A highly active and stable IrO x/SrIrO 3 catalyst for the oxygen evolution reaction

DOE PAGES

Seitz, Linsey C.; Dickens, Colin F.; Nishio, Kazunori; ...

2016-09-02

Oxygen electrochemistry plays a key role in renewable energy technologies such as fuel cells and electrolyzers, but the slow kinetics of the oxygen evolution reaction (OER) limit the performance and commercialization of such devices. Here we report an iridium oxide/strontium iridium oxide (IrO x/SrIrO 3) catalyst formed during electrochemical testing by strontium leaching from surface layers of thin films of SrIrO 3. This catalyst has demonstrated specific activity at 10 milliamps per square centimeter of oxide catalyst (OER current normalized to catalyst surface area), with only 270 to 290 millivolts of overpotential for 30 hours of continuous testing in acidicmore » electrolyte. Here, density functional theory calculations suggest the formation of highly active surface layers during strontium leaching with IrO 3 or anatase IrO 2 motifs. The IrO x/SrIrO 3 catalyst outperforms known IrO x and ruthenium oxide (RuO x) systems, the only other OER catalysts that have reasonable activity in acidic electrolyte.« less

A highly active and stable IrOx/SrIrO3 catalyst for the oxygen evolution reaction.

PubMed

Seitz, Linsey C; Dickens, Colin F; Nishio, Kazunori; Hikita, Yasuyuki; Montoya, Joseph; Doyle, Andrew; Kirk, Charlotte; Vojvodic, Aleksandra; Hwang, Harold Y; Norskov, Jens K; Jaramillo, Thomas F

2016-09-02

Oxygen electrochemistry plays a key role in renewable energy technologies such as fuel cells and electrolyzers, but the slow kinetics of the oxygen evolution reaction (OER) limit the performance and commercialization of such devices. Here we report an iridium oxide/strontium iridium oxide (IrO x /SrIrO 3 ) catalyst formed during electrochemical testing by strontium leaching from surface layers of thin films of SrIrO 3 This catalyst has demonstrated specific activity at 10 milliamps per square centimeter of oxide catalyst (OER current normalized to catalyst surface area), with only 270 to 290 millivolts of overpotential for 30 hours of continuous testing in acidic electrolyte. Density functional theory calculations suggest the formation of highly active surface layers during strontium leaching with IrO 3 or anatase IrO 2 motifs. The IrO x /SrIrO 3 catalyst outperforms known IrO x and ruthenium oxide (RuO x ) systems, the only other OER catalysts that have reasonable activity in acidic electrolyte. Copyright © 2016, American Association for the Advancement of Science.

Synthesis and luminescence properties of iridium(III) azide- and triazole-bisterpyridine complexes.

PubMed

Goldstein, Daniel C; Peterson, Joshua R; Cheng, Yuen Yap; Clady, Raphael G C; Schmidt, Timothy W; Thordarson, Pall

2013-07-26

We describe here the synthesis of azide-functionalised iridium(III) bisterpyridines using the "chemistry on the complex" strategy. The resulting azide-complexes are then used in the copper(I)-catalysed azide-alkyne Huisgen 1,3-dipolar cycloaddition "click chemistry" reaction to from the corresponding triazole-functionalised iridium(III) bisterpyridines. The photophysical characteristics, including lifetimes, of these compounds were also investigated. Interestingly, oxygen appears to have very little effect on the lifetime of these complexes in aqueous solutions. Unexpectedly, sodium ascorbate acid appears to quench the luminescence of triazole-functionalised iridium(III) bisterpyridines, but this effect can be reversed by the addition of copper(II) sulfate, which is known to oxidize ascorbate under aerobic conditions. The results demonstrate that iridium(III) bisterpyridines can be functionalized for use in "click chemistry" facilitating the use of these photophysically interesting complexes in the modification of polymers or surfaces, to highlight just two possible applications.

Analysis of Abrasive Blasting of DOP-26 Iridium Alloy

DOE Office of Scientific and Technical Information (OSTI.GOV)

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 processmore » 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.« less

A nanostructured electrode of IrOx foil on the carbon nanotubes for supercapacitors.

PubMed

Chen, Yi-Min; Cai, Jhen-Hong; Huang, Ying-Sheng; Lee, Kuei-Yi; Tsai, Dah-Shyang; Tiong, Kwong-Kau

2011-09-02

IrO(x) nanofoils (IrO(x)NF) of high surface area are sputtered on multi-wall carbon nanotubes (CNT) in the preparation of a structured electrode on a stainless steel (SUS) substrate for supercapacitor applications. This IrO(x)/CNT/SUS electrode is featured with intriguing IrO(x) curved foils of 2-3 nm in thickness and 400-500 nm in height, grown on top of the vertically aligned CNT film with a tube diameter of ∼ 40 nm. These nanofoils are moderately oxidized during reactive sputtering and appeared translucent under the electron microscope. Detailed structural analysis shows that they are comprised of contiguous grains of iridium metal, iridium dioxide, and glassy iridium oxide. Considerable Raman line broadening is also evidenced for the attributed nanosized iridium oxides. Two capacitive properties of the electrode are significantly enhanced with addition of the curved IrO(x) foils. First, IrO(x)NF reduces the electrode Ohmic resistance, which was measured at 3.5 Ω cm(2) for the CNT/SUS and 2.5 Ω cm(2) for IrO(x)NF/CNT/SUS using impedance spectroscopy. Second, IrO(x)NF raises the electrode capacitance from 17.7 F g(-1) (CNT/SUS) to 317 F g(-1) (IrO(x)/CNT/SUS), measured with cyclic voltammetry. This notable increase is further confirmed by the galvanostatic charge/discharge experiment, measuring 370 F g(-1) after 2000 uninterrupted cycles between - 1.0 and 0.0 V (versus Ag/AgCl).

A nanostructured electrode of IrOx foil on the carbon nanotubes for supercapacitors

NASA Astrophysics Data System (ADS)

Chen, Yi-Min; Cai, Jhen-Hong; Huang, Ying-Sheng; Lee, Kuei-Yi; Tsai, Dah-Shyang; Tiong, Kwong-Kau

2011-09-01

IrOx nanofoils (IrOxNF) of high surface area are sputtered on multi-wall carbon nanotubes (CNT) in the preparation of a structured electrode on a stainless steel (SUS) substrate for supercapacitor applications. This IrOx/CNT/SUS electrode is featured with intriguing IrOx curved foils of 2-3 nm in thickness and 400-500 nm in height, grown on top of the vertically aligned CNT film with a tube diameter of ~ 40 nm. These nanofoils are moderately oxidized during reactive sputtering and appeared translucent under the electron microscope. Detailed structural analysis shows that they are comprised of contiguous grains of iridium metal, iridium dioxide, and glassy iridium oxide. Considerable Raman line broadening is also evidenced for the attributed nanosized iridium oxides. Two capacitive properties of the electrode are significantly enhanced with addition of the curved IrOx foils. First, IrOxNF reduces the electrode Ohmic resistance, which was measured at 3.5 Ω cm2 for the CNT/SUS and 2.5 Ω cm2 for IrOxNF/CNT/SUS using impedance spectroscopy. Second, IrOxNF raises the electrode capacitance from 17.7 F g - 1 (CNT/SUS) to 317 F g - 1 (IrOx/CNT/SUS), measured with cyclic voltammetry. This notable increase is further confirmed by the galvanostatic charge/discharge experiment, measuring 370 F g - 1 after 2000 uninterrupted cycles between - 1.0 and 0.0 V (versus Ag/AgCl).

Surface-enhanced Raman spectroscopy on litographically constructed microelectrodes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhelyaskov, V.R.; Milne, E.T.; Weldon, M.K.

1995-12-31

A novel silicon substrate microelectrode array has been demonstrated to function as a surface-enhanced Raman Spectroscopy (SERS) microelectrode. SERS from adenosine and pyridine down to 10 mM concentration on silver coated iridium and gold microelectrode arrays have been observed with excitation at 532 nm and 633 nm correspondingly. Ag/AgCl reference electrode and platinum or integrated on the microelectrode iridium counter electrodes were used. Owing to the small area of the activated sites on the microelectrode (10 mm x 15 mm) the SERS signal exhibited a strong laser power dependence. The optimal laser power on the activated site was shown tomore » be in the order of x 100 mW. Good quality SERS spectra were recorded with exposure times of 10s and less. The small size of the electrodes makes them promising for studies in confined spaces. This includes potential applications as capillary electrophoreses detectors and probes of chemistry of biological organisms. A work on detection of lipids adhered to self-organized monolayers (SAM)s of alkanethiols on the activated microelectrodes is in progress.« less

Catalyst comprising Ir or Ir and Ru for hydrazine decomposition

NASA Technical Reports Server (NTRS)

Armstrong, Warren E. (Inventor); Voge, Hervey H. (Inventor); Ryland, Lloyd B. (Inventor)

1978-01-01

A catalyst for hydrazine decomposition consisting essentially of a carrier having a pore volume of at least 0.1 cubic centimeters per gram and a specific surface area, measured in square meters per gram, equal to 195 (C.sub.p + 0.013 + 0.736 V.sub.p) where C.sub.p is the specific heat capacity of the carrier at about 25.degree. C in calories per gram per degree and V.sub.p is the pore volume of the carrier in cubic centimeters per gram and metal of the group consisting of iridium, and mixtures consisting of iridium and ruthenium deposited on said carrier in an amount between 20% and about 40% by weight of the catalyst and distributed through the pores thereof in discrete particles sufficiently separated from each other so that they do not sinter or fuse together when the catalyst is at hydrazine decomposition temperature.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Babucci, Melike; Fang, Chia -Yu; Hoffman, Adam S.

1,3-Dialkylimidazolium ionic liquid coatings act as electron donors, increasing the selectivity for partial hydrogenation of 1,3-butadiene catalyzed by iridium complexes supported on high-surface-area γ-Al 2O 3. High-energy-resolution fluorescence detection X-ray absorption near-edge structure (HERFD XANES) measurements quantify the electron donation and are correlated with the catalytic activity and selectivity. Furthermore, the results demonstrate broad opportunities to tune electronic environments and catalytic properties of atomically dispersed supported metal catalysts.

Iridium complexes for electrocatalysis

DOEpatents

Sheehan, Stafford Wheeler; Hintermair, Ulrich; Thomsen, Julianne M; Brudvig, Gary W; Crabtree, Robert H

2017-10-17

Solution-phase (e.g., homogeneous) or surface-immobilized (e.g., heterogeneous) electrode-driven oxidation catalysts based on iridium coordination compounds which self-assemble upon chemical or electrochemical oxidation of suitable precursors and methods of making and using thereof are. Iridium species such as {[Ir(LX).sub.x(H.sub.2O).sub.y(.mu.-O)].sub.z.sup.m+}.sub.n wherein x, y, m are integers from 0-4, z and n from 1-4 and LX is an oxidation-resistant chelate ligand or ligands, such as such as 2(2-pyridyl)-2-propanolate, form upon oxidation of various molecular iridium complexes, for instance [Cp*Ir(LX)OH] or [(cod)Ir(LX)] (Cp*=pentamethylcyclopentadienyl, cod=cis-cis,1,5-cyclooctadiene) when exposed to oxidative conditions, such as sodium periodate (NaIO.sub.4) in aqueous solution at ambient conditions.

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

2016-07-07

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. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Ion beam processing of surgical materials

NASA Astrophysics Data System (ADS)

Williams, James M.; Buchanan, Raymond A.; Lee, In-Seop

1989-02-01

Ion beam processing has now achieved a secure place in surface treatment of biomaterials. This development is largely a result of the success of the process for wear prevention of orthopedic Ti-alloy in rubbing contact with ultrahigh molecular-weight polyethylene. Basic contributions of the authors in this area, together with other pertinent literature will be reviewed. Research in ion beam processing of biomaterials is turning to other areas. Among these, bioelectronics is considered to be a promising area for further effort. Pertinent experiments on effects of implantation of iridium into titanium and Ti-6Al-4V alloy on corrosion and charge injection properties are presented.

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.

Intracavitary irradiation of renal pyelocalyceal transitional cell carcinoma with iridium-192

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kadish, S.P.; Danford, R.; Felton, L.M.

1981-11-01

A case of multicentric urothelial transitional cell carcinoma is presented, in which the patient underwent a left ureteronephrectomy and in the remaining right kidney recurrent transitional cell carcinoma was found in the inferior calyx. Because this area was accessible via a cutaneous nephrostomy, it is treated with a combination of external beam radiation and intracavitary implantation with iridium-192. The iridium was placed in the vicinity of the tumor using an angiographic procedure. The technique successfully preserved remaining renal parenchyma. The case illustrates how angiography skills and procedures can be applied in a novel brachytherapy application.

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

Phosphorescence quenching of fac-tris(2-phenylpyridyl)iridium(iii) complexes in thin films on dielectric surfaces.

PubMed

Ribierre, J C; Ruseckas, A; Staton, S V; Knights, K; Cumpstey, N; Burn, P L; Samuel, I D W

2016-02-07

We study the influence of the film thickness on the time-resolved phosphorescence and the luminescence quantum yield of fac-tris(2-phenylpyridyl)iridium(iii) [Ir(ppy)3]-cored dendrimers deposited on dielectric substrates. A correlation is observed between the surface quenching velocity and the quenching rate by intermolecular interactions in the bulk film, which suggests that both processes are controlled by dipole-dipole interactions between Ir(ppy)3 complexes at the core of the dendrimers. It is also found that the surface quenching velocity decreases as the refractive index of the substrate is increased. This can be explained by partial screening of dipole-dipole interactions by the dielectric environment.

Intercalating cobalt between graphene and iridium (111): Spatially dependent kinetics from the edges

NASA Astrophysics Data System (ADS)

Vlaic, Sergio; Rougemaille, Nicolas; Kimouche, Amina; Burgos, Benito Santos; Locatelli, Andrea; Coraux, Johann

2017-10-01

Using low-energy electron microscopy, we image in real time the intercalation of a cobalt monolayer between graphene and the (111) surface of iridium. Our measurements reveal that the edges of a graphene flake represent an energy barrier to intercalation. Based on a simple description of the growth kinetics, we estimate this energy barrier and find small, but substantial, local variations. These local variations suggest a possible influence of the graphene orientation with respect to its substrate and of the graphene edge termination on the energy value of the barrier height. Besides, our measurements show that intercalated cobalt is energetically more favorable than cobalt on bare iridium, indicating a surfactant role of graphene.

Tuning the Selectivity of Single-Site Supported Metal Catalysts with Ionic Liquids

DOE PAGES

Babucci, Melike; Fang, Chia -Yu; Hoffman, Adam S.; ...

2017-09-11

1,3-Dialkylimidazolium ionic liquid coatings act as electron donors, increasing the selectivity for partial hydrogenation of 1,3-butadiene catalyzed by iridium complexes supported on high-surface-area γ-Al 2O 3. High-energy-resolution fluorescence detection X-ray absorption near-edge structure (HERFD XANES) measurements quantify the electron donation and are correlated with the catalytic activity and selectivity. Furthermore, the results demonstrate broad opportunities to tune electronic environments and catalytic properties of atomically dispersed supported metal catalysts.

Oxide Protective Coats for Ir/Re Rocket Combustion Chambers

NASA Technical Reports Server (NTRS)

Fortini, Arthur; Tuffias, Robert H.

2003-01-01

An improved material system has been developed for rocket engine combustion chambers for burning oxygen/ hydrogen mixtures or novel monopropellants, which are highly oxidizing at operating temperatures. The baseline for developing the improved material system is a prior iridium/rhenium system for chambers burning nitrogen tetroxide/monomethyl hydrazine mixtures, which are less oxidizing. The baseline combustion chamber comprises an outer layer of rhenium that provides structural support, plus an inner layer of iridium that acts as a barrier to oxidation of the rhenium. In the improved material system, the layer of iridium is thin and is coated with a thermal fatigue-resistant refractory oxide (specifically, hafnium oxide) that serves partly as a thermal barrier to decrease the temperature and thus the rate of oxidation of the rhenium. The oxide layer also acts as a barrier against the transport of oxidizing species to the surface of the iridium. Tests in which various oxygen/hydrogen mixtures were burned in iridium/rhenium combustion chambers lined with hafnium oxide showed that the operational lifetimes of combustion chambers of the improved material system are an order of magnitude greater than those of the baseline combustion chambers.

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.

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.

Achieving Zero Stress in Iridium, Chromium, and Nickel 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.

Isomerization Reaction of mer- to fac-Tris(2-phenylpyridinato-N,C2')Iridium(III) Monitored by Using Surface-Enhanced Raman Spectroscopy.

PubMed

Wu, Bo-Han; Huang, Min-Jie; Lai, Cheng-Chang; Cheng, Chien-Hong; Chen, I-Chia

2018-04-16

We developed a new method by enclosing the complex tris(2-phenylpyridinato-N,C2')Iridium(III), Ir(ppy) 3 with surfactant cetyltrimethylammonium bromide (CATB), coated with a thin layer of silica then bonded to the surface of silver nanoparticle. These samples were used to acquire surface-enhanced Raman scattering (SERS) spectra. The thickness of silica layer was controlled to have efficient phosphorescence quenching and Raman enhancement by metal nanoparticle. The SERS spectra of fac- and mer-Ir(ppy) 3 , recorded at 633 nm excitation, display distinct ring breathing mode features because the total symmetric vibrational bands were enhanced. This provides a convenient means to differentiate these isomers with great sensitivity and to study their isomerization process. A direct conversion reaction of mer- to fac- isomerization is identified with time constant 3.1 min when mer was irradiated with Xe light. Via thermal activation, under moderate conditions (pH 5.5 and 343 K), we observed an intermediate particularly with new bands 320/662 cm -1 after heating for 17.5 h, and then those bands disappeared to form fac-Ir(ppy) 3 . On the basis of DFT calculations, the intermediate is proposed to contain octahedral N-N Ir(ppy) 3 -HO-silica structure; band at 320 cm -1 is assigned to iridium oxygen stretching mode ν Ir-O of this intermediate. Under acidic conditions, pH 1-2 catalyzed by silanol in silica, byproduct with band at 353 cm -1 was observed. According to the SERS bands and the calculation, this byproduct is assigned to be iridium(III) siloxide, and the new band is assigned to ν Ir-O .

Iridium-coated micropore x-ray optics using dry etching of a silicon wafer and atomic layer deposition.

PubMed

Ogawa, Tomohiro; Ezoe, Yuichiro; Moriyama, Teppei; Mitsuishi, Ikuyuki; Kakiuchi, Takuya; Ohashi, Takaya; Mitsuda, Kazuhisa; Putkonen, Matti

2013-08-20

To enhance x-ray reflectivity of silicon micropore optics using dry etching of silicon (111) wafers, iridium coating is tested by use of atomic layer deposition. An iridium layer is successfully formed on sidewalls of tiny micropores with a pore width of 20 μm and depth of 300 μm. The film thickness is ∼20  nm. An enhanced x-ray reflectivity compared to that of silicon is confirmed at Ti K_α 4.51 keV, for what we believe to be the first time, with this type of optics. Some discrepancies from a theoretical reflectivity curve of iridium-coated silicon are noticed at small incident angles <1.3°. When a geometrical shadowing effect due to occultation by a ridge existing on the sidewalls is taken into account, the observed reflectivity becomes well represented by the modified theoretical curve. An estimated surface micro roughness of ∼1  nm rms is consistent with atomic force microscope measurements of the sidewalls.

Iridium contents in the Late Cretaceous-Early Tertiary clays in relation to the K/T boundary, North Jordan

NASA Astrophysics Data System (ADS)

Abboud, Iyad Ahmed

2016-06-01

The mineralogy, lithology, and geochemistry of five discrete laminations across the K/T boundary of clayey shale at the Yarmouk River area, Jordan, were examined. There were no marked changes in the mineralogy of the clayey shale within the K/T boundary. This outcrop consists of more than 100 m of Maastrichtian oil shale overlying about 20 m limestone. Marly limestone included many clay laminations from organic and volcanic origins, which are considered an evidence of the K/T boundary through detected iridium anomalies. Any of these particular lamellae range from 2 mm to 5 mm in thickness. Smectite was the predominant clay mineral in smectitic shale laminations. It was located at eight meters above the K/T boundary and includes some anomalous concentrations of iridium and traces of other elements. The analysis of geochemical platinum group at the K/T boundary clays showed anomalous enrichments of iridium, compared with other carbonate rocks as a result of weathering processes of oil shale, or through concentration from weathering of basalt flows, but not pointing to an impact process. The clays in late Maastrichtian have Ir-Sc prevailed anomalies and synchronize with increasing of terrigenous and volcanogenic traced elements. Kaolin, smectite, and volkonskoite were the dominant clay minerals at the K/T boundary with high concentrations of iridium. The concentration levels of iridium in some laminations of the Yarmouk sediments ranged between 1.6 and 7.8 ppb.

Grain Growth and Precipitation Behavior of Iridium Alloy DOP-26 During Long Term Aging

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pierce, Dean T.; Muralidharan, Govindarajan; Fox, Ethan E.

The influence of long term aging on grain growth and precipitate sizes and spatial distribution in iridium alloy DOP-26 was studied. Samples of DOP-26 were fabricated using the new process, recrystallized for 1 hour (h) at 1375 C, then aged at either 1300, 1400, or 1500 C for times ranging from 50 to 10,000 h. Grain size measurements (vertical and horizontal mean linear intercept and horizontal and vertical projection) and analyses of iridium-thorium precipitates (size and spacing) were made on the longitudinal, transverse, and rolling surfaces of the as-recrystallized and aged specimens from which the two-dimensional spatial distribution and meanmore » sizes of the precipitates were obtained. The results obtained from this study are intended to provide input to grain growth models.« less

Integration of High-Charge-Injection-Capacity Electrodes onto Polymer Softening Neural Interfaces.

PubMed

Arreaga-Salas, David E; Avendaño-Bolívar, Adrian; Simon, Dustin; Reit, Radu; Garcia-Sandoval, Aldo; Rennaker, Robert L; Voit, Walter

2015-12-09

Softening neural interfaces are implanted stiff to enable precise insertion, and they soften in physiological conditions to minimize modulus mismatch with tissue. In this work, a high-charge-injection-capacity iridium electrode fabrication process is detailed. For the first time, this process enables integration of iridium electrodes onto softening substrates using photolithography to define all features in the device. Importantly, no electroplated layers are utilized, leading to a highly scalable method for consistent device fabrication. The iridium electrode is metallically bonded to the gold conductor layer, which is covalently bonded to the softening substrate via sulfur-based click chemistry. The resulting shape-memory polymer neural interfaces can deliver more than 2 billion symmetric biphasic pulses (100 μs/phase), with a charge of 200 μC/cm(2) and geometric surface area (GSA) of 300 μm(2). A transfer-by-polymerization method is used in combination with standard semiconductor processing techniques to fabricate functional neural probes onto a thiol-ene-based, thin film substrate. Electrical stability is tested under simulated physiological conditions in an accelerated electrical aging paradigm with periodic measurement of electrochemical impedance spectra (EIS) and charge storage capacity (CSC) at various intervals. Electrochemical characterization and both optical and scanning electron microscopy suggest significant breakdown of the 600 nm-thick parylene-C insulation, although no delamination of the conductors or of the final electrode interface was observed. Minor cracking at the edges of the thin film iridium electrodes was occasionally observed. The resulting devices will provide electrical recording and stimulation of the nervous system to better understand neural wiring and timing, to target treatments for debilitating diseases, and to give neuroscientists spatially selective and specific tools to interact with the body. This approach has uses for cochlear implants, nerve cuff electrodes, penetrating cortical probes, spinal stimulators, blanket electrodes for the gut, stomach, and visceral organs and a host of other custom nerve-interfacing devices.

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).

Silica nanoparticles for micro-particle imaging velocimetry: fluorosurfactant improves nanoparticle stability and brightness of immobilized iridium(III) complexes.

PubMed

Lewis, David J; Dore, Valentina; Rogers, Nicola J; Mole, Thomas K; Nash, Gerard B; Angeli, Panagiota; Pikramenou, Zoe

2013-11-26

To establish highly luminescent nanoparticles for monitoring fluid flows, we examined the preparation of silica nanoparticles based on immobilization of a cyclometalated iridium(III) complex and an examination of the photophysical studies provided a good insight into the Ir(III) microenvironment in order to reveal the most suitable silica nanoparticles for micro particle imaging velocimetry (μ-PIV) studies. Iridium complexes covalently incorporated at the surface of preformed silica nanoparticles, [Ir-4]@Si500-Z, using a fluorinated polymer during their preparation, demonstrated better stability than those without the polymer, [Ir-4]@Si500, as well as an increase in steady state photoluminescence intensity (and therefore particle brightness) and lifetimes which are increased by 7-fold compared with nanoparticles with the same metal complex attached covalently throughout their core, [Ir-4]⊂Si500. Screening of the nanoparticles in fluid flows using epi-luminescence microscopy also confirm that the brightest, and therefore most suitable particles for microparticle imaging velocimetry (μ-PIV) measurements are those with the Ir(III) complex immobilized at the surface with fluorosurfactant, that is [Ir-4]@Si500-Z. μ-PIV studies demonstrate the suitability of these nanoparticles as nanotracers in microchannels.

Research of remote control for Chinese Antarctica Telescope based on iridium satellite communication

NASA Astrophysics Data System (ADS)

Xu, Lingzhe; Yang, Shihai

2010-07-01

Astronomers are ever dreaming of sites with best seeing on the Earth surface for celestial observation, and the Antarctica is one of a few such sites only left owing to the global air pollution. However, Antarctica region is largely unaccessible for human being due to lacking of fundamental living conditions, travel facilities and effective ways of communication. Worst of all, the popular internet source as a general way of communication scarcely exists there. Facing such a dilemma and as a solution remote control and data transmission for telescopes through iridium satellite communication has been put forward for the Chinese network Antarctic Schmidt Telescopes 3 (AST3), which is currently under all round research and development. This paper presents iridium satellite-based remote control application adapted to telescope control. The pioneer work in China involves hardware and software configuration utilizing techniques for reliable and secure communication, which is outlined in the paper too.

Prototyping iridium coated mirrors for x-ray astronomy

NASA Astrophysics Data System (ADS)

Döhring, Thorsten; Probst, Anne-Catherine; Stollenwerk, Manfred; Emmerich, Florian; Stehlíková, Veronika; Inneman, Adolf

2017-05-01

X-ray astronomy uses space-based telescopes to overcome the disturbing absorption of the Earth's atmosphere. The telescope mirrors are operating at grazing incidence angles and are coated with thin metal films of high-Z materials to get sufficient reflectivity for the high-energy radiation to be observed. In addition the optical payload needs to be light-weighted for launcher mass constrains. Within the project JEUMICO, an acronym for "Joint European Mirror Competence", the Aschaffenburg University of Applied Sciences and the Czech Technical University in Prague started a collaboration to develop mirrors for X-ray telescopes. The X-ray telescopes currently developed within this Bavarian- Czech project are of Lobster eye type optical design. Corresponding mirror segments use substrates of flat silicon wafers which are coated with thin iridium films, as this material is promising high reflectivity in the X-ray range of interest. The deposition of the iridium films is based on a magnetron sputtering process. Sputtering with different parameters, especially by variation of the argon gas pressure, leads to iridium films with different properties. In addition to investigations of the uncoated mirror substrates the achieved surface roughness has been studied. Occasional delamination of the iridium films due to high stress levels is prevented by chromium sublayers. Thereby the sputtering parameters are optimized in the context of the expected reflectivity of the coated X-ray mirrors. In near future measurements of the assembled mirror modules optical performances are planned at an X-ray test facility.

Study of iridium silicide monolayers using density functional theory

NASA Astrophysics Data System (ADS)

Popis, Minh D.; Popis, Sylvester V.; Oncel, Nuri; Hoffmann, Mark R.; ćakır, Deniz

2018-02-01

In this study, we investigated physical and electronic properties of possible two-dimensional structures formed by Si (silicon) and Ir (iridium). To this end, different plausible structures were modeled by using density functional theory and the cohesive energies calculated for the geometry of optimized structures, with the lowest equilibrium lattice constants. Among several candidate structures, we identified three mechanically (via elastic constants and Young's modulus), dynamically (via phonon calculations), and thermodynamically stable iridium silicide monolayer structures. The lowest energy structure has a chemical formula of Ir2Si4 (called r-IrSi2), with a rectangular lattice (Pmmn space group). Its cohesive energy was calculated to be -0.248 eV (per IrSi2 unit) with respect to bulk Ir and bulk Si. The band structure indicates that the Ir2Si4 monolayer exhibits metallic properties. Other stable structures have hexagonal (P-3m1) and tetragonal (P4/nmm) cell structures with 0.12 and 0.20 eV/f.u. higher cohesive energies, respectively. Our calculations showed that Ir-Si monolayers are reactive. Although O2 molecules exothermically dissociate on the surface of the free-standing iridium silicide monolayers with large binding energies, H2O molecules bind to the monolayers with a rather weak interaction.

Preparation of Ti/IrO2 Anode with Low Iridium Content by Thermal Decomposition Process: Electrochemical removal of organic pollutants in water

NASA Astrophysics Data System (ADS)

Yaqub, Asim; Isa, Mohamed Hasnain; Ajab, Huma; Kutty, S. R. M.; Ezechi, Ezerie H.; Farooq, Robina

2018-04-01

In this study IrO2 (Iridium oxide) was coated onto a titanium plate anode from a dilute (50 mg/10 ml) IrCl3×H2O salt solution. Coating was done at high temperature (550∘C) using thermal decomposition. Surface morphology and characteristics of coated surface of Ti/IrO2 anode were examined by FESEM and XRD. The coated anode was applied for electrochemical removal of organic pollutants from synthetic water samples in 100 mL compartment of batch electrochemical cell. About 50% COD removal was obtained at anode prepared with low Ir content solution while 72% COD removal was obtained with anode prepared at high Ir content. Maximum COD removal was obtained at 10 mA/cm2 current density.

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

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.

Hot rocket plume experiment - Survey and conceptual design. [of rhenium-iridium bipropellants

NASA Technical Reports Server (NTRS)

Millard, Jerry M.; Luan, Taylor W.; Dowdy, Mack W.

1992-01-01

Attention is given to a space-borne engine plume experiment study to fly an experiment which will both verify and quantify the reduced contamination from advanced rhenium-iridium earth-storable bipropellant rockets (hot rockets) and provide a correlation between high-fidelity, in-space measurements and theoretical plume and surface contamination models. The experiment conceptual design is based on survey results from plume and contamination technologists throughout the U.S. With respect to shuttle use, cursory investigations validate Hitchhiker availability and adaptability, adequate remote manipulator system (RMS) articulation and dynamic capability, acceptable RMS attachment capability, adequate power and telemetry capability, and adequate flight altitude and attitude/orbital capability.

Triplet exciton diffusion in fac-tris(2-phenylpyridine) iridium(III)-cored electroluminescent dendrimers

NASA Astrophysics Data System (ADS)

Namdas, Ebinazar B.; Ruseckas, Arvydas; Samuel, Ifor D. W.; Lo, Shih-Chun; Burn, Paul L.

2005-02-01

We have studied triplet-triplet annihilation in neat films of electrophosphorescent fac-tris(2-phenylpyridine) iridium(III) [Ir(ppy)3]-cored dendrimers containing phenylene- and carbazole-based dendrons with 2-ethylhexyloxy surface groups using time-resolved photoluminescence. From measured annihilation rates, the limiting current densities above which annihilation would dominate in dendrimer light-emitting devices are found to be >1A/cm2. The triplet exciton diffusion length varies in the range of 2-10 nm depending on the dendron size. The distance dependence of the nearest-neighbor hopping rate shows that energy transfer is dominated by the exchange mechanism.

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 vehicle, leading to the higher area-to-mass ratios of the fragments.

The first neural probe integrated with light source (blue laser diode) for optical stimulation and electrical recording.

PubMed

Park, HyungDal; Shin, Hyun-Joon; Cho, Il-Joo; Yoon, Eui-sung; Suh, Jun-Kyo Francis; Im, Maesoon; Yoon, Euisik; Kim, Yong-Jun; Kim, Jinseok

2011-01-01

In this paper, we report a neural probe which can selectively stimulate target neurons optically through Si wet etched mirror surface and record extracellular neural signals in iridium oxide tetrodes. Consequently, the proposed approach provides to improve directional problem and achieve at least 150/m gap distance between stimulation and recording sites by wet etched mirror surface in V-groove. Also, we developed light source, blue laser diode (OSRAM Blue Laser Diode_PL 450), integration through simple jig for one-touch butt-coupling. Furthermore, optical power and impedance of iridium oxide tetrodes were measured as 200 μW on 5 mW from LD and 206.5 k Ω at 1 kHz and we demonstrated insertion test of probe in 0.5% agarose-gel successfully. We have successfully transmitted a light of 450 nm to optical fiber through the integrated LD using by butt-coupling method.

Development of low-stress Iridium coatings for astronomical x-ray mirrors

NASA Astrophysics Data System (ADS)

Döhring, Thorsten; Probst, Anne-Catherine; Stollenwerk, Manfred; Wen, Mingwu; Proserpio, Laura

2016-07-01

Previously used mirror technologies are not suitable for the challenging needs of future X-ray telescopes. This is why the required high precision mirror manufacturing triggers new technical developments around the world. Some aspects of X-ray mirrors production are studied within the interdisciplinary project INTRAAST, a German acronym for "industry transfer of astronomical mirror technologies". The project is embedded in a cooperation of Aschaffenburg University of Applied Sciences and the Max-Planck-Institute for extraterrestrial Physics. One important task is the development of low-stress Iridium coatings for X-ray mirrors based on slumped thin glass substrates. The surface figure of the glass substrates is measured before and after the coating process by optical methods. Correlating the surface shape deformation to the parameters of coating deposition, here especially to the Argon sputtering pressure, allows for an optimization of the process. The sputtering parameters also have an influence on the coating layer density and on the micro-roughness of the coatings, influencing their X-ray reflection properties. Unfortunately the optimum coating process parameters seem to be contrarious: low Argon pressure resulted in better micro-roughness and higher density, whereas higher pressure leads to lower coating stress. Therefore additional measures like intermediate coating layers and temperature treatment will be considered for further optimization. The technical approach for the low-stress Iridium coating development, the experimental equipment, and the obtained first experimental results are presented within this paper.

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

A cyclometalated iridium(III) complex used as a conductor for the electrochemical sensing of IFN-γ

NASA Astrophysics Data System (ADS)

Miao, Xiangmin; Ko, Chung-Nga; Vellaisamy, Kasipandi; Li, Zongbing; Yang, Guanjun; Leung, Chung-Hang; Ma, Dik-Lung

2017-02-01

A novel iridium(III) complex was prepared and used as a conductor for sensitive and enzyme-free electrochemical detection of interferon gamma (IFN-γ). This assay is based on a dual signal amplification mechanism involving positively charged gold nanoparticles ((+)AuNPs) and hybridization chain reaction (HCR). To construct the sensor, nafion (Nf) and (+)AuNPs composite membrane was first immobilized onto the electrode surface. Subsequently, a loop-stem structured capture probe (CP) containing a special IFN-γ interact strand was modified onto the (+)AuNP surface via the formation of Au-S bonds. Upon addition of IFN-γ, the loop-stem structure of CP was opened, and the newly exposed “sticky” region of CP then hybridized with DNA hairpin-1 (H1), which in turn opened its hairpin structure for hybridizing with DNA hairpin-2 (H2). Happen of HCR between H1 and H2 thus generated a polymeric duplex DNA (dsDNA) chain. Meanwhile, the iridium(III) complex could interact with the grooves of the dsDNA polymer, producing a strong current signal that was proportional to IFN-γ concentration. Thus, sensitive detection of IFN-γ could be realized with a detection limit down to 16.3 fM. Moreover, satisfied results were achieved by using this method for the detection of IFN-γ in human serum samples.

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.

Roles of Thin Film Stress in Making Extremely Lightweight X-Ray Optics

NASA Technical Reports Server (NTRS)

Zhang, William W.

2010-01-01

X-ray optics typically must be coated with one of the noble metals, gold, platinum, or iridium, to enhance their photon collection area. In general, iridium is preferred to the other two because it generates the highest X-ray reflectivity in the I to 10 keV band. Unfortunately, iridium films typically have also the highest stress that can severely degrade the optical figure of the mirror substrate, resulting in a poorer image quality. In this paper we will report our work in understanding this stress and our method to counterbalance it. In particular we will also report on potential ways of using this stress to improve the substrate's optical figure, turning a bug into a desirable feature. This work is done in the context of developing an enabling technology for the International X-ray Observatory which is a collaborative mission of NASA, ESA, and JAXA, and expected to be launched into an L2 orbit in 2021.

Dinoflagellate and calcareous nannofossil response to sea-level change in Cretaceous-Tertiary boundary sections

DOE Office of Scientific and Technical Information (OSTI.GOV)

Habib, D.; Moshkovitz, S.; Kramer, C.

1992-02-01

Stratigraphic sections in south-central Alabama were studied to test palynological evidence of sea-level change across the Cretaceous-Tertiary boundary. New evidence from both calcareous nannofossils and dinoflagellate cysts places the regional disconformity in Alabama (Type 1 sequence boundary) virtually at the K-T boundary. This suggests that sea-level fall may have contributed to mass-extinction event. Dinoflagellate diversity varies between systems tract components of coastal onlap. This parameter is useful for interpreting sea-level change in this part of the section, because dinoflagellates did not participate in the mass extinction. The iridium spikes in the roadcut near Braggs are of earliest Danian age andmore » correlate in relative magnitude with the lower values reported from directly above the K-T boundary in the Gubbio stratotype section. Iridium was concentrated in marine flooding surfaces in episodes of higher productivity of algal organic matter at the time when the iridium-enriched ocean encroached on the shelf during the first Cenozoic episode of sea-level rise.« less

Testing of Wrought Iridium/Chemical Vapor Deposition Rhenium Rocket

NASA Technical Reports Server (NTRS)

Reed, Brian D.; Schneider, Steven J.

1996-01-01

A 22-N class, iridium/rhenium (Ir/Re) rocket chamber, composed of a thick (418 miocrometer) wrought iridium (Ir) liner and a rhenium substrate deposited via chemical vapor deposition, was tested over an extended period on gaseous oxygen/gaseous hydrogen (GO2/GH2) propellants. The test conditions were designed to produce species concentrations similar to those expected in an Earth-storable propellant combustion environment. Temperatures attained in testing were significantly higher than those expected with Earth-storable propellants, both because of the inherently higher combustion temperature of GO2/GH2 propellants and because the exterior surface of the rocket was not treated with a high-emissivity coating that would be applied to flight class rockets. Thus the test conditions were thought to represent a more severe case than for typical operational applications. The chamber successfully completed testing (over 11 hr accumulated in 44 firings), and post-test inspections showed little degradation of the Ir liner. The results indicate that use of a thick, wrought Ir liner is a viable alternative to the Ir coatings currently used for Ir/Re rockets.

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.

Integrated Microcalorimeters Using Ir TES And Sn Mushroom Absorbers

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chen, C.; Bogorin, D.; Galeazzi, M.

2006-09-07

Cryogenic microcalorimeters have the potential to meet the requirements of future x-ray missions. The University of Miami has recently started a program to fabricate fully integrated microcalorimeter arrays. We deposit high purity iridium thin film as Transition Edge Sensors (TES). We chose iridium because it has a bulk transition temperature of 112 mK and we expect single layer TES to have good reproducibility and long term stability. Also we use integrated tin film in a mushroom geometry as the absorbers to get high filling factor, low heat capacity and easy array manufacturing process. We present here our preliminary results inmore » both areas.« less

A Deep-Ocean Observatory with Near Real-time Telemetry

NASA Astrophysics Data System (ADS)

Berger, J.; Orcutt, J. A.; Laske, G.

