition. This has enabled comparisons with the values of past Ir-bearing horizons associated to impact-related mass-extinction events. Iridium concentration in the tailings (0.349 ppm) was 5-fold higher than the anomaly in the K-Pg at The Moody Creek Mine section (the highest values obtained from terrestrial sections). The oxidative weathering of the tailings caused the release of Ir and infiltration into the soil. Iridium distribution in depth indicates redistribution throughout the profile in relation to the change in the physico-chemical properties of the soil. With regard to the background concentration in the soil (0.056 ppm), anomalous values of Ir (0.129 ppm) can be detected to 11 cm below the layer of tailings. The correlation analysis between the Ir concentration and the main properties and constituents of the soils indicated a significant correlation with sulfur, iron, clay content, and pH. Selective extractions were made to study the forms in which Ir can be mobilized in the soil. The residual/insoluble fraction was >90% of the total Ir concentration in soil. Soluble-in-water concentration of Ir (1.5% of total) was detected in the uppermost 2-3 cm of the soil, which were directly affected by the leaching of acidic waters coming from the oxidation of the pyrite tailings. Iridium retention in the affected part of the soil reached 9% of the total Ir concentration; this retention could be related to the amorphous iron forms dissolved by the oxalic-oxalate extraction. However, according to our research, original Ir abundance could be secondarily modified, and then a direct analysis of the iridium values recorded in sediments could induce

  5. Nanostructured manganese oxides as highly active water oxidation catalysts: a boost from manganese precursor chemistry.

    PubMed

    Menezes, Prashanth W; Indra, Arindam; Littlewood, Patrick; Schwarze, Michael; Göbel, Caren; Schomäcker, Reinhard; Driess, Matthias

    2014-08-01

    We present a facile synthesis of bioinspired manganese oxides for chemical and photocatalytic water oxidation, starting from a reliable and versatile manganese(II) oxalate single-source precursor (SSP) accessible through an inverse micellar molecular approach. Strikingly, thermal decomposition of the latter precursor in various environments (air, nitrogen, and vacuum) led to the three different mineral phases of bixbyite (Mn2 O3 ), hausmannite (Mn3 O4 ), and manganosite (MnO). Initial chemical water oxidation experiments using ceric ammonium nitrate (CAN) gave the maximum catalytic activity for Mn2 O3 and MnO whereas Mn3 O4 had a limited activity. The substantial increase in the catalytic activity of MnO in chemical water oxidation was demonstrated by the fact that a phase transformation occurs at the surface from nanocrystalline MnO into an amorphous MnOx (1oxidizing agent. Photocatalytic water oxidation in the presence of [Ru(bpy)3 ](2+) (bpy=2,2'-bipyridine) as a sensitizer and peroxodisulfate as an electron acceptor was carried out for all three manganese oxides including the newly formed amorphous MnOx . Both Mn2 O3 and the amorphous MnOx exhibit tremendous enhancement in oxygen evolution during photocatalysis and are much higher in comparison to so far known bioinspired manganese oxides and calcium-manganese oxides. Also, for the first time, a new approach for the representation of activities of water oxidation catalysts has been proposed by determining the amount of accessible manganese centers. PMID:25044528

  6. A Supramolecularly Activated Radical Cation for Accelerated Catalytic Oxidation.

    PubMed

    Jiao, Yang; Li, Wan-Lu; Xu, Jiang-Fei; Wang, Guangtong; Li, Jun; Wang, Zhiqiang; Zhang, Xi

    2016-07-25

    Tuning the activity of radicals is crucial for radical reactions and radical-based materials. Herein, we report a supramolecular strategy to accelerate the Fenton reaction through the construction of supramolecularly activated radical cations. As a proof of the concept, cucurbit[7]uril (CB[7]) was introduced, through host-guest interactions, onto each side of a derivative of 1,4-diketopyrrolo[3,4-c]pyrrole (DPP), a model dye for Fenton oxidation. The DPP radical cation, the key intermediate in the oxidation process, was activated by the electrostatically negative carbonyl groups of CB[7]. The activation induced a drastic decrease in the apparent activation energy and greatly increased the reaction rate. This facile supramolecular strategy is a promising method for promoting radical reactions. It may also open up a new route for the catalytic oxidation of organic pollutants for water purification and widen the realm of supramolecular catalysis. PMID:27273046

  7. DETERMINATION OF HETEROGENEOUS ELECTRON TRANSFER RATE CONSTANTS AT MICROFABRICATED IRIDIUM ELECTRODES. (R825511C022)

    EPA Science Inventory

    There has been an increasing use of both solid metal and microfabricated iridium electrodes as substrates for various types of electroanalysis. However, investigations to determine heterogeneous electron transfer rate constants on iridium, especially at an electron beam evapor...

  8. Iridium complexes demonstrating broadband emission through controlled geometric distortion and applications thereof

    DOEpatents

    Li, Jian; Turner, Eric

    2016-04-12

    Iridium compounds and their uses are disclosed herein. For example, carbazole containing iridium compounds are disclosed. The compounds are useful in many devices, including, but not limited to, electroluminescent devices.

  9. IR-doped ruthenium oxide catalyst for oxygen evolution

    NASA Technical Reports Server (NTRS)

    Valdez, Thomas I. (Inventor); Narayanan, Sekharipuram R. (Inventor)

    2012-01-01

    A method for preparing a metal-doped ruthenium oxide material by heating a mixture of a doping metal and a source of ruthenium under an inert atmosphere. In some embodiments, the doping metal is in the form of iridium black or lead powder, and the source of ruthenium is a powdered ruthenium oxide. An iridium-doped or lead-doped ruthenium oxide material can perform as an oxygen evolution catalyst and can be fabricated into electrodes for electrolysis cells.

  10. IRIDIUM exposure increases c-fos expression in the mouse brain only at levels which likely result in tissue heating.

    PubMed

    Morrissey, J J; Raney, S; Heasley, E; Rathinavelu, P; Dauphinee, M; Fallon, J H

    1999-01-01

    With the rapid development of wireless communication technology over the last 20 years, there has been some public concern over possible health effects of long-term, low-level radiofrequency exposure from cellular telephones. As an initial step in compiling a database for risk analysis by government agencies, the effects of 1-h exposure of mice to a 1.6-GHz radiofrequency signal, given as either a continuous wave or pulse modulated at 11 Hz with a duty cycle of 4:1 and a pulse duration of 9.2 ms IRIDIUM), on c-fos gene expression in the brain was investigated. The IRIDIUM signal is the operating frequency for a ground-to-satellite-to-ground cellular communications web which has recently become fully operational, and was named as such due to the original designed employment of the same number of low orbiting satellites as there are electrons orbiting the nucleus of an iridium atom. The expression of c-fos was not significantly elevated in the brains of mice until exposure levels exceeded six times the peak dose and 30 times the whole body average dose as maximal cellular telephone exposure limits in humans. Higher level exposure using either continuous wave (analog) or IRIDIUM signals elevated c-fos to a similar extent, suggesting no obvious pulsed modulation-specific effects. The pattern of c-fos elevation in limbic cortex and subcortex areas at higher exposure levels is most consistent with a stress response due to thermal perception coupled with restraint and/or neuron activity near thermoregulatory regions, and not consistent with any direct interaction of IRIDIUM energy with brain tissue. PMID:10426505

  11. Catalytic dehydrogenation of cycloalkanes to arenes by a dihydrido iridium P-C-P pincer complex

    SciTech Connect

    Gupta, M.; Hagen, C.; Cramer, R.E.; Jensen, C.M.; Kaska, W.C.

    1997-01-29

    We recently found that the iridium P-C-P pincer complex IrH{sub 2}[C{sub 6}H{sub 3}-2,6-(CH{sub 2}-PBu{sup T}{sub 2}){sub 2}] (1) is a highly active, homogeneous catalyst for the transfer dehydrogenation of cyclooctane with unusual long-term stability at temperatures as high as 200 {degree}C. This reactivity has now been extended to the catalytic transfer dehydrogenation of cycloalkanes to arenes. We report this novel catalytic activity as well as the results of an X-ray structure determination of 1. 15 refs., 1 fig., 1 tab.

  12. Tubular solid oxide fuel cell demonstration activities

    SciTech Connect

    Veyo, S.E.

    1995-08-01

    The development of a viable fuel cell driven electrical power generation system involves not only the development of cell and stack technology, but also the development of the overall system concept, the strategy for control, and the ancillary subsystems. The design requirements used to guide system development must reflect a customer focus in order to evolve a commercial product. In order to obtain useful customer feedback, Westinghouse has practiced the deployment with customers of fully integrated, automatically controlled, packaged solid oxide fuel cell power generation systems. These field units have served to demonstrate to customers first hand the beneficial attributes of the SOFC, to expose deficiencies through experience in order to guide continued development, and to garner real world feedback and data concerning not only cell and stack parameters, but also transportation, installation, permitting and licensing, start-up and shutdown, system alarming, fault detection, fault response, and operator interaction.

  13. Paraoxonase Activity and Oxidative Status in Patients with Tinnitus

    PubMed Central

    Akyüz, Servet; Somuk, Battal Tahsin; Soyalic, Harun; Yılmaz, Beyhan; Taskin, Abdullah; Bilinc, Hasan; Aksoy, Nurten

    2016-01-01

    Background and Objectives The aim of this study was to investigate serum paraoxanase-1 (PON) activity, total oxidant status (TOS), total antioxidant status (TAS), and the oxidative stress index (OSI) in tinnitus; and to compare the results with data from healthy subjects. Subjects and Methods A total of 114 subjects-54 patients with tinnitus and 60 healthy controls were enrolled in this study. Serum PON activity, TOS, TAS, and OSI levels were measured. Results In the tinnitus group, TAS, and PON were significantly lower than in the control group (p<0.001). However, the TOS, and OSI levels were significantly higher in the tinnitus group than in the control group (p<0.001). Conclusions According to the data obtained from the present study, patients with tinnitus were exposed to potent oxidative stress. Oxidative stress may be the key contributing factor to the pathogenesis of tinnitus. PMID:27144229

  14. Testing of electroformed deposited iridium/powder metallurgy rhenium rockets

    NASA Technical Reports Server (NTRS)

    Reed, Brian D.; Dickerson, Robert

    1996-01-01

    High-temperature, oxidation-resistant chamber materials offer the thermal margin for high performance and extended lifetimes for radiation-cooled rockets. Rhenium (Re) coated with iridium (Ir) allow hours of operation at 2200 C on Earth-storable propellants. One process for manufacturing Ir/Re rocket chambers is the fabrication of Re substrates by powder metallurgy (PM) and the application of Ir coatings by using electroformed deposition (ED). ED Ir coatings, however, have been found to be porous and poorly adherent. The integrity of ED Ir coatings could be improved by densification after the electroforming process. This report summarizes the testing of two 22-N, ED Ir/PM Re rocket chambers that were subjected to post-deposition treatments in an effort to densify the Ir coating. One chamber was vacuum annealed, while the other chamber was subjected to hot isostatic pressure (HIP). The chambers were tested on gaseous oxygen/gaseous hydrogen propellants, at mixture ratios that simulated the oxidizing environments of Earth-storable propellants. ne annealed ED Ir/PM Re chamber was tested for a total of 24 firings and 4.58 hr at a mixture ratio of 4.2. After only 9 firings, the annealed ED Ir coating began to blister and spall upstream of the throat. The blistering and spalling were similar to what had been experienced with unannealed, as-deposited ED Ir coatings. The HIP ED Ir/PM Re chamber was tested for a total of 91 firings and 11.45 hr at mixture ratios of 3.2 and 4.2. The HIP ED Ir coating remained adherent to the Re substrate throughout testing; there were no visible signs of coating degradation. Metallography revealed, however, thinning of the HIP Ir coating and occasional pores in the Re layer upstream of the throat. Pinholes in the Ir coating may have provided a path for oxidation of the Re substrate at these locations. The HIP ED Ir coating proved to be more effective than vacuum annealed and as-deposited ED Ir. Further densification is still required to

  15. Engineering an iridium-containing metal-organic molecular capsule for induced-fit geometrical conversion and dual catalysis.

    PubMed

    Li, Xuezhao; Wu, Jinguo; Chen, Liyong; Zhong, Xiaoming; He, Cheng; Zhang, Rong; Duan, Chunying

    2016-08-11

    By introducing photoactive fac-tris(2-phenylpyridine)iridium moieties as a ligand backbone to constrain the coordination geometry of cobalt ions, a multifunctional Ir2Co3-type capsule was achieved and showed induced-fit capsule-capsule conversion by cooperative binding one carbonate anion with the equatorial Co(ii) centers. The capsule combined photocatalysis and transition metal activation synergistically and exhibited efficient catalytic ability on visible light-activated α-trichloromethylation. PMID:27320443

  16. Particulate Matter Oxidative Potential from Waste Transfer Station Activity

    PubMed Central

    Godri, Krystal J.; Duggan, Sean T.; Fuller, Gary W.; Baker, Tim; Green, David; Kelly, Frank J.; Mudway, Ian S.

    2010-01-01

    Background Adverse cardiorespiratory health is associated with exposure to ambient particulate matter (PM). The highest PM concentrations in London occur in proximity to waste transfer stations (WTS), sites that experience high numbers of dust-laden, heavy-duty diesel vehicles transporting industrial and household waste. Objective Our goal was to quantify the contribution of WTS emissions to ambient PM mass concentrations and oxidative potential. Methods PM with a diameter < 10 μm (PM10) samples were collected daily close to a WTS. PM10 mass concentrations measurements were source apportioned to estimate local versus background sources. PM oxidative potential was assessed using the extent of antioxidant depletion from a respiratory tract lining fluid model. Total trace metal and bioavailable iron concentrations were measured to determine their contribution to PM oxidative potential. Results Elevated diurnal PM10 mass concentrations were observed on all days with WTS activity (Monday–Saturday). Variable PM oxidative potential, bioavailable iron, and total metal concentrations were observed on these days. The contribution of WTS emissions to PM at the sampling site, as predicted by microscale wind direction measurements, was correlated with ascorbate (r = 0.80; p = 0.030) and glutathione depletion (r = 0.76; p = 0.046). Increased PM oxidative potential was associated with aluminum, lead, and iron content. Conclusions PM arising from WTS activity has elevated trace metal concentrations and, as a consequence, increased oxidative potential. PM released by WTS activity should be considered a potential health risk to the nearby residential community. PMID:20368130

  17. Oxidation of Ruthenium and Iridium Metal by XeF2 and Crystal Structure Determination of [Xe2F3][RuF6]·XeF2 and [Xe2F3][MF6] (M = Ru, Ir).

    PubMed

    Tramšek, Melita; Goreshnik, Evgeny; Tavčar, Gašper

    2016-01-01

    Salts containing [Xe2F3]+ cations and [MF6]- anions (M = Ru, Ir) were synthesized by the oxidation of metal with excess of XeF2 in anhydrous hydrogen fluoride (aHF) as a solvent. Single crystals of [Xe2F3][RuF6]·XeF2, [Xe2F3][RuF6] and [Xe2F3][IrF6] were grown by slow evaporation of the solvent. [Xe2F3][RuF6]·XeF2 crystallizes in a triclinic P-1 space group (a = 8.3362(1) Å, b = 8.8197(2) Å, c = 9.3026(4) Å; α = 68.27(1)°, β = 63.45(1)°, γ = 82.02°, V = 568.09(9) Å3 (Z = 2)). Discrete [Xe2F3]+, XeF2 and [RuF6]- units are found in the asymmetric unit. [Xe2F3][RuF6] and [Xe2F3][IrF6] compounds are isostructural and crystallize in a monoclinic Cc space group (a = 14.481(3) Å (Ru); 14.544(3) Å (Ir); b = 8.0837(8) Å (Ru), 8.0808(7) Å (Ir), c = 10.952(2) Å (Ru), 11.014(2) Å (Ir); β = 136.825(6)° (Ru), 139.954(7)°, V = 877.2(3) Å3 (Ru), 883.6(3) Å3 (Ir); Z = 4). The asymmetric unit in the [Xe2F3][MF6] (M = Ru, Ir) consists of one [Xe2F3]+ and one [MF6]- unit. PMID:27333561

  18. Activation of molecular oxygen and the nature of the active oxygen species for CO oxidation on oxide supported Au catalysts.

    PubMed

    Widmann, D; Behm, R J

    2014-03-18

    Although highly dispersed Au catalysts with Au nanoparticles (NPs) of a few nanometers in diameter are well-known for their high catalytic activity for several oxidation and reduction reactions already at rather low temperatures for almost 30 years, central aspects of the reaction mechanism are still unresolved. While most studies focused on the active site, the active Au species, and the effect of the support material, the most crucial step during oxidation reactions, the activation of molecular oxygen and the nature of the resulting active oxygen species (Oact), received more attention just recently. This is topic of this Account, which focuses on the formation, location, and nature of the Oact species present on metal oxide supported Au catalysts under typical reaction conditions, at room temperature and above. It is mainly based on quantitative temporal analysis of products (TAP) reactor measurements, which different from most spectroscopic techniques are able to detect and quantify these species even at the extremely low concentrations present under realistic reaction conditions. Different types of pulse experiments were performed, during which the highly dispersed, realistic powder catalysts are exposed to very low amounts of reactants, CO and/or O2, in order to form and reactively remove Oact species and gain information on their formation, nature, and the active site for Oact formation. Our investigations have shown that the active oxygen species for CO oxidation on Au/TiO2 for reaction at 80 °C and higher is a highly stable atomic species, which at 80 °C is formed only at the perimeter of the Au-oxide interface and whose reactive removal by CO is activated, but not its formation. From these findings, it is concluded that surface lattice oxygen represents the Oact species for the CO oxidation. Accordingly, the CO oxidation proceeds via a Au-assisted Mars-van Krevelen mechanism, during which surface lattice oxygen close to the Au NPs is removed by reaction

  19. The high-temperature impact properties of DOP-26 iridium

    SciTech Connect

    George, T.G.; Stevens, M.F. )

    1988-10-01

    A study of the impact properties of DOP-26 iridium (which contains 0.3% tungsten and --40 pm thorium) at temperatures of 600 to 1,440/sup 0/C revealed that the predominant mode of failure for the material is intergranular separation with occasional transgranular cleavage. DOP-26 iridium also appears to have a high notch sensitivity, in contrast to most other face-centered-cubic (fcc) metals; at elevated deformation temperatures, the dislocation substructure is similar to that of other fcc metals. In addition, regular arrays of pure edge character dislocations have been found. In the test specimens used in this study, the presence of Ir Th particles was observed within iridium grains. The existence of these particles indicates that the role of thorium is not well understood, particularly in light of the fact that previous studies, which depended on grain boundary segregation, have shown thorium to improve grain boundary cohesion.

  20. Biological activity of ellagitannins: Effects as anti-oxidants, pro-oxidants and metal chelators.

    PubMed

    Moilanen, Johanna; Karonen, Maarit; Tähtinen, Petri; Jacquet, Rémi; Quideau, Stéphane; Salminen, Juha-Pekka

    2016-05-01

    Ellagitannins are a subclass of hydrolysable tannins that have been suggested to function as defensive compounds of plants against herbivores. However, it is known that the conditions in the digestive tracts of different herbivores are variable, so it seems reasonable to anticipate that the reactivities and modes of actions of these ingested defensive compounds would also be different. A previous study on a few ellagitannins has shown that these polyphenolic compounds are highly oxidizable at high pH and that their bioactivity can be attributed to certain structural features. Herein, the activities of 13 ellagitannins using the deoxyribose assay were measured. The results provided information about the anti-oxidant, pro-oxidant and metal chelating properties of ellagitannins. Surprisingly, many of the tested ellagitannins exhibited pro-oxidant activities even at neutral pH and only moderate to low radical scavenging activities, although the metal chelating capacities of all tested ellagitannins were relatively high. PMID:26899362

  1. Neural activity triggers neuronal oxidative metabolism followed by astrocytic glycolysis.

    PubMed

    Kasischke, Karl A; Vishwasrao, Harshad D; Fisher, Patricia J; Zipfel, Warren R; Webb, Watt W

    2004-07-01

    We have found that two-photon fluorescence imaging of nicotinamide adenine dinucleotide (NADH) provides the sensitivity and spatial three-dimensional resolution to resolve metabolic signatures in processes of astrocytes and neurons deep in highly scattering brain tissue slices. This functional imaging reveals spatiotemporal partitioning of glycolytic and oxidative metabolism between astrocytes and neurons during focal neural activity that establishes a unifying hypothesis for neurometabolic coupling in which early oxidative metabolism in neurons is eventually sustained by late activation of the astrocyte-neuron lactate shuttle. Our model integrates existing views of brain energy metabolism and is in accord with known macroscopic physiological changes in vivo. PMID:15232110

  2. Ultrasound assisted, thermally activated persulfate oxidation of coal tar DNAPLs.

    PubMed

    Peng, Libin; Wang, Li; Hu, Xingting; Wu, Peihui; Wang, Xueqing; Huang, Chumei; Wang, Xiangyang; Deng, Dayi

    2016-11-15

    The feasibility of ultrasound assisted, thermally activated persulfate for effective oxidation of twenty 2-6 ringed coal tar PAHs in a biphasic tar/water system and a triphasic tar/soil/water system were investigated and established. The results indicate that ultrasonic assistance, persulfate and elevated reaction temperature are all required to achieve effective oxidation of coal tar PAHs, while the heating needed can be provided by ultrasonic induced heating as well. Further kinetic analysis reveals that the oxidation of individual PAH in the biphasic tar/water system follows the first-order kinetics, and individual PAH oxidation rate is primary determined by the mass transfer coefficients, tar/water interfacial areas, the aqueous solubility of individual PAH and its concentration in coal tar. Based on the kinetic analysis and experimental results, the contributions of ultrasound, persulfate and elevated reaction temperature to PAHs oxidation were characterized, and the effects of ultrasonic intensity and oxidant dosage on PAHs oxidation efficiency were investigated. In addition, the results indicate that individual PAH degradability is closely related to its reactivity as well, and the high reactivity of 4-6 ringed PAHs substantially improves their degradability. PMID:27450342

  3. High temperature solid oxide fuel development activities

    SciTech Connect

    Ray, E.R.

    1993-11-01

    This paper presents an overview of the Westinghouse tubular SOFC development activities and current program status. Goal is to develop a cell that can operate for 50,000 to 100,000 h. Test results are presented for multiple single cell tests which have now successfully exceeded 40,000 hours of continuous power operation at temperature. Two 25-kW SOFC customer tests units were delivered in 1992; a 20-kW SOFC system is bein manufactured and will be operated by Southern California Edison in 1995. Megawatt class generators are being developed.

  4. Experimental determination of the solubility of iridium in silicate melts: Preliminary results

    NASA Technical Reports Server (NTRS)

    Borisov, Alexander; Dingwell, Donald B.; Oneill, Hugh ST.C.; Palme, Herbert

    1992-01-01

    Little is known of the geochemical behavior of iridium. Normally this element is taken to be chalcophile and/or siderophile so that during planetary differentiation processes, e.g., core formation, iridium is extracted from silicate phases into metallic phases. Experimental determination of the metal/silicate partition coefficient of iridium is difficult simply because it is so large. Also there are no data on the solubility behavior of iridium in silicate melts. With information on the solubility of iridium in silicate melts it is possible, in combination with experimental data for Fe-Ir alloys, to calculate the partition coefficient between a metallic phase and a silicate melt.

  5. The Collision of Iridium 33 and Cosmos 2251: The Shape of Things to Come

    NASA Technical Reports Server (NTRS)

    Nicholas, Johnson

    2009-01-01

    The collision of Iridium 33 and Cosmos 2251 was the most severe accidental fragmentation on record. More than 1800 debris approx. 10 cm and larger were produced. If solar activity returns to normal, half of the tracked debris will reenter within five years. Less than 60 cataloged debris had reentered by 1 October 2009. Some debris from both satellites will remain in orbit through the end of the century. The collision rate of one every five years will increase without future removal of large derelict spacecraft and launch vehicle orbital stages.

  6. Field desorption of Na and Cs from graphene on iridium

    NASA Astrophysics Data System (ADS)

    Bernatskii, D. P.; Pavlov, V. G.

    2015-08-01

    Field electron and desorption microscopy has been used to study specific features of the field desorption of sodium and cesium ions adsorbed on the surface of iridium with graphene. It was found that adsorbed sodium atoms most strongly reduce the work function on graphene islands situated over densely packed faces of iridium. A strong electric field qualitatively similarly affects the sodium and cesium desorption processes from a field emitter to give two desorption phases and has no noticeable effect on the disintegration of the graphene layer.

  7. Partially Oxidized Sub-10 nm MnO Nanocrystals with High Activity for Water Oxidation Catalysis

    PubMed Central

    Jin, Kyoungsuk; Chu, Arim; Park, Jimin; Jeong, Donghyuk; Jerng, Sung Eun; Sim, Uk; Jeong, Hui-Yun; Lee, Chan Woo; Park, Yong-Sun; Yang, Ki Dong; Kumar Pradhan, Gajendra; Kim, Donghun; Sung, Nark-Eon; Hee Kim, Sun; Nam, Ki Tae

    2015-01-01

    The oxygen evolution reaction (OER) is considered a major bottleneck in the overall water electrolysis process. In this work, highly active manganese oxide nano-catalysts were synthesized via hot injection. Facile surface treatment generated Mn(III) species on monodisperse 10 nm MnO nanocrystals (NCs). Size dependency of MnO NCs on OER activity was also investigated. Surprisingly, the partially oxidized MnO NCs only required 530 mV @ 5 mA cm−2 under near neutral conditions. PMID:25998696

  8. Partially Oxidized Sub-10 nm MnO Nanocrystals with High Activity for Water Oxidation Catalysis

    NASA Astrophysics Data System (ADS)

    Jin, Kyoungsuk; Chu, Arim; Park, Jimin; Jeong, Donghyuk; Jerng, Sung Eun; Sim, Uk; Jeong, Hui-Yun; Lee, Chan Woo; Park, Yong-Sun; Yang, Ki Dong; Kumar Pradhan, Gajendra; Kim, Donghun; Sung, Nark-Eon; Hee Kim, Sun; Nam, Ki Tae

    2015-05-01

    The oxygen evolution reaction (OER) is considered a major bottleneck in the overall water electrolysis process. In this work, highly active manganese oxide nano-catalysts were synthesized via hot injection. Facile surface treatment generated Mn(III) species on monodisperse 10 nm MnO nanocrystals (NCs). Size dependency of MnO NCs on OER activity was also investigated. Surprisingly, the partially oxidized MnO NCs only required 530 mV @ 5 mA cm-2 under near neutral conditions.

  9. Persulfate activation during exertion of total oxidant demand.

    PubMed

    Teel, Amy L; Elloy, Farah C; Watts, Richard J

    2016-09-01

    Total oxidant demand (TOD) is a parameter that is often measured during in situ chemical oxidation (ISCO) treatability studies. The importance of TOD is based on the concept that the oxidant demand created by soil organic matter and other reduced species must be overcome before contaminant oxidation can proceed. TOD testing was originally designed for permanganate ISCO, but has also recently been applied to activated persulfate ISCO. Recent studies have documented that phenoxides activate persulfate; because soil organic matter is rich in phenolic moieties, it may activate persulfate rather than simply exerting TOD. Therefore, the generation of reactive oxygen species was investigated in three soil horizons of varied soil organic carbon content over 5-day TOD testing. Hydroxyl radical may have been generated during TOD exertion, but was likely scavenged by soil organic matter. A high flux of reductants + nucleophiles (e.g. alkyl radicals + superoxide) was generated as TOD was exerted, resulting in the rapid destruction of the probe compound hexachloroethane and the common groundwater contaminant trichloroethylene (TCE). The results of this research document that, unlike permanganate TOD, contaminant destruction does occur as TOD is exerted in persulfate ISCO systems and is promoted by the activation of persulfate by soil organic matter. Future treatability studies for persulfate ISCO should consider contaminant destruction as TOD is exerted, and the potential for persulfate activation by soil organic matter. PMID:27269993

  10. Metabolic activation of carcinogenic ethylbenzene leads to oxidative DNA damage.

    PubMed

    Midorikawa, Kaoru; Uchida, Takafumi; Okamoto, Yoshinori; Toda, Chitose; Sakai, Yoshie; Ueda, Koji; Hiraku, Yusuke; Murata, Mariko; Kawanishi, Shosuke; Kojima, Nakao

    2004-12-01

    Ethylbenzene is carcinogenic to rats and mice, while it has no mutagenic activity. We have investigated whether ethylbenzene undergoes metabolic activation, leading to DNA damage. Ethylbenzene was metabolized to 1-phenylethanol, acetophenone, 2-ethylphenol and 4-ethylphenol by rat liver microsomes. Furthermore, 2-ethylphenol and 4-ethylphenol were metabolically transformed to ring-dihydroxylated metabolites such as ethylhydroquinone and 4-ethylcatechol, respectively. Experiment with 32P-labeled DNA fragment revealed that both ethylhydroquinone and 4-ethylcatechol caused DNA damage in the presence of Cu(II). These dihydroxylated compounds also induced the formation of 8-oxo-7,8-dihydro-2'-deoxyguanosine in calf thymus DNA in the presence of Cu(II). Catalase, methional and Cu(I)-specific chelator, bathocuproine, significantly (P<0.05) inhibited oxidative DNA damage, whereas free hydroxyl radical scavenger and superoxide dismutase did not. These results suggest that Cu(I) and H2O2 produced via oxidation of ethylhydroquinone and 4-ethylcatechol are involved in oxidative DNA damage. Addition of an endogenous reductant NADH dramatically enhanced 4-ethylcatechol-induced oxidative DNA damage, whereas ethylhydroquinone-induced DNA damage was slightly enhanced. Enhancing effect of NADH on oxidative DNA damage by 4-ethylcatechol may be explained by assuming that reactive species are generated from the redox cycle. In conclusion, these active dihydroxylated metabolites would be involved in the mechanism of carcinogenesis by ethylbenzene. PMID:15560893

  11. Synthesis of new heteroscorpionate iridium(I) and iridium(III) complexes.

    PubMed

    Roa, A E; Campos, J; Paneque, M; Salazar, V; Otero, A; Lara-Sánchez, A; Rodríguez, A M; López-Solera, I; Gómez, M V

    2015-04-21

    The reactivity of different heteroscorpionate ligands based on bis(pyrazol-1-yl)methane, with different iridium-(i) and -(iii) precursors is reported. The reaction of the heteroscorpionate lithium salts "Li(bdmpza)", [bdmpza = bis(3,5-dimethylpyrazol-1-yl)acetate], "Li(bdmpzdta)" [bdmpzdta = bis(3,5-dimethylpyrazol-1-yl)dithioacetate] and "Li(S)-mbpam" [(S)-mbpam = (S)-(-)-N-α-methylbenzyl-2,2-bis(3,5-dimethylpyrazol-1-yl)acetamidate] with 1 equivalent of [IrCl3(THF)3] in THF for 18 h affords high yields of neutral and anionic heteroscorpionate chloride iridium complexes [IrCl2(bdmpza)(THF)] (), [Li(THF)4][IrCl3(bdmpzdta)] () and [IrCl2{(S)-mbpam})(THF)] (). Solution of complex in acetonitrile at room temperature leads to complex [IrCl2{(S)-mbpam})(NCCH3)] (). Complexes and were isolated as enantiopure compounds. The reaction of the lithium salt "Li(bdmpza)" with [IrCl(η(4)-CH2[double bond, length as m-dash]C(Me)C(Me)[double bond, length as m-dash]CH2)]2 in THF for 18 h gave the Ir(i) complex [Ir(bdmpza)(η(4)-CH2[double bond, length as m-dash]C(Me)C(Me)[double bond, length as m-dash]CH2)] (). The reaction of complex with CO (2 atm) at room temperature leads to a new complex of Ir(iii), [Ir(bdmpza)(k(2)-CH2C(Me)[double bond, length as m-dash]C(Me)CH2)(CO)] (). Treatment of heteroscorpionate ligand precursors "Li(bdmpza)" and "Li(bdmpzdta)" with [IrCp*Cl2]2 in THF yielded the iridium(iii) complexes [Ir2Cp*2Cl2(bdmpzx)] (x = a , x = dta ). These complexes have helical chirality due to the demands of the fixed pyrazole rings. The stereoisomerism and the self-assembly processes of these helicates have been studied in some detail in solution by NMR spectroscopy and in the solid state by X-ray diffraction. Mixtures of M- and P-handed enantiomers were obtained. Complex undergoes a decarboxylation process initiated by the HCl generated in the previous step leading to the known ionic complex [IrClCp*(bdmpm)][IrCl3Cp*] [bdmpm = bis(3,5-dimethylpyrazol-1-yl)methane] (). The

  12. [Level of nitric oxide in the kidneys during apoptosis activation].

    PubMed

    Komarievtseva, I O; Orlova, O A; Blahodarenko, Ie A

    2002-01-01

    The content of nitric oxide stable metabolites in a tissue of kidneys of rats in conditions of activation of apoptosis was investigated. Research was carried out in two models: acute renal failure and a hypertrophy of a unique kidney after a unilateral nephrectomy. Detection of apoptosis was carried out by definition of DNA fragmentation. Substantial increase of the nitric oxide stable metabolites contents is revealed at activation of apoptosis in both models. Change of a ratio of the contents of nitrite--anions in relation to the general contents of NO2- + NO3- is revealed, indicating the role of peroxide processes in effect of nitric oxide and its metabolites on the cell. PMID:14964872

  13. 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.

  14. Hysteresis in the Active Oxidation of SiC

    NASA Technical Reports Server (NTRS)

    Jacobson, Nathan S.; Harder, Bryan J.; Myers, Dwight L.

    2011-01-01

    Si and SiC show both passive oxidation behavior where a protective film of SiO2 forms and active oxidation behavior where a volatile suboxide SiO(g) forms. The active-to-passive and passive-to-active oxidation transitions are explored for both Si and SiC. Si shows a dramatic difference between the P(O2) for the two transitions of 10-4 bar. The active-to-passive transition is controlled by the condition for SiO2/Si equilibrium and the passive-to-active transition is controlled by the decomposition of SiO2. In the case of SiC, the P(O2) for these transitions are much closer. The active-to-passive transition appears to be controlled by the condition for SiO2/SiC equilibrium. The passive-to-active transition appears to be controlled by the interfacial reaction of SiC and SiO2 and subsequent generation of gases at the interface which leads to scale breakdown.

  15. Impact of Sulfur Oxides on Mercury Capture by Activated Carbon

    SciTech Connect

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

    2007-09-15

    Recent field tests of mercury removal with activated carbon injection (ACI) have revealed that mercury capture is limited in flue gases containing high concentrations of sulfur oxides (SOx). In order to gain a more complete understanding of the impact of SOx on ACI, mercury capture was tested under varying conditions of SO2 and SO3 concentrations using a packed bed reactor and simulated flue gas (SFG). The final mercury content of the activated carbons is independent of the SO2 concentration in the SFG, but the presence of SO3 inhibits mercury capture even at the lowest concentration tested (20 ppm). The mercury removal capacity decreases as the sulfur content of the used activated carbons increases from 1 to 10%. In one extreme case, an activated carbon with 10% sulfur, prepared by H2SO4 impregnation, shows almost no mercury capacity. The results suggest that mercury and sulfur oxides are in competition for the same binding sites on the carbon surface.

  16. Wet oxidative regeneration of activated carbon loaded with reactive dye.

    PubMed

    Shende, R V; Mahajani, V V

    2002-01-01

    Wet Oxidative Regeneration (WOR) of powdered activated carbon (PAC) and granular activated carbon (GAC) loaded with the reactive dyes, namely chemictive brilliant blue R and cibacron turquoise blue G, was studied. Attempts were made to regenerate the loaded carbons designated now as spent carbon. A slurry (10% w/v) of spent carbon in distilled water was oxidized by wet oxidation in the temperature range of 150-250 degrees C using oxygen partial pressures between 0.69-1.38 MPa in an 1 1 SS 316 autoclave. The percent regeneration was determined from a ratio, X(RC)/X(VC), corresponding to an equilibrium adsorption capacity of regenerated carbon/equilibrium adsorption capacity of virgin carbon from an initial adsorption period of 3 h. It was observed that the regeneration mainly occurred due to the oxidation of the adsorbates taking place on the surface of carbon. It was possible to regenerate the spent GAC and PAC to the extent of more than 98% (approximately X(RC)/X(VC) > 0.98) by wet oxidation. After four consecutive cycles of adsorption and regeneration using the same stocks of GAC, carbon weight loss observed at 200 degrees C was about 40%. SEM studies of the regenerated carbon showed widening of the pores and loss of structure between the adjacent pores as compared with the virgin carbon. PAC was found to be more suitable as compared with GAC for the adsorption and wet oxidative regeneration processes to treat the aqueous solution containing lower concentration of unhydrolyzed reactive dye. The suitability of wet oxidative regeneration is demonstrated at a bench scale to treat the synthetic reactive dye solution. PMID:11942707

  17. A potential biomarker for fatigue: Oxidative stress and anti-oxidative activity.

    PubMed

    Fukuda, Sanae; Nojima, Junzo; Motoki, Yukari; Yamaguti, Kouzi; Nakatomi, Yasuhito; Okawa, Naoko; Fujiwara, Kazumi; Watanabe, Yasuyoshi; Kuratsune, Hirohiko

    2016-07-01

    We sought to determine whether oxidative stress and anti-oxidative activity could act as biomarkers that discriminate patients with chronic fatigue syndrome (CFS) from healthy volunteers at acute and sub-acute fatigue and resting conditions. We calculated the oxidative stress index (OSI) from reactive oxygen metabolites-derived compounds (d-ROMs) and the biological antioxidant potential (BAP). We determined changes in d-ROMs, BAP, and OSI in acute and sub-acute fatigue in two healthy groups, and compared their values at rest between patients with CFS (diagnosed by Fukuda 1994 criteria) and another group of healthy controls. Following acute fatigue in healthy controls, d-ROMs and OSI increased, and BAP decreased. Although d-ROMs and OSI were significantly higher after sub-acute fatigue, BAP did not decrease. Resting condition yielded higher d-ROMs, higher OSI, and lower BAP in patients with CFS than in healthy volunteers, but lower d-ROMs and OSI when compared with sub-acute controls. BAP values did not significantly differ between patients with CFS and controls in the sub-acute condition. However, values were significantly higher than in the resting condition for controls. Thus, measured of oxidative stress (d-ROMS) and anti-oxidative activity (BAP) might be useful for discriminating acute, sub-acute, and resting fatigue in healthy people from patients with CFS, or for evaluating fatigue levels in healthy people. PMID:27224647

  18. Understanding Interactions between Manganese Oxide and Gold That Lead to Enhanced Activity for Electrocatalytic Water Oxidation

    PubMed Central

    2015-01-01

    To develop active nonprecious metal-based electrocatalysts for the oxygen evolution reaction (OER), a limiting reaction in several emerging renewable energy technologies, a deeper understanding of the activity of the first row transition metal oxides is needed. Previous studies of these catalysts have reported conflicting results on the influence of noble metal supports on the OER activity of the transition metal oxides. Our study aims to clarify the interactions between a transition metal oxide catalyst and its metal support in turning over this reaction. To achieve this goal, we examine a catalytic system comprising nanoparticulate Au, a common electrocatalytic support, and nanoparticulate MnOx, a promising OER catalyst. We conclusively demonstrate that adding Au to MnOx significantly enhances OER activity relative to MnOx in the absence of Au, producing an order of magnitude higher turnover frequency (TOF) than the TOF of the best pure MnOx catalysts reported to date. We also provide evidence that it is a local rather than bulk interaction between Au and MnOx that leads to the observed enhancement in the OER activity. Engineering improvements in nonprecious metal-based catalysts by the addition of Au or other noble metals could still represent a scalable catalyst as even trace amounts of Au are shown to lead a significant enhancement in the OER activity of MnOx. PMID:24661269

  19. Understanding interactions between manganese oxide and gold that lead to enhanced activity for electrocatalytic water oxidation.

    PubMed

    Gorlin, Yelena; Chung, Chia-Jung; Benck, Jesse D; Nordlund, Dennis; Seitz, Linsey; Weng, Tsu-Chien; Sokaras, Dimosthenis; Clemens, Bruce M; Jaramillo, Thomas F

    2014-04-01

    To develop active nonprecious metal-based electrocatalysts for the oxygen evolution reaction (OER), a limiting reaction in several emerging renewable energy technologies, a deeper understanding of the activity of the first row transition metal oxides is needed. Previous studies of these catalysts have reported conflicting results on the influence of noble metal supports on the OER activity of the transition metal oxides. Our study aims to clarify the interactions between a transition metal oxide catalyst and its metal support in turning over this reaction. To achieve this goal, we examine a catalytic system comprising nanoparticulate Au, a common electrocatalytic support, and nanoparticulate MnO(x), a promising OER catalyst. We conclusively demonstrate that adding Au to MnO(x) significantly enhances OER activity relative to MnO(x) in the absence of Au, producing an order of magnitude higher turnover frequency (TOF) than the TOF of the best pure MnO(x) catalysts reported to date. We also provide evidence that it is a local rather than bulk interaction between Au and MnO(x) that leads to the observed enhancement in the OER activity. Engineering improvements in nonprecious metal-based catalysts by the addition of Au or other noble metals could still represent a scalable catalyst as even trace amounts of Au are shown to lead a significant enhancement in the OER activity of MnO(x). PMID:24661269

  20. The Iridium (tm) system: Personal communications anytime, anyplace

    NASA Technical Reports Server (NTRS)

    Hatlelid, John E.; Casey, Larry

    1993-01-01

    The Iridium system is designed to provide handheld personal communications between diverse locations around the world at any time and without prior knowledge of the location of the personal units. This paper provides an overview of the system, the services it provides, its operation, and an overview of the commercial practices and relatively high volume satellite production techniques which will make the system cost effective. A constellation of 66 satellites will provide an orbiting, spherical-shell, infrastructure for this global calling capability. The satellites act as tall cellular towers and allow convenient operation for portable handheld telephones. The system will provide a full range of services including voice, paging, data, geolocation, and fax capabilities. Motorola is a world leader in the production of high volume, high quality, reliable telecommunications hardware. One of Iridium's goals is to apply these production techniques to high reliability space hardware. Concurrent engineering, high performance work teams, advanced manufacturing technologies, and improved assembly and test methods are some of the techniques that will keep the Iridium system cost effective. Mobile, global, flexible personal communications are coming that will allow anyone to call or receive a call from/to anyplace at anytime. The Iridium system will provide communications where none exist today. This connectivity will allow increased information transfer, open new markets for various business endeavors, and in general increase productivity and development.

  1. Iridium alloy Clad Vent Set manufacturing qualification studies

    NASA Astrophysics Data System (ADS)

    Ulrich, George B.

    Metallurgical qualification studies to demonstrate the manufacturing readiness of the iridium alloy Clad Vent Set (CVS) for the General Purpose Heat Source program at the Oak Ridge Y-12 Plant are described. Microstructural data for various materials/test conditions are presented.

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

    SciTech Connect

    Robinson, R.; Thoennessen, M.