2014-12-01

We describe an autonomously deployable, deep-ocean observatory designed to provide long term and near-real-time observations from sites far offshore. The key feature of this new system is its ability to telemeter sensor data from the seafloor to shore without a cable or moored surface buoy. In the future the observatory will be deployable without a ship. The first application of this system is seismology. While permanent ocean seismic stations on the seafloor have long been a goal of global seismology, today there are still no ocean bottom stations in the Global Seismographic Network, mostly for reasons of life-cycle costs. Yet real-time data from stations in oceanic areas are critical for both national and international agencies in monitoring and characterizing earthquakes, tsunamis, and nuclear explosions. The system comprises an ocean bottom instrumentation package and a free-floating surface communications gateway, which uses a Liquid Robotics wave glider. The glider consists of a surfboard-sized float propelled by a tethered, submerged glider, which converts wave motion into thrust. For navigation, the wave gliders are equipped with a small computer, a GPS receiver, a rudder, solar panels and batteries, and an Iridium satellite modem. Wave gliders have demonstrated trans-oceanic range combined with long-term station holding. The 'communications gateway,' which provides the means of communicating between the ocean bottom package and land comprises a wave glider and a towed acoustic communications 'tow body'. Acoustic communications connect the subsea instruments and the surface gateway while communications between the gateway and land is provided by the Iridium satellite constellation. Tests of the surface gateway in 4350 m of water demonstrated the ability to send four channels of compressed 24-bit, 1 sample per second data from the ocean bottom to the gateway with an average power draw of approximately 0.2 W.

Micromachined electrode array

DOEpatents

Okandan, Murat; Wessendorf, Kurt O.

2007-12-11

An electrode array is disclosed which has applications for neural stimulation and sensing. The electrode array, in certain embodiments, can include a plurality of electrodes each of which is flexibly attached to a common substrate using a plurality of springs to allow the electrodes to move independently. In other embodiments of the electrode array, the electrodes can be fixed to the substrate. The electrode array can be formed from a combination of bulk and surface micromachining, and can include electrode tips having an electroplated metal (e.g. platinum, iridium, gold or titanium) or a metal oxide (e.g. iridium oxide) for biocompatibility. The electrode array can be used to form a part of a neural prosthesis, and is particularly well adapted for use in an implantable retinal prosthesis.

Radioisotopic heat source

DOEpatents

Sayell, E.H.

1973-10-23

A radioisotopic heat source is described which includes a core of heat productive, radioisotopic material, an impact resistant layer of graphite surrounding said core, and a shell of iridium metal intermediate the core and the impact layer. The source may also include a compliant mat of iridium between the core and the iridium shell, as well as an outer covering of iridium metal about the entire heat source. (Official Gazette)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Purwaningsih, Anik

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 ofmore » calculation of radial dose function and anisotropic dose distribution for Iridium-192 source type H01 were compared with another model of Iridium-192 source.« less

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

PubMed

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

1983-12-09

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).

Sudden death at the end of the Mesozoic

USGS Publications Warehouse

Emiliani, C.; Kraus, E.B.; Shoemaker, E.M.

1981-01-01

A paleoecological analysis of the fossil record before and after the Cretaceous/Tertiary boundary indicates that the widespread extinctions and biological stresses around the boundary are best explained in terms of a sudden, significant, but short temperature rise. L. Alvarez and co-authors, having found an enrichment in iridium at the same boundary, postulated that it was associated with the impact of an extraterrestrial body. If this body struck the ocean, the water injected into the atmosphere may have led to a transient increase in the global surface temperature. This temperature pulse may have been primarily responsible for the effects observed in the biosphere. The pattern of extinction of higher plant species suggests that splash down occurred in the northern Pacific-Bering Sea area. ?? 1981.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Song, Bo; Nelson, Kevin; Jin, Helena

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 barmore » 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.« less

Possibility to realize spin-orbit-induced correlated physics in iridium fluorides

NASA Astrophysics Data System (ADS)

Rossi, M.; Retegan, M.; Giacobbe, C.; Fumagalli, R.; Efimenko, A.; Kulka, T.; Wohlfeld, K.; Gubanov, A. I.; Moretti Sala, M.

2017-06-01

Recent theoretical predictions of "unprecedented proximity" of the electronic ground state of iridium fluorides to the SU(2) symmetric jeff=1 /2 limit, relevant for superconductivity in iridates, motivated us to investigate their crystal and electronic structure. To this aim, we performed high-resolution x-ray powder diffraction, Ir L3-edge resonant inelastic x-ray scattering, and quantum chemical calculations on Rb2[IrF6] and other iridium fluorides. Our results are consistent with the Mott insulating scenario predicted by Birol and Haule [Phys. Rev. Lett. 114, 096403 (2015), 10.1103/PhysRevLett.114.096403], but we observe a sizable deviation of the jeff=1 /2 state from the SU(2) symmetric limit. Interactions beyond the first coordination shell of iridium are negligible, hence the iridium fluorides do not show any magnetic ordering down to at least 20 K. A larger spin-orbit coupling in iridium fluorides compared to oxides is ascribed to a reduction of the degree of covalency, with consequences on the possibility to realize spin-orbit-induced strongly correlated physics in iridium fluorides.

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.

Flexible retinal electrode array

DOEpatents

Okandan, Murat [Albuquerque, NM; Wessendorf, Kurt O [Albuquerque, NM; Christenson, Todd R [Albuquerque, NM

2006-10-24

An electrode array which has applications for neural stimulation and sensing. The electrode array can include a large number of electrodes each of which is flexibly attached to a common substrate using a plurality of springs to allow the electrodes to move independently. The electrode array can be formed from a combination of bulk and surface micromachining, with electrode tips that can include an electroplated metal (e.g. platinum, iridium, gold or titanium) or a metal oxide (e.g. iridium oxide) for biocompatibility. The electrode array can be used to form a part of a neural prosthesis, and is particularly well adapted for use in an implantable retinal prosthesis where the electrodes can be tailored to provide a uniform gentle contact pressure with optional sensing of this contact pressure at one or more of the electrodes.

Platinum Group Coatings for Refractory Metals

DTIC Science & Technology

1984-06-01

temperatures and deposition was very slow. We decided to try iridium hexaflouride, Siridium trichloride hydrate, iridiuw carbonyl and tris-acetyl acetonato...T:*ouu sue. CO. Rhenium Refractory Metals 03 1 d.pRsiý C rg Iridium Coatings 2i 8 bapo i 10. ASSTRACT Won#~.. on mov ofot~sfte.. iad k.dhItfV by b...b q Oxidation resistant coatings of iridium on rhenium substrates have been produced by chemical vapor deposition from an iridium acetyl acetonate

Area-Selective Atomic Layer Deposition of Metal Oxides on Noble Metals through Catalytic Oxygen Activation

PubMed Central

2017-01-01

Area-selective atomic layer deposition (ALD) is envisioned to play a key role in next-generation semiconductor processing and can also provide new opportunities in the field of catalysis. In this work, we developed an approach for the area-selective deposition of metal oxides on noble metals. Using O2 gas as co-reactant, area-selective ALD has been achieved by relying on the catalytic dissociation of the oxygen molecules on the noble metal surface, while no deposition takes place on inert surfaces that do not dissociate oxygen (i.e., SiO2, Al2O3, Au). The process is demonstrated for selective deposition of iron oxide and nickel oxide on platinum and iridium substrates. Characterization by in situ spectroscopic ellipsometry, transmission electron microscopy, scanning Auger electron spectroscopy, and X-ray photoelectron spectroscopy confirms a very high degree of selectivity, with a constant ALD growth rate on the catalytic metal substrates and no deposition on inert substrates, even after 300 ALD cycles. We demonstrate the area-selective ALD approach on planar and patterned substrates and use it to prepare Pt/Fe2O3 core/shell nanoparticles. Finally, the approach is proposed to be extendable beyond the materials presented here, specifically to other metal oxide ALD processes for which the precursor requires a strong oxidizing agent for growth. PMID:29503508

Synthesis of benzimidazoles via iridium-catalyzed acceptorless dehydrogenative coupling.

PubMed

Sun, Xiang; Lv, Xiao-Hui; Ye, Lin-Miao; Hu, Yu; Chen, Yan-Yan; Zhang, Xue-Jing; Yan, Ming

2015-07-21

Iridium-catalyzed acceptorless dehydrogenative coupling of tertiary amines and arylamines has been developed. A number of benzimidazoles were prepared in good yields. An iridium-mediated C-H activation mechanism is suggested. This finding represents a novel strategy for the synthesis of benzimidazoles.

Iridium catalysis: application of asymmetric reductive hydrogenation.

PubMed

Cadu, Alban; Andersson, Pher G

2013-10-28

Iridium, despite being one of the least abundant transition metals, has found several uses. N,P-ligated iridium catalysts are used to perform many highly selective reactions. These methodologies have been developed extensively over the past 15 years. More recently, the application of iridium N,P catalysts in asymmetric hydrogenation has been a focus of research to find novel applications and to expand on their current synthetic utility. The aim of this perspective is to highlight the advances made by the Andersson group.

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.

Concepts for Cost-Effective Enhanced Cryosat Continuity: Opportunity in the Iridium PRIME Context

NASA Astrophysics Data System (ADS)

Le Roy, Y.; Caubet, E.; Silverstrin, P.; Legrand, C.

2016-08-01

The Iridium-PRIME offer, recently initiated by the Iridium company, consists in hosting payloads on customized low cost Iridium-NEXT platforms on which the main telecom mission antenna (L-band) is removed. This leaves significant resources in terms of mass, volume and power consumption to host up to three payloads on these customized platforms. The Iridium-PRIME satellites will be inserted in the Iridium-NEXT constellation to take benefit of the low cost operation service (command, control and data telemetry through the life time of the Iridium-PRIME mission). Given the synergy between schedules of the Iridium-PRIME program (launches starting around 2020) and of a possible CryoSat Follow-On (FO) mission (launch around 2022) and the adequacy of the available on-board resources for such a mission, ESA tasked Thales Alenia Space, as responsible for the SIRAL radar instrument of the currently in-orbit CryoSat mission, to study the feasibility of a concept for enhanced continuity of CryoSat on an Iridium- PRIME satellite as potential low-cost fast-track solution. The study aimed to define a cost-effective topographic payload including not only the SIRAL radar but also the necessary sub-systems to retrieve the SIRAL antenna baseline attitude (star trackers) with high accuracy and to perform a Precise Orbit Determination (POD). All these aspects are presented in this paper. In addition, possible evolutions/improvements of the Ku-band radar instrument were analysed and are presented: adding a Ka-band nadir measurement capability and a Ku-band or Ka-band wide swath mode measurement capability. The transmission issue for the SIRAL science data is also discussed in the paper.

Comparison of iridium- and ruthenium-based, Pt-surface-enriched, nanosize catalysts for the oxygen-reduction reaction

NASA Astrophysics Data System (ADS)

Kaplan, D.; Goor, M.; Alon, M.; Tsizin, S.; Burstein, L.; Rosenberg, Y.; Popov, I.; Peled, E.

2016-02-01

Pt-surface-enriched nanosize catalysts (Pt-SENS catalysts) with ruthenium and iridium cores, supported on XC72, were synthesized and characterized. The structure and composition of the catalysts are determined by Energy-Dispersive X-ray Spectroscopy (EDS), X-ray Photoelectron Spectroscopy (XPS), Scanning Transmission Electron Microscopy (STEM) and X-Ray Diffraction (XRD). Electrochemical characterization tests, including oxygen-reduction-catalysis activity and durability studies of catalysts are performed with the use of cyclic-voltammetry and rotating-disk-electrode (RDE) techniques at room temperature. The ORR activity of the homemade catalysts is also compared to ORR activity of commercial 50%Pt/C catalyst. It is determined that the Ir-based catalyst (Pt/Ir/XC72) shows higher ORR activity in terms of A g-1 of Pt (at 0.85 V vs. RHE) than the Ru-based catalyst (Pt/Ru/XC72) and the commercial 50%Pt/C. The Ru-based catalyst shows similar ORR activity in terms of A g-1 of Pt, to that of the commercial 50%Pt/C, but with much lower durability.

Antibacterial activity of microstructured sacrificial anode thin films by combination of silver with platinum group elements (platinum, palladium, iridium).

PubMed

Köller, Manfred; Bellova, Petri; Javid, Siyamak Memar; Motemani, Yahya; Khare, Chinmay; Sengstock, Christina; Tschulik, Kristina; Schildhauer, Thomas A; Ludwig, Alfred

2017-05-01

Five different Ag dots arrays (16 to 400dots/mm 2 ) were fabricated on a continuous platinum, palladium, or iridium thin film and for comparison also on titanium film by sputter deposition and photolithographic patterning. To analyze the antibacterial activity of these microstructured films Staphylococcus aureus (S. aureus) were placed onto the array surfaces and cultivated overnight. To analyze the viability of planktonic as well as surface adherent bacteria, the applied bacterial fluid was subsequently aspirated, plated on blood agar plates and adherent bacteria were detected by fluorescence microscopy. A particular antibacterial effect towards S. aureus was induced by Ag dot arrays on each of the platinum group thin film (sacrificial anode system for Ag) in contrast to Ag dot arrays fabricated on the Ti thin films (non-sacrificial anode system for Ag). Among platinum group elements the Ir-Ag system exerted the highest antibacterial activity which was accompanied by most advanced dissolution of the Ag dots and Ag ion release compared to Ag dots on Pt or Pd. Copyright © 2016 Elsevier B.V. All rights reserved.

Treatment of carcinoma of the penis by iridium 192 wire implant

DOE Office of Scientific and Technical Information (OSTI.GOV)

Daly, N.J.; Douchez, J.; Combes, P.F.

1982-07-01

Since 1971, a group of 22 adult patients with squamous cell carcinoma of the penis have been treated by iridium 192 wire implants. There were 6 T1 tumors, 14 T2 tumors and 2 T3; only one patient (T3) presented with local failure after implant. Local necrosis occurred in 2 patients without local tumoral recurrence, but was sufficient enough to warrant amputation. Thus 19/22 (86%) patients were locally cured with penile conservation. In these patients the most frequent posttherapeutic complication is chronic urethral stenosis (9/19 patients, 47%) requiring repeated instrumental dilations. Four patients presented with initial inguinal mestastatic nodes; only onemore » was cured by radiosurgical treatment. Among patients without metastatic nodes at the time of diagnosis, none had delayed metastatic nodes. Three patients died of nodal evolution, 5 patients died of intercurrent disease without evidence of disease and 14 are now alive and NED. It appears that iridium 192 wire implant is the most effective conservative treatment of invasive squamous cell carcinoma of the penis; however, these results confirm that no particular treatment is required for inguinal nodal areas for patients who initially present with no disease.« less

Techniques for Achieving Zero Stress in Thin Films of Iridium, Chromium, and Nickel

NASA Technical Reports Server (NTRS)

Broadway, David M.; O'Dell, Stephen L.; Ramsey, Brian D.; Weimer, Jeffrey

2015-01-01

We examine techniques for achieving zero intrinsic stress in thin films of iridium, chromium, and nickel deposited by magnetron sputter deposition. The intrinsic stress is further correlated to the microstructural features and physical properties such as surface roughness and optical density at a scale appropriate to soft X-ray wavelengths. 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-arcsecond resolution through various deposition techniques 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 and deposition rate, including the existence of a critical argon process pressure that results in zero film stress which scales linearly with the atomic mass of the sputtered species. While the effect of stress reversal with argon pressure has been previously reported by Hoffman and others for nickel and chromium, we report this effect for iridium. In addition to stress reversal, we identify zero stress in the optical functioning iridium layer shortly after island coalescence for low process pressures at a film thickness of approximately 35nm. The measurement of the low values of stress during deposition was achieved with the aid of a sensitive in-situ instrument capable of a minimum detectable level of stress, assuming a 35nm thick film, in the range of 0.40-6.0 MPa for <111> oriented crystalline silicon substrate thicknesses of 70-280 microns, respectively.

Electrochemical Dissolution of Iridium and Iridium Oxide Particles in Acidic Media: Transmission Electron Microscopy, Electrochemical Flow Cell Coupled to Inductively Coupled Plasma Mass Spectrometry, and X-ray Absorption Spectroscopy Study.

PubMed

Jovanovič, Primož; Hodnik, Nejc; Ruiz-Zepeda, Francisco; Arčon, Iztok; Jozinović, Barbara; Zorko, Milena; Bele, Marjan; Šala, Martin; Šelih, Vid Simon; Hočevar, Samo; Gaberšček, Miran

2017-09-13

Iridium-based particles, regarded as the most promising proton exchange membrane electrolyzer electrocatalysts, were investigated by transmission electron microscopy and by coupling of an electrochemical flow cell (EFC) with online inductively coupled plasma mass spectrometry. Additionally, studies using a thin-film rotating disc electrode, identical location transmission and scanning electron microscopy, as well as X-ray absorption spectroscopy have been performed. Extremely sensitive online time-and potential-resolved electrochemical dissolution profiles revealed that Ir particles dissolve well below oxygen evolution reaction (OER) potentials, presumably induced by Ir surface oxidation and reduction processes, also referred to as transient dissolution. Overall, thermally prepared rutile-type IrO 2 particles are substantially more stable and less active in comparison to as-prepared metallic and electrochemically pretreated (E-Ir) analogues. Interestingly, under OER-relevant conditions, E-Ir particles exhibit superior stability and activity owing to the altered corrosion mechanism, where the formation of unstable Ir(>IV) species is hindered. Due to the enhanced and lasting OER performance, electrochemically pre-oxidized E-Ir particles may be considered as the electrocatalyst of choice for an improved low-temperature electrochemical hydrogen production device, namely a proton exchange membrane electrolyzer.

Carbon Dioxide Utilization by the Five-Membered Ring Products of Cyclometalation Reactions

PubMed Central

Omae, Iwao

2016-01-01

In carbon dioxide utilization by cyclometalated five-membered ring products, the following compounds are used in four types of applications: 1. 2-Phenylpyrazole iridium compounds, pincer phosphine iridium compounds and 2-phenylimidazoline iridium compounds are used as catalysts for both formic acid production from CO2 and H2, and hydrogen production from the formic acid. This formic acid can be a useful agent for H2 production and storage for fuel cell electric vehicles. 2. Other chemicals, e.g., dimethyl carbonate, methane, methanol and CO, are produced with dimethylaminomethylphenyltin compounds, pincer phosphine iridium compounds, pincer phosphine nickel compound and ruthenium carbene compound or 2-phenylpyridine iridium compounds, and phenylbenzothiazole iridium compounds as the catalysts for the reactions with CO2. 3. The five-membered ring intermediates of cyclometalation reactions with the conventional substrates react with carbon dioxide to afford their many types of carboxylic acid derivatives. 4. Carbon dioxide is easily immobilized at room temperature with immobilizing agents such as pincer phosphine nickel compounds, pincer phosphine palladium compounds, pincer N,N-dimethylaminomethyltin compounds and tris(2-pyridylthio)methane zinc compounds. PMID:28503084

Carbon Dioxide Utilization by the Five-Membered Ring Products of Cyclometalation Reactions.

PubMed

Omae, Iwao

2016-04-01

In carbon dioxide utilization by cyclometalated five-membered ring products, the following compounds are used in four types of applications: 1. 2-Phenylpyrazole iridium compounds, pincer phosphine iridium compounds and 2-phenylimidazoline iridium compounds are used as catalysts for both formic acid production from CO 2 and H 2 , and hydrogen production from the formic acid. This formic acid can be a useful agent for H 2 production and storage for fuel cell electric vehicles. 2. Other chemicals, e.g. , dimethyl carbonate, methane, methanol and CO, are produced with dimethylaminomethylphenyltin compounds, pincer phosphine iridium compounds, pincer phosphine nickel compound and ruthenium carbene compound or 2-phenylpyridine iridium compounds, and phenylbenzothiazole iridium compounds as the catalysts for the reactions with CO 2 . 3. The five-membered ring intermediates of cyclometalation reactions with the conventional substrates react with carbon dioxide to afford their many types of carboxylic acid derivatives. 4. Carbon dioxide is easily immobilized at room temperature with immobilizing agents such as pincer phosphine nickel compounds, pincer phosphine palladium compounds, pincer N , N -dimethylaminomethyltin compounds and tris(2-pyridylthio)methane zinc compounds.

Iridium clusters in KLTL zeolite: Synthesis, structural characterization, and catalysis of toluene hydrogenation and n-hexane dehydrocyclization

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhao, A.; Jentoft, R.E.; Gates, B.C.

Iridium clusters incorporating about six atoms each, on average, were prepared in KLTL zeolite by decarbonylation (in H{sub 2} at 400{degrees}C) of iridium carbonyl clusters formed by treatment of adsorbed [Ir(CO){sub 2}(acac)] in CO at 1 atm and 175{degrees}C. The supported species were characterized by infrared and extended X-ray absorption fine structure (EXAFS) spectroscopies. The iridium carbonyls formed from [Ir(CO){sub 2}(acac)] were predominantly [HIr{sub 4}(CO){sub 11}]{sup -} with a small amount of [Ir(CO){sub 4}]{sup -}. The synthesis chemistry of iridium carbonyls in the basic KLTL zeolite parallels that in basic solutions. Shifts of the {nu}{sub CO} bands of the iridiummore » carbonyl clusters relative to those of the same clusters in solution indicate strong interactions between the clusters and zeolite cations. The decarbonylated sample, approximated as Ir{sub 6}/KLTL zeolite, is catalytically active for toluene hydrogenation at 60-100{degrees}C, with the activity being approximately the same as those of Ir{sub 4} and Ir{sub 6} clusters supported on metal oxides, but an order of magnitude less than that of a conventional supported iridium catalyst consisting of aggregates of about 50 atoms each, on average. The catalyst is also active for conversion of n-hexane + H{sub 2} at 340-420{degrees}C, but the selectivity for aromatization is low and that for hydrogenolysis is high, consistent with earlier results for conventionally prepared (salt-derived) iridium clusters of about the same size supported in KLTL zeolite. The zeolite-supported iridium clusters are the first prepared from both salt and organometallic precursors; the results indicate that the organometallic and conventional preparation routes lead to supported iridium clusters having similar structures and catalytic properties. 59 refs., 6 figs., 7 tabs.« less

Performance enhancement in organic photovoltaic solar cells using iridium (Ir) ultra-thin surface modifier (USM)

NASA Astrophysics Data System (ADS)

Pandey, Rina; Lim, Ju Won; Kim, Jung Hyuk; Angadi, Basavaraj; Choi, Ji Won; Choi, Won Kook

2018-06-01

In this study, Iridium (Ir) metallic layer as an ultra-thin surface modifier (USM) was deposited on ITO coated glass substrate using radio frequency magnetron sputtering for improving the photo-conversion efficiency of organic photovoltaic cells. Ultra-thin Ir acts as a surface modifier replacing the conventional hole transport layer (HTL) PEDOT:PSS in organic photovoltaic (OPV) cells with two different active layers P3HT:PC60BM and PTB7:PC70BM. The Ir USM (1.0 nm) coated on ITO glass substrate showed transmittance of 84.1% and work function of >5.0 eV, which is higher than that of ITO (4.5-4.7 eV). The OPV cells with Ir USM (1.0 nm) exhibits increased power conversion efficiency of 3.70% (for P3HT:PC60BM active layer) and 7.28% (for PTB7:PC70BM active layer) under 100 mW/cm2 illumination (AM 1.5G) which are higher than those of 3.26% and 6.95% for the same OPV cells but with PEDOT:PSS as HTL instead of Ir USM. The results reveal that the chemically stable Ir USM layer could be used as an alternative material for PEDOT:PSS in organic photovoltaic cells.

Iridium Anomaly Approximately Synchronous with Terminal Eocene Extinctions

NASA Astrophysics Data System (ADS)

Alvarez, Walter; Asaro, Frank; Michel, Helen V.; Alvarez, Luis W.

1982-05-01

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.

Feasibility Analysis on the Utilization of the Iridium Satellite Communications Network for Resident Space Objects in Low Earth Orbit

DTIC Science & Technology

2013-03-21

Coordinate System (from STK ) .................................. 15 Figure 7. Iridium Satellite Viewing Geometry from Ground User...44 Figure 15. Iridium Constellation Model in STK with Single FOV Spot Beams ............. 58 Figure 16...60 Table 11. Numeric RAAN Values Represented as Two Categoric Factors .................... 67 Table 12. Spacecraft RAAN Values in STK

DOE Office of Scientific and Technical Information (OSTI.GOV)

Song, Bo; Nelson, Kevin; Lipinski, Ronald J.

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 analyzedmore » 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 (750°C and 1030°C). 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.« less

Cell and method for electrolysis of water and anode

NASA Technical Reports Server (NTRS)

Aylward, J. R. (Inventor)

1981-01-01

An electrolytic cell for converting water vapor to oxygen and hydrogen include an anode comprising a foraminous conductive metal substrate with a 65-85 weight percent iridium oxide coating and 15-35 weight percent of a high temperature resin binder. A matrix member contains an electrolyte to which a cathode substantially inert. The foraminous metal member is most desirably expanded tantalum mesh, and the cell desirably includes reservoir elements of porous sintered metal in contact with the anode to receive and discharge electrolyte to the matrix member as required. Upon entry of a water vapor containing airstream into contact with the outer surface of the anode and thence into contact with iridium oxide coating, the water vapor is electrolytically converted to hydrogen ions and oxygen with the hydrogen ions migrating through the matrix to the cathode and the oxygen gas produced at the anode to enrich the air stream passing by the anode.

Vacuum deposition of iridium on large astronomical mirrors for use in the far UV

NASA Technical Reports Server (NTRS)

Herzig, H.; Spencer, R. S.

1982-01-01

An iridium coating has been deposited by electron-beam evaporation on a 0.91-m mirror which serves as the telescope primary of a sounding rocket instrument for far-UV spectrometry. The evaporation was carried out by applying 8 kV at 400 mA to the electron gun. Zone refined Ir of 99.99% purity was used, and the electron beam was electromagnetically swept over the surface of the evaporant. Under these conditions, deposition rates of 0.55 A/sec were achieved. The reflectance distribution achieved at a wavelength of 584 A was extremely uniform; the mean reflectance was 21.2% with a standard deviation of only 0.3%. This represents a substantial improvement over Al + MgF2 and Al + LiF coatings for applications involving multiple reflections and weak signals, as might be expected in a high-resolution spectrograph studying distant celestial objects.

Corrosion-Resistant Container for Molten-Material Processing

NASA Technical Reports Server (NTRS)

Stern, Theodore G.; McNaul, Eric

2010-01-01

In a carbothermal process, gaseous methane is passed over molten regolith, which is heated past its melting point to a temperature in excess of 1,625 C. At this temperature, materials in contact with the molten regolith (or regolith simulant) corrode and lose their structural properties. As a result, fabricating a crucible to hold the molten material and providing a method of contact heating have been problematic. Alternative containment approaches use a large crucible and limit the heat zone of the material being processed, which is inefficient because of volume and mass constraints. Alternative heating approaches use non-contact heating, such as by laser or concentrated solar energy, which can be inefficient in transferring heat and thus require higher power heat sources to accomplish processing. The innovation is a combination of materials, with a substrate material having high structural strength and stiffness and high-temperature capability, and a coating material with a high corrosion resistance and high-temperature capability. The material developed is a molybdenum substrate with an iridium coating. Creating the containment crucible or heater jacket using this material combination requires only that the molybdenum, which is easily processed by conventional methods such as milling, electric discharge machining, or forming and brazing, be fabricated into an appropriate shape, and that the iridium coating be applied to any surfaces that may come in contact with the corrosive molten material. In one engineering application, the molybdenum was fashioned into a container for a heat pipe. Since only the end of the heat pipe is used to heat the regolith, the container has a narrowing end with a nipple in which the heat pipe is snugly fit, and the external area of this nipple, which contacts the regolith to transfer heat into it, is coated with iridium. At the time of this reporting, no single material has been found that can perform the functions of this combination of materials, and other combinations of materials have not proven to be survivable to the corrosiveness of this environment. High-temperature processing of materials with similar constituencies as lunar regolith is fairly common. The carbo-thermal process is commonly used to make metallurgical-grade silicon for the semiconductor and solar-cell industries.

Space Based Communications

NASA Technical Reports Server (NTRS)

Simpson, James; Denson, Erik; Valencia, Lisa; Birr, Richard

2003-01-01

Current space lift launches on the Eastern and Western Range require extensive ground-based real-time tracking, communications and command/control systems. These are expensive to maintain and operate and cover only limited geographical areas. Future spaceports will require new technologies to provide greater launch and landing opportunities, support simultaneous missions, and offer enhanced decision support models and simulation capabilities. These ranges must also have lower costs and reduced complexity while continuing to provide unsurpassed safety to the public, flight crew, personnel, vehicles and facilities. Commercial and government space-based assets for tracking and communications offer many attractive possibilities to help achieve these goals. This paper describes two NASA proof-of-concept projects that seek-to exploit the advantages of a space-based range: Iridium Flight Modem and Space-Based Telemetry and Range Safety (STARS). Iridium Flight Modem uses the commercial satellite system Iridium for extremely low cost, low rate two-way communications and has been successfully tested on four aircraft flights. A sister project at Goddard Space Flight Center's (GSFC) Wallops Flight Facility (WFF) using the Globalstar system has been tested on one rocket. The basic Iridium Flight Modem system consists of a L1 carrier Coarse/Acquisition (C/A)-Code Global Positioning System (GPS) receiver, an on-board computer, and a standard commercial satellite modem and antennas. STARS uses the much higher data rate NASA owned Tracking and Data Relay Satellite System (TDRSS), a C/A-Code GPS receiver, an experimental low-power transceiver, custom built command and data handler processor, and digitized flight termination system (FTS) commands. STARS is scheduled to fly on an F-15 at Dryden Flight Research Center in the spring of 2003, with follow-on tests over the next several years.

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.

Revisiting the collision risk with cataloged objects for the Iridium and COSMO-SkyMed satellite constellations

NASA Astrophysics Data System (ADS)

Pardini, Carmen; Anselmo, Luciano

2017-05-01

After two decades of slightly declining growth rate, the population of cataloged objects around the Earth increased by more than 56% in just a couple of years, from January 2007 to February 2009, due to two collisions in space involving the catastrophic destruction of three intact satellites (Fengyun 1C, Cosmos 2251 and Iridium 33) in high inclination orbits. Both events had occurred in the altitude range already most affected by previous launch activity and breakups. In 2011 a detailed analysis had been carried out to analyze the consequences of these fragmentations, in particular concerning the evolution of the collision risk for the Iridium and COSMO-SkyMed satellite constellations. Five years after such first assessment, the cataloged objects environment affecting the two constellations was revisited to evaluate how the situation had evolved due to the varying contribution of the above mentioned breakup fragments and the space activities carried out in the meantime. Being distributed, at 778 km, over six nearly polar orbit planes separated by just 30° at the equator, the Iridium satellites represent a very good gauge for checking the evolution of the environment in the most critical low Earth region. In approximately five years, from May 2011 to June 2016, the average flux of cataloged objects on the Iridium satellites increased by about 14%, to 1.59×10-5 m-2 per year. The cataloged fragments of Fengyun 1C, Cosmos 2251 and Iridium 33 still accounted for, on average, 54% of the total flux. More than 39% of the latter was associated with the Fengyun 1C fragments, about 11% with the Cosmos 2251 fragments and less than 4% with the Iridium 33 fragments. Specifically concerning the mutual interaction among the Iridium 33 debris and the parent constellation, the progressive dispersion and rather fast decay of the fragments below the Iridium operational altitude, coupled with a slow differential plane precession and low average relative velocities with respect to four of the six constellation planes, determined in five years, on average, a decline of the flux by about 31%, i.e. to about 5.75×10-7 m-2 per year. The decrease occurred in each constellation plane, even though with different rates and percentages, due to the varying relative orbit geometry. From May 2011 to June 2016, the mean flux of cataloged objects on the COSMO-SkyMed satellites, at 623 km, increased by about 26%, to 7.24×10-6 m-2 per year. The Fengyun 1C, Cosmos 2251 and Iridium 33 cataloged fragments accounted for, on average, about 1/4 of the total, with 12% due to Fengyun 1C, 8% to Cosmos 2251 and 4% to Iridium 33.

Air-Deployable Profiling Floats for Tropical Cyclone Research

NASA Astrophysics Data System (ADS)

Jayne, S. R.; Robbins, P.; Owens, B.; Ekholm, A.; Dufour, J. E.; Sanabia, E.

2016-02-01

The development of a smaller profiling float that can be launched from Hurricane Hunter aircraft offers the opportunity to monitor the upper-ocean thermal structure over a time span of many months. These Argo-type profiling floats can be deployed in advance of, or during, a tropical cyclone from any aircraft equipped with an A-sized (AXBT) launch tube, or from the stern ramp of a C-130. The floats have the same dimensions as an AXBT and weigh about 8.5 kg. Upon deployment, the floats parachute to the surface, detach and automatically begin their programmed mission. The recorded temperature data is averaged over 1-meter bins that are reported back via the Iridium satellite phone network, which is then automatically processed and posted to the GTS. The floats are also reprogrammable via the 2-way communication afforded by Iridium. We report on the results of deployments during the 2014 and 2015 hurricane seasons. Unique observations of the ocean response from Hurricane Ignacio are particularly noteworthy and will be presented. Further plans for continued development of floats include measuring salinity (from an inductive conductivity sensor) and observations of the surface wave field (measured by an onboard accelerometer) will also be described.

Electrochemical etching technique of platinum-iridium tips for scanning tunneling microscopy

NASA Astrophysics Data System (ADS)

Herrera, Oscar

The scanning tunneling microscope (STM) allows researchers to investigate atomic and molecular structures and properties of nanomaterials. Through the quantum tunneling effect a charge is transferred between the surface of the material and a Platinum-Iridium (Pt-Ir) tip. The production of Pt-Ir tips by electrochemical etching (ECE) has been developed as an alternative technique, to achieve enhanced scanned images of samples, in contrast to the standard mechanical method (SMM). The sharpness apex structure is an essential feature during scanning in order to provide reliable data. We generated a control group of tips by the SMM technique and another group by the ECE technique to investigate the resolution effectiveness in scanning of graphite. The etching of the tips was produced using an auto-variable transformer running a 30 V AC in a 1.5 and 4.0 M CaCl2 solution. The scanning of the graphite surface was conducted at 7x7 nm image width, 0.2 seconds time/line, 256 points/line and 0.05 V for tip voltage. ECE etched tips displayed consistent image resolution, and the sharpness of the tip apex was generally uniform.

Preparation of iridium targets by electrodeposition for neutron capture cross section measurements

DOE PAGES

Bond, Evelyn M.; Moody, W. Allen; Arnold, Charles; ...

2016-03-01

Here, the preparation of 191Ir and 193Ir electrodeposits for neutron capture cross-section measurements at the detector for advanced neutron capture experiments located at the at Los Alamos Neutron Science Center is described. The electrodeposition of iridium in the desired thickness of 0.4–1 mg/cm 2 is challenging. Better yields and thicknesses were obtained using electrodeposition from isopropyl alcohol solutions than from ammonium sulfate solutions. 191Ir and 193Ir targets were initially prepared using the standard single-sided electrodeposition cell. Iridium electrodepositions using a double-sided electrodeposition cell were developed and were optimized, resulting in thick, uniform iridium deposits. LA UR 15-22475.

Palladium, platinum, rhodium, ruthenium, and iridium in chromitites from the Massif du Sud and Tiebaghi massif, New Caledonia.

USGS Publications Warehouse

Page, N.J.; Cassard, D.; Haffty, J.

1982-01-01

The massive and disseminated podiform chromitites from 43 mines and other occurrences in the area contain up to (in ppb) Pd 9, Pt 45, Rh 31, Ir 410 and Ru 1300. The possble origins of the chromitites are discussed. -K.A.R.

Application of AirCell Cellular AMPS Network and Iridium Satellite System Dual Mode Service to Air Traffic Management

NASA Technical Reports Server (NTRS)

Shamma, Mohammed A.

2004-01-01

The AirCell/Iridium dual mode service is evaluated for potential applications to Air Traffic Management (ATM) communication needs. The AirCell system which is largely based on the Advanced Mobile Phone System (AMPS) technology, and the Iridium FDMA/TDMA system largely based on the Global System for Mobile Communications(GSM) technology, can both provide communication relief for existing or future aeronautical communication links. Both have a potential to serve as experimental platforms for future technologies via a cost effective approach. The two systems are well established in the entire CONUS and globally hence making it feasible to utilize in all regions, for all altitudes, and all classes of aircraft. Both systems have been certified for air usage. The paper summarizes the specifications of the AirCell/Iridium system, as well as the ATM current and future links, and application specifications. the paper highlights the scenarios, applications, and conditions under which the AirCell/Iridium technology can be suited for ATM Communication.

Dynamic High-temperature Testing of an Iridium Alloy in Compression at High-strain Rates: Dynamic High-temperature Testing

DOE PAGES

Song, B.; Nelson, K.; Lipinski, R.; ...

2014-08-21

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-strain -rate performance are needed for understanding high-speed impacts in severe 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. In our study, we analyzed the difficulties encountered in high-temperature Kolsky bar testing of thin iridium alloy specimens in compression. We made appropriate modifications using themore » current high-temperature Kolsky bar technique in order to obtain reliable compressive stress–strain response of an iridium alloy at high-strain rates (300–10 000 s -1) and temperatures (750 and 1030°C). The compressive stress–strain response of the iridium alloy showed significant sensitivity to both strain rate and temperature.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, Jian; Turner, Eric

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.

Molecular organization of a water-insoluble iridium(III) complex in mixed monolayers.

PubMed

Giner-Casares, Juan J; Pérez-Morales, Marta; Bolink, Henk J; Muñoz, Eulogia; de Miguel, Gustavo; Martín-Romero, María T; Camacho, Luis

2007-11-01

In this work, organized mixed monolayers containing a cationic water-insoluble iridium(III) complex, Ir-dye, [Ir(ppy)(2)(tmphen)]PF(6), (tmphen = 3,4,7,8-tetramethyl-1,10-phenanthroline, and ppy = 2-phenylpyridine), and an anionic lipid matrix, DMPA, dimyristoyl-phosphatidic acid, with different molar proportions, were formed by the co-spreading method at the air-water interface. The presence of the dye at the interface, as well as the molecular organization of the mixed films, is deduced from surface techniques such as pi-A isotherms, Brewster angle microscopy (BAM) and reflection spectroscopy. The results obtained remark the formation of an equimolar mixed film, Ir-dye/DMPA = 1:1. BAM images reveal a whole homogeneous monolayer, with gradually increasing reflectivity along the compression process up to reaching the collapse of this equimolecular monolayer at pi approximately equal to 37 mNm(-1). Increasing the molar ratio of DMPA in the mixture, the excess of lipid molecules organizes themselves forming dark flower-like domains of pure DMPA at high surface pressures, coexisting with the mixed Ir-dye/DMPA = 1:1 monolayer. On the other hand, unstable mixed monolayers are obtained by using an initial dye surface concentration higher than the equimolecular one. These mixed Langmuir monolayers have been successfully transferred onto solid substrates by the LB (Langmuir-Blodgett) technique.

ADDOSS: Autonomously Deployed Deep-ocean Seismic System - Communications Gateway for Ocean Observatories

NASA Astrophysics Data System (ADS)

Laske, Gabi; Berger, Jon; Orcutt, John; Babcock, Jeff

2014-05-01

We describe an autonomously deployable, communications gateway designed to provide long-term and near real-time data from ocean observatories. The key features of this new system are its abilities to telemeter sensor data from the seafloor to shore without cables or moorings, and to be deployed without a ship, thereby greatly reducing life-cycle costs. The free-floating surface communications gateway utilizes a Liquid Robotics wave glider comprising a surfboard-sized float towed by a tethered, submerged glider, which converts wave motion into thrust. For navigation, the wave glider is equipped with a small computer, a GPS receiver, a rudder, solar panels and batteries, and an Iridium satellite modem. Acoustic communications connect the subsea instruments and the surface gateway while communications between the gateway and land are provided by the Iridium satellite constellation. Wave gliders have demonstrated trans-oceanic range and long-term station keeping capabilities. The acoustics communications package is mounted in a shallow tow body which utilizes a WHOI micro modem and a Benthos low frequency, directional transducer. A matching modem and transducer is mounted on the ocean bottom package. Tests of the surface gateway in 4350 m of water demonstrated an acoustic efficiency of approximately 396 bits/J. For example, it has the ability to send 4 channels of compressed, 1 sample per second data from the ocean bottom to the gateway with an average power draw of approximately 0.15 W and a latency of less than 3 minutes. This gateway is used to send near real-time data from a broadband ocean bottom seismic observatory, first during short week-to-months long test deployments but will ultimately be designed for a two-year operational life. Such data from presently unobserved oceanic areas are critical for both national and international agencies in monitoring and characterizing earthquakes, tsunamis, and nuclear explosions. We present initial results from a two short-term OBS test deployments off-shore La Jolla, at water depths of 1000 m and of nearly 4000 m.

Electrochemical and Spectroscopic Investigation of Molten Chloroaluminates and Related Solvents

DTIC Science & Technology

1988-11-07

chemistry of iridium carbonyl complexes known to be active Fischer-Tropsch catalysts (described below). These studies represent the first successful in...electrochemical studies, e. g., doole potential step chronocoulometry, of this system are in progress. 3: hemistry of iridium carbonyls in sodium...chloroaluminates’/The iridium carbonyl species 1r4(CO)12 and IrCl(CO)3 have previously been shown to serve as Fischer-Tropsch catalysts in acidic sodium

On the structural and electronic properties of Ir-silicide nanowires on Si(001) surface

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fatima,; Hossain, Sehtab; Mohottige, Rasika

Iridium (Ir) modified Silicon (Si) (001) surface is studied with Scanning Tunneling Microscopy/Spectroscopy (STM/STS) and Density Functional Theory (DFT). A model for Ir-silicide nanowires based on STM images and ab-initio calculations is proposed. According to our model, the Ir adatom is on the top of the substrate dimer row and directly binds to the dimer atoms. I-V curves measured at 77 K shows that the nanowires are metallic. DFT calculations confirm strong metallic nature of the nanowires.

The United States Air Force Small Business Innovation Research Program

DTIC Science & Technology

1990-01-01

impossible to draw, and very - satellite’s mass consists of the exists in the metal iridium , which difficult to machine. They also 0 propellant...needed for orbit is ductile and pore free. Iridium tend to be expensive, so that insertion and altitude control, bonds to, but does not react with, cutting...thin layers lifespan is 2400F and 10 hours coatings of iridium , but this track of exotic materials with precisely respectively, record was reversed in

Novel Design of Iridium Phosphors with Pyridinylphosphinate Ligands for High-Efficiency Blue Organic Light-emitting Diodes

PubMed Central

Wu, Zheng-Guang; Jing, Yi-Ming; Lu, Guang-Zhao; Zhou, Jie; Zheng, You-Xuan; Zhou, Liang; Wang, Yi; Pan, Yi

2016-01-01

Due to the high quantum efficiency and wide scope of emission colors, iridium (Ir) (III) complexes have been widely applied as guest materials for OLEDs (organic light-emitting diodes). Contrary to well-developed Ir(III)-based red and green phosphorescent complexes, the efficient blue emitters are rare reported. Like the development of the LED, the absence of efficient and stable blue materials hinders the widely practical application of the OLEDs. Inspired by this, we designed two novel ancillary ligands of phenyl(pyridin-2-yl)phosphinate (ppp) and dipyridinylphosphinate (dpp) for efficient blue phosphorescent iridium complexes (dfppy)2Ir(ppp) and (dfppy)2Ir(dpp) (dfppy = 2-(2,4-difluorophenyl)pyridine) with good electron transport property. The devices using the new iridium phosphors display excellent electroluminescence (EL) performances with a peak current efficiency of 58.78 cd/A, a maximum external quantum efficiency of 28.3%, a peak power efficiency of 52.74 lm/W and negligible efficiency roll-off ratios. The results demonstrated that iridium complexes with pyridinylphosphinate ligands are potential blue phosphorescent materials for OLEDs. PMID:27929124

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.

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.

Thin Refractory Films on Fused Silica Crucibles

DTIC Science & Technology

1988-07-01

9 4.1.4 Iridium 11 4.1.5 Boron Nitride (BN) 11 4.2 Adherence Testing 13 4.3 Metallography 13 5.0 Conclusions and Recommendations 16 Accession For...Chamber 4 2. Schematic of Crucible Coating Apparatus (SiC, NbN, and TiB 2) 6 3. Schematic of CVD Apparatus for Iridium 7 4. Schematic of Apparatus for...ultrahigh-purity coatings of silicon carbide (SiC), niobium nitride (NbN), titanium diboride (TiB2), iridium , and boron nitride (BN) onto the interior

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-walled oxide coatings are better suited for repeated thermal cycling than the thick-walled coating, while thicker coatings may be required for operation in aggressively oxidizing environments.

An iridium oxide microelectrode for monitoring acute local pH changes of endothelial cells.

PubMed

Ng, Shu Rui; O'Hare, Danny

2015-06-21

pH sensors were fabricated by anodically electrodepositing iridium oxide films (AEIROFs) onto microelectrodes on chips and coated with poly(ethyleneimine) (PEI) for mechanical stability. These demonstrate super-Nernstian response to pH from pH 4.0 to 7.7 in chloride-free phosphate buffer. The surface of the chip was coated with fibronectin for the attachment of porcine aortic endothelial cells (PAECs). The working capability of the pH sensor for monitoring acute local pH changes was investigated by stimulating the PAECs with thrombin. Our results show that thrombin induced acute extracellular acidification of PAECs and dissolution of fibronectin, causing the local pH to decrease. The use of PD98059, a mitogen-activated protein kinase (MAPK) inhibitor, reduced extracellular acidification and an increase in local pH was observed. This study shows that our pH sensors can facilitate the investigation of acute cellular responses to stimulation by monitoring the real-time, local pH changes of cells attached to the sensors.

Ocean Dynamics: Vietnam DRI

DTIC Science & Technology

2014-09-30

floor. OBJECTIVES To identify the phenomena involved in the cascade of energy from mesoscales to turbulent scales. In particular, we wish to quantify the...data from the profiler to the surface buoy. The WW Iridium telemetry system was tested on the WW moored over the continental shelf. Telemetry...2580 email: ajlucas@ucsd.edu Award: N00014-12-1-0635 LONG-TERM GOALS To gain a more complete understanding of ocean dynamical processes

A Colorimetric and Luminescent Dual-Modal Assay for Cu(II) Ion Detection Using an Iridium(III) Complex

PubMed Central

Ma, Dik-Lung; He, Hong-Zhang; Chan, Daniel Shiu-Hin; Wong, Chun-Yuen; Leung, Chung-Hang

2014-01-01

A novel iridium(III) complex-based chemosensor bearing the 5,6-bis(salicylideneimino)-1,10-phenanthroline ligand receptor was developed, which exhibited a highly sensitive and selective color change from colorless to yellow and a visible turn-off luminescence response upon the addition of Cu(II) ions. The interactions of this iridium(III) complex with Cu2+ ions and thirteen other cations have been investigated by UV-Vis absorption titration, emission titration, and 1H NMR titration. PMID:24927177

A metal–organic framework immobilised iridium pincer complex

DOE PAGES

Rimoldi, Martino; Nakamura, Akitake; Vermeulen, Nicolaas A.; ...

2016-05-10

An iridium pincer complex has been immobilised in the metal–organic framework NU-1000. The stable Ir-pincer modified NU-1000 is catalytically active in the hydrogenation of alkenes in condensed phase and under flow conditions.

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

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.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Song, B.; Nelson, K.; Lipinski, R.

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-strain -rate performance are needed for understanding high-speed impacts in severe 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. In our study, we analyzed the difficulties encountered in high-temperature Kolsky bar testing of thin iridium alloy specimens in compression. We made appropriate modifications using themore » current high-temperature Kolsky bar technique in order to obtain reliable compressive stress–strain response of an iridium alloy at high-strain rates (300–10 000 s -1) and temperatures (750 and 1030°C). The compressive stress–strain response of the iridium alloy showed significant sensitivity to both strain rate and temperature.« less

Thermodynamic characterization of hydrogen interaction with iridium polyhydride complexes

DOE Office of Scientific and Technical Information (OSTI.GOV)

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,more » indicating stronger hydrogen bonding. {copyright} {ital 1999 Materials Research Society.}« less

Development of U.S. Government General Technical Requirements for UAS Flight Safety Systems Utilizing the Iridium Satellite Constellation

NASA Technical Reports Server (NTRS)

Murray, Jennifer; Birr, Richard

2010-01-01

This slide presentation reviews the development of technical requirements for Unmanned Aircraft Systems (UAS) utilization of the Iridium Satellite Constellation to provide flight safety. The Federal Aviation Authority (FAA) required an over-the-horizon communication standard to guarantee flight safety before permitting widespread UAS flights in the National Air Space (NAS). This is important to ensure reliable control of UASs during loss-link and over-the-horizon scenarios. The core requirement was to utilize a satellite system to send GPS tracking data and other telemetry from a flight vehicle down to the ground. Iridium was chosen as the system because it is one of the only true satellite systems that has world wide coverage, and the service has a highly reliable link margin. The Iridium system, the flight modems, and the test flight are described.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bond, Evelyn M.; Moody, W. Allen; Arnold, Charles

Here, the preparation of 191Ir and 193Ir electrodeposits for neutron capture cross-section measurements at the detector for advanced neutron capture experiments located at the at Los Alamos Neutron Science Center is described. The electrodeposition of iridium in the desired thickness of 0.4–1 mg/cm 2 is challenging. Better yields and thicknesses were obtained using electrodeposition from isopropyl alcohol solutions than from ammonium sulfate solutions. 191Ir and 193Ir targets were initially prepared using the standard single-sided electrodeposition cell. Iridium electrodepositions using a double-sided electrodeposition cell were developed and were optimized, resulting in thick, uniform iridium deposits. LA UR 15-22475.

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.

Negative thermal ion mass spectrometry of osmium, rhenium, and iridium

NASA Technical Reports Server (NTRS)

Creaser, R. A.; Papanastassiou, D. A.; Wasserburg, G. J.

1991-01-01

This paper describes a technique for obtaining, in a conventional surface ionization mass spectrometer, intense ion beams of negatively charged oxides of Os, Re, and Ir by thermal ionization. It is shown that the principal ion species of these ions are OsO3(-), ReO4(-), and IrO2(-), respectively. For Re-187/Os-187 studies, this technique offers the advantage of isotopic analyses without prior chemical separation of Re from Os.

SO2 adsorption on silica supported iridium.

PubMed

Bounechada, Djamela; Anderson, David P; Skoglundh, Magnus; Carlsson, Per-Anders

2017-02-28

The interaction of SO 2 with Ir/SiO 2 was studied by simultaneous in situ diffuse reflectance infrared Fourier transform spectroscopy and mass spectrometry, exposing the sample to different SO 2 concentrations ranging from 10 to 50 ppm in the temperature interval 200-400 °C. Evidences of adsorption of sulfur species in both absence and presence of oxygen are found. For a pre-reduced sample in the absence of oxygen, SO 2 disproportionates such that the iridium surface is rapidly saturated with adsorbed S while minor amounts of formed SO 3 may adsorb on SiO 2 . Adding oxygen to the feed leads to the oxidation of sulfide species that either (i) desorb as SO 2 and/or SO 3 , (ii) remain at metal sites in the form of adsorbed SO 2 , or (iii) spillover to the oxide support and form sulfates (SO 4 2- ). Notably, significant formation of sulfates on silica is possible only in the presence of both SO 2 and O 2 , suggesting that SO 2 oxidation to SO 3 is a necessary first step in the mechanism of formation of sulfates on silica. During the formation of sulfates, a concomitant removal/rearrangement of surface silanol groups is observed. Finally, the interaction of SO 2 with Ir/SiO 2 depends primarily on the temperature and type of gas components but only to a minor extent on the inlet SO 2 concentration.

SO2 adsorption on silica supported iridium

NASA Astrophysics Data System (ADS)

Bounechada, Djamela; Anderson, David P.; Skoglundh, Magnus; Carlsson, Per-Anders

2017-02-01

The interaction of SO2 with Ir/SiO2 was studied by simultaneous in situ diffuse reflectance infrared Fourier transform spectroscopy and mass spectrometry, exposing the sample to different SO2 concentrations ranging from 10 to 50 ppm in the temperature interval 200-400 °C. Evidences of adsorption of sulfur species in both absence and presence of oxygen are found. For a pre-reduced sample in the absence of oxygen, SO2 disproportionates such that the iridium surface is rapidly saturated with adsorbed S while minor amounts of formed SO3 may adsorb on SiO2. Adding oxygen to the feed leads to the oxidation of sulfide species that either (i) desorb as SO2 and/or SO3, (ii) remain at metal sites in the form of adsorbed SO2, or (iii) spillover to the oxide support and form sulfates (SO42-). Notably, significant formation of sulfates on silica is possible only in the presence of both SO2 and O2, suggesting that SO2 oxidation to SO3 is a necessary first step in the mechanism of formation of sulfates on silica. During the formation of sulfates, a concomitant removal/rearrangement of surface silanol groups is observed. Finally, the interaction of SO2 with Ir/SiO2 depends primarily on the temperature and type of gas components but only to a minor extent on the inlet SO2 concentration.

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.

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).

Effect of the magnetism of impurities on their diffusion in metals: Bulk diffusion of iron, cobalt, and rhodium in iridium single crystals

NASA Astrophysics Data System (ADS)

Klotsman, S. M.; Tatarinova, G. N.

2008-12-01

The coefficients and parameters of the temperature dependences of the coefficients of bulk diffusion of Fe, Co, Rh, and Au atomic probes (APs) in iridium single crystals (mono-Ir) have been determined from the diffusion profiles obtained using secondary-ion mass spectrometry of the diffusion zones. The enthalpies of activation of diffusion of Fe, Co, and Rh APs are considerably lower than the enthalpy of activation of selfdiffusion in mono-Ir. This is caused by the negative contributions of the intraatomic exchange energy and energy of relaxation of the environment of the d transition APs to the enthalpy of interaction of magnetically active APs with the vacancies in the iridium lattice. The interaction energy of partners in such complexes and the relationships between the magnetic moments of d transition APs in complexes with vacancies have been estimated. The Rh APs in complexes with vacancies in iridium possess stable magnetic moments.

A theoretical study on the mechanistic highlights behind the Brønsted-acid dependent mer-fac isomerization of homoleptic carbenic iridium complexes for PhOLEDs.

PubMed

Setzer, Tobias; Lennartz, Christian; Dreuw, Andreas

2017-06-06

Recently, a successful Brønsted-acid mediated geometric isomerization of the meridional homoleptic carbenic iridium(iii) complexes tris-(N-phenyl,N-methyl-benzimidazol-2-yl)iridium(iii) (1) and tris-(N-phenyl,N-benzyl-benzimidazol-2-yl)iridium(iii) (2) into their facial form has been reported. In the present work the pronounced acid-dependency of this particular isomerization procedure is revisited and additional mechanistic pathways are taken into account. Moreover, the acid-induced material decomposition is addressed. All calculations are carried out using density functional theory (DFT) while the environmental effects in solution are accounted for by the COSMO-RS model. The simulated results clearly reveal the outstanding importance of the complex interplay between acid strength, coordinating power of the corresponding base and the steric influence of the ligand system in contrast to the plain calculation of minimum energy pathways for selected complexes. Eventually, general rules to enhance the material-specific reaction yields are provided.

Metal Ir coatings on endocardial electrode tips, obtained by MOCVD

NASA Astrophysics Data System (ADS)

Vikulova, Evgeniia S.; Kal'nyi, Danila B.; Shubin, Yury V.; Kokovkin, Vasily V.; Morozova, Natalya B.; Hassan, Aseel; Basova, Tamara V.

2017-12-01

The present work demonstrates the application of the Metal-Organic Chemical Vapor Deposition technique to fabricate metal iridium coatings onto the pole tips of endocardial electrodes. Using iridium (III) acetylacetonate as a volatile precursor, the target coatings were successfully applied to the working surface of cathodes and anodes of pacemaker electrodes in the flow type reactor in hydrogen atmosphere at deposition temperature of 550 °C. The coating samples were characterized by means of XRD, SEM, Raman- and XPS-spectroscopies. The formation of non-textured coatings with fractal-like morphology and 7-24 nm crystallite size has been realized. The electrochemical properties of the coatings were investigated by cyclic voltammetry and electrochemical impedance spectroscopy. The charge storage capacity values of the electrochemically activated samples were 17.0-115 mC cm-2 and 14.4-76.5 mC cm-2 for measurements carried out in 0.1 M sulfuric acid and in phosphate buffer saline solutions, respectively. A comparison of some characteristics of the samples obtained with commercially available cathode of pacemaker electrodes is also presented.

Recommended values of clean metal surface work functions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Derry, Gregory N., E-mail: gderry@loyola.edu; Kern, Megan E.; Worth, Eli H.

2015-11-15

A critical review of the experimental literature for measurements of the work functions of clean metal surfaces of single-crystals is presented. The tables presented include all results found for low-index crystal faces except cases that were known to be contaminated surfaces. These results are used to construct a recommended value of the work function for each surface examined, along with an uncertainty estimate for that value. The uncertainties are based in part on the error distribution for all measured work functions in the literature, which is included here. The metals included in this review are silver (Ag), aluminum (Al), goldmore » (Au), copper (Cu), iron (Fe), iridium (Ir), molybdenum (Mo), niobium (Nb), nickel (Ni), palladium (Pd), platinum (Pt), rhodium (Rh), ruthenium (Ru), tantalum (Ta), and tungsten (W)« less

Electrodeposition of nickel-iridium alloy films from aqueous solutions

NASA Astrophysics Data System (ADS)

Wu, Wangping; Jiang, Jinjin; Jiang, Peng; Wang, Zhizhi; Yuan, Ningyi; Ding, Jianning

2018-03-01

Nickel-iridium (Ni-Ir) alloy films were electrodeposited from aqueous solutions on copper substrates under galvanostatic conditions. The effects of bath composition and deposition time on the faradaic efficiency (FE), partial current densities, chemical composition, morphology and crystallographic structure of the films were studied. The results show that the Ni-Ir alloys with Ir content as high as 37 at% and FE as high as 44% were obtained. Increase in concentration of citric acid had little or no effect on the composition of the alloys, but resulted in a significant decrease in FE and partial current densities of Ni and Ir. The FE and the partial current density of Ni slightly decreased with increasing Ir3+ concentration, however, Ir content increased while partial current density of Ir remained stable. The increase of Ni2+ concentration could result in the increase of the FE and the rate of Ni-Ir deposition, and even no cracks formed on the surface. The surface average roughness and root mean square roughness of the film were 6.8 ± 0.3 nm and 5.4 ± 0.3 nm, respectively. The mixture phases contained significant amounts of Ni oxides and a small amount of metallic Ni, Ir and Ir oxides on the surface. After argon ion sputter cleaning, the film was mainly composed of metallic Ni and Ir. The film consisted of the amorphous and nanocrystalline phases. The Ni content in the deposits was higher than that in the electrolyte, the co-deposition of Ni-Ir alloy was a normal deposition.

ARTICLES: Microwave Assisted Synthesis of a New Triplet Iridium(III) Pyrazine Complex

NASA Astrophysics Data System (ADS)

Wu, Qiu-hua; Wang, Chuan-hong; Song, Xi-ming; Zhang, Guo-lin

2010-06-01

A new cyclometalated iridium(III) complex Ir(DPP)3 (DPP = 2,3-diphenylpyrazine) was prepared by reaction of DPP with iridium trichloride hydrate under microwave irradiation. The structure of the complex was confirmed by elemental analysis, 1H NMR, and mass spectroscopy. The UV-Vis absorption and photoluminescent properties of the complex were investigated. The complex shows strong 1MLCT (singlet metal to ligand charge-transfer) and 3MLCT (triplet metal to ligand charge-transfer) absorption at 382 and 504 nm, respectively. The complex also shows strong photoluminescence at 573 nm at room temperature. These results suggest the complex to be a promising phosphorescent material.

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.

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.

Dynamic High-Temperature Tensile Characterization of an Iridium Alloy with Kolsky Tension Bar Techniques

DOE PAGES

Song, Bo; Nelson, Kevin; Lipinski, Ronald; ...

2015-05-29

In this study, conventional Kolsky tension bar techniques were modified to characterize an iridium alloy in tension at elevated strain rates and temperatures. The specimen was heated to elevated temperatures with an induction coil heater before dynamic loading; whereas, a cooling system was applied to keep the bars at room temperature during heating. A preload system was developed to generate a small pretension load in the bar system during heating in order to compensate for the effect of thermal expansion generated in the high-temperature tensile specimen. A laser system was applied to directly measure the displacements at both ends ofmore » the tensile specimen in order to calculate the strain in the specimen. A pair of high-sensitivity semiconductor strain gages was used to measure the weak transmitted force due to the low flow stress in the thin specimen at elevated temperatures. The dynamic high-temperature tensile stress–strain curves of a DOP-26 iridium alloy were experimentally obtained at two different strain rates (~1000 and 3000 s -1) and temperatures (~750 and 1030°C). The effects of strain rate and temperature on the tensile stress–strain response of the iridium alloy were determined. Finally, the iridium alloy exhibited high ductility in stress–strain response that strongly depended on strain-rate and temperature.« less

Combustion interaction with radiation-cooled chambers

NASA Technical Reports Server (NTRS)

Rosenberg, S. D.; Jassowski, D. M.; Barlow, R.; Lucht, R.; Mccarty, K.

1990-01-01

Over 15 hours of thruster operation at temperatures between 1916 and 2246 C without failure or erosion has been demonstrated using iridium-coated rhenium chamber materials with nitrogen tetroxide/monomethylhydrazine propellants operating over a mixture ratio range of 1.60-2.05. Research is now under way to provide a basic understanding of the mechanisms which make high-temperature operation possible and to extend the capability to a wider range of conditions, including other propellant combinations and chamber materials. Techniques have been demonstrated for studying surface fracture phenomena. These include surface Raman and Auger for study of oxide formation, surface Raman and X-ray diffraction to determine the oxide phase, Auger to study oxide stoichiometry, and sputter Auger to study interdiffusion of alloy species.

First Applications of DoD Iridium RUDICS in the NSF Polar Programs

NASA Astrophysics Data System (ADS)

Valentic, T.; Stehle, R.

2008-12-01

We will present the first deployment and application of the new Iridium RUDICS service to remote instrumentation projects within the National Science Foundation's polar programs. The rise of automated observing networks has increased the demand for real-time connectivity to remote instruments, not only for immediate access to data, but to also interrogate health and status. Communicating with field sites in the polar regions is complicated by the remoteness from existing infrastructure, low temperatures and limited connection options. Sites located above 78° latitude are not able to see geostationary satellites, leaving the Iridium constellation as the only one that provide a direct connection. Some others, such as Orbcomm, only provide a store-and-forward service. Iridium is often used as a dial up modem to establish a PPP connection to the Internet with data files transferred via FTP. On low-bandwidth, high-latency networks like Iridium (2400bps with ping times of seconds), this approach is time consuming and inefficient. The dial up time alone takes upwards of a minute, and standard TCP/IP and FTP protocols are hampered by the long latencies. Minimizing transmission time is important for reducing battery usage and connection costs. The new Iridium RUDICS service can be used for more efficient transfers. RUDICS is an acronym for "Router-based Unstructured Digital Inter-working Connectivity Solution" and provides a direct connection between an instrument in the field and a server on the Internet. After dialing into the Iridium gateway, a socket connection is opened to a registered port on a user's server. Bytes sent to or from the modem appear at the server's socket. The connection time is reduced to about 10 seconds because the modem training and PPP negotiation stages are eliminated. The remote device does not need to have a full TCP/IP stack, allowing smaller instruments such as data loggers to directly handle the data transmission. Alternative protocols can be deployed that better exploit the characteristics of the Iridium channel. In addition, the setup naturally scales to handle hundreds of remote devices, an important aspect for larger sensor networks. As part of the NSF's Arctic Research Support and Logistics Services, we have deployed RUDICS systems with three different research projects. These are the first NSF RUDICS deployments for projects using the Department of Defense Iridium gateway, which allows for unlimited connection time at a flat monthly rate for US government users. The first project is O-Buoy, an IPY-OASIS project for self-contained, autonomous observations of atmospheric chemical species in the polar marine boundary layer. The second project is collection of low-power instrument towers on Alaska's North Slope at Imnavait Creek, part of the Arctic Observation Network (AON). Lastly, the autonomous instrument platform at Ivotuk, Alaska, uses RUDICS to provide telemetry about the renewable energy systems. A set of real-time web displays allow researchers for each project to monitor their remote sites and access real-time data.

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.

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.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Du W.; Su D.; Wang Q.

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. Themore » 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 technology by replacing Pt with low-cost, highly active Ir-based catalysts.« less

Connecting Land-Based Networks to Ships

DTIC Science & Technology

2012-09-01

LAN Local Area Network LEO Low Earth Orbit LOS Line Of Sight MAC Media Access Control MANET Mobile Ad Hoc Networking ME Mobile...orbit – LEO ). Iridium satellite communication system is an example of LEO , while Inmarsat uses MEO and GEO. GEO satellites are the most common type...August 2012, http://www.cosmote.gr/cosmoportal/page/T25/section/Cover/ loc /en_U.S. [41] WIND, “Network Coverage map,” August 2012, http

76 FR 46313 - Notice of Issuance of Final Determination Concerning Iridium Satellite Telephones

Federal Register 2010, 2011, 2012, 2013, 2014

2011-08-02

... modulates them into radio streams that communicate with the Iridium gateway network infrastructure using a... (DSP) cores, made in China, and two radio frequency (RF) backend chips, made in Taiwan. The bill of... marking of a cellular phone. CBP found that a digital mobile telephone was substantially transformed in...

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.

Balancing activity, stability and conductivity of nanoporous core-shell iridium/iridium oxide oxygen evolution catalysts

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kim, Yong-Tae; Lopes, Pietro Papa; Park, Shin-Ae

The selection of oxide materials for catalyzing the Oxygen Evolution Reaction in acid-based electrolyzers must be guided by the proper balance between activity, stability and conductivity – a challenging mission of great importance for delivering affordable and environmentally friendly hydrogen. Here we report that the highly conductive nanoporous architecture of an iridium oxide shell on a metallic iridium core, formed through the fast dealloying of osmium from an Ir25Os75 alloy, exhibits an exceptional balance between oxygen evolution activity and stability as quantified by the Activity-Stability FactorASF. Based on this metric, the nanoporous Ir/IrO2 morphology of dealloyed Ir25Os75 shows a factormore » of ~30 improvement ASFrelative to conventional Ir-based oxide materials and a ~8 times improvement over dealloyed Ir25Os75 nanoparticles due to optimized stability and conductivity, respectively. We propose that the Activity-Stability FactorASF is the key “metric” for determining the technological relevance of oxide-based anodic water electrolyzer catalysts.« less

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.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yang, Dong; Chen, Mingyang; Martinez-Macias, Claudia

In this study, the adsorption of N 2 on structurally well-defined dealuminated HY zeolite-supported iridium diethylene complexes was investigated. Iridium dinitrogen complexes formed when the sample was exposed to N 2 in H 2 at 298 K, as shown by infrared spectra recorded with isotopically labeled N 2. Four supported species formed in various flowing gases: Ir(N 2), Ir(N 2)(N 2), Ir(C 2H 5)(N 2), and Ir(H)(N 2). Their interconversions are summarized in a reaction network, showing, for example, that, in the presence of N 2, Ir(N 2) was the predominant dinitrogen species at temperatures of 273-373 K. Ir(CO)(N 2)more » formed transiently in flowing CO, and in the presence of H 2, 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.« less

Mono- and bis-tolyl­terpyridine iridium(III) complexes

PubMed Central

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

2010-01-01

The first structure report of trichlorido[4′-(p-tolyl)-2,2′:6′,2′′-terpyridine]iridium(III) dimethyl sulfoxide solvate, [IrCl3(C22H17N3)]·C2H6OS, (I), is presented, along with a higher-symmetry setting of previously reported bis­[4′-(p-tolyl)-2,2′:6′,2′′-terpyridine]iridium(III) tris­(hexa­fluorido­phosphate) acetonitrile disolvate, [Ir(C22H17N3)2](PF6)3·2C2H3N, (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 PF6 − anion lie on twofold axes in this structure, making half of the mol­ecule unique. PMID:20203396

Mono- and bis-tolylterpyridine iridium(III) complexes

DOE Office of Scientific and Technical Information (OSTI.GOV)

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

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.more » The iridium complex and one PF{sub 6}{sup -} anion lie on twofold axes in this structure, making half of the molecule unique.« less

Investigating a 65-Ma-Old Smoking Gun: Deep Drilling of the Chicxulub Impact Structure

NASA Astrophysics Data System (ADS)

Dressler, B. O.; Sharpton, V. L.; Morgan, J.; Buffler, R.; Moran, D.; Smit, J.; Stöffler, D.; Urrutia, J.

The Phanerozoic paleontological record is marked by several biological extinction events. One of them, at the Cretaceous/Tertiary (K/T) boundary, was responsible for the demise of about 5% of genera and 75% of species, including the dinosaurs. These drastic and abrupt changes in the development of life on Earth puzzled paleontologists in the past. Many a cause was put forward to account for them, amongst them climate changes, disease, or overspecialization. About 20 years ago, Alvarez et al. [1980] discovered a high iridium concentration in an Italian K/T boundary clay layer. They proposed that the iridium was derived from an extra-terrestrial impact 65 Ma ago and that the impact was the cause for the K/T boundary extinctions. The iridium layer was subsequently found at K/T boundary locations worldwide. Further evidence for a K/T impact came from the discovery of shocked quartz, nano-diamonds, glass spherules, and nickel-rich spinels in microkrystites in the iridium-rich layer. There was evidence for an impact event, but no crater.

Deep Blue Phosphorescent Organic Light-Emitting Diodes with CIEy Value of 0.11 and External Quantum Efficiency up to 22.5.

PubMed

Li, Xiaoyue; Zhang, Juanye; Zhao, Zifeng; Wang, Liding; Yang, Hannan; Chang, Qiaowen; Jiang, Nan; Liu, Zhiwei; Bian, Zuqiang; Liu, Weiping; Lu, Zhenghong; Huang, Chunhui

2018-03-01

Organic light-emitting diodes (OLEDs) based on red and green phosphorescent iridium complexes are successfully commercialized in displays and solid-state lighting. However, blue ones still remain a challenge on account of their relatively dissatisfactory Commission International de L'Eclairage (CIE) coordinates and low efficiency. After analyzing the reported blue iridium complexes in the literature, a new deep-blue-emitting iridium complex with improved photoluminescence quantum yield is designed and synthesized. By rational screening host materials showing high triplet energy level in neat film as well as the OLED architecture to balance electron and hole recombination, highly efficient deep-blue-emission OLEDs with a CIE at (0.15, 0.11) and maximum external quantum efficiency (EQE) up to 22.5% are demonstrated. Based on the transition dipole moment vector measurement with a variable-angle spectroscopic ellipsometry method, the ultrahigh EQE is assigned to a preferred horizontal dipole orientation of the iridium complex in doped film, which is beneficial for light extraction from the OLEDs. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Regio- and Enantioselective N-Allylations of Imidazole, Benzimidazole, and Purine Heterocycles Catalyzed by Single-Component Metallacyclic Iridium Complexes

PubMed Central

Stanley, Levi M.

2010-01-01

Highly regio- and enantioselective iridium-catalyzed N-allylations of benzimidazoles, imidazoles, and purines have been developed. N-Allylated benzimidazoles and imidazoles were isolated in high yields (up to 97%) with high branched-to-linear selectivity (up to 99:1) and enantioselectivity (up to 98% ee) from the reactions of benzimidazole and imidazole nucleophiles with unsymmetrical allylic carbonates in the presence of single component, ethylene-bound, metallacyclic iridium catalysts. N-Allylated purines were also obtained in high yields (up to 91%) with high N9:N7 selectivity (up to 96:4), high branched-to-linear selectivity (98:2), and high enantioselectivity (up to 98% ee) under similar conditions. The reactions encompass a range of benzimidazole, imidazole, and purine nucleophiles, as well as a variety of unsymmetrical aryl, heteroaryl, and aliphatic allylic carbonates. Competition experiments between common amine nucleophiles and the heterocyclic nitrogen nucleophiles studied in this work illustrate the effect of nucleophile pKa on the rate of iridium-catalyzed N-allylation reactions. Kinetic studies on the allylation of benzimidazole catalyzed by metallacyclic iridium-phosphoramidite complexes, in combination with studies on the deactivation of these catalysts in the presence of heterocyclic nucleophiles, provide insight into the effects of the structure of the phosphoramidite ligands on the stability of the metallacyclic catalysts. The data obtained from these studies has led to the development of N-allylations of benzimidazoles and imidazoles in the absence of an exogenous base. PMID:19480431

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.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Han, Chang W.; Iddir, Hakim; Uzun, Alper

To address the challenge of fast, direct atomic-scale visualization of the diffusion of atoms and clusters on surfaces, we used aberration-corrected scanning transmission electron microscopy (STEM) with high scan speeds (as little as ~0.1 s per frame) to visualize the diffusion of (1) a heavy atom (Ir) on the surface of a support consisting of light atoms, MgO(100), and (2) an Ir 3 cluster on MgO(110). Sequential Z-contrast images elucidate the diffusion mechanisms, including the hopping of Ir1 and the rotational migration of Ir 3 as two Ir atoms remain anchored to the surface. Density functional theory (DFT) calculations providedmore » estimates of the diffusion energy barriers and binding energies of the iridium species to the surfaces. The results show how the combination of fast-scan STEM and DFT calculations allow real-time visualization and fundamental understanding of surface diffusion phenomena pertaining to supported catalysts and other materials.« less

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 misinterpretations. The comparison between the actual example and the fossil record belonging to terrestrial settings, can be considered as a valuable approach, especially when Iridium data were used by researchers to interpret the impact-related mass-extinction events in the past.

129Xe on Ir(111): NMR study of xenon on a metal single crystal surface

PubMed Central

Jänsch, H. J.; Gerhard, P.; Koch, M.

2004-01-01

NMR experiments of 129Xe adsorbed on an iridium single crystal surface are reported. Very high nuclear polarization (Pz ≈ 0.7) makes the experiment possible. A coverage of less then one monolayer is investigated on the Ir(111) surface with an area of 0.8 cm2. The observed resonance line shifts are very large and highly anisotropic. We find σiso = 1,032 ± 11 ppm and σan = 291 ± 33 ppm, which are far above the typical range of physisorption. The highly ordered substrate leads to homogeneous conditions for the xenon atoms, as seen in the narrow linewidth of 20 ppm. Chemical shifts under physisorption conditions are not large enough to totally explain the results. Knight shift can clearly be identified as the cause of the findings. This shift shows the presence of conduction electrons of the metallic substrate at the xenon nucleus and thus the mixing of metallic and atomic states at the Fermi level. Such mixing is in accordance with recent Hartree–Fock and density functional calculations of similar van der Waals adsorption systems. Quantitative comparisons, however, fail completely. The size and ratio of σan and σiso are pure ground-state properties in a structurally simple system. They are accessible to theory and provide detailed local information that can serve as a benchmark for theory. PMID:15361579

High temperature oxidation-resistant thruster research

NASA Technical Reports Server (NTRS)

Wooten, John R.; Lansaw, P. Tina

1990-01-01

A program was conducted for NASA-LeRC by Aerojet Propulsion Division to establish the technology base for a new class of long-life, high-performance, radiation-cooled bipropellant thrusters capable of operation at temperatures over 2200 C (4000 F). The results of a systematic, multi-year program are described starting with the preliminary screening tests which lead to the final material selection. Life greater than 15 hours was demonstrated on a workhorse iridium-lined rhenium chamber at chamber temperatures between 2000 and 2300 C (3700 and 4200 F). The chamber was fabricated by the Chemical Vapor Deposition at Ultramet. The program culminated in the design, fabrication, and hot-fire test of an NTO/MMH 22-N (5-lbF) class thruster containing a thin wall iridium-lined rhenium thrust chamber with a 150:1 area ratio nozzle. A specific impulse of 310 seconds was measured and front-end thermal management was achieved for steady state and several pulsing duty cycles. The resulting design represents a 20 second specific impulse improvement over conventional designs in which the use of disilicide coated columbium chambers limit operation to 1300 C (2400 F).

Iridium Concentrations and Abundances of Meteoritic Ejecta from the Eltanin Impact in Sediment Cores from Polarstern Expedition ANT XII/4

NASA Technical Reports Server (NTRS)

Kyte, Frank T.

2002-01-01

The abundances of meteoritic ejecta from the Eltanin asteroid impact have been examined in several sediment cores recovered by the FS Polarstern during expedition ANT XII/4 using elemental concentrations of iridium and weights of coarse ejecta debris. Three cores with well-preserved impact deposits, PS204-1, PS2708-1, and PS2709-1, each contain Ir and ejecta fluences similar to those found in USNS Eltanin core E13-4. Small Ir anomalies and traces of ejecta were found in cores PS2706-1 and PS2710-1, but since these cores lack well-defined deposits, these are considered to be reworked and not representative of the fallout. No evidence of ejecta was found in cores PS2802-1 and PS2705-1. These results confirm earlier speculation that the Eltanin impact resulted in deposits of ejecta with up to 1 gram/sq centimeter of depris over a wide area of the ocean floor. However, there are sill large uncertainties over the actual regional or global extent of this unique sediment deposit.

Method for the preparation of metal colloids in inverse micelles and product preferred by the method

DOEpatents

Wilcoxon, Jess P.

1992-01-01

A method is provided for preparing catalytic elemental metal colloidal particles (e.g. gold, palladium, silver, rhodium, iridium, nickel, iron, platinum, molybdenum) or colloidal alloy particles (silver/iridium or platinum/gold). A homogeneous inverse micelle solution of a metal salt is first formed in a metal-salt solvent comprised of a surfactant (e.g. a nonionic or cationic surfactant) and an organic solvent. The size and number of inverse micelles is controlled by the proportions of the surfactant and the solvent. Then, the metal salt is reduced (by chemical reduction or by a pulsed or continuous wave UV laser) to colloidal particles of elemental metal. After their formation, the colloidal metal particles can be stabilized by reaction with materials that permanently add surface stabilizing groups to the surface of the colloidal metal particles. The sizes of the colloidal elemental metal particles and their size distribution is determined by the size and number of the inverse micelles. A second salt can be added with further reduction to form the colloidal alloy particles. After the colloidal elemental metal particles are formed, the homogeneous solution distributes to two phases, one phase rich in colloidal elemental metal particles and the other phase rich in surfactant. The colloidal elemental metal particles from one phase can be dried to form a powder useful as a catalyst. Surfactant can be recovered and recycled from the phase rich in surfactant.

UV-light promoted C-H bond activation of benzene and fluorobenzenes by an iridium(i) pincer complex.

PubMed

Hauser, Simone A; Emerson-King, Jack; Habershon, Scott; Chaplin, Adrian B

2017-03-28

Iridium(i) carbonyl complex [Ir(2,6-(P t Bu 2 CH 2 ) 2 C 6 H 3 )(CO)] undergoes reversible C-H bond activation of benzene and a series of fluorobenzenes on UV irradiation. Exclusive ortho-selectivity is observed in reactions of fluorobenzene and 1,2-difluorobenzene.

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.

α-Arylation/Heteroarylation of Chiral α-Aminomethyltrifluoroborates by Synergistic Iridium Photoredox/Nickel Cross-Coupling Catalysis.

PubMed

El Khatib, Mirna; Serafim, Ricardo Augusto Massarico; Molander, Gary A

2016-01-04

Direct access to complex, enantiopure benzylamine architectures using a synergistic iridium photoredox/nickel cross-coupling dual catalysis strategy has been developed. New C(sp(3))-C(sp(2)) bonds are forged starting from abundant and inexpensive natural amino acids. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Chiral imidate-ferrocenylphosphanes: synthesis and application as P,N-ligands in iridium(I)-catalyzed hydrogenation of unfunctionalized and poorly functionalized olefins.

PubMed

Bert, Katrien; Noël, Timothy; Kimpe, Wim; Goeman, Jan L; Van der Eycken, Johan

2012-11-14

A small library of chiral imidate-ferrocenylphosphane ligands was efficiently synthesized (8 examples) and evaluated in the iridium(I)-catalyzed hydrogenation of unfunctionalized and poorly functionalized olefins. These catalysts perform very well in a range of examples (yields and ee's up to 100%).