    2012-09-15

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

  3. Magnetostratigraphy, Late devonian iridium anomaly, and impact hypotheses

    SciTech Connect

    Hurley, N.F.; Van der Voo, R. )

    1990-04-01

    Paleomagnetism, sedimentology, and fine-scale stratigraphy have been integrated to explain the origin of an iridium anomaly in the Late Devonian of Western Australia. Thermal demagnetization experiments were carried out on 93 specimens of marginal-slope limestone form the northern Canning Basin. Samples are from a condensed sequence of deep-water (> 100 m) Frutexites microstromatolites. Frutexites is a shrublike cyanobacterial organism that probably precipitated hematite, or a metastable precursor, from sea water. When plotted within the microstratigraphic framework for the study area, the observed characteristic directions from the sampled interval (14.5 cm thick) are in five discrete, layer-parallel, normal- and reversed-polarity zones. The measured northeast-southwest declinations and shallow inclinations probably record Late Devonian magnetostratigraphy on a centimetre scale. The Frutexites bed studied there occurs close to the Frasnian/Famennian (Late Devonian) boundary, a time of mass extinction of a wide variety of marine organisms throughout the world. Anomalously high iridium concentrations observed in the Frutexites bed have suggested to some authors that the mass extinction was caused by meteorite impact. This study concludes that iridium, which is present over the span of five layer-parallel magnetic reversals, was concentrated over a long period of time by biologic processes. Thus, the Canning Basin iridium anomaly may be unrelated to meteorite impact.

  4. The Iridium (tm) system: Personal communications anytime, anyplace

    NASA Astrophysics Data System (ADS)

    Hatlelid, John E.; Casey, Larry

    The Iridium system is designed to provide handheld personal communications between diverse locations around the world at any time and without prior knowledge of the location of the personal units. This paper provides an overview of the system, the services it provides, its operation, and an overview of the commercial practices and relatively high volume satellite production techniques which will make the system cost effective. A constellation of 66 satellites will provide an orbiting, spherical-shell, infrastructure for this global calling capability. The satellites act as tall cellular towers and allow convenient operation for portable handheld telephones. The system will provide a full range of services including voice, paging, data, geolocation, and fax capabilities. Motorola is a world leader in the production of high volume, high quality, reliable telecommunications hardware. One of Iridium's goals is to apply these production techniques to high reliability space hardware. Concurrent engineering, high performance work teams, advanced manufacturing technologies, and improved assembly and test methods are some of the techniques that will keep the Iridium system cost effective. Mobile, global, flexible personal communications are coming that will allow anyone to call or receive a call from/to anyplace at anytime. The Iridium system will provide communications where none exist today. This connectivity will allow increased information transfer, open new markets for various business endeavors, and in general increase productivity and development.

  5. Mononuclear iridium dinitrogen complexes bonded to zeolite HY

    SciTech Connect

    Yang, Dong; Chen, Mingyang; Martinez-Macias, Claudia; Dixon, David A.; Gates, Bruce C.

    2014-11-07

    In this study, the adsorption of N2 on structurally well-defined dealuminated HY zeolite-supported iridium diethylene complexes was investigated. Iridium dinitrogen complexes formed when the sample was exposed to N2 in H2 at 298 K, as shown by infrared spectra recorded with isotopically labeled N2. Four supported species formed in various flowing gases: Ir(N2), Ir(N2)(N2), Ir(C2H5)(N2), and Ir(H)(N2). Their interconversions are summarized in a reaction network, showing, for example, that, in the presence of N2, Ir(N2) was the predominant dinitrogen species at temperatures of 273-373 K. Ir(CO)(N2) formed transiently in flowing CO, and in the presence of H2, rather stable iridium hydride complexes formed. Here, four structural models of each iridium complex bonded at the acidic sites of the zeolite were employed in a computational investigation, showing that the calculated vibrational frequencies agree well with experiment when full calculations are done at the level of density functional theory, independent of the size of the model of the zeolite.

  6. Achieving Zero Stress in Iridium, Chromium, and Nickle Thin Films

    NASA Technical Reports Server (NTRS)

    Broadway, David M.; Weimer, Jeffrey; Gurgew, Danielle; Lis, Tomasz; Ramsey, Brian D.; O'Dell, Stephen L.; Ames, A.; Bruni, R.

    2015-01-01

    We examine a method for achieving zero intrinsic stress in thin films of iridium, chromium, and nickel deposited by magnetron sputter deposition. The examination of the stress in these materials is motivated by efforts to advance the optical performance of light-weight x-ray space telescopes into the regime of sub-arc second resolution that rely on control of the film stress to values within 10-100 MPa. A characteristic feature of the intrinsic stress behavior in chromium and nickel is their sensitivity to the magnitude and sign of the intrinsic stress with argon gas pressure, including the existence of a critical pressure that results in zero film stress. This critical pressure scales linearly with the film's density. While the effect of stress reversal with argon pressure has been previously reported by Hoffman and others for nickel and chromium, we have discovered a similar behavior for iridium. Additionally, we have identified zero stress in iridium shortly after island coalescence. This feature of film growth is used for achieving a total internal stress of -2.89 MPa for a 15.8 nm thick iridium film. The surface roughness of this low-stress film was examined using scanning probe microscopy (SPM) and x-ray reflectivity (XRR) at CuKa and these results presented and discussed.

  7. Achieving zero stress in iridium, chromium, and nickel thin films

    NASA Astrophysics Data System (ADS)

    Broadway, David M.; Weimer, Jeffrey; Gurgew, Danielle; Lis, Tomasz; Ramsey, Brian D.; O'Dell, Stephen L.; Gubarev, Mikhail; Ames, A.; Bruni, R.

    2015-05-01

    We examine a method for achieving zero intrinsic stress in thin films of iridium, chromium, and nickel deposited by magnetron sputter deposition. The examination of the stress in these materials is motivated by efforts to advance the optical performance of light-weight x-ray space telescopes into the regime of sub-arc second resolution. A characteristic feature of the intrinsic stress behavior in chromium and nickel is their sensitivity to the magnitude and sign of the intrinsic stress with argon gas pressure, including the existence of a critical pressure that results in zero film stress. This critical pressure scales linearly with the film's density. While the effect of stress reversal with argon pressure has been previously reported by Hoffman and others for nickel and chromium, we have discovered a similar behavior for the intrinsic stress in iridium films. Additionally, we have identified zero stress in iridium shortly after island coalescence in the high adatom mobility growth regime. This feature of film growth is used for achieving a total internal stress of -2.89 MPa for a 15.8 nm thick iridium film with a surface roughness of 5.0 +/- 0.5Å based on x-ray reflectivity (XRR) measurement at CuKα. The surface topography was also examined using atomic force microscopy (AFM). The examination of the stress in these films has been performed with a novel in-situ measurement device. The methodology and sensitivity of the in-situ instrument is also described herein.

  8. Modulation of nitric oxide synthase activity in macrophages

    PubMed Central

    Jorens, P. G.; Matthys, K. E.

    1995-01-01

    L-Arginine is converted to the highly reactive and unstable nitric oxide (NO) and L-citrulline by an enzyme named nitric oxide synthase (NOS). NO decomposes into other nitrogen oxides such as nitrite (NO2-) and nitrate (NO2-), and in the presence of superoxide anion to the potent oxidizing agent peroxynitrite (ONOO−). Activated rodent macrophages are capable of expressing an inducible form of this enzyme (iNOS) in response to appropriate stimuli, i.e., lipopolysaccharide (LPS) and interferon-γ (IFNγ). Other cytokines can modulate the induction of NO biosynthesis in macrophages. NO is a major effector molecule of the anti-microbial and cytotoxic activity of rodent macrophages against certain micro-organisms and tumour cells, respectively. The NO synthesizing pathway has been demonstrated in human monocytes and other cells, but its role in host defence seems to be accessory. A delicate functional balance between microbial stimuli, host-derived cytokines and hormones in the microenvironment regulates iNOS expression. This review will focus mainly on the known and proposed mechanisms of the regulation of iNOS induction, and on agents that can modulate NO release once the active enzyme has been expressed in the macrophage. PMID:18475620

  9. Nitric oxide generated from isoniazid activation by KatG: source of nitric oxide and activity against Mycobacterium tuberculosis.

    PubMed

    Timmins, Graham S; Master, Sharon; Rusnak, Frank; Deretic, Vojo

    2004-08-01

    Isonicotinic acid hydrazide (INH) is a frontline antituberculosis agent. Once taken up by Mycobacterium tuberculosis, INH requires activation by the catalase-peroxidase KatG, converting INH from its prodrug form into a range of bactericidal reactive species. Here we used 15N-labeled INH together with electron paramagnetic resonance spin trapping techniques to demonstrate that nitric oxide (NO*) is generated from oxidation at the hydrazide nitrogens during the activation of INH by M. tuberculosis KatG. We also observed that a specific scavenger of NO* provided protection against the antimycobacterial activity of INH in bacterial culture. No significant increases in mycobacterial protein nitration were detected, suggesting that NOdot; and not peroxynitrite, a nitrating metabolite of NO*, is involved in antimycobacterial action. In conclusion, INH-derived NO* has biological activity, which directly contributes to the antimycobacterial action of INH. PMID:15273113

  10. IRIDIUM OXIDE PH MICROELECTRODE. (R825549C027)

    EPA Science Inventory

    The perspectives, information and conclusions conveyed in research project abstracts, progress reports, final reports, journal abstracts and journal publications convey the viewpoints of the principal investigator and may not represent the views and policies of ORD and EPA. Concl...

  11. Oxidative Stress and Maxi Calcium-Activated Potassium (BK) Channels

    PubMed Central

    Hermann, Anton; Sitdikova, Guzel F.; Weiger, Thomas M.

    2015-01-01

    All cells contain ion channels in their outer (plasma) and inner (organelle) membranes. Ion channels, similar to other proteins, are targets of oxidative impact, which modulates ion fluxes across membranes. Subsequently, these ion currents affect electrical excitability, such as action potential discharge (in neurons, muscle, and receptor cells), alteration of the membrane resting potential, synaptic transmission, hormone secretion, muscle contraction or coordination of the cell cycle. In this chapter we summarize effects of oxidative stress and redox mechanisms on some ion channels, in particular on maxi calcium-activated potassium (BK) channels which play an outstanding role in a plethora of physiological and pathophysiological functions in almost all cells and tissues. We first elaborate on some general features of ion channel structure and function and then summarize effects of oxidative alterations of ion channels and their functional consequences. PMID:26287261

  12. Catalysts for oxidation of mercury in flue gas

    DOEpatents

    Granite, Evan J.; Pennline, Henry W.

    2010-08-17

    Two new classes of catalysts for the removal of heavy metal contaminants, especially mercury (Hg) from effluent gases. Both of these classes of catalysts are excellent absorbers of HCl and Cl.sub.2 present in effluent gases. This adsorption of oxidizing agents aids in the oxidation of heavy metal contaminants. The catalysts remove mercury by oxidizing the Hg into mercury (II) moieties. For one class of catalysts, the active component is selected from the group consisting of iridium (Ir) and iridum-platinum (Ir/Pt) alloys. The Ir and Ir/Pt alloy catalysts are especially corrosion resistant. For the other class of catalyst, the active component is partially combusted coal or "Thief" carbon impregnated with Cl.sub.2. Untreated Thief carbon catalyst can be self-activating in the presence of effluent gas streams. The Thief carbon catalyst is disposable by means of capture from the effluent gas stream in a particulate collection device (PCD).

  13. Oxidative stress, activity behaviour and body mass in captive parrots.

    PubMed

    Larcombe, S D; Tregaskes, C A; Coffey, J; Stevenson, A E; Alexander, L G; Arnold, K E

    2015-01-01

    Many parrot species are kept in captivity for conservation, but often show poor reproduction, health and survival. These traits are known to be influenced by oxidative stress, the imbalance between the production of reactive oxygen species (ROS) and ability of antioxidant defences to ameliorate ROS damage. In humans, oxidative stress is linked with obesity, lack of exercise and poor nutrition, all of which are common in captive animals. Here, we tested whether small parrots (budgerigars, Melopsittacus undulatus) maintained in typical pet cages and on ad libitum food varied in oxidative profile, behaviour and body mass. Importantly, as with many birds held in captivity, they did not have enough space to engage in extensive free flight. Four types of oxidative damage, single-stranded DNA breaks (low-pH comet assay), alkali-labile sites in DNA (high-pH comet assay), sensitivity of DNA to ROS (H2O2-treated comet assay) and malondialdehyde (a byproduct of lipid peroxidation), were uncorrelated with each other and with plasma concentrations of dietary antioxidants. Without strenuous exercise over 28 days in a relatively small cage, more naturally 'active' individuals had more single-stranded DNA breaks than sedentary birds. High body mass at the start or end of the experiment, coupled with substantial mass gain, were all associated with raised sensitivity of DNA to ROS. Thus, high body mass in these captive birds was associated with oxidative damage. These birds were not lacking dietary antioxidants, because final body mass was positively related to plasma levels of retinol, zeaxanthin and α-tocopherol. Individuals varied widely in activity levels, feeding behaviour, mass gain and oxidative profile despite standardized living conditions. DNA damage is often associated with poor immunocompetence, low fertility and faster ageing. Thus, we have candidate mechanisms for the limited lifespan and fecundity common to many birds kept for conservation purposes. PMID:27293729

  14. Spectroscopic characterization of alumina-supported bis(allyl)iridium complexes : site-isolation, reactivity, and decomposition studies.

    SciTech Connect

    Trovitch, R. J.; Guo, N.; Janicke, M. T.; Li, H.; Marshall, C. L.; Miller, J. T.; Sattelberger, A. P.; John, K. D.; Baker, R. T.; LANL; Univ. of Ottawa

    2010-01-01

    The covalent attachment of tris(allyl)iridium to partially dehydroxylated ?-alumina is found to proceed via surface hydroxyl group protonation of one allyl ligand to form an immobilized bis(allyl)iridium moiety, (?AlO)Ir(allyl)2, as characterized by CP-MAS 13C NMR, inductively coupled plasma-mass spectrometry, and Ir L3 edge X-ray absorption spectroscopy. Extended X-ray absorption fine-structure (EXAFS) measurements taken on unsupported Ir(allyl)3 and several associated tertiary phosphine addition complexes suggest that the ?3-allyl ligands generally account for an Ir-C coordination number of 2 rather than 3, with an average Ir-C distance of 2.16 A. Using this knowledge, combined EXAFS and X-ray absorption near-edge structure studies reveal that a small amount of Ir0 is also formed upon reaction of Ir(allyl)3 with the surface. It was found that the addition of either 2,6-dimethylphenyl isocyanide or carbon monoxide to the supported complex allows spectroscopic identification of the supported bis(allyl)iridium complexes, (?AlO)Ir(allyl)2(CNAr) [Ar = 2,6-(CH3)2C6H4] and (?AlO)Ir(allyl)2(CO)2, respectively. Although samples of the supported bis(allyl)iridium complex are active for the dehydrogenation of cyclohexane to benzene at temperatures between 180 and 220C, in situ temperature-programmed reaction XAFS and continuous-flow reactor studies suggest that Ir0 nanoparticles, rather than a well-defined Ir3+ complex, are responsible for the observed activity.

  15. The cellular uptake and localization of non-emissive iridium(III) complexes as cellular reaction-based luminescence probes.

    PubMed

    Li, Chunyan; Liu, Yi; Wu, Yongquan; Sun, Yun; Li, Fuyou

    2013-01-01

    Improvement of cellular uptake and subcellular resolution remains a major obstacle in the successful and broad application of cellular optical probes. In this context, we design and synthesize seven non-emissive cyclometalated iridium(III) solvent complexes [Ir(CˆN)(2)(solv)(2)](+)L(-) (LIr2-LIr8, in which CˆN = 2-phenylpyridine (ppy) or its derivative; solv = DMSO, H(2)O or CH(3)CN; L(-) = PF(6)(-) or OTf(-)) applicable in live cell imaging to facilitate selective visualization of cellular structures. Based on the above variations (including different counter ions, solvent ligands, and CˆN ligands), structure-activity relationship analyses reveal a number of clear correlations: (1) variations in counter anions and solvent ligands of iridium(III) complexes do not affect cellular imaging behavior, and (2) length of the side carbon chain in CˆN ligands has significant effects on cellular uptake and localization/accumulation of iridium complexes in living cells. Moreover, investigation of the uptake mechanism via low-temperature and metabolism inhibitor assays reveal that [Ir(4-Meppy)(2)(CH(3)CN)(2)](+)OTf(-) (LIr5) with 2-phenylpyridine derivative with side-chain of methyl group at the 4-position as CˆN ligand permeates the outer and nuclear membranes of living cells through an energy-dependent, non-endocytic entry pathway, and translocation of the complex from the cell periphery towards the perinuclear region possibly occurs through a microtubule-dependent transport pathway. Nuclear pore complexes (NPCs) appear to selectively control the transport of iridium(III) complexes between the cytoplasm and nucleus. A generalization of trends in behavior and structure-activity relationships is presented, which should provide further insights into the design and optimization of future probes. PMID:23131533

  16. Antibacterial Activity of Polymer Coated Cerium Oxide Nanoparticles

    PubMed Central

    Shah, Vishal; Shah, Shreya; Shah, Hirsh; Rispoli, Fred J.; McDonnell, Kevin T.; Workeneh, Selam; Karakoti, Ajay; Kumar, Amit; Seal, Sudipta

    2012-01-01

    Cerium oxide nanoparticles have found numerous applications in the biomedical industry due to their strong antioxidant properties. In the current study, we report the influence of nine different physical and chemical parameters: pH, aeration and, concentrations of MgSO4, CaCl2, KCl, natural organic matter, fructose, nanoparticles and Escherichia coli, on the antibacterial activity of dextran coated cerium oxide nanoparticles. A least-squares quadratic regression model was developed to understand the collective influence of the tested parameters on the anti-bacterial activity and subsequently a computer-based, interactive visualization tool was developed. The visualization allows us to elucidate the effect of each of the parameters in combination with other parameters, on the antibacterial activity of nanoparticles. The results indicate that the toxicity of CeO2 NPs depend on the physical and chemical environment; and in a majority of the possible combinations of the nine parameters, non-lethal to the bacteria. In fact, the cerium oxide nanoparticles can decrease the anti-bacterial activity exerted by magnesium and potassium salts. PMID:23110109

  17. Oxidation of methionine residues in proteins of activated human neutrophils.

    PubMed Central

    Fliss, H; Weissbach, H; Brot, N

    1983-01-01

    A simple assay for the detection of 35S-labeled methionine sulfoxide residues in proteins is described. The assay, which is based on the ability of CNBr to react with methionine but not with methionine sulfoxide, requires the prelabeling of cellular proteins with [35S]methionine. The assay was used to study the extent of methionine oxidation in newly synthesized proteins of both activated and quiescent human neutrophils. In cells undergoing a phorbol 12-myristate 13-acetate-induced respiratory burst, about 66% of all methionine residues in newly synthesized proteins were oxidized to the sulfoxide derivative, as compared with 9% in cells not treated with the phorbol ester. In contrast, quantitation of methionine sulfoxide content in the total cellular protein by means of amino acid analysis showed that only 22% of all methionine residues were oxidized in activated cells as compared with 9% in quiescent cells. It is proposed that methionine residues in nascent polypeptide chains are more susceptible to oxidation than those in completed proteins. PMID:6580633

  18. The oxidative activities of membrane vesicles from Bacillus caldolyticus. Energy-dependence of succinate oxidation.

    PubMed

    Dawson, A G; Chappell, J B

    1978-02-15

    movement of H(+) by the protonmotive force. 7. In support of the foregoing conclusion it was shown that the reduction of fumarate by NADH was an energy-conserving process. 8. If the activities of vesicles accurately represent those of the intact organism it appears that in B. caldolyticus the reduction of fumarate to succinate at the expense of reducing equivalents from NADH is energetically favoured over succinate oxidation even under aerobic conditions. This may be related to the need for an ample supply of succinate for haem synthesis in order to provide cytochromes for the organism. PMID:205211

  19. Antioxidant activity of levan coated cerium oxide nanoparticles.

    PubMed

    Kim, Sun-Jung; Chung, Bong Hyun

    2016-10-01

    Levan coated cerium oxide nanoparticles (LCNPs) with the enhanced antioxidant activity were successfully synthesized and characterized. Levan and their derivatives are attractive for biomedical applications attributable to their antioxidant, anti-inflammation and anti-tumor properties. LCNPs were synthesized using the one-pot and green synthesis system with levan. For production of nanoparticles, levan plays a role as a stabilizing and reducing agent. Fourier transform infrared spectroscopy (FT-IR) analysis showed that LCNPs successfully synthesized. The morphology and size of nanoparticles were confirmed by transmission electron microscopy (TEM) and dynamic light scattering (DLS). LCNPs have good water solubility and stability. The conjugation of levan with cerium oxide nanoparticles improved antioxidant activity. Moreover the level of ROS was reduced after treatment of LCNPs to H2O2 stimulated NIH3T3 cells. These results demonstrate that the LCNPs are useful for applying of treatment of ROS induced diseases. PMID:27312651

  20. Formation of C-C Bonds via Iridium-Catalyzed Hydrogenation and Transfer Hydrogenation.

    PubMed

    Bower, John F; Krische, Michael J

    2011-01-01

    The formation of C-C bonds via catalytic hydrogenation and transfer hydrogenation enables carbonyl and imine addition in the absence of stoichiometric organometallic reagents. In this review, iridium-catalyzed C-C bond-forming hydrogenations and transfer hydrogenations are surveyed. These processes encompass selective, atom-economic methods for the vinylation and allylation of carbonyl compounds and imines. Notably, under transfer hydrogenation conditions, alcohol dehydrogenation drives reductive generation of organoiridium nucleophiles, enabling carbonyl addition from the aldehyde or alcohol oxidation level. In the latter case, hydrogen exchange between alcohols and π-unsaturated reactants generates electrophile-nucleophile pairs en route to products of hydro-hydroxyalkylation, representing a direct method for the functionalization of carbinol C-H bonds. PMID:21822399

  1. Iridium-catalysed direct C-C coupling of methanol and allenes

    NASA Astrophysics Data System (ADS)

    Moran, Joseph; Preetz, Angelika; Mesch, Ryan A.; Krische, Michael J.

    2011-04-01

    Methanol is an abundant (35 million metric tons per year), renewable chemical feedstock, yet its use as a one-carbon building block in fine chemical synthesis is highly underdeveloped. Using a homogeneous iridium catalyst developed in our laboratory, methanol engages in a direct C-C coupling with allenes to furnish higher alcohols that incorporate all-carbon quaternary centres, free of stoichiometric by-products. A catalytic mechanism that involves turnover-limiting methanol oxidation, a consequence of the high energetic demand of methanol dehydrogenation, is corroborated through a series of competition kinetics experiments. This process represents the first catalytic C-C coupling of methanol to provide discrete products of hydrohydroxymethylation.

  2. High performance optical oxygen sensors based on iridium complexes exhibiting interchromophore energy shuttling.

    PubMed

    Medina-Rodríguez, Santiago; Denisov, Sergey A; Cudré, Yanouk; Male, Louise; Marín-Suárez, Marta; Fernández-Gutiérrez, Alberto; Fernández-Sánchez, Jorge F; Tron, Arnaud; Jonusauskas, Gediminas; McClenaghan, Nathan D; Baranoff, Etienne

    2016-05-10

    A doubly pyrene-grafted bis-cyclometallated iridium complex with engineered electronically excited states demonstrates reversible electronic energy transfer between adjacent chromophores giving rise to extremely long-lived red luminescence in solution (τ = 480 μs). Time-resolved spectroscopic studies afforded determination of pertinent photophysical parameters including rates of energy transfer and energy distribution between constituent chromophores in the equilibrated excited molecule (ca. 98% on the organic chromophores). Incorporation into a nanostructured metal-oxide matrix (AP200/19) gave highly sensitive O2 sensing films, as the detection sensitivity was 200-300% higher than with the commonly used PtTFPP and approaches the sensitivity of the best O2-sensing dyes reported to date. PMID:27094953

  3. Formation of C-C Bonds via Iridium-Catalyzed Hydrogenation and Transfer Hydrogenation

    NASA Astrophysics Data System (ADS)

    Bower, John F.; Krische, Michael J.

    The formation of C-C bonds via catalytic hydrogenation and transfer hydrogenation enables carbonyl and imine addition in the absence of stoichiometric organometallic reagents. In this review, iridium-catalyzed C-C bond-forming hydrogenations and transfer hydrogenations are surveyed. These processes encompass selective, atom-economic methods for the vinylation and allylation of carbonyl compounds and imines. Notably, under transfer hydrogenation conditions, alcohol dehydrogenation drives reductive generation of organoiridium nucleophiles, enabling carbonyl addition from the aldehyde or alcohol oxidation level. In the latter case, hydrogen exchange between alcohols and π-unsaturated reactants generates electrophile-nucleophile pairs en route to products of hydro-hydroxyalkylation, representing a direct method for the functionalization of carbinol C-H bonds.

  4. Oxidative stress, activity behaviour and body mass in captive parrots

    PubMed Central

    Larcombe, S. D.; Tregaskes, C. A.; Coffey, J.; Stevenson, A. E.; Alexander, L. G.; Arnold, K. E.

    2015-01-01

    Many parrot species are kept in captivity for conservation, but often show poor reproduction, health and survival. These traits are known to be influenced by oxidative stress, the imbalance between the production of reactive oxygen species (ROS) and ability of antioxidant defences to ameliorate ROS damage. In humans, oxidative stress is linked with obesity, lack of exercise and poor nutrition, all of which are common in captive animals. Here, we tested whether small parrots (budgerigars, Melopsittacus undulatus) maintained in typical pet cages and on ad libitum food varied in oxidative profile, behaviour and body mass. Importantly, as with many birds held in captivity, they did not have enough space to engage in extensive free flight. Four types of oxidative damage, single-stranded DNA breaks (low-pH comet assay), alkali-labile sites in DNA (high-pH comet assay), sensitivity of DNA to ROS (H2O2-treated comet assay) and malondialdehyde (a byproduct of lipid peroxidation), were uncorrelated with each other and with plasma concentrations of dietary antioxidants. Without strenuous exercise over 28 days in a relatively small cage, more naturally ‘active’ individuals had more single-stranded DNA breaks than sedentary birds. High body mass at the start or end of the experiment, coupled with substantial mass gain, were all associated with raised sensitivity of DNA to ROS. Thus, high body mass in these captive birds was associated with oxidative damage. These birds were not lacking dietary antioxidants, because final body mass was positively related to plasma levels of retinol, zeaxanthin and α-tocopherol. Individuals varied widely in activity levels, feeding behaviour, mass gain and oxidative profile despite standardized living conditions. DNA damage is often associated with poor immunocompetence, low fertility and faster ageing. Thus, we have candidate mechanisms for the limited lifespan and fecundity common to many birds kept for conservation purposes. PMID

  5. Anticancer activity of Ficus religiosa engineered copper oxide nanoparticles.

    PubMed

    Sankar, Renu; Maheswari, Ramasamy; Karthik, Selvaraju; Shivashangari, Kanchi Subramanian; Ravikumar, Vilwanathan

    2014-11-01

    The design, synthesis, characterization and application of biologically synthesized nanomaterials have become a vital branch of nanotechnology. There is a budding need to develop a method for environmentally benign metal nanoparticle synthesis, that do not use toxic chemicals in the synthesis protocols to avoid adverse effects in medical applications. Here, it is a report on an eco-friendly process for rapid synthesis of copper oxide nanoparticles using Ficus religiosa leaf extract as reducing and protecting agent. The synthesized copper oxide nanoparticles were confirmed by UV-vis spectrophotometer, absorbance peaks at 285 nm. The copper oxide nanoparticles were analyzed with field emission-scanning electron microscope (FE-SEM), Fourier transform infrared (FT-IR) spectroscopy, dynamic light scattering (DLS) and X-ray diffraction (XRD) spectrum. The FE-SEM and DLS analyses exposed that copper oxide nanoparticles are spherical in shape with an average particle size of 577 nm. FT-IR spectral analysis elucidates the occurrence of biomolecules required for the reduction of copper oxide ions. Zeta potential studies showed that the surface charge of the formed nanoparticles was highly negative. The XRD pattern revealed that synthesized nanoparticles are crystalline in nature. Further, biological activities of the synthesized nanoparticles were confirmed based on its stable anti-cancer effects. The apoptotic effect of copper oxide nanoparticles is mediated by the generation of reactive oxygen species (ROS) involving the disruption of mitochondrial membrane potential (Δψm) in A549 cells. The observed characteristics and results obtained in our in vitro assays suggest that the copper nanoparticles might be a potential anticancer agent. PMID:25280701

  6. Complete reaction mechanisms of mercury oxidation on halogenated activated carbon.

    PubMed

    Rungnim, Chompoonut; Promarak, Vinich; Hannongbua, Supa; Kungwan, Nawee; Namuangruk, Supawadee

    2016-06-01

    The reaction mechanisms of mercury (Hg) adsorption and oxidation on halogenated activated carbon (AC) have been completely studied for the first time using density functional theory (DFT) method. Two different halogenated AC models, namely X-AC and X-AC-X (X=Cl, Br, I), were adopted. The results revealed that HgX is found to be stable-state on the AC edge since its further desorption from the AC as HgX, or further oxidation to HgX2, are energetically unfavorable. Remarkably, the halide type does not significantly affect the Hg adsorption energy but it strongly affects the activation energy barrier of HgX formation, which obviously increases in the order HgIBr-AC>Cl-AC. Thus, the study of the complete reaction mechanism is essential because the adsorption energy can not be used as a guideline for the rational material design in the halide impregnated AC systems. The activation energy is an important descriptor for the predictions of sorbent reactivity to the Hg oxidation process. PMID:26943019

  7. Uniform 2 nm gold nanoparticles supported on iron oxides as active catalysts for CO oxidation reaction: Structure-activity relationship

    DOE PAGESBeta

    Guo, Yu; Senanayake, Sanjaya; Gu, Dong; Jin, Zhao; Du, Pei -Pei; Si, Rui; Xu, Wen -Qian; Huang, Yu -Ying; Tao, Jing; Song, Qi -Sheng; et al

    2015-01-12

    Uniform Au nanoparticles (~2 nm) with narrow size-distribution (standard deviation: 0.5–0.6 nm) supported on both hydroxylated (Fe_OH) and dehydrated iron oxide (Fe_O) have been prepared by either deposition-precipitation (DP) or colloidal-deposition (CD) methods. Different structural and textural characterizations were applied to the dried, calcined and used gold-iron oxide samples. The transmission electron microscopy (TEM) and high-resolution TEM (HRTEM) described the high homogeneity in the supported Au nanoparticles. The ex-situ and in-situ X-ray absorption fine structure (XAFS) characterization monitored the electronic and short-range local structure of active gold species. The synchrotron-based in-situ X-ray diffraction (XRD), together with the corresponding temperature-programmed reductionmore » by hydrogen (H₂-TPR), indicated a structural evolution of the iron-oxide supports, correlating to their reducibility. An inverse order of catalytic activity between DP (Au/Fe_OH < Au/Fe_O) and CD (Au/Fe_OH > Au/Fe_O) was observed. Effective gold-support interaction results in a high activity for gold nanoparticles, locally generated by the sintering of dispersed Au atoms on the oxide support in the DP synthesis, while a hydroxylated surface favors the reactivity of externally introduced Au nanoparticles on Fe_OH support for the CD approach. This work reveals why differences in the synthetic protocol translate to differences in the catalytic performance of Au/FeOx catalysts with very similar structural characteristics in CO oxidation.« less

  8. Uniform 2 nm gold nanoparticles supported on iron oxides as active catalysts for CO oxidation reaction: Structure-activity relationship

    SciTech Connect

    Guo, Yu; Senanayake, Sanjaya; Gu, Dong; Jin, Zhao; Du, Pei -Pei; Si, Rui; Xu, Wen -Qian; Huang, Yu -Ying; Tao, Jing; Song, Qi -Sheng; Jia, Chun -Jia; Schueth, Ferdi

    2015-01-12

    Uniform Au nanoparticles (~2 nm) with narrow size-distribution (standard deviation: 0.5–0.6 nm) supported on both hydroxylated (Fe_OH) and dehydrated iron oxide (Fe_O) have been prepared by either deposition-precipitation (DP) or colloidal-deposition (CD) methods. Different structural and textural characterizations were applied to the dried, calcined and used gold-iron oxide samples. The transmission electron microscopy (TEM) and high-resolution TEM (HRTEM) described the high homogeneity in the supported Au nanoparticles. The ex-situ and in-situ X-ray absorption fine structure (XAFS) characterization monitored the electronic and short-range local structure of active gold species. The synchrotron-based in-situ X-ray diffraction (XRD), together with the corresponding temperature-programmed reduction by hydrogen (H₂-TPR), indicated a structural evolution of the iron-oxide supports, correlating to their reducibility. An inverse order of catalytic activity between DP (Au/Fe_OH < Au/Fe_O) and CD (Au/Fe_OH > Au/Fe_O) was observed. Effective gold-support interaction results in a high activity for gold nanoparticles, locally generated by the sintering of dispersed Au atoms on the oxide support in the DP synthesis, while a hydroxylated surface favors the reactivity of externally introduced Au nanoparticles on Fe_OH support for the CD approach. This work reveals why differences in the synthetic protocol translate to differences in the catalytic performance of Au/FeOx catalysts with very similar structural characteristics in CO oxidation.

  9. Simulation of dose distribution for iridium-192 brachytherapy source type-H01 using MCNPX

    SciTech Connect

    Purwaningsih, Anik

    2014-09-30

    Dosimetric data for a brachytherapy source should be known before it used for clinical treatment. Iridium-192 source type H01 was manufactured by PRR-BATAN aimed to brachytherapy is not yet known its dosimetric data. Radial dose function and anisotropic dose distribution are some primary keys in brachytherapy source. Dose distribution for Iridium-192 source type H01 was obtained from the dose calculation formalism recommended in the AAPM TG-43U1 report using MCNPX 2.6.0 Monte Carlo simulation code. To know the effect of cavity on Iridium-192 type H01 caused by manufacturing process, also calculated on Iridium-192 type H01 if without cavity. The result of calculation of radial dose function and anisotropic dose distribution for Iridium-192 source type H01 were compared with another model of Iridium-192 source.

  10. Simulation of dose distribution for iridium-192 brachytherapy source type-H01 using MCNPX

    NASA Astrophysics Data System (ADS)

    Purwaningsih, Anik

    2014-09-01

    Dosimetric data for a brachytherapy source should be known before it used for clinical treatment. Iridium-192 source type H01 was manufactured by PRR-BATAN aimed to brachytherapy is not yet known its dosimetric data. Radial dose function and anisotropic dose distribution are some primary keys in brachytherapy source. Dose distribution for Iridium-192 source type H01 was obtained from the dose calculation formalism recommended in the AAPM TG-43U1 report using MCNPX 2.6.0 Monte Carlo simulation code. To know the effect of cavity on Iridium-192 type H01 caused by manufacturing process, also calculated on Iridium-192 type H01 if without cavity. The result of calculation of radial dose function and anisotropic dose distribution for Iridium-192 source type H01 were compared with another model of Iridium-192 source.

  11. Dexmedetomidine inhibits vasoconstriction via activation of endothelial nitric oxide synthase.

    PubMed

    Nong, Lidan; Ma, Jue; Zhang, Guangyan; Deng, Chunyu; Mao, Songsong; Li, Haifeng; Cui, Jianxiu

    2016-09-01

    Despite the complex vascular effects of dexmedetomidine (DEX), its actions on human pulmonary resistance arteries remain unknown. The present study tested the hypothesis that DEX inhibits vascular tension in human pulmonary arteries through the endothelial nitric oxide synthase (eNOS) mediated production of nitric oxide (NO). Pulmonary artery segments were obtained from 62 patients who underwent lung resection. The direct effects of DEX on human pulmonary artery tension and changes in vascular tension were determined by isometric force measurements recorded on a myograph. Arterial contractions caused by increasing concentrations of serotonin with DEX in the presence or absence of L-NAME (endothelial nitric oxide synthase inhibitor), yohimbine (α2-adrenoceptor antagonist) and indomethacin (cyclooxygenase inhibitor) as antagonists were also measured. DEX had no effect on endothelium-intact pulmonary arteries, whereas at concentrations of 10(-8)~10(-6) mol/L, it elicited contractions in endothelium-denuded pulmonary arteries. DEX (0.3, 1, or 3×10(-9) mmol/L) inhibited serotonin-induced contraction in arteries with intact endothelium in a dose-dependent manner. L-NAME and yohimbine abolished DEX-induced inhibition, whereas indomethacin had no effect. No inhibitory effect was observed in endothelium-denuded pulmonary arteries. DEX-induced inhibition of vasoconstriction in human pulmonary arteries is mediated by NO production induced by the activation of endothelial α2-adrenoceptor and nitric oxide synthase. PMID:27610030

  12. Dexmedetomidine inhibits vasoconstriction via activation of endothelial nitric oxide synthase

    PubMed Central

    Nong, Lidan; Ma, Jue; Zhang, Guangyan; Deng, Chunyu; Mao, Songsong; Li, Haifeng

    2016-01-01

    Despite the complex vascular effects of dexmedetomidine (DEX), its actions on human pulmonary resistance arteries remain unknown. The present study tested the hypothesis that DEX inhibits vascular tension in human pulmonary arteries through the endothelial nitric oxide synthase (eNOS) mediated production of nitric oxide (NO). Pulmonary artery segments were obtained from 62 patients who underwent lung resection. The direct effects of DEX on human pulmonary artery tension and changes in vascular tension were determined by isometric force measurements recorded on a myograph. Arterial contractions caused by increasing concentrations of serotonin with DEX in the presence or absence of L-NAME (endothelial nitric oxide synthase inhibitor), yohimbine (α2-adrenoceptor antagonist) and indomethacin (cyclooxygenase inhibitor) as antagonists were also measured. DEX had no effect on endothelium-intact pulmonary arteries, whereas at concentrations of 10–8~10–6 mol/L, it elicited contractions in endothelium-denuded pulmonary arteries. DEX (0.3, 1, or 3×10–9 mmol/L) inhibited serotonin-induced contraction in arteries with intact endothelium in a dose-dependent manner. L-NAME and yohimbine abolished DEX-induced inhibition, whereas indomethacin had no effect. No inhibitory effect was observed in endothelium-denuded pulmonary arteries. DEX-induced inhibition of vasoconstriction in human pulmonary arteries is mediated by NO production induced by the activation of endothelial α2-adrenoceptor and nitric oxide synthase. PMID:27610030

  13. Synthesis and photocatalytic activity of electrospun niobium oxide nanofibers

    SciTech Connect

    Qi, Shishun; Zuo, Ruzhong; Liu, Yi; Wang, Yu

    2013-03-15

    Graphical abstract: Different morphologies are obtained for the electrospun niobium oxide nanofibers with different phase structures. The nanofibers of the two phase structures present different band gap value and the light absorption. Hexagonal phase nanofibers show better photocatalytic activity compared with the orthorhombic nanofibers. Highlights: ► Niobium oxide nanofibers of two phase structures were fabricated by electrospinning. ► Photocatalytic properties of the niobium oxide nanofibers were first explored. ► Nanofibers of different phase structures showed different photocatalytic activities. ► Reasons for the differences in the photocatalysis were carefully discussed. - Abstract: Niobium oxide (Nb{sub 2}O{sub 5}) nanofibers have been synthesized by sol–gel based electrospinning technique. Pure hexagonal phase (H-Nb{sub 2}O{sub 5}) and orthorhombic phase (O-Nb{sub 2}O{sub 5}) nanofibers were obtained by thermally annealing the electrospun Nb{sub 2}O{sub 5}/polyvinylpyrrolidone composite fibers in air at 500 °C and 700 °C, respectively. The fibers were characterized using the X-ray diffraction, scanning electron microscopy, specific surface area analyzer and UV–vis diffuse reflectance spectroscopy. Photocatalytic activities of the obtained nanofibers were evaluated depending on the degradation of methyl orange. The results indicate that the heat-treatment temperature, the crystalline structure and the morphology affected the physical and chemical properties of the as-prepared Nb{sub 2}O{sub 5} nanofibers. The H-Nb{sub 2}O{sub 5} nanofibers obtained at lower temperature showed better potential for the application as a promising photocatalyst.

  14. Effect of Nitric Oxide on the Antifungal Activity of Oxidative Stress and Azoles Against Candida albicans.

    PubMed

    Li, De-Dong; Yang, Chang-Chun; Liu, Ping; Wang, Yan; Sun, Yan

    2016-06-01

    Nitric oxide (NO) is a small molecule with a wide range of biological activities in mammalian and bacteria. However, the role of NO in fungi, especially Candida albicans, is not clear. In this study, we confirmed the generation of endogenous NO in C. albicans, and found that the production of endogenous NO in C. albicans was associated with nitric oxide synthase pathway. Our results further indicated that the production of endogenous NO in C. albicans was reduced under oxidative stress such as menadione or H2O2 treatment. Meanwhile, exogenous NO donor, sodium nitroprusside (SNP), synergized with H2O2 against C. albicans. Interestingly, SNP could inhibit the antifungal effect of azoles against C. albicans in vitro, suggesting that NO might be involved in the resistance of C. albicans to antifungals. Collectively, this study demonstrated the production of endogenous NO in C. albicans, and indicated that NO may play an important role in the response of C. albicans to oxidative stress and azoles. PMID:27570314

  15. Antimicrobial activity of the metals and metal oxide nanoparticles.

    PubMed

    Dizaj, Solmaz Maleki; Lotfipour, Farzaneh; Barzegar-Jalali, Mohammad; Zarrintan, Mohammad Hossein; Adibkia, Khosro

    2014-11-01

    The ever increasing resistance of pathogens towards antibiotics has caused serious health problems in the recent years. It has been shown that by combining modern technologies such as nanotechnology and material science with intrinsic antimicrobial activity of the metals, novel applications for these substances could be identified. According to the reports, metal and metal oxide nanoparticles represent a group of materials which were investigated in respect to their antimicrobial effects. In the present review, we focused on the recent research works concerning antimicrobial activity of metal and metal oxide nanoparticles together with their mechanism of action. Reviewed literature indicated that the particle size was the essential parameter which determined the antimicrobial effectiveness of the metal nanoparticles. Combination therapy with the metal nanoparticles might be one of the possible strategies to overcome the current bacterial resistance to the antibacterial agents. However, further studies should be performed to minimize the toxicity of metal and metal oxide nanoparticles to apply as proper alternatives for antibiotics and disinfectants especially in biomedical applications. PMID:25280707

  16. Impact of sulfur oxides on mercury capture by activated carbon.

    PubMed

    Presto, Albert A; Granite, Evan J

    2007-09-15

    Recent field tests of mercury removal with activated carbon injection (ACI) have revealed that mercury capture is limited in flue gases containing high concentrations of sulfur oxides (SOx). In order to gain a more complete understanding of the impact of SOx on ACl, mercury capture was tested under varying conditions of SO2 and SO3 concentrations using a packed bed reactor and simulated flue gas (SFG). The final mercury content of the activated carbons is independent of the SO2 concentration in the SFG, but the presence of SO3 inhibits mercury capture even at the lowest concentration tested (20 ppm). The mercury removal capacity decreases as the sulfur content of the used activated carbons increases from 1 to 10%. In one extreme case, an activated carbon with 10% sulfur, prepared by H2SO4 impregnation, shows almost no mercury capacity. The results suggest that mercury and sulfur oxides are in competition for the same binding sites on the carbon surface. PMID:17948811

  17. Design and photocatalytic activity of nanosized zinc oxides

    NASA Astrophysics Data System (ADS)

    Gancheva, M.; Markova-Velichkova, M.; Atanasova, G.; Kovacheva, D.; Uzunov, I.; Cukeva, R.