Efficient near-infrared emission of π-extended cyclometalated iridium complexes based on pyrene in solution-processed polymer light-emitting diode

NASA Astrophysics Data System (ADS)

Liu, Yu; Hao, Zhaoran; Meng, Fanyuan; Wang, Pu; Yang, Liang; Wang, Yafei; Pei, Yong; Su, Shijian

2018-05-01

A novel iridium complex grafting hole-transporting triphenylamine (TPA) unit onto cyclometalated ligand, namely t-BuPyrPyTPA)2Ir(acac), was successfully synthesized and characterized. The photophysical, electrochemical and DFT/TD-DFT calculation, as well as electroluminescence properties of this iridium complex were fully investigated. Meanwhile, the PLEDs employing (t-BuPyrPyTPA)2Ir(acac) as dopant presented stable NIR emission peaked at 697 nm and a shoulder at 764 nm with a highest external quantum efficiency (EQE) of 0.56% at 4 wt% dopant concentration. These results demonstrate that expanding the conjugation length of the ligand is an effective way to achieve NIR emission.

The treatment of malignant diseases in Romania using stainless steel encapsulated iridium-192 sources

NASA Astrophysics Data System (ADS)

Stanef, I.; Matache, G.; Ciocǎltei, V.; Gheorghiev, G.

1994-01-01

Iridium-192 sources supplied by the Institute for Nuclear Physics and Engineering have been used in Romanian radiotherapy clinics since 1980. The source assembly is sealed in a protective stainless steel sheath which satisfies the requirements of international standards. Since this sheath acts as a filter to change the characteristic spectrum it has been necessary to determine experimentally an accurate value of the specific gamma-ray constant. Some clinical aspects of the complex treatment of carcinomas with iridium-192 are reviewed. Results of the calculation of the dose distribution around single and multiple sources are given for different applications in the treatment of carcinomas of the vaginal and uterine cervix, oral cavity, rectum and vagina.

In situ high-temperature characterization of AlN-based surface acoustic wave devices

NASA Astrophysics Data System (ADS)

Aubert, Thierry; Bardong, Jochen; Legrani, Ouarda; Elmazria, Omar; Badreddine Assouar, M.; Bruckner, Gudrun; Talbi, Abdelkrim

2013-07-01

We report on in situ electrical measurements of surface acoustic wave delay lines based on AlN/sapphire structure and iridium interdigital transducers between 20 °C and 1050 °C under vacuum conditions. The devices show a great potential for temperature sensing applications. Burnout is only observed after 60 h at 1050 °C and is mainly attributed to the agglomeration phenomena undergone by the Ir transducers. However, despite the vacuum conditions, a significant oxidation of the AlN film is observed, pointing out the limitation of the considered structure at least at such extreme temperatures. Original structures overcoming this limitation are then proposed and discussed.

Iridium Short Burst Data: Two-Way, Robust, Reliable, Low Power Communications for Oceanographic Data Transmission Applications

NASA Astrophysics Data System (ADS)

Roggenstein, E. B.; Hensley, W.

2011-12-01

Over the past two hundred years, water level observations in coastal areas have been used to help mariners navigate oceans and estuaries, cartographers develop nautical charts, government agencies regulate boundaries, and scientists gain a better understanding of various physical processes in the ocean. As technology has progressed the latency in providing these data to the user has been reduced. The National Oceanic and Atmospheric Administration's (NOAA) Center for Operational Oceanographic Products and Services (CO-OPS) provides near real-time oceanographic and meteorological data to support navigation, coastal managers, and storm surge and tsunami warning programs. CO-OPS maintains the National Water Level Observation Network (NWLON), a system of over 200 stations for the coastal United States, Great Lakes, Caribbean islands, and Pacific island territories. CO-OPS also supports the NOAA Physical Oceanographic Real Time Systems° (PORTS), which are currently operating in 21 US ports. With an expanding role in Arctic and Alaska support, CO-OPS has identified a need for a robust and reliable data communications pathway to supplement the existing Geostationary Operational Environmental Systems (GOES) network, which has limitations at high latitudes. Iridium satellite Short Burst Data (SBD) services offer a global coverage, including remote Arctic regions outside of GOES coverage. Previous testing conducted by CO-OPS has shown a great potential for the SBD service including continuous near-real-time 6 minute data transmissions from two CO-OPS test water level stations located in Guam, with >99.9% data return. Also, successful transmissions of hourly wave statistics were demonstrated with a with a test system that employed a Nortek Acoustic Wave and Current (AWAC) instrument in Chesapeake Bay were accomplished. Data transmissions involved a buoy-mounted SIM-less SBD modem. Independent of location, data can be transmitted from a remote instrument platform to Iridium satellites with a latency of just 15 seconds. Successful test demonstrations have led to discussions regarding prospective work to integrate these small modems into CO-OPS current meters that are mounted on United States Coast Guard (USCG) Aid to Navigation (ATON) buoys, improving the reliability of the real-time transmission pathway between data collection and data reporting via PORTS °. Overall, this work has shown that with careful evaluation of data needs, commercial Iridium service can be economically used to accomplish telemetry requirements. It also shows potential for event-driven high frequency data transmission options, for applications such as marine warning systems. CO-OPS efforts to test and evaluate Iridium communications oceanographic observatories reported on here has been a collaborative endeavor with the United States Army Corp Engineers (USACE) Field Research Facility (FRF) in Duck, NC, the USACE Cold Regions Research Engineering Laboratory (CRREL) in Hanover, NH, NAL Research Inc, Sutron Corporation,and Nortek USA.

Electrochemical Deposition of Nanostructured Conducting Polymer Coatings on Neural Prosthetic Devices

NASA Astrophysics Data System (ADS)

Yang, Junyan; Martin, David

2003-03-01

Micromachined neural prosthetic devices facilitate the functional stimulation of and recording from the central nervous system (CNS). These devices have been fabricated to consist of silicon shanks that have gold or iridium sites along their surface. Our goal is to improve the biocompatibility and long-term performance of the neural prosthetic probes when they are implanted chronically in the brain. In our most recent efforts we have established that electrochemical polymerization can be used to deposit fuzzy coatings of conducting polymers specifically on the electrode sites. For neural prosthetic devices that are intended for long term implantation, we need to develop surfaces that provide intimate contact and promote efficient signal transport at the interface of the microelectrode array and brain tissue. We have developed methods to rapidly and reliably fabricate nanostructured conducting polymer coatings on the electrode probes using templated and surfactant-mediated techniques. Conducting polymer nanomushrooms and nanohairs of polypyrrole (PPy) were electrochemically polymerized onto the functional sites of neural probes by using either nanoporous block copolymers thin films, "track-etched" polycarbonate films or anodic aluminium oxide membranes as templates. Nanofibers of conducting polymers have also been successfully obtained by polymerizations in the presence of surfactants. The influence of current density, monomer concentration, surfactant concentration, and deposition charge on the thickness and morphology of the nanostructured conducting polymer coatings has been studied by optical, scanned probe, scanning electron and transmission electron microscopy. As compared with the normal nodular morphology of polypyrrole, the nanostructured morphologies grown from the neural electrode result in fuzzy coatings with extremely high surface area. The electrical properties of the polymer coatings were studied by Impedance Spectroscopy (IS) and Cyclic Voltammetry (CV). The significant drop in impedance in magnitude and phase angle is consistent with an increase of the surface area due to the roughened surface morphology.

Self-diffusion on iridium (100). A structure investigation by field-ion microscopy

NASA Astrophysics Data System (ADS)

Friedl, A.; Schütz, O.; Müller, K.

1992-04-01

An iridium atom was thermally activated for diffusion on the (100) terrace of an Ir tip. The residence sites of the atom between diffusion cycles were recorded by means of a computer-controlled video system which generates a map of all occupied sites. For a field evaporated tip at low temperature this map is a c(2 × 2) grid indicating that only every other fourfold hollow in every other row of an undistor ted (100) surface can be occupied by a diffusing atom. This extraordinary behaviour was already reported by Chen and Tsong [Phys. Rev. Lett. 64 (1990) 3147]. The authors base their interpretation on an exchange diffusion mechanism. As an alternative explanation we propose a local adsorbate induced (2 × 2) reconstruction of the substrate. After heating the same terrace to temperatures above 500 K the residence map of the Ir atom indicates a (1 × 1) structure which, however, contains residues of a c(2 × 2) diffusion pattern: while the diffusion still takes place mainly on a c(2 × 2) sublattice, the diffusion path changes occasionally from one sublattice to the other. This can also be understood by local adsorbate induced distortions.

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…

Enhanced CO2 electroreduction efficiency through secondary coordination effects on a pincer iridium catalyst.

PubMed

Ahn, Steven T; Bielinski, Elizabeth A; Lane, Elizabeth M; Chen, Yanqiao; Bernskoetter, Wesley H; Hazari, Nilay; Palmore, G Tayhas R

2015-04-07

An iridium(III) trihydride complex supported by a pincer ligand with a hydrogen bond donor in the secondary coordination sphere promotes the electrocatalytic reduction of CO2 to formate in water/acetonitrile with excellent Faradaic efficiency and low overpotential. Preliminary mechanistic experiments indicate formate formation is facile while product release is a kinetically difficult step.

Satellite Telemetry and Command using Big LEO Mobile Telecommunications Systems

NASA Technical Reports Server (NTRS)

Huegel, Fred

1998-01-01

Various issues associated with satellite telemetry and command using Big LEO mobile telecommunications systems are presented in viewgraph form. Specific topics include: 1) Commercial Satellite system overviews: Globalstar, ICO, and Iridium; 2) System capabilities and cost reduction; 3) Satellite constellations and contact limitations; 4) Capabilities of Globalstar, ICO and Iridium with emphasis on Globalstar; and 5) Flight transceiver issues and security.

Iridium-192 Production for Cancer Treatment

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rostelato, M.E.C.M.; Silva, C.P.G.; Rela, P.R.

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.

Extracellular pH monitoring for use in closed-loop vagus nerve stimulation

NASA Astrophysics Data System (ADS)

Cork, Simon C.; Eftekhar, Amir; Mirza, Khalid B.; Zuliani, Claudio; Nikolic, Konstantin; Gardiner, James V.; Bloom, Stephen R.; Toumazou, Christofer

2018-02-01

Objective. Vagal nerve stimulation (VNS) has shown potential benefits for obesity treatment; however, current devices lack physiological feedback, which limit their efficacy. Changes in extracellular pH (pHe) have shown to be correlated with neural activity, but have traditionally been measured with glass microelectrodes, which limit their in vivo applicability. Approach. Iridium oxide has previously been shown to be sensitive to fluctuations in pH and is biocompatible. Iridium oxide microelectrodes were inserted into the subdiaphragmatic vagus nerve of anaesthetised rats. Introduction of the gut hormone cholecystokinin (CCK) or distension of the stomach was used to elicit vagal nerve activity. Main results. Iridium oxide microelectrodes have sufficient pH sensitivity to readily detect changes in pHe associated with both CCK and gastric distension. Furthermore, a custom-made Matlab script was able to use these changes in pHe to automatically trigger an implanted VNS device. Significance. This is the first study to show pHe changes in peripheral nerves in vivo. In addition, the demonstration that iridium oxide microelectrodes are sufficiently pH sensitive as to measure changes in pHe associated with physiological stimuli means they have the potential to be integrated into closed-loop neurostimulating devices.

Installing an additional emission quenching pathway in the design of iridium(III)-based phosphorogenic biomaterials for bioorthogonal labelling and imaging.

PubMed

Li, Steve Po-Yam; Yip, Alex Man-Hei; Liu, Hua-Wei; Lo, Kenneth Kam-Wing

2016-10-01

We report the synthesis, characterization, photophysical and electrochemical behaviour and biological labelling applications of new phosphorogenic bioorthogonal probes derived from iridium(III) polypyridine complexes containing a 1,2,4,5-tetrazine moiety. In contrast to common luminescent cyclometallated iridium(III) polypyridine complexes, these tetrazine complexes are almost non-emissive due to effective Förster resonance energy transfer (FRET) and/or photoinduced electron transfer (PET) from the excited iridium(III) polypyridine unit to the appended tetrazine moiety. However, they exhibited significant emission enhancement upon reacting with (1R,8S,9s)-bicyclo[6.1.0]non-4-yn-9-ylmethanol (BCN-OH) (ca. 19.5-121.9 fold) and BCN-modified bovine serum albumin (BCN-BSA) (ca. 140.8-1133.7 fold) as a result of the conversion of the tetrazine unit to a non-quenching pyridazine derivative. The complexes were applied to image azide-modified glycans in live cells using a homobifunctional crosslinker, 1,13-bis((1R,8S,9s)-bicyclo[6.1.0]non-4-yn-9-ylmethyloxycarbonylamino)-4,7,10-trioxatridecane (bis-BCN). Copyright © 2016 Elsevier Ltd. All rights reserved.

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.

Investigation of Coatings for Langmuir Probes in an Oxygen-Rich Space Environment

NASA Astrophysics Data System (ADS)

Samaniego, J. I.; Wang, X.; Andersson, L.; Malaspina, D.; Ergun, R.; Horanyi, M.

2017-12-01

The surface properties of the Langmuir probes, such as the one on the MAVEN mission, will change after exposure to upper planetary atmospheres where high concentrations of atomic oxygen and other oxidizing compounds are present. TiN (Titanium Nitride) or DAG (a resin based graphite dispersion) are the most common coatings for current Langmuir probes, yet both of these coatings pose issues when exposed to oxygen-rich space environment. TiN showed reduced surface conductivity while the DAG layers erode with exposure to oxygen. It is known that Iridium (Ir) and Rhenium (Rh) are difficult to oxidize and maintain high conductivity even in their oxidized forms, suggesting them to be good candidates for probe coatings. Oxidation of most metals creates a resistive layer on the surface of the probe that will affect the amount of current being collected at a given voltage during the probe sweep and therefore affect the accuracy of plasma parameters determined by the Langmuir probe (e.g. density, temperature). We present the results of the oxidation effect on the current-voltage curves (I-V curves) and therefore the resulting measured plasma parameters of Ir and Rh wire probes compared with other control metals and coatings (Cu, Ni, TiN) in controlled plasma environments. The oxidation process is performed in an oxygen plasma chamber in which both O+ and O2+ are created and accelerated toward the probes with energies < 10 eV. An argon plasma chamber is used to compare the probe's I-V curves before and after the oxidation process. Our preliminary results indicate that iridium shows the least effect of oxidation on the probe measurements. The second objective of this study is to identify methods that can be used in orbit to clean the surface of Langmuir probes to minimize the effect of exposure to oxidizing compounds.

Phosphorescent Organic Light-Emitting Devices: Working Principle and Iridium Based Emitter Materials

PubMed Central

Kappaun, Stefan; Slugovc, Christian; List, Emil J. W.

2008-01-01

Even though organic light-emitting device (OLED) technology has evolved to a point where it is now an important competitor to liquid crystal displays (LCDs), further scientific efforts devoted to the design, engineering and fabrication of OLEDs are required for complete commercialization of this technology. Along these lines, the present work reviews the essentials of OLED technology putting special focus on the general working principle of single and multilayer OLEDs, fluorescent and phosphorescent emitter materials as well as transfer processes in host materials doped with phosphorescent dyes. Moreover, as a prototypical example of phosphorescent emitter materials, a brief discussion of homo- and heteroleptic iridium(III) complexes is enclosed concentrating on their synthesis, photophysical properties and approaches for realizing iridium based phosphorescent polymers. PMID:19325819

Anodic iridium oxide films: An UPS study of emersed electrodes

NASA Astrophysics Data System (ADS)

Kötz, E. R.; Neff, H.

1985-09-01

Formation of anodic iridium oxide films has been monitored using Ultraviolet Photoemission Spectroscopy (UPS) of the emersed electrodes. The potential dependent valence band spectra clearly show the onset of oxide formation at about 0.6 V versus SCE. The density of states at the Fermi level and the positron of the Fermi level with respect to the maximum of the t 2g band of the oxide indicates a transition from metallic to semiconducting behaviour of the oxide. Protonation of the oxide is associated with increased emission from OH species. A linear correlation between electrode potential and workfunction change is observed for the metal as well as for the oxide. Our results confirm known band theory models and provide a fundamental understanding of the electrochromism of anodic iridium oxide films.

Thermionic energy converter investigations

NASA Technical Reports Server (NTRS)

Goodale, D. B.; Lee, C.; Lieb, D.; Oettinger, P. E.

1979-01-01

This paper presents evaluation of a variety of thermionic converter configurations to obtain improved efficiency. A variable-spacing diode using an iridium emitter gave emission properties comparable to platinum, but the power output from a sintered LaB6 collector diode was not consistent with its work function. Reflectivities above 0.5 were measured at thermal energies on oxygenated-cesiated surfaces using a field emission retarding potential gun. Performance of converters with structured electrodes and the characteristics of a pulsed triode were studied as a function of emitter, collector, cesium reservoir, interelectrode spacing, xenon pressure, and pulsing parameters.

Molecular metal catalysts on supports: organometallic chemistry meets surface science.

PubMed

Serna, Pedro; Gates, Bruce C

2014-08-19

Recent advances in the synthesis and characterization of small, essentially molecular metal complexes and metal clusters on support surfaces have brought new insights to catalysis and point the way to systematic catalyst design. We summarize recent work unraveling effects of key design variables of site-isolated catalysts: the metal, metal nuclearity, support, and other ligands on the metals, also considering catalysts with separate, complementary functions on supports. The catalysts were synthesized with the goal of structural simplicity and uniformity to facilitate incisive characterization. Thus, they are essentially molecular species bonded to porous supports chosen for their high degree of uniformity; the supports are crystalline aluminosilicates (zeolites) and MgO. The catalytic species are synthesized in reactions of organometallic precursors with the support surfaces; the precursors include M(L)2(acetylacetonate)1-2, with M = Ru, Rh, Ir, or Au and the ligands L = C2H4, CO, or CH3. Os3(CO)12 and Ir4(CO)12 are used as precursors of supported metal clusters, and some such catalysts are made by ship-in-a-bottle syntheses to trap the clusters in zeolite cages. The simplicity and uniformity of the supported catalysts facilitate precise structure determinations, even in reactive atmospheres and during catalysis. The methods of characterizing catalysts in reactive atmospheres include infrared (IR), extended X-ray absorption fine structure (EXAFS), X-ray absorption near edge structure (XANES), and nuclear magnetic resonance (NMR) spectroscopies, and complementary methods include density functional theory and atomic-resolution aberration-corrected scanning transmission electron microscopy for imaging of individual metal atoms. IR, NMR, XANES, and microscopy data demonstrate the high degrees of uniformity of well-prepared supported species. The characterizations determine the compositions of surface metal complexes and clusters, including the ligands and the metal-support bonding and structure, which identify the supports as ligands with electron-donor properties that influence reactivity and catalysis. Each of the catalyst design variables has been varied independently, illustrated by mononuclear and tetranuclear iridium on zeolite HY and on MgO and by isostructural rhodium and iridium (diethylene or dicarbonyl) complexes on these supports. The data provide examples resolving the roles of the catalyst design variables and place the catalysis science on a firm foundation of organometallic chemistry linked with surface science. Supported molecular catalysts offer the advantages of characterization in the absence of solvents and with surface-science methods that do not require ultrahigh vacuum. Families of supported metal complexes have been made by replacement of ligands with others from the gas phase. Spectroscopically identified catalytic reaction intermediates help to elucidate catalyst performance and guide design. The methods are illustrated for supported complexes and clusters of rhodium, iridium, osmium, and gold used to catalyze reactions of small molecules that facilitate identification of the ligands present during catalysis: alkene dimerization and hydrogenation, H-D exchange in the reaction of H2 with D2, and CO oxidation. The approach is illustrated with the discovery of a highly active and selective MgO-supported rhodium carbonyl dimer catalyst for hydrogenation of 1,3-butadiene to give butenes.

A Comparison of Long-Duration Secondary-Power Schemes for Space Vehicles

DTIC Science & Technology

1959-02-02

to:" 3. Iridium . 19_ 7I? d 2.454 5,300 Beta. eak G- ’al 1.000 4.52 10’ N SulIphur -35 b7 W8 119 445 BtLA I1.00 3.72 IS Availat’Nt, _i es 5 Calo1.r...BROMIDE 28 84 41 tar area. BISMUrTH TRICHLORIDE 435 826 99 ZINC CHLORIDE 541 1349 378 case of a space power system, this receiving tem- Working-Fluid

Coordination chemistry and catalytic activity of N-heterocyclic carbene iridium(I) complexes.

PubMed

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

2009-09-21

Iridium complexes [(CO)2Ir(NHC-R)Cl] (R = Et-, 3a; PhCH2-, 3b; CH3OCH2CH2-, 3c; o-CH3OC6H4CH2-, 3d; NHC: N-heterocyclic carbene) are prepared via the carbene transfer from [(NHC-R)W(CO)5] to [Ir(COD)Cl]2. By using substitution with 13CO, we are able to estimate the activation energy (G) of the CO-exchange in 3a-d, which are in the range of 12-13 kcal mol-1, significantly higher than those for the phosphine analog [(CO)2Ir(PCy3)Cl]. Reactions of 3b and 3d with an equimolar amount of PPh3 result in the formation of the corresponding [(NHC-R)Ir(CO)(PPh3)Cl] with the phosphine and NHC in trans arrangement. In contrast, the analogous reaction of 3a or 3c with phosphine undergoes substitution followed by the anion metathesis to yield the corresponding di-substituted [(NHC-R)Ir(CO)(PPh3)2]BF4 (5) directly. Treatment of 3b or 3d with excess of PPh3 leads to the similar product of disubstitution 5b and 5d. The analysis for the IR data of carbonyliridium complexes provides the estimation of electron-donating power of NHCs versus phosphines. The NHC moiety on the iridium center cannot be replaced by phosphines, even 1,2-bis(diphenylphohino)ethane (dppe). All the carbene moieties on the iridium complexes are inert toward sulfur treatment, indicating a strong interaction between NHC and the iridium centers. Complexes 3a-c are active on the catalysis of the oxidative cyclization of 2-(o-aminophenyl)ethanol to yield the indole compound. The phosphine substituted complexes or analogs are less active.

Controlling charge balance and exciton recombination by bipolar host in single-layer organic light-emitting diodes

NASA Astrophysics Data System (ADS)

Qiao, Xianfeng; Tao, Youtian; Wang, Qiang; Ma, Dongge; Yang, Chuluo; Wang, Lixiang; Qin, Jingui; Wang, Fosong

2010-08-01

Highly efficient single-layer organic light-emitting diodes with reduced efficiency roll-off are demonstrated by using a bipolar host material of 2,5-bis(2-(9H-carbazol-9-yl)phenyl)-1,3,4-oxadiazole (o-CzOXD) doped with iridium complexes as the emissive layer. For example, the green single-layer device, employing fac-tris(2-phenylpyridine)iridium Ir(ppy)3 as dopant, shows a peak current efficiency of 45.57 cd A-1, corresponding to external quantum efficiency (EQE) of 12.42%, and still exhibits efficiencies of 45.26 cd A-1 and 40.42 cd A-1 at luminance of 1000 and 10 000 cd m-2, respectively. In addition, the yellow and red single-layer devices, with bis(2-(9,9- diethyl-9H-fluoren-2-yl)-1-phenyl-1H-benzoimidazol-N ,C3)iridium(acetylacetonate) (fbi)2Ir(acac) and bis(1-phenylisoquinolinolato-C2,N)iridium(acetylacetonate) (piq)2Ir(acac) as emitter, also show high EQE of 7.04% and 7.28%, respectively. The transport properties of o-CzOXD film are well investigated by current-voltage measurement, from which both hole and electron mobility are determined. It is found that the o-CzOXD shows appealing bipolar transport character, which is favor for the balanced charge distribution in the whole doped zone. More importantly, the multifunctional role of hole trapping and electron transporting of the iridium complex in o-CzOXD further balances the charge carriers and broadens the recombination zone. As a result, the recombination of electrons and holes is significantly improved and the triplet-triplet annihilation and triplet-polaron quenching processes are effectively suppressed, eventually leading to the high efficiency as well as the reduced efficiency roll-off.

Crystal structures of fac-tri-chlorido-tris-(tri-methyl-phosphane-κP)rhodium(III) monohydrate and fac-tri-chlorido-tris-(tri-methyl-phosphane-κP)rhodium(III) methanol hemisolvate: rhodium structures that are isotypic with their iridium analogs.

PubMed

Merola, Joseph S; Franks, Marion A

2015-02-01

The crystal structures of two solvates of fac-tri-chlorido-tris-(tri-methyl-phosphane-κP)rhodium(III) are reported, i.e. one with water in the crystal lattice, fac-[RhCl3(Me3P)3]·H2O, and one with methanol in the crystal lattice, fac-[RhCl3(Me3P)3]·0.5CH3OH. These rhodium compounds exhibit distorted octahedral coordination spheres at the metal and are isotypic with the analogous iridium compounds previously reported by us [Merola et al. (2013 ▶). Polyhedron, 54, 67-73]. Comparison is made between the rhodium and iridium compounds, highlighting their isostructural relationships.

Self-assembly of an electronically conductive network through microporous scaffolds.

PubMed

Sebastian, H Bri; Bryant, Steven L

2017-06-15

Electron transfer spanning significant distances through a microporous structure was established via the self-assembly of an electronically conductive iridium oxide nanowire matrix enveloping the pore walls. Microporous formations were simulated using two scaffold materials of varying physical and chemical properties; paraffin wax beads, and agar gel. Following infiltration into the micropores, iridium nanoparticles self-assembled at the pore wall/ethanol interface. Subsequently, cyclic voltammetry was employed to electrochemically crosslink the metal, erecting an interconnected, and electronically conductive metal oxide nanowire matrix. Electrochemical and spectral characterization techniques confirmed the formation of oxide nanowire matrices encompassing lengths of at least 1.6mm, 400× distances previously achieved using iridium nanoparticles. Nanowire matrices were engaged as biofuel cell anodes, where electrons were donated to the nanowires by a glucose oxidizing enzyme. Copyright © 2017 Elsevier Inc. All rights reserved.

Nanostructured F doped IrO2 electro-catalyst powders for PEM based water electrolysis

NASA Astrophysics Data System (ADS)

Kadakia, Karan Sandeep; Jampani, Prashanth H.; Velikokhatnyi, Oleg I.; Datta, Moni Kanchan; Park, Sung Kyoo; Hong, Dae Ho; Chung, Sung Jae; Kumta, Prashant N.

2014-12-01

Fluorine doped iridium oxide (IrO2:F) powders with varying F content ranging from 0 to 20 wt.% has been synthesized by using a modification of the Adams fusion method. The precursors (IrCl4 and NH4F) are mixed with NaNO3 and heated to elevated temperatures to form high surface area nanomaterials as electro-catalysts for PEM based water electrolysis. The catalysts were then coated on a porous Ti substrate and have been studied for the oxygen evolution reaction in PEM based water electrolysis. The IrO2:F with an optimum composition of IrO2:10 wt.% F shows remarkably superior electrochemical activity and chemical stability compared to pure IrO2. The results have also been supported via kinetic studies by conducting rotating disk electrode (RDE) experiments. The RDE studies confirm that the electro-catalysts follow the two electron transfer reaction for electrolysis with calculated activation energy of ∼25 kJ mol-1. Single full cell tests conducted also validate the superior electrochemical activity of the 10 wt.% F doped IrO2.

Wire-in-Tube IrOx Architectures: Alternative Label-Free Immunosensor for Amperometric Immunoassay toward α-Fetoprotein.

PubMed

Li, Qingling; Liu, Dali; Xu, Lin; Xing, Ruiqing; Liu, Wei; Sheng, Kuang; Song, Hongwei

2015-10-14

A sensitive, label-free immunosensor based on iridium oxide (IrOx, 0≤x≤2) nanofibers, which were synthesized through a simple one-spinneret electrospinning method, was first developed for immunoassay of the cancer biomarker α-fetoprotein (AFP). The specific wire-in-tube nanostructure could be obtained and the composition of IrOx nanofibers also could be controlled through changing the annealing temperature. The unique structure and properties of IrOx nanofibers obtained at 500 °C not only led to increased electrode surface area and accelerated electron transfer kinetics but also could provide a highly stable matrix for the convenient conjugation of biomolecules together with chitosan (CS). The good electrochemical properties of the IrOx-nanofiber-modified immunosensor allowed one to detect AFP over a wide concentration range from 0.05 to 150 ng/mL, with a detection limit of 20 pg/mL. The proposed immunosensor also has been used to determine AFP in human serum with satisfactory results. The present protocol was shown to be quite promising for clinical screening of cancer biomarkers and point-of-care diagnostics applications.

Development of very large electrode arrays for epiretinal stimulation (VLARS)

PubMed Central

2014-01-01

Background Retinal implants have been developed to treat blindness causing retinal degenerations such as Retinitis pigmentosa (RP). The retinal stimulators are covering only a small portion of the retina usually in its center. To restore not only central vision but also a useful visual field retinal stimulators need to cover a larger area of the retina. However, large area retinal stimulators are much more difficult to implant into an eye. Some basic questions concerning this challenge should be answered in a series of experiments. Methods Large area retinal stimulators were fabricated as flexible multielectrode arrays (MEAs) using silicon technology with polyimide as the basic material for the substrate. Electrodes were made of gold covered with reactively sputtered iridium oxide. Several prototype designs were considered and implanted into enucleated porcine eyes. The prototype MEAs were also used as recording devices. Results Large area retinal stimulator MEAs were fabricated with a diameter of 12 mm covering a visual angle of 37.6° in a normal sighted human eye. The structures were flexible enough to be implanted in a folded state through an insertion nozzle. The implants could be positioned onto the retinal surface and fixated here using a retinal tack. Recording of spontaneous activity of retinal neurons was possible in vitro using these devices. Conclusions Large flexible MEAs covering a wider area of the retina as current devices could be fabricated using silicon technology with polyimide as a base material. Principal surgical techniques were established to insert such large devices into an eye and the devices could also be used for recording of retinal neural activity. PMID:24502253

Global fire at the Cretaceous-Tertiary boundary

NASA Technical Reports Server (NTRS)

Wolbach, Wendy S.; Gilmour, Iain; Anders, Edward; Orth, Charles J.; Brooks, Robert R.

1988-01-01

Cretaceous-Tertiary boundary clays rich in iridium from five sites in Europe and New Zealand were investigated. The clays are found to be 100-10,000-fold-enriched in elemental carbon (mainly soot), which is isotopically uniform and apparently comes from a single global fire. The soot layer coincides with the iridium layer, suggesting that the fire was triggered by meteorite impact and began before the ejecta had settled.

The Death of the Dinosaurs: 27 Years Later (LBNL Summer Lecture Series)

ScienceCinema

Muller, Rich [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Dept. of Physics

2017-12-15

Summer Lecture Series 2006: Rich Muller, a Berkeley Lab physicist, discusses Nobel laureate Luis Alvarez and colleagues' 1979 discovery that an asteroid impact killed the dinosaurs. He also discusses what scientists have learned in the subsequent 27 years. Alvarez's team detected unusual amounts of iridium in sedimentary layers. They attributed the excess iridium to an impact from a large asteroid. His talk was presented June 30, 2006.

What caused the mass extinction An extraterrestrial impact

DOE Office of Scientific and Technical Information (OSTI.GOV)

Alvarez, W.; Asaro, F.

1990-10-01

The authors and other investigators discovered iridium in the clays that mark the sudden disappearance of dinosaurs from the fossil record. Because iridium is rare in the earth's crust but abundant in some meteorites, they concluded that a giant meteorite collided with the earth, hurling megatons of debris into the atmosphere. This paper describes and discusses the accumulating evidence that suggests an asteroid or comet caused the Cretaceous extinction.

Syntheses of the hexahydroindene cores of indanomycin and stawamycin by combinations of iridium-catalyzed asymmetric allylic alkylations and intramolecular Diels-Alder reactions.

PubMed

Gärtner, Martin; Satyanarayana, Gedu; Förster, Sebastian; Helmchen, Günter

2013-01-02

Short and concise syntheses of the hexahydroindene cores of the antibiotics indanomycin (X-14547 A) and stawamycin are presented. Key methods used are an asymmetric iridium-catalyzed allylic alkylation, a modified Julia olefination, a Suzuki-Miyaura coupling, and an intramolecular Diels-Alder reaction. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The Death of the Dinosaurs: 27 Years Later (LBNL Summer Lecture Series)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Muller, Rich

2006-06-30

Summer Lecture Series 2006: Rich Muller, a Berkeley Lab physicist, discusses Nobel laureate Luis Alvarez and colleagues' 1979 discovery that an asteroid impact killed the dinosaurs. He also discusses what scientists have learned in the subsequent 27 years. Alvarez's team detected unusual amounts of iridium in sedimentary layers. They attributed the excess iridium to an impact from a large asteroid. His talk was presented June 30, 2006.

High-temperature compatibility study of iridium (DOP-26 alloy) with graphite and plutonia

DOE Office of Scientific and Technical Information (OSTI.GOV)

Axler, K.M.; Eash, D.T.

1987-12-01

This report outlines the materials compatibility tests conducted on DOP-26 iridium alloy and carbon. The carbon used was in the form of woven graphite as present in the impact shell used to encase plutonia in nuclear heat sources. In addition, compatibility tests of the DOP-26 alloy with plutonia are described. The reactivity observed in both systems is discussed. 4 refs., 6 figs.

Process of making supported catalyst

DOEpatents

Schwarz, James A.; Subramanian, Somasundaram

1992-01-01

Oxide supported metal catalysts have an additional metal present in intimate association with the metal catalyst to enhance catalytic activity. In a preferred mode, iridium or another Group VIII metal catalyst is supported on a titania, alumina, tungsten oxide, silica, or composite oxide support. Aluminum ions are readsorbed onto the support and catalyst, and reduced during calcination. The aluminum can be added as aluminum nitrate to the iridium impregnate solution, e.g. chloroiridic acid.

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

USGS Publications Warehouse

Millard, H.T.

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??.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Song, Bo; Nelson, Kevin; Lipinski, Ronald

In this study, conventional Kolsky tension bar techniques were modified to characterize an iridium alloy in tension at elevated strain rates and temperatures. The specimen was heated to elevated temperatures with an induction coil heater before dynamic loading; whereas, a cooling system was applied to keep the bars at room temperature during heating. A preload system was developed to generate a small pretension load in the bar system during heating in order to compensate for the effect of thermal expansion generated in the high-temperature tensile specimen. A laser system was applied to directly measure the displacements at both ends ofmore » the tensile specimen in order to calculate the strain in the specimen. A pair of high-sensitivity semiconductor strain gages was used to measure the weak transmitted force due to the low flow stress in the thin specimen at elevated temperatures. The dynamic high-temperature tensile stress–strain curves of a DOP-26 iridium alloy were experimentally obtained at two different strain rates (~1000 and 3000 s -1) and temperatures (~750 and 1030°C). The effects of strain rate and temperature on the tensile stress–strain response of the iridium alloy were determined. Finally, the iridium alloy exhibited high ductility in stress–strain response that strongly depended on strain-rate and temperature.« less

The kinetics and mechanism of the organo-iridium catalysed racemisation of amines.

PubMed

Stirling, Matthew J; Mwansa, Joseph M; Sweeney, Gemma; Blacker, A John; Page, Michael I

2016-08-07

The dimeric iodo-iridium complex [IrCp*I2]2 (Cp* = pentamethylcyclopentadiene) is an efficient catalyst for the racemisation of secondary and tertiary amines at ambient and higher temperatures with a low catalyst loading. The racemisation occurs with pseudo-first-order kinetics and the corresponding four rate constants were obtained by monitoring the time dependence of the concentrations of the (R) and (S) enantiomers starting with either pure (R) or (S) and show a first-order dependence on catalyst concentration. Low temperature (1)H NMR data is consistent with the formation of a 1 : 1 complex with the amine coordinated to the iridium and with both iodide anions still bound to the metal-ion, but at the higher temperatures used for kinetic studies binding is weak and so no saturation zero-order kinetics are observed. A cross-over experiment with isotopically labelled amines demonstrates the intermediate formation of an imine which can dissociate from the iridium complex. Replacing the iodides in the catalyst by other ligands or having an amide substituent in Cp* results in a much less effective catalysts for the racemisation of amines. The rate constants for a deuterated amine yield a significant primary kinetic isotope effect kH/kD = 3.24 indicating that hydride transfer is involved in the rate-limiting step.

Design of Research on Performance of a New Iridium Coordination Compound for the Detection of Hg2.

PubMed

Ma, Hailing; Tsai, Sang-Bing

2017-10-16

Heavy metal pollution has become one of the most significant pollution problems encountered by our country in terms of environment protection. In addition to the significant effects of heavy metals on the human body and other organisms through water, food chain enrichment and other routes, heavy metals involved in daily necessities beyond the level limit could also affect people's lives, so the detection of heavy metals is extremely important. Ir (III) coordination compound, considered to be one of the best phosphorescent sensing materials, is characterized by high luminous efficiency, easy modification of the ligand and so on, and it has potential applications in the field of heavy metal detection. This project aims to product a new Ir (III) functional coordination compound by designing a new auxiliary ligand and a main ligand with a sulfur identification unit, in order to systematically investigate the application of iridium coordination compound in the detection of the heavy metal Hg 2+ . With the introduction of the sulfur identification unit, selective sensing of Hg 2+ could be achieved. Additionally, a new auxiliary ligand is also introduced to produce a functional iridium coordination compound with high quantum efficiency, and to diversify the application of iridium coordination compound in this field.

Phosphorescent binuclear iridium complexes based on terpyridine-carboxylate: an experimental and theoretical study.

PubMed

Andreiadis, Eugen S; Imbert, Daniel; Pécaut, Jacques; Calborean, Adrian; Ciofini, Ilaria; Adamo, Carlo; Demadrille, Renaud; Mazzanti, Marinella

2011-09-05

The phosphorescent binuclear iridium(III) complexes tetrakis(2-phenylpyridine)μ-(2,2':6',2''-terpyridine-6,6''-dicarboxylic acid)diiridium (Ir1) and tetrakis(2-(2,4-difluorophenyl) pyridine))μ-(2,2':6',2''-terpyridine-6,6''-dicarboxylic acid)diiridium (Ir2) were synthesized in a straightforward manner and characterized using X-ray diffraction, NMR, UV-vis absorption, and emission spectroscopy. The complexes have similar solution structures in which the two iridium centers are equivalent. This is further confirmed by the solid state structure of Ir2. The newly reported complexes display intense luminescence in dichloromethane solutions with maxima at 538 (Ir1) and 477 nm (Ir2) at 298 K (496 and 468 nm at 77 K, respectively) and emission quantum yields reaching ~18% for Ir1. The emission quantum yield for Ir1 is among the highest values reported for dinuclear iridium complexes. It shows only a 11% decrease with respect to the emission quantum yield reported for its mononuclear analogue, while the molar extinction coefficient is roughly doubled. This suggests that such architectures are of potential interest for the development of polymetallic assemblies showing improved optical properties. DFT and time-dependent-DFT calculations were performed on the ground and excited states of the complexes to provide insights into their structural, electronic, and photophysical properties.

A Robotic Communications Gateway for Ocean Observations

NASA Astrophysics Data System (ADS)

Orcutt, J. A.; Berger, J.; Laske, G.; Babcock, J.

2015-12-01

We describe a new technology that can provide real-time telemetry of sensor data from the ocean bottom. The breakthrough technology that makes this system possible is an autonomous surface vehicle called the Wave Glider developed by Liquid Robotics, Inc. of Sunnyvale, CA., which harvests wave and solar energy for motive and electrical power. The free-floating surface communications gateway uses a Liquid Robotics wave glider comprising a surfboard-sized float towed by a tethered, submerged glider, which converts wave motion into thrust. For navigation, the wave glider is equipped with a small computer, a GPS receiver, a rudder, solar panels and batteries, and an Iridium satellite modem. Acoustic communications connect the subsea instruments and the surface gateway while communications between the gateway and land are provided by the Iridium satellite constellation. Wave gliders have demonstrated trans-oceanic range and long-term station keeping capabilities. The topside acoustics communications package is mounted in a shallow tow body, which uses a WHOI micro modem and a Benthos low frequency, directional transducer. A matching bottom side modem and transducer are mounted on the ocean bottom package. Tests of the surface gateway in 4000 m of water demonstrated an acoustic efficiency of approximately 256 bits/J. For example, it has the ability to send four channels of compressed, one sample per second data from the ocean bottom to the gateway with an average power draw of approximately 0.36 W and a latency of about three minutes. This gateway is used to send near-real-time data from a broadband ocean bottom seismic observatory; we are presently designing and constructing a seafloor package with a two-year operational life. We have found that for frequencies f where f<10mHz, 35mHz < f < 120mHz and f>~3Hz, the vertical component, seafloor system noise characteristics are generally superior to similar observatories on land. Increasing the density of these stations over the majority of the surface of Earth; that is, the oceans will greatly enhance the resolution of deep Earth structure and serve civil needs including tsunami warning. The robotic technology is readily applicable for other ocean observations.

Possible world-wide middle miocene iridium anomaly and its relationship to periodicity of impacts and extinctions

NASA Technical Reports Server (NTRS)

Asaro, F.; Alvarez, W.; Michel, H. V.; Alvarez, L. W.; Anders, Mark H.; Montanari, A.; Kennett, James P.

1988-01-01

In a study of one million years of Middle Miocene sediment deposition in ODP Hole 689B in the Weddell Sea near Antarctica, a single iridium (Ir) anomaly of 44 (+ or - 10) x 10 to the 12th gram Ir per gram rock (ppt) was observed in core 6H, section 3, 50 to 60 cm, after background contributions associated with manganese precipitates and clay are subtracted. The ODP Hole 689B is 10,000 km away from another site, DSDP Hole 588B in the Tasman Sea north of New Zealand, where a single Ir anomaly of 144 + or - 7 ppt over a background of 11 ppt was found in an earlier study of 3 million years of deposition. From chemical measurements the latter deposition was thought to be impact-related. Ir measurements were made, following neutron activation, with the Iridium Coincidence Spectrometer. The age vs depth calibration curves given in the DSDP and ODP preliminary reports indicate the ages of the Iranomalies are identical, 11.7 million years, but the absolute and relative uncertainties in the curves are not known. Based on the newest age data the age estimate is 10 million years. As the Ir was deposited at the two sites at about the same time and they are one quarter of the way around the world from each other it seems likely that the deposition was world-wide. The impact of a large asteroid or comet could produce the wide distribution, and this data is supportive of the impact relationship deduced for Deep Sea Drilling Project (DSDP) 588B from the chemical evidence. If the surface densities of Ir at the two sites are representative of the world-wide average, the diameter of a Cl type asteroid containing the necessary Ir would be 3 + or - 1 km, which is large enough to cause world-wide darkness and hence extinctions although the latter point is disputed.

Spin-coated epoxy resin embedding technique enables facile SEM/FIB thickness determination of porous metal oxide ultra-thin films.

PubMed

Peña, B; Owen, G Rh; Dettelbach, K E; Berlinguette, C P

2018-01-25

A facile nonsubjective method was designed to measure porous nonconductive iron oxide film thickness using a combination of a focused ion beam (FIB) and scanning electron microscopy. Iron oxide films are inherently nonconductive and porous, therefore the objective of this investigation was to optimize a methodology that would increase the conductivity of the film to facilitate high resolution imaging with a scanning electron microscopy and to preserve the porous nature of the film that could potentially be damaged by the energy of the FIB. Sputter coating the sample with a thin layer of iridium before creating the cross section with the FIB decreased sample charging and drifting, but differentiating the iron layer from the iridium coating with backscattered electron imaging was not definitive, making accurate assumptions of the delineation between the two metals difficult. Moreover, the porous nature of the film was lost due to beam damage following the FIB process. A thin layer plastication technique was therefore used to embed the porous film in epoxy resin that would provide support for the film during the FIB process. However, the thickness of the resin created using conventional thin layer plastication processing varied across the sample, making the measuring process only possible in areas where the resin layer was at its thinnest. Such variation required navigating the area for ideal milling areas, which increased the subjectivity of the process. We present a method to create uniform thin resin layers, of controlled thickness, that are ideal for quantifying the thickness of porous nonconductive films with FIB/scanning electron microscopy. © 2018 The Authors Journal of Microscopy © 2018 Royal Microscopical Society.

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.

Formal oxidative addition of a C-H bond by a 16e iridium(i) complex involves metal-ligand cooperation.

PubMed

Kumar, Amit; Feller, Moran; Ben-David, Yehoshoa; Diskin-Posner, Yael; Milstein, David

2018-05-10

The first example of oxidative addition of a C-H bond to a square planar d8-Iridium complex, without any external additive, such as an acid, is described. Our mechanistic investigations show that metal-ligand cooperation through aromatization-dearomatization of the lutidine backbone is involved in this process, and that the actual C-H activation step occurs through an Ir(iii) intermediate.

Unclassified Publications of Lincoln Laboratory, 1 January - 31 December 1989. Volume 15

DTIC Science & Technology

1989-12-01

BOLTZMANN MACHINE JA-6051 JA-6290 BEAM PATH CONDITIONING BORON CONTAINING MOLECULES MS-8143 JA-6135 BEAM STEERING BORON TRICHLORIDE MS-8285 JA-6129...BERNZOMATIC TOTE TORCH BORON TRICHLORIDE -ARGON DISCHARGE JA-6260 JA-6129 BIAS CORRELATION BOUNDARY LAYER JA-6326 JA-6192, MS-8141 BINARY INTEGRATION BROADBAND...MS-8345 MODULATORS IRIDIUM MS-7998 JA-6192 67 Subject Index IRIDIUM SILICIDE SCHOTTKY-BARRIER KWAJALEIN DISCRIMINATION SYSTEM INFRARED DETECTORS JA

USSR Report, Chemistry

DTIC Science & Technology

1985-10-22

Compounds (A. A. Putyatin, K. N. Semenenko, et al.; ZHURNAL OBSHCHEY KHIMII, No 3, Mar 85) 19 Enthalpy of Mixing of Arsenic Trichloride With Selected...dimethylhydrazine (I) on applied iridium catalyst Ir/Al20., (30% by wt.) was reported recently by the authors in reference 1. Though the catalyst was...catalyst is almost 10 times greater than for the iridium catalyst for the conversion of (I). The calculated values of activity at 200°C are Aj- -3.4

Formic acid acting as an efficient oxygen scavenger in four-electron reduction of oxygen catalyzed by a heterodinuclear iridium-ruthenium complex in water.

PubMed

Fukuzumi, Shunichi; Kobayashi, Takeshi; Suenobu, Tomoyoshi

2010-09-01

A heterodinuclear iridium-ruthenium complex [Ir(III)(Cp*)(H(2)O)(bpm)Ru(II)(bpy)(2)](SO(4))(2) (Cp* = eta(5)-pentamethyl-cyclopentadienyl, bpm = 2,2'-bipyrimidine, bpy = 2,2'-bipyridine) acts as an effective catalyst for removal of dissolved O(2) by the four-electron reduction of O(2) with formic acid in water at an ambient temperature.

Base-free production of H2 by dehydrogenation of formic acid using an iridium-bisMETAMORPhos complex.

PubMed

Oldenhof, Sander; de Bruin, Bas; Lutz, Martin; Siegler, Maxime A; Patureau, Frederic W; van der Vlugt, Jarl Ivar; Reek, Joost N H

2013-08-26

Erase the base: An iridium complex based on a cooperative ligand that functions as an internal base is reported. This complex can rapidly and cleanly dehydrogenate formic acid in absence of external base, a reaction that is required if formic acid is to be exploited as an energy carrier (see scheme). Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

Code of Federal Regulations, 2014 CFR

2014-01-01

... 16 Commercial Practices 1 2014-01-01 2014-01-01 false Misuse of the words âplatinum,â âiridium,â... markings and descriptions. (1) Use of the word “Platinum” or any abbreviation, without qualification, to... unfair or deceptive: (1) The following abbreviations for each of the PGM may be used for quality marks on...

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

Code of Federal Regulations, 2010 CFR

2010-01-01

... 16 Commercial Practices 1 2010-01-01 2010-01-01 false Misuse of the words âplatinum,â âiridium,â... markings and descriptions. (1) Use of the word “Platinum” or any abbreviation, without qualification, to... descriptions that are not considered unfair or deceptive: (1) The following abbreviations for each of the PGM...

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

Code of Federal Regulations, 2011 CFR

2011-01-01

... 16 Commercial Practices 1 2011-01-01 2011-01-01 false Misuse of the words âplatinum,â âiridium,â... markings and descriptions. (1) Use of the word “Platinum” or any abbreviation, without qualification, to... unfair or deceptive: (1) The following abbreviations for each of the PGM may be used for quality marks on...

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

Code of Federal Regulations, 2013 CFR

2013-01-01

... 16 Commercial Practices 1 2013-01-01 2013-01-01 false Misuse of the words âplatinum,â âiridium,â... markings and descriptions. (1) Use of the word “Platinum” or any abbreviation, without qualification, to... unfair or deceptive: (1) The following abbreviations for each of the PGM may be used for quality marks on...

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

Code of Federal Regulations, 2012 CFR

2012-01-01

... 16 Commercial Practices 1 2012-01-01 2012-01-01 false Misuse of the words âplatinum,â âiridium,â... markings and descriptions. (1) Use of the word “Platinum” or any abbreviation, without qualification, to... unfair or deceptive: (1) The following abbreviations for each of the PGM may be used for quality marks on...

Highly efficient hydrogenation of carbon dioxide to formate catalyzed by iridium(iii) complexes of imine-diphosphine ligands.

PubMed

Liu, Chong; Xie, Jian-Hua; Tian, Gui-Long; Li, Wei; Zhou, Qi-Lin

2015-05-01

A new iridium catalyst containing an imine-diphosphine ligand has been developed, which showed high efficiency for the hydrogenation of CO 2 to formate (yield up to 99%, TON up to 450 000). A possible catalytic mechanism is proposed, in which the imine group of the catalyst plays a key role in the cleavage of H 2 and the activation of CO 2 .

Synthesis and crystal structure of the iridium(I) carbene complex with a pair of hydrogen wing tips

DOE Office of Scientific and Technical Information (OSTI.GOV)

Huang, H.-Y.; Chen, Z.-M.; Wang, Y.

The iridium(I) cyclooctadiene complex with two (3-tert-butylimidazol-2-ylidene) ligands [(H-Im{sup t}Bu){sub 2}Ir(COD)]{sup +}PF{sub 6}{sup −} (C{sub 22}H{sub 32}PF{sub 6}IrN{sub 4}) has been prepared, and its crystal structure is determined by X-ray diffraction. Complex exhibits slightly distorted square planar configurations around the metal atom, which is coordinated by two H-Im{sup t}Bu ligands and one cyclooctadiene group. The new iridium carbene complex has a pair of hydrogen wing tips. The Ir−C{sub carbene} bond lengths are 2.066(5) and 2.052(5) Å, and the bond angle C−Ir−C between these bonds is 95.54(19)°. The dihedral angle between two imidazol-2-ylidene rings is 86.42°.

A measurement system of high-temperature oxidation environment with ultrasonic Ir0.6Rth0.4 alloy thermometry.

PubMed

Wei, Yanlong; Wang, Gao; Gao, Yubin; Liu, Zhengguang; Xu, Lin; Tian, Miao; Yuan, Dongfang; Ren, Haiping; Zhou, Hanchang; Yang, Lu; Shi, Xueshun; Xiao, Zhaoqian

2018-04-03

Iridium-rhodium is generally applied as a thermocouple material, with max operating temperature about 2150 °C. In this study, a ultrasonic temperature measurement system was designed by using Iridium-rhodium (60%Ir-40%Rh) alloy as an acoustic waveguide sensor material, and the system was preliminarily tested in a high-temperature oxidation environment. The result of ultrasonic temperature measurement shows that this system can indeed work stably in high-temperature oxidation environments. The relationship between temperature and delay time of ultrasonic thermometry up to 2200 °C was illustrated. Iridium-rhodium materials were also investigated in order to fully elucidate the proposed waveguide sensor's performance in a high-temperature oxidation environment. This system lays a foundation for further application of high-temperature measurement. Copyright © 2018. Published by Elsevier B.V.

Development of an IrO x micro pH sensor array on flexible polymer substrate

NASA Astrophysics Data System (ADS)

Huang, Wen-Ding; Wang, Jianqun; Ativanichayaphong, Thermpon; Chiao, Mu; Chiao, J. C.

2008-03-01

pH sensor is an essential component used in many chemical, food, and bio-material industries. Conventional glass electrodes have been used to construct pH sensors, however, have some disadvantages in specific applications. It is difficult to use glass electrodes for in vivo biomedical or food monitoring applications due to size limitation and no deformability. In this paper, we present design and fabrication processes of a miniature iridium oxide thin film pH sensor array on flexible polymer substrates. The amorphous iridium oxide thin film was used as the sensing material. A sol-gel dip-coating process of iridium oxide film was demonstrated in this paper. A super-Nernstian response has been measured on individual sensors of the array with a slope of -71.6+/-3 mV/pH at 25°C within the pH range between 2.83 and 11.04.

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).

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).

Iridium: Global OTH data communications for high altitude scientific ballooning

NASA Astrophysics Data System (ADS)

Denney, A.

While the scientific community is no stranger to embracing commercially available technologies, the growth and availability of truly affordable cutting edge technologies is opening the door to an entirely new means of global communications. For many years high altitude ballooning has provided science an alternative to costly satellite based experimental platforms. As with any project, evolution becomes an integral part of development. Specifically in the NSBF ballooning program, where flight durations have evolved from the earlier days of hours to several weeks and plans are underway to provide missions up to 100 days. Addressing increased flight durations, the harsh operational environment, along with cumbersome and outdated systems used on existing systems, such as the balloon vehicles Support Instrumentation Package (SIP) and ground-based systems, a new Over-The-Horizon (OTH) communications medium is sought. Current OTH equipment planning to be phased-out include: HF commanding systems, ARGOS PTT telemetry downlinks and INMARSAT data terminals. Other aspects up for review in addition to the SIP to utilize this communications medium include pathfinder balloon platforms - thereby, adding commanding abilities and increased data rates, plus providing a package for ultra-small experiments to ride aloft. Existing communication systems employed by the National Scientific Balloon Facility ballooning program have been limited not only by increased cost, slow data rates and "special government use only" services such as TDRSS (Tracking and Data Relay Satellite System), but have had to make special provisions to geographical flight location. Development of the Support Instrumentation Packages whether LDB (Long Duration Balloon), ULDB (Ultra Long Duration Balloon) or conventional ballooning have been plagued by non-standard systems configurations requiring additional support equipment for different regions and missions along with a myriad of backup for redundancy. Several 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.

Fabrication and investigation of three-dimensional ferroelectric capacitors for the application of FeRAM

NASA Astrophysics Data System (ADS)

Yeh, Chia-Pin; Lisker, Marco; Kalkofen, Bodo; Burte, Edmund P.

2016-03-01

Ferroelectric capacitors made by lead zirconate titanate (PZT) thin films and iridium electrodes are fabricated on three-dimensional structures and their properties are investigated. The iridium films are grown by Plasma Enhanced MOCVD at 300°C, while the PZT films are deposited by thermal MOCVD at different process temperatures between 450°C and 550°C. The step coverage and composition uniformity of the PZT films on trench holes and lines are investigated. Phase separation of PZT films has been observed on both 3D and planar structures. No clear dependences of the crystallization and composition of PZT on 3D structure topography have been found. STEM EDX line scans show a uniform Zr/(Zr+Ti) concentration ratio along the 3D profile but the variation of the Pb/(Zr+Ti) concentration ratio is large because of the phase separation. 3D ferroelectric capacitors show good ferroelectric properties but have much higher leakage currents than 2D ferroelectric capacitors. Nevertheless, during cycling tests the degradation of the remnant polarization between 2D and 3D capacitors is similar after 109 switching cycles. In addition, the sidewalls and bottoms of the 3D structures seem to have comparable remnant polarizations with the horizontal top surfaces.

Studying the glial cell response to biomaterials and surface topography for improving the neural electrode interface

NASA Astrophysics Data System (ADS)

Ereifej, Evon S.

Neural electrode devices hold great promise to help people with the restoration of lost functions, however, research is lacking in the biomaterial design of a stable, long-term device. Current devices lack long term functionality, most have been found unable to record neural activity within weeks after implantation due to the development of glial scar tissue (Polikov et al., 2006; Zhong and Bellamkonda, 2008). The long-term effect of chronically implanted electrodes is the formation of a glial scar made up of reactive astrocytes and the matrix proteins they generate (Polikov et al., 2005; Seil and Webster, 2008). Scarring is initiated when a device is inserted into brain tissue and is associated with an inflammatory response. Activated astrocytes are hypertrophic, hyperplastic, have an upregulation of intermediate filaments GFAP and vimentin expression, and filament formation (Buffo et al., 2010; Gervasi et al., 2008). Current approaches towards inhibiting the initiation of glial scarring range from altering the geometry, roughness, size, shape and materials of the device (Grill et al., 2009; Kotov et al., 2009; Kotzar et al., 2002; Szarowski et al., 2003). Literature has shown that surface topography modifications can alter cell alignment, adhesion, proliferation, migration, and gene expression (Agnew et al., 1983; Cogan et al., 2005; Cogan et al., 2006; Merrill et al., 2005). Thus, the goals of the presented work are to study the cellular response to biomaterials used in neural electrode fabrication and assess surface topography effects on minimizing astrogliosis. Initially, to examine astrocyte response to various materials used in neural electrode fabrication, astrocytes were cultured on platinum, silicon, PMMA, and SU-8 surfaces, with polystyrene as the control surface. Cell proliferation, viability, morphology and gene expression was measured for seven days in vitro. Results determined the cellular characteristics, reactions and growth rates of astrocytes grown on PMMA resembled closely to that of cells grown on the control surface, thus confirming the biocompatibility of PMMA. Additionally, the astrocyte GFAP gene expressions of cells grown on PMMA were lower than the control, signifying a lack of astrocyte reactivity. Based on the findings from the biomaterials study, it was decided to optimize PMMA by changing the surface characteristic of the material. Through the process of hot embossing, nanopatterns were placed on the surface in order to test the hypothesis that nanopatterning can improve the cellular response to the material. Results of this study agreed with current literature showing that topography effects protein and cell behavior. It was concluded that for the use in neural electrode fabrication and design, the 3600mm/gratings pattern feature sizes were optimal. The 3600 mm/gratings pattern depicted cell alignment along the nanopattern, less protein adsorption, less cell adhesion, proliferation and viability, inhibition of GFAP and MAP2k1 compared to all other substrates tested. Results from the initial biomaterials study also indicated platinum was negatively affected the cells and may not be a suitable material for neural electrodes. This lead to pursuing studies with iridium oxide and platinum alloy wires for the glial scar assay. Iridium oxide advantages of lower impedance and higher charge injection capacity would appear to make iridium oxide more favorable for neural electrode fabrication. However, results of this study demonstrate iridium oxide wires exhibited a more significant reactive response as compared to platinum alloy wires. Astrocytes cultured with platinum alloy wires had less GFAP gene expression, lower average GFAP intensity, and smaller glial scar thickness. Results from the nanopatterning PMMA study prompted a more thorough investigation of the nanopatterning effects using an organotypic brain slice model. PDMS was utilized as the substrate due to its optimal physical properties. Confocal and SEM imaging illustrated cells from the brain tissue slices were aligned along the nanopattern on the PDMS pins. Decreases in several inflammatory markers (GFAP, TNFα, IL-1beta) determined from gene expression analysis, was shown with the nanopatterned PDMS pins. Results of this study confirm nanopatterning not only influences cell morphology, but alters molecular cascades within the cells as well. The results of these studies provide essential information for the neural electrode research community. There is a lack of information available in the scientific community on acceptable and effective materials for neural electrode fabrication. The results of the presented studies provide more information which could lead to classifying guidelines to create biocompatible neural electrode materials. This research project was partially supported by the Wayne State University President's Translational Enhancement Award and by the Kales Scholarship for Biomedical Engineering students.

Electrocatalyst for alcohol oxidation at fuel cell anodes

DOEpatents

Adzic, Radoslav [East Setauket, NY; Kowal, Andrzej [Cracow, PL

2011-11-02

In some embodiments a ternary electrocatalyst is provided. The electrocatalyst can be used in an anode for oxidizing alcohol in a fuel cell. In some embodiments, the ternary electrocatalyst may include a noble metal particle having a surface decorated with clusters of SnO.sub.2 and Rh. The noble metal particles may include platinum, palladium, ruthenium, iridium, gold, and combinations thereof. In some embodiments, the ternary electrocatalyst includes SnO.sub.2 particles having a surface decorated with clusters of a noble metal and Rh. Some ternary electrocatalysts include noble metal particles with clusters of SnO.sub.2 and Rh at their surfaces. In some embodiments the electrocatalyst particle cores are nanoparticles. Some embodiments of the invention provide a fuel cell including an anode incorporating the ternary electrocatalyst. In some aspects a method of using ternary electrocatalysts of Pt, Rh, and SnO.sub.2 to oxidize an alcohol in a fuel cell is described.

JPL-20180522-GRACFOf-0001-Twin Spacecraft Launch to Track Earth's Water Movement

NASA Image and Video Library

2018-05-22

A U.S./German space mission to track the continuous movement of water and other changes in Earth's mass on and beneath the planet's surface successfully launched at 12:47 p.m. PDT, May 22, 2018, from the California coast. The twin spacecraft of the Gravity Recovery and Climate Experiment Follow-On (GRACE-FO), a joint NASA/German Research Centre for Geosciences (GFZ) mission, lifted off on a SpaceX Falcon 9 rocket from Space Launch Complex-4E at Vandenberg Air Force Base in California, sharing their ride into space with five Iridium NEXT communications satellites.

Iridium-catalyzed direct tetraborylation of perylene bisimides.

PubMed

Teraoka, Takuro; Hiroto, Satoru; Shinokubo, Hiroshi

2011-05-20

Treatment of perylene bisimides (PBIs) with bis(pinacolato)diboron in the presence of an iridium catalyst provides tetraborylated PBIs at 2,5,8,11-positions in good yields with perfect regioselectivity. The planar structure of the perylene core has been confirmed by X-ray diffraction analysis. Oxidation of tetraborylated PBI with hydroxylamine hydrochloride affords tetrahydroxy PBI in excellent yield, which exhibits a substantially blue-shifted absorption spectrum due to an intramolecular hydrogenbonding interaction between carbonyl and hydroxy groups.

Iridium(iii) phosphorescent complexes with dual stereogenic centers: single crystal, electronic circular dichroism evidence and circularly polarized luminescence properties.

PubMed

Li, Tian-Yi; Zheng, You-Xuan; Zhou, Yong-Hui

2016-12-06

Iridium complexes with a chiral metal center and chiral carbons, Λ/Δ-(dfppy) 2 Ir(chty-R) and Λ/Δ-(dfppy) 2 Ir(chty-S), were synthesized and characterized. These isomers have the same steady-state photophysical properties, and obvious offsets in ECD spectra highlight both the chiral sources. Each enantiomeric couple shows mirror-image CPL bands with a dissymmetry factor in the order of 10 -3 .

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.

Synthesis and electrophosphorescence of iridium complexes containing benzothiazole-based ligands.

PubMed

Liu, Di; Ren, Huicai; Deng, Lijun; Zhang, Ting

2013-06-12

Four heteroleptic bis-cyclometalated iridium(III) complexes containing 2-aryl-benzothiazole ligands, in which the aryl is dibenzofuran-2-yl [Ir(O-bt)2(acac)], dibenzothiophene-2-yl [Ir(S-bt)2(acac)], dibenzothiophene-S,S-dioxide-2-yl [Ir(SO2-bt)2(acac)] and 4-(diphenylphosphoryl)phenyl [Ir(PO-bt)2(acac)], have been synthesized and characterized for use in organic light-emitting diodes (OLEDs). These complexes emit bright yellow (551 nm) to orange-red (598 nm) phosphorescence at room temperature, the peak wavelengths of which can be finely tuned depending upon the electronic properties of the aryl group in the 2-position of benzothiazole. The strong electron-withdrawing aryls such as dibenzothiophene-S,S-dioxide2-yl and 4-(diphenylphosphoryl)phenyl caused bathochromatic shift of the iridium complex phosphorescence. These iridium complexes were used as doped emitters to fabricate yellow to orange-red OLEDs and good performance was obtained. In particular, a maximum luminance efficiency of 58.4 cd A(-1) (corresponding to 30.6 lm W(-1) and 19%) with CIE coordinates of (0.45, 0.52) was achieved for Ir(O-bt)2(acac)-based yellow device. Furthermore, the yellow emitting Ir(S-bt)2(acac) was used to fabricate two-element white OLED that exhibited a high efficiency of 32.4 cd A(-1) with CIE coordinates of (0.28, 0.44).

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.

Diastereo- and enantioselective iridium-catalyzed allylation of cyclic ketone enolates: synergetic effect of ligands and barium enolates.

PubMed

Chen, Wenyong; Chen, Ming; Hartwig, John F

2014-11-12

We report asymmetric allylic alkylation of barium enolates of cyclic ketones catalyzed by a metallacyclic iridium complex containing a phosphoramidite ligand derived from (R)-1-(2-naphthyl)ethylamine. The reaction products contain adjacent quaternary and tertiary stereocenters. This process demonstrates that unstabilized cyclic ketone enolates can undergo diastereo- and enantioselective Ir-catalyzed allylic substitution reactions with the proper choice of enolate countercation. The products of these reactions can be conveniently transformed to various useful polycarbocyclic structures.

Study of performance characteristics of noble metal thermocouple materials to 2000 C

NASA Technical Reports Server (NTRS)

Freeze, P. D.; Thomas, D.; Edelman, S.; Stern, J.

1972-01-01

Three performance characteristics of noble metal thermocouples in various environments are discussed. Catalytic effects cause significant errors when noble metal thermocouple materials are exposed to air containing unburned gases in temperature ranges from 25 C to 1500 C. The thermoelectric stability of the iridium 40 rhodium to iridium thermocouple system at 2000 C in an oxidizing medium is described. The effects of large and small temperature gradients on the accuracy and stability of temperature measurements are analyzed.

The Marine Geochemistry of Rhenium, Iridium and Platinum

DTIC Science & Technology

1991-09-01

6000C) with MoS 2. Ir enrichments in volcanic gases and sublimates have been measured at two hot-spot volcanoes ( Kilauea (Olmez et al. 1986) and...W. H. Zoller. (1986). "Iridium emissions from Kilauea volcano ." J. Geophvs. Res, 91(B1): 653-663. Orth, C. J., L. R. Quintana, J. S. Gilmore, J. E...Geological Society of London Special Publication. 158 Hildebrand, A.R., W.V. Boynton, and W.H. Zoller. (1984). " Kilauea volcano aerosols: evidence in

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.

Diastereo- and enantioselective iridium-catalyzed allylation of cyclic ketone enolates: Synergetic effect of ligands and barium enolates

DOE PAGES

Chen, Wenyong; Chen, Ming; Hartwig, John F.

2014-10-22

Here, we report asymmetric allylic alkylation of barium enolates of cyclic ketones catalyzed by a metallacyclic iridium complex containing a phosphoramidite ligand derived from ( R)-1-(2-naphthyl)ethylamine. The reaction products contain adjacent quaternary and tertiary stereocenters. This process demonstrates that unstabilized cyclic ketone enolates can undergo diastereo- and enantioselective Ir-catalyzed allylic substitution reactions with the proper choice of enolate countercation. The products of these reactions can be conveniently transformed to various useful polycarbocyclic structures.

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, with high branched-to-linear ratios and high enantioselectivities. Parallel mechanistic studies had revealed the metallacyclic structure of the active catalyst, and subsequent experiments with the purposefully formed metallacycle increased the reaction scope dramatically. Aromatic amines, azoles, ammonia, and amides and carbamates as ammonia equivalents all reacted with high selectivities and yields. Moreover, weakly basic enolates (such as silyl enol ethers) and enolate equivalents (such as enamines) also reacted, and other research groups have used this catalyst to conduct reactions of stabilized carbon nucleophiles in the absence of additional base. One hallmark of the reactions catalyzed by this iridium system is the invariably high enantioselectivity, which reflects a high stereoselectivity for formation of the allyl intermediate. Enantioselectivity typically exceeds 95%, regioselectivity for formation of branched over linear products is usually near 20:1, and yields generally exceed 75% and are often greater than 90%. Thus, the development of iridium catalysts for enantioselective allylic substitution shows how studies of reaction mechanism can lead to a particularly active and a remarkably general system for an enantioselective process. In this case, a readily accessible catalyst effects allylic substitution, with high enantioselectivity and regioselectivity complementary to that of the venerable palladium systems. PMID:20873839

Blue light emission from cyclometallated iridium (III) cyano complexes: Syntheses, crystal structures, and photophysical properties

DOE PAGES

Sanner, Robert D.; Cherepy, Nerine J.; Young, Jr., Victor G.

2015-11-02

In this study, we describe the synthesis and crystal structures of four iridium compounds containing the 2-(4,6-difluorophenyl)pyridyl ligand. Cleavage of dichloro-bridged iridium(III) dimers with phosphorus ligands leads to (46dfppy)2Ir(L)(Cl) where L = PPh 3 or P(OPh) 3. Treatment of the chloro compounds with cyanide forms the cyano complexes (46dfppy) 2Ir(L)(CN). All complexes exhibit a trans effect in their molecular structures due to the phosphorus ligands, with the phosphite having a greater effect than the phosphine. With L = PPh 3, blue photoluminescence with CIE coordinates (x = 0.16, y = 0.24), quantum yield of 0.66 ± 0.15 and 4.5 ±more » 0.5 μs decay time is measured. For L = P(OPh) 3, blue photoluminescence with CIE coordinates (x = 0.16, y = 0.21), quantum yield of 0.65 ± 0.15 and 2.9 ± 0.3 μs decay time is measured.« less

Operando Evidence for a Universal Oxygen Evolution Mechanism on Thermal and Electrochemical Iridium Oxides.

PubMed

Saveleva, Viktoriia A; Wang, Li; Teschner, Detre; Jones, Travis; Gago, Aldo S; Friedrich, K Andreas; Zafeiratos, Spyridon; Schlögl, Robert; Savinova, Elena R

2018-06-07

Progress in the development of proton exchange membrane (PEM) water electrolysis technology requires decreasing the anode overpotential, where the sluggish multistep oxygen evolution reaction (OER) occurs. This calls for an understanding of the nature of the active OER sites and reaction intermediates, which are still being debated. In this work, we apply synchrotron radiation-based near-ambient pressure X-ray photoelectron and absorption spectroscopies under operando conditions in order to unveil the nature of the reaction intermediates and shed light on the OER mechanism on electrocatalysts most widely used in PEM electrolyzers-electrochemical and thermal iridium oxides. Analysis of the O K-edge and Ir 4f spectra backed by density functional calculations reveals a universal oxygen anion red-ox mechanism regardless of the nature (electrochemical or thermal) of the iridium oxide. The formation of molecular oxygen is considered to occur through a chemical step from the electrophilic O I- species, which itself is formed in an electrochemical step.

Colorimetric and luminescent bifunctional iridium(III) complexes for the sensitive recognition of cyanide ions

NASA Astrophysics Data System (ADS)

Chen, Xiudan; Wang, Huili; Li, Jing; Hu, Wenqin; Li, Mei-Jin

2017-02-01

Two new cyclometalated iridium(III) complexes [(ppy)2Irppz]Cl (1) and [(ppy)2Irbppz]Cl (2) (where ppy = 2-phenylpyridine, ppz = 4,7-phenanthrolino-5,6:5,6-pyrazine, bppz = 2.3-di-2-pyridylpyrazine), were designed and synthesized. The structure of [(ppy)2Irppz]Cl was determined by single crystal X-ray diffraction. Their photophysical properties were also studied. This kind of complexes could coordinate with Cu2 +, the photoluminescence (PL) of the complex was quenched, and the color changed from orange-red to green. The forming M-Cu (M: complexes 1 and 2) ensemble could be further utilized as a colorimetric and emission ;turn-on; bifunctional detection for CN-, especially for complex 1-Cu2 + showed a high sensitivity toward CN- with a limit of diction is 97 nM. Importantly, this kind of iridium(III) complexes shows a unique recognition of cyanide ions over other anions which makes it an eligible sensing probe for cyanide ions.

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.

A Luminescent Cocaine Detection Platform Using a Split G-Quadruplex-Selective Iridium(III) Complex and a Three-Way DNA Junction Architecture.

PubMed

Ma, Dik-Lung; Wang, Modi; He, Bingyong; Yang, Chao; Wang, Wanhe; Leung, Chung-Hang

2015-09-02

In this study, a series of 10 in-house cyclometalated iridium(III) complexes bearing different auxiliary ligands were tested for their selectivity toward split G-quadruplex in order to construct a label-free switch-on cocaine detection platform employing a three-way junction architecture and a G-quadruplex motif as a signal output unit. Through two rounds of screening, we discovered that the iridium(III) complex 7 exhibited excellent selectivity toward the intermolecular G-quadruplex motif. A detection limit as low as 30 nM for cocaine can be achieved by this sensing approach with a linear relationship between luminescence intensity and cocaine concentration established from 30 to 300 nM. Furthermore, this sensing approach could detect cocaine in diluted oral fluid. We hope that our simple, signal-on, label-free oligonucleotide-based sensing method for cocaine using a three-way DNA junction architecture could act as a useful platform in bioanalytical research.

Iridium-Based Nanowires as Highly Active, Oxygen Evolution Reaction Electrocatalysts

DOE Office of Scientific and Technical Information (OSTI.GOV)

Alia, Shaun M.; Shulda, Sarah; Ngo, Chilan

Iridium-nickel (Ir-Ni) and iridium-cobalt (Ir-Co) nanowires have been synthesized by galvanic displacement and studied for their potential to increase the performance and durability of electrolysis systems. Performances of Ir-Ni and Ir-Co nanowires for the oxygen evolution reaction (OER) have been measured in rotating disk electrode half-cells and single-cell electrolyzers and compared with commercial baselines and literature references. The nanowire catalysts showed improved mass activity, by more than an order of magnitude compared with commercial Ir nanoparticles in half-cell tests. The nanowire catalysts also showed greatly improved durability, when acid-leached to remove excess Ni and Co. Both Ni and Co templatesmore » were found to have similarly positive impacts, although specific differences between the two systems are revealed. In single-cell electrolysis testing, nanowires exceeded the performance of Ir nanoparticles by 4-5 times, suggesting that significant reductions in catalyst loading are possible without compromising performance.« less

Solid-phase extraction of iridium from soil and water samples by using activated carbon cloth prior to its spectrophotometric determination.

PubMed

Ozkantar, Nebiye; Yilmaz, Erkan; Soylak, Mustafa; Tuzen, Mustafa

2015-08-01

A solid-phase extraction method for separation and preconcentration of Ir(IV) ion by using activated carbon cloth (ACC) has been presented. Ir(IV) as their 1-(2-pyridylazo) 2-naphtol (PAN) chelate was adsorbed on ACC at pH 2.0 and was eluted from ACC with acidic dimethylformamide (DMF). The Ir(IV) concentration was determined at 536 nm as Ir(IV)-PAN complex by using UV-vis spectrophotometer. The analytical parameters including pH, sample and eluent flow rates, amount of PAN, eluent type, concentration, and sample volume were optimized. The effects of foreign ions on the recoveries of iridium were also investigated. The preconcentration factor was calculated as 60. The limit of detection (LOD) and the limit of quantification (LOQ) of the method were found as 0.039 and 0.129 μg L(-1), respectively. The method was applied to soil and water samples for iridium determination.

Iridium-Based Nanowires as Highly Active, Oxygen Evolution Reaction Electrocatalysts

DOE PAGES

Alia, Shaun M.; Shulda, Sarah; Ngo, Chilan; ...

2018-01-22

Iridium-nickel (Ir-Ni) and iridium-cobalt (Ir-Co) nanowires have been synthesized by galvanic displacement and studied for their potential to increase the performance and durability of electrolysis systems. Performances of Ir-Ni and Ir-Co nanowires for the oxygen evolution reaction (OER) have been measured in rotating disk electrode half-cells and single-cell electrolyzers and compared with commercial baselines and literature references. The nanowire catalysts showed improved mass activity, by more than an order of magnitude compared with commercial Ir nanoparticles in half-cell tests. The nanowire catalysts also showed greatly improved durability, when acid-leached to remove excess Ni and Co. Both Ni and Co templatesmore » were found to have similarly positive impacts, although specific differences between the two systems are revealed. In single-cell electrolysis testing, nanowires exceeded the performance of Ir nanoparticles by 4-5 times, suggesting that significant reductions in catalyst loading are possible without compromising performance.« less

Light-emitting dendrimer film morphology: A neutron reflectivity study

NASA Astrophysics Data System (ADS)

Vickers, S. V.; Barcena, H.; Knights, K. A.; Thomas, R. K.; Ribierre, J.-C.; Gambino, S.; Samuel, I. D. W.; Burn, P. L.; Fragneto, Giovanna

2010-06-01

We have used neutron reflectivity (NR) measurements to probe the physical structure of phosphorescent dendrimer films. The dendrimers consisted of fac-tris(2-phenylpyridyl)iridium(III) cores, biphenyl-based dendrons (first or second generation), and perdeuterated 2-ethylhexyloxy surface groups. We found that the shape and hydrodynamic radius of the dendrimer were both important factors in determining the packing density of the dendrimers. "Cone" shaped dendrimers were found to pack more effectively than "spherical" dendrimers even when the latter had a smaller radius. The morphology of the films determined by NR was consistent with the measured photoluminescence and charge transporting properties of the materials.

Modulated infrared radiant source

NASA Technical Reports Server (NTRS)

Stewart, W. F.; Edwards, S. F.; Vann, D. S.; Mccormick, R. F.

1981-01-01

A modulated, infrared radiant energy source was developed to calibrate an airborne nadir-viewing pressure modulated radiometer to be used to detect from Earth orbit trace gases in the troposphere. The technique used an 8 cm long, 0.005 cm diameter platinum-iridium wire as an isothermal, thin line radiant energy source maintained at 1200 K. A + or - 20 K signal, oscillating at controllable frequencies from dc to 20 Hz, was superimposed on it. This periodic variation of the line source energy was used to verify the pressure modulated radiometer's capability to distinguish between the signal variations caused by the Earth's background surface and the signal from the atmospheric gases of interest.

Large impacts and climatic catastrophes on the early Earth

NASA Technical Reports Server (NTRS)

Melosh, H. J.

1991-01-01

Radiometric data of cratered lunar surfaces suggest that the cratering rate on the ancient Moon was substantially larger than the present rate before about 3.2 Gyr. Since the cratering rate was higher than present on the Moon, it seems likely that is was similarly higher on the Earth. Recently the occurrence of beds of spherules up to 2m thick was reported in 3.2 to 3.5 Gyr old Archean rocks. These spherule beds closely resemble the 3 mm thick spherule beds associated with the K/T boundary (including elevated iridium abundances), widely believed to have been deposited in association of a 10 km diameter comet or asteroid.

Single Crystal Membranes

NASA Technical Reports Server (NTRS)

Stormont, R. W.; Morrison, A.

1974-01-01

Single crystal a- and c-axis tubes and ribbons of sodium beta-alumina and sodium magnesium beta-alumina were grown from sodium oxide rich melts. Additional experiments grew ribbon crystals containing sodium magnesium beta, beta double prime, beta triple prime, and beta quadruple prime. A high pressure crystal growth chamber, sodium oxide rich melts, and iridium for all surfaces in contact with the melt were combined with the edge-defined, film-fed growth technique to grow the single crystal beta-alumina tubes and ribbons. The crystals were characterized using metallographic and X-ray diffraction techniques, and wet chemical analysis was used to determine the sodium, magnesium, and aluminum content of the grown crystals.