    2016-04-01

    Zinc oxide particles with various morphologies were successfully prepared via three synthesis methods: precipitation; tribophysical treatment and sonochemistry. The as-synthesized samples were characterized by X-ray diffraction (XRD); infrared spectroscopy (IR); scanning electron microscope (SEM); BET specific surface area; electron-paramagnetic resonance (EPR), UV-Vis absorption/diffuse reflectance and X-ray photoelectron spectroscopy (XPS). Photocatalytic activities of the samples were evaluated by degradation of Malachite Green (MG) in an aqueous solution under UV and visible irradiation. The obtained ZnO powders possess crystallites size below 20 nm. The ZnO with spherical particles were obtained by precipitation method. The sonochemistry approach leads to preparation of ZnO with nanorod particles. The calculated band gaps of various ZnO powders belong to the range from 3.12 to 3.30 eV. The obtained polycrystalline zinc oxides exhibit good photocatalytic activity which is strongly influenced by the preparation conditions. The nanorod ZnO exhibits high photocatalytic activity under UV irradiation which is attributed to the morphology and the geometric surface of the particles. The ZnO obtained by precipitation has better photocatalytic efficiency under visible irradiation due to high B.E.T. specific surface area and the low level of band gap. Tribophysical treatment of a particle size-homogeneous system leads to deterioration of the photocatalytic activity of the material.

  18. Impact of sulfur oxides on mercury capture by activated carbon

    SciTech Connect

    Albert A. Presto; Evan J. Granite

    2007-09-15

    Recent field tests of mercury removal with activated carbon injection (ACI) have revealed that mercury capture is limited in flue gases containing high concentrations of sulfur oxides (SOx). In order to gain a more complete understanding of the impact of SOx on ACI, mercury capture was tested under varying conditions of SO{sub 2} and SO{sub 3} concentrations using a packed bed reactor and simulated flue gas (SFG). The final mercury content of the activated carbons is independent of the SO{sub 2} concentration in the SFG, but the presence of SO{sub 3} inhibits mercury capture even at the lowest concentration tested (20 ppm). The mercury removal capacity decreases as the sulfur content of the used activated carbons increases from 1 to 10%. In one extreme case, an activated carbon with 10% sulfur, prepared by H{sub 2}SO{sub 4} impregnation, shows almost no mercury capacity. The results suggest that mercury and sulfur oxides are in competition for the same binding sites on the carbon surface. 30 refs., 3 figs., 2 tabs.

  19. Iridium alloy clad vent set manufacturing qualification studies

    NASA Astrophysics Data System (ADS)

    Ulrich, George B.

    1991-01-01

    Qualification studies have been successfully conducted to demonstrate iridium alloy Clad Vent Set (CVS) manufacturing readiness for the General Purpose Heat Source (GPHS) program at the Oak Ridge Y-12 Plant. These studies were joint comparison evaluations of both the Y-12 Plant and EG&G Mound G-MAT) products. Note: EG&G-MAT formerly manufactured the iridium alloy CVS. The comparison evaluations involved work in a number of areas; however, only the CVS cup metallurgical evalution will be presented here. The initial metallurgical comparisons in conjunction with follow-up metallurgical work showed the Y-12 Plant CVS product to be comparable to the fully qualified (for Galileo and Ulysses missions) EG&G-MAT product. This allowed the Y-12 Plant to commence pilot production of CVS components for potential use in the CRAF and CASSINI missions.

  20. Network flexibility of the IRIDIUM (R) Global Mobile Satellite System

    NASA Technical Reports Server (NTRS)

    Hutcheson, Jonathan; Laurin, Mala

    1995-01-01

    The IRIDIUM system is a global personal communications system supported by a constellation of 66 low earth orbit (LEO) satellites and a collection of earth-based 'gateway' switching installations. Like traditional wireless cellular systems, coverage is achieved by a grid of cells in which bandwidth is reused for spectral efficiency. Unlike any cellular system ever built, the moving cells can be shared by multiple switching facilities. Noteworthy features of the IRIDIUM system include inter-satellite links, a GSM-based telephony architecture, and a geographically controlled system access process. These features, working in concert, permit flexible and reliable administration of the worldwide service area by gateway operators. This paper will explore this unique concept.

  1. Photoswitchable azobenzene-appended iridium(iii) complexes.

    PubMed

    Pérez-Miqueo, J; Altube, A; García-Lecina, E; Tron, A; McClenaghan, N D; Freixa, Z

    2016-09-21

    Iridium(iii) cyclometalated complexes have been used as models to study the effect that extended conjugation and substitution pattern has on the photochromic behavior of azobenzene-appended 2-phenylpyridyl (ppy) ligands. For this purpose four azobenzene-containing ppy ligands were synthesized. With these ligands, nine iridium(iii) complexes containing up to three appended azobenzenes were synthesized. Analysis of their photochromic behaviour by means of UV-vis and (1)H-NMR spectroscopy permitted us to conclude that the light-induced trans-to-cis isomerization of the azobenzene was strongly inhibited upon coordination to the Ir(iii) cation when the electronic conjugation was extended along the whole ligand. The use of an aliphatic spacer unit (either -CH2- or -OCH2-) between the azobenzene and the ppy fragment of the ligand sufficed to disrupt the electronic communication, and obtain photochromic organometallic complexes. PMID:27460186

  2. Water-soluble iridium phosphorescent complexes for OLED applications

    NASA Astrophysics Data System (ADS)

    Eum, Min-Sik; Yoon, Heekoo; Kim, Tae Hyung

    2012-09-01

    Newly prepared water-soluble iridium phosphorescent complexes, trans-[Ir(ppy)(PAr3)2(H)L]0,+ (ppy = bidentate 2-phenylpyridinato anionic ligand; L= Cl (1), CO (2), CN- (3); H being trans to the nitrogen of ppy ligand; PAr3 (TPPTS) = P(m-C6H4SO3Na)3), have been synthesized and characterized. Those complexes containing water-soluble phosphine ligands can emit any color region as altering cyclometalated ligands in aqueous media with high quantum efficiencies. Even though these water-soluble phosphorescent iridium complexes can be the sensing probe for toxic CO gas and CN anion, they will be capable of promising materials in the solution processible OLED applications.

  3. Olefin hydroaryloxylation catalyzed by pincer-iridium complexes.

    PubMed

    Haibach, Michael C; Guan, Changjian; Wang, David Y; Li, Bo; Lease, Nicholas; Steffens, Andrew M; Krogh-Jespersen, Karsten; Goldman, Alan S

    2013-10-01

    Aryl alkyl ethers, which are widely used throughout the chemical industry, are typically produced via the Williamson ether synthesis. Olefin hydroaryloxylation potentially offers a much more atom-economical alternative. Known acidic catalysts for hydroaryloxylation, however, afford very poor selectivity. We report the organometallic-catalyzed intermolecular hydroaryloxylation of unactivated olefins by iridium "pincer" complexes. These catalysts do not operate via the hidden Brønsted acid pathway common to previously developed transition-metal-based catalysts. The reaction is proposed to proceed via olefin insertion into an iridium-alkoxide bond, followed by rate-determining C-H reductive elimination to yield the ether product. The reaction is highly chemo- and regioselective and offers a new approach to the atom-economical synthesis of industrially important ethers and, potentially, a wide range of other oxygenates. PMID:24028199

  4. Biosynthesis of nitric oxide activates iron regulatory factor in macrophages.

    PubMed Central

    Drapier, J C; Hirling, H; Wietzerbin, J; Kaldy, P; Kühn, L C

    1993-01-01

    Biosynthesis of nitric oxide (NO) from L-arginine modulates activity of iron-dependent enzymes, including mitochondrial acontiase, an [Fe-S] protein. We examined the effect of NO on the activity of iron regulatory factor (IRF), a cytoplasmic protein which modulates both ferritin mRNA translation and transferrin receptor mRNA stability by binding to specific mRNA sequences called iron responsive elements (IREs). Murine macrophages were activated with interferon-gamma and lipopolysaccharide to induce NO synthase activity and cultured in the presence or absence of NG-substituted analogues of L-arginine which served as selective inhibitors of NO synthesis. Measurement of the nitrite concentration in the culture medium was taken as an index of NO production. Mitochondria-free cytosols were then prepared and aconitase activity as well as IRE binding activity and induction of IRE binding activity were correlated and depended on NO synthesis after IFN-gamma and/or LPS stimulation. Authentic NO gas as well as the NO-generating compound 3-morpholinosydnonimine (SIN-1) also conversely modulated aconitase and IRE binding activities of purified recombinant IRF. These results provide evidence that endogenously produced NO may modulate the post-transcriptional regulation of genes involved in iron homeostasis and support the hypothesis that the [Fe-S] cluster of IRF mediates iron-dependent regulation. Images PMID:7504626

  5. Rhizosphere activity and methane oxidation in a temperate forest soil

    NASA Astrophysics Data System (ADS)

    Moody, Catherine S.; Subke, Jens-Arne; Voke, Naomi R.; Holden, Robert D.; Ineson, Phil; Arn Teh, Yit

    2010-05-01

    Methane (CH4) concentrations in the Earth's atmosphere have increased dramatically over recent decades. An abundance of studies indicate that the magnitude of natural methane efflux from wetlands is likely to increase due to climate change. However, the role of vegetation and soils in upland methane oxidation are less well understood. Well-aerated soils are known to be sites of methane oxidation, and amongst a range of abiotic environmental parameters, soil moisture has been identified as critical regulator of the methane oxidation rates. However, the role of microbial activity within the soil, particularly C turnover in the plant rhizosphere, has not been investigated as a means for regulating methanotrophy. We combined a continuous soil CO2 efflux system (Li-Cor Biosciences, LI-8100) with a Cavity-Ringdown-Spectroscopy Fast Greenhouse Gas Analyser (Los Gatos Research Inc.) to measure soil CH4 oxidation in a pine forest in NE England. The soil has a shallow organic layer overlaying a well-draining sandy gley soil. Fluxes were measured from three different collar treatments: (1) excluding both root and ectomycorrhizal (EM) hyphae by trenching using deep collars, (2) excluding roots but allowing access by EM hyphae, and (3) unmodified forest soil (i.e. including both roots and EM hyphae). All collars were protected from natural throughfall, and received weekly-averaged amounts of throughfall based on collections in the stand. Data from two months in early summer 2009 indicate that CH4 oxidation in collars with an intact rhizosphere is more than twice that of either of the exclusion treatments (averaging approx. 90 g ha-1 d-1 in that period). We observed higher fluxes when soils were dryer (i.e. with increasing time since watering), indicating a significant influence of moisture. Despite the confounding effects of soil moisture associated with root water uptake in the unmodified soil collars, we argue that rhizosphere activity is an overlooked component in

  6. Antioxidant Activities and Oxidative Stabilities of Some Unconventional Oilseeds.

    PubMed

    Uluata, Sibel; Ozdemir, Nurhayat

    2012-04-01

    The oils of some unconventional oilseeds (hemp, radish, terebinth, stinging nettle, laurel) were obtained by a cold-press method in which the total oil content, fatty acids, tocopherol isomers, some metal contents (Ca, Mg, Fe, Cu), antioxidant activity and oxidative stability were determined. The total oil content was determined ranging between 30.68 and 43.12%, and the oil samples had large amounts of unsaturated fatty acids, with oleic acid and linoleic acid. Of all the oils, terebinth seed oil had the highest α-tocopherol content (102.21 ± 1.01 mg/kg oil). Laurel oilseed had the highest antiradical activity in both the DPPH and ABTS assays. The peroxide value of the non-oxidized oils ranged between 0.51 and 3.73 mequiv O(2)/kg oil. The TBARS value of the non-oxidized oils ranged between 0.68 ± 0.02 and 6.43 ± 0.48 mmol MA equiv/g oil. At 110 °C, the Rancimat induction period of the oils ranged between 1.32 and 43.44 h. The infrared spectra of the samples were recorded by FTIR spectroscopy. The absorbance values of the spectrum bands were observed and it was determined that some of the chemical groups of oxidized oils caused changes in absorbance. As a result of the present research, the analyzed oils could be evaluated as an alternative to traditionally consumed vegetable oils or as additives to them. PMID:22467958

  7. Site-dependent catalytic activity of graphene oxides towards oxidative dehydrogenation of propane.

    PubMed

    Tang, Shaobin; Cao, Zexing

    2012-12-28

    Graphene oxides (GOs) may offer extraordinary potential in the design of novel catalytic systems due to the presence of various oxygen functional groups and their unique electronic and structural properties. Using first-principles calculations, we explore the plausible mechanisms for the oxidative dehydrogenation (ODH) of propane to propene by GOs and the diffusion of the surface oxygen-containing groups under an external electric field. The present results show that GOs with modified oxygen-containing groups may afford high catalytic activity for the ODH of propane to propene. The presence of hydroxyl groups around the active sites provided by epoxides can remarkably enhance the C-H bond activation of propane and the activity enhancement exhibits strong site dependence. The sites of oxygen functional groups on the GO surface can be easily tuned by the diffusion of these groups under an external electric field, which increases the reactivity of GOs towards ODH of propane. The chemically modified GOs are thus quite promising in the design of metal-free catalysis. PMID:22801590

  8. Influence of Metal Oxides on Platinum Activity towards Methanol Oxidation in H2 SO4 solution.

    PubMed

    Hameed, R M Abdel; Amin, R S; El-Khatib, K M; Fetohi, Amani E

    2016-04-01

    Pt-CeO2 /C, Pt-TiO2 /C, and Pt-ZrO2 /C electrocatalysts were prepared by using a modified microwave-assisted polyol process. Physical characterization was performed by using XRD, TEM, and EDX analyses. The incorporation of different metal oxides increased the dispersion degree of Pt nanoparticles and reduced their diameter to 2.50 and 2.33 nm when TiO2 and ZrO2 were introduced to Pt/C, respectively. The electrocatalytic activity of various electrocatalysts was examined towards methanol oxidation in H2 SO4 solution by using cyclic voltammetry, chronoamperometry, and electrochemical impedance spectroscopy. Among the studied composites, Pt-ZrO2 /C was selected to be a candidate electrocatalyst for better electrochemical performance in direct methanol fuel cells. PMID:26748621

  9. Luminescence of carbazolyl-containing polymers doped with iridium chelates

    NASA Astrophysics Data System (ADS)

    Skryshevskii, Yu. A.

    2008-05-01

    White light emission is shown to be obtainable at room temperature through the mixing of poly-N-vinylcarbazole (PVC) host fluorescence with fac-tris(2-phenylpyridyl)Ir(III) [Ir(ppy)3] and bis[2-(2'-benzothienyl)pyridinato-N,C3'](acetylacetonate)iridium (III) [Btp2Ir(acac)] dopant phosphorescence whereas at very low temperature through the superposition of poly-N-epoxypropyl-3,6-dibromocarbazole (3,6-DBrPEPC) host and Btp2Ir(acac) dopant phosphorescence emissions. The balance between basic colors is adjusted by the variation of triplet-emitter dopant concentrations. Spin-allowed singlet-singlet energy transfer from the host to iridium chelate dopants by the Forster mechanism is the dominant process in PVC. Spin-forbidden triplet-singlet transfer by the Forster mechanism from the host to the dopant occurs at low temperatures in 3,6-DBrPEPC due to strong spin-orbit coupling induced by the heavy bromine atoms. Spin-allowed transfer from the same host’s triplet excited state to the iridium chelate occurs via electron exchange at high temperatures.

  10. Thermodynamic characterization of hydrogen interaction with iridium polyhydride complexes

    SciTech Connect

    Zidan, R.A.; Rocheleau, R.E.

    1999-01-01

    Hydrogen interaction with solid iridium complexes IrXH{sub 2}(PPr3{sup i}){sub 2} (X=Cl, I) was investigated. Gaseous hydrogen was found to react reversibly with solid chloro-iridium complex IrClH{sub 2}(PPr3{sup i}){sub 2} forming IrClH{sub 2}(PPr3{sup i}){sub 2}H{sub 2}. The relative partial molal enthalpy and entropy were obtained from equilibrium isotherms at different hydrogen concentrations. The decrease in entropy with increasing hydrogen concentration and the absence of plateaus in the equilibrium isotherms were consistent with a single phase solid solution with two chemical components. Hydrogen release from solid iodo-iridium complex IrIH{sub 2}(PPr3{sup i}){sub 2}H{sub 2} was not observed at temperatures up to 350 K, indicating stronger hydrogen bonding. {copyright} {ital 1999 Materials Research Society.}

  11. Advances in iridium alloy processing in FY 1988

    SciTech Connect

    Ohriner, E.K.; Heestand, R.L.

    1989-12-01

    A new process for the production of DOP-26 iridium alloy blanks is being evaluated and optimized. The alloy is prepared by electron-beam (EB) melting of Ir-0.3% W powder compacts followed by doping with aluminum and thorium by arc melting. Drop-cast alloy rod segments are EB welded together into an electrode that is arc melted to produce an ingot for extrusion and subsequent sheet rolling and blanking. Initial results showed rejections for ultrasonic indications for alloy blanks fabricated by this process to be very low. Subsequently, some ingots have exhibited delaminations in the sheet, leading to blank rejection rates similar to that obtained in the standard process. The occurrence of ultrasonic indications in the blanks are now shown to be associated with the presence of subsurface flaws in the arc-melted ingot that are not healed during extrusion or the subsequent rolling of the sheet. There is substantial evidence indicating that the occurrence of surface and subsurface flaws in the ingots are exacerbated by the relatively small clearances between the electrode and the side wall of the 51-mm-diam mold. These results obtained from experimental melts, with both stainless steel and scrap iridium alloy materials, have led to a recommendation for arc melting in a large 63-mm-diam mold. The fabrication of blanks from this larger diameter ingot is under way. The efficiency of iridium material utilization in the new process is also discussed. 2 refs., 23 figs., 12 tabs.

  12. Mononuclear iridium dinitrogen complexes bonded to zeolite HY

    DOE PAGESBeta

    Yang, Dong; Chen, Mingyang; Martinez-Macias, Claudia; Dixon, David A.; Gates, Bruce C.

    2014-11-07

    In this study, the adsorption of N2 on structurally well-defined dealuminated HY zeolite-supported iridium diethylene complexes was investigated. Iridium dinitrogen complexes formed when the sample was exposed to N2 in H2 at 298 K, as shown by infrared spectra recorded with isotopically labeled N2. Four supported species formed in various flowing gases: Ir(N2), Ir(N2)(N2), Ir(C2H5)(N2), and Ir(H)(N2). Their interconversions are summarized in a reaction network, showing, for example, that, in the presence of N2, Ir(N2) was the predominant dinitrogen species at temperatures of 273-373 K. Ir(CO)(N2) formed transiently in flowing CO, and in the presence of H2, rather stable iridiummore » hydride complexes formed. Here, four structural models of each iridium complex bonded at the acidic sites of the zeolite were employed in a computational investigation, showing that the calculated vibrational frequencies agree well with experiment when full calculations are done at the level of density functional theory, independent of the size of the model of the zeolite.« less

  13. Mono- and bis-tolylterpyridine iridium(III) complexes

    SciTech Connect

    Hinkle, Lindsay M.; Young, Jr., Victor G.; Mann, Kent R.

    2012-01-20

    The first structure report of trichlorido[4'-(p-tolyl)-2,2':6',2{double_prime}-terpyridine]iridium(III) dimethyl sulfoxide solvate, [IrCl{sub 3}(C{sub 22}H{sub 17}N{sub 3})] {center_dot} C{sub 2}H{sub 6}OS, (I), is presented, along with a higher-symmetry setting of previously reported bis[4'-(p-tolyl)-2,2':6',2{double_prime}-terpyridine]iridium(III) tris(hexafluoridophosphate) acetonitrile disolvate, [Ir(C{sub 22}H{sub 17}N{sub 3})2](PF{sub 6}){sub 3} {center_dot} 2C{sub 2}H{sub 3}N, (II) [Yoshikawa, Yamabe, Kanehisa, Kai, Takashima & Tsukahara (2007). Eur. J. Inorg. Chem. pp. 1911-1919]. For (I), the data were collected with synchrotron radiation and the dimethyl sulfoxide solvent molecule is disordered over three positions, one of which is an inversion center. The previously reported structure of (II) is presented in the more appropriate C2/c space group. The iridium complex and one PF{sub 6}{sup -} anion lie on twofold axes in this structure, making half of the molecule unique.

  14. Effects of poly(ethylene glycol) tert-octylphenyl ether on tris(2-phenylpyridine)iridium(III)-tripropylamine electrochemiluminescence.

    PubMed

    Cole, Christopher; Muegge, Brian D; Richter, Mark M

    2003-02-01

    The effects of the nonionic surfactant Triton X-100 (poly(ethylene glycol) tert-octylphenyl ether) on the properties of tris(2-phenylpyridine)iridium(III) (Ir(ppy)3, where ppy = 2-phenylpyridine, electrochemiluminescence (ECL) have been investigated. Anodic oxidation of Ir(ppy)3 produces ECL in the presence of tri-n-propylamine (TPrA) in aqueous surfactant solution. Increases in ECL efficiency (> or = 10-fold) and TPrA oxidation current (> or = 2.0-fold) have been observed in surfactant media. The data support adsorption of surfactant on the electrode surface, thus facilitating TPrA and Ir(ppy)3 oxidation and leading to higher ECL efficiencies. PMID:12585490

  15. Study of Chromium Oxide Activities in EAF Slags

    NASA Astrophysics Data System (ADS)

    Yan, Baijun; Li, Fan; Wang, Hui; Sichen, Du

    2016-02-01

    The activity coefficients of chromium in Cu-Cr melts were determined by equilibrating liquid copper with solid Cr2O3 in CO-CO2 atmosphere. The temperature dependence of the activity coefficients of chromium in Cu-Cr melts could be expressed as lg γ_{Cr}(s)^{0} = { 3 2 5 9( ± 1 8 6} )/T - 0. 5 9( { ± 0. 1} ). Based on the above results, the activities of bivalent and trivalent chromium oxide in some slags at 1873 K (1600 °C) were measured. The slags were equilibrated with Cu-Cr melts under two oxygen partial pressures ( {p_{O}_{ 2} }} } = 6.9 × 10-4 and 1.8 × 10-6 Pa, respectively). The morphology of the quenched slags and the solubility of chromium oxide in the melts were investigated by EPMA, SEM, and XRD. Under both oxygen partial pressures, the slags were saturated by the solid solution MgAl2- x Cr x O4- δ . At the low oxygen partial pressure (1.8 × 10-6 Pa), the content of Cr in the liquid phase varied from 0.4 to 1.6 mass pct with the total Cr content in the slags increasing from 1.3 to 10.8 mass pct. At the high oxygen partial pressure (6.9 × 10-4 Pa), the content of Cr in the liquid phase decreased to the level of 0.2 to 0.6 mass pct. Both the activities of CrO and Cr2O3 in slag were found to increase approximately linearly with the increase of the total Cr content in slag. While the oxygen partial pressure had minor effect on the activity of Cr2O3 in the slag, it had significant effect on the activity of CrO.

  16. Semiconductor films on flexible iridium substrates

    DOEpatents

    Goyal, Amit

    2005-03-29

    A laminate semiconductor article includes a flexible substrate, an optional biaxially textured oxide buffer system on the flexible substrate, a biaxially textured Ir-based buffer layer on the substrate or the buffer system, and an epitaxial layer of a semiconductor. Ir can serve as a substrate with an epitaxial layer of a semiconductor thereon.

  17. Results of an Iridium-Based Data Communication System Providing Internet Access to Polar Expeditions

    NASA Astrophysics Data System (ADS)

    Mohammad, A.; Frost, V.; Braaten, D.

    2003-12-01

    The Polar Radar for Ice Sheet Measurements (PRISM) Project at the University of Kansas has developed and field-tested a versatile communications system for use by researchers in high-latitude Polar Regions. The PRISM project is developing advanced intelligent remote sensing technology that involves radar systems, an autonomous rover, and communications systems to measure detailed ice sheet characteristics, and to determine bed conditions (frozen or wet) below active ice sheets in both Greenland and Antarctica. We also have a very strong public outreach and educational program aimed at K-12 educators and students that requires data, voice and video feeds from Polar field locations in near real time. Hence, PRISM requires a robust communications system for use in the field between a base camp and the mobile remote sensing system, and from the field back to the University of Kansas and onto the Internet. The communication system that has been developed is truly mobile and is relatively inexpensive. We initially considered various satellite services during the design phase of this project. The two feasible options for high-latitude locations were Iridium, with its low-bit-rate service (2.4 Kb/s), and Inmarsat/Intelsat with broadband service. We selected the Iridium option for testing and development because it provided coverage in both Antarctica and Greenland. To achieve higher capacity communications, the multilink point-to-point protocol (MLPPP) implemented in Linux was tuned to operate efficiently over the Iridium satellite system. This mechanism combines multiple channels to obtain a seamless data connection with a capacity equal to the sum of the individual link rates. We used four Iridium modems to obtain an aggregate capacity of about 9.6 Kb/s. Standard Internet protocols (TCP/IP) were then used to provide end-to-end connectivity. The communications system field experiments were conducted at the NorthGRIP ice core drilling camp in Greenland (75° 06' N, 42° 20

  18. Highly concentrated active nonlinear media based on oxides

    SciTech Connect

    Bakin, D.V.; Dorozhkin, L.M.; Krasilov, Yu.I.; Kuznetsov, N.T.; Potemkin, A.V.; Tadzhi-Aglaev, K.S.; Shestakov, A.V.

    1987-07-01

    Important characteristics of highly concentrated active nonlinear media were studied which were based on oxide compounds of phosphates, niobates, tantalates, and titanates of neodymium with alkaline earth metals. Compounds of the indicated classes were synthesized and their spectral luminescent and nonlinear optical properties were studied. Single crystals were grown from the selected compounds (5-8mm) and preliminary measurements of the laser and nonlinear optical parameters were taken. Formulas are given for materials that demonstrated high nonlinear and luminescent properties simultaneously. Spectroscopic and nonlinear optical properties of some oxygen compounds of rare earth elements are shown.

  19. Redox Potentials, Laccase Oxidation, and Antilarval Activities of Substituted Phenols

    PubMed Central

    Prasain, Keshar; Nguyen, Thi D. T.; Gorman, Maureen J.; Barrigan, Lydia M.; Peng, Zeyu; Kanost, Michael R.; Syed, Lateef U.; Li, Jun; Zhu, Kun Yan; Hua, Duy H.

    2012-01-01

    Laccases are copper-containing oxidases that are involved in sclerotization of the cuticle of mosquitoes and other insects. Oxidation of exogenous compounds by insect laccases may have the potential to produce reactive species toxic to insects. We investigated two classes of substituted phenolic compounds, halogenated di- and trihydroxybenzenes and substituted di-tert-butylphenols, on redox potential, oxidation by laccase and effects on mosquito larval growth. An inverse correlation between the oxidation potentials and laccase activity of halogenated hydroxybenzenes was found. Substituted di-tert-butylphenols however were found to impact mosquito larval growth and survival. In particular, 2,4-di-tert-butyl-6-(3-methyl-2-butenyl)phenol (15) caused greater than 98% mortality of Anopheles gambiae larvae in a concentration of 180 nM, whereas 2-(3,5-di-tert-butyl-4-hydroxyphenyl)-2-methylpropanal oxime (13) and 6,8-di-tert-butyl-2,2-dimethyl-3,4-dihydro-2H-chromene (33) caused 93% and 92% mortalities in concentrations of 3.4 and 3.7 μM, respectively. Larvae treated with di-tert-butylphenolic compounds died just before pupation. PMID:22300888

  20. Characterization and metal sorptive properties of oxidized active carbon.

    PubMed

    Strelko, Vladimir; Malik, Danish J

    2002-06-01

    A commercial activated carbon Chemviron F 400 has been oxidized using nitric acid in order to introduce a variety of acidic surface functional groups. Both unoxidized and oxidized carbon samples were characterized using nitrogen porosimetry, elemental analysis, pH titration, Boehm's titration, and electrophoretic mobility measurements. Results show that oxidation treatment reduced surface area and pore volume. However, the carbon surface acquires an acidic character with carboxylic groups being the dominant surface functional groups. The modified sample displays cation-exchange properties over a wide range of pH values and exhibits polyfunctional nature. Both carbon samples were challenged for the removal of transition metals such as copper(II), nickel(II), cobalt(II), zinc(II), and manganese(II). The affinity series Mn2+Zn2+ has been found to coincide with the general stability sequence of metal complexes (the Irving-Williams series). The higher preference displayed by carbons toward copper(II) is a consequence of the fact that copper(II) often forms distorted and more stable octahedral complexes. PMID:16290653

  1. Defluorination of Aqueous Perfluorooctanesulfonate by Activated Persulfate Oxidation

    PubMed Central

    Yang, Shewei; Cheng, Jianhua; Sun, Jian; Hu, Yongyou; Liang, Xiaoyan

    2013-01-01

    Activated persulfate oxidation technologies based on sulfate radicals were first evaluated for defluorination of aqueous perfluorooctanesulfonate (PFOS). The influences of catalytic method, time, pH and K2S2O8 amounts on PFOS defluorination were investigated. The intermediate products during PFOS defluorination were detected by using LC/MS/MS. The results showed that the S2O82− had weak effect on the defluorination of PFOS, while the PFOS was oxidatively defluorinated by sulfate radicals in water. The defluorination efficiency of PFOS under various treatment was followed the order: HT (hydrothermal)/K2S2O8 > UV (ultraviolet)/K2S2O8 > Fe2+/K2S2O8 > US (ultrasound)/K2S2O8. Low pH was favorable for the PFOS defluorination with sulfate radicals. Increase in the amount of S2O82− had positive effect on PFOS defluorination. However, further increase in amounts of S2O82− caused insignificant improvement in PFOS defluorination due to elimination of sulfate radicals under high concentration of S2O82−. CF3(CF2)nCOOH (n = 0–6) were detected as intermediates during PFOS defluorination. Sulfate radicals oxidation and hydrolysis were the main mechanisms involved in defluorination process of PFOS. PMID:24116016

  2. Impaired enzymatic defensive activity, mitochondrial dysfunction and proteasome activation are involved in RTT cell oxidative damage.

    PubMed

    Cervellati, Carlo; Sticozzi, Claudia; Romani, Arianna; Belmonte, Giuseppe; De Rasmo, Domenico; Signorile, Anna; Cervellati, Franco; Milanese, Chiara; Mastroberardino, Pier Giorgio; Pecorelli, Alessandra; Savelli, Vinno; Forman, Henry J; Hayek, Joussef; Valacchi, Giuseppe

    2015-10-01

    A strong correlation between oxidative stress (OS) and Rett syndrome (RTT), a rare neurodevelopmental disorder affecting females in the 95% of the cases, has been well documented although the source of OS and the effect of a redox imbalance in this pathology has not been yet investigated. Using freshly isolated skin fibroblasts from RTT patients and healthy subjects, we have demonstrated in RTT cells high levels of H2O2 and HNE protein adducts. These findings correlated with the constitutive activation of NADPH-oxidase (NOX) and that was prevented by a NOX inhibitor and iron chelator pre-treatment, showing its direct involvement. In parallel, we demonstrated an increase in mitochondrial oxidant production, altered mitochondrial biogenesis and impaired proteasome activity in RTT samples. Further, we found that the key cellular defensive enzymes: glutathione peroxidase, superoxide dismutase and thioredoxin reductases activities were also significantly lower in RTT. Taken all together, our findings suggest that the systemic OS levels in RTT can be a consequence of both: increased endogenous oxidants as well as altered mitochondrial biogenesis with a decreased activity of defensive enzymes that leads to posttranslational oxidant protein modification and a proteasome activity impairment. PMID:26189585

  3. Evaluation of Molybdenum as a Surrogate for Iridium in the GPHS Weld Development

    SciTech Connect

    Stine, Andrew Martin; Pierce, Stanley W.; Moniz, Paul F.

    2015-10-17

    The welding equipment used for welding iridium containers (clads) at Los Alamos National Laboratory is twenty five years old and is undergoing an upgrade. With the upgrade, there is a requirement for requalification of the welding process, and the opportunity for process improvement. Testing of the new system and requalification will require several welds on iridium test parts and clads, and any efforts to improve the process will add to the need for iridium parts. The extreme high cost of iridium imposes a severe limitation on the extent of test welding that can be done. The 2 inch diameter, 0.027 inch thick, iridium blank disc that the clad cup is formed from, is useful for initial weld trials, but it costs $5000. The development clad sets needed for final tests and requalification cost $15,000 per set. A solution to iridium cost issue would be to do the majority of the weld development on a less expensive surrogate metal with similar weld characteristics. One such metal is molybdenum. Since its melting index (melting temperature x thermal conductivity) is closest to iridium, welds on molybdenum should be similar in size for a given weld power level. Molybdenum is inexpensive; a single 2 inch molybdenum disc costs only $9. In order to evaluate molybdenum as a surrogate for iridium, GTA welds were first developed to provide full penetration on 0.030 inch thick molybdenum discs at speeds of 20, 25, and 30 inches per minute (ipm). These weld parameters were then repeated on the standard 0.027 inch thick iridium blanks. The top surface and bottom surface (root) width and grain structure of the molybdenum and iridium welds were compared, and similarities were evident between the two metals. Due to material and thickness differences, the iridium welds were approximately 35% wider than the molybdenum welds. A reduction in iridium weld current of 35% produce welds slightly smaller than the molybdenum welds yet showed that current could be scaled according to molybdenum/iridium

  4. Rockot Launch Vehicle Commercial Operations for Grace and Iridium Program

    NASA Astrophysics Data System (ADS)

    Viertel, Y.; Kinnersley, M.; Schumacher, I.

    2002-01-01

    The GRACE mission and the IRIDIUM mission on ROCKOT launch vehicle are presented. Two identical GRACE satellites to measure in tandem the gravitational field of the earth with previously unattainable accuracy - it's called the Gravity Research and Climate Experiment, or and is a joint project of the U.S. space agency, NASA and the German Centre for Aeronautics and Space Flight, DLR. In order to send the GRACE twins into a 500x500 km , 89deg. orbit, the Rockot launch vehicle was selected. A dual launch of two Iridium satellites was scheduled for June 2002 using the ROCKOT launch vehicle from Plesetsk Cosmodrome in Northern Russia. This launch will inject two replacement satellites into a low earth orbit (LEO) to support the maintenance of the Iridium constellation. In September 2001, Eurockot successfully carried out a "Pathfinder Campaign" to simulate the entire Iridium mission cycle at Plesetsk. The campaign comprised the transport of simulators and related equipment to the Russian port-of-entry and launch site and also included the integration and encapsulation of the simulators with the actual Rockot launch vehicle at Eurockot's dedicated launch facilities at Plesetsk Cosmodrome. The pathfinder campaign lasted four weeks and was carried out by a joint team that also included Khrunichev, Russian Space Forces and Eurockot personnel on the contractors' side. The pathfinder mission confirmed the capability of Eurockot Launch Services to perform the Iridium launch on cost and on schedule at Plesetsk following Eurockot's major investment in international standard preparation, integration and launch facilities including customer facilities and a new hotel. In 2003, Eurockot will also launch the Japanese SERVI'S-1 satellite for USEF. The ROCKOT launch vehicle is a 3 stage liquid fuel rocket whose first 2 stages have been adapted from the Russian SS-19. A third stage, called "Breeze", can be repeatedly ignited and is extraordinarily capable of manoeuvre. Rockot can place

  5. Activation of peroxisome proliferator-activated receptor-{alpha} enhances fatty acid oxidation in human adipocytes

    SciTech Connect

    Lee, Joo-Young; Hashizaki, Hikari; Goto, Tsuyoshi; Sakamoto, Tomoya; Takahashi, Nobuyuki; Kawada, Teruo

    2011-04-22

    Highlights: {yields} PPAR{alpha} activation increased mRNA expression levels of adipocyte differentiation marker genes and GPDH activity in human adipocytes. {yields} PPAR{alpha} activation also increased insulin-dependent glucose uptake in human adipocytes. {yields} PPAR{alpha} activation did not affect lipid accumulation in human adipocytes. {yields} PPAR{alpha} activation increased fatty acid oxidation through induction of fatty acid oxidation-related genes in human adipocytes. -- Abstract: Peroxisome proliferator-activated receptor-{alpha} (PPAR{alpha}) is a key regulator for maintaining whole-body energy balance. However, the physiological functions of PPAR{alpha} in adipocytes have been unclarified. We examined the functions of PPAR{alpha} using human multipotent adipose tissue-derived stem cells as a human adipocyte model. Activation of PPAR{alpha} by GW7647, a potent PPAR{alpha} agonist, increased the mRNA expression levels of adipocyte differentiation marker genes such as PPAR{gamma}, adipocyte-specific fatty acid-binding protein, and lipoprotein lipase and increased both GPDH activity and insulin-dependent glucose uptake level. The findings indicate that PPAR{alpha} activation stimulates adipocyte differentiation. However, lipid accumulation was not changed, which is usually observed when PPAR{gamma} is activated. On the other hand, PPAR{alpha} activation by GW7647 treatment induced the mRNA expression of fatty acid oxidation-related genes such as CPT-1B and AOX in a PPAR{alpha}-dependent manner. Moreover, PPAR{alpha} activation increased the production of CO{sub 2} and acid soluble metabolites, which are products of fatty acid oxidation, and increased oxygen consumption rate in human adipocytes. The data indicate that activation of PPAR{alpha} stimulates both adipocyte differentiation and fatty acid oxidation in human adipocytes, suggesting that PPAR{alpha} agonists could improve insulin resistance without lipid accumulation in adipocytes. The expected

  6. Highly Ordered Mesoporous Cobalt-Containing Oxides: Structure, Catalytic Properties, and Active Sites in Oxidation of Carbon Monoxide.

    PubMed

    Gu, Dong; Jia, Chun-Jiang; Weidenthaler, Claudia; Bongard, Hans-Josef; Spliethoff, Bernd; Schmidt, Wolfgang; Schüth, Ferdi

    2015-09-01

    Co3O4 with a spinel structure is a very active oxide catalyst for the oxidation of CO. In such catalysts, octahedrally coordinated Co(3+) is considered to be the active site, while tetrahedrally coordinated Co(2+) is assumed to be basically inactive. In this study, a highly ordered mesoporous CoO has been prepared by H2 reduction of nanocast Co3O4 at low temperature (250 °C). The as-prepared CoO material, which has a rock-salt structure with a single Co(2+) octahedrally coordinated by lattice oxygen in Fm3̅m symmetry, exhibited unexpectedly high activity for CO oxidation. Careful investigation of the catalytic behavior of mesoporous CoO catalyst led to the conclusion that the oxidation of surface Co(2+) to Co(3+) causes the high activity. Other mesoporous spinels (CuCo2O4, CoCr2O4, and CoFe2O4) with different Co species substituted with non/low-active metal ions were also synthesized to investigate the catalytically active site of cobalt-based catalysts. The results show that not only is the octahedrally coordinated Co(3+) highly active but also the octahedrally coordinated Co(2+) species in CoFe2O4 with an inverse spinel structure shows some activity. These results suggest that the octahedrally coordinated Co(2+) species is easily oxidized and shows high catalytic activity for CO oxidation. PMID:26301797

  7. Natural Product Nitric Oxide Chemistry: New Activity of Old Medicines

    PubMed Central

    Jiang, Hong; Torregrossa, Ashley C.; Parthasarathy, Deepa K.; Bryan, Nathan S.

    2012-01-01

    The use of complementary and alternative medicine (CAM) as a therapy and preventative care measure for cardiovascular diseases (CVD) may prove to be beneficial when used in conjunction with or in place of conventional medicine. However, the lack of understanding of a mechanism of action of many CAMs limits their use and acceptance in western medicine. We have recently recognized and characterized specific nitric oxide (NO) activity of select alternative and herbal medicines that may account for many of their reported health benefits. The ability of certain CAM to restore NO homeostasis both through enhancing endothelial production of NO and by providing a system for reducing nitrate and nitrite to NO as a compensatory pathway for repleting NO bioavailability may prove to be a safe and cost-effective strategy for combating CVD. We will review the current state of science behind NO activity of herbal medicines and their effects on CVD. PMID:22548122

  8. Redox Active Thiol Sensors of Oxidative and Nitrosative Stress

    PubMed Central

    2012-01-01

    Abstract Significance: The reactivity of the thiol in the side chain of cysteines is exploited by bacterial regulatory proteins that sense and respond to reactive oxygen and nitrogen species. Recent Advances: Charged residues and helix dipoles diminish the pKa of redox active cysteines, resulting in a thiolate that is stabilized by neighboring polar amino acids. The reaction of peroxides with thiolates generates a sulfenic acid (–SOH) intermediate that often gives rise to a reversible disulfide bond. Peroxide-induced intramolecular and intermolecular disulfides and intermolecular mixed disulfides modulate the signaling activity of members of the LysR/OxyR, MarR/OhrR, and RsrA family of transcriptional regulators. Thiol-dependent regulators also help bacteria resist the nitrosative and nitroxidative stress. −SOHs, mixed disulfides, and S-nitrosothiols are some of the post-translational modifications induced by nitrogen oxides in the thiol groups of OxyR and SsrB bacterial regulatory proteins. Sulfenylation, disulfide bond formation, S-thiolation, and S-nitrosylation are reversible modifications amenable to feedback regulation by antioxidant and antinitrosative repair systems. The structural and functional changes engaged in the thiol-dependent sensing of reactive species have been adopted by several regulators to foster bacterial virulence during exposure to products of NADPH phagocyte oxidase and inducible nitric oxide synthase. Critical Issues: Investigations with LysR/OxyR, MarR/OhrR, and RsrA family members have helped in an understanding of the mechanisms by which thiols in regulatory proteins react with reactive species, thereby activating antioxidant and antinitrosative gene expression. Future Directions: To define the determinants that provide selectivity of redox active thiolates for some reactive species but not others is an important challenge for future investigations. Antioxid. Redox Signal. 17, 1201–1214. PMID:22257022

  9. Acceleration of catalytic activity of calcium oxide for biodiesel production.

    PubMed

    Kawashima, Ayato; Matsubara, Koh; Honda, Katsuhisa

    2009-01-01

    This research was aimed at studying the acceleration of the catalytic activity of calcium oxide (CaO) for developing an effective heterogeneous catalyst for biodiesel production by the transesterification of plant oil with methanol. CaO was activated by pretreatment with methanol and was used for the transesterification reaction. The activation and transesterification reaction conditions were examined. The obtained optimal reaction conditions were 0.1-g CaO, 3.9-g methanol, 15-g rapeseed oil, and 1.5-h activation time at room temperature that provided methyl ester in approximately 90% yield within a reaction time of 3h at 60 degrees C. The activation mechanism was also investigated, and the proposed mechanism is as follows. By pretreatment with methanol, a small amount of CaO gets converted into Ca(OCH(3))(2) that acts as an initiating reagent for the transesterification reaction and produces glycerin as a by-product. Subsequently, a calcium-glycerin complex, formed due to the reaction of CaO with glycerin, functions as the main catalyst and accelerates the transesterification reaction. PMID:18684617

  10. Sodium channel activation mechanisms. Insights from deuterium oxide substitution

    SciTech Connect

    Alicata, D.A.; Rayner, M.D.; Starkus, J.G. )

    1990-04-01

    Schauf and Bullock, using Myxicola giant axons, demonstrated that solvent substitution with deuterium oxide (D2O) significantly affects both sodium channel activation and inactivation kinetics without corresponding changes in gating current or tail current rates. They concluded that (a) no significant component of gating current derives from the final channel opening step, and (b) channels must deactivate (during tail currents) by a different pathway from that used in channel opening. By contrast, Oxford found in squid axons that when a depolarizing pulse is interrupted by a brief (approximately 100 microseconds) return to holding potential, subsequent reactivation (secondary activation) is very rapid and shows almost monoexponential kinetics. Increasing the interpulse interval resulted in secondary activation rate returning towards control, sigmoid (primary activation) kinetics. He concluded that channels open and close (deactivate) via the same pathway. We have repeated both sets of observations in crayfish axons, confirming the results obtained in both previous studies, despite the apparently contradictory conclusions reached by these authors. On the other hand, we find that secondary activation after a brief interpulse interval (50 microseconds) is insensitive to D2O, although reactivation after longer interpulse intervals (approximately 400 microseconds) returns towards a D2O sensitivity similar to that of primary activation. We conclude that D2O-sensitive primary activation and D2O-insensitive tail current deactivation involve separate pathways. However, D2O-insensitive secondary activation involves reversal of the D2O-insensitive deactivation step. These conclusions are consistent with parallel gate models, provided that one gating particle has a substantially reduced effective valence.