Computationally Probing the Performance of Hybrid, Heterogeneous, and Homogeneous Iridium-Based Catalysts for Water Oxidation

DOE Office of Scientific and Technical Information (OSTI.GOV)

García-Melchor, Max; Vilella, Laia; López, Núria

2016-04-29

An attractive strategy to improve the performance of water oxidation catalysts would be to anchor a homogeneous molecular catalyst on a heterogeneous solid surface to create a hybrid catalyst. The idea of this combined system is to take advantage of the individual properties of each of the two catalyst components. We use Density Functional Theory to determine the stability and activity of a model hybrid water oxidation catalyst consisting of a dimeric Ir complex attached on the IrO 2(110) surface through two oxygen atoms. We find that homogeneous catalysts can be bound to its matrix oxide without losing significant activity.more » Hence, designing hybrid systems that benefit from both the high tunability of activity of homogeneous catalysts and the stability of heterogeneous systems seems feasible.« less

Carbon Nanotube Tip Probes: Stability and Lateral Resolution in Scanning Probe Microscopy and Application to Surface Science to Semiconductors

NASA Technical Reports Server (NTRS)

Nguyen, Cattien V.; Chao, Kuo-Jen; Stevens, Ramsey M. D.; Delzeit, Lance; Cassell, Alan; Han, Jie; Meyyappan, M.; Arnold, James (Technical Monitor)

2001-01-01

In this paper we present results on the stability and lateral resolution capability of carbon nanotube (CNT) scanning probes as applied to atomic force microscopy (AFM). Surface topography images of ultra-thin films (2-5 nm thickness) obtained with AFM are used to illustrate the lateral resolution capability of single-walled carbon nanotube probes. Images of metal films prepared by ion beam sputtering exhibit grain sizes ranging from greater than 10 nm to as small as approximately 2 nm for gold and iridium respectively. In addition, imaging stability and lifetime of multi-walled carbon nanotube scanning probes are studied on a relatively hard surface of silicon nitride (Si3N4). AFM images Of Si3N4 surface collected after more than 15 hrs of continuous scanning show no detectable degradation in lateral resolution. These results indicate the general feasibility of CNT tips and scanning probe microscopy for examining nanometer-scale surface features of deposited metals as well as non-conductive thin films. AFM coupled with CNT tips offers a simple and nondestructive technique for probing a variety of surfaces, and has immense potential as a surface characterization tool in integrated circuit manufacturing.

Polymeric mercaptosilane-modified platinum electrodes for elimination of interferants in glucose biosensors.

PubMed

Jung, S K; Wilson, G S

1996-02-15

An oxidase-based glucose sensor has been developed that uses a mercaptosilane-modified platinum electrode to achieve selectivity of electrochemical interferants. A platinum-iridium (9:1) wire (0.178 mm o.d., sensing area of 1.12 mm2) is modified with (3-mercaptopropyl)trimethoxysilane. The modified sensors show excellent operational stability for more than 5 days. Glucose oxidase is immobilized on the modified surface (i) by using 3-maleimidopropionic acid as a linker or (ii) by cross-liking with bovine serum albumin using glutaraldehyde. Sensitivities in the range of 9.97 nA/mM glucose are observed when the enzyme is immobilized by method ii. Lower sensitivities (1.13 x 10(-1) nA/mM glucose) are observed when immobilization method i is employed. In terms of linear response range, the sensor enzyme-immobilized by method i is superior to that immobilized by method ii. The linearity is improved upon coating the enzyme layer with polyurethane. The sensor immobilized by method ii and coated with polyurethane exhibits a linear range to 15 mM glucose and excellent selectivity to glucose (0.47 nA/mM) against interferants such as ascorbic acid, uric acid, and acetaminophen.

Hydrogen transfer reduction of polyketones catalyzed by iridium complexes: a novel route towards more biocompatible materials.

PubMed

Milani, Barbara; Crottib, Corrado; Farnetti, Erica

2008-09-14

Transfer hydrogenation from 2-propanol to CO/4-methylstyrene and CO/styrene polyketones was catalyzed by [Ir(diene)(N-N)X] (N-N = nitrogen chelating ligand; X = halogen) in the presence of a basic cocatalyst. The reactions were performed using dioxane as cosolvent, in order to overcome problems due to low polyketone solubility. The polyalcohols were obtained in yields up to 95%, the conversions being markedly dependent on the nature of the ligands coordinated to iridium as well as on the experimental conditions.

Bioinspired enantioselective synthesis of crinine-type alkaloids via iridium-catalyzed asymmetric hydrogenation of enones† †Electronic supplementary information (ESI) available. See DOI: 10.1039/c7sc02112g Click here for additional data file.

PubMed Central

Zuo, Xiao-Dong; Guo, Shu-Min; Yang, Rui

2017-01-01

A bioinspired enantioselective synthesis of crinine-type alkaloids has been developed by iridium-catalyzed asymmetric hydrogenation of racemic cycloenones. The method features a biomimetic stereodivergent resolution of the substrates bearing a remote arylated quaternary stereocenter. Using this protocol, 24 crinine-type alkaloids and 8 analogues were synthesized in a concise and rapid way with high yield and high enantioselectivity. PMID:28989653

Levitation of iridium and liquid mercury by ultrasound.

PubMed

Xie, W J; Cao, C D; Lü, Y J; Wei, B

2002-09-02

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.

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.

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.

Iridium-Catalyzed Diastereoselective and Enantioselective Allylic Substitutions with Acyclic α-Alkoxy Ketones

DOE PAGES

Jiang, Xingyu; Chen, Wenyong; Hartwig, John F.

2016-04-01

The asymmetric alkylation of acyclic ketones is a longstanding challenge in organic synthesis. Here, are the diastereoselective and enantioselective allylic substitutions with acyclic α-alkoxy ketones catalyzed by a metallacyclic iridium complex to form products with contiguous stereogenic centers derived from the nucleophile and electrophile. These reactions occur between allyl methyl carbonates and unstabilized copper(I) enolates generated in situ from acyclic α-alkoxy ketones. The resulting products can be readily converted into enantioenriched tertiary alcohols and tetrahydrofuran derivatives without erosion of enantiomeric purity.

Iridium-Catalyzed Diastereoselective and Enantioselective Allylic Substitutions with Acyclic α-Alkoxy Ketones

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jiang, Xingyu; Chen, Wenyong; Hartwig, John F.

The asymmetric alkylation of acyclic ketones is a longstanding challenge in organic synthesis. Here, are the diastereoselective and enantioselective allylic substitutions with acyclic α-alkoxy ketones catalyzed by a metallacyclic iridium complex to form products with contiguous stereogenic centers derived from the nucleophile and electrophile. These reactions occur between allyl methyl carbonates and unstabilized copper(I) enolates generated in situ from acyclic α-alkoxy ketones. The resulting products can be readily converted into enantioenriched tertiary alcohols and tetrahydrofuran derivatives without erosion of enantiomeric purity.

Science Innovation Through Industry Partnership: Lessons from AMPERE in Bridging the Federal Sponsor/Private Corporation Divide

NASA Astrophysics Data System (ADS)

Anderson, B. J.; Korth, H.; Erlandson, R. E.

2017-12-01

The Active Magnetosphere and Planetary Electrodynamics Response Experiment (AMPERE) was made possible by harnessing an fortuitous capability of the Iridium Communications constellation of 70 polar orbiting satellites. In 1996 it was realized that the attitude magnetometers on-board the Iridium satellites, then in fabrication, could potentially be used to obtain the first ever global and continuous measurements of the Birkeland currents with a sufficiently short re-sampling cadence (10 minutes) to track the dynamic evolution of the large-scale currents. The experience of taking this idea from 1996 through various research grant supported efforts, mission of opportunity proposal attempts, and finally through funding and implementation as a National Science Foundation geospace facility, revealed a number of challenges both in proposing innovative solutions to existing sponsor programs and also in working between the federal sponsor community and the private commercial space environment. Implementing AMPERE required a code change to on-board software on the Iridium satellites and it proved necessary to engage NASA to adjust the solicitation language to allow AMPERE. For NASA proposals we also encountered a conflict with respect to federal sponsorship such that the original business configuration of Iridium could not accept the accounting regime implied by a sub-contract derived from a federal contract acquisition. Subsequent mission of opportunity efforts encountered various other challenges including the cancellation of an explorer to fund the exploration initiative in 2001. The facilities proposal to NSF was almost not submitted owing a funding vehicle disparity between the preferred proposer structure (contract) vs NSF's requirement to fund only grants and a final hurdle concerned the structure of the contract with Iridium which was initially a sub-contract but was changed to a fixed-price data purchase due to NSF's limitations on funding fee-bearing engineering services. More general differences in the federal procurement timeline versus the corporate decision making timeline were also encountered. These lessons in the industry/federal partnership for innovative science are discussed as they may offer guidance for future efforts.

Partial analysis of experiment LDEF A-0114

NASA Technical Reports Server (NTRS)

Gregory, J. C.

1986-01-01

Due to delays in manifesting the return of the Long Duration Exposure Facility from space, attention was concentrated on extracting the maximum information from the EIOM-2 (oxygen interaction with materials experiment) flown on STS-8 in September 1983. An analysis was made of the optical surfaces exposed during that flight and an assessment made of the effect of the 5 eV atomic oxygen upon their physical and chemical properties. The surfaces studied were of two types: high-purity thin films sputtered or evaporated onto 2.54-cm diam lambda/20 fused silica optical flats, and highly polished bulk samples. Rapid etching of carbon and carbonaceous surfaces was observed with polycarbonate CR-39 showing the largest etch of any substrate flown and measured. Of the metals tested, only osmium and silver showed large effects, the former being heavily etched and the later forming a very thick layer of oxide. The first measurable effects on iridium, aluminum, nickel, tungsten and niobium thin films are reported.

Highly Reversible Water Oxidation at Ordered Nanoporous Iridium Electrodes Based on an Original Atomic Layer Deposition.

PubMed

Schlicht, Stefanie; Haschke, Sandra; Mikhailovskii, Vladimir; Manshina, Alina; Bachmann, Julien

2018-05-01

Nanoporous iridium electrodes are prepared and electrochemically investigated towards the water oxidation (oxygen evolution) reaction. The preparation is based on 'anodic' aluminum oxide templates, which provide straight, cylindrical nanopores. Their walls are coated using atomic layer deposition (ALD) with a newly developed reaction which results in a metallic iridium layer. The ALD film growth is quantified by spectroscopic ellipsometry and X-ray reflectometry. The morphology and composition of the electrodes are characterized by scanning electron microscopy, energy-dispersive X-ray spectroscopy, and X-ray diffraction. Their catalytic activity is quantified for various pore geometries by cyclic voltammetry, steady-state electrolysis, and electrochemical impedance spectroscopy. With an optimal pore length of L ≈17-20 μm, we achieve current densities of J =0.28 mA cm -2 at pH 5 and J =2.4 mA cm -2 at pH 1. This platform is particularly competitive for achieving moderate current densities at very low overpotentials, that is, for a high degree of reversibility in energy storage.

Tuning the properties of metal–organic framework nodes as supports of single-site iridium catalysts: node modification by atomic layer deposition of aluminium

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yang, Dong; Momeni, Mohammad R.; Demir, Hakan

The metal–organic framework NU-1000, with Zr 6-oxo, hydroxo, and aqua nodes, was modified by incorporation of hydroxylated Al(iii) ions by ALD-like chemistry with [Al(CH 3) 2(iso-propoxide)] 2followed by steam (ALD = atomic layer deposition). Al ions were installed to the extent of approximately 7 per node. Single-site iridium diethylene complexes were anchored to the nodes of the modified and unmodified MOFs by reaction with Ir(C 2H 4) 2(acac) (acac = acetylacetonate) and converted to Ir(CO) 2complexes by treatment with CO. Infrared spectra of these supported complexes show that incorporation of Al weakened the electron donor tendency of the MOF. Correspondingly,more » the catalytic activity of the initial supported iridium complexes for ethylene hydrogenation increased, as did the selectivity for ethylene dimerization. The results of density functional theory calculations with a simplified model of the nodes incorporating Al(iii) ions are in qualitative agreement with some catalyst performance data.« less

Earth Radiation Imbalance from a Constellation of 66 Iridium Satellites: Technological Aspects

NASA Technical Reports Server (NTRS)

Wiscombe, W.; Chiu, C. J-Y.

2012-01-01

Iridium Communications Inc. is launching a new generation of polar orbiting communication satellites in 2015-2017. Iridium will provide a hosted payload bay on each of the 66 satellites (plus 6 in-space spares). This offers the potential for a paradigm shift in the way we measure Earth radiation imbalance from space, as well as massive cost savings. Because the constellation provides 24/7 global coverage, there is no need to account for diurnal cycle via extrapolations from uncalibrated narrowband geostationary imagers. And the spares can be rolled over to view the Sun and deep space, then transfer their calibration to the other members of the constellation during the frequent cross-overs. In part using simulations of the constellation viewing realistic Earth scenes, this presentation will address the technological aspects of such a constellation: (1) the calibration strategy; (2) the highly-accurate and stable radiometers for measuring outgoing flux; and (3) the GRACE-inspired algorithms for representing the outgoing flux field in spherical harmonics and thus achieving rv500-km spatial resolution and two-hour temporal resolution.

New cyclometalated Iridium(III) beta-dicetone complex as phosphorescent dopant in Organic light emitting devices

NASA Astrophysics Data System (ADS)

Ivanov, P.; Petrova, P.; Stanimirov, S.; Tomova, R.

2017-01-01

A new Bis[4-(benzothiazolato-N,C2‧-2-yl)-N,N-dimethylaniline]Iridium(III) acetylacetonate (Me2N-bt) 2Ir(acac) was synthesized and identified by 1H NMR and elemental analysis. The application of the new compound as a dopant in the hole transporting layer (HTL) of Organic light emitting diode (OLED) structure: HTL/EL/ETL, where HTL was N,N’-bis(3-methylphenyl)-N,N’-diphenylbenzidine (TPD), incorporated in Poly(N-vinylcarbazole) (PVK) matrix, EL - electroluminescent layer of Bis(8-hydroxy-2-methylquinoline)-(4-phenylpheno-xy)aluminum (BAlq) and ETL - electron-transporting layer of Tris-(8-hydroxyquinoline) aluminum (Alq3) or Bis[2-(2-benzothiazoly) phenolato]zinc (Zn(btz)2). We established that the electroluminescent spectra of OLEDs at different concentrations of the dopant were basically the sum of the greenish-blue emission of BAlq and yellowish-green emission of Ir complex. It was found that with increasing of the dopant concentration the relative electroluminescent intensity of Iridium complex emission increased and this of BAlq decreased and as a result the fine tuning of OLED color was observed.

Cross-couplings in the elaboration of luminescent bis-terpyridyl iridium complexes: the effect of extended or inhibited conjugation on emission.

PubMed

Leslie, Wendy; Batsanov, Andrei S; Howard, Judith A K; Williams, J A Gareth

2004-02-21

The utility of Suzuki cross-coupling methodology for the in situ elaboration of bromo-functionalised bis-terpyridyl iridium(III) complexes has been explored. The complex [Ir(tpy)(tpy-phi-Br)]3+ [tpy-phi-Br = 4'-(4-bromophenyl)-2,2':6',2''-terpyridine] undergoes palladium-catalysed cross-coupling with aryl boronic acids to yield biaryl-substituted complexes directly. The biphenyl and 4-cyanobiphenyl-substituted products display relatively intense, long-lived (tau > 100 mus) yellow emission in degassed aqueous solution at room temperature, assigned to a 3pi-pi* state. A 4-aminobiphenyl-substituted analogue displays an additional low energy absorbance band, attributed to an intraligand charge-transfer (ILCT) excited state, and is scarcely emissive under the same conditions. The iridium(III) complex of 4'-mesityl-terpyridine is also reported. Its emission is much shorter-lived, with a spectral profile resembling that of unsubstituted [Ir(tpy)2]3+, confirming the need for the attainment of a roughly coplanar geometry for stabilisation of the 3pi-pi* excited state.

Time-resolved EPR study on the photoexcited triplet state of the electron-donor-acceptor complex formed in the system of fac-tris[2-(4-octyl-phenyl) pyridine] iridium(III) and tetracene.

PubMed

Zhebin, Fu; Shuhei, Yoshioka; Hisao, Murai

2014-01-09

The physical properties of the phosphorescent organic light-emitting diode material fac-tris(phenylpyridine) iridium(III), Ir(ppy)3, have been reported with experimental and theoretical studies. Here, the photochemical properties of the excited triplet state of partially modified fac-tris[2-(4-octyl-phenyl) pyridine] iridium(III), Ir(C8ppy)3, were investigated using time-resolved electron paramagnetic resonance (tr-EPR) and optical methods by adding tetracene in the toluene solution. The tr-EPR observation at 77 K revealed the following two species: the excited triplet state of tetracene and another triplet species with zero field splitting parameters of |D| = 0.088 cm(-1) and |E| = 0.018 cm(-1) with characteristic spin polarization. The latter species was assigned to the electron-donor-acceptor (EDA) complex formed between Ir(C8ppy)3 and tetracene. The mechanism of formation and the properties of this EDA complex, including the information on the principal axes of (3)Ir(C8ppy)3*, are discussed.

Treatment of malignant biliary obstruction by endoscopic implantation of iridium 192 using a new double lumen endoprosthesis

DOE Office of Scientific and Technical Information (OSTI.GOV)

Siegel, J.H.; Lichtenstein, J.L.; Pullano, W.E.

1988-07-01

Iridium 192 seeds contained in a ribbon were preloaded into a new double lumen 11 Fr endoprosthesis which was then inserted into malignant strictures of the bile duct and ampulla and left in place for 48 hours until 5000 rads were delivered to the tumor. The procedure was carried out in 14 patients (7 women, 7 men; mean age, 63.2 years; range, 46 to 86 years). Six patients were treated for cholangiocarcinomas, four with pancreatic carcinomas, and four with ampullary carcinomas. No complications occurred. The mean survival of the group was 7 months (range, 3 days to 27 months). Thismore » new technique provides both intraluminal brachytherapy and biliary drainage and is inserted intraduodenally across the papilla of Vater avoiding puncture of the liver and external hardware required by the percutaneous technique and hardware necessitated with a nasobiliary tube. Following removal of the iridium prosthesis, a large caliber endoprosthesis is inserted for continued decompression. Because of proven efficacy of endoprostheses, this new technique should be considered when intraluminal irradiation is indicated.« less

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.

PCM Thermal Control of Nickel-Hydrogen Batteries

DTIC Science & Technology

1993-06-01

Iridium , Global Star, etc - The new satellite mobile telephone systems under development call for constellations of LEO satellites. A thermal problem unique...C6H4CI2 -16.7 88 2 4,6-dimethylindan C11H14 -16.7 88 3 2,2-dimethylpropane C5H12 -16.6 45 4 arsenic trichloride AsCl3 -16 56 5 quinoline C9H7N -15.6 84 6...discharge are: 0 SPACE-BASED RADAR - SBR is expected to have a surge power lasting about 9 minutes. 0 IRIDIUM - The high traffic associated with

Carbene complexes of rhodium and iridium from tripodal N-heterocyclic carbene ligands: synthesis and catalytic properties.

PubMed

Mas-Marzá, Elena; Poyatos, Macarena; Sanaú, Mercedes; Peris, Eduardo

2004-03-22

Two tripodal trisimidazolium ligand precursors have been tested in the synthesis of new N-heterocyclic carbene rhodium and iridium complexes. [Tris(3-methylbenzimidazolium-1-yl)]methane sulfate gave products with coordination of the decomposed precursor. [1,1,1-Tris(3-butylimidazolium-1-yl)methyl]ethane trichloride (TIMEH(3)(Bu)) coordinated to the metal in a chelate and bridged-chelate form, depending on the reaction conditions. The crystal structures of two of the products are described. The compounds resulting from the coordination with TIME(Bu) were tested in the catalytic hydrosilylation of terminal alkynes.

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.

Vapor deposition of thin films

DOEpatents

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

1992-01-01

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

LUNAR RECEIVING LABORATORY (LRL) - CLARK, ROBERT, DR. - JSC

NASA Image and Video Library

1973-11-05

S73-36161 (November 1973) --- In the Radiation Counting Laboratory sixty feet underground at JSC, Dr. Robert S. Clark prepares to load pieces of iridium foil -- sandwiched between plastic sheets -- into the laboratory's radiation detector. The iridium foil strips were worn by the crew of the second Skylab flight in personal radiation dosimeters throughout their 59 1/2 days in space. Inside the radiation detector assembly surrounded by 28 tons of lead shielding, the sample will be tested to determine the total neutron dose to which the astronauts were exposed during their long stay aboard the space station. Photo credit: NASA

Serendipitous preparation of fac-(aceto-nitrile-κN)tri-chlorido-[(1,2,5,6-η)-cyclo-octa-1,5-diene]iridium(III).

PubMed

Morris, David M; Merola, Joseph S

2015-04-01

A reaction between [(COD)IrCl]2 (COD is cyclo-octa-1,5-diene), HCl and indene failed to provide the hoped for chlorido-indenyliridium dimer, but instead produced the title compound, [IrCl3(CH3CN)(C8H12)], which is an octa-hedral complex of iridium(III) with a chelating cyclo-octa-1,5-diene ligand, three chloride ligands in a fac arrangement, and one aceto-nitrile ligand. Attempts to devise a rational synthesis for the title compound were unsuccessful.

Preparation of boron doped diamond modified by iridium for electroreduction of carbon dioxide (CO2)

NASA Astrophysics Data System (ADS)

Ichzan, A. M.; Gunlazuardi, J.; Ivandini, T. A.

2017-04-01

Electroreduction of carbon dioxide (CO2) at iridium oxide-modified boron-doped diamond (IrOx-BDD) electrodes in aqueous electrolytes was studied by voltammetric method. The aim of this study was to find out the catalytic effect of IrOx to produce fine chemicals contained of two or more carbon atoms (for example acetic acid) in high percentage. Characterization using FE-SEM and XPS indicated that IrO2 can be deposited at BDD electrode, whereas characterization using cyclic voltammetry indicated that the electrode was applicable to be used as working electrode for CO2 electroreduction.

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 payloads of up to 1900 kilograms in near- earth orbit. The rocket is 29 meters long with a diameter of 2.5 meters. The launch weight is about 107 tons. Satellite launches with Rockot are a service offered and carried out by Eurockot Launch Service GmbH. It is a European Russian joint venture which is 51% controlled by Astrium and 49 % by Khrunichev, Russia's leading launch vehicle firm. The Rockot vehicles can be launched from Plesetsk in northern Russia and Baikonur in Kazakhstan. EUROCKOT provides a wide choice of flight-proven adapters and multi-satellite platforms to the customer to allow such payloads to be accommodated. These range from the Russian Single Pyro Point Attachment System (SPPA)

Diffusion mechanisms in chemical vapor-deposited iridium coated on chemical vapor-deposited rhenium

NASA Technical Reports Server (NTRS)

Hamilton, J. C.; Yang, N. Y. C.; Clift, W. M.; Boehme, D. R.; Mccarty, K. F.; Franklin, J. E.

1992-01-01

Radiation-cooled rocket thruster chambers have been developed which use CVD Re coated with CVD Ir on the interior surface that is exposed to hot combustion gases. The Ir serves as an oxidation barrier which protects the structural integrity-maintaining Re at elevated temperatures. The diffusion kinetics of CVD materials at elevated temperatures is presently studied with a view to the prediction and extension of these thrusters' performance limits. Line scans for Ir and Re were fit on the basis of a diffusion model, in order to extract relevant diffusion constants; the fastest diffusion process is grain-boundary diffusion, where Re diffuses down grain boundaries in the Ir overlayer.

AIAA Survivability Technical Committee Draft

NASA Technical Reports Server (NTRS)

Shipman, Jim; Williamson, Joel

1997-01-01

A relatively new area of interest in aerospace systems survivability is the growing threat of spacecraft penetration by orbital debris. Orbital debris, or "space junk", is composed of the man-made remnants of non-functioning spacecraft still orbiting the Earth. NASA estimates that there are currently over 100,000 orbital debris particles 1 centimeter in diameter or larger that cannot be tracked by existing radar, with the population growing at approximately 4% per year in low earth orbits. With an average velocity of over 8.7 km/sec, these projectiles can penetrate and disable many vulnerable spacecraft systems. Since the likelihood of spacecraft penetration increases with spacecraft surface area, large spacecraft (such as the International Space Station) and communication satellite fleets (such as Iridium) have begun to adopt survivability enhancement strategies similar to those employed by combat aircraft. Collision avoidance maneuvers are commonly practiced by the Space Shuttle and are planned by the International Space Station to decrease their susceptibility to impact by trackable orbital debris; likewise, improved shielding, internal equipment placement, and improved crew operations following penetration can reduce the vulnerability of spacecraft to loss following orbital debris impact. Computer simulations such as the Manned Spacecraft and Crew Survivability (MSCSurv) program at the NASA-Marshall Space Flight Center have recently been developed to quantify and reduce the likelihood of crew or spacecraft loss following orbital debris penetration. The AIAA Survivability Technical Committee is working to enable the transfer of military-developed survivability technologies to help the aerospace industry cope with this growing threat.

Photo-catalyzed surface hydrolysis of iridium(iii) ions on semiconductors: a facile method for the preparation of semiconductor/IrOx composite photoanodes toward oxygen evolution reaction.

PubMed

Wu, Qingyong; Xu, Di; Xue, Ning; Liu, Tengyi; Xiang, Min; Diao, Peng

2016-12-21

We previously reported that the hydrolysis of Ir 3+ in homogeneous solution could be triggered by irradiation with light whose energy was larger than a threshold value. In this work, we demonstrated that, by introducing Fe 2 O 3 particles into solution, the incident light energy-restriction for the photo-catalyzed hydrolysis could be broken and the hydrolysis occurred at the Fe 2 O 3 /solution interface. The photo-generated holes on the Fe 2 O 3 surface played a key role in oxidizing Ir(iii) to Ir(iv) species and triggered the deposition of IrO x . We showed that this photo-catalyzed surface hydrolysis is a universal phenomenon that takes place on the surface of many n-type semiconductors such as Fe 2 O 3 , TiO 2 , and Ag 3 PO 4 . As IrO x is an efficient catalyst for oxygen evolution reaction, surface hydrolysis is a general, facile and efficient strategy to prepare semiconductor/IrO x composites, which can be used as anodic materials for photoelectrochemical water splitting.

Steering Asymmetric Lewis Acid Catalysis Exclusively with Octahedral Metal-Centered Chirality.

PubMed

Zhang, Lilu; Meggers, Eric

2017-02-21

Catalysts for asymmetric synthesis must be chiral. Metal-based asymmetric catalysts are typically constructed by assembling chiral ligands around a central metal. In this Account, a new class of effective chiral Lewis acid catalysts is introduced in which the octahedral metal center constitutes the exclusive source of chirality. Specifically, the here discussed class of catalysts are composed of configurationally stable, chiral-at-metal Λ-configured (left-handed propeller) or Δ-configured (right-handed propeller) iridium(III) or rhodium(III) complexes containing two bidentate cyclometalating 5-tert-butyl-2-phenylbenzoxazole (dubbed IrO and RhO) or 5-tert-butyl-2-phenylbenzothiazole (dubbed IrS and RhS) ligands in addition to two exchange-labile acetonitriles. They are synthetically accessible in an enantiomerically pure fashion through a convenient auxiliary-mediated synthesis. Such catalysts are of interest due to their intrinsic structural simplicity (only achiral ligands) and the prospect of an especially effective asymmetric induction due to the intimate contact between the chiral metal center and the metal-coordinated substrates or reagents. With respect to chiral Lewis acid catalysis, the bis-cyclometalated iridium and rhodium complexes provide excellent catalytic activities and asymmetric inductions for a variety of reactions including Michael additions, Friedel-Crafts reactions, cycloadditions, α-aminations, α-fluorinations, Mannich reactions, and a cross-dehydrogenative coupling. Mechanistically, substrates such as 2-acyl imidazoles are usually activated by two-point binding. Exceptions exist as for example for an efficient iridium-catalyzed enantioselective transfer hydrogenation of arylketones with ammonium formate, which putatively proceeds through an iridium-hydride intermediate. The bis-cyclometalated iridium complexes catalyze visible-light-induced asymmetric reactions by intertwining asymmetric catalysis and photoredox catalysis in a unique fashion. This has been applied to the visible-light-induced α-alkylation of 2-acyl imidazoles (and in some instances 2-acylpyridines) with acceptor-substituted benzyl, phenacyl, trifluoromethyl, perfluoroalkyl, and trichloromethyl groups, in addition to photoinduced oxidative α-aminoalkylations and a photoinduced stereocontrolled radical-radical coupling, each employing a single iridium complex. In all photoinduced reaction schemes, the iridium complex serves as a chiral Lewis acid catalyst and at the same time as precursor of in situ assembled photoactive species. The nature of these photoactive intermediates then determines their photochemical properties and thereby the course of the asymmetric photoredox reactions. The bis-cyclometalated rhodium complexes are also very useful for asymmetric photoredox catalysis. Less efficient photochemical properties are compensated with a more rapid ligand exchange kinetics, which permits higher turnover frequencies of the catalytic cycle. This has been applied to a visible-light-induced enantioselective radical α-amination of 2-acyl imidazoles. In this reaction, an intermediate rhodium enolate is supposed to function as a photoactivatable smart initiator to initiate and reinitiate an efficient radical chain process. If a more efficient photoactivation is required, a rhodium-based Lewis acid can be complemented with a photoredox cocatalyst, and this has been applied to efficient catalytic asymmetric alkyl radical additions to acceptor-substituted alkenes. We believe that this class of chiral-only-at-metal Lewis acid catalysts will be of significant value in the field of asymmetric synthesis, in particular in combination with visible-light-induced redox chemistry, which has already resulted in novel strategies for asymmetric synthesis of chiral molecules. Hopefully, this work will also pave the way for the development of other asymmetric catalysts featuring exclusively octahedral centrochirality.

Carbon-fluorine bond activation coupled with carbon-hydrogen bond formation alpha to iridium: kinetics, mechanism, and diastereoselectivity.

PubMed

Garratt, Shaun A; Hughes, Russell P; Kovacik, Ivan; Ward, Antony J; Willemsen, Stefan; Zhang, Donghui

2005-11-09

Reactions of iridium(fluoroalkyl)hydride complexes CpIr(PMe(3))(CF(2)R(F))Y (R(F) = F, CF(3); Y = H, D) with LutHX (Lut = 2,6-dimethylpyridine; X = Cl, I) results in C-F activation coupled with hydride migration to give CpIr(PMe(3))(CYFR(F))X as variable mixtures of diastereomers. Solution conformations and relative diastereomer configurations of the products have been determined by (19)F{(1)H}HOESY NMR to be (S(C), S(Ir))(R(C), R(Ir)) for the kinetic diastereomer and (R(C), S(Ir))(S(C), R(Ir)) for its thermodynamic counterpart. Isotope labeling experiments using LutDCl/CpIr(PMe(3))(CF(2)R(F))H and CpIr(PMe(3))(CF(2)R(F))D/LutHCl) showed that, unlike a previously studied system, H/D exchange is faster than protonation of the alpha-CF bond, giving an identical mixture of product isotopologues from both reaction mixtures. The kinetic rate law shows a first-order dependence on the concentration of iridium substrate, but a half-order dependence on that of LutHCl; this is interpreted to mean that LutHCl dissociates to give HCl as the active protic source for C-F bond activation. Detailed kinetic studies are reported, which demonstrate that lack of complete diastereoselectivity is not a function of the C-F bond activation/H migration steps but that a cationic intermediate plays a double role in loss of diastereoselectivity; the intermediate can undergo epimerization at iridium before being trapped by halide and can also catalyze the epimerization of kinetic diastereomer product to thermodynamic product. A detailed mechanism is proposed and simulations performed to fit the kinetic data.

Microwave irradiation for the facile synthesis of transition-metal nanoparticles (NPs) in ionic liquids (ILs) from metal-carbonyl precursors and Ru-, Rh-, and Ir-NP/IL dispersions as biphasic liquid-liquid hydrogenation nanocatalysts for cyclohexene.

PubMed

Vollmer, Christian; Redel, Engelbert; Abu-Shandi, Khalid; Thomann, Ralf; Manyar, Haresh; Hardacre, Christopher; Janiak, Christoph

2010-03-22

Stable chromium, molybdenum, tungsten, manganese, rhenium, ruthenium, osmium, cobalt, rhodium, and iridium metal nanoparticles (M-NPs) have been reproducibly obtained by facile, rapid (3 min), and energy-saving 10 W microwave irradiation (MWI) under an argon atmosphere from their metal-carbonyl precursors [M(x)(CO)(y)] in the ionic liquid (IL) 1-butyl-3-methylimidazolium tetrafluoroborate ([BMIm][BF(4)]). This MWI synthesis is compared to UV-photolytic (1000 W, 15 min) or conventional thermal decomposition (180-250 degrees C, 6-12 h) of [M(x)(CO)(y)] in ILs. The MWI-obtained nanoparticles have a very small (<5 nm) and uniform size and are prepared without any additional stabilizers or capping molecules as long-term stable M-NP/IL dispersions (characterization by transmission electron microscopy (TEM), transmission electron diffraction (TED), and dynamic light scattering (DLS)). The ruthenium, rhodium, or iridium nanoparticle/IL dispersions are highly active and easily recyclable catalysts for the biphasic liquid-liquid hydrogenation of cyclohexene to cyclohexane with activities of up to 522 (mol product) (mol Ru)(-1) h(-1) and 884 (mol product) (mol Rh)(-1) h(-1) and give almost quantitative conversion within 2 h at 10 bar H(2) and 90 degrees C. Catalyst poisoning experiments with CS(2) (0.05 equiv per Ru) suggest a heterogeneous surface catalysis of Ru-NPs.

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.

Reverse saturable absorption (RSA) in fluorinated iridium derivatives

NASA Astrophysics Data System (ADS)

Ferry, Michael J.; O'Donnell, Ryan M.; Bambha, Neal; Ensley, Trenton R.; Shensky, William M.; Shi, Jianmin

2017-08-01

The photophysical properties of cyclometallated iridium compounds are beneficial for nonlinear optical (NLO) applications, such as the design of reverse saturable absorption (RSA) materials. We report on the NLO characterization of a family of compounds of the form [Ir(pbt)2(LX)], where pbt is 2-phenylbenzothiazole and LX is a beta-diketonate ligand. In particular, we investigate the effects of trifluoromethylation on compound solubility and photophysics compared to the parent acetylacetonate (acac) version. The NLO properties, such as the singlet and triplet excited-state cross sections, of these compounds were measured using the Z-scan technique. The excited-state lifetimes were determined from visible transient absorption spectroscopy.

Reversible Interconversion between 2,5-Dimethylpyrazine and 2,5-Dimethylpiperazine by Iridium-Catalyzed Hydrogenation/Dehydrogenation for Efficient Hydrogen Storage.

PubMed

Fujita, Ken-Ichi; Wada, Tomokatsu; Shiraishi, Takumi

2017-08-28

A new hydrogen storage system based on the hydrogenation and dehydrogenation of nitrogen heterocyclic compounds, employing a single iridium catalyst, has been developed. Efficient hydrogen storage using relatively small amounts of solvent compared with previous systems was achieved by this new system. Reversible transformations between 2,5-dimethylpyrazine and 2,5-dimethylpiperazine, accompanied by the uptake and release of three equivalents of hydrogen, could be repeated almost quantitatively at least four times without any loss of efficiency. Furthermore, hydrogen storage under solvent-free conditions was also accomplished. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

It's Not a Big Sky After All: Justification for a Close Approach Prediction and Risk Assessment Process

NASA Technical Reports Server (NTRS)

Newman, Lauri Kraft; Frigm, Ryan; McKinley, David

2009-01-01

There is often skepticism about the need for Conjunction Assessment from mission operators that invest in the "big sky theory", which states that the likelihood of a collision is so small that it can be neglected. On 10 February 2009, the collision between Iridium 3; and Cosmos 2251 provided an indication that this theory is invalid and that a CA process should be considered for all missions. This paper presents statistics of the effect of the Iridium/Cosmos collision on NASA's Earth Science Constellation as well as results of analyses which characterize the debris environment for NASA's robotic missions.

Iridium-Catalyzed Kinetic Asymmetric Transformations of Racemic Allylic Benzoates

PubMed Central

Stanley, Levi M.; Bai, Chen; Ueda, Mitsuhiro; Hartwig, John F.

2010-01-01

Versatile methods for iridium-catalyzed, kinetic asymmetric substitution of racemic, branched allylic esters are reported. These reactions occur with a variety of aliphatic, aryl, and heteroaryl allylic benzoates to form the corresponding allylic substitution products in high yields (74–96%) with good to excellent enantioselectivity (84–98% ee) with a scope that encompasses a range of anionic carbon and heteroatom nucleophiles. These kinetic asymmetric processes occur with distinct stereochemical courses for racemic aliphatic and aromatic allylic benzoates, and the high reactivity of branched allylic benzoates enables enantioselective allylic substitutions that are slow or poorly selective with linear allylic electrophiles. PMID:20552969

Readily Accessible and Highly Efficient Ferrocene-Based Amino-Phosphine-Alcohol (f-Amphol) Ligands for Iridium-Catalyzed Asymmetric Hydrogenation of Simple Ketones.

PubMed

Yu, Jianfei; Duan, Meng; Wu, Weilong; Qi, Xiaotian; Xue, Peng; Lan, Yu; Dong, Xiu-Qin; Zhang, Xumu

2017-01-18

We have successfully developed a series of novel and modular ferrorence-based amino-phosphine-alcohol (f-Amphol) ligands, and applied them to iridium-catalyzed asymmetric hydrogenation of various simple ketones to afford the corresponding chiral alcohols with excellent enantioselectivities and conversions (98-99.9 % ee, >99 % conversion, turnover number up to 200 000). Control experiments and density functional theory (DFT) calculations have shown that the hydroxyl group of our f-Amphol ligands played a key role in this asymmetric hydrogenation. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

Measurements of the hard-x-ray reflectivity of iridium

DOE Office of Scientific and Technical Information (OSTI.GOV)

Romaine, S.; Bruni, R.; Gorenstein, P.

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.

Measurements of the hard-x-ray reflectivity of iridium.

PubMed

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.

Triazolylidene-Iridium Complexes with a Pendant Pyridyl Group for Cooperative Metal-Ligand Induced Catalytic Dehydrogenation of Amines.

PubMed

Valencia, Marta; Pereira, Ana; Müller-Bunz, Helge; Belderraín, Tomás R; Pérez, Pedro J; Albrecht, Martin

2017-07-03

Two iridium(III) complexes containing a C,N-bidentate pyridyl-triazolylidene ligand were prepared that are structurally very similar but differ in their pendant substituent. Whereas complex 1 contains a non-coordinating pyridyl unit, complex 2 has a phenyl group on the triazolylidene substituent. The presence of the basic pyridyl unit has distinct effects on the catalytic activity of the complex in the oxidative dehydrogenation of benzylic amines, inducing generally higher rates, higher selectivity towards formation of imines versus secondary amines, and notable quantities of tertiary amines when compared to the phenyl-functionalized analogue. The role of the pyridyl functionality has been elucidated from a set of stoichiometric experiments, which demonstrate hydrogen bonding between the pendant pyridyl unit and the amine protons of the substrate. Such N pyr ⋅⋅⋅H-N interactions are demonstrated by X-ray diffraction analysis, 1 H NMR, and IR spectroscopy, and suggest a pathway of substrate bond-activation that involves concerted substrate binding through the Lewis acidic iridium center and the Lewis basic pyridyl site appended to the triazolylidene ligand, in agreement with ligand-metal cooperative substrate activation. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Impact of various lipophilic substituents on ruthenium(II), rhodium(III) and iridium(III) salicylaldimine-based complexes: synthesis, in vitro cytotoxicity studies and DNA interactions.