  11. Treatment of activated carbon to enhance catalytic activity for reduction of nitric oxide with ammonia

    SciTech Connect

    Ku, B.J.; Rhee, H.K. . Dept. of Chemical Engineering); Lee, J.K.; Park, D. )

    1994-11-01

    Catalytic activity of activated carbon treated with various techniques was examined in a fixed bed reactor for the reduction of nitric oxide with ammonia at 150 C. Activated carbon derived from coconut shell impregnated with an aqueous solution of ammonium sulfate, further treated with sulfuric acid, dried at 120 C, and then heated in an inert gas stream at 400 C, showed the highest catalytic activity within the range of experimental conditions. The enhancement of catalytic activity of modified activated carbon could be attributed to the increase in the amount of oxygen function groups which increased the adsorption site for ammonia. Catalytic activity of activated carbons depended on the surface area and the oxygen content as well.

  12. Oxide muonics: I. Modelling the electrical activity of hydrogen in semiconducting oxides

    NASA Astrophysics Data System (ADS)

    Cox, S. F. J.; Lord, J. S.; Cottrell, S. P.; Gil, J. M.; Alberto, H. V.; Keren, A.; Prabhakaran, D.; Scheuermann, R.; Stoykov, A.

    2006-01-01

    A shallow-to-deep instability of hydrogen defect centres in narrow-gap oxide semiconductors is revealed by a study of the electronic structure and electrical activity of their muonium counterparts, a methodology that we term 'muonics'. In CdO, Ag2O and Cu2O, paramagnetic muonium centres show varying degrees of delocalization of the singly occupied orbital, their hyperfine constants spanning 4 orders of magnitude. PbO and RuO2, on the other hand, show only electronically diamagnetic muon states, mimicking those of interstitial protons. Muonium in CdO shows shallow-donor behaviour, dissociating between 50 and 150 K the effective ionization energy of 0.1 eV is at some variance with the effective-mass model but illustrates the possibility of hydrogen doping, inducing n-type conductivity as in the wider-gap oxide, ZnO. For Ag2O, the principal donor level is deeper (0.25 eV) but ionization is nonetheless complete by room temperature. Striking examples of level-crossing and RF resonance spectroscopy reveal a more complex interplay of several metastable states in this case. In Cu2O, muonium has quasi-atomic character and is stable to 600 K, although the electron orbital is substantially more delocalized than in the trapped-atom states known in certain wide-gap dielectric oxides. Its eventual disappearance towards 900 K, with an effective ionization energy of 1 eV, defines an electrically active level near mid-gap in this material.

  13. Real-Time Characterization of Formation and Breakup of Iridium Clusters in Highly Dealuminated Zeolite Y

    SciTech Connect

    Uzun, Alper; Gates, Bruce C.

    2009-01-15

    The chemistry of formation of iridium clusters from mononuclear iridium diethylene complexes anchored in dealuminated Y zeolite, and their subsequent breakup -- all including changes in the metal-metal, metal-support, and metal-ligand interactions -- is demonstrated by time-resolved EXAFS, XANES, and IR spectroscopy.

  14. Phosphorescent Imaging of Living Cells Using a Cyclometalated Iridium(III) Complex

    PubMed Central

    Ma, Dik-Lung; Zhong, Hai-Jing; Fu, Wai-Chung; Chan, Daniel Shiu-Hin; Kwan, Hiu-Yee; Fong, Wang-Fun; Chung, Lai-Hon; Wong, Chun-Yuen; Leung, Chung-Hang

    2013-01-01

    A cell permeable cyclometalated iridium(III) complex has been developed as a phosphorescent probe for cell imaging. The iridium(III) solvato complex [Ir(phq)2(H2O]2)] preferentially stains the cytoplasm of both live and dead cells with a bright luminescence. PMID:23457478

  15. Protein kinase Cδ regulates endothelial nitric oxide synthase expression via Akt activation and nitric oxide generation

    PubMed Central

    Sud, Neetu; Wedgwood, Stephen; Black, Stephen M.

    2008-01-01

    In this study, we explore the roles of the delta isoform of PKC (PKCδ) in the regulation of endothelial nitric oxide synthase (eNOS) activity in pulmonary arterial endothelial cells isolated from fetal lambs (FPAECs). Pharmacological inhibition of PKCδ with either rottlerin or with the peptide, δV1-1, acutely attenuated NO production, and this was associated with a decrease in phosphorylation of eNOS at Ser1177 (S1177). The chronic effects of PKCδ inhibition using either rottlerin or the overexpression of a dominant negative PKCδ mutant included the downregulation of eNOS gene expression that was manifested by a decrease in both eNOS promoter activity and protein expression after 24 h of treatment. We also found that PKCδ inhibition blunted Akt activation as observed by a reduction in phosphorylated Akt at position Ser473. Thus, we conclude that PKCδ is actively involved in the activation of Akt. To determine the effect of Akt on eNOS signaling, we overexpressed a dominant negative mutant of Akt and determined its effect of NO generation, eNOS expression, and phosphorylation of eNOS at S1177. Our results demonstrated that Akt inhibition was associated with decreased NO production that correlated with reduced phosphorylation of eNOS at S1177, and decreased eNOS promoter activity. We next evaluated the effect of endogenously produced NO on eNOS expression by incubating FPAECs with the eNOS inhibitor 2-ethyl-2-thiopseudourea (ETU). ETU significantly inhibited NO production, eNOS promoter activity, and eNOS protein levels. Together, our data indicate involvement of PKCδ-mediated Akt activation and NO generation in maintaining eNOS expression. PMID:18192589

  16. Development of structure-activity relationship for metal oxide nanoparticles

    NASA Astrophysics Data System (ADS)

    Liu, Rong; Zhang, Hai Yuan; Ji, Zhao Xia; Rallo, Robert; Xia, Tian; Chang, Chong Hyun; Nel, Andre; Cohen, Yoram

    2013-05-01

    Nanomaterial structure-activity relationships (nano-SARs) for metal oxide nanoparticles (NPs) toxicity were investigated using metrics based on dose-response analysis and consensus self-organizing map clustering. The NP cellular toxicity dataset included toxicity profiles consisting of seven different assays for human bronchial epithelial (BEAS-2B) and murine myeloid (RAW 264.7) cells, over a concentration range of 0.39-100 mg L-1 and exposure time up to 24 h, for twenty-four different metal oxide NPs. Various nano-SAR building models were evaluated, based on an initial pool of thirty NP descriptors. The conduction band energy and ionic index (often correlated with the hydration enthalpy) were identified as suitable NP descriptors that are consistent with suggested toxicity mechanisms for metal oxide NPs and metal ions. The best performing nano-SAR with the above two descriptors, built with support vector machine (SVM) model and of validated robustness, had a balanced classification accuracy of ~94%. An applicability domain for the present data was established with a reasonable confidence level of 80%. Given the potential role of nano-SARs in decision making, regarding the environmental impact of NPs, the class probabilities provided by the SVM nano-SAR enabled the construction of decision boundaries with respect to toxicity classification under different acceptance levels of false negative relative to false positive predictions.Nanomaterial structure-activity relationships (nano-SARs) for metal oxide nanoparticles (NPs) toxicity were investigated using metrics based on dose-response analysis and consensus self-organizing map clustering. The NP cellular toxicity dataset included toxicity profiles consisting of seven different assays for human bronchial epithelial (BEAS-2B) and murine myeloid (RAW 264.7) cells, over a concentration range of 0.39-100 mg L-1 and exposure time up to 24 h, for twenty-four different metal oxide NPs. Various nano-SAR building models were

  17. Iridium abundance maxima at the latest Ordovician mass extinction horizon, Yangtze Basin, China: Terrestrial or extraterrestrial

    SciTech Connect

    Kun Wang; Chatterton, B.D.E. ); Attrep, M. Jr; Orth, C.J. )

    1992-01-01

    Neutron activation analyses of the Chinese Ordovician/Silurian (O/S) boundary sections at two distant localities in the Yangtze Basin, spanning the horizon of a major latest Ordovician global extinction event, show the maxima of iridium abundances to be coincident with the extinction horizon at the base of the graptolite Glyptograptus persculputs zone. The 0.23 ppb Ir maximum in the Yichang type section is almost as large as the late Eocene impact Ir anomaly. However, the authors have observed that the Ir abundances in the Chinese sections are closely correlated with the sedimentation rates, and therefore have concluded that Ir maxima do not indicate a cataclysmic extraterrestrial impact at this extinction level.

  18. Chemoselective hydrogenation of functionalized nitroarenes and imines by using carbon nanofiber-supported iridium nanoparticles.

    PubMed

    Motoyama, Yukihiro; Taguchi, Masahiro; Desmira, Nelfa; Yoon, Seong-Ho; Mochida, Isao; Nagashima, Hideo

    2014-01-01

    The reaction of three types of carbon nanofibers (CNFs; platelet: CNF-P, tubular: CNF-T, herringbone: CNF-H) with Ir4(CO)12 in mesitylene at 165 °C provided the corresponding CNF-supported iridium nanoparticles, Ir/CNFs (Ir content=2.3-2.6 wt.%). Transmission electron microscopy (TEM) studies of these Ir/CNF samples revealed that size-controlled Ir nanoparticles (average particle size of 1.1-1.5 nm) existed on the CNFs. Among the three Ir/CNF samples, Ir/CNF-T showed an excellent catalytic activity and chemoselectivity towards hydrogenation of functionalized nitroarenes and imines; the corresponding aniline derivatives were obtained with high turnover numbers at ambient temperature under 10 tm of H2 , and the catalyst is reusable. Ir/CNF-T was also effective for the reductive N-alkylation of anilines with carbonyl compounds. PMID:24347068

  19. Cyclometalated iridium(III) complexes as mitochondria-targeted anticancer agents.

    PubMed

    Xiong, Kai; Chen, Yu; Ouyang, Cheng; Guan, Rui-Lin; Ji, Liang-Nian; Chao, Hui

    2016-06-01

    Four cyclometalated iridium(III) complexes [Ir(dfppy)2(L)](+) (dfppy = 2-(2,4-difluorophenyl)pyridine, L = 6-(pyridin-2-yl)-1,3,5-triazine-2,4-diamine, Ir1; 6-(isoquinolin-1-yl)-1,3,5-triazine-2,4-diamine, Ir2; 6-(quinolin-2-yl)-1,3,5-triazine-2,4-diamine, Ir3; 6-(isoquinolin-3-yl)-1,3,5-triazine-2,4-diamine, Ir4) have been synthesized and characterized. Distinct from cisplatin, Ir1-Ir4 could specifically target mitochondria and induced apoptosis against various cancer cell lines, especially for cisplatin resistant cells. ICP-MS results indicated that Ir1-Ir4 were taken up via different mechanism for cancer cells and normal cells, which resulted in their high selectivity. The structure-activity relationship and signaling pathways were also discussed. PMID:27039888

  20. The influence of transition metal oxides on the kinetics of Li2O2 oxidation in Li-O2 batteries: high activity of chromium oxides.

    PubMed

    Yao, Koffi P C; Lu, Yi-Chun; Amanchukwu, Chibueze V; Kwabi, David G; Risch, Marcel; Zhou, Jigang; Grimaud, Alexis; Hammond, Paula T; Bardé, Fanny; Shao-Horn, Yang

    2014-02-14

    Reducing the energy loss associated with Li2O2 electrochemical oxidation is paramount to the development of efficient rechargeable lithium-oxygen (Li-O2) batteries for practical use. The influence of a series of perovskites with different eg filling on the kinetics of Li2O2 oxidation was examined using Li2O2-prefilled electrodes. While LaCrO3 is inactive for oxygen evolution upon water oxidation in alkaline solution, it was found to provide the highest specific current towards Li2O2 oxidation among all the perovskites examined. Further exploration of Cr-based catalysts showed that Cr nanoparticles (Cr NP) with an average particle size of 40 nm, having oxidized surfaces, had comparable surface area activities to LaCrO3 but much greater mass activities. Unlike Pt/C and Ru/C that promote electrolyte oxidation in addition to Li2O2 oxidation, no evidence of enhanced electrolyte oxidation was found for Cr NP relative to Vulcan carbon. X-ray absorption spectroscopy at the O K and Cr L edge revealed a redox process of Cr(3+) ↔ Cr(6+) on the surface of Cr NP upon Li2O2 oxidation, which might be responsible for the enhanced oxidation kinetics of Li2O2 and the reduced charging voltages of Li-O2 batteries. PMID:24352578

  1. Depolarization of mitochondria in neurons promotes activation of nitric oxide synthase and generation of nitric oxide.

    PubMed

    Katakam, Prasad V G; Dutta, Somhrita; Sure, Venkata N; Grovenburg, Samuel M; Gordon, Angellica O; Peterson, Nicholas R; Rutkai, Ibolya; Busija, David W

    2016-05-01

    The diverse signaling events following mitochondrial depolarization in neurons are not clear. We examined for the first time the effects of mitochondrial depolarization on mitochondrial function, intracellular calcium, neuronal nitric oxide synthase (nNOS) activation, and nitric oxide (NO) production in cultured neurons and perivascular nerves. Cultured rat primary cortical neurons were studied on 7-10 days in vitro, and endothelium-denuded cerebral arteries of adult Sprague-Dawley rats were studied ex vivo. Diazoxide and BMS-191095 (BMS), activators of mitochondrial KATP channels, depolarized mitochondria in cultured neurons and increased cytosolic calcium levels. However, the mitochondrial oxygen consumption rate was unaffected by mitochondrial depolarization. In addition, diazoxide and BMS not only increased the nNOS phosphorylation at positive regulatory serine 1417 but also decreased nNOS phosphorylation at negative regulatory serine 847. Furthermore, diazoxide and BMS increased NO production in cultured neurons measured with both fluorescence microscopy and electron spin resonance spectroscopy, which was sensitive to inhibition by the selective nNOS inhibitor 7-nitroindazole (7-NI). Diazoxide also protected cultured neurons against oxygen-glucose deprivation, which was blocked by NOS inhibition and rescued by NO donors. Finally, BMS induced vasodilation of endothelium denuded, freshly isolated cerebral arteries that was diminished by 7-NI and tetrodotoxin. Thus pharmacological depolarization of mitochondria promotes activation of nNOS leading to generation of NO in cultured neurons and endothelium-denuded arteries. Mitochondrial-induced NO production leads to increased cellular resistance to lethal stress by cultured neurons and to vasodilation of denuded cerebral arteries. PMID:26945078

  2. MnOx-CeO2-Al2O3 mixed oxides for soot oxidation: activity and thermal stability.

    PubMed

    Wu, Xiaodong; Liu, Shuang; Weng, Duan; Lin, Fan; Ran, Rui

    2011-03-15

    MnO(x)-CeO(2)-Al(2)O(3) mixed oxides were prepared by impregnating manganese acetate and cerium nitrate on alumina powders using the sol-gel method. The thermal stabilities of MnO(x)-CeO(2) and Al(2)O(3)-modified mixed oxides were evaluated by treating at 800 °C in dry air flow for 20h. The introduction of Al(2)O(3) markedly increases the textural stability of the catalyst with a relatively high dispersion of MnO(x) and CeO(2), remaining a strong synergistic effect between these two oxides. The NO oxidation activity of the ternary oxides experiences a smaller loss after high-temperature calcination, and a low soot oxidation temperature is attained in the presence of NO. PMID:21276659

  3. Iridium-catalyzed enantioselective hydrogenation of imines in supercritical carbon dioxide

    SciTech Connect

    Kainz, S.; Brinkmann, A.; Leitner, W.; Pfaltz, A.

    1999-07-14

    Supercritical carbon dioxide (scCO{sub 2}) was shown to be a reaction medium with unique properties for highly efficient iridium-catalyzed enantioselective hydrogenation of prochiral imines. Cationic iridium(I) complexes with chiral phosphinodihydrooxazoles, modified with perfluoroalkyl groups in the ligand or in the anion, were synthesized and tested in the hydrogenation of N-(1-phenylethylidene)aniline. Both the side chains and the lipophilic anions increased the solubility, but the choice of the anion also had a dramatic effect on the enantioselectivity with tetrakis-3,5-bis(trifluoromethyl)phenylborate (BARF) leading to the highest asymmetric induction. (R)-N-phenyl-1-phenylethylamine was formed quantitatively within 1 h in scCO{sub 2}[d(CO{sub 2}) = 0.75 g mL{sup {minus}1}] at 40 C and a H{sub 2} pressure of 30 bar with enantiomeric excesses of up to 81% using 0.078 mol % catalyst. The use of scCO{sub 2} instead of conventional solvents such as CH{sub 2}Cl{sub 2} allowed the catalyst loading to be lowered significantly owing to a change in the rate profile of the reaction. the homogeneous nature of the catalytically active species under the reaction conditions was demonstrated and was found to depend strongly on the composition of the reaction mixture and especially on the presence of the substrate. Utilizing the selective extractive properties of scCO{sub 2}, the product could be readily separated from the catalyst, which could be recycled several times without significant loss of activity and enantioselectivity. High-pressure FT-IR and NMR investigations revealed that the reactivity of the products to form the corresponding carbamic acids plays an important role for the application of this new methodology.

  4. Iridium: Global OTH data communications for high altitude scientific ballooning

    NASA Astrophysics Data System (ADS)

    Denney, A.

    beneficial points provided by the Iridium platform include pure global accessibility (as well as polar), cost effectiveness because it is available as a COTS (Commercially Off The Shelf) technology, reliability in that the equipment must operate in extreme conditions (near space), integration and development time into current systems must be minimized. As a bonus Motorola and NAL Research Corporation are developing SBD (Short Burst Data) into the Iridium network. This may lead the way to a global IP (Internet Protocol) node based ballooning platform. The Iridium satellite data modems employ the Iridium Low-Earth Orbit (LEO) satellite network. The scope of this paper is to introduce an OTH communications alternative, albeit not necessarily a primary one, to existing ballooning platforms using COTS based emerging technologies. Design aspects, characteristics, actual flight testing statistics, principles of the Iridium modems and communication paths are described including payload and support instrumentation interfacing. Not limited to high altitude ballooning, the Iridium communications platform opens a new era in remote commanding and data retrieval.

  5. Low Temperature Nitridation of Si Oxide Utilizing Activated Nitrogen

    NASA Astrophysics Data System (ADS)

    Uraoka, Yukiharu; Yano, Hiroshi; Hatayama, Tomoaki; Fuyuki, Takashi

    2002-06-01

    Oxynitride or nitride films are promising materials as a substitute for silicon dioxide because of their high dielectric constant and blocking effect on B penetration. The purpose of this work is to fabricate ultrathin oxynitride films by nitridation of thermal oxide utilizing activated nitrogen at very low temperature. We analyzed nitrogen concentration in the films using X-ray photoelectron spectroscopy. It was confirmed that 9.6 at.%nitrogen was introduced, and that NSi2O was dominant in nitrided films at temperatures as low as 400°C. We succeeded in decreasing the leakage current by one order of magnitude by nitridation of films with thicknesses of 40-60 nm.

  6. Iridium(iii)-catalyzed regioselective direct arylation of sp(2) C-H bonds with diaryliodonium salts.

    PubMed

    Gao, Pan; Liu, Li; Shi, Zhuangzhi; Yuan, Yu

    2016-08-01

    A regioselective direct arylation of arenes and olefins at the ortho position is reported. The key to the high selectivity is the appropriate choice of diaryliodonium salts as the arylating reagent in the presence of a cationic iridium(iii) catalyst. The coordination of the metal with an oxygen atom or a nitrogen atom and subsequent C-H activation allows for direct arylation with coupling partners. This reaction proceeds under mild reaction conditions and with a high tolerance of various functional groups including many halide functional groups. PMID:27381238

  7. Water-Soluble Iridium-NHC-Phosphine Complexes as Catalysts for Chemical Hydrogen Batteries Based on Formate.

    PubMed

    Horváth, Henrietta; Papp, Gábor; Szabolcsi, Roland; Kathó, Ágnes; Joó, Ferenc

    2015-09-21

    Molecular hydrogen, obtained by water electrolysis or photocatalytic water splitting, can be used to store energy obtained from intermittent sources such as wind and solar power. The storage and safe transportation of H2 , however, is an open and central question in such a hydrogen economy. Easy-to-synthesize, water-soluble iridium-N-heterocyclic carbene-phosphine (Ir(I) -NHC-phosphine) catalysts show unprecedented high catalytic activity in dehydrogenation of aqueous sodium formate. Fast reversible generation and storage of hydrogen can be achieved with these catalysts by a simple decrease or increase in the hydrogen pressure, respectively. PMID:26289830

  8. Copper oxide nanoparticles inhibit the metabolic activity of Saccharomyces cerevisiae.

    PubMed

    Mashock, Michael J; Kappell, Anthony D; Hallaj, Nadia; Hristova, Krassimira R

    2016-01-01

    Copper oxide nanoparticles (CuO NPs) are used increasingly in industrial applications and consumer products and thus may pose risk to human and environmental health. The interaction of CuO NPs with complex media and the impact on cell metabolism when exposed to sublethal concentrations are largely unknown. In the present study, the short-term effects of 2 different sized manufactured CuO NPs on metabolic activity of Saccharomyces cerevisiae were studied. The role of released Cu(2+) during dissolution of NPs in the growth media and the CuO nanostructure were considered. Characterization showed that the 28 nm and 64 nm CuO NPs used in the present study have different primary diameter, similar hydrodynamic diameter, and significantly different concentrations of dissolved Cu(2+) ions in the growth media released from the same initial NP mass. Exposures to CuO NPs or the released Cu(2+) fraction, at doses that do not have impact on cell viability, showed significant inhibition on S. cerevisiae cellular metabolic activity. A greater CuO NP effect on the metabolic activity of S. cerevisiae growth under respiring conditions was observed. Under the tested conditions the observed metabolic inhibition from the NPs was not explained fully by the released Cu ions from the dissolving NPs. PMID:26178758

  9. Oxidized amylose with high carboxyl content: A promising solubilizer and carrier of linalool for antimicrobial activity.

    PubMed

    Zhou, Ying; Ye, Youxin; Zhang, Wenwen; Li, Songling; Chen, Jing; Wang, Shiting; Li, Defu; Mu, Changdao

    2016-12-10

    The oxidized amyloses with different carboxyl content were prepared to include linalool for antimicrobial activity in aqueous environment. The results show that linalool can be effectively reserved from volatilization through encapsulation into amylose and oxidized amyloses. The inclusion ability of oxidized amyloses towards linalool is decreasing with the increase of oxidation level due to the depolymerization of amylose. However, the solubilization effect of oxidized amyloses to linalool is enhanced efficiently owning to the high water solubility of oxidized amyloses. It is interesting that the inclusion complexes have good antimicrobial activity in aqueous environment. Linalool solubilized by oxidized amyloses presents better antimicrobial performance than that solubilized by amylose, mainly resulting from that amylose-linalool inclusion complex would aggregate and retrograde fast in aqueous solution, which is disadvantageous for the release of linalool. The study suggests that oxidized amylose is a promising solubilizer and carrier of linalool for antimicrobial activity in aqueous environment. PMID:27577891

  10. Permanent iridium modifier deposited on tungsten and zirconium-treated platforms in electrothermal atomic absorption spectrometry: vaporization of bismuth, silver and tellurium

    NASA Astrophysics Data System (ADS)

    Slaveykova, Vera I.; Lampugnani, Leonardo; Tsalev, Dimiter L.; Sabbatini, L.; De Giglio, Elvira

    1999-04-01

    The stabilizing role of permanent iridium modifier deposited on tungsten-treated (WTP) and zirconium-treated (ZrTP) platforms of transversely heated graphite atomizer (THGA) was studied in detail by electrothermal atomic absorption spectrometry (ETAAS) and different surface techniques in model experiments for Ag, Bi and Te. The comparison of the stabilizing efficiency of permanent Ir modifier on WTP and ZrTP and each of the single components, reveals the better effect of Ir on WTP and Ir itself. The extent of analyte losses during pre-atomization and the strength of analyte association with the modifier were estimated by the plotting of `differential vaporization curves'. The existence of double peaks of Ag, Bi and Te in WTP and Ir on WTP was confirmed and possible reasons for their formation were discussed. The absorbance profiles presented as differential curves reveal an existence of at least two different types of precursors determining processes of atom generation. The observed differences in the behavior of Ir permanent modifier on WTP and ZrTP, respectively, were explained by the different extent of iridium-tungsten and iridium-zirconium interaction and surface distribution. XRF, ESCA and SEM studies reveal non-uniform distribution of the modifier on the graphite substrate and the presence of oxide containing species on the surface.

  11. Levitation of Iridium and Liquid Mercury by Ultrasound

    NASA Astrophysics Data System (ADS)

    Xie, W. J.; Cao, C. D.; Lü, Y. J.; Wei, B.

    2002-08-01

    Single-axis acoustic levitation of the heaviest solid (iridium, ρ=22.6 g cm-3) and liquid (mercury, ρ=13.6 g cm-3 on the Earth is achieved by greatly enhancing both the levitation force and stability through optimizing the geometric parameters of the levitator. The acoustically levitated Pb-Sn eutectic alloy melt (ρ=8.5 g cm-3) is highly undercooled by up to 38K, which results in a microstructural transition of ``lamellae-broken lamellae-dendrites.'' The drastic enhancement of levitation capability indicates a broader application range of single-axis acoustic levitation.

  12. Luminescent cyclometallated iridium(III) complexes having acetylide ligands

    SciTech Connect

    Thompson, Mark E.; Bossi, Alberto; Djurovich, Peter Ivan

    2014-09-02

    The present invention relates to phosphorescent (triplet-emitting) organometallic materials. The phosphorescent materials of the present invention comprise Ir(III)cyclometallated alkynyl complexes for use as triplet light-emitting materials. The Ir(III)cyclometallated alkynyl complexes comprise at least one cyclometallating ligand and at least one alkynyl ligand bonded to the iridium. Also provided is an organic light emitting device comprising an anode, a cathode and an emissive layer between the anode and the cathode, wherein the emissive layer comprises a Ir(III)cyclometallated alkynyl complex as a triplet emitting material.

  13. Determination of iridium in mafic rocks by atomic absorption

    USGS Publications Warehouse

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

    1970-01-01

    Iridium is determined in mineralized mafic rocks by atomic absorption after fire-assay concentration into a gold bead. Interelement interferences in the atomic-absorption determination are removed and Ir sensitivity is increased by buffering the solutions with a mixture of copper and sodium sulphates. Substantial amounts of Ag, Al, Au, Bi, Ca, Cd, Co, Cr, Fe, Ho, Hg, K, La, Mg, Mn, Mo, Ni, Pb, Te, Ti, V, Y, Zn and platinum metals can be tolerated in the atomic-absorption determination. The sensitivity and detection limits are 3.2 and 0.25 ppm of Ir, respectively. ?? 1970.

  14. Measurements of the hard-x-ray reflectivity of iridium

    SciTech Connect

    Romaine, S.; Bruni, R.; Gorenstein, P.; Zhong, Z

    2007-01-10

    In connection with the design of a hard-x-ray telescope for the Constellation X-Ray Observatory we measured the reflectivity of an iridium-coated zerodur substrate as a function of angle at 55, 60, 70, and 80 keV at the National Synchrotron Light Source of Brookhaven National Laboratory. The optical constants were derived from the reflectivity data. The real component of the index of refraction is in excellent agreement with theoretical values at all four energies. However, the imaginary component, which is related to the mass attenuation coefficient, is 50% to 70% larger at 55, 60, and 70 keV than theoretical values.

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

    NASA Technical Reports Server (NTRS)

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

    1973-01-01

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

  16. Iridium-Catalyzed Reductive Nitro-Mannich Cyclization

    PubMed Central

    Gregory, Alex W; Chambers, Alan; Hawkins, Alison; Jakubec, Pavol; Dixon, Darren J

    2015-01-01

    A new chemoselective reductive nitro-Mannich cyclization reaction sequence of nitroalkyl-tethered lactams has been developed. Relying on the rapid and chemoselective iridium(I)-catalyzed reduction of lactams to the corresponding enamine, subsequent nitro-Mannich cyclization of tethered nitroalkyl functionality provides direct access to important alkaloid natural-product-like structures in yields up to 81 % and in diastereoselectivities that are typically good to excellent. An in-depth understanding of the reaction mechanism has been gained through NMR studies and characterization of reaction intermediates. The new methodology has been applied to the total synthesis of (±)-epi-epiquinamide in four steps. PMID:25399919

  17. Highly Enantioselective Iridium-Catalyzed Hydrogenation of Cyclic Enamides.

    PubMed

    Salomó, Ernest; Orgué, Sílvia; Riera, Antoni; Verdaguer, Xavier

    2016-07-01

    The MaxPHOX-Ir catalyst system provided the highest selectivity ever reported for the reduction of cyclic enamides derived from α- and β-tetralones. This result indicates that iridium catalysts are also proficient in reducing alkenes bearing metal-coordinating groups. In the present system, selectivity was pressure-dependent: In most cases, a decrease in the H2 pressure to 3 bar resulted in an increase in enantioselectivity. Moreover, the process can be carried out in environmentally friendly solvents, such as methanol and ethyl acetate, with no loss of selectivity. PMID:27186653

  18. Levitation of iridium and liquid mercury by ultrasound.

    PubMed

    Xie, W J; Cao, C D; Lü, Y J; Wei, B

    2002-09-01

    Single-axis acoustic levitation of the heaviest solid (iridium, rho=22.6 g cm(-3)) and liquid (mercury, rho=13.6 g cm(-3) on the Earth is achieved by greatly enhancing both the levitation force and stability through optimizing the geometric parameters of the levitator. The acoustically levitated Pb-Sn eutectic alloy melt (rho=8.5 g cm(-3)) is highly undercooled by up to 38 K, which results in a microstructural transition of "lamellae-broken lamellae-dendrites." The drastic enhancement of levitation capability indicates a broader application range of single-axis acoustic levitation. PMID:12225198

  19. Biologically Active Polymers from Spontaneous Carotenoid Oxidation: A New Frontier in Carotenoid Activity

    PubMed Central

    Johnston, James B.; Nickerson, James G.; Daroszewski, Janusz; Mogg, Trevor J.; Burton, Graham W.

    2014-01-01

    In animals carotenoids show biological activity unrelated to vitamin A that has been considered to arise directly from the behavior of the parent compound, particularly as an antioxidant. However, the very property that confers antioxidant activity on some carotenoids in plants also confers susceptibility to oxidative transformation. As an alternative, it has been suggested that carotenoid oxidative breakdown or metabolic products could be the actual agents of activity in animals. However, an important and neglected aspect of the behavior of the highly unsaturated carotenoids is their potential to undergo addition of oxygen to form copolymers. Recently we reported that spontaneous oxidation of ß-carotene transforms it into a product dominated by ß-carotene-oxygen copolymers. We now report that the polymeric product is biologically active. Results suggest an overall ability to prime innate immune function to more rapidly respond to subsequent microbial challenges. An underlying structural resemblance to sporopollenin, found in the outer shell of spores and pollen, may allow the polymer to modulate innate immune responses through interactions with the pattern recognition receptor system. Oxygen copolymer formation appears common to all carotenoids, is anticipated to be widespread, and the products may contribute to the health benefits of carotenoid-rich fruits and vegetables. PMID:25360750

  20. Biologically active polymers from spontaneous carotenoid oxidation: a new frontier in carotenoid activity.

    PubMed

    Johnston, James B; Nickerson, James G; Daroszewski, Janusz; Mogg, Trevor J; Burton, Graham W

    2014-01-01

    In animals carotenoids show biological activity unrelated to vitamin A that has been considered to arise directly from the behavior of the parent compound, particularly as an antioxidant. However, the very property that confers antioxidant activity on some carotenoids in plants also confers susceptibility to oxidative transformation. As an alternative, it has been suggested that carotenoid oxidative breakdown or metabolic products could be the actual agents of activity in animals. However, an important and neglected aspect of the behavior of the highly unsaturated carotenoids is their potential to undergo addition of oxygen to form copolymers. Recently we reported that spontaneous oxidation of ß-carotene transforms it into a product dominated by ß-carotene-oxygen copolymers. We now report that the polymeric product is biologically active. Results suggest an overall ability to prime innate immune function to more rapidly respond to subsequent microbial challenges. An underlying structural resemblance to sporopollenin, found in the outer shell of spores and pollen, may allow the polymer to modulate innate immune responses through interactions with the pattern recognition receptor system. Oxygen copolymer formation appears common to all carotenoids, is anticipated to be widespread, and the products may contribute to the health benefits of carotenoid-rich fruits and vegetables. PMID:25360750

  1. Heme activation by DNA: isoguanine pentaplexes, but not quadruplexes, bind heme and enhance its oxidative activity

    PubMed Central

    Shumayrikh, Nisreen; Huang, Yu Chuan; Sen, Dipankar

    2015-01-01

    Guanine-rich, single-stranded, DNAs and RNAs are able to fold to form G-quadruplexes that are held together by guanine base quartets. G-quadruplexes are known to bind ferric heme [Fe(III)-protoporphyrin IX] and to strongly activate such bound hemes toward peroxidase (1-electron oxidation) as well as oxygenase/peroxygenase (2-electron oxidation) activities. However, much remains unknown about how such activation is effected. Herein, we investigated whether G-quadruplexes were strictly required for heme activation or whether related multi-stranded DNA/RNA structures such as isoguanine (iG) quadruplexes and pentaplexes could also bind and activate heme. We found that iG-pentaplexes did indeed bind and activate heme comparably to G-quadruplexes; however, iG-quadruplexes did neither. Earlier structural and computational studies had suggested that while the geometry of backbone-unconstrained iG-quintets templated by cations such as Na+ or NH4+ was planar, that of iG-quartets deviated from planarity. We hypothesize that the binding as well as activation of heme by DNA or RNA is strongly supported by the planarity of the nucleobase quartet or quintet that interacts directly with the heme. PMID:25824944

  2. Local structure of Iridium organometallic catalysts covalently bonded to carbon nanotubes.

    NASA Astrophysics Data System (ADS)

    Blasco, J.; Cuartero, V.; Subías, G.; Jiménez, M. V.; Pérez-Torrente, J. J.; Oro, L. A.; Blanco, M.; Álvarez, P.; Blanco, C.; Menéndez, R.

    2016-05-01

    Hybrid catalysts based on Iridium N-heterocyclic carbenes anchored to carbon nanotubes (CNT) have been studied by XAFS spectroscopy. Oxidation of CNT yields a large amount of functional groups, mainly hydroxyl groups at the walls and carboxylic groups at the tips, defects and edges. Different kinds of esterification reactions were performed to functionalize oxidized CNT with imidazolium salts. Then, the resulting products were reacted with an Ir organometallic compound to form hybrid catalysts efficient in hydrogen transfer processes. XANES spectroscopy agree with the presence of Ir(I) in these catalysts and the EXAFS spectra detected differences in the local structure of Ir atoms between the initial Ir organometallic compound and the Ir complexes anchored to the CNT. Our results confirm that the halide atom, present in the Ir precursor, was replaced by oxygen from -OH groups at the CNT wall in the first coordination shell of Ir. The lability of this group accounts for the good recyclability and the good efficiency shown by these hybrid catalysts.

  3. Mitochondrial Oxidative Stress Corrupts Coronary Collateral Growth by Activating Adenosine Monophosphate Activated Kinase-α Signaling

    PubMed Central

    Pung, Yuh Fen; Sam, Wai Johnn; Stevanov, Kelly; Enrick, Molly; Chen, Chwen-Lih; Kolz, Christopher; Thakker, Prashanth; Hardwick, James P.; Chen, Yeong-Renn; Dyck, Jason R.B.; Yin, Liya; Chilian, William M.

    2015-01-01

    Objective Our goal was to determine the mechanism by which mitochondrial oxidative stress impairs collateral growth in the heart. Approach and Results Rats were treated with rotenone (mitochondrial complex I inhibitor that increases reactive oxygen species production) or sham-treated with vehicle and subjected to repetitive ischemia protocol for 10 days to induce coronary collateral growth. In control rats, repetitive ischemia increased flow to the collateral-dependent zone; however, rotenone treatment prevented this increase suggesting that mitochondrial oxidative stress compromises coronary collateral growth. In addition, rotenone also attenuated mitochondrial complex I activity and led to excessive mitochondrial aggregation. To further understand the mechanistic pathway(s) involved, human coronary artery endothelial cells were treated with 50 ng/ mL vascular endothelial growth factor, 1 µmol/L rotenone, and rotenone/vascular endothelial growth factor for 48 hours. Vascular endothelial growth factor induced robust tube formation; however, rotenone completely inhibited this effect (P<0.05 rotenone versus vascular endothelial growth factor treatment). Inhibition of tube formation by rotenone was also associated with significant increase in mitochondrial superoxide generation. Immunoblot analyses of human coronary artery endothelial cells with rotenone treatment showed significant activation of adenosine monophosphate activated kinase (AMPK)-α and inhibition of mammalian target of rapamycin and p70 ribosomal S6 kinase. Activation of AMPK-α suggested impairments in energy production, which was reflected by decrease in O2 consumption and bioenergetic reserve capacity of cultured cells. Knockdown of AMPK-α (siRNA) also preserved tube formation during rotenone, suggesting the negative effects were mediated by the activation of AMPK-α. Conversely, expression of a constitutively active AMPK-α blocked tube formation. Conclusions We conclude that activation of AMPK

  4. Conversion of carbohydrate biomass to γ-valerolactone by using water-soluble and reusable iridium complexes in acidic aqueous media.

    PubMed

    Deng, Jin; Wang, Yan; Pan, Tao; Xu, Qing; Guo, Qing-Xiang; Fu, Yao

    2013-07-01

    Mild-mannered manipulation: A catalytic method for the conversion of carbohydrate biomass to γ-valerolactone in acidic aqueous media has been developed. The water-soluble iridium complexes were observed to be extremely catalytically active for providing γ-valerolactone in high yields with high TONs. The homogeneous catalysts can also be recycled and reused by applying a simple phase separation process. PMID:23757330

  5. Bond Fission and Non-Radiative Decay in Iridium(III) Complexes.

    PubMed

    Zhou, Xiuwen; Burn, Paul L; Powell, Benjamin J

    2016-06-01

    We investigate the role of metal-ligand bond fission in the nonradiative decay of excited states in iridium(III) complexes with applications in blue organic light-emitting diodes (OLEDs). We report density functional theory (DFT) calculations of the potential energy surfaces upon lengthening an iridium-nitrogen (Ir-N) bond. In all cases we find that for bond lengths comparable to those of the ground state the lowest energy state is a triplet with significant metal-to-ligand change transfer character ((3)MLCT). But, as the Ir-N bond is lengthened there is a sudden transition to a regime where the lowest excited state is a triplet with significant metal centered character ((3)MC). Time-dependent DFT relativistic calculations including spin-orbit coupling perturbatively show that the radiative decay rate from the (3)MC state is orders of magnitude slower than that from the (3)MLCT state. The calculated barrier height between the (3)MLCT and (3)MC regimes is clearly correlated with previously measured nonradiative decay rates, suggesting that thermal population of the (3)MC state is the dominant nonradiative decay process at ambient temperature. In particular, fluorination both drives the emission of these complexes to a deeper blue color and lowers the (3)MLCT-(3)MC barrier. If the Ir-N bond is shortened in the (3)MC state another N atom is pushed away from the Ir, resulting in the breaking of this bond, suggesting that once the Ir-N bond breaks the damage to the complex is permanent-this will have important implications for the lifetimes of devices using this type of complex as the active material. The consequences of these results for the design of more efficient blue phosphors for OLED applications are discussed. PMID:27175618

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

    USGS Publications Warehouse

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

    1974-01-01

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

  7. Measurement of nitrous oxide reductase activity in aquatic sediments

    SciTech Connect

    Miller, L.G.; Oremland, R.S.; Paulsen, S.

    1986-01-01

    Denitrification in aquatic sediments was measured by an N/sub 2/O reductase assay. Sediments consumed small added quantities of N/sub 2/O over short periods (a few hours). In experiments with sediment slurries, N/sub 2/O reductase activity was inhibited by 0/sub 2/, C/sub 2/H/sub 2/, heat treatment, and by high levels of nitrate (1 mM) or sulfide (10 mM). However, ambient levels of nitrate (<100 ..mu..M) did not influence activity, and moderate levels (about 150 ..mu..M) induced only a short lag before reductase activity began. Moderate levels of sulfide (<1 mM) had no effect on N/sub 2/O reductase activity. Nitrous oxide reductase displayed Michaelis-Menten kinetics in sediments from freshwater, estuarine, and alkaline-saline environments. An in situ assay was devised in which a solution of N/sub 2/O was injected into sealed glass cores containing intact sediment. Two estimates of net rates of denitrification in San Francisco Bay under approximated in situ conditions were 0.009 and 0.041 mmol of N/sub 2/O per m/sup 2/ per h. Addition of chlorate to inhibit denitrification in these intact-core experiments (to estimate gross rates of N/sub 2/O consumption) resulted in approximately a 14% upward revision of estimates of net rates. These results were comparable to an in situ estimate of 0.022 mmol of N/sub 2/O per m/sup 2/ per h made with the acetylene block assay.

  8. Effects of Potassium Permanganate Oxidation on Subsurface Microbial Activity

    NASA Technical Reports Server (NTRS)

    Rowland, Martin A.; Brubaker, Gaylen R.; Westray, Mark; Morris, Damon; Kohler, Keisha; McCool, Alex (Technical Monitor)

    2001-01-01

    In situ chemical oxidation has the potential for degrading large quantities of organic contaminants and can be more effective and timely than traditional ex situ treatment methods. However, there is a need to better characterize the potential effects of this treatment on natural processes. This study focuses on potential inhibition to anaerobic dechlorination of trichloroethene (TCE) in soils from a large manufacturing facility as a result of in situ oxidation using potassium permanganate (KMn04)Previous microcosm studies established that natural attenuation occurs on-site and that it is enhanced by the addition of ethanol to the system. A potential remediation scheme for the site involves the use of potassium permanganate to reduce levels of TCE in heavily contaminated areas, then to inject ethanol into the system to "neutralize" excess oxidant and enhance microbial degradation. However, it is currently unknown whether the exposure of indigenous microbial populations to potassium permanganate may adversely affect biological reductive dechlorination by these microorganisms. Consequently, additional microcosm studies were conducted to evaluate this remediation scheme and assess the effect of potassium permanganate addition on biological reductive dechlorination of TCE. Samples of subsurface soil and groundwater were collected from a TCE-impacted area of the site. A portion of the soil was pretreated with nutrients and ethanol to stimulate microbial activity, while the remainder of the soil was left unamended. Soil/groundwater microcosms were prepared in sealed vials using the nutrient-amended and unamended soils, and the effects of potassium permanganate addition were evaluated using two permanganate concentrations (0.8 and 2.4 percent) and two contact times (1 and 3 weeks). TCE was then re-added to each microcosm and TCE and dichloroethene (DCE) concentrations were monitored to determine the degree to which microbial dechlorination occurred following chemical

  9. Nitric oxide induces caspase activity in boar spermatozoa.

    PubMed

    Moran, J M; Madejón, L; Ortega Ferrusola, C; Peña, F J

    2008-07-01

    Nitric oxide (NO) is a highly reactive free radical that plays a key role in intra- and intercellular signaling. Production of radical oxygen species and an apoptotic-like phenomenon have recently been implicated in cryodamage during sperm cryopreservation. The objective of the present study was to evaluate the effect of sodium nitroprusside (SNP), an NO donor, on boar sperm viability. Semen samples were pooled from four boars that were routinely used for artificial insemination. Flow cytometry was used to compare semen incubated with SNP to control semen. Specifically, NO production was measured using the NO indicator dye diaminofluorescein diacetate, and caspase activity was determined using the permeable pan-caspase inhibitor Z-VAD linked to FITC. SNP induced a significant increase in the percentage of sperm cells showing caspase activity, from 9.3% in control samples to 76.2% in SNP-incubated samples (P<0.01). This study suggests that NO is a major free radical involved in boar sperm damage. PMID:18433854

  10. Activation Energy of Tantalum-Tungsten Oxide Thermite Reaction

    SciTech Connect

    Cervantes, O; Kuntz, J; Gash, A; Munir, Z

    2010-02-25

    The activation energy of a high melting temperature sol-gel (SG) derived tantalum-tungsten oxide thermite composite was determined using the Kissinger isoconversion method. The SG derived powder was consolidated using the High Pressure Spark Plasma Sintering (HPSPS) technique to 300 and 400 C to produce pellets with dimensions of 5 mm diameter by 1.5 mm height. A custom built ignition setup was developed to measure ignition temperatures at high heating rates (500-2000 C {center_dot} min{sup -1}). Such heating rates were required in order to ignite the thermite composite. Unlike the 400 C samples, results show that the samples consolidated to 300 C undergo an abrupt change in temperature response prior to ignition. This change in temperature response has been attributed to the crystallization of the amorphous WO{sub 3} in the SG derived Ta-WO{sub 3} thermite composite and not to a pre-ignition reaction between the constituents. Ignition temperatures for the Ta-WO{sub 3} thermite ranged from approximately 465-670 C. The activation energy of the SG derived Ta-WO{sup 3} thermite composite consolidated to 300 and 400 C were determined to be 37.787 {+-} 1.58 kJ {center_dot} mol{sup -1} and 57.381 {+-} 2.26 kJ {center_dot} mol{sup -1}, respectively.

  11. Activation energy of tantalum-tungsten oxide thermite reactions

    SciTech Connect

    Cervantes, Octavio G.; Munir, Zuhair A.; Kuntz, Joshua D.; Gash, Alexander E.

    2011-01-15

    The activation energy of a sol-gel (SG) derived tantalum-tungsten oxide thermite composite was determined using the Kissinger isoconversion method. The SG derived powder was consolidated using the high-pressure spark plasma sintering (HPSPS) technique at 300 and 400 C. The ignition temperatures were investigated under high heating rates (500-2000 C min{sup -1}). Such heating rates were required in order to ignite the thermite composite. Samples consolidated at 300 C exhibit an abrupt change in temperature response prior to the main ignition temperature. This change in temperature response is attributed to the crystallization of the amorphous WO{sub 3} in the SG derived Ta-WO{sub 3} thermite composite and not to a pre-ignition reaction between the constituents. Ignition temperatures for the Ta-WO{sub 3} thermite ranged from approximately 465 to 670 C. The activation energies of the SG derived Ta-WO{sub 3} thermite composite consolidated at 300 and 400 C were determined to be 38{+-} 2 kJ mol{sup -1} and 57 {+-} 2 kJ mol{sup -1}, respectively. (author)

  12. Oxidation of pharmaceutically active compounds by a ligninolytic fungal peroxidase.

    PubMed

    Eibes, Gemma; Debernardi, Gianfranco; Feijoo, Gumersindo; Moreira, M Teresa; Lema, Juan M

    2011-06-01

    Pharmaceuticals are an important group of emerging pollutants with increasing interest due to their rising consumption and the evidence for ecotoxicological effects associated to trace amounts in aquatic environments. In this paper, we assessed the potential degradation of a series of pharmaceuticals: antibiotics (sulfamethoxazole), antidepressives (citalopram hydrobromide and fluoxetine hydrochloride), antiepileptics (carbamazepine), anti-inflammatory drugs (diclofenac and naproxen) and estrogen hormones (estrone, 17β-estradiol, 17α-ethinylestradiol) by means of a versatile peroxidase (VP) from the ligninolytic fungus Bjerkandera adusta. The effects of the reaction conditions: VP activity, organic acid concentration and H(2)O(2) addition rate, on the kinetics of the VP based oxidation system were evaluated. Diclofenac and estrogens were completely degraded after only 5-25 min even with a very low VP activity (10 U l(-1)). High degradation percentages (80%) were achieved for sulfamethoxazole and naproxen. Low or undetectable removal yields were observed for citalopram (up to 18%), fluoxetine (lower than 10%) and carbamazepine (not degraded). PMID:20972884

  13. Direct 2-acetoxylation of quinoline N-oxides via copper catalyzed C-H bond activation.

    PubMed

    Chen, Xuan; Zhu, Chongwei; Cui, Xiuling; Wu, Yangjie

    2013-08-01

    An efficient and direct 2-acetoxylation of quinoline N-oxides via copper(I) catalyzed C-H bond activation has been developed. This transformation was achieved using TBHP as an oxidant in the cross-dehydrogenative coupling (CDC) reaction of quinoline N-oxides with aldehydes, and provided a practical pathway to 2-acyloxyl quinolines. PMID:23793162

  14. Porous platinum mesoflowers with enhanced activity for methanol oxidation reaction

    SciTech Connect

    Zhuang Lina; Wang Wenjin; Hong Feng; Yang Shengchun; You Hongjun; Fang Jixiang; Ding Bingjun

    2012-07-15

    Porous Pt and Pt-Ag alloy mesoflowers (MFs) with about 2 {mu}m in diameter and high porosity were synthesized using Ag mesoflowers as sacrificial template by galvanic reaction. The silver content in Pt-Ag alloys can be facilely controlled by nitric acid treatment. And the pure Pt MFs can be obtained by selective removal of silver element from Pt{sub 72}Ag{sub 28} MFs electrochemically. Both Pt{sub 45}Ag{sub 55}, Pt{sub 72}Ag{sub 28} and pure Pt show a high catalytic performance in methanol oxidation reaction (MOR). Especially, pure Pt MFs exhibited a 2 to 3 times current density enhancement in MOR compared with the commercial used Pt black, which can be attributed to their porous nanostructure with 3-dimentional nature and small crystal sizes. - Graphical Abstract: The CVs of MOR on Pt (red) and Pt black (green) catalysts in 0.1 M HClO{sub 4} and 0.5 M CH{sub 3}OH for specific mass current. The insert shows the SEM images of two porous Pt MFs. Platinum mesoflowers (MFs) with about 2 {mu}m in diameter and high porosity were synthesised with Ag mesoflowers as sacrificial template by galvanic replacement. The porous Pt MFs exhibited a more than 3 times enhancement in electrocatalytic performance for methanol oxidation reaction compared the commercial used Pt black. Highlights: Black-Right-Pointing-Pointer Porous Pt and Pt-Ag mesoflowers (MFs) were synthesized using Ag MFs sacrifical template. Black-Right-Pointing-Pointer Pt MFs presents an improved catalytic activity in MOR compared with Pt black. Black-Right-Pointing-Pointer We provided a facile approach for the development of high performance Pt electrocatalysts for fuel cells.

  15. Dynamic high-temperature characterization of an iridium alloy in tension

    SciTech Connect

    Song, Bo; Nelson, Kevin; Jin, Helena; Lipinski, Ronald J.; Bignell, John; Ulrich, G. B.; George, E. P.

    2015-09-01

    Iridium alloys have been utilized as structural materials for certain high-temperature applications, due to their superior strength and ductility at elevated temperatures. The mechanical properties, including failure response at high strain rates and elevated temperatures of the iridium alloys need to be characterized to better understand high-speed impacts at elevated temperatures. A DOP-26 iridium alloy has been dynamically characterized in compression at elevated temperatures with high-temperature Kolsky compression bar techniques. However, the dynamic high-temperature compression tests were not able to provide sufficient dynamic high-temperature failure information of the iridium alloy. In this study, we modified current room-temperature Kolsky tension bar techniques for obtaining dynamic tensile stress-strain curves of the DOP-26 iridium alloy at two different strain rates (~1000 and ~3000 s-1) and temperatures (~750°C and ~1030°C). The effects of strain rate and temperature on the tensile stress-strain response of the iridium alloy were determined. The DOP-26 iridium alloy exhibited high ductility in stress-strain response that strongly depended on both strain rate and temperature.

  16. Microindentation hardness evaluation of iridium alloy clad vent set cups

    NASA Astrophysics Data System (ADS)

    Ulrich, George B.; DeRoos, Larry F.; Stinnette, Samuel E.

    1993-01-01

    An iridium alloy, DOP-26, is used as cladding for 238PuO2 fuel in radioisotope heat sources for space power systems. Presently, DOP-26 iridium alloy clad vent sets (CVS) are being manufactured at the Oak Ridge Y-12 Plant for potential use in the National Aeronautics and Space Administration's Cassini mission to Saturn. Wrought/ground/stress relieved blanks are warm formed into CVS cups. These cups are then annealed to recrystallize the material for subsequent fabrication/assembly operations as well as for final use. One of the cup manufacturing certification requirements is to test for Vickers microindentation hardness. New microindentation hardness specification limits, 210 to 310 HV, have been established for a test load of 1000 grams-force (gf). The original specification limits, 250 to 350 HV, were for 200 gf testing. The primary reason for switching to a higher test load was to reduce variability in the test data. The DOP-26 alloy exhibits microindentation hardness load dependence, therefore, new limits were needed for 1000 gf testing. The new limits were established by testing material from 15 CVS cups using 200 gf and 1000 gf loads and then statistically analyzing the data. Additional work using a Knoop indenter and a 10 gf load indicated that the DOP-26 alloy grain boundaries have higher hardnesses than the grain interiors.

  17. Microindentation hardness evaluation of iridium alloy clad vent set cups

    SciTech Connect

    Ulrich, G.B.; DeRoos, L.F.; Stinnette, S.E.

    1992-05-15

    An iridium alloy, DOP-26, is used as cladding for {sup 238}PuO{sup 2} fuel in radioisotope heat sources for space power systems. Presently, DOP-26 iridium alloy clad vent sets (CVS) are being manufactured at the Oak Ridge Y-12 Plant for potential use in the National Aeronautics and Space Administration`s Cassini mission to Saturn. Wrought/ground/stress relieved blanks are warm formed into CVS cups. These cups are then annealed to recrystallize the material for subsequent fabrication/assembly operations as well as for final use. One of the cup manufacturing certification requirements is to test for Vickers microindentation hardness. New microindentation hardness specification limits, 210 to 310 HV, have been established for a test load of 1000 grams-force (gf). The original specification limits, 250 to 350 HV, were for 200 gf testing. The primary reason for switching to a higher test load was to reduce variability in the test data. The DOP-26 alloy exhibits microindentation hardness load dependence, therefore, new limits were needed for 1000 gf testing. The new limits were established by testing material from 15 CVS cups using 200 gf and 1000 gf loads and then statistically analyzing the data. Additional work using a Knoop indenter and a 10 gf load indicated that the DOP-26 alloy grain boundaries have higher hardnesses than the grain interiors.

  18. Microindentation hardness evaluation of iridium alloy clad vent set cups

    SciTech Connect

    Ulrich, G.B.; DeRoos, L.F.; Stinnette, S.E.

    1992-05-15

    An iridium alloy, DOP-26, is used as cladding for {sup 238}PuO{sup 2} fuel in radioisotope heat sources for space power systems. Presently, DOP-26 iridium alloy clad vent sets (CVS) are being manufactured at the Oak Ridge Y-12 Plant for potential use in the National Aeronautics and Space Administration's Cassini mission to Saturn. Wrought/ground/stress relieved blanks are warm formed into CVS cups. These cups are then annealed to recrystallize the material for subsequent fabrication/assembly operations as well as for final use. One of the cup manufacturing certification requirements is to test for Vickers microindentation hardness. New microindentation hardness specification limits, 210 to 310 HV, have been established for a test load of 1000 grams-force (gf). The original specification limits, 250 to 350 HV, were for 200 gf testing. The primary reason for switching to a higher test load was to reduce variability in the test data. The DOP-26 alloy exhibits microindentation hardness load dependence, therefore, new limits were needed for 1000 gf testing. The new limits were established by testing material from 15 CVS cups using 200 gf and 1000 gf loads and then statistically analyzing the data. Additional work using a Knoop indenter and a 10 gf load indicated that the DOP-26 alloy grain boundaries have higher hardnesses than the grain interiors.

  19. Microindentation hardness evaluation of iridium alloy clad vent set cups

    SciTech Connect

    Ulrich, G.B.; DeRoos, L.F.; Stinnette, S.E. )

    1993-01-15

    An iridium alloy, DOP-26, is used as cladding for [sup 238]PuO[sub 2] fuel in radioisotope heat sources for space power systems. Presently, DOP-26 iridium alloy clad vent sets (CVS) are being manufactured at the Oak Ridge Y-12 Plant for potential use in the National Aeronautics and Space Administration's Cassini mission to Saturn. Wrought/ground/stress relieved blanks are warm formed into CVS cups. These cups are then annealed to recrystallize the material for subsequent fabrication/assembly operations as well as for final use. One of the cup manufacturing certification requirements is to test for Vickers microindentation hardness. New microindentation hardness specification limits, 210 to 310 HV, have been established for a test load of 1000 grams-force (gf). The original specification limits, 250 to 350 HV, were for 200 gf testing. The primary reason for switching to a higher test load was to reduce variability in the test data. The DOP-26 alloy exhibits microindentation hardness load dependence, therefore, new limits were needed for 1000 gf testing. The new limits were established by testing material from 15 CVS cups using 200 gf and 1000 gf loads and then statistically analyzing the data. Additional work using a Knoop indenter and a 10 gf load indicated that the DOP-26 alloy grain boundaries have higher hardnesses than the grain interiors.

  20. Synthesis and Photophysical Studies of Iridium Complexes Having Different Ligands

    NASA Astrophysics Data System (ADS)

    Rho, Hyeon Hee; Park, Gui Youn; Ha, Yunkyoung; Kim, Young Sik

    2006-01-01

    The synthesis and photophysical study of efficient phosphorescent iridium(III) complexes having two different (C∧N) ligands are reported. In order to improve the luminescence efficiency by avoiding triplet-triplet (T-T) annihilation, the iridium complexes, Ir(ppy)2(piq) and Ir(ppy)2(piq-F), are designed and prepared where ppy, piq and piq-F represent 2-phenylpyridine, 1-(phenyl)isoquinoline and 2-(4'-fluorophenyl)isoquinoline, respectively. Two ppy ligands and a piq derivative act as a source of energy supply and a piq derivative acts as a chromophore. Since Ir(ppy)3, Ir(piq)3 and Ir(piq-F)3 can be placed in the metal-to-ligand charge transfer (MLCT) excited state, they absorb light effectively. When Ir(ppy)2(piq-F) is placed in excited state, the excitation energy is neither quenched nor deactivated but quickly intramolecular transferred from two ppy ligands to one luminescent piq-F ligand. This can occure because the triplet energy level of ppy is higher than that of piq-F and light is emitted from piq-F ligand in the end. Thus, Ir(ppy)2(piq-F) shows strong photoluminescence originated from piq-F ligand because piq-F ligand is known to have a shorter lifetime than that of ppy ligand. To analyze luminescent mechanism, we calculated these complexes having two different ligand sets theoretically by using computational method.

  1. Analysis of Abrasive Blasting of DOP-26 Iridium Alloy

    SciTech Connect

    Ohriner, Evan Keith; Zhang, Wei; Ulrich, George B

    2012-01-01

    The effects of abrasive blasting on the surface geometry and microstructure of DOP-26 iridium alloy (Ir-0.3% W-0.006% Th 0.005% Al) have been investigated. Abrasive blasting has been used to control emissivity of components operating at elevated temperature. The effects of abrasive blasting conditions on surface morphology were investigated both experimentally and by numerical modeling. The simplified model, based on finite element analysis of a single angular particle impacting on Ir alloy disk, calculates the surface deformation and residual strain distribution. The experimental results and modeling results both indicate that the surface geometry is not sensitive to the abrasive blast process conditions of nozzle pressure and standoff distance considered in this study. On the other hand, the modeling results suggest that the angularity of the abrasive particle has an important role in determining surface geometry, which in turn, affects the emissivity. Abrasive blasting causes localized surface strains and localized recrystallization, but it does not affect grain size following extended exposure at elevated temperature. The dependence of emissivity of the DOP-26 alloy on mean surface slope follows a similar trend to that reported for pure iridium.

  2. Influence of support hydroxides on the catalytic activity of oxidized gold clusters

    SciTech Connect

    Veith, Gabriel M; Lupini, Andrew R; Pennycook, Stephen J; Dudney, Nancy J

    2010-01-01

    Gold oxide nanoparticles were prepared on the native surface and a hydroxylated surface of a non-porous TiO2 support (Degussa P25). Scanning transmission electron microscopy results show the formation of similarly sized clusters on both support materials (1.86 and 1.61 nm clusters on the native oxide and the hydroxylated oxide respectively). X-ray absorption near edge spectroscopy and X-ray photoelectron spectroscopy clearly indicate the formation of Au3+ rich oxide nanoparticles. Despite the similar cluster sizes and oxidation states the gold oxide clusters grown on the hydroxylated surface were at least 180 times more catalytically active for the oxidation of carbon monoxide then those grown on the native oxide surface. These hydroxides are conveniently introduced during the solution phase synthesis of gold catalysts and play a dominate, but previously unrecognized, role in the catalytic properties of both oxidized and metallic gold particles.

  3. Oxygen tension limits nitric oxide synthesis by activated macrophages.

    PubMed Central

    McCormick, C C; Li, W P; Calero, M

    2000-01-01

    Previous studies have established that constitutive calcium-dependent ('low-output') nitric oxide synthase (NOS) is regulated by oxygen tension. We have investigated the role of oxygen tension in the synthesis of NO by the 'high-output' calcium-independent NOS in activated macrophages. Hypoxia increased macrophage NOS gene expression in the presence of one additional activator, such as lipopolysaccharide or interferon-gamma, but not in the presence of both. Hypoxia markedly reduced the synthesis of NO by activated macrophages (as measured by accumulation of nitrite and citrulline), such that, at 1% oxygen tension, NO accumulation was reduced by 80-90%. The apparent K(m) for oxygen calculated from cells exposed to a range of oxygen tensions was found to be 10.8%, or 137 microM, O(2) This value is considerably higher than the oxygen tension in tissues, and is virtually identical to that reported recently for purified recombinant macrophage NOS. The decrease in NO synthesis did not appear to be due to diminished arginine or cofactor availability, since arginine transport and NO synthesis during recovery in normoxia were normal. Analysis of NO synthesis during hypoxia as a function of extracellular arginine indicated that an altered V(max), but not K(m)(Arg), accounted for the observed decrease in NO synthesis. We conclude that oxygen tension regulates the synthesis of NO in macrophages by a mechanism similar to that described previously for the calcium-dependent low-output NOS. Our data suggest that oxygen tension may be an important physiological regulator of macrophage NO synthesis in vivo. PMID:10970783

  4. Metal-Ligand Cooperativity in a Methandiide-Derived Iridium Carbene Complex.

    PubMed

    Weismann, Julia; Waterman, Rory; Gessner, Viktoria H

    2016-03-01

    The synthesis, electronic structure, and reactivity of the first Group 9 carbene complex, [Cp*IrL] [L=C(Ph2 PS)(SO2 Ph)] (2), based on a dilithio methandiide are reported. Spectroscopic as well as computational studies have shown that, despite using a late transition-metal precursor, sufficient charge transfer occurred from the methandiide to the metal, resulting in a stable, nucleophilic carbene species with pronounced metal-carbon double-bond character. The potential of this iridium complex in the activation of a series of E-H bonds by means of metal-ligand cooperation has been tested. These studies have revealed distinct differences in the reactivity of 2 compared to a previously reported ruthenium analogue. Whereas attempts to activate the O-H bond in different phenol derivatives resulted in ligand cleavage, H-H and Si-H activation as well as dehydrogenation of isopropanol have been accomplished. These reactions are driven by the transformation of the carbene to an alkyl ligand. Contrary to a previously reported ruthenium carbene system, the dihydrogen activation has been found to proceed by a stepwise mechanism, with the activation first taking place solely at the metal. The activated products further reacted to afford a cyclometalated complex through liberation of the activated substrates. In the case of triphenylsilane, cyclometalation could thus be induced by a substoichiometric (i.e., catalytic) amount of silane. PMID:26748420

  5. Selective Electrocatalytic Activity of Ligand Stabilized Copper Oxide Nanoparticles

    SciTech Connect

    Kauffman, Douglas R; Ohodnicki, Paul R; Kail, Brian W; Matranga, Christopher

    2011-01-01

    Ligand stabilization can influence the surface chemistry of Cu oxide nanoparticles (NPs) and provide unique product distributions for electrocatalytic methanol (MeOH) oxidation and CO{sub 2} reduction reactions. Oleic acid (OA) stabilized Cu{sub 2}O and CuO NPs promote the MeOH oxidation reaction with 88% and 99.97% selective HCOH formation, respectively. Alternatively, CO{sub 2} is the only reaction product detected for bulk Cu oxides and Cu oxide NPs with no ligands or weakly interacting ligands. We also demonstrate that OA stabilized Cu oxide NPs can reduce CO{sub 2} into CO with a {approx}1.7-fold increase in CO/H{sub 2} production ratios compared to bulk Cu oxides. The OA stabilized Cu oxide NPs also show 7.6 and 9.1-fold increases in CO/H{sub 2} production ratios compared to weakly stabilized and non-stabilized Cu oxide NPs, respectively. Our data illustrates that the presence and type of surface ligand can substantially influence the catalytic product selectivity of Cu oxide NPs.

  6. Alpha-induced reactions in iridium

    SciTech Connect

    Bhardwaj, M.K.; Rizvi, I.A.; Chaubey, A.K. )

    1992-05-01

    The excitation function of ({alpha},{ital xn}) reactions on {sup 191}Ir (abundance 37.3%) and on {sup 193}Ir (abundance 62.7%) has been measured for the 17--55 MeV alpha-particle bombarding energy range. The stacked foil activation technique and {gamma}-ray spectroscopy were used to determine the cross sections. The experimental data were compared with calculated values obtained by means of a geometry-dependent hybrid model. The initial exciton number {ital n}{sub 0}=4 with {ital n}=2, {ital p}=2, and {ital h}=0 gives the best agreements with the presently measured results. To calculate the excitation function theoretically a computer code was used. This set of excitation functions provides a data basis for probing the validity of combined equilibrium and preequilibrium reaction models in a considerable energy range.

  7. Addition of Iridium to the Biopolymer Mediated Synthesis of YBa2Cu3O7 δ

    NASA Astrophysics Data System (ADS)

    Wimbush, Stuart C.; Marx, Werner; Barth, Andreas; Hall, Simon R.

    This work represents the first study into the addition of iridium into the solgel synthesis of the high temperature superconductor YBa2Cu3O7δ (Y123). Through a biopolymermediated synthetic approach, the homogeneous nature of the precursor sol and the preferred nucleation and growth of Y123 phases allow for a high yield of superconducting nanoparticles with no suppression of the superconducting critical temperature, even at high levels (40 wt%) of iridium addition. We attribute this to iridium not substituting into the Y123 crystal lattice, instead forming an associate phase.

  8. Enhanced dewaterability of waste activated sludge by Fe(II)-activated peroxymonosulfate oxidation.

    PubMed

    Liu, Jun; Yang, Qi; Wang, Dongbo; Li, Xiaoming; Zhong, Yu; Li, Xin; Deng, Yongchao; Wang, Liqun; Yi, Kaixin; Zeng, Guangming

    2016-04-01

    The effect of Fe(II)-activated peroxymonosulfate (Fe(II)-PMS) oxidation on the waste activated sludge (WAS) dewatering and its mechanisms were investigated in this study. The capillary suction time (CST), specific resistance to filterability (SRF) of sludge and water content (WC) of dewatered sludge cake were chosen as the main parameters to evaluate the sludge dewaterability. Experimental results showed that Fe(II)-PMS effectively disintegrated sludge and improved sludge dewaterability. High CST and SRF reduction (90% and 97%) was achieved at the optimal conditions of PMS (HSO5(-)) 0.9mmol/gVSS, Fe(II) 0.81mmol/gVSS, and pH 6.8. Extracellular polymeric substances (EPS) and three-dimensional excitation-emission matrix (3D-EEM) fluorescence spectroscopy before and after Fe(II)-PMS oxidation were determined to explain the enhanced dewatering mechanism. The release of EPS-bound water induced by the destruction of EPS was the primary reason for the improvement of sludge dewaterability during Fe(II)-PMS oxidation. PMID:26851897

  9. A preliminary study of factors affecting the calibration stability of the iridium versus iridium-40 percent rhodium thermocouple

    NASA Technical Reports Server (NTRS)

    Ahmed, Shaffiq; Germain, Edward F.; Daryabeigi, Kamran; Alderfer, David W.; Wright, Robert E.

    1987-01-01

    An iridium versus iridium-40% rhodium thermocouple was studied. Problems associated with the use of this thermocouple for high temperature applications (up to 2000 C) were investigated. The metallurgical studies included X-ray, macroscopic, resistance, and metallographic studies. The thermocouples in the as-received condition from the manufacturer revealed large amounts of internal stress caused by cold working during manufacturing. The thermocouples also contained a large amount of inhomogeneities and segregations. No phase transformations were observed in the alloy up to 1100 C. It was found that annealing the thermocouple at 1800 C for two hours, and then at 1400 C for 2 to 3 hours yielded a fine grain structure, relieving some of the strains, and making the wire more ductile. It was also found that the above annealing procedure stabilized the thermal emf behavior of the thermocouple for application below 1800 C (an improvement from + or - 1% to + or - 0.02% within the range of the test parameters used).

  10. Active Site Structure and Peroxidase Activity of Oxidatively Modified Cytochrome c Species in Complexes with Cardiolipin.

    PubMed

    Capdevila, Daiana A; Oviedo Rouco, Santiago; Tomasina, Florencia; Tortora, Verónica; Demicheli, Verónica; Radi, Rafael; Murgida, Daniel H

    2015-12-29

    We report a resonance Raman and UV-vis characterization of the active site structure of oxidatively modified forms of cytochrome c (Cyt-c) free in solution and in complexes with cardiolipin (CL). The studied post-translational modifications of Cyt-c include methionine sulfoxidation and tyrosine nitration, which lead to altered heme axial ligation and increased peroxidase activity with respect to those of the wild-type protein. In spite of the structural and activity differences between the protein variants free in solution, binding to CL liposomes induces in all cases the formation of a spectroscopically identical bis-His axial coordination conformer that more efficiently promotes lipid peroxidation. The spectroscopic results indicate that the bis-His form is in equilibrium with small amounts of high-spin species, thus suggesting a labile distal His ligand as the basis for the CL-induced increase in enzymatic activity observed for all protein variants. For Cyt-c nitrated at Tyr74 and sulfoxidized at Met80, the measured apparent binding affinities for CL are ∼4 times larger than for wild-type Cyt-c. On the basis of these results, we propose that these post-translational modifications may amplify the pro-apoptotic signal of Cyt-c under oxidative stress conditions at CL concentrations lower than for the unmodified protein. PMID:26620444

  11. Activation of Peroxymonosulfate by Benzoquinone: A Novel Nonradical Oxidation Process.

    PubMed

    Zhou, Yang; Jiang, Jin; Gao, Yuan; Ma, Jun; Pang, Su-Yan; Li, Juan; Lu, Xue-Ting; Yuan, Li-Peng

    2015-11-01

    The reactions between peroxymonosulfate (PMS) and quinones were investigated for the first time in this work, where benzoquinone (BQ) was selected as a model quinone. It was demonstrated that BQ could efficiently activate PMS for the degradation of sulfamethoxazole (SMX; a frequently detected antibiotic in the environments), and the degradation rate increased with solution pH from 7 to 10. Interestingly, quenching studies suggested that neither hydroxyl radical (•OH) nor sulfate radical (SO4•-) was produced therein. Instead, the generation of singlet oxygen (1O2) was proved by using two chemical probes (i.e., 2,2,6,6-tetramethyl-4-piperidinol and 9,10-diphenylanthracene) with the appearance of 1O2 indicative products detected by electron paramagnetic resonance spectrometry and liquid chromatography mass spectrometry, respectively. A catalytic mechanism was proposed involving the formation of a dioxirane intermediate between PMS and BQ and the subsequent decomposition of this intermediate into 1O2. Accordingly, a kinetic model was developed, and it well described the experimental observation that the pH-dependent decomposition rate of PMS was first-order with respect to BQ. These findings have important implications for the development of novel nonradical oxidation processes based on PMS, because 1O2 as a moderately reactive electrophile may suffer less interference from background organic matters compared with nonselective •OH and SO4•-. PMID:26452059

  12. UV-activated persulfate oxidation and regeneration of NOM-Saturated granular activated carbon.

    PubMed

    An, Dong; Westerhoff, Paul; Zheng, Mengxin; Wu, Mengyuan; Yang, Yu; Chiu, Chao-An

    2015-04-15

    A new method of ultraviolet light (UV) activated persulfate (PS) oxidation was investigated to regenerate granular activated carbon (GAC) in drinking water applications. The improvements in iodine and methylene blue numbers measured in the GAC after ultraviolet- (UV) activated persulfate suggested that the GAC preloaded with natural organic matter (NOM) was chemically regenerated. An experimental matrix for UV-activated persulfate regeneration included a range of persulfate doses and different UV wavelengths. Over 87% of the initial iodine number for GAC was restored under the optimum conditions, perfulfate dosage 60 g/L and UV exposure 1.75 × 10(4) mJ/cm(2). The persulfate dosages had little effect on the recovery of the methylene blue number, which was approximately 65%. Persulfate activation at 185 nm was superior to activation at 254 nm. UV activation of persulfate in the presence of GAC produced acid, lowering the solution pH. Higher persulfate concentrations and UV exposure resulted in greater GAC regeneration. Typical organic and inorganic byproducts (e.g., benzene compounds and sulfate ions) were measured as a component of treated water quality safety. This study provides a proof-of-concept that can be used to optimize pilot-scale and full-scale UV-activated persulfate for regeneration of NOM-saturated GAC. PMID:25697692

  13. Physicochemical properties and catalytic activity of metal tetraphenyl porphins in the oxidation of alkylaromatic hydrocarbons

    NASA Astrophysics Data System (ADS)

    Kobotaeva, N. S.; Skorokhodova, T. S.; Kokova, D. A.

    2013-06-01

    We consider the effect of complexing metal in a tetraphenylporphin molecule on its catalytic activity in oxidizing alkylaromatic hydrocarbons by molecular oxygen. The catalytic activity of metal porphyrins (Co, Cu, Zn, Mn, and In TPP) is found to depend on their oxidation potentials and the distribution of electron density in the molecule. The electron-donating compound imidazole is shown to affect the oxidation rate.

  14. Sub-Chronic Oral Exposure to Iridium (III) Chloride Hydrate in Female Wistar Rats: Distribution and Excretion of the Metal

    PubMed Central

    Iavicoli, Ivo; Fontana, Luca; Bergamaschi, Antonio; Conti, Marcelo Enrique; Pino, Anna; Mattei, Daniela; Bocca, Beatrice; Alimonti, Alessandro

    2012-01-01

    Iridium tissue distribution and excretion in female Wistar rats following oral exposure to iridium (III) chloride hydrate in drinking water (from 1 to 1000 ng/ml) in a sub-chronic oral study were determined. Samples of urine, feces, blood and organs (kidneys, liver, lung, spleen and brain) were collected at the end of exposure. The most prominent fractions of iridium were retained in kidney and spleen; smaller amounts were found in lungs, liver and brain. Iridium brain levels were lower than those observed in other tissues but this finding can support the hypothesis of iridium capability to cross the blood brain barrier. The iridium kidney levels rose significantly with the administered dose. At the highest dose, important amounts of the metal were found in serum, urine and feces. Iridium was predominantly excreted via feces with a significant linear correlation with the ingested dose, which is likely due to low intestinal absorption of the metal. However, at the higher doses iridium was also eliminated through urine. These findings may be useful to help in the understanding of the adverse health effects, particularly on the immune system, of iridium dispersed in the environment as well as in identifying appropriate biological indices of iridium exposure. PMID:22942873

  15. Persulfate Oxidation Regeneration of Granular Activated Carbon: Reversible Impacts on Sorption Behavior

    EPA Science Inventory

    Chemical oxidation regeneration of granular activated carbon (GAC) is a developing technology that can be carried out utilizing thermally-activated persulfate. During chemical regeneration of GAC, aggressive oxidative conditions lead to high acidity (pH < 2) and the accumulation ...

  16. Perovskite-supported palladium for methane oxidation - structure-activity relationships.

    PubMed

    Eyssler, Arnim; Lu, Ye; Matam, Santhosh Kumar; Weidenkaff, Anke; Ferri, Davide

    2012-01-01

    Palladium is the precious metal of choice for methane oxidation and perovskite-type oxides offer the possibility to stabilize it as PdO, considered crucial for catalytic activity. Pd can adopt different oxidation and coordination states when associated with perovskite-type oxides. Here, we review our work on the effect of perovskite composition on the oxidation and coordination states of Pd and its influence on catalytic activity for methane oxidation in the case of typical Mn, Fe and Co perovskite-based oxidation catalysts. Especially X-ray absorption near edge structure (XANES) spectroscopy is shown to be crucial to fingerprint the different coordination states of Pd. Pd substitutes Fe and Co in the octahedral sites but without modifying catalytic activity with respect to the Pd-free perovskite. On LaMnO(3) palladium is predominantly exposed at the surface thus bestowing catalytic activity for methane oxidation. However, the occupancy of B-cation sites of the perovskite structure by Pd can be exploited to cyclically activate Pd and to protect it from particle growth. This is explicitly demonstrated for La(Fe, Pd)O(3), where catalytic activity for methane oxidation is enhanced under oscillating redox conditions at 500 °C, therefore paving the way to the practical application in three-way catalysts for stoichiometric natural gas engines. PMID:23211725

  17. Role of dietary fish oil on nitric oxide synthase activity and oxidative status in mice red blood cells.

    PubMed

    Martins, Marcela A; Moss, Monique B; Mendes, Iara K S; Águila, Márcia B; Mandarim-de-Lacerda, Carlos Alberto; Brunini, Tatiana M C; Mendes-Ribeiro, Antônio Cláudio

    2014-12-01

    The consumption of n-3 polyunsaturated fatty acids (PUFAs) derived from fish oil concomitant with a reduced intake of saturated fats is associated with cardiovascular benefits, which may result from the participation of nitric oxide (NO). In contrast, PUFAs are vulnerable to peroxidation, which could affect the oxidative stability of the cell and reduce NO bioavailability. Therefore, we investigated the effects of high fat diets with increasing amounts of fish oil (0-40% of energy) in place of lard on the l-arginine-NO pathway, the arginase pathway and oxidative status in mice red blood cells (RBC). We found that l-arginine transport, as well as NO synthase (NOS) expression and activity, was enhanced by the highest doses of fish oil (30 and 40%). In contrast, diets rich in lard led to NOS expression and activity impairment. Arginase expression was not significantly affected by any of the dietary regimens. No significant difference in protein and lipid oxidative markers was observed among any of the fish-oil fed mice; only lard feeding induced protein damage in addition to a decreased superoxide dismutase activity. These data suggest that a substantial dose of fish oil, but not low doses, activates the RBC l-arginine-NO pathway without resulting in oxidative damage. PMID:25317541

  18. Oxidative Stress Impairs the Stimulatory Effect of S100 Proteins on Protein Phosphatase 5 Activity.

    PubMed

    Yamaguchi, Fuminori; Tsuchiya, Mitsumasa; Shimamoto, Seiko; Fujimoto, Tomohito; Tokumitsu, Hiroshi; Tokuda, Masaaki; Kobayashi, Ryoji

    2016-01-01

    Oxidative stress is the consequence of an imbalance between the production of harmful reactive oxygen species and the cellular antioxidant system for neutralization, and it activates multiple intracellular signaling pathways, including apoptosis signal-regulating kinase 1 (ASK1). Protein phosphatase 5 (PP5) is a serine/threonine phosphatase involved in oxidative stress responses. Previously, we reported that S100 proteins activate PP5 in a calcium-dependent manner. S100 proteins belong to a family of small EF-hand calcium-binding proteins involved in many processes such as cell proliferation, differentiation, apoptosis, and inflammation. Therefore, we investigated the effects of oxidative stress on S100 proteins, their interaction with PP5, and PP5 enzyme activity. Recombinant S100A2 was easily air-oxidized or Cu-oxidized, and oxidized S100A2 formed cross-linked dimers and higher molecular-mass complexes. The binding of oxidized S100A2 to PP5 was reduced, resulting in decreased PP5 activation in vitro. Oxidation also impaired S100A1, S100A6, S100B, and S100P to activate PP5, although the low dose of oxidized S100 proteins still activated PP5. Hydrogen peroxide (H2O2) induced S100A2 oxidation in human keratinocytes (HaCaT) and human hepatocellular carcinoma (Huh-7) cells. Furthermore, H2O2 reduced the binding of S100A2 to PP5 and decreased PP5 activation in HaCaT and Huh-7 cells. Importantly, even the low dose of S100A2 achieved by knocking down increased dephosphorylation of ASK1 and reduced caspase 3/7 activity in Huh-7 cells treated with H2O2. These results indicate that oxidative stress impairs the ability of S100 proteins to bind and activate PP5, which in turn modulates the ASK1-mediated signaling cascades involved in apoptosis. PMID:27600583

  19. Analysis and Implications of the Iridium 33-Cosmos 2251 Collision

    NASA Astrophysics Data System (ADS)

    Kelso, T. S.

    On 2009 February 10, Iridium 33--an operational US communications satellite in low-Earth orbit--was struck and destroyed by Cosmos 2251--a long-defunct Russian communications satellite. This is the first time since the dawn of the Space Age that two satellites have collided in orbit. To better understand the circumstances of this event and the ramifications for avoiding similar events in the future, this paper provides a detailed analysis of the predictions leading up to the collision, using various data sources, and looks in detail at the collision, the evolution of the debris clouds, and the long-term implications for satellite operations. The only publicly available system available to satellite operators for screening for close approaches, SOCRATES, did predict this close approach, but it certainly wasn't the closest approach predicted for the week of February 10. In fact, at the time of the collision, SOCRATES ranked this close approach 152 of the 11,428 within 5 km of any payload. A detailed breakdown is provided to help understand the limitations of screening for close approaches using the two-line orbital element sets. Information is also provided specifically for the Iridium constellation to provide an understanding of how these limitations affect decision making for satellite operators. Post-event analysis using high-accuracy orbital data sources will be presented to show how that information might have been used to prevent this collision, had it been available and used. Analysis of the collision event, along with the distribution of the debris relative to the original orbits, will be presented to help develop an understanding of the geometry of the collision and the near-term evolution of the resulting debris clouds. Additional analysis will be presented to show the long-term evolution of the debris clouds, including orbital lifetimes, and estimate the increased risk for operations conducted by Iridium and other satellite operators in the low-Earth orbit

  20. Immunosuppressive activity induced by nitric oxide in culture supernatant of activated rat alveolar macrophages.

    PubMed Central

    Kawabe, T; Isobe, K I; Hasegawa, Y; Nakashima, I; Shimokata, K

    1992-01-01

    Alveolar macrophages (AM) from normal rats had immunosuppressive activity to mitogen-induced proliferative responses of splenic lymphocytes. We studied the mechanism and the implication of the nitric oxide synthetase pathway in AM-mediated suppression of concanavalin A (Con A)-induced lymphocyte proliferation. The culture supernatant from AM cultures alone did not have immunosuppressive activity to Con A-induced proliferative responses of non-adherent spleen cells (n-ad SC), but the culture supernatant from co-culture of AM and autologous n-ad SC had this activity. Con A-pulsed AM also liberated the immunosuppressive factor. When AM and autologous n-ad SC were cultured separately under the condition that medium could freely communicate, the culture supernatant did not suppress the Con A-induced proliferative response of n-ad SC. This indicated that the immunosuppressive factor was liberated when AM was activated by cell-to-cell contact with n-ad SC. Further, we examined the immunosuppressive activity of the culture supernatant of co-culture of AM and autologous n-ad SC to Con A-induced responses of allogeneic n-ad SC and xenogeneic murine n-ad SC, and allogeneic mixed leucocyte reaction, and found that this culture supernatant could suppress all these proliferative responses. Nitrate (NO2-) synthesis was markedly augmented in the culture supernatants of Con A-pulsed AM and co-culture of AM and n-ad SC. NG-monomethyl-L-arginine (MMA), a specific competitive inhibitor of the nitric oxide synthetase pathway (NOSP), extinguished both NO2- synthesis by AM and AM-mediated immunosuppressive activity. These data suggest that NOSP was important in AM-mediated suppression of Con A-induced lymphocyte proliferation. PMID:1385798

  1. Electrochemical oxidation of fluoroquinolone antibiotics: Mechanism, residual antibacterial activity and toxicity change.