PubMed

Cassells, Irwin; Stringer, Tameryn; Hutton, Alan T; Prince, Sharon; Smith, Gregory S

2018-05-30

A series of bidentate salicylaldimine ligands was prepared and reacted with either [RuCl(µ-Cl)(p-cymene)] 2 , [RhCl(µ-Cl)(Cp*)] 2 or [IrCl(µ-Cl)(Cp*)] 2 . All of the compounds were characterised using an array of spectroscopic and analytical techniques, namely, nuclear magnetic resonance (NMR) spectroscopy, infrared (IR) spectroscopy and mass spectrometry. Single crystal X-ray diffraction (XRD) was used to confirm the bidentate coordination mode of the salicylaldimine ligand to the metal centre. The platinum group metal (PGM) complexes were screened against the MCF7 breast cancer cell line. The ruthenium and iridium salicylaldimine complexes showed comparable or greater cytotoxicity than cisplatin against the MCF7 cancer cells, as well as greater cytotoxicity than their rhodium counterparts. Three of the salicylaldimine complexes showed potent activity in the range 18-21 µM. Two of these complexes had a greater affinity for cancerous cells than for CHO non-cancerous cells (SI > 4). Preliminary mechanistic studies suggest that the ruthenium complexes undergo solvation prior to 5'-GMP binding, whereas the iridium complexes were inert to the solvation process.

Comparison of Superconducting Transition Characteristics of Two Iridium/Gold Bilayer Transition Edge Sensor Devices

NASA Astrophysics Data System (ADS)

Kunieda, Yuichi; Fukuda, Daiji; Ohno, Masashi; Takahashi, Hiroyuki; Nakazawa, Masaharu; Inou, Tadashi; Ataka, Manabu

2004-05-01

We are developing a high-energy-resolution X-ray microcalorimeter for X-ray fluorescent spectrometry using a superconducting transition edge sensor (TES) that consists of a bilayer of iridium and gold (Ir/Au). In this paper, we have studied the superconducting transition characteristics of two different bilayer structures. Type 1 is a simple stacked bilayer where a square-pattern film of iridium is covered with an identical pattern of gold. Type 2 is based on the Type 1 Ir/Au film, however, it has Au side banks. The resistance-temperature characteristics of these films are investigated by a four-wired resistance measurement method. As a result, the transition curve of Type 2 obeyed the Ginzburg-Landau (GL) theory; however, the transition curve of Type 1 was entirely different from that of Type 2. The reason there was a difference in these transition curves of the two devices is discussed in terms of the difference in the electric current distribution inside TESs. Even if we assume a uniform bilayer film and a uniform proximity effect over the entire film, the current density inside the device affects the characteristics of the transition curves.

Controlling T c of Iridium films using interfacial proximity effects

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hennings-Yeomans, R; Chang, CL; Ding, J

High precision calorimetry using superconducting transition edge sensors requires the use of superconducting films with a suitable T c, depending on the application. To advance high-precision macrocalorimetry, we require low-T c films that are easy to fabricate. A simple and effective way to suppress T c of superconducting Iridium through the proximity effect is demonstrated by using Ir/Pt bilayers as well as Au/Ir/Au trilayers. While Ir/Au films fabricated by applying heat to the substrate during Ir deposition have been used in the past for superconducting sensors, we present results of T c suppression on Iridium by deposition at room temperature in Au/Ir/Au trilayers and Ir/Pt bilayers in the range ofmore » $$\\sim$$20-100~mK. Measurements of the relative impedance between the Ir/Pt bilayers and Au/Ir/Au trilayers fabricated show factor of $$\\sim$$10 higher values in the Ir/Pt case. These new films could play a key role in the development of scalable superconducting transition edge sensors that require low-T c films to minimize heat capacity and maximize energy resolution, while keeping high-yield fabrication methods.« less

Phase diagram and electrical behavior of silicon-rich iridium silicide compounds

NASA Technical Reports Server (NTRS)

Allevato, C. E.; Vining, Cronin B.

1992-01-01

The iridium-silicon phase diagram on the silicon-rich side was investigated by means of X-ray powder diffraction, density, differential thermal analysis, metalography, microprobe analysis, and electrical resistivity. Attempts were made to prepare eight previously reported silicon-rich iridium silicide compounds by arc melting and Bridgman-like growth. However, microprobe analysis identified only four distinct compositions: IrSi, Ir3Si4, Ir3Si5 and IrSi sub about 3. The existence of Ir4Si5 could not be confirmed in this study, even though the crystal structure has been previously reported. Differential thermal analysis (DTA) in conjunction with X-ray powder diffraction confirm polymorphism in IrSi sub about 3, determined to have orthorhombic and monoclinic unit cells in the high and low temperature forms. A eutectic composition alloy of 83 +/- 1 atomic percent silicon was observed between IrSi sub about 3 and silicon. Ir3Si4 exhibits distinct metallic behavior while Ir3Si5 is semiconducting. Both and IrSi and IrSi sub about 3 exhibit nearly temperature independent electrical resistivities on the order of 5-10 x 10 exp -6 ohms-m.

Interstitial radiation therapy for carcinoma of the penis using iridium 192 wires: the Henri Mondor experience (1970-1979)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mazeron, J.J.; Langlois, D.; Lobo, P.A.

1984-10-01

From 1970 to 1979, a group of 50 patients was treated for squamous cell carcinoma of the penis by interstitial irradiation using an afterloading technique and iridium 192 wires. The group included 9 patients with T1 tumors, 27 with T2 tumors, and 14 with T3 tumors. Forty-five patients presented with no metastatic inguinal nodes (NO), 3 patients with N1 nodes, and 2 patients had N3 nodes. After treatment, 11 patients (1 T1, 6 T2 and 4 T3) developed local recurrences. Three patients developed post-therapeutic necrosis which necessitated partial amputation in 2 cases. Eight patients developed post-therapeutic urethral stenosis, which requiredmore » surgical treatment in three of the cases. Twenty-one percent of the patients died of their disease. The authors advocate interstitial irradiation using iridium 192 wires for the treatment of non-infiltrating or moderately infiltrating squamous cell carcinoma of the penis in which the largest dimension does no exceed 4 cm. When regular follow-up can be assurred, it is reasonable to forgo prophylactic treatment of the inguinal nodes in patients presenting without groin metastasis.« less

Experimental and theoretical studies of structural and photophysical properties of a novel heteroleptic cyclometalated iridium(III) complex with 8-hydroxyquinoline-phenylazo ligand

NASA Astrophysics Data System (ADS)

Maity, Amit; Sinha, Debopam; Rajak, Kajal Krishna

2018-04-01

One novel heteroleptic iridium(III) complex with cyclometalated 2-phenylquinoline(2-phq) was synthesized by the stoichiometric reaction of [Ir(2-phq)2Cl]2, i.e, Bis-[μ-chlorodi-(2-phenylquinoline)iridium(III)] and HL ligand, where L- is deprotonated form of azo ligand prepared from 8-hydroxyquinoline and aniline in a 1:1 proportion of dichloromethane and ethanol solvent at argon atmosphere in presence of mild base triethylamine in stoichiometric ratio. The prepared complex was characterized by 1H NMR, ESI-mass spectrometry, IR spectroscopy and most accurately by X-ray single crystallography. The photo physical properties like absorption and emission, i.e, photoluminescence in liquid state as well as solid state were studied exclusively. The experimental electrochemical study was also done with cyclic voltammetry. The theoretical investigations of the photo physical properties were done by DFT and TDDFT calculations. The ground state excitation transitions of the complex arise from 1ILCT and 1MLCT transition. The UV-Vis and photoluminescence transition was also investigated by NTO analysis. The triplet state emission transition was characterized by 3MLCT and some portion of 3ILCT transition.

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 SiC chip circuitry.

FOXSI: Properties of optics and detectors for hard-X rays

NASA Astrophysics Data System (ADS)

Buitrago-Casas, Juan Camilo; Glesener, Lindsay; Christe, Steven; Krucker, Sam; Ishikawa, Shin-nosuke; Foster, Natalie

2015-04-01

The Focusing Optics X-ray Solar Imager (FOXSI) is a state-of-the-art direct focusing X-ray telescope designed to observe the Sun. This experiment completed its second flight onboard a sounding rocket last December 11, 2014 from the White Sands Missile Range in New Mexico. The optics use a set of iridium-coated nickel/cobalt mirrors made using a replication technique based on an electroformed perfect polished surface. Since this technique creates full shells that no need to be co-aligned with other segments, an angular resolution of up to ~5 arcsec is gotten. The FOXSI focal plane consists of seven double-sided strip detectors. Five Silicon and 2 CdTe detectors were used during the second flight.We present on various properties of Wolter-I optics that are applicable to solar HXR observation, including ray-tracing simulations of the single-bounce (“ghost ray”) patterns from sources outside the field of view and angular resolution for different source angles and effective area measurements of the FOXSI optics. We also present the detectors calibration results, paying attention to energy resolution (~0.5 keV), energy thresholds (~4-15 keV for Silicon and ~4-20 keV for CdTe detectors), and spatial coherence of these values over the entire detector.

Ultrasonic spray coating polymer and small molecular organic film for organic light-emitting devices.

PubMed

Liu, Shihao; Zhang, Xiang; Zhang, Letian; Xie, Wenfa

2016-11-22

Ultrasonic spray coating process (USCP) with high material -utilization, low manufacture costs and compatibility to streamline production has been attractive in researches on photoelectric devices. However, surface tension exists in the solvent is still a huge obstacle to realize smooth organic film for organic light emitting devices (OLEDs) by USCP. Here, high quality polymer anode buffer layer and small molecular emitting layer are successfully realized through USCP by introducing extra-low surface tension diluent and surface tension control method. The introduction of low surface tension methyl alcohol is beneficial to the formation of poly (3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS) films and brings obvious phase separation and improved conductivity to PEDOT:PSS film. Besides, a surface tension control method, in which new stable tension equilibrium is built at the border of wetting layer, is proposed to eliminate the effect of surface tension during the solvent evaporation stage of ultrasonic spray coating the film consists of 9,9-Spirobifluoren-2-yl-diphenyl-phosphine oxide doped with 10 wt% tris [2-(p -tolyl) pyridine] iridium (III). A smooth and homogenous small molecular emitting layer without wrinkles is successfully realized. The effectiveness of the ultrasonic spray coating polymer anode buffer layer and small molecular emitting layer are also proved by introducing them in OLEDs.

Ultrasonic spray coating polymer and small molecular organic film for organic light-emitting devices

NASA Astrophysics Data System (ADS)

Liu, Shihao; Zhang, Xiang; Zhang, Letian; Xie, Wenfa

2016-11-01

Ultrasonic spray coating process (USCP) with high material -utilization, low manufacture costs and compatibility to streamline production has been attractive in researches on photoelectric devices. However, surface tension exists in the solvent is still a huge obstacle to realize smooth organic film for organic light emitting devices (OLEDs) by USCP. Here, high quality polymer anode buffer layer and small molecular emitting layer are successfully realized through USCP by introducing extra-low surface tension diluent and surface tension control method. The introduction of low surface tension methyl alcohol is beneficial to the formation of poly (3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS) films and brings obvious phase separation and improved conductivity to PEDOT:PSS film. Besides, a surface tension control method, in which new stable tension equilibrium is built at the border of wetting layer, is proposed to eliminate the effect of surface tension during the solvent evaporation stage of ultrasonic spray coating the film consists of 9,9-Spirobifluoren-2-yl-diphenyl-phosphine oxide doped with 10 wt% tris [2-(p -tolyl) pyridine] iridium (III). A smooth and homogenous small molecular emitting layer without wrinkles is successfully realized. The effectiveness of the ultrasonic spray coating polymer anode buffer layer and small molecular emitting layer are also proved by introducing them in OLEDs.

Ultrasonic spray coating polymer and small molecular organic film for organic light-emitting devices

PubMed Central

Liu, Shihao; Zhang, Xiang; Zhang, Letian; Xie, Wenfa

2016-01-01

Ultrasonic spray coating process (USCP) with high material -utilization, low manufacture costs and compatibility to streamline production has been attractive in researches on photoelectric devices. However, surface tension exists in the solvent is still a huge obstacle to realize smooth organic film for organic light emitting devices (OLEDs) by USCP. Here, high quality polymer anode buffer layer and small molecular emitting layer are successfully realized through USCP by introducing extra-low surface tension diluent and surface tension control method. The introduction of low surface tension methyl alcohol is beneficial to the formation of poly (3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS) films and brings obvious phase separation and improved conductivity to PEDOT:PSS film. Besides, a surface tension control method, in which new stable tension equilibrium is built at the border of wetting layer, is proposed to eliminate the effect of surface tension during the solvent evaporation stage of ultrasonic spray coating the film consists of 9,9-Spirobifluoren-2-yl-diphenyl-phosphine oxide doped with 10 wt% tris [2-(p -tolyl) pyridine] iridium (III). A smooth and homogenous small molecular emitting layer without wrinkles is successfully realized. The effectiveness of the ultrasonic spray coating polymer anode buffer layer and small molecular emitting layer are also proved by introducing them in OLEDs. PMID:27874030

High-Pressure Lightweight Thrusters

NASA Technical Reports Server (NTRS)

Holmes, Richard; McKechnie, Timothy; Shchetkovskiy, Anatoliy; Smirnov, Alexander

2013-01-01

Returning samples of Martian soil and rock to Earth is of great interest to scientists. There were numerous studies to evaluate Mars Sample Return (MSR) mission architectures, technology needs, development plans, and requirements. The largest propulsion risk element of the MSR mission is the Mars Ascent Vehicle (MAV). Along with the baseline solid-propellant vehicle, liquid propellants have been considered. Similar requirements apply to other lander ascent engines and reaction control systems. The performance of current state-ofthe- art liquid propellant engines can be significantly improved by increasing both combustion temperature and pressure. Pump-fed propulsion is suggested for a single-stage bipropellant MAV. Achieving a 90-percent stage propellant fraction is thought to be possible on a 100-kg scale, including sufficient thrust for lifting off Mars. To increase the performance of storable bipropellant rocket engines, a high-pressure, lightweight combustion chamber was designed. Iridium liner electrodeposition was investigated on complex-shaped thrust chamber mandrels. Dense, uniform iridium liners were produced on chamber and cylindrical mandrels. Carbon/carbon composite (C/C) structures were braided over iridium-lined mandrels and densified by chemical vapor infiltration. Niobium deposition was evaluated for forming a metallic attachment flange on the carbon/ carbon structure. The new thrust chamber was designed to exceed state-of-the-art performance, and was manufactured with an 83-percent weight savings. High-performance C/Cs possess a unique set of properties that make them desirable materials for high-temperature structures used in rocket propulsion components, hypersonic vehicles, and aircraft brakes. In particular, more attention is focused on 3D braided C/Cs due to their mesh-work structure. Research on the properties of C/Cs has shown that the strength of composites is strongly affected by the fiber-matrix interfacial bonding, and that weakening interface realizes pseudo-plastic behavior with significant increase in the tensile strength. The investigation of high-temperature strength of C/Cs under high-rate heating (critical for thrust chambers) shows that tensile and compression strength increases from 70 MPa at room temperature to 110 MPa at 1,773 K, and up to 125 MPa at 2,473 K. Despite these unique properties, the use of C/Cs is limited by its high oxidation rate at elevated temperatures. Lining carbon/carbon chambers with a thin layer of iridium or iridium and rhenium is an innovative way to use proven refractory metals and provide the oxidation barrier necessary to enable the use of carbon/ carbon composites. Due to the lower density of C/Cs as compared to SiC/SiC composites, an iridium liner can be added to the C/C structure and still be below the overall thruster weight. Weight calculations show that C/C, C/C with 50 microns of Ir, and C/C with 100 microns of Ir are of less weight than alternative materials for the same construction.

Fundamental quantum noise mapping with tunnelling microscopes tested at surface structures of subatomic lateral size.

PubMed

Herz, Markus; Bouvron, Samuel; Ćavar, Elizabeta; Fonin, Mikhail; Belzig, Wolfgang; Scheer, Elke

2013-10-21

We present a measurement scheme that enables quantitative detection of the shot noise in a scanning tunnelling microscope while scanning the sample. As test objects we study defect structures produced on an iridium single crystal at low temperatures. The defect structures appear in the constant current images as protrusions with curvature radii well below the atomic diameter. The measured power spectral density of the noise is very near to the quantum limit with Fano factor F = 1. While the constant current images show detailed structures expected for tunnelling involving d-atomic orbitals of Ir, we find the current noise to be without pronounced spatial variation as expected for shot noise arising from statistically independent events.

Upper Ocean Profiles Measurements with ASIP

NASA Astrophysics Data System (ADS)

Ward, B.; Callaghan, A. H.; Fristedt, T.; Vialard, J.; Cuypers, Y.; Weller, R. A.; Grosch, C. E.

2009-04-01

This presentation describes results from the Air-Sea Interaction Profiler (ASIP), an autonomous profiling instrument for upper ocean measurements. The measurements from ASIP are well suited to enhancing research on air-sea interfacial and near surface processes. Autonomous profiling is accomplished with a thruster, which submerges ASIP to a programmed depth. Once this depth is reached the positively buoyant instrument will ascend to the surface acquiring data. ASIP can profile from a maximum depth of 100 m to the surface, allowing both mixed layer and near-surface measurements to be conducted. The sensor payload on ASIP include microstructure sensors (two shear probes and a thermistor); a slow response accurate thermometer; a pair of conductivity sensors; pressure for a record of depth; PAR for measurements of light absorption in the water column. Other non-environmental sensors are acceleration, rate, and heading for determination of vehicle motion. Power is provided with rechargable lithium-ion batteries, supplying 1000 Whr, allowing approximately 300 profiles. ASIP also contains an iridium/GPS system, which allows realtime reporting of its position. ASIP was deployed extensively during the Cirene Indian Ocean campaign and our results focus on the data from the temperature, salinity, light, and shear sensors.

A fine pointed glucose oxidase immobilized electrode for low-invasive amperometric glucose monitoring.

PubMed

Li, Jiang; Koinkar, Pankaj; Fuchiwaki, Yusuke; Yasuzawa, Mikito

2016-12-15

A low invasive type glucose sensor, which has a sensing region at the tip of a fine pointed electrode, was developed for continuous glucose monitoring. Platinum-iridium alloy electrode with a surface area of 0.045mm(2) was settled at the middle of pointed PEEK (Polyetheretherketone) tubing and was employed as sensing electrode. Electrodeposition of glucose oxidase in the presence of surfactant, Triton X-100, was performed for high-density enzyme immobilization followed by the electropolymerization of o-phenylenediamine for the formation of functional entrapping and permselective polymer membrane. Ag/AgCl film was coated on the surface of PEEK tubing as reference electrode. Amperometric responses of the prepared sensors to glucose were measured at a potential of 0.60V (vs. Ag/AgCl). The prepared electrode showed the sensitivity of 2.55μA/cm(2) mM with high linearity of 0.9986, within the glucose concentration range up to 21mM. The detection limit (S/N=3) was determined to be 0.11mM. The glucose sensor properties were evaluated in phosphate buffer solution and in vivo monitoring by the implantation of the sensors in rabbit, while conventional needle type sensors as a reference were used. The results showed that change in output current of the proposed sensor fluctuated similar with one in output current of the conventional needle type sensors, which was also in similar accordance with actual blood sugar level measured by commercially glucose meter. One-point calibration method was used to calibrate the sensor output current. Copyright © 2016 Elsevier B.V. All rights reserved.

Science Discoveries Enabled by Hosting Optical Imagers on Commercial Satellite Constellations

NASA Astrophysics Data System (ADS)

Erlandson, R. E.; Kelly, M. A.; Hibbitts, C.; Kumar, C.; Dyrud, L. P.

2012-12-01

The advent of commercial space activities that utilize large space-based constellations provide a new and cost effective opportunity to acquire multi-point observations. Previously, a custom designed space-based constellation, while technically feasible, would require a substantial monetary investment. However, commercial industry has now been entertaining the concept of hosting payloads on their space-based constellations resulting in low-cost access to space. Examples, include the low Earth orbit Iridium Next constellation as well as communication satellites in geostationary. In some of these constellations data distribution can be provided in real time, a feature relevant to applications in the areas of space weather and disaster monitoring. From the perspective of new scientific discoveries enabled by low cost access to space, the cost and thus value proposition is dramatically changed. For example, a constellation of sixty-six satellites (Iridium Next), hosting a single band or multi-spectral imager can now provide observations of the aurora with a spatial resolution of a few hundred meters at all local times and in both hemispheres simultaneously. Remote sensing of clouds is another example where it is now possible to acquire global imagery at resolutions between 100-1000m. Finally, land use imagery is another example where one can use either imaging or spectrographic imagers to solve a multitude of problems. In this work, we will discuss measurement architectures and the multi-disciplinary scientific discoveries that are enable by large space based constellations.

Final Technical Report: Tandem and Bimetallic Catalysts for Oxidative Dehydrogenation of Light Hydrocarbon with Renewable Feedstock

DOE Office of Scientific and Technical Information (OSTI.GOV)

Abu-Omar, Mahdi

2017-01-06

An estimated 490 million metric tons of lignocellulosic biomass is available annually from U.S. agriculture and forestry. With continuing concerns over greenhouse gas emission, the development of efficient catalytic processes for conversion of biomass derived compounds is an important area of research. Since carbohydrates and polyols are rich in oxygen, approximately one oxygen atom per carbon, removal of hydroxyl groups via deoxygenation is needed. The necessary hydrogen required for hydrodeoxygenation (HDO) would either come from reforming biomass itself or from steam reforming of natural gas. Both processes contribute to global CO2 emission. The hope is that eventually renewable sources suchmore » as wind and solar for hydrogen production will become more viable and economic in the future. In the meantime, unconventional natural gas production in North America has boomed. As a result, light hydrocarbons present an opportunity when coupled with biomass derived oxygenates to generate valuable products from both streams without co-production of carbon dioxide. This concept is the focus of our current funding period. The objective of the project requires coupling two different types of catalysis, HDO and dehydrogenation. Our hypothesis was formulated around our success in establishing oxorhenium catalysts for polyol HDO reactions and known literature precedence for the use of iridium hydrides in alkane dehydrogenation. To examine our hypothesis we set out to investigate the reaction chemistry of binuclear complexes of oxorhenium and iridium hydride.« less

High temperature thruster technology for spacecraft propulsion

NASA Technical Reports Server (NTRS)

Schneider, Steven J.

1991-01-01

A technology program intended to develop high-temperature oxidation-resistant thrusters for spacecraft applications is considered. The program will provide the requisite material characterizations and fabrication to incorporate iridium coated rhenium material into small rockets for spacecraft propulsion. This material increases the operating temperature of thrusters to 2200 C, a significant increase over the 1400 C of the silicide-coated niobium chambers currently used. Stationkeeping class 22 N engines fabricated from iridium-coated rhenium have demonstrated steady state specific impulses 20-25 seconds higher than niobium chambers. These improved performances are obtained by reducing or eliminating the fuel film cooling requirements in the combustion chamber while operating at the same overall mixture ratio as conventional engines.

Cyclometalated Iridium(III) Carbene Phosphors for Highly Efficient Blue Organic Light-Emitting Diodes.

PubMed

Chen, Zhao; Wang, Liqi; Su, Sikai; Zheng, Xingyu; Zhu, Nianyong; Ho, Cheuk-Lam; Chen, Shuming; Wong, Wai-Yeung

2017-11-22

Five deep blue carbene-based iridium(III) phosphors were synthesized and characterized. Interestingly, one of them can be fabricated into deep blue, sky blue and white organic light-emitting diodes (OLEDs) through changing the host materials and exciton blocking layers. These deep and sky blue devices exhibit Commission Internationale de l'Éclairage (CIE) coordinates of (0.145, 0.186) and (0.152, 0.277) with external quantum efficiency (EQE) of 15.2% and 9.6%, respectively. The EQE of the deep blue device can be further improved up to 19.0% by choosing a host with suitable energy level of its lowest unoccupied molecular orbital (LUMO).

Activity and Durability of Iridium Nanoparticles in the Oxygen Evolution Reaction

DOE Office of Scientific and Technical Information (OSTI.GOV)

Alia, Shaun M.; Rasimick, Brian; Ngo, Chilan

Unsupported iridium (Ir) nanoparticles, that serve as standard oxygen evolution reaction (OER) catalysts in acidic electrolyzers, were investigated for electrochemical performance and durability in rotating disk electrode (RDE) half-cells. Fixed potential holds and potential cycling were applied to probe the durability of Ir nanoparticles, and performance losses were found to be driven by particle growth (coarsening) at moderate potential (1.4 to 1.6 V) and Ir dissolution at higher potential (>/=1.8 V). Several different commercially available samples were evaluated and standardized conditions for performance comparison are reported. In conclusion, the electrocatalyst RDE results have also been compared to results obtained formore » performance and durability in electrolysis cells.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Genevée, Pascal, E-mail: pascal-genevee@chimie-paristech.fr, E-mail: a.szeghalmi@uni-jena.de; Ahiavi, Ernest; Janunts, Norik

The authors report on the formation of blisters during the atomic layer deposition of iridium using iridium acetylacetonate and oxygen precursors. Films deposited on fused silica substrates led to sparsely distributed large blisters while in the case of silicon with native oxide additional small blisters with a high density was observed. It is found that the formation of blisters is favored by a higher deposition temperature and a larger layer thickness. Postdeposition annealing did not have a significant effect on the formation of blisters. Finally, changing purge duration during the film growth allowed us to avoid blistering and evidenced thatmore » impurities released from the film in gas phase were responsible for the formation of blisters.« less

Editing the stereochemical elements in an iridium catalyst for enantioselective allylic amination

PubMed Central

Leitner, Andreas; Shu, Chutian; Hartwig, John F.

2004-01-01

Individual diastereomeric phosphoramidites and mixtures of diastereomeric phosphoramidites were evaluated in the iridium-catalyzed amination of allylic carbonates. The original process was conducted with a phosphoramidite ligand containing a resolved 2,2-dihydroxy-1,1-binaphthyl (BINOL) group and a diastereomerically and enantiomerically pure bis(phenethyl)amino group. Evaluation of the structure of the active catalyst and relative rates for reactions in the presence of catalysts containing diastereomeric ligands led to the identification of a phosphoramidite that provided the amination product with enantiomeric excess similar to the original, more structurally and stereochemically complex ligand and that contains a racemic BINOLate and an N-benzylphenethylamino group on phosphorus. PMID:15067140

Enantioselective construction of C-chiral allylic sulfilimines via the iridium-catalyzed allylic amination with S,S-diphenylsulfilimine: asymmetric synthesis of primary allylic amines† †Electronic supplementary information (ESI) available. See DOI: 10.1039/c4sc01317d Click here for additional data file.

PubMed Central

Grange, Rebecca L.; Clizbe, Elizabeth A.; Counsell, Emma J.

2015-01-01

We have devised a highly regio- and enantioselective iridium-catalyzed allylic amination reaction with the sulfur-stabilized aza-ylide, S,S-diphenylsulfilimine. This process provides a robust and scalable method for the construction of aryl-, alkyl- and alkenyl-substituted C-chiral allylic sulfilimines, which are important functional groups for organic synthesis. Additionally, the combination of the allylic amination with an in situ deprotection of the sulfilimine constitutes a convenient one-pot protocol for the construction of chiral nonracemic primary allylic amines. PMID:28936319

Iridium-Catalysed ortho-Directed Deuterium Labelling of Aromatic Esters--An Experimental and Theoretical Study on Directing Group Chemoselectivity.

PubMed

Devlin, Jennifer; Kerr, William J; Lindsay, David M; McCabe, Timothy J D; Reid, Marc; Tuttle, Tell

2015-06-25

Herein we report a combined experimental and theoretical study on the deuterium labelling of benzoate ester derivatives, utilizing our developed iridium N-heterocyclic carbene/phosphine catalysts. A range of benzoate esters were screened, including derivatives with electron-donating and -withdrawing groups in the para- position. The substrate scope, in terms of the alkoxy group, was studied and the nature of the catalyst counter-ion was shown to have a profound effect on the efficiency of isotope exchange. Finally, the observed chemoselectivity was rationalized by rate studies and theoretical calculations, and this insight was applied to the selective labelling of benzoate esters bearing a second directing group.

Activity and Durability of Iridium Nanoparticles in the Oxygen Evolution Reaction

DOE PAGES

Alia, Shaun M.; Rasimick, Brian; Ngo, Chilan; ...

2016-07-15

Unsupported iridium (Ir) nanoparticles, that serve as standard oxygen evolution reaction (OER) catalysts in acidic electrolyzers, were investigated for electrochemical performance and durability in rotating disk electrode (RDE) half-cells. Fixed potential holds and potential cycling were applied to probe the durability of Ir nanoparticles, and performance losses were found to be driven by particle growth (coarsening) at moderate potential (1.4 to 1.6 V) and Ir dissolution at higher potential (>/=1.8 V). Several different commercially available samples were evaluated and standardized conditions for performance comparison are reported. In conclusion, the electrocatalyst RDE results have also been compared to results obtained formore » performance and durability in electrolysis cells.« less

Test experience, 490 N high performance (321 sec Isp) engine

NASA Technical Reports Server (NTRS)

Schoenman, L.; Rosenberg, S. D.; Jassowski, D. M.

1992-01-01

Engines with area ratios of 44:1 and 286:1 are tested by means of hot fire tests using the NTO/MMH bipropellant to maximize the performance of the combined technologies. The low-thrust engine systems are designed with oxidation resistant materials that can operate at temperatures of more than 2204 C for tens of hours. The chamber is attached to the injector in a configuration that prevents overheating of the injector, valve, and the spacecraft interface. Three injectors with 44:1 area ratios are capable of nominal specific impulse values of 309 sec, and a performance of 321 lbf-sec/lbm is noted for an all-welded engine assembly with area ratio of 286:1. The all-welded engine is shown to have an acceptable design margin for thermal characteristics. High-performance liquid apogee engines are shown to perform optimally when based on iridium/rhenium chamber technology, use of a special platelet injector, and the minimization of losses due to fuel-film cooling.

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.

Detection and removal of impurities in nitric oxide generated from air by pulsed electrical discharge.

PubMed

Yu, Binglan; Blaesi, Aron H; Casey, Noel; Raykhtsaum, Grigory; Zazzeron, Luca; Jones, Rosemary; Morrese, Alexander; Dobrynin, Danil; Malhotra, Rajeev; Bloch, Donald B; Goldstein, Lee E; Zapol, Warren M

2016-11-30

Inhalation of nitric oxide (NO) produces selective pulmonary vasodilation without dilating the systemic circulation. However, the current NO/N 2 cylinder delivery system is cumbersome and expensive. We developed a lightweight, portable, and economical device to generate NO from air by pulsed electrical discharge. The objective of this study was to investigate and optimize the purity and safety of NO generated by this device. By using low temperature streamer discharges in the plasma generator, we produced therapeutic levels of NO with very low levels of nitrogen dioxide (NO 2 ) and ozone. Despite the low temperature, spark generation eroded the surface of the electrodes, contaminating the gas stream with metal particles. During prolonged NO generation there was gradual loss of the iridium high-voltage tip (-90 μg/day) and the platinum-nickel ground electrode (-55 μg/day). Metal particles released from the electrodes were trapped by a high-efficiency particulate air (HEPA) filter. Quadrupole mass spectroscopy measurements of effluent gas during plasma NO generation showed that a single HEPA filter removed all of the metal particles. Mice were exposed to breathing 50 parts per million of electrically generated NO in air for 28 days with only a scavenger and no HEPA filter; the mice did not develop pulmonary inflammation or structural changes and iridium and platinum particles were not detected in the lungs of these mice. In conclusion, an electric plasma generator produced therapeutic levels of NO from air; scavenging and filtration effectively eliminated metallic impurities from the effluent gas. Copyright © 2016 Elsevier Inc. All rights reserved.

Detection and Removal of Impurities in Nitric Oxide Generated from Air by Pulsed Electrical Discharge

PubMed Central

Yu, Binglan; Blaesi, Aron H.; Casey, Noel; Raykhtsaum, Grigory; Zazzeron, Luca; Jones, Rosemary; Morrese, Alexander; Dobrynin, Danil; Malhotra, Rajeev; Bloch, Donald B.; Goldstein, Lee E.; Zapol, Warren M.

2016-01-01

Inhalation of nitric oxide (NO) produces selective pulmonary vasodilation without dilating the systemic circulation. However, the current NO/N2 cylinder delivery system is cumbersome and expensive. We developed a lightweight, portable, and economical device to generate NO from air by pulsed electrical discharge. The objective of this study was to investigate and optimize the purity and safety of NO generated by this device. By using low temperature streamer discharges in the plasma generator, we produced therapeutic levels of NO with very low levels of nitrogen dioxide (NO2) and ozone. Despite the low temperature, spark generation eroded the surface of the electrodes, contaminating the gas stream with metal particles. During prolonged NO generation there was gradual loss of the iridium high-voltage tip (−90 µg/day) and the platinum-nickel ground electrode (−55 µg/day). Metal particles released from the electrodes were trapped by a high-efficiency particulate air (HEPA) filter. Quadrupole mass spectroscopy measurements of effluent gas during plasma NO generation showed that a single HEPA filter removed all of the metal particles. Mice were exposed to breathing 50 parts per million of electrically generated NO in air for 28 days with only a scavenger and no HEPA filter; the mice did not develop pulmonary inflammation or structural changes and iridium and platinum particles were not detected in the lungs of these mice. In conclusion, an electric plasma generator produced therapeutic levels of NO from air; scavenging and filtration effectively eliminated metallic impurities from the effluent gas. PMID:27592386

[Brachytherapy in France: current situation and economic outlook due to the unavailability of iridium wires].

PubMed

Le Vu, B; Boucher, S

2014-10-01

In 2013, about 6000 patients were treated with brachytherapy, the number diminishing by 2.6% per year since 2008. Prostate, breast and gynecological cancers are the most common types of cancers. Since 2008, the number of brachytherapy facilities has decreased by 18%. In medicoeconomic terms, brachytherapy faces many problems: the coding system is outdated; brachytherapy treatments cost as much as internal radiation; fees do not cover costs; since iridium wire has disappeared from the market, the technique will be transferred to more expensive high-speed or pulse dose rates. The French financing grid based on the national study of costs lags behind changes in such treatments and in the best of cases, hospitals resorting to alternatives such as in-hospital brachytherapy are funded at 46% of their additional costs. Brachytherapy is a reference technique. With intense pressure on hospital pricing, financing brachytherapy facilities will become even more problematic as a consequence of the disappearance of iridium 192 wires. The case of brachytherapy illustrates the limits of the French financing system and raises serious doubts as to its responsiveness. Copyright © 2014 Société française de radiothérapie oncologique (SFRO). Published by Elsevier SAS. All rights reserved.

A new generation of high performance engines for spacecraft propulsion

NASA Technical Reports Server (NTRS)

Rosenberg, Sanders D.; Schoenman, Leonard

1991-01-01

Experimental data validating advanced engine designs at three thrust levels (5, 15, and 100 lbF) is presented. All of the three engine designs considered employ a Moog bipropellant torque motor valve, platelet injector design, and iridium-lined rhenium combustion chamber. Attention is focused on the performance, robustness, duration, and flexibility characteristics of the engines. It is noted that the 5- and 15-lbF thrust engines can deliver a steady state specific impulse in excess of 310 lbF-sec/lbm at an area ratio of 150:1, while the 150-lbF thrust engines deliver a steady state specific impulse of 320 lbF-sec/lbm at an area ratio of 250:1. The hot-fire test results reveal specific impulse improvements of 15 to 25 sec over conventional fuel film cooled columbium chamber designs while operating at maximum chamber temperatures.

Imino Transfer Hydrogenation Reductions.

PubMed

Wills, Martin

2016-04-01

This review contains a summary of recent developments in the transfer hydrogenation of C=N bonds, with a particularly focus on reports from within the last 10 years and asymmetric transformations. However, earlier work in the area is also discussed in order to provide context for the more recent results described. I focus strongly on the Ru/TsDPEN class of asymmetric transfer hydrogenation reactions originally reported by Noyori et al., together with examples of their applications, particularly to medically valuable target molecules. The recent developments in the area of highly active imine-reduction catalysts, notably those based on iridium, are also described in some detail. I discuss diastereoselective reduction methods as a route to the synthesis of chiral amines using transfer hydrogenation. The recent development of a methodology for positioning reduction complexes within chiral proteins, permitting the generation of asymmetric reduction products through a directed modification of the protein environment in a controlled manner, is also discussed.

The Moulin Explorer: A Novel Instrument to Study Greenland Ice Sheet Melt-Water Flow.

NASA Astrophysics Data System (ADS)

Behar, A.; Wang, H.; Elliott, A.; O'Hern, S.; Martin, S.; Lutz, C.; Steffen, K.; McGrath, D.; Phillips, T.

2008-12-01

Recent data shows that the Greenland ice sheet has been melting at an accelerated rate over the past decade. This melt water flows from the surface of the glacier to the bedrock below by draining into tubular crevasses known as moulins. Some believe these pathways eventually converge to nearby lakes and possibly the ocean. The Moulin Explorer Probe has been developed to traverse autonomously through these moulins. It uses in-situ pressure, temperature, and three-axis accelerometer sensors to log data. At the end of its journey, the probe will surface and send GPS coordinates using an Iridium satellite tracker so it may be retrieved via helicopter or boat. The information gathered when retrieved can be used to map the pathways and water flow rate through the moulins. This work was performed at the Jet Propulsion Laboratory- California Institute of Technology, under contract to NASA. Support was provided by the NASA Earth Science, Cryosphere program

Sensor Access to the Cellular Microenvironment Using the Sensing Cell Culture Flask.

PubMed

Kieninger, Jochen; Tamari, Yaara; Enderle, Barbara; Jobst, Gerhard; Sandvik, Joe A; Pettersen, Erik O; Urban, Gerald A

2018-04-26

The Sensing Cell Culture Flask (SCCF) is a cell culture monitoring system accessing the cellular microenvironment in 2D cell culture using electrochemical microsensors. The system is based on microfabricated sensor chips embedded in standard cell culture flasks. Ideally, the sensor chips could be equipped with any electrochemical sensor. Its transparency allows optical inspection of the cells during measurement. The surface of the sensor chip is in-plane with the flask surface allowing undisturbed cell growth on the sensor chip. A custom developed rack system allows easy usage of multiple flasks in parallel within an incubator. The presented data demonstrates the application of the SCCF with brain tumor (T98G) and breast cancer (T-47D) cells. Amperometric oxygen sensors were used to monitor cellular respiration with different incubation conditions. Cellular acidification was accessed with potentiometric pH sensors using electrodeposited iridium oxide films. The system itself provides the foundation for electrochemical monitoring systems in 3D cell culture.

Ultra-miniaturization of a planar amperometric sensor targeting continuous intradermal glucose monitoring.

PubMed

Ribet, Federico; Stemme, Göran; Roxhed, Niclas

2017-04-15

An ultra-miniaturized electrochemical biosensor for continuous glucose monitoring (CGM) is presented. The aim of this work is to demonstrate the possibility of an overall reduction in sensor size to allow minimally invasive glucose monitoring in the interstitial fluid in the dermal region, in contrast to larger state-of-the-art systems, which are necessarily placed in the subcutaneous layer. Moreover, the reduction in size might be a key factor to improve the stability and reliability of transdermal sensors, due to the reduction of the detrimental foreign body reaction and of consequent potential failures. These advantages are combined with lower invasiveness and discomfort for patients. The realized device consists of a microfabricated three-electrode enzymatic sensor with a total surface area of the sensing portion of less than 0.04mm 2 , making it the smallest fully integrated planar amperometric glucose sensor area reported to date. The working electrode and counter electrode consist of platinum and are functionalized by drop casting of three polymeric membranes. The on-chip iridium oxide (IrOx) pseudo-reference electrode provides the required stability for measurements under physiological conditions. The device is able to dynamically and linearly measure glucose concentrations in-vitro over the relevant physiological range, while showing sufficient selectivity to known interfering species present in the interstitial fluid, with resolution and sensitivity (1.51nA/mM) comparable to that of state-of-art commercial CGM systems. This work can therefore enable less invasive and improved CGM in patients affected by diabetes. Copyright © 2016 Elsevier B.V. All rights reserved.

Effect of the substituents on the photophysical, electrochemical and electroluminescence properties of OLED dopant Iridium bis(2-phenylbenzothiozolato- N,C2')(acetylacetonate)

NASA Astrophysics Data System (ADS)

Ivanov, P.; Tomova, R.; Petrova, P.