    PubMed

    Zhu, Linyan; Santiago-Schübel, Beatrix; Xiao, Hongxia; Hollert, Henner; Kueppers, Stephan

    2016-10-01

    In this paper, we studied the electrochemical oxidation mechanisms of three typical fluoroquinolone antibiotics (FQs), and investigated residual antibacterial activity and toxicity changes after oxidation processes. Electrochemistry coupled to mass spectrometry (EC-MS) was used to study the oxidation processes of ciprofloxacin (CIP), norfloxacin (NOR) and ofloxacin (OFL). Eight oxidation products for each parent compound were identified and their chemical structures were elucidated. The transformation trend of each product, with the continuous increase of voltage from 0 to 3000 mV, was recorded by online EC-MS. The oxidation pathways were proposed based on the structural information and transformation trends of oxidation products. We found the oxidation mechanisms of FQs consisted of the hydroxylation and cleavage of piperazinyl ring via reactions with hydroxyl radicals, while the fluoroquinolone core remained intact. The antibacterial activity of the parent compounds and their oxidation mixtures was estimated using zone inhibition tests for gram-negative bacteria Salmonella typhimurium. It was found that the oxidation mixtures of CIP and NOR retained the antibacterial properties with lower activity compared to their parent compounds, while the antibacterial activity of OFL was almost eliminated after oxidation. Furthermore, the toxicity of the three FQs and their oxidation mixtures were evaluated using algal growth inhibition test (Desmodesmus subspicatus). The median effective concentration (EC50) values for the algal inhibition tests were calculated for the end point of growth rate. The toxicity of CIP and NOR to green algae after electrochemical oxidation, remained unchanged, while that of OFL significantly increased. The results presented in this paper contribute to an understanding of the electrochemical oxidation mechanisms of FQs, and highlight the potential environmental risks of FQs after electrochemical oxidation processes. PMID:27318447

  2. Preparation and photocatalytic activity of TiO2-exfoliated graphite oxide composite using an ecofriendly graphite oxidation method

    NASA Astrophysics Data System (ADS)

    Baldissarelli, Vanessa Zanon; de Souza, Thiago; Andrade, Luisa; Oliveira, Luiz Fernando Cappa de; José, Humberto Jorge; Moreira, Regina de Fátima Peralta Muniz

    2015-12-01

    A simple and effective stepwise-method was developed to produce expanded exfoliated graphite oxide (EGO). Using a combination of ozone exposure and thermal treatment we demonstrate that a graphite surface can be modified to generate a graphene-like surface containing oxygen and sp3 carbon. This expanded exfoliated graphite oxide is useful for the production, through thermal treatment, of photocatalytic TiO2-EGO composites which are more active than those produce by the Hummers method. The photocatalytic activity of TiO2-EGO in methylene blue (MB) bleaching under UV light is enhanced in comparison with TiO2 P25.

  3. The use of organolithium reagents for the synthesis of 4-aryl-2-phenylpyridines and their corresponding iridium(iii) complexes.

    PubMed

    Davidson, Ross; Hsu, Yu-Ting; Batchelor, Thomas; Yufit, Dmitry; Beeby, Andrew

    2016-07-28

    A versatile palladium-free route for the synthesis of 4-aryl-substituted phenylpyridines (ppy), starting from tert-butyl 4-oxopiperidine-1-carboxylate, is reported. Reaction with an aryllithium, followed by trifluoroacetic acid dehydration/deprotection and oxidation with 2-iodoylbenzoic acid and finally phenylation, gave 4 ligands (L(1-4)H): 2,4-diphenylpyridine, 4-(4-methoxyphenyl)-2-phenylpyridine, 2-phenyl-4-(o-tolyl)pyridine and 4-mesityl-2-phenylpyridine. These ligands were coordinated to iridium to give the corresponding Ir(L)2(A) complexes (Ir1-7), where A = ancillary ligand acetylacetate or 2-picolinate. This was used to demonstrate that, through a combination of ancillary ligand choice and torsional twisting between the 4-aryl substituents of the ppy ligands, it is possible to tune the phosphorescent emission of the complexes in the range 502-560 nm. PMID:27346376

  4. Laminar iridium coating produced by pulse current electrodeposition from chloride molten salt

    NASA Astrophysics Data System (ADS)

    Zhu, Li'an; Bai, Shuxin; Zhang, Hong; Ye, Yicong

    2013-10-01

    Due to the unique physical and chemical properties, Iridium (Ir) is one of the most promising oxidation-resistant coatings for refractory materials above 1800 °C in aerospace field. However, the Ir coatings prepared by traditional methods are composed of columnar grains throughout the coating thickness. The columnar structure of the coating is considered to do harm to its oxidation resistance. The laminar Ir coating is expected to have a better high-temperature oxidation resistance than the columnar Ir coating does. The pulse current electrodeposition, with three independent parameters: average current density (Jm), duty cycle (R) and pulse frequency (f), is considered to be a promising method to fabricate layered Ir coating. In this study, laminar Ir coatings were prepared by pulse current electrodeposition in chloride molten salt. The morphology, roughness and texture of the coatings were determined by scanning electron microscope (SEM), profilometer and X-ray diffraction (XRD), respectively. The results showed that the laminar Ir coatings were composed of a nucleation layer with columnar structure and a growth layer with laminar structure. The top surfaces of the laminar Ir coatings consisted of cauliflower-like aggregates containing many fine grains, which were separated by deep grooves. The laminar Ir coating produced at the deposition condition of 20 mA/cm2 (Jm), 10% (R) and 6 Hz (f) was quite smooth (Ra 1.01 ± 0.09 μm) with extremely high degree of preferred orientation of <1 1 1>, and its laminar structure was well developed with clear boundaries and uniform thickness of sub-layers.

  5. 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.

  6. Markers of oxidative stress and erythrocyte antioxidant enzyme activity in older men and women with differing physical activity.

    PubMed

    Rowiński, Rafał; Kozakiewicz, Mariusz; Kędziora-Kornatowska, Kornelia; Hübner-Woźniak, Elżbieta; Kędziora, Józef

    2013-11-01

    The aim of the present study was to examine the relationship between markers of oxidative stress and erythrocyte antioxidant enzyme activity and physical activity in older men and women. The present study included 481 participants (233 men and 248 women) in the age group 65-69 years (127 men and 125 women) and in the age group 90 years and over (106 men and 123 women). The classification of respondents by physical activity was based on answers to the question if, in the past 12 months, they engaged in any pastimes which require physical activity. The systemic oxidative stress status was assessed by measuring plasma iso-PGF2α and protein carbonyl concentration as well as erythrocyte antioxidant enzymes activity, i.e., superoxide dismutase (SOD), catalase (CAT), glutathione peroxidase (GPx), and glutathione reductase (GR). The concentration of plasma iso-PGF2α and protein carbonyls (CP) was lower in groups of younger men and women compared to the respective older groups. In all examined groups, physical activity resulted in decrease of these oxidative stress markers and simultaneously caused adaptive increase in the erythrocyte SOD activity. Additionally, in active younger men CAT, GPx, and GR activities were higher than in sedentary ones. In conclusion, oxidative stress increase is age-related, but physical activity can reduce oxidative stress markers and induce adaptive increase in the erythrocyte antioxidant enzyme activity, especially SOD, even in old and very old men and women. PMID:23911531

  7. Exceptionally Active and Stable Spinel Nickel Manganese Oxide Electrocatalysts for Urea Oxidation Reaction.

    PubMed

    Periyasamy, Sivakumar; Subramanian, Palaniappan; Levi, Elena; Aurbach, Doron; Gedanken, Aharon; Schechter, Alex

    2016-05-18

    Spinel nickel manganese oxides, widely used materials in the lithium ion battery high voltage cathode, were studied in urea oxidation catalysis. NiMn2O4, Ni1.5Mn1.5O4, and MnNi2O4 were synthesized by a simple template-free hydrothermal route followed by a thermal treatment in air at 800 °C. Rietveld analysis performed on nonstoichiometric nickel manganese oxide-Ni1.5Mn1.5O4 revealed the presence of three mixed phases: two spinel phases with different lattice parameters and NiO unlike the other two spinels NiMn2O4 and MnNi2O4. The electroactivity of nickel manganese oxide materials toward the oxidation of urea in alkaline solution is evaluated using cyclic voltammetric measurements. Ni1.5Mn1.5O4 exhibits excellent redox characteristics and lower charge transfer resistances in comparison with other compositions of nickel manganese oxides and nickel oxide prepared under similar conditions.The Ni1.5Mn1.5O4modified electrode oxidizes urea at 0.29 V versus Ag/AgCl with a corresponding current density of 6.9 mA cm(-2). At a low catalyst loading of 50 μg cm(-2), the urea oxidation current density of Ni1.5Mn1.5O4 in alkaline solution is 7 times higher than that of nickel oxide and 4 times higher than that of NiMn2O4 and MnNi2O4, respectively. PMID:27123873

  8. Iridium-alloy processing experience in FY 1990

    SciTech Connect

    Ohriner, E.K.

    1991-11-01

    Iridium-alloy blanks and foil are produced at the Oak Ridge National Laboratory for use as fuel cladding material in radioisotope thermoelectric generators for space power sources. Until 1984, the material was produced from small, 500-g drop castings. A new process has been developed in which consumable electrodes of about 10 kg are melted, extruded, and then rolled to produce the sheet products. The work performed during FY 1990 included the consumable-electrode arc melting of four ingots and the extruding and rolling to sheet of four billets. Significant improvements made in the extruding and arc-melting processes during FY 1989 have been demonstrated to dramatically increase the rate of blank acceptance in nondestructive evaluations. Efforts to improve the rolling practice and to better characterize intermetallic particle distributions in the sheet are also described.

  9. Iridium-alloy processing experience in FY 1989

    SciTech Connect

    Ohriner, E.K.

    1990-11-01

    Iridium-alloy blanks and foil are produced at the Oak Ridge National Laboratory for use as fuel cladding material in radioisotope thermoelectric generators for space power sources. Until 1984, the material was produced from small 500-g drop castings. A new process has been developed in which consumable electrodes of about 10 kg are arc melted, extruded, and then rolled to produce the sheet products. The work performed during FY 1989 included the arc melting of three electrodes and the extruding and rolling to sheet of three billets. Significant improvements have been made in the extruding and arc-melting processes. Preliminary results show that these improvements have had an important effect in increasing the rate of blank acceptance in nondestructive evaluations. 4 refs., 33 figs., 11 tabs.

  10. Intercalation of graphene on iridium with samarium atoms

    NASA Astrophysics Data System (ADS)

    Afanas'eva, E. Yu.; Rut'kov, E. V.; Gall, N. R.

    2016-07-01

    Intercalation of graphene on Ir (111) with Sm atoms is studied by methods of thermal desorption spectroscopy and thermionic emission. It is shown that adsorption of samarium at T = 300 K on graphene to concentrations of N ≤ 6 × 1014 atoms cm-2 followed by heating of the substrate leads to practically complete escape of adsorbate underneath the graphene layer. At N > 6 × 1014 atoms cm-2 and increasing temperature, a fraction of adsorbate remains on graphene in the form of two-dimensional "gas" and samarium islands and are desorbed in the range of temperatures of 1000-1200 K. Samarium remaining under the graphene is desorbed from the surface in the temperature range 1200-2150 K. Model conceptions for the samarium-graphene-iridium system in a wide temperature range are developed.

  11. Iridium abundance maxima in the Upper Cenomanian extinction interval

    NASA Technical Reports Server (NTRS)

    Orth, C. J.; Attrep, M., Jr.; Mao, X. Y.; Kauffman, E. G.; Diner, R.

    1988-01-01

    Two iridium abundance peaks, both 0.11 ppb (whole-rock basis) over a local background of 0.017 ppb, have been found in Middle Cretaceous marine rocks near Pueblo, Colorado. They occur just below the 92-million-year-old Cenomanian-Turonian (C-T) stage boundary. No other peaks were found in 45 meters of strata (about 2.5 million years of deposition) above and below the boundary interval. The broad lower peak straddles the first in a series of extinctions of benthic and nektonic macrobiota which comprise the C-T extinction event. The sharp upper peak occurs stratigraphically about 1.2 meters above the lower peak. The excess Ir might be from meteoroid impacts.

  12. Comparative modelling of chemical ordering in palladium-iridium nanoalloys

    SciTech Connect

    Davis, Jack B. A.; Johnston, Roy L.; Rubinovich, Leonid; Polak, Micha

    2014-12-14

    Chemical ordering in “magic-number” palladium-iridium nanoalloys has been studied by means of density functional theory (DFT) computations, and compared to those obtained by the Free Energy Concentration Expansion Method (FCEM) using derived coordination dependent bond energy variations (CBEV), and by the Birmingham Cluster Genetic Algorithm using the Gupta potential. Several compositions have been studied for 38- and 79-atom particles as well as the site preference for a single Ir dopant atom in the 201-atom truncated octahedron (TO). The 79- and 38-atom nanoalloy homotops predicted for the TO by the FCEM/CBEV are shown to be, respectively, the global minima and competitive low energy minima. Significant reordering of minima predicted by the Gupta potential is seen after reoptimisation at the DFT level.

  13. Iridium satellites help map electrical currents in space

    NASA Astrophysics Data System (ADS)

    Showstack, Randy

    The satellite constellation of Iridium LLC, which filed for Chapter 11 bankruptcy in 1999 after it failed to win enough business for its commercial satellite communications services, is still orbiting at an altitude of about 780 kilometers. Now, however, the satellites are helping to write a new chapter in understanding space weather.Magnetometers onboard each of the system's 66 polar-orbiting satellites are working in conjunction with the high-frequency, multinational Super Dual Auroral Radar Network, or SuperDARN, to provide the first continuous measurements of electrical currents between Earth's upper atmosphere and space. These tools also are generating the first global maps of electrical power flowing into the polar upper atmosphere.

  14. Inhibition of Beta-Amyloid Fibrillation by Luminescent Iridium(III) Complex Probes

    PubMed Central

    Lu, Lihua; Zhong, Hai-Jing; Wang, Modi; Ho, See-Lok; Li, Hung-Wing; Leung, Chung-Hang; Ma, Dik-Lung

    2015-01-01

    We report herein the application of kinetically inert luminescent iridium(III) complexes as dual inhibitors and probes of beta-amyloid fibrillogenesis. These iridium(III) complexes inhibited Aβ1–40 peptide aggregation in vitro, and protected against Aβ-induced cytotoxicity in neuronal cells. Furthermore, the complexes differentiated between the aggregated and unaggregated forms of Aβ1–40 peptide on the basis of their emission response. PMID:26419607

  15. Determination of ruthenium and iridium in anode coatings by atomic-absorption spectroscopy.

    PubMed

    Harrington, D E; Bramstedt, W R

    A method is described for the determination of ruthenium and iridium coated on an electrode surface. The coating is chemically removed from the electrode by fusion with alkali, and the resulting solution prepared for analysis. Interelement interferences are eliminated by using a titanium-potassium matrix solution as a releasing agent. Recovery and precision data are given for ruthenium and iridium. The AAS determination of ruthenium compares favourably with a standard colorimetric method. PMID:18961657

  16. Iridium-Catalyzed Enantioselective Hydroalkynylation of Enamides for the Synthesis of Homopropargyl Amides.

    PubMed

    Bai, Xiao-Yan; Wang, Zi-Xuan; Li, Bi-Jie

    2016-07-25

    Reported is an iridium-catalyzed asymmetric hydroalkynylation of enamides with terminal alkynes. The reaction occurs regioselectively at the β-position of an enamide to produce homopropargyl amides. Good to high enantioselectivity was observed with an iridium complex ligated by a chiral bis(phosphine) ligand. This method provides a straightforward route to synthesize chiral homopropargyl amides with a stereocenter β to the amide. PMID:27111577

  17. Inhibition of Beta-Amyloid Fibrillation by Luminescent Iridium(III) Complex Probes

    NASA Astrophysics Data System (ADS)

    Lu, Lihua; Zhong, Hai-Jing; Wang, Modi; Ho, See-Lok; Li, Hung-Wing; Leung, Chung-Hang; Ma, Dik-Lung

    2015-09-01

    We report herein the application of kinetically inert luminescent iridium(III) complexes as dual inhibitors and probes of beta-amyloid fibrillogenesis. These iridium(III) complexes inhibited Aβ1-40 peptide aggregation in vitro, and protected against Aβ-induced cytotoxicity in neuronal cells. Furthermore, the complexes differentiated between the aggregated and unaggregated forms of Aβ1-40 peptide on the basis of their emission response.

  18. Pollution Control Meets Sustainability: Structure-Activity Studies on New Iron Oxide-Based CO Oxidation Catalysts.

    PubMed

    Schoch, Roland; Bauer, Matthias

    2016-08-01

    A new class of catalysts for the oxidation of CO based on iron oxide as a biocompatible, earth-abundant and non-toxic metal is presented. The catalytic activities achieved with these catalysts provide promising milestones towards the substitution of noble metals in CO oxidation catalysts. The catalysts can be obtained by using iron core-shell nanoparticle precursors. The metal used for the shell material determines whether the iron core is integrated in or isolated from the support. The active iron site is effectively integrated into the γ-Al2 O3 support if an aluminum shell is present in the core-shell precursor. When the metal used for the shell is different from the support, an isolated structure is formed. Using this directed synthesis approach, different iron oxide species can be obtained and their structural differences are linked to distinct catalytic activities, as demonstrated by combined in-depth analytical studies using XRD, X-ray absorption spectroscopy (XAS), UV/Vis, and Brunauer-Emmett-Teller (BET) analysis. The key species responsible for high catalytic activity is identified as isolated tetrahedrally coordinated Fe(III) centers, whereas aggregation leads to a reduction in activity. PMID:27440425

  19. Resveratrol-loaded Nanoparticles Induce Antioxidant Activity against Oxidative Stress

    PubMed Central

    Kim, Jae-Hwan; Park, Eun-Young; Ha, Ho-Kyung; Jo, Chan-Mi; Lee, Won-Jae; Lee, Sung Sill; Kim, Jin Wook

    2016-01-01

    Resveratrol acts as a free radical scavenger and a potent antioxidant in the inhibition of numerous reactive oxygen species (ROS). The function of resveratrol and resveratrol-loaded nanoparticles in protecting human lung cancer cells (A549) against hydrogen peroxide was investigated in this study. The 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulphonic acid (ABTS) assay was performed to evaluate the antioxidant properties. Resveratrol had substantially high antioxidant capacity (trolox equivalent antioxidant capacity value) compared to trolox and vitamin E since the concentration of resveratrol was more than 50 μM. Nanoparticles prepared from β-lactoglobulin (β-lg) were successfully developed. The β-lg nanoparticle showed 60 to 146 nm diameter in size with negatively charged surface. Non-cytotoxicity was observed in Caco-2 cells treated with β-lg nanoparticles. Fluorescein isothiocynate-conjugated β-lg nanoparticles were identified into the cell membrane of Caco-2 cells, indicating that nanoparticles can be used as a delivery system. Hydrogen peroxide caused accumulation of ROS in a dose- and time-dependent manner. Resveratrol-loaded nanoparticles restored H2O2-induced ROS levels by induction of cellular uptake of resveratrol in A549 cells. Furthermore, resveratrol activated nuclear factor erythroid 2-related factor 2-Kelch ECH associating protein 1 (Nrf2-Keap1) signaling in A549 cells, thereby accumulation of Nrf2 abundance, as demonstrated by western blotting approach. Overall, these results may have implications for improvement of oxidative stress in treatment with nanoparticles as a biodegradable and non-toxic delivery carrier of bioactive compounds. PMID:26732454

  20. Effect of chromium oxide as active site over TiO2-PILC for selective catalytic oxidation of NO.

    PubMed

    Zhang, Jingxin; Zhang, Shule; Cai, Wei; Zhong, Qin

    2013-12-01

    This study introduced TiO2-pillared clays (TiO2-PILC) as a support for the catalytic oxidation of NO and analyzed the performance of chromium oxides as the active site of the oxidation process. Cr-based catalysts were prepared by a wet impregnation method. It was found that the 10 wt.% chromium doping on the support achieved the best catalytic activity. At 350 degrees C, the NO conversion was 61% under conditions of GHSV = 23600 hr(-1). The BET data showed that the support particles had a mesoporous structure. H2-TPR showed that Cr(10)TiP (10 wt.% Cr doping on TiO2-PILC) clearly exhibited a smooth single peak. EPR and XPS were used to elucidate the oxidation process. During the NO + O2 adsorption, the intensity of evolution of superoxide ions (O2(-)) increased. The content of Cr3+ on the surface of the used catalyst was 40.37%, but when the used catalyst continued adsorbing NO, the Cr3+ increased to 50.28%. Additionally, O(alpha)/O(beta) increased markedly through the oxidation process. The NO conversion decreased when SO2 was added into the system, but when the SO2 was removed, the catalytic activity recovered almost up to the initial level. FT-IR spectra did not show a distinct characteristic peak of SO4(2-). PMID:24649682

  1. A quantitative structure--activity relationship model for the intrinsic activity of uncouplers of oxidative phosphorylation.

    PubMed

    Spycher, Simon; Escher, Beate I; Gasteiger, Johann

    2005-12-01

    A quantitative structure-activity relationship (QSAR) has been derived for the prediction of the activity of phenols in uncoupling oxidative and photophosphorylation. Twenty-one compounds with experimental data for uncoupling activity as well as for the acid dissociation constant, pKa, and for partitioning constants of the neutral and the charged species into model membranes were analyzed. From these measured data, the effective concentration in the membrane was derived, which allowed the study of the intrinsic activity of uncouplers within the membrane. A linear regression model for the intrinsic activity could be established using the following three descriptors: solvation free energies of the anions, an estimate for heterodimer formation describing transport processes, and pKa values describing the speciation of the phenols. In a next step, the aqueous effect concentrations were modeled by combining the model for the intrinsic uncoupling activity with descriptors accounting for the uptake into membranes. Results obtained with experimental membrane-water partitioning data were compared with the results obtained with experimental octanol-water partition coefficients, log Kow, and with calculated log Kow values. The properties of these different measures of lipophilicity were critically discussed. PMID:16359176

  2. Process for catalytically oxidizing cycloolefins, particularly cyclohexene

    DOEpatents

    Mizuno, Noritaka; Lyon, David K.; Finke, Richard G.

    1993-01-01

    This invention is a process for catalytically oxidizing cycloolefins, particularly cyclohexenes, to form a variety of oxygenates. The catalyst used in the process is a covalently bonded iridium-heteropolyanion species. The process uses the catalyst in conjunction with a gaseous oxygen containing gas to form 2-cyclohexen-1-ol and also 2-cyclohexen-1-one.

  3. New yellow-emitting phosphorescent cyclometalated iridium(III) complex

    NASA Astrophysics Data System (ADS)

    Ivanov, P.; Tomova, R.; Petrova, P.; Stanimirov, S.; Petkov, I.

    2012-12-01

    We have synthesized a new yellow iridium complex Iridium(III) bis[2-phenylbenzothiazolato-N,C2']-(1-phenylicosane-1,3-dionate) (bt)2Ir(bsm), based on the benzothiazole derivative. The synthesized molecule was identified by 1H NMR and elemental analysis. The UV-Visible absorption and photoluminescence (PL) spectra of (bt)Ir2(bsm) in CH2Cl2 solution were found at 273 nm and 559 nm, respectively. The complex was used as a dopant into a hole-transporting layer (HTL) in a multilayered organic light emitting device (OLED) structure: ITO/doped-HTL/EL/ETL/M. ITO was a transparent anode of In2O3:SnO2, M- a metallic Al cathode, HTL- 4,4'-bis(9H-carbazol-9-yl)biphenyl (CBP) incorporated in poly(N-vinylcarbazole) (PVK) matrix, EL- electroluminescent layer of bis(8-hydroxy-2-methylquinoline)-(4-phenylphenoxy)aluminum (BAlq) and ETL- electron-transporting layer of tris(8-hydroxyquinolinato)aluminum (Alq3). The electroluminescent (EL) spectra of OLEDs were basically the sum of the emissions of BAlq at 496 nm and the emission of (bt)2Ir(bsm) at 559 nm. With increasing (bt)2Ir(bsm) concentration, the relative electroluminescent intensity of greenish-blue emission (at 496 nm) decreased, while the yellow (at 559 nm) - increased and CIE coordinates of the device shifted from (0.21, 0.33) at 0 wt % to (0.40, 0.48) at 8 wt % of the dopant. It was found that OLED with 0.5 wt % (bt)2Ir(bsm) had the best performance and stable color chromaticity at various voltages.

  4. The Electric Dipole Moment of Iridium Monosilicide, IrSi

    NASA Astrophysics Data System (ADS)

    Le, Anh; Steimle, Timothy C.; Cheng, Lan; Stanton, John F.

    2013-06-01

    The optical spectrum of iridium monosilicide (IrSi) was recently observed using REMPI spectroscopy in the range 17200 to 23850 cm^{-1}. The observation was supported by an ab initio calculation which predicted a X^{2}Δ_{5/2} state. Here, we report on the analysis of the optical Stark effect for the X^{2}Δ_{5/2} and [16.0]1.5 (v=6) states. The (6,0)[16.0]1.5 - X^{2}Δ_{5/2} and the (7,0)[16.0]3.5- X^{2}Δ_{5/2} bands of IrSi have been recorded using high-resolution laser-induced fluorescence spectroscopy. The observed optical Stark shifts for the ^{193}IrSi and ^{191}IrSi isotopologues were analyzed to produce the electric dipole moments of -0.4139(64)D and 0.7821(63)D for the X^{2}Δ_{5/2} and [16.0]1.5 (v=6) states, respectively. The negative sign of electric dipole moment of the X^{2}Δ_{5/2} state is supported by high-level quantum-chemical calculations employing all-electron scalar-relativistic CCSD(T) method augmented with spin-orbit corrections as well as corrections due to full triple excitations. In particular, electron-correlation effects have been shown to be essential in the prediction of the negative sign of the dipole moment. A comparison with other iridium containing molecules will be made. Maria A. Garcia, Carolin Vietz, Fernando Ruipérez, Michael D. Morse, and Ivan Infante, Kimika Fakultatea, Euskal Herriko. J. Chem. Phys., (submitted)

  5. Dynamic high-temperature characterization of an iridium alloy in compression at high strain rates.

    SciTech Connect

    Song, Bo; Nelson, Kevin; Lipinski, Ronald J.; Bignell, John L.; Ulrich, G. B.; George, E. P.

    2014-06-01

    Iridium alloys have superior strength and ductility at elevated temperatures, making them useful as structural materials for certain high-temperature applications. However, experimental data on their high-temperature high-strain-rate performance are needed for understanding high-speed impacts in severe elevated-temperature environments. Kolsky bars (also called split Hopkinson bars) have been extensively employed for high-strain-rate characterization of materials at room temperature, but it has been challenging to adapt them for the measurement of dynamic properties at high temperatures. Current high-temperature Kolsky compression bar techniques are not capable of obtaining satisfactory high-temperature high-strain-rate stress-strain response of thin iridium specimens investigated in this study. We analyzed the difficulties encountered in high-temperature Kolsky compression bar testing of thin iridium alloy specimens. Appropriate modifications were made to the current high-temperature Kolsky compression bar technique to obtain reliable compressive stress-strain response of an iridium alloy at high strain rates (300 10000 s-1) and temperatures (750ÀC and 1030ÀC). Uncertainties in such high-temperature high-strain-rate experiments on thin iridium specimens were also analyzed. The compressive stress-strain response of the iridium alloy showed significant sensitivity to strain rate and temperature.

  6. Inhibition of the p53/hDM2 protein-protein interaction by cyclometallated iridium(III) compounds

    PubMed Central

    Liu, Li-Juan; He, Bingyong; Miles, Jennifer A.; Wang, Wanhe; Mao, Zhifeng; Che, Weng Ian; Lu, Jin-Jian; Chen, Xiu-Ping; Wilson, Andrew J.; Ma, Dik-Lung; Leung, Chung-Hang

    2016-01-01

    Inactivation of the p53 transcription factor by mutation or other mechanisms is a frequent event in tumorigenesis. One of the major endogenous negative regulators of p53 in humans is hDM2, a ubiquitin E3 ligase that binds to p53 causing proteasomal p53 degradation. In this work, a library of organometallic iridium(III) compounds were synthesized and evaluated for their ability to disrupt the p53/hDM2 protein-protein interaction. The novel cyclometallated iridium(III) compound 1 [Ir(eppy)2(dcphen)](PF6) (where eppy = 2-(4-ethylphenyl)pyridine and dcphen = 4, 7-dichloro-1, 10-phenanthroline) blocked the interaction of p53/hDM2 in human amelanotic melanoma cells. Finally, 1 exhibited anti-proliferative activity and induced apoptosis in cancer cell lines consistent with inhibition of the p53/hDM2 interaction. Compound 1 represents the first reported organometallic p53/hDM2 protein-protein interaction inhibitor. PMID:26883110

  7. Calcium-Oxidant Signaling Network Regulates AMP-activated Protein Kinase (AMPK) Activation upon Matrix Deprivation*

    PubMed Central

    Sundararaman, Ananthalakshmy; Amirtham, Usha; Rangarajan, Annapoorni

    2016-01-01

    The AMP-activated protein kinase (AMPK) has recently been implicated in anoikis resistance. However, the molecular mechanisms that activate AMPK upon matrix detachment remain unexplored. In this study, we show that AMPK activation is a rapid and sustained phenomenon upon matrix deprivation, whereas re-attachment to the matrix leads to its dephosphorylation and inactivation. Because matrix detachment leads to loss of integrin signaling, we investigated whether integrin signaling negatively regulates AMPK activation. However, modulation of focal adhesion kinase or Src, the major downstream components of integrin signaling, failed to cause a corresponding change in AMPK signaling. Further investigations revealed that the upstream AMPK kinases liver kinase B1 (LKB1) and Ca2+/calmodulin-dependent protein kinase kinase β (CaMKKβ) contribute to AMPK activation upon detachment. In LKB1-deficient cells, we found AMPK activation to be predominantly dependent on CaMKKβ. We observed no change in ATP levels under detached conditions at early time points suggesting that rapid AMPK activation upon detachment was not triggered by energy stress. We demonstrate that matrix deprivation leads to a spike in intracellular calcium as well as oxidant signaling, and both these intracellular messengers contribute to rapid AMPK activation upon detachment. We further show that endoplasmic reticulum calcium release-induced store-operated calcium entry contributes to intracellular calcium increase, leading to reactive oxygen species production, and AMPK activation. We additionally show that the LKB1/CaMKK-AMPK axis and intracellular calcium levels play a critical role in anchorage-independent cancer sphere formation. Thus, the Ca2+/reactive oxygen species-triggered LKB1/CaMKK-AMPK signaling cascade may provide a quick, adaptable switch to promote survival of metastasizing cancer cells. PMID:27226623

  8. Bulk binary ZrO2-based oxides as highly active alternative-type catalysts for non-oxidative isobutane dehydrogenation.

    PubMed

    Otroshchenko, Tatyana; Radnik, Jörg; Schneider, Matthias; Rodemerck, Uwe; Linke, David; Kondratenko, Evgenii V

    2016-06-21

    Bulk binary ZrO2-based oxides efficiently catalyse non-oxidative dehydrogenation of isobutane to isobutylene. Their activity strongly depends on the kind of second metal oxide. So designed CrZrOx showed superior activity to industrially relevant catalysts with supported Pt or CrOx species. It was also stable under alternating dehydrogenation and oxidative regeneration cycles over ca. 110 h under different reaction conditions between 550 and 600 °C. PMID:27277540

  9. In situ oxidation of carbon-encapsulated cobalt nanocapsules creates highly active cobalt oxide catalysts for hydrocarbon combustion.

    PubMed

    Wang, Han; Chen, Chunlin; Zhang, Yexin; Peng, Lixia; Ma, Song; Yang, Teng; Guo, Huaihong; Zhang, Zhidong; Su, Dang Sheng; Zhang, Jian

    2015-01-01

    Combustion catalysts have been extensively explored to reduce the emission of hydrocarbons that are capable of triggering photochemical smog and greenhouse effect. Palladium as the most active material is widely applied in exhaust catalytic converter and combustion units, but its high capital cost stimulates the tremendous research on non-noble metal candidates. Here we fabricate highly defective cobalt oxide nanocrystals via a controllable oxidation of carbon-encapsulated cobalt nanoparticles. Strain gradients induced in the nanoconfined carbon shell result in the formation of a large number of active sites featuring a considerable catalytic activity for the combustion of a variety of hydrocarbons (methane, propane and substituted benzenes). For methane combustion, the catalyst displays a unique activity being comparable or even superior to the palladium ones. PMID:26074206

  10. In situ oxidation of carbon-encapsulated cobalt nanocapsules creates highly active cobalt oxide catalysts for hydrocarbon combustion

    NASA Astrophysics Data System (ADS)

    Wang, Han; Chen, Chunlin; Zhang, Yexin; Peng, Lixia; Ma, Song; Yang, Teng; Guo, Huaihong; Zhang, Zhidong; Su, Dang Sheng; Zhang, Jian

    2015-06-01

    Combustion catalysts have been extensively explored to reduce the emission of hydrocarbons that are capable of triggering photochemical smog and greenhouse effect. Palladium as the most active material is widely applied in exhaust catalytic converter and combustion units, but its high capital cost stimulates the tremendous research on non-noble metal candidates. Here we fabricate highly defective cobalt oxide nanocrystals via a controllable oxidation of carbon-encapsulated cobalt nanoparticles. Strain gradients induced in the nanoconfined carbon shell result in the formation of a large number of active sites featuring a considerable catalytic activity for the combustion of a variety of hydrocarbons (methane, propane and substituted benzenes). For methane combustion, the catalyst displays a unique activity being comparable or even superior to the palladium ones.

  11. In situ oxidation of carbon-encapsulated cobalt nanocapsules creates highly active cobalt oxide catalysts for hydrocarbon combustion

    PubMed Central

    Wang, Han; Chen, Chunlin; Zhang, Yexin; Peng, Lixia; Ma, Song; Yang, Teng; Guo, Huaihong; Zhang, Zhidong; Su, Dang Sheng; Zhang, Jian

    2015-01-01

    Combustion catalysts have been extensively explored to reduce the emission of hydrocarbons that are capable of triggering photochemical smog and greenhouse effect. Palladium as the most active material is widely applied in exhaust catalytic converter and combustion units, but its high capital cost stimulates the tremendous research on non-noble metal candidates. Here we fabricate highly defective cobalt oxide nanocrystals via a controllable oxidation of carbon-encapsulated cobalt nanoparticles. Strain gradients induced in the nanoconfined carbon shell result in the formation of a large number of active sites featuring a considerable catalytic activity for the combustion of a variety of hydrocarbons (methane, propane and substituted benzenes). For methane combustion, the catalyst displays a unique activity being comparable or even superior to the palladium ones. PMID:26074206

  12. Characterization of extracellular Mn2+-oxidizing activity and isolation of an Mn2+-oxidizing protein from Leptothrix discophora SS-1.

    PubMed

    Adams, L F; Ghiorse, W C

    1987-03-01

    Supernatant fluid from Leptothrix discophora SS-1 cultures possessed high Mn2+-ozidizing activity. Studies of temperature and pH optima, chemical inhibition, and protease sensitivity suggested that the activity may be enzymatic. Kinetic studies of unconcentrated supernatant fluid indicated an apparent Km of 7 microM Mn2+ in the 1 to 200 microM Mn2+ range. The greatest Vmax value observed was 1.4 nmol of Mn2+ oxidized min-1 micrograms of protein-1 in unconcentrated samples. When the supernatant fluid was concentrated on DEAE-cellulose and the activity was eluted with MgSO4, an Mn2+-oxidizing protein was detected in the concentrate by sodium dodecyl sulfate-polyacrylamide gel electrophoresis. The Mn2+-oxidizing protein appeared to have a molecular weight of 110,000 in 10% polyacrylamide gels and of 100,000 in 8% gels. Periodic acid-Schiff base staining of overloaded polyacrylamide gels showed that the DEAE-cellulose concentrate contained abundant high-molecular-weight polysaccharides; concurrent staining of the Mn2+-oxidizing band suggested that it too contained carbohydrate components. Isolation of the protein was achieved by subjecting the DEAE-cellulose concentrate to Sephacryl gel filtration in the presence of 1% sodium dodecyl sulfate, followed by preparative electrophoresis and reverse-polarity elution. However, these procedures resulted in loss of a large proportion of the activity, which precluded recovery of the protein in significant quality. PMID:3818545

  13. Iridium-bipyridine periodic mesoporous organosilica catalyzed direct C-H borylation using a pinacolborane.

    PubMed

    Maegawa, Yoshifumi; Inagaki, Shinji

    2015-08-01

    Heterogeneous catalysis for direct C-H borylation of arenes and heteroarenes in the combination of iridium (Ir) complex fixed on periodic mesoporous organosilica containing bipyridine ligands within the framework (Ir-BPy-PMO) and pinacolborane (HBpin) is reported. Ir-BPy-PMO showed higher catalytic activity toward the borylation of benzene with inexpensive HBpin compared to expensive bis(pinacolato)diboron (B2pin2). The precatalyst could be handled without the use of a glove box. The catalyst was easily recovered from reaction mixtures by simple filtration under air. The recovered catalyst still showed good catalytic activity for at least three more times for the borylation of benzene. A variety of arenes and heteroarenes were successfully borylated with high boron efficiency by Ir-BPy-PMO using HBpin, whereas almost no activity was observed for borylation of some heteroarenes with B2pin2. The system using Ir-BPy-PMO and HBpin was also utilized in syntheses of multi-boronated thiophene-based building blocks containing ladder-, acenefused-, and fused-thiophene skeletons. The combination of a stable and reusable solid catalyst and inexpensive HBpin is expected to be superior to conventional approaches for the development of industrial applications. PMID:25748945

  14. Inhibition, Inactivation, and Recovery of Ammonia-Oxidizing Activity in Cometabolism of Trichloroethylene by Nitrosomonas europaea

    PubMed Central

    Hyman, M. R.; Russell, S. A.; Ely, R. L.; Williamson, K. J.; Arp, D. J.

    1995-01-01

    The kinetics of the cometabolism of trichloroethylene (TCE) by the ammonia-oxidizing soil bacterium Nitrosomonas europaea in short-term (<10-min) incubations were investigated. Three individual effects of TCE cometabolism on this bacterium were characterized. First, we observed that TCE is a potent competitive inhibitor of ammonia oxidation by N. europaea. The K(infi) value for TCE (30 (mu)M) is similar to the K(infm) for ammonia (40 (mu)M). Second, we examined the toxicity associated with TCE cometabolism by N. europaea. Stationary-phase cells of N. europaea oxidized approximately 60 nmol of TCE per mg of protein before ammonia-oxidizing activity was completely inactivated by reactive intermediates generated during TCE oxidation. At the TCE concentrations used in these experiments, ammonia did not provide significant protection against inactivation. Third, we have determined the ability of cells to recover ammonia-oxidizing activity after exposure to TCE. Cells recovering from TCE inactivation were compared with cells recovering from the specific inactivation of ammonia-oxidizing activity by light. The recovery kinetics were indistinguishable when 40% or less of the activity was inactivated. However, at increased levels of inactivation, TCE-inactivated cells did not recover as rapidly as light-inactivated cells. The kinetics of recovery appear to be dependent on both the extent of inactivation of ammonia-oxidizing activity and the degree of specificity of the inactivating treatment. PMID:16534997

  15. Promotion effect of manganese oxide on the electrocatalytic activity of Pt/C for methanol oxidation in acid medium

    NASA Astrophysics Data System (ADS)

    Abdel Hameed, R. M.; Fetohi, Amani E.; Amin, R. S.; El-Khatib, K. M.

    2015-12-01

    The modification of Pt/C by incorporating metal oxides for electrocatalytic oxidation of methanol has gained major attention because of the efficiency loss during the course of long-time operation. This work describes the preparation of Pt-MnO2/C electrocatalysts through a chemical route using ethylene glycol or a mixture of ethylene glycol and sodium borohydride as a reducing agent. The crystallite structure and particle size of synthesized electrocatalysts are determined using X-ray diffraction (XRD) and transmission electron microscopy (TEM). The addition of MnO2 improves the dispersion of Pt nanoparticles. The electrocatalytic activity of Pt-MnO2/C towards methanol oxidation in H2SO4 solution is investigated using cyclic voltammetry and electrochemical impedance spectroscopy. The onset potential value of methanol oxidation peak is negatively shifted by 169 mV when MnO2 is introduced to Pt/C. Moreover, the charge transfer resistance value at Pt-MnO2/C is about 10 times as low as that at Pt/C. Chronoamperometry and chronopotentiometry show that CO tolerance is greatly improved at Pt-MnO2/C. The increased electrocatalytic activity and enhanced ability to clean platinum surface elect manganese oxide as a suitable promoter for the anode performance in direct methanol fuel cells (DMFCs).

  16. Parallel activation of mitochondrial oxidative metabolism with increased cardiac energy expenditure is not dependent on fatty acid oxidation in pigs

    PubMed Central

    Zhou, Lufang; Cabrera, Marco E; Huang, Hazel; Yuan, Celvie L; Monika, Duda K; Sharma, Naveen; Bian, Fang; Stanley, William C

    2007-01-01

    Steady state concentrations of ATP and ADP in vivo are similar at low and high cardiac workloads; however, the mechanisms that regulate the activation of substrate metabolism and oxidative phosphorylation that supports this stability are poorly understood. We tested the hypotheses that (1) there is parallel activation of mitochondrial and cytosolic dehydrogenases in the transition from low to high workload, which increases NADH/NAD+ ratio in both compartments, and (2) this response does not require an increase in fatty acid oxidation (FAO). Anaesthetized pigs were subjected to either sham treatment, or an abrupt increase in cardiac workload for 5 min with dobutamine infusion and aortic constriction. Myocardial oxygen consumption and FAO were increased 3- and 2-fold, respectively, but ATP and ADP concentrations did not change. NADH-generating pathways were rapidly activated in both the cytosol and mitochondria, as seen in a 40% depletion in glycogen stores, a 3.6-fold activation of pyruvate dehydrogenase, and a 50% increase in tissue NADH/NAD+. Simulations from a multicompartmental computational model of cardiac energy metabolism predicted that parallel activation of glycolysis and mitochondrial metabolism results in an increase in the NADH/NAD+ ratio in both cytosol and mitochondria. FAO was blocked by 75% in a third group of pigs, and a similar increase in and the NAHD/NAD+ ratio was observed. In conclusion, in the transition to a high cardiac workload there is rapid parallel activation of substrate oxidation that results in an increase in the NADH/NAD+ ratio. PMID:17185335

  17. Radiation induced chemical activity at iron and copper oxide surfaces

    NASA Astrophysics Data System (ADS)

    Reiff, Sarah C.

    The radiolysis of three iron oxides, two copper oxides, and aluminum oxide with varying amounts of water were performed using gamma-rays and 5 MeV 4He ions. The adsorbed water on the surfaces was characterized using temperature programmed desorption and diffuse reflectance infrared spectroscopy, which indicated that all of the oxides had chemisorbed water on the surface. Physisorbed water was observed on the Fe2O 3 and Al2O3 surfaces as well. Molecular hydrogen was produced from adsorbed water only on Fe2O3 and Al 2O3, while the other compounds did not show any hydrogen production due to the low amounts of water on the surfaces. Slurries of varying amounts of water were also examined for hydrogen production, and they showed yields that were greater than the yield for bulk water. However, the yields of hydrogen from the copper compounds were much lower than those of the iron suggesting that the copper oxides are relatively inert to radiation induced damage to nearby water. X-ray diffraction measurements did not show any indication of changes to the bulk crystal structure due to radiolysis for any of the oxides. The surfaces of the oxides were analyzed using Raman spectroscopy and X-ray photoelectron spectroscopy (XPS). For the iron samples, FeO and Fe3O4, Raman spectroscopy revealed areas of Fe2O3 had formed following irradiation with He ions. XPS indicated the formation of a new oxygen species on the iron oxide surfaces. Raman spectroscopy of the copper oxides did not reveal any changes in the surface composition, however, XPS measurements showed a decrease in the amount of OH groups on the surface of Cu2O, while for the CuO samples the amount of OH groups were found to increase following radiolysis. Pristine Al2O3 showed the presence of a surface oxyhydroxide layer which was observed to decrease following radiolysis, consistent with the formation of molecular hydrogen.

  18. Demulsification of Redox-Active Emulsions by Chemical Oxidation.

    PubMed

    Takahashi, Yutaka; Koizumi, Nanami; Kondo, Yukishige

    2016-08-01

    This article reports the influence of redox reactions on emulsions of n-octane and an aqueous solution of a ferrocene-containing surfactant (FTMA; (11-ferrocenylundecyl)trimethylammonium bromide). Above a certain surfactant concentration, stable O/W emulsions were formed from an aqueous solution of reduced FTMA; in contrast, mixtures of n-octane and an aqueous solution of oxidized FTMA did not form emulsions at any surfactant concentration. Furthermore, adding an oxidant to the stable O/W emulsions of reduced FTMA led to coalescence of the oil (octane) droplets in the emulsions, and subsequently, the oil and water (aqueous FTMA solution) phases fully separated from the emulsions, i.e., demulsification occurred. Equilibrated interfacial tension measurements indicate that oxidation of the ferrocenyl group in FTMA brings about an increase in the interfacial tension between the octane and aqueous surfactant solution phases. From these results, we concluded that the oxidation of reduced FTMA to oxidized FTMA led to the desorption of surfactant molecules adsorbed at the interface of the octane/aqueous surfactant solution, leading to demulsification. PMID:27402350

  19. Histochemical study of the nitric oxide synthase activity in experimental trichinellosis.

    PubMed

    Hadaś, E; Gustowska, L; Boczoń, K; Janczewska, D

    1999-01-01

    Nitric oxide plays a critical role in a variety of biological activities. It has been nicknamed a "killer" and "mediator" due to its toxic and signalling properties. Apart from its regular physiological function, nitric oxide indirectly participates in infectious diseases. Our report seems to be the first presentation of the nitric oxide synthase participation in the host biochemical defence mechanisms and in morphological transformation of muscle cells in trichinellosis. PMID:16883715

  20. The regioselective hydroformylation of vinylsilanes. A remarkable difference in the selectivity and reactivity of cobalt, rhodium, and iridium catalysts

    SciTech Connect

    Crudden, C.M.; Alper, H.

    1994-06-03

    Rhodium, iridium, and cobalt complexes were evaluated as catalysts for hydroformylation of vinylsilanes. Regioselectivities, product structures, and reaction yields were widely variable for these catalysts.

  1. Activated carbon for aerobic oxidation: Benign approach toward 2-benzoylbenzimidazoles and 2-benzoylbenzoxazoles synthesis

    PubMed Central

    Bao, Kai; Li, Fuqing; Liu, Hanjing; Wang, Zhiwei; Shen, Qirong; Wang, Jian; Zhang, Weige

    2015-01-01

    A general strategy involving a novel and highly efficient aerobic benzylic oxidation promoted by cheap, reusable activated carbon in water is developed. Application of this method has been demonstrated in the benign synthesis of bioactive 2-benzoylbenzimidazoles and 2-benzoylbenzoxazoles derivatives. Furthermore, the activated carbon catalyst could be recovered and reused at least three times without significantly losing its activity. Preliminary research suggests that the oxidation mechanism may involve intermediate hydroperoxidation and that a portion of the final carbonyl product is obtained through a secondary benzylic alcohol intermediate. Finally, theoretical calculations reveal that the oxidation yield is closely associated with the electric density at the benzylic position of the substrate. PMID:26041483

  2. Voluntary locomotor activity mitigates oxidative damage associated with isolation stress in the prairie vole (Microtus ochrogaster)

    PubMed Central

    Fletcher, Kelsey L.; Whitley, Brittany N.; Treidel, Lisa A.; Thompson, David; Williams, Annie; Noguera, Jose C.; Stevenson, Jennie R.; Haussmann, Mark F.

    2015-01-01

    Organismal performance directly depends on an individual's ability to cope with a wide array of physiological challenges. For social animals, social isolation is a stressor that has been shown to increase oxidative stress. Another physiological challenge, routine locomotor activity, has been found to decrease oxidative stress levels. Because we currently do not have a good understanding of how diverse physiological systems like stress and locomotion interact to affect oxidative balance, we studied this interaction in the prairie vole (Microtus ochrogaster). Voles were either pair housed or isolated and within the isolation group, voles either had access to a moving wheel or a stationary wheel. We found that chronic periodic isolation caused increased levels of oxidative stress. However, within the vole group that was able to run voluntarily, longer durations of locomotor activity were associated with less oxidative stress. Our work suggests that individuals who demonstrate increased locomotor activity may be better able to cope with the social stressor of isolation. PMID:26179798

  3. Voluntary locomotor activity mitigates oxidative damage associated with isolation stress in the prairie vole (Microtus ochrogaster).

    PubMed

    Fletcher, Kelsey L; Whitley, Brittany N; Treidel, Lisa A; Thompson, David; Williams, Annie; Noguera, Jose C; Stevenson, Jennie R; Haussmann, Mark F

    2015-07-01

    Organismal performance directly depends on an individual's ability to cope with a wide array of physiological challenges. For social animals, social isolation is a stressor that has been shown to increase oxidative stress. Another physiological challenge, routine locomotor activity, has been found to decrease oxidative stress levels. Because we currently do not have a good understanding of how diverse physiological systems like stress and locomotion interact to affect oxidative balance, we studied this interaction in the prairie vole (Microtus ochrogaster). Voles were either pair housed or isolated and within the isolation group, voles either had access to a moving wheel or a stationary wheel. We found that chronic periodic isolation caused increased levels of oxidative stress. However, within the vole group that was able to run voluntarily, longer durations of locomotor activity were associated with less oxidative stress. Our work suggests that individuals who demonstrate increased locomotor activity may be better able to cope with the social stressor of isolation. PMID:26179798

  4. Arginase activity and nitric oxide levels in patients with obstructive sleep apnea syndrome

    PubMed Central

    Yüksel, Meral; Okur, Hacer Kuzu; Pelin, Zerrin; Öğünç, Ayliz Velioğlu; Öztürk, Levent

    2014-01-01

    OBJECTIVE: Obstructive sleep apnea syndrome is characterized by repetitive obstruction of the upper airways, and it is a risk factor for cardiovascular diseases. There have been several studies demonstrating low levels of nitric oxide in patients with obstructive sleep apnea syndrome compared with healthy controls. In this study, we hypothesized that reduced nitric oxide levels would result in high arginase activity. Arginase reacts with L-arginine and produces urea and L-ornithine, whereas L-arginine is a substrate for nitric oxide synthase, which produces nitric oxide. METHODS: The study group consisted of 51 obstructive sleep apnea syndrome patients (M/F: 43/8; mean age 49±10 years of age) and 15 healthy control subjects (M/F: 13/3; mean age 46±14 years of age). Obstructive sleep apnea syndrome patients were divided into two subgroups based on the presence or absence of cardiovascular disease. Nitric oxide levels and arginase activity were measured via an enzyme-linked immunosorbent assay of serum samples. RESULTS: Serum nitric oxide levels in the control subjects were higher than in the obstructive sleep apnea patients with and without cardiovascular diseases (p<0.05). Arginase activity was significantly higher (p<0.01) in obstructive sleep apnea syndrome patients without cardiovascular diseases compared with the control group. Obstructive sleep apnea syndrome patients with cardiovascular diseases had higher arginase activity than the controls (p<0.001) and the obstructive sleep apnea syndrome patients without cardiovascular diseases (p<0.05). CONCLUSION: Low nitric oxide levels are associated with high arginase activity. The mechanism of nitric oxide depletion in sleep apnea patients suggests that increased arginase activity might reduce the substrate availability of nitric oxide synthase and thus could reduce nitric oxide levels. PMID:24714832

  5. Salidroside Suppresses HUVECs Cell Injury Induced by Oxidative Stress through Activating the Nrf2 Signaling Pathway.

    PubMed

    Zhu, Yao; Zhang, Ya-Jie; Liu, Wei-Wei; Shi, Ai-Wu; Gu, Ning

    2016-01-01

    Oxidative stress plays an important role in the pathogenesis of cardiovascular diseases. Salidroside (SAL), one of the main effective constituents of Rhodiola rosea, has been reported to suppress oxidative stress-induced cardiomyocyte injury and necrosis by promoting transcription of nuclear factor E2-related factor 2 (Nrf2)-regulated genes such as heme oxygenase-1 (HO-1) and NAD(P)H dehydrogenase (quinone1) (NQO1). However, it has not been indicated whether SAL might ameliorate endothelial injury induced by oxidative stress. Here, our study demonstrated that SAL might suppress HUVEC cell injury induced by oxidative stress through activating the Nrf2 signaling pathway. The results of our study indicated that SAL decreased the levels of intercellular reactive oxygen species (ROS) and malondialdehyde (MDA), and improved the activities of superoxide dismutase (SOD) and catalase (CAT), resulting in protective effects against oxidative stress-induced cell damage in HUVECs. It suppressed oxidative stress damage by inducing Nrf2 nuclear translocation and activating the expression of Nrf2-regulated antioxidant enzyme genes such as HO-1 and NQO1 in HUVECs. Knockdown of Nrf2 with siRNA abolished the cytoprotective effects against oxidative stress, decreased the expression of Nrf2, HO-1, and NQO1, and inhibited the nucleus translocation of Nrf2 in HUVECs. This study is the first to demonstrate that SAL suppresses HUVECs cell injury induced by oxidative stress through activating the Nrf2 signaling pathway. PMID:27517893

  6. The chemical origin and catalytic activity of coinage metals: from oxidation to dehydrogenation.

    PubMed

    Syu, Cih-Ying; Yang, Hao-Wen; Hsu, Fu-Hsing; Wang, Jeng-Han

    2014-04-28

    The high oxidation activity of coinage metals (Cu, Ag and Au) has been widely applied in various important reactions, such as oxidation of carbon monoxide, alkenes or alcohols. The catalytic behavior of those inert metals has mostly been attributable to their size effect, the physical effect. In the present study, the chemical effects on their high oxidation activity have been investigated. We mechanistically examine the direct and oxidative dehydrogenation (partial oxidation) reactions of ethanol to acetaldehyde on a series of transition metals (groups 9, 10 and 11) with identical physical characteristics and varied chemical origins using density functional theory (DFT) calculations and electronic structure analyses at the GGA-PW91 level. The energetic results show that coinage metals have much lower activation energies and higher exothermicities for the oxidative dehydrogenation steps although they have higher energy for the direct dehydrogenation reaction. In the electronic structure analyses, coinage metals with saturated d bands can efficiently donate electrons to O* and OH*, or other electronegative adspecies, and better promote their p bands to higher energy levels. The negatively charged O* and OH* with high-lying p bands are responsible for lowering the energies in oxidative steps. The mechanistic understanding well explains the better oxidation activity of coinage metals and provides valuable information on their utilization in other useful applications, for example, the dehydrogenation process. PMID:24626959

  7. Aldosterone Increases Oxidant Stress to Impair Guanylyl Cyclase Activity by Cysteinyl Thiol Oxidation in Vascular Smooth Muscle Cells*S⃞

    PubMed Central

    Maron, Bradley A.; Zhang, Ying-Yi; Handy, Diane E.; Beuve, Annie; Tang, Shiow-Shih; Loscalzo, Joseph; Leopold, Jane A.

    2009-01-01

    Hyperaldosteronism is associated with impaired endothelium-dependent vascular reactivity owing to increased reactive oxygen species and decreased bioavailable nitric oxide (NO·); however, the effects of aldosterone on vasodilatory signaling pathways in vascular smooth muscle cells (VSMC) remain unknown. Soluble guanylyl cyclase (GC) is a heterodimer that is activated by NO· to convert cytosolic GTP to cGMP, a second messenger required for normal VSMC relaxation. Here, we show that aldosterone (10-9-10-7 mol/liter) diminishes GC activity by activating NADPH oxidase in bovine aortic VSMC to increase reactive oxygen species levels and induce oxidative posttranslational modification(s) of Cys-122, a β1-subunit cysteinyl residue demonstrated previously to modulate NO· sensing by GC. In VSMC treated with aldosterone, Western immunoblotting detected evidence of GC β1-subunit disulfide bonding, whereas mass spectrometry analysis of a homologous peptide containing the Cys-122-bearing sequence exposed to conditions of increased oxidant stress confirmed cysteinyl sulfinic acid (m/z 435), sulfonic acid (m/z 443), and disulfide (m/z 836) bond formation. The functional effect of these modifications was examined by transfecting COS-7 cells with wild-type GC or mutant GC containing an alanine substitution at Cys-122 (C122A). Exposure to aldosterone or hydrogen peroxide (H2O2) significantly decreased cGMP levels in cells expressing wild-type GC. In contrast, aldosterone or H2O2 did not influence cGMP levels in cells expressing the mutant C122A GC, confirming that oxidative modification of Cys-122 specifically impairs GC activity. These findings demonstrate that pathophysiologically relevant concentrations of aldosterone increase oxidant stress to convert GC to an NO·-insensitive state, resulting in disruption of normal vasodilatory signaling pathways in VSMC. PMID:19141618

  8. Biocompatibility and charge injection property of iridium film formed by ion beam assisted deposition.

    PubMed

    Lee, In-Seop; Whang, Chung-Nam; Park, Jong-Chul; Lee, Dong-Hee; Seo, Won-Sun

    2003-06-01

    Iridium thin film formed by electron-beam evaporation with simultaneous bombardment of Ar ion beam was evaluated for a stimulating neural electrode. The electrochemical behavior of as-deposited Ir film on Ni-Ti sample was almost identical to bulk Ir by producing much higher open-circuit corrosion potential and much lower anodic current density than the uncoated Ni-Ti in both 1N sulfuric acid and saline solution. The charge injection capability of Ir film was compared with that of Pt electrode currently used mostly as a stimulating neural electrode. The charge density of Pt was small and unchanged with increasing number of activating cycles in 0.1M H(2)SO(4), whilst the Ir film continuously produced increases in charge density. The charge injection density of Ir film in physiological solution was higher for the more activated sample under the identical stimulating condition. Attachment and proliferation with PC12 cells on Ir-coated CP Ti without applying electrical stimulation was similar to the polished CP Ti. A network of neurons and extending axons were formed on Ir film. PMID:12699658

  9. Low activation energy, high-quality oxidation of Si and Ge using neutral beam

    NASA Astrophysics Data System (ADS)

    Wada, Akira; Endo, Kazuhiko; Masahara, Meishoku; Huang, Chi-Hsien; Samukawa, Seiji

    2011-05-01

    In this letter, we investigated the mechanism that forms thin silicon and germanium oxide films with a high-quality interface using a low-temperature neutral beam oxidation (NBO) process. Because NBO has high reactivity due to bombardment by energetic oxygen-neutral beams even at low substrate temperatures, we found that an extremely low activation energy for the atomic layer oxidation reaction could be achieved during the process itself. As a result, there was little suboxide at the interface between the oxide films and the semiconductor, and device characteristics with a high performance were observed.

  10. Shape-dependent bactericidal activity of copper oxide nanoparticle mediated by DNA and membrane damage

    SciTech Connect

    Laha, Dipranjan; Pramanik, Arindam; Laskar, Aparna; Jana, Madhurya; Pramanik, Panchanan; Karmakar, Parimal

    2014-11-15

    Highlights: • Spherical and sheet shaped copper oxide nanoparticles were synthesized. • Physical characterizations of these nanoparticles were done by TEM, DLS, XRD, FTIR. • They showed shape dependent antibacterial activity on different bacterial strain. • They induced both membrane damage and ROS mediated DNA damage in bacteria. - Abstract: In this work, we synthesized spherical and sheet shaped copper oxide nanoparticles and their physical characterizations were done by the X-ray diffraction, fourier transform infrared spectroscopy, transmission electron microscopy and dynamic light scattering. The antibacterial activity of these nanoparticles was determined on both gram positive and gram negative bacterial. Spherical shaped copper oxide nanoparticles showed more antibacterial property on gram positive bacteria where as sheet shaped copper oxide nanoparticles are more active on gram negative bacteria. We also demonstrated that copper oxide nanoparticles produced reactive oxygen species in both gram negative and gram positive bacteria. Furthermore, they induced membrane damage as determined by atomic force microscopy and scanning electron microscopy. Thus production of and membrane damage are major mechanisms of the bactericidal activity of these copper oxide nanoparticles. Finally it was concluded that antibacterial activity of nanoparticles depend on physicochemical properties of copper oxide nanoparticles and bacterial strain.

  11. Microfluidic Electrochemical Sensor for On-line Monitoring of Aerosol Oxidative Activity

    PubMed Central

    Sameenoi, Yupaporn; Koehler, Kirsten; Shapiro, Jeff; Boonsong, Kanokporn; Sun, Yele; Collett, Jeffrey; Volckens, John; Henry, Charles S.

    2012-01-01

    Particulate matter (PM) air pollution has a significant impact on human morbidity and mortality; however, the mechanisms of PM-induced toxicity are poorly defined. A leading hypothesis states that airborne PM induces harm by generating reactive oxygen species (ROS) in and around human tissues, leading to oxidative stress. We report here, a system employing a microfluidic electrochemical sensor coupled directly to a Particle-into-Liquid-Sampler (PILS) system to measure aerosol oxidative activity in an on-line format. The oxidative activity measurement is based on the dithiothreitol assay (DTT assay) where after oxidized by PM, the remaining reduced DTT was analyzed by the microfluidic sensor. The sensor consists of an array of working, reference, and auxiliary electrodes fabricated in a poly(dimethylsiloxane) (PDMS)-based microfluidic device. Cobalt (II) phthalocyanine (CoPC)-modified carbon paste was used as the working electrode material allowing selective detection of reduced DTT. The electrochemical sensor was validated off-line against the traditional DTT assay using filter samples taken from urban environments and biomass burning events. After off-line characterization, the sensor was coupled to a PILS to enable on-line sampling/analysis of aerosol oxidative activity. Urban dust and industrial incinerator ash samples were aerosolized in an aerosol chamber and analyzed for their oxidative activity. The on-line sensor reported DTT consumption rates (oxidative activity) in good correlation with aerosol concentration (R2 from 0.86–.97) with a time-resolution of approximately 3 minutes. PMID:22651886

  12. SIRT1 activating compounds reduce oxidative stress and prevent cell death in neuronal cells

    PubMed Central

    Khan, Reas S.; Fonseca-Kelly, Zoe; Callinan, Catherine; Zuo, Ling; Sachdeva, Mira M.; Shindler, Kenneth S.

    2012-01-01

    Activation of SIRT1, an NAD+-dependent deacetylase, prevents retinal ganglion cell (RGC) loss in optic neuritis, an inflammatory demyelinating optic nerve disease. While SIRT1 deacetylates numerous protein targets, downstream mechanisms of SIRT1 activation mediating this neuroprotective effect are unknown. SIRT1 increases mitochondrial function and reduces oxidative stress in muscle and other cells, and oxidative stress occurs in neuronal degeneration. We examined whether SIRT1 activators reduce oxidative stress and promote mitochondrial function in neuronal cells. Oxidative stress, marked by reactive oxygen species (ROS) accumulation, was induced in RGC-5 cells by serum deprivation, or addition of doxorubicin or hydrogen peroxide, and resulted in significant cell loss. SIRT1 activators resveratrol (RSV) and SRTAW04 reduced ROS levels and promoted cell survival in RGC-5 cells as well as primary RGC cultures. Effects were blocked by SIRT1 siRNA. SIRT1 activators also increased expression of succinate dehydrogenase (SDH), a mitochondrial enzyme, and promoted deacetylation of PGC-1α, a co-enzyme involved in mitochondrial function. Results show SIRT1 activators prevent cell loss by reducing oxidative stress and promoting mitochondrial function in a neuronal cell line. Results suggest SIRT1 activators can mediate neuroprotective effects during optic neuritis by these mechanisms, and they have the potential to preserve neurons in other neurodegenerative diseases that involve oxidative stress. PMID:23293585

  13. Molecular Basis for Enzymatic Sulfite Oxidation -- HOW THREE CONSERVED ACTIVE SITE RESIDUES SHAPE ENZYME ACTIVITY

    SciTech Connect

    Bailey, Susan; Rapson, Trevor; Johnson-Winters, Kayunta; Astashkin, Andrei; Enemark, John; Kappler, Ulrike

    2008-11-10

    Sulfite dehydrogenases (SDHs) catalyze the oxidation and detoxification of sulfite to sulfate, a reaction critical to all forms of life. Sulfite-oxidizing enzymes contain three conserved active site amino acids (Arg-55, His-57, and Tyr-236) that are crucial for catalytic competency. Here we have studied the kinetic and structural effects of two novel and one previously reported substitution (R55M, H57A, Y236F) in these residues on SDH catalysis. Both Arg-55 and His-57 were found to have key roles in substrate binding. An R55M substitution increased Km(sulfite)(app) by 2-3 orders of magnitude, whereas His-57 was required for maintaining a high substrate affinity at low pH when the imidazole ring is fully protonated. This effect may be mediated by interactions of His-57 with Arg-55 that stabilize the position of the Arg-55 side chain or, alternatively, may reflect changes in the protonation state of sulfite. Unlike what is seen for SDHWT and SDHY236F, the catalytic turnover rates of SDHR55M and SDHH57A are relatively insensitive to pH (~;;60 and 200 s-1, respectively). On the structural level, striking kinetic effects appeared to correlate with disorder (in SDHH57A and SDHY236F) or absence of Arg-55 (SDHR55M), suggesting that Arg-55 and the hydrogen bonding interactions it engages in are crucial for substrate binding and catalysis. The structure of SDHR55M has sulfate bound at the active site, a fact that coincides with a significant increase in the inhibitory effect of sulfate in SDHR55M. Thus, Arg-55 also appears to be involved in enabling discrimination between the substrate and product in SDH.

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

    PubMed

    Hung, Chang-Mao

    2009-04-15

    Aqueous solutions of 400-1000 mg/L of ammonia were oxidized in a trickle-bed reactor (TBR) in this study of nanoscale platinum-palladium-rhodium composite oxide catalysts, which were prepared by the co-precipitation of H(2)PtCl(6), Pd(NO(3))(3) and Rh(NO(3))(3). Hardly any of the dissolved ammonia was removed by wet oxidation in the absence of any catalyst, whereas about 99% of the ammonia was reduced during wet oxidation over nanoscale platinum-palladium-rhodium composite oxide catalysts at 503 K in an oxygen partial pressure of 2.0 MPa. A synergistic effect exists in the nanoscale platinum-palladium-rhodium composite structure, which is the material with the highest ammonia reduction activity. The nanometer-sized particles were characterized by TEM, XRD and FTIR. The effect of the initial concentration and reaction temperature on the removal of ammonia from the effluent streams was also studied at a liquid hourly space velocity of under 9 h(-1) in the wet catalytic processes. PMID:18657902

  15. High reactivity of nanosized niobium oxide cluster cations in methane activation: A comparison with vanadium oxides.

    PubMed

    Ding, Xun-Lei; Wang, Dan; Wu, Xiao-Nan; Li, Zi-Yu; Zhao, Yan-Xia; He, Sheng-Gui

    2015-09-28

    The reactions between methane and niobium oxide cluster cations were studied and compared to those employing vanadium oxides. Hydrogen atom abstraction (HAA) reactions were identified over stoichiometric (Nb2O5)N(+) clusters for N as large as 14 with a time-of-flight mass spectrometer. The reactivity of (Nb2O5)N(+) clusters decreases as the N increases, and it is higher than that of (V 2O5)N(+) for N ≥ 4. Theoretical studies were conducted on (Nb2O5)N(+) (N = 2-6) by density functional calculations. HAA reactions on these clusters are all favorable thermodynamically and kinetically. The difference of the reactivity with respect to the cluster size and metal type (Nb vs V) was attributed to thermodynamics, kinetics, the electron capture ability, and the distribution of the unpaired spin density. Nanosized Nb oxide clusters show higher HAA reactivity than V oxides, indicating that niobia may serve as promising catalysts for practical methane conversion. PMID:26429016

  16. High reactivity of nanosized niobium oxide cluster cations in methane activation: A comparison with vanadium oxides

    SciTech Connect

    Ding, Xun-Lei E-mail: chemzyx@iccas.ac.cn; Wang, Dan; Wu, Xiao-Nan; Li, Zi-Yu; Zhao, Yan-Xia E-mail: chemzyx@iccas.ac.cn; He, Sheng-Gui

    2015-09-28

    The reactions between methane and niobium oxide cluster cations were studied and compared to those employing vanadium oxides. Hydrogen atom abstraction (HAA) reactions were identified over stoichiometric (Nb{sub 2}O{sub 5}){sub N}{sup +} clusters for N as large as 14 with a time-of-flight mass spectrometer. The reactivity of (Nb{sub 2}O{sub 5}){sub N}{sup +} clusters decreases as the N increases, and it is higher than that of (V {sub 2}O{sub 5}){sub N}{sup +} for N ≥ 4. Theoretical studies were conducted on (Nb{sub 2}O{sub 5}){sub N}{sup +} (N = 2–6) by density functional calculations. HAA reactions on these clusters are all favorable thermodynamically and kinetically. The difference of the reactivity with respect to the cluster size and metal type (Nb vs V) was attributed to thermodynamics, kinetics, the electron capture ability, and the distribution of the unpaired spin density. Nanosized Nb oxide clusters show higher HAA reactivity than V oxides, indicating that niobia may serve as promising catalysts for practical methane conversion.

  17. Effect of amines as activators on the alcohol-oxidizing activity of pyrroloquinoline quinone-dependent quinoprotein alcohol dehydrogenase.

    PubMed

    Takeda, Kouta; Ishida, Takuya; Igarashi, Kiyohiko; Samejima, Masahiro; Nakamura, Nobuhumi; Ohno, Hiroyuki

    2014-01-01

    Pyrroloquinoline quinone-dependent quinoprotein alcohol dehydrogenases (PQQ-ADH) require ammonia or primary amines as activators in in vitro assays with artificial electron acceptors. We found that PQQ-ADH from Pseudomonas putida KT2440 (PpADH) was activated by various primary amines, di-methylamine, and tri-methylamine. The alcohol oxidation activity of PpADH was strongly enhanced and the affinity for substrates was also improved by pentylamine as an activator. PMID:25229857

  18. Understanding the role of gold nanoparticles in enhancing the catalytic activity of manganese oxides in water oxidation reactions.

    PubMed

    Kuo, Chung-Hao; Li, Weikun; Pahalagedara, Lakshitha; El-Sawy, Abdelhamid M; Kriz, David; Genz, Nina; Guild, Curtis; Ressler, Thorsten; Suib, Steven L; He, Jie

    2015-02-16

    The Earth-abundant and inexpensive manganese oxides (MnOx) have emerged as an intriguing type of catalysts for the water oxidation reaction. However, the overall turnover frequencies of MnOx catalysts are still much lower than that of nanostructured IrO2 and RuO2 catalysts. Herein, we demonstrate that doping MnOx polymorphs with gold nanoparticles (AuNPs) can result in a strong enhancement of catalytic activity for the water oxidation reaction. It is observed that, for the first time, the catalytic activity of MnOx/AuNPs catalysts correlates strongly with the initial valence of the Mn centers. By promoting the formation of Mn(3+) species, a small amount of AuNPs (<5%) in α-MnO2/AuNP catalysts significantly improved the catalytic activity up to 8.2 times in the photochemical and 6 times in the electrochemical system, compared with the activity of pure α-MnO2. PMID:25284796

  19. Oxidative Profile and δ-Aminolevulinate Dehydratase Activity in Healthy Pregnant Women with Iron Supplementation.

    PubMed

    De Lucca, Leidiane; Rodrigues, Fabiane; Jantsch, Letícia B; Neme, Walter S; Gallarreta, Francisco M P; Gonçalves, Thissiane L

    2016-01-01

    An oxidative burst occurs during pregnancy due to the large consumption of oxygen in the tissues and an increase in metabolic demands in response to maternal physiological changes and fetal growth. This study aimed to determine the oxidative profile and activity of δ-aminolevulinate dehydratase (δ-ALA-D) in pregnant women who received iron supplementation. Oxidative stress parameters were evaluated in 25 pregnant women with iron supplementation, 25 pregnant women without supplementation and 25 non-pregnant women. The following oxidative stress parameters were evaluated: thiobarbituric acid reactive substances (TBARS), protein thiol groups (P-SH), non-protein thiol levels (NP-SH), vitamin C levels, catalase and δ-ALA-D activity. Markers of oxidative stress and cell damage, such as TBARS in plasma were significantly higher in pregnant women without supplementation. Levels of P-SH, NP-SH and δ-ALA-D activity were significantly lower in pregnant women without supplementation compared to non-pregnant and pregnant women with supplementation, while vitamin C levels were significantly lower in pregnant women without supplementation when compared to non-pregnant women. The increase in the generation of oxidative species and decrease of antioxidants suggest the loss of physiological oxidative balance during normal pregnancy, which was not observed in pregnant women with iron supplementation, suggesting a protective effect of iron against oxidative damage. PMID:27153075

  20. Oxidative Profile and δ-Aminolevulinate Dehydratase Activity in Healthy Pregnant Women with Iron Supplementation

    PubMed Central

    De Lucca, Leidiane; Rodrigues, Fabiane; Jantsch, Letícia B.; Neme, Walter S.; Gallarreta, Francisco M. P.; Gonçalves, Thissiane L.

    2016-01-01

    An oxidative burst occurs during pregnancy due to the large consumption of oxygen in the tissues and an increase in metabolic demands in response to maternal physiological changes and fetal growth. This study aimed to determine the oxidative profile and activity of δ-aminolevulinate dehydratase (δ-ALA-D) in pregnant women who received iron supplementation. Oxidative stress parameters were evaluated in 25 pregnant women with iron supplementation, 25 pregnant women without supplementation and 25 non-pregnant women. The following oxidative stress parameters were evaluated: thiobarbituric acid reactive substances (TBARS), protein thiol groups (P-SH), non-protein thiol levels (NP-SH), vitamin C levels, catalase and δ-ALA-D activity. Markers of oxidative stress and cell damage, such as TBARS in plasma were significantly higher in pregnant women without supplementation. Levels of P-SH, NP-SH and δ-ALA-D activity were significantly lower in pregnant women without supplementation compared to non-pregnant and pregnant women with supplementation, while vitamin C levels were significantly lower in pregnant women without supplementation when compared to non-pregnant women. The increase in the generation of oxidative species and decrease of antioxidants suggest the loss of physiological oxidative balance during normal pregnancy, which was not observed in pregnant women with iron supplementation, suggesting a protective effect of iron against oxidative damage. PMID:27153075

  1. Application of Silver and Silver Oxide Nanoparticles Impregnated on Activated Carbon to the Degradation of Bromate.

    PubMed

    Choi, J S; Lee, H; Park, Y K; Kim, S J; Kim, B J; An, K H; Kim, B H; Jung, S C

    2016-05-01

    Silver and silver oxide nanoparticles were impregnated on the surface of powdered activated carbon (PAC) using a single-step liquid phase plasma (LPP) method. Spherical silver and silver oxide nanoparticles of 20 to 100 nm size were dipersed evenly on the surface of PAC. The impregnated PAC exhibited a higher activity for the decomposition of bromate than bare PAC. The XPS, Raman and EDX analyses showed that the Ag/PAC composites synthesized by the LPP process. PMID:27483780

  2. The active sites of supported silver particle catalysts in formaldehyde oxidation.

    PubMed

    Chen, Yaxin; Huang, Zhiwei; Zhou, Meijuan; Hu, Pingping; Du, Chengtian; Kong, Lingdong; Chen, Jianmin; Tang, Xingfu

    2016-08-01

    Surface silver atoms with upshifted d-orbitals are identified as the catalytically active sites in formaldehyde oxidation by correlating their activity with the number of surface silver atoms, and the degree of the d-orbital upshift governs the catalytic performance of the active sites. PMID:27406403

  3. A Microfluidic Paper-Based Analytical Device (μPAD) for Aerosol Oxidative Activity

    PubMed Central

    Sameenoi, Yupaporn; Panymeesamer, Pantila; Supalakorn, Natcha; Koehler, Kirsten; Chailapakul, Orawon; Henry, Charles S.; Volckens, John

    2013-01-01

    Human exposure to particulate matter (PM) air pollution has been linked with respiratory, cardiovascular, and neurodegenerative diseases, in addition to various cancers. Consistent among all of these associations is the hypothesis that PM induces inflammation and oxidative stress in the affected tissue. Consequently, a variety of assays have been developed to quantify the oxidative activity of PM as a means to characterize its ability to induced oxidative stress. The vast majority of these assays rely on high-volume, fixed-location sampling methods due to limitations in assay sensitivity and detection limit. As a result, our understanding of how personal exposure contributes to the intake of oxidative air pollution is limited. To further this understanding, we present a microfluidic paper-based analytical device (μPAD) for measuring PM oxidative activity on filters collected by personal sampling. The μPAD is inexpensive to fabricate and provides fast and sensitive analysis of aerosol oxidative activity. The oxidative activity measurement is based on the dithiothreitol assay (DTT assay), uses colorimetric detection, and can be completed in the field within 30 min following sample collection. The μPAD assay was validated against the traditional DTT assay using 13 extracted aerosol samples including urban aerosols, biomass burning PM, cigarette smoke and incense smoke. The results showed no significant differences in DTT consumption rate measured by the two methods. To demonstrate the utility of the approach, personal samples were collected to estimate human exposures to PM from indoor air, outdoor air on a clean day, and outdoor air on a wildfire-impacted day in Fort Collins, CO. Filter samples collected on the wildfire day gave the highest oxidative activity on a mass normalized basis, whereas typical ambient background air showed the lowest oxidative activity. PMID:23227907

  4. Surface activity of poly(ethylene oxide)-block-poly(propylene oxide)-block-poly(ethylene oxide) copolymers

    SciTech Connect

    Alexandridis, P.; Athanassiou, V.; Fukuda, Shinya; Hatton, T.A. )

    1994-08-01

    The surface tension of aqueous solutions of seven poly(ethylene oxide)-block-poly(propylene oxide)-block-poly(ethylene oxide) (PEO-PPO-PEO) Pluronic copolymers, covering a wide range of molecular weights (3400-14600) and PPO/PEO ratios (0.19-1.79), was determined over the 10[sup [minus]5]-10% w/v concentration range, at two temperatures (25 and 35[degree]C). Two breaks (changes in slope) were observed in the surface tension vs log concentration curve for most of the copolymers. The low-concentration break, occurring at bulk copolymer concentrations of approximately 10[sup [minus]3]%, is believed to originate from rearrangement of the copolymer molecules on the surface at complete coverage of the air/water interface. The breaks at the high-concentration part of the surface tension curve occurred at concentrations that correspond to the critical micellization concentration values as determined by a dye solubilization technique. The surface area per copolymer molecule, A, increased as a function of the number of EO segments, N[sub EO], obeying a scaling law (A [approx] N[sub EO][sup 1/2]) similar to that of lower molecular weight C[sub i]E[sub j] nonionic surfactants. 56 refs., 6 figs., 2 tabs.

  5. Air Oxidation of Activated Carbon to Synthesize a Biomimetic Catalyst for Hydrolysis of Cellulose.

    PubMed

    Shrotri, Abhijit; Kobayashi, Hirokazu; Fukuoka, Atsushi

    2016-06-01

    Oxygenated carbon catalyzes the hydrolysis of cellulose present in lignocellulosic biomass by utilizing the weakly acidic functional groups on its surface. Here we report the synthesis of a biomimetic carbon catalyst by simple and economical air-oxidation of a commercially available activated carbon. Air- oxidation at 450-500 °C introduced 2000-2400 μmol g(-1) of oxygenated functional groups on the material with minor changes in the textural properties. Selectivity towards the formation of carboxylic groups on the catalyst surface increased with the increase in oxidation temperature. The degree of oxidation on carbon catalyst was found to be proportional to its activity for hydrolysis of cellulose. The hydrolysis of eucalyptus in the presence of carbon oxidized at 475 °C afforded glucose yield of 77 % and xylose yield of 67 %. PMID:27115288

  6. First stages of silicon oxidation with the activation relaxation technique

    NASA Astrophysics Data System (ADS)

    Ganster, Patrick; Béland, Laurent Karim; Mousseau, Normand

    2012-08-01

    Using the art nouveau method, we study the initial stages of silicon oxide formation. After validating the method's parameters with the characterization of point defects diffusion mechanisms in pure Stillinger-Weber silicon, which allows us to recover some known results and to detail vacancy and self-interstitial diffusion paths, the method is applied onto a system composed of an oxygen layer deposited on a silicon substrate. We observe the oxygen atoms as they move rapidly into the substrate. From these art nouveau simulations, we extract the energy barriers of elementary mechanisms involving oxygen atoms and leading to the formation of an amorphouslike silicon oxide. We show that the kinetics of formation can be understood in terms of the energy barriers between various coordination environments.

  7. Cysteamine Modulates Oxidative Stress and Blocks Myofibroblast Activity in CKD

    PubMed Central

    Bahrami, Nadia M.; Ren, Shuyu; Pasichnyk, Katie; Williams, Juliana M.; Gangoiti, Jon A.; Lopez-Guisa, Jesus M.; Yamaguchi, Ikuyo; Barshop, Bruce A.; Duffield, Jeremy S.; Eddy, Allison A.

    2014-01-01

    Therapy to slow the relentless expansion of interstitial extracellular matrix that leads to renal functional decline in patients with CKD is currently lacking. Because chronic kidney injury increases tissue oxidative stress, we evaluated the antifibrotic efficacy of cysteamine bitartrate, an antioxidant therapy for patients with nephropathic cystinosis, in a mouse model of unilateral ureteral obstruction. Fresh cysteamine (600 mg/kg) was added to drinking water daily beginning on the day of surgery, and outcomes were assessed on days 7, 14, and 21 after surgery. Plasma cysteamine levels showed diurnal variation, with peak levels similar to those observed in patients with cystinosis. In cysteamine-treated mice, fibrosis severity decreased significantly at 14 and 21 days after unilateral ureteral obstruction, and renal oxidized protein levels decreased at each time point, suggesting reduced oxidative stress. Consistent with these results, treatment of cultured macrophages with cysteamine reduced cellular generation of reactive oxygen species. Furthermore, treatment with cysteamine reduced α-smooth muscle actin–positive interstitial myofibroblast proliferation and mRNA levels of extracellular matrix proteins in mice and attenuated myofibroblast differentiation and proliferation in vitro, but did not augment TGF-β signaling. In a study of renal ischemia reperfusion, cysteamine therapy initiated 10 days after injury and continued for 14 days decreased renal fibrosis by 40%. Taken together, these data suggest previously unrecognized antifibrotic actions of cysteamine via TGF-β–independent mechanisms that include oxidative stress reduction and attenuation of the myofibroblast response to kidney injury and support further investigation into the potential benefit of cysteamine therapy in the treatment of CKD. PMID:24009239

  8. Oxidative stress is required for mechanical ventilation-induced protease activation in the diaphragm

    PubMed Central

    Smuder, Ashley J.; Wu, Min; Hudson, Matthew B.; Nelson, W. Bradley; Powers, Scott K.

    2010-01-01

    Prolonged mechanical ventilation (MV) results in diaphragmatic weakness due to fiber atrophy and contractile dysfunction. Recent work reveals that activation of the proteases calpain and caspase-3 is required for MV-induced diaphragmatic atrophy and contractile dysfunction. However, the mechanism(s) responsible for activation of these proteases remains unknown. To address this issue, we tested the hypothesis that oxidative stress is essential for the activation of calpain and caspase-3 in the diaphragm during MV. Cause-and-effect was established by prevention of MV-induced diaphragmatic oxidative stress using the antioxidant Trolox. Treatment of animals with Trolox prevented MV-induced protein oxidation and lipid peroxidation in the diaphragm. Importantly, the Trolox-mediated protection from MV-induced oxidative stress prevented the activation of calpain and caspase-3 in the diaphragm during MV. Furthermore, the avoidance of MV-induced oxidative stress not only averted the activation of these proteases but also rescued the diaphragm from MV-induced diaphragmatic myofiber atrophy and contractile dysfunction. Collectively, these findings support the prediction that oxidative stress is required for MV-induced activation of calpain and caspase-3 in the diaphragm and are consistent with the concept that antioxidant therapy can retard MV-induced diaphragmatic weakness. PMID:20203072

  9. Templated electrodeposition and photocatalytic activity of cuprous oxide nanorod arrays.

    PubMed

    Haynes, Keith M; Perry, Collin M; Rivas, Marlene; Golden, Teresa D; Bazan, Antony; Quintana, Maria; Nesterov, Vladimir N; Berhe, Seare A; Rodríguez, Juan; Estrada, Walter; Youngblood, W Justin

    2015-01-14

    Cuprous oxide (Cu2O) nanorod arrays have been prepared via a novel templated electrodeposition process and were characterized for their photocatalytic behavior in nonaqueous photoelectrochemical cells. Zinc oxide (ZnO) nanorod films serve as sacrificial templates for the in situ formation of polymer nanopore membranes on transparent conductive oxide substrates. Nitrocellulose and poly(lactic acid) are effective membrane-forming polymers that exhibit different modes of template formation, with nitrocellulose forming conformal coatings on the ZnO surface while poly(lactic acid) acts as an amorphous pore-filling material. Robust template formation is sensitive to the seeding method used to prepare the precursor ZnO nanorod films. Photoelectrochemical cells prepared from electrodeposited Cu2O films using methyl viologen as a redox shuttle in acetonitrile electrolyte exhibit significant charge recombination that can be partially suppressed by a combination of surface passivation methods. Surface-passivated nanostructured Cu2O films show enhanced photocurrent relative to planar electrodeposited Cu2O films of similar thickness. We have obtained the highest photocurrent ever reported for electrodeposited Cu2O in a nonaqueous photoelectrochemical cell. PMID:25455203

  10. Activation of the hypothalamic-pituitary-adrenal stress axis induces cellular oxidative stress

    PubMed Central

    Spiers, Jereme G.; Chen, Hsiao-Jou Cortina; Sernia, Conrad; Lavidis, Nickolas A.

    2015-01-01

    Glucocorticoids released from the adrenal gland in response to stress-induced activation of the hypothalamic-pituitary-adrenal (HPA) axis induce activity in the cellular reduction-oxidation (redox) system. The redox system is a ubiquitous chemical mechanism allowing the transfer of electrons between donor/acceptors and target molecules during oxidative phosphorylation while simultaneously maintaining the overall cellular environment in a reduced state. The objective of this review is to present an overview of the current literature discussing the link between HPA axis-derived glucocorticoids and increased oxidative stress, particularly focussing on the redox changes observed in the hippocampus following glucocorticoid exposure. PMID:25646076

  11. Enantioselective hydrogenation. III. Methyl pyruvate hydrogenation catalyzed by alkaloid-modified iridium

    SciTech Connect

    Simons, K.E.; Johnston, P.; Plum, H.; Wells, P.B.; Ibbotson, A.

    1994-12-01

    Enantioselective hydrogenation of methyl pyruvate, MeCOCOOMe to methyl lactate, MeCH(OH)COOMe, is catalyzed in solution at room temperature by supported iridium catalysts modified with cinchona alkaloids. Modification with cinchonidine or quinine yields R-lactate in excess, whereas modification with cinchonine or quinidine favors S-lactate formation. Ir/SiO{sub 2} catalysts (20%) calcined at 393 to 573 K and reduced at 523 to 593 K were highly active for racemic hydrogenation in the absence of a modifier (rates typically 1.8 mol h{sup -1} g{sub cat}{sup -1}) and were comparably active when modified with cinchonidine but gave an enantiomeric excess of about 30%. Use of higher calcination or reduction temperatures led to substantially inferior activity and selectivity. The high rates recorded for both racemic and enantioselective reactions are dependent on the catalysts being activated before use by a procedure involving exposure of the catalyst to air after the initial reduction. Use of a Cl-free precursor gave an Ir/SiO{sub 2} catalyst (20%) of superior activity but inferior enantioselectivity. Ir/CaCO{sub 3} (5%) was more active for racemic hydrogenation than for enantioselective hydrogenation, but provided the highest value of the enantiomeric excess 39%. Kinematics of reaction are reported. Exchange of H for D in 10,11-dihydrocinchonidine at room temperature over Ir/CaCO{sub 3} occurred in the quinoline moiety but not in the quinuclidine ring system, indicating that the alkaloid was adsorbed to the Ir surface via the interaction of its {pi}-electron system. For both silica-supported and calcium carbonate-supported Ir, the presence of chloride ion in the catalyst was advantageous for the achievement of enantioselectivity. 25 refs., 2 figs., 3 tabs.

  12. In Vitro Oxidation of Collagen Promotes the Formation of Advanced Oxidation Protein Products and the Activation of Human Neutrophils.

    PubMed

    Bochi, Guilherme Vargas; Torbitz, Vanessa Dorneles; de Campos, Luízi Prestes; Sangoi, Manuela Borges; Fernandes, Natieli Flores; Gomes, Patrícia; Moretto, Maria Beatriz; Barbisan, Fernanda; da Cruz, Ivana Beatrice Mânica; Moresco, Rafael Noal

    2016-04-01

    The accumulation of advanced oxidation protein products (AOPPs) has been linked to several pathological conditions. Here, we investigated collagen as a potential source for AOPP formation and determined the effects of hypochlorous acid (HOCl)-treated collagen (collagen-AOPPs) on human neutrophil activity. We also assessed whether alpha-tocopherol could counteract these effects. Exposure to HOCl increased the levels of collagen-AOPPs. Collagen-AOPPs also stimulated the production of AOPPs, nitric oxide (NO), superoxide radicals (O2 (-)), and HOCl by neutrophils. Collagen-AOPPs induced apoptosis and decreased the number of viable cells. Alpha-tocopherol prevented the formation of collagen-AOPPs, strongly inhibited the collagen-AOPP-induced production of O2 (-) and HOCl, and increased the viability of neutrophils. Our results suggest that collagen is an important protein that interacts with HOCl to form AOPPs, and consequently, collagen-AOPP formation is related to human neutrophil activation and cell death. PMID:26920846

  13. Method of treating intermetallic alloy hydrogenation/oxidation catalysts for improved impurity poisoning resistance, regeneration and increased activity

    DOEpatents

    Wright, Randy B.

    1992-01-01

    Alternate, successive high temperature oxidation and reduction treatments, in either order, of intermetallic alloy hydrogenation and intermetallic alloy oxidation catalysts unexpectedly improves the impurity poisoning resistance, regeneration capacity and/or activity of the catalysts. The particular alloy, and the final high temperature treatment given alloy (oxidation or reduction) will be chosen to correspond to the function of the catalyst (oxidation or hydrogenation).

  14. Screening SIRT1 Activators from Medicinal Plants as Bioactive Compounds against Oxidative Damage in Mitochondrial Function

    PubMed Central

    Wang, Yi; Liang, Xinying; Chen, Yaqi; Zhao, Xiaoping

    2016-01-01

    Sirtuin type 1 (SIRT1) belongs to the family of NAD+ dependent histone deacetylases and plays a critical role in cellular metabolism and response to oxidative stress. Traditional Chinese medicines (TCMs), as an important part of natural products, have been reported to exert protective effect against oxidative stress in mitochondria. In this study, we screened SIRT1 activators from TCMs and investigated their activities against mitochondrial damage. 19 activators were found in total by in vitro SIRT1 activity assay. Among those active compounds, four compounds, ginsenoside Rb2, ginsenoside F1, ginsenoside Rc, and schisandrin A, were further studied to validate the SIRT1-activation effects by liquid chromatography-mass spectrometry and confirm their activities against oxidative damage in H9c2 cardiomyocytes exposed to tert-butyl hydroperoxide (t-BHP). The results showed that those compounds enhanced the deacetylated activity of SIRT1, increased ATP content, and inhibited intracellular ROS formation as well as regulating the activity of Mn-SOD. These SIRT1 activators also showed moderate protective effects on mitochondrial function in t-BHP cells by recovering oxygen consumption and increasing mitochondrial DNA content. Our results suggested that those compounds from TCMs attenuated oxidative stress-induced mitochondrial damage in cardiomyocytes through activation of SIRT1. PMID:26981165

  15. Triiodothyronine activates lactate oxidation without impairing fatty acid oxidation and improves weaning from extracorporeal membrane oxygenation

    SciTech Connect

    Kajimoto, Masaki; Ledee, Dolena R.; Xu, Chun; Kajimoto, Hidemi; Isern, Nancy G.; Portman, Michael A.

    2014-01-01

    Background: Extracorporeal membrane oxygenation (ECMO) provides a rescue for children with severe cardiac failure. We previously showed that triiodothyronine (T3) improves cardiac function by modulating pyruvate oxidation during weaning. This study was focused on fatty acid (FA) metabolism modulated by T3 for weaning from ECMO after cardiac injury. Methods: Nineteen immature piglets (9.1-15.3 kg) were separated into 3 groups with ECMO (6.5 hours) and wean: normal circulation (Group-C);transient coronary occlusion (10 minutes) followed by ECMO (Group-IR); and IR with T3 supplementation (Group-IR-T3). 13-Carbon labeled lactate, medium-chain and long-chain FAs were infused as oxidative substrates. Substrate fractional contribution to the citric acid cycle (FC) was analyzed by 13-Carbon nuclear magnetic resonance. Results: ECMO depressed circulating T3 levels to 40% baseline at 4 hours and were restored in Group-IR-T3. Group-IR decreased cardiac power, which was not fully restorable and 2 pigs were lost because of weaning failure. Group-IR also depressed FC-lactate, while the excellent contractile function and energy efficiency in Group-IR-T3 occurred along with a marked FC-lactate increase and [ATP]/[ADP] without either decreasing FC-FAs or elevating myocardial oxygen consumption over Group-C or -IR. Conclusions: T3 releases inhibition of lactate oxidation following ischemia-reperfusion injury without impairing FA oxidation. These findings indicate that T3 depression during ECMO is maladaptive, and that restoring levels improves metabolic flux and enhances contractile function during weaning.

  16. Solution-processable phosphorescence based on iridium-cored small molecules with the trifluoromethyl group

    NASA Astrophysics Data System (ADS)

    Zhang, Wenguan; He, Zhiqun; Wang, Yongsheng; Zhao, Shengmin

    2015-04-01

    A novel cyclometallated ligand 2-(4-(2‧-ethylhexyloxy)phenyl)-5-trifluoromethyl-pyridine (EHO-5CF3-ppy) was synthesized, and two solution-processable iridium complexes bis[2-(4-(2‧-ethylhexyloxy)phenyl)-5-trifluoromethylpyridinto-C3, N] iridium (acetylacetonate) (EHO-5CF3-ppy)2Ir(acac) (5) and bis[2-(4-(2‧-ethylhexyl-oxy)phenyl)-5-trifluoromethylpyridinto-C3, N] iridium (2-picolinic acid) (EHO-5CF3-ppy)2Ir(pic) (6) were afforded. Trifluoromethyl and dendritic ethylhexyloxy group were incorporated into iridium ligands to tune luminescent color, to reduce luminescence quenching and to improve the solution-processable property. Photoluminescent spectra of 5 and 6 in tetrahydrofuran peaked at around 540 and 523 nm. Electrophosphorescent devices were fabricated using 5 and 6 as dopant emitters (2%), which exhibited electroluminescent (EL) peaks at 536 and 524 nm, and current efficiencies of 10.4 and 16.7 cd/A, respectively. With the concentration of iridium complexes increasing to 8%, the main EL peak showed a 4 nm of red shift and a distinct shoulder peak occurred at 583 nm for 5 or 560 nm for 6, respectively. Maximum external quantum efficiencies of the devices at the concentration of 2% and 8% were 2.8% and 4.2% for 5, 4.7% and 4.8% for 6. These indicated that 5 and 6 were efficient solution-processable emitters.

  17. The Boreas concept for imaging polar winds from the Iridium-NEXT constellation

    NASA Astrophysics Data System (ADS)

    Chesters, Dennis; Riishojgaard, Lars Peter

    2008-08-01

    The Iridium communications satellite constellation is a swarm of 66 LEO satellites in 6 pole-crossing orbits. Iridium LLC plans a NEXT generation to be launched 2013-16, and has invited secondary "bolt and go" payloads from Earthobserving agencies. A swarm of infrared imagers on Iridium-NEXT could track water vapor and clouds to estimate the unobserved winds above the 55-60 degree latitude limit of geosynchronous satellite imagery. This kind of polar overpass data has been demonstrated to significantly improve medium-range weather forecasts by tracking water vapor features at 6.7 microns in successive images near the pole from NASA's MODIS instruments. A "Boreas" instrument design is proposed for a push-broom imager combining two miniature sensors: uncooled microbolometric cameras gathering 4- band infrared radiometry, and small star trackers providing attitude information. An autonomous instrument package has been designed with low mass, power, and data rate. The "Boreas" instrument would use the Iridium constellation itself to relay the raw imagery from 3 successive images to ground stations that would navigate the data and extract wind vectors. Wind vectors could be generated automatically for the polar caps every few hours, and delivered for assimilation into numerical weather models during Iridium-NEXT operations, during 2016-2030.

  18. The high-temperature work function of sintered dilute solution tungsten-iridium alloys

    SciTech Connect

    D'Cruz, L.A.; Bosch, D.R.; Jacobsen, D.L. )

    1993-02-01

    The effect of transition element additives molybdenum, rhenium, iridium, and osmium on the effective work function of tungsten has been the focus of thermionics research for several years. In this study, iridium-added tungsten powder mixtures were cold compacted and sintered to produce a range of tungsten-iridium electrodes. An electron emission study was subsequently carried out to evaluate the work function behavior of the consolidated alloys. The work function was obtained from measurements of the current emitted from the electrode surface under ultrahigh vacuum conditions in the temperature range of 1,800 to 2,500 K using a vacuum emission vehicle (VEV). The data show that the magnitude of the work function in these alloys varied with temperature. Microstructural evaluation of the alloys indicated that the tested surfaces displayed accentuated thermal etching of the grain boundaries together with the fact that the final grain sizes in the sintered alloys were three to five times smaller than those found in equivalent arc-melted alloys that were studied in earlier work. Scanning electron microscopy (SEM) micrographs of the tested surfaces of the sintered alloys containing the highest iridium levels ([approximately]2 wt%) show a high level of structural distortion, particularly in the vicinity of grain boundaries and corners. The extent of these distortions was found to vary with the iridium content, i.e., the W-IR3M and W-IR2M. The samples with compositions lower than 0.5 wt% Ir were virtually devoid of distortions.

  19. Morin modulates the oxidative stress-induced NF-kappaB pathway through its anti-oxidant activity.

    PubMed

    Kim, Ji Min; Lee, Eun Kyeong; Park, Gwangli; Kim, Mi Kyung; Yokozawa, Takako; Yu, Byung Pal; Chung, Hae Young

    2010-04-01

    Morin is a flavone that has anti-inflammatory effects through a mechanism that is not well understood. Based on the extreme sensitive nature of the transcription factor, NF-kB to redox change, it is postulated that morin's anti-NF-kappaB activation likely depends on its ability to scavenge excessive reactive species [RS]. The present study assessed the extent of morin's ability to modulate RS-induced NF-kappaB activation through its scavenging activity. Results indicate that morin neutralized RS in vitro and inhibited t-BHP-induced RS generation. It also examined morin for suppressed redox-sensitive transcription factor NF-kappaB activation via reduced DNA binding activity, I kappaB alpha phosphorylation and p65/p50 nuclear translocation. The more important finding was that suppression of the NF-kappaB cascade by morin was modulated through the ERK and p38 MAPKs signal transduction pathways in endothelial cells. As a consequence, morin's anti-oxidant effect extended expression level of NF-kappaB dependent pro-inflammatory genes, thereby reducing COX-2, iNOS and 5-LOX. The data indicate that morin has strong anti-oxidative power against RS-induced NF-kappaB modulation through the ERK and p38 MAPKs signalling pathways by its RS scavenging activity. The significance of the current study is the new revelation that morin may have potential as an effective anti-inflammatory therapeutic agent. PMID:20187708

  20. Coumarin-appended phosphorescent cyclometalated iridium(iii) complexes as mitochondria-targeted theranostic anticancer agents.

    PubMed

    Ye, Rui-Rong; Tan, Cai-Ping; Ji, Liang-Nian; Mao, Zong-Wan

    2016-08-16

    Theranostic anticancer agents incorporating anticancer properties with capabilities for real-time treatment assessment are appealing candidates for chemotherapy. The design of mitochondria-targeted cytotoxic drugs represents a promising approach to target tumors selectively and overcome resistance to current anticancer therapies. In this work, three coumarin-appended phosphorescent cyclometalated iridium(iii) complexes 1-3 have been explored as mitochondria-targeted theranostic anticancer agents. These complexes display rich photophysical properties, which facilitate the study of their intracellular fate. All three complexes can specifically target mitochondria and show much higher antiproliferative activities than cisplatin against various cancer cells including cisplatin-resistant cells. 1-3 can penetrate into human cervical carcinoma (HeLa) cells quickly and efficiently, and they can carry out theranostic functions by simultaneously inducing and monitoring the morphological changes in mitochondria. Mechanism studies show that 1-3 exert their anticancer efficacy by initiating a cascade of events related to mitochondrial dysfunction. Genome-wide transcriptional and Connectivity Map analyses reveal that the cytotoxicity of complex 3 is associated with pathways involved in mitochondrial dysfunction and apoptosis. PMID:27139504

  1. Iridium profile for 10 million years across the Cretaceous-Tertiary boundary at Gubbio (Italy)

    NASA Technical Reports Server (NTRS)

    Alvarez, Walter; Asaro, Frank; Montanari, Alessandro

    1990-01-01

    The iridium anomaly at the Cretaceous-Tertiary (KT) boundary was discovered in the pelagic limestone sequence at Gubbio on the basis of 12 samples analyzed by neutron activation analysis (NAA) and was interpreted as indicating impact of a large extraterrestrial object at exactly the time of the KT mass extinction. Continuing controversy over the shape of the Ir profile at the Gubbio KT boundary and its interpretation called for a more detailed follow-up study. Analysis of a 57-meter-thick, 10-million-year-old part of the Gubbio sequence using improved NAA techniques revealed that there is only one Ir anomaly at the KT boundary, but this anomaly shows an intricate fine structure, the origin of which cannot yet be entirely explained. The KT Ir anomaly peaks in a 1-centimeter-thick clay layer, where the average Ir concentration is 3000 parts per trillion (ppt); this peak is flanked by tails with Ir concentrations of 20 to 80 ppt that rise above a background of 12 to 13 ppt. The fine structure of the tails is probably due in part to lateral reworking, diffusion, burrowing, and perhaps Milankovitch cyclicity.

  2. CO2 hydrogenation catalyzed by iridium complexes with a proton-responsive ligand

    SciTech Connect

    Onishi, Naoya; Xu, Shaoan; Manaka, Yuichi; Suna, Yuki; Wang, Wan -Hui; Muckerman, James T.; Fujita, Etsuko; Himeda, Yuichiro

    2015-02-18

    In this study, the catalytic cycle for the production of formic acid by CO₂ hydrogenation and the reverse reaction has received renewed attention because they are viewed as offering a viable scheme for hydrogen storage and release. In this Forum Article, CO₂ hydrogenation catalyzed by iridium complexes bearing N^N-bidentate ligands is reported. We describe how a ligand containing hydroxyl groups as proton-responsive substituents enhances catalytic performance by an electronic effect of the oxyanions and a pendent-base effect through secondary coordination sphere interaction. In particular, [(Cp*IrCl)₂(TH2BPM)]Cl₂ (Cp* = pentamethyl cyclopentadienyl, TH2BPM = 4,4',6,6'-tetrahydroxy-2,2'-bipyrimidine) promotes enormously the catalytic hydrogenation of CO₂ by these synergistic effects under atmospheric pressure and at room temperature. Additionally, newly designed complexes with azole-type ligands are applied to CO₂ hydrogenation. The catalytic efficiencies of the azole-type complexes are much higher than that of the unsubstituted bipyridine complex [Cp*Ir(bpy)(OH₂)]SO₄. Furthermore, the introduction of one or more hydroxyl groups into ligands such as 2-pyrazolyl-6-hydroxypyridine, 2-pyrazolyl-4,6-dihydroxyl pyrimidine, and 4-pyrazolyl-2,6-dihydroxyl pyrimidine enhanced catalytic activity. It is clear that the incorporation of electron-donating hydroxyl groups into proton-responsive ligands is effective for promoting the hydrogenation of CO₂.

  3. CO2 hydrogenation catalyzed by iridium complexes with a proton-responsive ligand

    DOE PAGESBeta

    Onishi, Naoya; Xu, Shaoan; Manaka, Yuichi; Suna, Yuki; Wang, Wan -Hui; Muckerman, James T.; Fujita, Etsuko; Himeda, Yuichiro

    2015-02-18

    In this study, the catalytic cycle for the production of formic acid by CO₂ hydrogenation and the reverse reaction has received renewed attention because they are viewed as offering a viable scheme for hydrogen storage and release. In this Forum Article, CO₂ hydrogenation catalyzed by iridium complexes bearing N^N-bidentate ligands is reported. We describe how a ligand containing hydroxyl groups as proton-responsive substituents enhances catalytic performance by an electronic effect of the oxyanions and a pendent-base effect through secondary coordination sphere interaction. In particular, [(Cp*IrCl)₂(TH2BPM)]Cl₂ (Cp* = pentamethyl cyclopentadienyl, TH2BPM = 4,4',6,6'-tetrahydroxy-2,2'-bipyrimidine) promotes enormously the catalytic hydrogenation of CO₂ bymore » these synergistic effects under atmospheric pressure and at room temperature. Additionally, newly designed complexes with azole-type ligands are applied to CO₂ hydrogenation. The catalytic efficiencies of the azole-type complexes are much higher than that of the unsubstituted bipyridine complex [Cp*Ir(bpy)(OH₂)]SO₄. Furthermore, the introduction of one or more hydroxyl groups into ligands such as 2-pyrazolyl-6-hydroxypyridine, 2-pyrazolyl-4,6-dihydroxyl pyrimidine, and 4-pyrazolyl-2,6-dihydroxyl pyrimidine enhanced catalytic activity. It is clear that the incorporation of electron-donating hydroxyl groups into proton-responsive ligands is effective for promoting the hydrogenation of CO₂.« less

  4. Active site diversification of P450cam with indole generates catalysts for benzylic oxidation reactions

    PubMed Central

    Herter, Susanne; Kranz, David C; Turner, Nicholas J

    2015-01-01

    Summary Cytochrome P450 monooxygenases are useful biocatalysts for C–H activation, and there is a need to expand the range of these enzymes beyond what is naturally available. A panel of 93 variants of active self-sufficient P450cam[Tyr96Phe]-RhFRed fusion enzymes with a broad diversity in active site amino acids was developed by screening a large mutant library of 16,500 clones using a simple, highly sensitive colony-based colorimetric screen against indole. These mutants showed distinct fingerprints of activity not only when screened in oxidations of substituted indoles but also for unrelated oxidations such as benzylic hydroxylations. PMID:26664590

  5. Arginase activity in mitochondria - An interfering factor in nitric oxide synthase activity assays

    SciTech Connect

    Venkatakrishnan, Priya; Nakayasu, Ernesto S.; Almeida, Igor C.; Miller, R.T.

    2010-04-09

    Previously, in tightly controlled studies, using three independent, yet complementary techniques, we refuted the claim that a mitochondrial nitric oxide synthase (mtNOS) isoform exists within pure, rat liver mitochondria (MT). Of those techniques, the NOS-catalyzed [{sup 14}C]-L-arginine to [{sup 14}C]-L-citrulline conversion assay (NOS assay) with MT samples indicated a weak, radioactive signal that was NOS-independent . Aliquots of samples from the NOS assays were then extracted with acetone, separated by high performance thin-layer chromatography (HPTLC) and exposed to autoradiography. Results obtained from these samples showed no radioactive band for L-citrulline. However, a fast-migrating, diffuse, radioactive band was observed in the TLC lanes loaded with MT samples. In this manuscript, we identify and confirm that this radioactive signal in MT samples is due to the arginase-catalyzed conversion of [{sup 14}C]-L-arginine to [{sup 14}C]-urea. The current results, in addition to reconfirming the absence of NOS activity in rat liver MT, also show the need to include arginase inhibitors in studies using MT samples in order to avoid confounding results when using NOS activity assays.

  6. Iridium containing honeycomb Delafossites by topotactic cation exchange.

    PubMed

    Roudebush, John H; Ross, K A; Cava, R J

    2016-06-01

    We report the structure and magnetic properties of two new iridium-based honeycomb Delafossite compounds, Cu3NaIr2O6 and Cu3LiIr2O6, formed by a topotactic cation exchange reaction. The starting materials Na2IrO3 and Li2IrO3, which are based on layers of IrO6 octahedra in a honeycomb lattice separated by layers of alkali ions, are transformed to the title compounds by a topotactic exchange reaction through heating with CuCl below 450 °C; higher temperature reactions cause decomposition. The new compounds display dramatically different magnetic behavior from their parent compounds - Cu3NaIr2O6 has a ferromagnetic like magnetic transition at 10 K, while Cu3LiIr2O6 retains the antiferromagnetic transition temperature of its parent compound but displays significantly stronger dominance of antiferromagnetic coupling between spins. These results reveal that a surprising difference in the magnetic interactions between the magnetic Ir ions has been induced by a change in the non-magnetic interlayer species. A combination of neutron and X-ray powder diffraction is used for the structure refinement of Cu3NaIr2O6 and both compounds are compared to their parent materials. PMID:27147423

  7. High Strain Rate Tensile Testing of DOP-26 Iridium

    SciTech Connect

    Schneibel, Joachim H; Carmichael Jr, Cecil Albert; George, Easo P

    2007-11-01

    The iridium alloy DOP-26 was developed through the Radioisotope Power Systems Program in the Office of Nuclear Energy of the Department of Energy. It is used for clad vent set cups containing radioactive fuel in radioisotope thermoelectric generator (RTG) heat sources which provide electric power for spacecraft. This report describes mechanical testing results for DOP-26. Specimens were given a vacuum recrystallization anneal of 1 hour at 1375 C and tested in tension in orientations parallel and perpendicular to the rolling direction of the sheet from which they were fabricated. The tests were performed at temperatures ranging from room temperature to 1090 C and strain rates ranging from 1 x 10{sup -3} to 50 s{sup -1}. Room temperature testing was performed in air, while testing at elevated temperatures was performed in a vacuum better than 1 x 10{sup -4} Torr. The yield stress (YS) and the ultimate tensile stress (UTS) decreased with increasing temperature and increased with increasing strain rate. Between 600 and 1090 C, the ductility showed a slight increase with increasing temperature. Within the scatter of the data, the ductility did not depend on the strain rate. The reduction in area (RA), on the other hand, decreased with increasing strain rate. The YS and UTS values did not differ significantly for the longitudinal and transverse specimens. The ductility and RA values of the transverse specimens were marginally lower than those of the longitudinal specimens.

  8. Earth's Radiation Imbalance from a Constellation of 66 Iridium Satellites

    NASA Astrophysics Data System (ADS)

    Chiu, J. C.; Wiscombe, W. J.

    2012-04-01

    The Earth Radiation Imbalance (ERI) at the top of the atmosphere is the primary driving force for climate change. If ERI is not zero, then Earth's temperature, both oceanic and atmospheric, will change gradually over time, tending toward a new steady state. The best estimates of current ERI from climate models range from 0.4 to 0.9 W/m2 (the imbalance being caused mainly by increasing CO2), but current satellite systems do not have the accuracy to measure ERI to even one significant digit. In this paper, we will describe a proposed constellation of 66 Earth radiation budget instruments, to be hosted on Iridium satellites. This system represents a quantum leap over current systems in several ways, in particular in providing ERI to at least one significant digit, thus enabling a crucial test of climate models. Because of its 24/7 coverage, the system will also provide ERI at three-hourly time scales without requiring extrapolations from narrowband geostationary instruments. This would allow studies of ERI's response to fast-evolving phenomena like dust storms and hurricanes. This offers a new, synoptic view of Earth radiation budget that will transform it from a monthly average into a dynamical variable alongside standard meteorological variables like temperature and pressure.

  9. Flavone inhibits nitric oxide synthase (NOS) activity, nitric oxide production and protein S-nitrosylation in breast cancer cells

    SciTech Connect

    Zhu, Wenzhen; Yang, Bingwu; Fu, Huiling; Ma, Long; Liu, Tingting; Chai, Rongfei; Zheng, Zhaodi; Zhang, Qunye; Li, Guorong

    2015-03-13

    As the core structure of flavonoids, flavone has been proved to possess anticancer effects. Flavone's growth inhibitory functions are related to NO. NO is synthesized by nitric oxide synthase (NOS), and generally increased in a variety of cancer cells. NO regulates multiple cellular responses by S-nitrosylation. In this study, we explored flavone-induced regulations on nitric oxide (NO)-related cellular processes in breast cancer cells. Our results showed that, flavone suppresses breast cancer cell proliferation and induces apoptosis. Flavone restrains NO synthesis by does-dependent inhibiting NOS enzymatic activity. The decrease of NO generation was detected by fluorescence microscopy and flow cytometry. Flavone-induced inhibitory effect on NOS activity is dependent on intact cell structure. For the NO-induced protein modification, flavone treatment significantly down-regulated protein S-nitrosylation, which was detected by “Biotin-switch” method. The present study provides a novel, NO-related mechanism for the anticancer function of flavone. - Highlights: • Flavone inhibits proliferation and induces apoptosis in MCF-7 cells. • Flavone decreases nitric oxide production by inhibiting NOS enzymatic activity in breast cancer cells. • Flavone down-regulates protein S-nitrosylation.

  10. Comparative Study of Antidiabetic Activity and Oxidative Stress Induced by Zinc Oxide Nanoparticles and Zinc Sulfate in Diabetic Rats.

    PubMed

    Nazarizadeh, Ali; Asri-Rezaie, Siamak

    2016-08-01

    In the current study, antidiabetic activity and toxic effects of zinc oxide nanoparticles (ZnO) were investigated in diabetic rats compared to zinc sulfate (ZnSO4) with particular emphasis on oxidative stress parameters. One hundred and twenty male Wistar rats were divided into two healthy and diabetic groups, randomly. Each major group was further subdivided into five subgroups and then orally supplemented with various doses of ZnO (1, 3, and 10 mg/kg) and ZnSO4 (30 mg/kg) for 56 consecutive days. ZnO showed greater antidiabetic activity compared to ZnSO4 evidenced by improved glucose disposal, insulin levels, and zinc status. The altered activities of erythrocyte antioxidant enzymes as well as raised levels of lipid peroxidation and a marked reduction of total antioxidant capacity were observed in rats receiving ZnO. ZnO nanoparticles acted as a potent antidiabetic agent, however, severely elicited oxidative stress particularly at higher doses. PMID:26349687

  11. Activity and stability of the oxygen evolution reaction on electrodeposited Ru and its thermal oxides

    NASA Astrophysics Data System (ADS)

    Kim, Jin Yeong; Choi, Jihui; Kim, Ho Young; Hwang, Eunkyoung; Kim, Hyoung-Juhn; Ahn, Sang Hyun; Kim, Soo-Kil

    2015-12-01

    The activity and stability of Ru metal and its thermal oxide films for the oxygen evolution reaction (OER) were investigated. The metallic Ru films were prepared by electrodeposition on a Ti substrate and then thermally oxidized at various temperatures under atmospheric conditions. During long-term operation of the OER with cyclic voltammetry (CV) in H2SO4 electrolyte, changes in the properties of the Ru and its thermal oxides were monitored in terms of their morphology, crystal structure, and electronic structure. In the initial stages of the OER, all of the Ru thermal oxide films underwent an activation process that was related to the continuous removal of low-activity Ru oxides from the surface. With further cycling, the OER activity decreased. The rate of decrease was different for each Ru film and was related to the annealing temperatures. Monitoring of material properties indicates that the amount of stable anhydrous RuO2 is important for OER stability because it prevents both the severe dissolution of metallic Ru beneath the oxide surface and the formation of a less active hydrous RuO2 at the surface.

  12. Cold catalytic recovery of loaded activated carbon using iron oxide-based nanoparticles.

    PubMed

    Bach, Altai; Zelmanov, Grigory; Semiat, Raphael

    2008-01-01

    A novel approach for the recovery of spent activated carbon by an advanced oxidation process using iron oxide-based nanocatalysts was proposed and investigated. Model organic contaminants, such as ethylene glycol and phenol, were chosen for this study as water pollutants. It was shown that there are several advantages in using catalytic oxidation recovery of activated carbon with iron oxide-based nanocatalysts: low temperature reactivity of catalytic recovery without heating; and a relatively large number of adsorption-recovery cycles, without a reduction in the adsorptive properties of the virgin activated carbon or without a performance decrease from the first adsorption-recovery cycle of the new modified adsorptive properties of the activated carbon. The catalytic recovery takes place without ultraviolet light or any visible radiation sources. Results show a high efficiency of catalytic recovery of spent activated carbon using iron oxide-based nanocatalysts. A 97-99% efficiency of spent activated carbon catalytic regeneration was achieved under chosen conditions after 15-20 min of reaction. The process may be also considered as cold in situ recovery of active carbon. PMID:17826818

  13. Trimetallic Au/Pt/Rh Nanoparticles as Highly Active Catalysts for Aerobic Glucose Oxidation

    NASA Astrophysics Data System (ADS)

    Zhang, Haijun; Cao, Yingnan; Lu, Lilin; Cheng, Zhong; Zhang, Shaowei

    2015-02-01

    This paper reports the findings of an investigation of the correlations between the catalytic activity for aerobic glucose oxidation and the composition of Au/Pt/Rh trimetallic nanoparticles (TNPs) with average diameters of less than 2.0 nm prepared by rapid injection of NaBH4. The prepared TNPs were characterized by UV-Vis, TEM, and HR-TEM. The catalytic activity of the alloy-structured TNPs for aerobic glucose oxidation is several times higher than that of Au monometallic nanoparticles with nearly the same particle size. The catalytic activities of the TNP catalysts were dependent not only on the composition, but also on the electronic structure. The high catalytic activities of the Au/Pt/Rh TNPs can be ascribed to the formed negative-charged Au atoms due to electron donation of Rh neighboring atoms acting as catalytically active sites for aerobic glucose oxidation.

  14. Structure-Activity Relationship in Nanostructured Copper-Ceria-Based Preferential CO Oxidation Catalysts

    SciTech Connect

    Gamarra,D.; Munuera, G.; Hungria, A.; Fernandez-Garcia, M.; Conesa, J.; Midgley, P.; Wang, X.; Hanson, J.; Rodriguez, J.; Martinez-Arias, A.

    2007-01-01

    Two series of nanostructured oxidized copper-cerium catalysts with varying copper loadings, and prepared, respectively, by impregnation of ceria and by coprecipitation of the two components within reverse microemulsions, have been characterized in detail at structural and electronic levels by X-ray diffraction (XRD), Raman spectroscopy, high-resolution electron microscopy (HREM), X-ray energy dispersive spectroscopy (XEDS), X-ray photoelectron spectroscopy (XPS) (including Ar{sup +}-sputtering), and X-ray absorption fine structure (XAFS). These results have been correlated with analysis of their catalytic properties for preferential oxidation of CO in a H{sub 2}-rich stream (CO-PROX), complemented by Operando-DRIFTS. A relevant difference between the two series of catalysts concerns the nature of the support for the surface-dispersed copper oxide entities, which is essentially ceria for the samples prepared by impregnation and a Ce-Cu mixed oxide for those prepared by microemulsion-coprecipitation. The existence of copper segregation in the form of copper oxide or copper-enriched Cu-Ce mixed oxides for the latter type of samples is uniquely revealed by nanoprobe XEDS and XPS Ar{sup +}-sputtering experiments. The CO oxidation activity under CO-PROX conditions is correlated to the degree of support-promoted reduction achieved by the dispersed copper oxide particles under reaction conditions. Nevertheless, catalysts which display higher CO oxidation activity are generally more efficient also for the undesired H{sub 2} oxidation reaction. The balance between both reactions results in differences in the CO-PROX activity between the two series of catalysts which are examined on the basis of the structural differences found.

  15. Rhizosphere heterogeneity shapes abundance and activity of sulfur-oxidizing bacteria in vegetated salt marsh sediments

    PubMed Central

    Thomas, François; Giblin, Anne E.; Cardon, Zoe G.; Sievert, Stefan M.

    2014-01-01

    Salt marshes are highly productive ecosystems hosting an intense sulfur (S) cycle, yet little is known about S-oxidizing microorganisms in these ecosystems. Here, we studied the diversity and transcriptional activity of S-oxidizers in salt marsh sediments colonized by the plant Spartina alterniflora, and assessed variations with sediment depth and small-scale compartments within the rhizosphere. We combined next-generation amplicon sequencing of 16S rDNA and rRNA libraries with phylogenetic analyses of marker genes for two S-oxidation pathways (soxB and rdsrAB). Gene and transcript numbers of soxB and rdsrAB phylotypes were quantified simultaneously, using newly designed (RT)-qPCR assays. We identified a diverse assemblage of S-oxidizers, with Chromatiales and Thiotrichales being dominant. The detection of transcripts from S-oxidizers was mostly confined to the upper 5 cm sediments, following the expected distribution of root biomass. A common pool of species dominated by Gammaproteobacteria transcribed S-oxidation genes across roots, rhizosphere, and surrounding sediment compartments, with rdsrAB transcripts prevailing over soxB. However, the root environment fine-tuned the abundance and transcriptional activity of the S-oxidizing community. In particular, the global transcription of soxB was higher on the roots compared to mix and rhizosphere samples. Furthermore, the contribution of Epsilonproteobacteria-related S-oxidizers tended to increase on Spartina roots compared to surrounding sediments. These data shed light on the under-studied oxidative part of the sulfur cycle in salt marsh sediments and indicate small-scale heterogeneities are important factors shaping abundance and potential activity of S-oxidizers in the rhizosphere. PMID:25009538

  16. Increased oxidative stress in pemphigus vulgaris is related to disease activity and HLA-association.

    PubMed

    Shah, Amit Aakash; Dey-Rao, Rama; Seiffert-Sinha, Kristina; Sinha, Animesh A

    2016-06-01

    Pemphigus vulgaris (PV) is a rare blistering skin disorder characterized by the disadhesion of keratinocytes due to autoantibody attack against epidermal targets including desmoglein (Dsg) 3, Dsg 1 and possibly other adhesion and non-adhesion molecules. The mechanisms leading to immune-mediated pathology in PV are multifactorial and not fully understood. Recently, oxidative stress (antioxidant/oxidant disequilibrium) has been proposed as a contributory mechanism of autoimmune skin diseases, including PV. In this study, we directly assessed oxidative stress via measurement of total antioxidant capacity (TAC) using ELISA in 47 PV patients, 25 healthy controls and 18 bullous pemphigoid (BP) patients. We also performed microarray gene expression analysis on a separate set of 21 PV patients and 10 healthy controls to evaluate transcriptional dysregulation in oxidative stress-related pathways. Our data indicate that there is a significant reduction in TAC levels in PV patients compared with healthy controls, as well as BP patients. Furthermore, PV patients with active disease have significantly lower TAC levels than PV patients in remission. We also find that HLA allele status has a significant influence on oxidative stress. These findings are corroborated by microarray analysis showing differentially expressed genes involved in oxidative stress between the aforementioned groups. Collectively, our findings provide support for a role of oxidative stress in PV. Whether increased oxidative stress leads to disease manifestation and/or activity, or if disease activity leads to increased oxidative stress remains unknown. Future longitudinal studies may help to further elucidate the relationship between PV and oxidative stress. PMID:26911801

  17. Oxidative DNA adducts after Cu(2+)-mediated activation of dihydroxy PCBs: role of reactive oxygen species.

    PubMed

    Spencer, Wendy A; Lehmler, Hans-Joachim; Robertson, Larry W; Gupta, Ramesh C

    2009-05-15

    Polychlorinated biphenyls (PCBs) are toxic industrial chemicals, complete carcinogens, and efficacious tumor promoters. However, the mechanism(s) of PCB-mediated carcinogenicity remains largely undefined. One likely pathway by which these agents may play a role in carcinogenesis is the generation of oxidative DNA damage by redox cycling of dihydroxylated PCB metabolites. We have now employed a new (32)P-postlabeling system to examine novel oxidative DNA lesions induced by Cu(2+)-mediated activation of PCB metabolites. (32)P postlabeling of DNA incubated with various PCB metabolites resulted in over a dozen novel polar oxidative DNA adducts that were chromatographically similar for all active agents. The most potent metabolites tested were the hydroquinones (hydroxyl groups arranged para to each other), yielding polar oxidative adduct levels ranging from 55 to 142 adducts/10(6) nucleotides. PCB catechols, or ortho-dihydroxy metabolites, were up to 40% less active than their corresponding hydroquinone congeners, whereas monohydroxylated and quinone metabolites did not produce detectable oxidative damage over that of vehicle. With the exception of 2,4,5-Cl-2',5'-dihydroxybiphenyl, this oxidative DNA damage seemed to be inversely related to chlorine content: no chlorine approximately mono->di->trichlorinated metabolites. Importantly, copper, but not iron, was essential for activation of the PCB metabolites to these polar oxidative DNA adducts, because in its absence or in the presence of the Cu(+)-specific scavenger bathocuproine, no adducts were detected. Intervention studies with known reactive oxygen species (ROS) modifiers suggested that H(2)O(2), singlet oxygen, hydroxyl radical, and superoxide may also be involved in this PCB-mediated oxidative DNA damage. These data indicate a mechanistic role for several ROS, in addition to copper, in PCB-induced DNA damage and provide further support for oxidative DNA damage in PCB-mediated carcinogenesis. PMID:19233261

  18. Cell signaling through protein kinase C oxidation and activation.

    PubMed

    Cosentino-Gomes, Daniela; Rocco-Machado, Nathália; Meyer-Fernandes, José Roberto

    2012-01-01

    Due to the growing importance of cellular signaling mediated by reactive oxygen species (ROS), proteins that are reversibly modulated by these reactant molecules are of high interest. In this context, protein kinases and phosphatases, which act coordinately in the regulation of signal transduction through the phosphorylation and dephosphorylation of target proteins, have been described to be key elements in ROS-mediated signaling events. The major mechanism by which these proteins may be modified by oxidation involves the presence of key redox-sensitive cysteine residues. Protein kinase C (PKC) is involved in a variety of cellular signaling pathways. These proteins have been shown to contain a unique structural feature that is susceptible to oxidative modification. A large number of scientific studies have highlighted the importance of ROS as a second messenger in numerous cellular processes, including cell proliferation, gene expression, adhesion, differentiation, senescence, and apoptosis. In this context, the goal of this review is to discuss the mechanisms by which PKCs are modulated by ROS and how these processes are involved in the cellular response. PMID:23109817

  19. Anaerobic oxidation of methane: an "active" microbial process.

    PubMed

    Cui, Mengmeng; Ma, Anzhou; Qi, Hongyan; Zhuang, Xuliang; Zhuang, Guoqiang

    2015-02-01

    The anaerobic oxidation of methane (AOM) is an important sink of methane that plays a significant role in global warming. AOM was first found to be coupled with sulfate reduction and mediated by anaerobic methanotrophic archaea (ANME) and sulfate-reducing bacteria (SRB). ANME, often forming consortia with SRB, are phylogenetically related to methanogenic archaea. ANME-1 is even able to produce methane. Subsequently, it has been found that AOM can also be coupled with denitrification. The known microbes responsible for this process are Candidatus Methylomirabilis oxyfera (M. oxyfera) and Candidatus Methanoperedens nitroreducens (M. nitroreducens). Candidatus Methylomirabilis oxyfera belongs to the NC10 bacteria, can catalyze nitrite reduction through an "intra-aerobic" pathway, and may catalyze AOM through an aerobic methane oxidation pathway. However, M. nitroreducens, which is affiliated with ANME-2d archaea, may be able to catalyze AOM through the reverse methanogenesis pathway. Moreover, manganese (Mn(4+) ) and iron (Fe(3+) ) can also be used as electron acceptors of AOM. This review summarizes the mechanisms and associated microbes of AOM. It also discusses recent progress in some unclear key issues about AOM, including ANME-1 in hypersaline environments, the effect of oxygen on M. oxyfera, and the relationship of M. nitroreducens with ANME. PMID:25530008

  20. Oxidized LDL induces an oxidative stress and activates the tumor suppressor p53 in MRC5 human fibroblasts.

    PubMed

    Mazière, C; Meignotte, A; Dantin, F; Conte, M A; Mazière, J C

    2000-09-24

    It is now well established that oxidized LDL (OxLDL) is involved in the progression of the atheromatous plaque via several mechanisms, including its cytotoxicity toward the arterial wall. Our study demonstrates that a 4-h incubation of cultured human fibroblasts with 25-75 microg/ml OxLDL induced a dose-dependent increase in the intracellular levels of reactive oxygen species (ROS) and lipid peroxidation end products (TBARS). This effect was markedly prevented by the antioxidant vitamin E. The lipid extract of OxLDL partially reproduced the action of the LDL particle itself. Concomitantly, OxLDL enhanced the DNA binding activity of p53 measured by electrophoretic mobility shift assay, and the intracellular protein level of p53 determined by immunoblot analysis. Cycloheximide prevented the OxLDL-induced augmentation in both p53 binding activity and intracellular level. Again, the lipid extract of OxLDL reproduced the effect of OxLDL on p53 binding activity, whereas vitamin E prevented it. These results indicate that OxLDL initiates an intracellular oxidative stress by means of its lipid peroxidation products, leading to the activation of the tumour suppressor p53 by enhancement of p53 protein synthesis. This effect might be related to the cytotoxic effect of OxLDL since the activation of p53 is known to lead to cell cycle arrest, necrosis or apoptosis. PMID:11027537