2014-12-01

The effect of two substituents: clorine and 1,3-diphenylpropane-1,3-dionate, placed on different position in the molecule of Iridium (III) bis(2-phenylbenzothiozolato-N,C2')- (acetylacetonate) (bt)2Ir(acac), on its electrochemical behaviour, photophysical and electroluminescence properties were investigated. Three complexes (bt)2Ir(acac), Iridium (III) bis[2-(4-chlorophenyl)benzothiazolato-N,C2']-acetylacetonate (Clbt)2Ir(acac), in which the Cl atom was introduced on the 4-position in the benzothiazole ring, and the new Iridium (Ill) bis[2 -phenylbenzothiazolato -N,C2'] -(1,3 -diphenylpropane-1,3 -dionate) (bt)2Ir(dbm), where ancillary acetylacetonate ligand was replaced by 1,3-diphenylpropane-1,3-dionate, were synthesized and characterised by 1H-NMR and elemental analysis. The HOMO/LUMO energy levels of the complexes were determined by cyclic voltammetry (CV) and their properties were established by UV-Visible and fluorescence spectroscopy. The application of (Clbt)2Ir(acac), (bt)2Ir(bsm) and (bt)2Ir(acac) as dopants in hole transporting layer (HTL) of Organic light- emitting diodes(OLEDs). It was found that with respect to the reference (bt)2Ir(acac): both LUMO and HOMO of the substituted complexes were shifted to more positive values accordingly with 0.23 and 0.19 eV for (Clbt)2Ir(acac) and 0.14 and 0.12 eV for (bt)2Ir(dbm). OLEDs doped with 1 w% of the complexes irradiated the warm white light with Commission internationale de l'eclairage (CIE) coordinates: 0.24;0.38 for (Clbt)2Ir(acac), 0.30;0.44 for (bt)2Ir(acac) and 0.28;0.46 for (bt)2Ir(dbm). Devices doped with 10 w% of all complexes irradiated in the yellow orange region of the spectrum.

The New Positioning Technology for Sea Recovery Operations in Japan

NASA Astrophysics Data System (ADS)

Shoji, Yasuhiro; Yoshida, Tetsuya; Fuke, Hideyuki; Iijima, Issei; Izutsu, Naoki; Kato, Yoichi; Matsuzaka, Yukihiko; Namiki, Michiyoshi; Sato, Takatoshi; Tamura, Keisuke; Toriumi, Michihiko; Kakehashi, Yuya; Mizuta, Eiichi

2012-07-01

In Japan which has few flat plain and high population density, it is very difficult to drop a balloon safely on to the land. Hence balloons launched from Japan have always been dropped on the sea. In order to recover the balloons and the gondolas floating on the sea surely and rapidly, and to keep the gondolas and ships safe, much efforts and innovations have been made. Ones of the important innovations are positioning buoys. A buoy attached on a balloon gondola floats independently after the splash down, and informs its position to the recovery team. We had developed some types of such buoys; `radio beacon buoy' transmits a pattern of radio signal to navigate the recovery boats to the gondola. Another type of the buoys, `GPS ARGOS buoy,' finds its position with the GPS and sends the information to the balloon base via ARGOS satellite communication network. These technologies had contributed so much to the sea recovery operations however they also had some limitations. Recently, a new positioning buoy with better performance has developed; `Iridium buoy' detects the position with the GPS, and informs it to the balloon base via the Iridium satellite communication network and the internet. The Iridium buoy provides the accurate position surely and immediately with good time resolution. Furthermore the information can be received by very common devices which can receive e-mails. Thanks to the new buoy, the balloon operation team can always know where the gondola is on the sea more precisely, more simultaneously and more easily. That enables the operation team to inform the gondola's location to the authorities concerned as well as the recovery team, which contributes to the safety of both of the gondola and the sea traffics. In this presentation, the Iridium Buoy will be introduced mainly. Also the overview of the present sea recovery operation with the buoy and the past operations will be mentioned

Applications of Iridium-Catalyzed Asymmetric Allylic Substitution Reactions in Target-Oriented Synthesis.

PubMed

Qu, Jianping; Helmchen, Günter

2017-10-17

Metal catalyzed allylic substitution is a cornerstone of organometallic and synthetic chemistry. Enantioselective versions have been developed with catalysts derived from transition metals, most notably molybdenum, nickel, ruthenium, rhodium, iridium, palladium, and copper. The palladium- and the iridium-catalyzed versions have turned out to be particularly versatile in organic synthesis because of the very broad scope of the nucleophile and great functional group compatibility. Assets of the iridium-catalyzed reaction are the formation of branched, chiral products from simple monosubstituted allylic substrates, high degrees of regio- and enantioselectivity, and use of modular, readily available chiral ligands. The possibility to use carbon, nitrogen, oxygen, and sulfur compounds as well as fluoride as nucleophiles allows a wide range of chiral building blocks to be prepared. Our Account begins with the presentation of fundamental reaction schemes and chiral ligands. We will focus our discussion on reactions promoted by phosphoramidite ligands, though numerous chiral ligands have been employed. The subsequent section presents a brief overview of reaction mechanism and experimental conditions. Two versions of the iridium-catalyzed allylic substitution have emerged. In type 1 reactions (introduced in 1997), linear allylic esters are commonly used as substrates under basic reaction conditions. In type 2 reactions (introduced in 2007), environmentally friendly branched allylic alcohols can be reacted under acidic conditions; occasionally, derivatives of allylic alcohols have also been applied. A unique feature of the type 2 reactions is that highly electrophilic allylic intermediates can be brought to reaction with weakly activated alkenes. The subsequent text is ordered according to the strategies followed to transform allylic substitution products to desired targets, most of which are natural products or drugs. Syntheses starting with an intermolecular allylic substitution are discussed first. Some fairly complex targets, for example, the potent nitric oxide inhibitor (-)-nyasol and the drug (-)-protrifenbute, have been synthesized via less than five steps from simple starting materials. Most targets discussed are cyclic compounds. Intermolecular allylic substitution with subsequent ring closing metathesis is a powerful strategy for their synthesis. Highlights are stereodivergent syntheses of Δ 9 -tetrahydrocannabinols (THC), wherein iridium- and organocatalysis are combined (dual catalysis). The combination of allylic alkylation with a Diels-Alder reaction was utilized to synthesize the ketide apiosporic acid and the drug fesoterodine (Toviaz). Sequential allylic amination, hydroboration and Suzuki-Miyaura coupling generates enones suitable for conjugate addition reactions; this strategy was employed in syntheses of a variety of alkaloids, for example, the poison frog alkaloid (+)-cis-195A (pumiliotoxin C). Intramolecular substitutions offer interesting possibilities to build up stereochemical complexity via short synthetic routes. For example, in diastereoselective cyclizations of chiral compounds, substrate control can be overruled by catalyst control in order to generate cis- and trans-isomers selectively from a given precursor. This approach was used to prepare a variety of piperidine and pyrrolidine alkaloids. Finally, complex polycyclic structures, including the structurally unusual indolosesquiterpenoid mycoleptodiscin A, have been generated diastereo- and enantioselectively from olefins by polyene cyclizations and from electron-rich arenes, such as indoles, in dearomatization reactions.

Metal-ligand cooperation in catalytic intramolecular hydroamination: a computational study of iridium-pyrazolato cooperative activation of aminoalkenes.

PubMed

Tobisch, Sven

2012-06-04

The present study comprehensively explores diverse mechanistic pathways for intramolecular hydroamination of prototype 2,2-dimethyl-4-penten-1-amine by Cp*Ir chloropyrazole (1; Cp*=pentamethylcyclopentadienyl) in the presence of KOtBu base with the aid of density functional theory (DFT) calculations. The most accessible mechanistic pathway for catalytic turnover commences from Cp*Ir pyrazolato (Pz) substrate adduct 2⋅S, representing the catalytically competent compound and proceeds via initial electrophilic activation of the olefin C=C bond by the metal centre. It entails 1) facile and reversible anti nucleophilic amine attack on the iridium-olefin linkage; 2) Ir-C bond protonolysis via stepwise transfer of the ammonium N-H proton at the zwitterionic [Cp*IrPz-alkyl] intermediate onto the metal that is linked to turnover-limiting, reductive, cycloamine elimination commencing from a high-energy, metastable [Cp*IrPz-hydrido-alkyl] species; and 3) subsequent facile cycloamine liberation to regenerate the active catalyst species. The amine-iridium bound 2 a⋅S likely corresponds to the catalyst resting state and the catalytic reaction is expected to proceed with a significant primary kinetic isotope. This study unveils the vital role of a supportive hydrogen-bonded network involving suitably aligned β-basic pyrazolato and cycloamido moieties together with an external amine molecule in facilitating metal protonation and reductive elimination. Cooperative hydrogen bonding thus appears pivotal for effective catalysis. The mechanistic scenario is consonant with catalyst performance data and furthermore accounts for the variation in performance for [Cp*IrPz] compounds featuring a β- or γ-basic pyrazolato unit. As far as the route that involves amine N-H bond activation is concerned, a thus far undocumented pathway for concerted amidoalkene → cycloamine conversion through olefin protonation by the pyrazole N-H concurrent with N-C ring closure is disclosed as a favourable scenario. Although not practicable in the present system, this pathway describes a novel mechanistic variant in late transition metal-ligand bifunctional hydroamination catalysis that can perhaps be viable for tailored catalyst designs. The insights revealed herein concerning the operative mechanism and the structure-reactivity relationships will likely govern the rational design of late transition metal-ligand bifunctional catalysts and facilitate further conceptual advances in the area. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Dose rate in brachytherapy using after-loading machine: pulsed or high-dose rate?

PubMed

Hannoun-Lévi, J-M; Peiffert, D

2014-10-01

Since February 2014, it is no longer possible to use low-dose rate 192 iridium wires due to the end of industrial production of IRF1 and IRF2 sources. The Brachytherapy Group of the French society of radiation oncology (GC-SFRO) has recommended switching from iridium wires to after-loading machines. Two types of after-loading machines are currently available, based on the dose rate used: pulsed-dose rate or high-dose rate. In this article, we propose a comparative analysis between pulsed-dose rate and high-dose rate brachytherapy, based on biological, technological, organizational and financial considerations. Copyright © 2014 Société française de radiothérapie oncologique (SFRO). Published by Elsevier SAS. All rights reserved.

Influence of iridium doping in MgB2 superconducting wires

NASA Astrophysics Data System (ADS)

Grivel, J.-C.

2018-04-01

MgB2 wires with iridium doping were manufactured using the in-situ technique in a composite Cu-Nb sheath. Reaction was performed at 700 °C, 800 °C or 900 °C for 1 h in argon atmosphere. A maximum of about 1.5 at.% Ir replaces Mg in MgB2. The superconducting transition temperature is slightly lowered by Ir doping. The formation of IrMg3 and IrMg4 secondary phase particles is evidenced, especially for a nominal stoichiometry with 2.0 at.% Ir doping. The critical current density and accommodation field of the wires are strongly dependent on the Ir content and are generally weakened in the presence of Ir, although the effect is less pronounced at lower temperatures.

Enantiopure Ferrocene-Based Planar-Chiral Iridacycles: Stereospecific Control of Iridium-Centred Chirality.

PubMed

Arthurs, Ross A; Ismail, Muhammad; Prior, Christopher C; Oganesyan, Vasily S; Horton, Peter N; Coles, Simon J; Richards, Christopher J

2016-02-24

Reaction of [IrCp*Cl2 ]2 with ferrocenylimines (Fc=NAr, Ar=Ph, p-MeOC6 H4 ) results in ferrocene C-H activation and the diastereoselective synthesis of half-sandwich iridacycles of relative configuration Sp *,RIr *. Extension to (S)-2-ferrocenyl-4-(1-methylethyl)oxazoline gave highly diastereoselective control over the new elements of planar chirality and metal-based pseudo-tetrahedral chirality, to give both neutral and cationic half-sandwich iridacycles of absolute configuration Sc ,Sp ,RIr . Substitution reactions proceed with retention of configuration, with the planar chirality controlling the metal-centred chirality through an iron-iridium interaction in the coordinatively unsaturated cationic intermediate. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Electrical Measurements on Iridium Dioxide Nanorods

NASA Astrophysics Data System (ADS)

Lin, Y. H.; Lee, T. C.; Lin, J. J.; Chang, H. M.; Huang, Y. S.

2006-09-01

Iridium dioxide (IrO2) nanorods have been prepared by metal-organic chemical vapor deposition method. Applying the standard electron-beam lithography technique, a single nanorod with a diameter of 110 nm is contacted by three Cr/Au fingers from above. The resistance measurements on this nanorod have been performed between 10 and 300 K, using different probe configurations. We observe that the resistivity ρ of the nanorod has a value ⩽ 120 μΩ cm at 300 K. On the other hand, the temperature dependence of the contact resistance R obeys the law logR ∝ T-1/2 below 100 K. The conduction process through the contact is ascribed to the transport of electrons via hopping in granular metals accidentally formed at the contact region.

Size and Electronic Modulation of Iridium Nanoparticles on Nitrogen Functionalized Carbon toward Advanced Electrocatalysts for Alkaline Water Splitting.

PubMed

Wang, Hua; Ming, Mei; Hu, Min; Xu, Caili; Wang, Yi; Zhang, Yun; Gao, Daojiang; Bi, Jian; Fan, Guangyin; Hu, Jin-Song

2018-06-14

Developing efficient catalytic materials for electrochemical water splitting is important. Herein, uniformly dispersed and size-controllable iridium (Ir) nanoparticles (NPs) were prepared using a nitrogen-functionalized carbon (Ir/CN) as the support. We found that nitrogen function can simultaneously modulate the size of Ir NPs to substantially enhance the catalytically active sites and adjust the electronic structure of Ir, thereby promoting electrocatalytic activity for water splitting. Consequently, the as-synthesized Ir/CN shows excellent electrocatalytic performance with overpotentials of 12 and 265 mV for hydrogen and oxygen evolution reactions in basic medium, respectively. These findings may pave a way for designing and synthesizing other similar materials as efficient catalysts for electrochemical water splitting.

Photonics of a conjugated organometallic Pt-Ir polymer and its model compounds exhibiting hybrid CT excited states.

PubMed

Soliman, Ahmed M; Fortin, Daniel; Zysman-Colman, Eli; Harvey, Pierre D

2012-04-13

Trans- dichlorobis(tri-n-butylphosphine)platinum(II) reacts with bis(2- phenylpyridinato)-(5,5'-diethynyl-2,2'-bipyridine)iridium(III) hexafluorophosphate to form the luminescent conjugated polymer poly[trans-[(5,5'-ethynyl-2,2'-bipyridine)bis(2- phenylpyridinato)-iridium(III)]bis(tri-n-butylphosphine)platinum(II)] hexafluorophosphate ([Pt]-[Ir])n. Gel permeation chromatography indicates a degree of polymerization of 9 inferring the presence of an oligomer. Comparison of the absorption and emission band positions and their temperature dependence, emission quantum yields, and lifetimes with those for models containing only the [Pt] or the [Ir] units indicates hybrid excited states including features from both chromophores. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Detection of triglyceride using an iridium nano-particle catalyst based amperometric biosensor.

PubMed

Liao, Wei-Yin; Liu, Chung-Chiun; Chou, Tse-Chuan

2008-12-01

The detection and quantification of triglyceride (TG) using an iridium nano-particle modified carbon based biosensor was successfully carried out in this study. The detection procedures were based on the electrochemical detection of enzymatically produced NADH. TG was hydrolyzed by lipase and the glycerol produced was catalytically oxidized by NAD-dependent glycerol dehydrogenase producing NADH in a solution containing NAD(+). Glyceryl tributyrate, a short chain triglyceride, was chosen as the substrate for the evaluation of this TG biosensor in bovine serum and human serum. A linear response to glyceryl tributyrate in the concentration range of 0 to 10 mM and a sensitivity of 7.5 nA mM(-1) in bovine serum and 7.0 nA mM(-1) in human serum were observed experimentally. The potential interference of species such as uric acid (UA) and ascorbic acid (AA) was assessed. The incorporation of a selected surfactant and an increase in the incubation temperature appeared to enhance the performance of this biosensor. The conditions for the determination of TG levels in bovine serum using this biosensor were optimized, with sunflower seed oil being used as an analyte to simulate the detection of TG in blood. The experimental results demonstrated that this iridium nano-particle modified working electrode based biosensor provided a relatively simple means for the accurate determination of TG in serum.

Dual-emissive Polymer Dots for Rapid Detection of Fluoride in Pure Water and Biological Systems with Improved Reliability and Accuracy

PubMed Central

Zhao, Qiang; Zhang, Chuanqi; Liu, Shujuan; Liu, Yahong; Zhang, Kenneth Yin; Zhou, Xiaobo; Jiang, Jiayang; Xu, Wenjuan; Yang, Tianshe; Huang, Wei

2015-01-01

It is of paramount importance to develop new probes that can selectively, sensitively, accurately and rapidly detect fluoride in aqueous media and biological systems, because F- is found to be closely related to many health and environmental concerns. Herein, a dual-emissive conjugated polyelectrolyte P1 containing phosphorescent iridium(III) complex was designed and synthesized, which can form ultrasmall polymer dots (Pdots) in aqueous media. The F--responsive tert-butyldiphenylsilyl moiety was introduced into iridium(III) complex as the signaling unit for sensing F− with the quenched phosphorescence. Thus, the dual-emissive Pdots can rapidly and accurately detect F− in aqueous media and live cells as a ratiometric probe by measuring the change in the ratio of the F−-sensitive red phosphorescence from iridium(III) complex to the F−-insensitive blue fluorescence from polyfluorene. Moreover, the interaction of Pdots with F− also changes its emission lifetime, and the lifetime-based detection of F− in live cells has been realized through photoluminescence lifetime imaging microscopy for the first time. Both the ratiometric luminescence and lifetime imaging have been demonstrated to be resistant to external influences, such as the probe’s concentration and excitation power. This study provides a new perspective for the design of promising Pdots-based probes for biological applications. PMID:26552859

New iridium dopants forg white phosphorescent devices: enhancement of efficiency and color stability by an energy-harvesting layer.

PubMed

Chou, Ho-Hsiu; Li, Yi-Kai; Chen, Yu-Han; Chang, Ching-Chih; Liao, Chuang-Yi; Cheng, Chien-Hong

2013-07-10

A new light blue complex (fmoppy)2Ir(tfpypz) [bis(4'-fluoro-6'-methoxylphenyl pyridinato)-iridium(III)-3-(trifluoromethyl)-5-(pyridin-2-yl)-1,2,4-triazolate] and a new orange complex (dpiq)2Ir(acac) [bis(3,4-diphenylisoquinoline)-iridium(III)-acetylacetonate] were synthesized. These two complexes were used as the dopants for the fabrication of two-element white phosphorescent devices. Via the introduction of a thin energy-harvesting layer (EHL) to harvest the extra energy and exciton from the emission zone, highly efficient two-element white devices with excellent color stability were created. One of the best devices shows yellow-white color emission with an extremely high external quantum efficiency (EQE) of 21.5% and a current efficiency of 68.8 cd/A. The other device gave a pure white emission with an external quantum efficiency of 19.2% and a current efficiency of 53.2 cd/A. At a high brightness of 1000 cd/m(2), the EQE still remains as high as 18.9 and 17.2%. With a brightness of 1000-10000 cd/m(2), the CIE coordinates of these two devices shift by only (0.02, ≤0.01). The white phosphorescent devices with the EHL showed much higher efficiency and better color stability than the one without the EHL.

The kinetics and mechanism of the organo-iridium-catalysed enantioselective reduction of imines.

PubMed

Stirling, Matthew J; Sweeney, Gemma; MacRory, Kerry; Blacker, A John; Page, Michael I

2016-04-14

The iridium complex of pentamethylcyclopentadiene and (S,S)-1,2-diphenyl-N'-tosylethane-1,2-diamine is an effective catalyst for the asymmetric transfer hydrogenation of imine substrates under acidic conditions. Using the Ir catalyst and a 5 : 2 ratio of formic acid : triethylamine as the hydride source for the asymmetric transfer hydrogenation of 1-methyl-3,4-dihydroisoquinoline and its 6,7-dimethoxy substituted derivative, in either acetonitrile or dichloromethane, shows unusual enantiomeric excess (ee) profiles for the product amines. The reactions initially give predominantly the (R) enantiomer of the chiral amine products with >90% ee but which then decreases significantly during the reaction. The decrease in ee is not due to racemisation of the product amine, but because the rate of formation of the (R)-enantiomer follows first-order kinetics whereas that for the (S)-enantiomer is zero-order. This difference in reaction order explains the change in selectivity as the reaction proceeds - the rate formation of the (R)-enantiomer decreases exponentially with time while that for the (S)-enantiomer remains constant. A reaction scheme is proposed which requires rate-limiting hydride transfer from the iridium hydride to the iminium ion for the first-order rate of formation of the (R)-enantiomer amine and rate-limiting dissociation of the product for the zero-order rate of formation of the (S)-enantiomer.

Measurement of activation cross sections of alpha particle induced reactions on iridium up to an energy of 50 MeV.

PubMed

Takács, S; Ditrói, F; Szűcs, Z; Aikawa, M; Haba, H; Komori, Y; Saito, M

2018-06-01

Cross sections of alpha particle induced nuclear reactions on iridium were investigated using a 51.2-MeV alpha particle beam. The standard stacked-foil target technique and the activation method were applied. The activity of the reaction products was assessed without chemical separation using high resolution gamma-ray spectrometry. Excitation functions for production of gold, platinum and iridium isotopes ( 196m2 Au, 196m,g Au, 195m,g Au, 194 Au, 193 m,g Au, 192 Au, 191m,g Au, 191 Pt, 195m Pt, 194g Ir, 194m Ir, 192g Ir, 190g Ir and 189 Ir) were determined and compared with available earlier measured experimental data and results of theoretical calculations using TALYS code system. Cross section data were reported for the first time for the nat Ir(α,x) 196m2 Au, nat Ir(α,x) 196m,g Au, nat Ir(α,x) 191 Pt, nat Ir(α,x) 195m Pt, nat Ir(α,x) 194g Ir, nat Ir(α,x) 194m Ir, nat Ir(α,x) 190g Ir and nat Ir(α,x) 189 Ir processes. A possible production route for 195m Pt, the potentially important radionuclide in nuclear medicine, is discussed. Copyright © 2018 Elsevier Ltd. All rights reserved.

High-Performance Computer Modeling of the Cosmos-Iridium Collision

DOE Office of Scientific and Technical Information (OSTI.GOV)

Olivier, S; Cook, K; Fasenfest, B

2009-08-28

This paper describes the application of a new, integrated modeling and simulation framework, encompassing the space situational awareness (SSA) enterprise, to the recent Cosmos-Iridium collision. This framework is based on a flexible, scalable architecture to enable efficient simulation of the current SSA enterprise, and to accommodate future advancements in SSA systems. In particular, the code is designed to take advantage of massively parallel, high-performance computer systems available, for example, at Lawrence Livermore National Laboratory. We will describe the application of this framework to the recent collision of the Cosmos and Iridium satellites, including (1) detailed hydrodynamic modeling of the satellitemore » collision and resulting debris generation, (2) orbital propagation of the simulated debris and analysis of the increased risk to other satellites (3) calculation of the radar and optical signatures of the simulated debris and modeling of debris detection with space surveillance radar and optical systems (4) determination of simulated debris orbits from modeled space surveillance observations and analysis of the resulting orbital accuracy, (5) comparison of these modeling and simulation results with Space Surveillance Network observations. We will also discuss the use of this integrated modeling and simulation framework to analyze the risks and consequences of future satellite collisions and to assess strategies for mitigating or avoiding future incidents, including the addition of new sensor systems, used in conjunction with the Space Surveillance Network, for improving space situational awareness.« less

Anthropogenic disturbance of element cycles at the Earth's surface.

PubMed

Sen, Indra S; Peucker-Ehrenbrink, Bernhard

2012-08-21

The extent to which humans are modifying Earth's surface chemistry can be quantified by comparing total anthropogenic element fluxes with their natural counterparts (Klee and Graedel, 2004). We quantify anthropogenic mass transfer of 77 elements from mining, fossil fuel burning, biomass burning, construction activities, and human apportionment of terrestrial net primary productivity, and compare it to natural mass transfer from terrestrial and marine net primary productivity, riverine dissolved and suspended matter fluxes to the ocean, soil erosion, eolian dust, sea-salt spray, cosmic dust, volcanic emissions, and for helium, hydrodynamic escape from the Earth's atmosphere. We introduce an approach to correct for losses during industrial processing of elements belonging to geochemically coherent groups, and explicitly incorporate uncertainties of element mass fluxes through Monte Carlo simulations. We find that at the Earth's surface anthropogenic fluxes of iridium, osmium, helium, gold, ruthenium, antimony, platinum, palladium, rhenium, rhodium and chromium currently exceed natural fluxes. For these elements mining is the major factor of anthropogenic influence, whereas petroleum burning strongly influences the surficial cycle of rhenium. Our assessment indicates that if anthropogenic contributions to soil erosion and eolian dust are considered, anthropogenic fluxes of up to 62 elements surpass their corresponding natural fluxes.

Assessment of Boron Doped Diamond Electrode Quality and Application to In Situ Modification of Local pH by Water Electrolysis.

PubMed

Read, Tania L; Macpherson, Julie V

2016-01-06

Boron doped diamond (BDD) electrodes have shown considerable promise as an electrode material where many of their reported properties such as extended solvent window, low background currents, corrosion resistance, etc., arise from the catalytically inert nature of the surface. However, if during the growth process, non-diamond-carbon (NDC) becomes incorporated into the electrode matrix, the electrochemical properties will change as the surface becomes more catalytically active. As such it is important that the electrochemist is aware of the quality and resulting key electrochemical properties of the BDD electrode prior to use. This paper describes a series of characterization steps, including Raman microscopy, capacitance, solvent window and redox electrochemistry, to ascertain whether the BDD electrode contains negligible NDC i.e. negligible sp(2) carbon. One application is highlighted which takes advantage of the catalytically inert and corrosion resistant nature of an NDC-free surface i.e. stable and quantifiable local proton and hydroxide production due to water electrolysis at a BDD electrode. An approach to measuring the local pH change induced by water electrolysis using iridium oxide coated BDD electrodes is also described in detail.

Assessment of Boron Doped Diamond Electrode Quality and Application to In Situ Modification of Local pH by Water Electrolysis

PubMed Central

Read, Tania L.; Macpherson, Julie V.

2016-01-01

Boron doped diamond (BDD) electrodes have shown considerable promise as an electrode material where many of their reported properties such as extended solvent window, low background currents, corrosion resistance, etc., arise from the catalytically inert nature of the surface. However, if during the growth process, non-diamond-carbon (NDC) becomes incorporated into the electrode matrix, the electrochemical properties will change as the surface becomes more catalytically active. As such it is important that the electrochemist is aware of the quality and resulting key electrochemical properties of the BDD electrode prior to use. This paper describes a series of characterization steps, including Raman microscopy, capacitance, solvent window and redox electrochemistry, to ascertain whether the BDD electrode contains negligible NDC i.e. negligible sp2 carbon. One application is highlighted which takes advantage of the catalytically inert and corrosion resistant nature of an NDC-free surface i.e. stable and quantifiable local proton and hydroxide production due to water electrolysis at a BDD electrode. An approach to measuring the local pH change induced by water electrolysis using iridium oxide coated BDD electrodes is also described in detail. PMID:26779959

Optimization of pillar electrodes in subretinal prosthesis for enhanced proximity to target neurons

NASA Astrophysics Data System (ADS)

Flores, Thomas; Lei, Xin; Huang, Tiffany; Lorach, Henri; Dalal, Roopa; Galambos, Ludwig; Kamins, Theodore; Mathieson, Keith; Palanker, Daniel

2018-06-01

Objective. High-resolution prosthetic vision requires dense stimulating arrays with small electrodes. However, such miniaturization reduces electrode capacitance and penetration of electric field into tissue. We evaluate potential solutions to these problems with subretinal implants based on utilization of pillar electrodes. Approach. To study integration of three-dimensional (3D) implants with retinal tissue, we fabricated arrays with varying pillar diameter, pitch, and height, and implanted beneath the degenerate retina in rats (Royal College of Surgeons, RCS). Tissue integration was evaluated six weeks post-op using histology and whole-mount confocal fluorescence imaging. The electric field generated by various electrode configurations was calculated in COMSOL, and stimulation thresholds assessed using a model of network-mediated retinal response. Main results. Retinal tissue migrated into the space between pillars with no visible gliosis in 90% of implanted arrays. Pillars with 10 μm height reached the middle of the inner nuclear layer (INL), while 22 μm pillars reached the upper portion of the INL. Electroplated pillars with dome-shaped caps increase the active electrode surface area. Selective deposition of sputtered iridium oxide onto the cap ensures localization of the current injection to the pillar top, obviating the need to insulate the pillar sidewall. According to computational model, pillars having a cathodic return electrode above the INL and active anodic ring electrode at the surface of the implant would enable six times lower stimulation threshold, compared to planar arrays with circumferential return, but suffer from greater cross-talk between the neighboring pixels. Significance. 3D electrodes in subretinal prostheses help reduce electrode-tissue separation and decrease stimulation thresholds to enable smaller pixels, and thereby improve visual acuity of prosthetic vision.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rimoldi, Martino; Nakamura, Akitake; Vermeulen, Nicolaas A.

An iridium pincer complex has been immobilised in the metal–organic frameworkNU-1000. The stable Ir-pincer modifiedNU-1000is catalytically active in the hydrogenation of alkenes in condensed phase and under flow conditions.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rimoldi, Martino; Nakamura, Akitake; Vermeulen, Nicolaas A.

An iridium pincer complex has been immobilised in the metal–organic framework NU-1000. The stable Ir-pincer modified NU-1000 is catalytically active in the hydrogenation of alkenes in condensed phase and under flow conditions.

Reducing Iridium Loading in Oxygen Evolution Reaction Electrocatalysts Using Core–Shell Particles with Nitride Cores

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tackett, Brian M.; Sheng, Wenchao; Kattel, Shyam

Here, the oxygen evolution reaction (OER) has broad applications in electrochemical devices, but it often requires expensive and scarce Ir-based catalysts in acid electrolyte. Presented here is a framework to reduce Ir loading by combining core–shell iridium/metal nitride morphologies using in situ experiments and density functional theory (DFT) calculations. Several group VIII transition metal (Fe, Co, and Ni) nitrides are studied as core materials, with Ir/Fe 4N core–shell particles showing enhancement in both OER activity and stability. In situ X-ray absorption fine structure measurements are used to determine the structure and stability of the core–shell catalysts under OER conditions. DFTmore » calculations are used to demonstrate adsorbate binding energies as descriptors of the observed activity trends.« less

Comparison of dye doping and ultrathin emissive layer in white organic light-emitting devices with dual emissive layers

NASA Astrophysics Data System (ADS)

Wang, Xu; Qi, Yige; Yu, Junsheng

2014-09-01

White organic light-emitting devices (WOLEDs) with combined doping emissive layer (EML) and ultrathin EML have been fabricated to investigate the effect of each EML on the electroluminescent (EL) performance of the WOLEDs. Through tailoring doping concentration of bis[(4,6-difluorophenyl)-pyridinato-N,C2'](picolinate) iridium(III) (FIrpic) and thickness of ultrathin bis[2-(4-tertbutylphenyl)benzothiazolato-N,C2'] iridium (acetylacetonate) [(tbt)2Ir(acac)] EML, it is found that the change in the doping ratio of FIrpic significantly influenced the EL efficiencies and spectra, while the alteration of ultrathin EML thickness had much milder effect on the EL performance. The results indicated that ultrathin EML is in favor of reproducibility in mass production compared with doping method.

Welding of unique and advanced alloys for space and high-temperature applications: welding and weldability of iridium and platinum alloys

DOE PAGES

David, Stan A.; Miller, Roger G.; Feng, Zhili

2016-08-31

Advances have been made in developing alloys for space power systems for spacecraft that travel long distances to various planets. The spacecraft are powered by radioisotope thermoelectric generators (RTGs) and the fuel element in RTGs is plutonia. For safety and containment of the radioactive fuel element, the heat source is encapsulated in iridium or platinum alloys. Ir and Pt alloys are the alloys of choice for encapsulating radioisotope fuel pellets. Ir and Pt alloys were chosen because of their high-temperature properties and compatibility with the oxide fuel element and the graphite impact shells. This review addresses the alloy design andmore » welding and weldability of Ir and Pt alloys for use in RTGs.« less

Reducing Iridium Loading in Oxygen Evolution Reaction Electrocatalysts Using Core–Shell Particles with Nitride Cores

DOE PAGES

Tackett, Brian M.; Sheng, Wenchao; Kattel, Shyam; ...

2018-02-16

Here, the oxygen evolution reaction (OER) has broad applications in electrochemical devices, but it often requires expensive and scarce Ir-based catalysts in acid electrolyte. Presented here is a framework to reduce Ir loading by combining core–shell iridium/metal nitride morphologies using in situ experiments and density functional theory (DFT) calculations. Several group VIII transition metal (Fe, Co, and Ni) nitrides are studied as core materials, with Ir/Fe 4N core–shell particles showing enhancement in both OER activity and stability. In situ X-ray absorption fine structure measurements are used to determine the structure and stability of the core–shell catalysts under OER conditions. DFTmore » calculations are used to demonstrate adsorbate binding energies as descriptors of the observed activity trends.« less

Welding of unique and advanced alloys for space and high-temperature applications: welding and weldability of iridium and platinum alloys

DOE Office of Scientific and Technical Information (OSTI.GOV)

David, Stan A.; Miller, Roger G.; Feng, Zhili

Advances have been made in developing alloys for space power systems for spacecraft that travel long distances to various planets. The spacecraft are powered by radioisotope thermoelectric generators (RTGs) and the fuel element in RTGs is plutonia. For safety and containment of the radioactive fuel element, the heat source is encapsulated in iridium or platinum alloys. Ir and Pt alloys are the alloys of choice for encapsulating radioisotope fuel pellets. Ir and Pt alloys were chosen because of their high-temperature properties and compatibility with the oxide fuel element and the graphite impact shells. This review addresses the alloy design andmore » welding and weldability of Ir and Pt alloys for use in RTGs.« less

Water Oxidation Catalysis via Size-Selected Iridium Clusters

DOE Office of Scientific and Technical Information (OSTI.GOV)

Halder, Avik; Liu, Cong; LIU, ZHUN

The detailed mechanism and efficacy of four electron electrochemical water oxidation depend critically upon the detailed atomic structure of each catalytic site, which are numerous and diverse in most metal oxides anodes. In order to limit the diversity of sites, arrays of discrete iridium clusters with identical metal atom number (Ir-2, Ir-4, or Ir-8) were deposited in submonolayer coverage on conductive oxide supports, and the electrochemical properties and activity of each was evaluated. Exceptional electroactivity for the oxygen evolving reaction (OER) was observed for all cluster samples in acidic electrolyte. Reproducible cluster-size-dependent trends in redox behavior were also resolved. First-principlesmore » computational models of the individual discrete-size clusters allow correlation of catalytic-site structure and multiplicity with redox behavior.« less

Iridium-mediated isomerization-cyclization of bicyclic Pauson-Khand derived allylic alcohols.

PubMed

Kavanagh, Yvonne; Chaney, Cíara M; Muldoon, Jimmy; Evans, Paul

2008-11-07

Treatment of 2-(toluene-4-sulfonyl)-2,3,4,4a,5,6-hexahydro-1H-[2]pyrindin-6-ol 10, accessed from the diastereoselective Luche reduction of a Pauson-Khand derived bicylic cyclopentenone, with a catalytic amount of (1,5-cyclooctadiene)(pyridine)(tricyclohexylphosphine)iridium(I) hexafluorophosphate 1 (Crabtree's catalyst) under a hydrogen atmosphere resulted in the formation of 4-(toluene-4-sulfonyl)-2-oxa-4-azatricyclo[5.2.1.0(3,8)]decane 12 as a single diastereoisomer. This process is likely to proceed via an initial Ir(I)-mediated isomerization of the alkene to form an N-sulfonyl enamine 11, followed by cyclization. Evidence to support this came when, after short reaction periods, 11 was isolated, characterized spectroscopically, and on resubmission to the reaction conditions formed 12.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Xu, Songchen; Manna, Kuntal; Ellern, Arkady

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 spectroscopicmore » 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-[Ir](H)(Ph) complex. Alternatively, the rhodium carbonyl 5 or iridium isocyanide {PhB(OxMe2)2ImMes}Ir(CO)CNtBu (15) reacts with PhSiH3 in the dark to form the silyl compound {PhB(OxMe2)2ImMes}RhH(SiH2Ph)CO (14) or {PhB(OxMe2)2ImMes}IrH(SiH2Ph)CNtBu (17). These examples demonstrate the enhanced thermal reactivity of {PhB(OxMe2)2ImMes}-supported iridium and rhodium carbonyl compounds in comparison to tris(oxazolinyl)borate, tris(pyrazolyl)borate, and cyclopentadienyl-supported compounds.« less

Design of a Low-cost Oil Spill Tracking Buoy

NASA Astrophysics Data System (ADS)

Zhao, Y.; Hu, X.; Yu, F.; Dong, S.; Chen, G.

2017-12-01

As the rapid development of oil exploitation and transportation, oil spill accidents, such as Prestige oil spill, Gulf of Mexico oil spill accident and so on, happened frequently in recent years which would result in long-term damage to the environment and human life. It would be helpful for rescue operation if we can locate the oil slick diffusion area in real time. Equipped with GNSS system, current tracking buoys(CTB), such as Lagrangian drifting buoy, Surface Velocity Program (SVP) drifter, iSLDMB (Iridium self locating datum marker buoy) and Argosphere buoy, have been used as oil tracking buoy in oil slick observation and as validation tools for oil spill simulation. However, surface wind could affect the movement of oil slick, which couldn't be reflected by CTB, thus the oil spill tracking performance is limited. Here, we proposed an novel oil spill tracking buoy (OSTB) which has a low cost of less than $140 and is equipped with Beidou positioning module and sails to track oil slick. Based on hydrodynamic equilibrium model and ocean dynamic analysis, the wind sails and water sails are designed to be adjustable according to different marine conditions to improve tracking efficiency. Quick release device is designed to assure easy deployment from air or ship. Sea experiment was carried out in Jiaozhou Bay, Northern China. OSTB, SVP, iSLDMB, Argosphere buoy and a piece of oil-simulated rubber sheet were deployed at the same time. Meanwhile, oil spill simulation model GNOME (general NOAA operational modeling environment) was configured with the wind and current field, which were collected by an unmanned surface vehicle (USV) mounted with acoustic Doppler current profilers (ADCP) and wind speed and direction sensors. Experimental results show that the OSTB has better relevance with rubber sheet and GNOME simulation results, which validate the oil tracking ability of OSTB. With low cost and easy deployment, OSTB provides an effective way for oil spill numerical modeling validation and quick response to oil spill accidents.

MUG-OBS - Multiparameter Geophysical Ocean Bottom System : a new instrumental approach to monitor earthquakes.

NASA Astrophysics Data System (ADS)

hello, yann; Charvis, Philippe; Yegikyan, Manuk; verfaillie, Romain; Rivet, Diane

2016-04-01

Real time monitoring of seismic activity is a major issue for early warning of earthquakes and tsunamis. It can be done using regional scale wired nodes, such as Neptune in Canada and in the U.S, or DONET in Japan. Another approach to monitor seismic activity at sea is to deploying repeatedly OBS array like during the amphibious Cascadia Initiative (four time 1-year deployments), the Japanese Pacific Array (broadband OBSs "ocean-bottom broadband dispersion survey" with 2-years autonomy), the Obsismer program in the French Lesser Antilles (eight time 6-months deployments) and the Osisec program in Ecuador (four time 6-months deployments). These autonomous OBSs are self-recovered or recovered using an ROV. These systems are costly including ship time, and require to recover the OBS before to start working on data. Among the most recent alternative we developed a 3/4 years autonomy ocean bottom system with 9 channels (?) allowing the acquisition of different seismic or environmental parameters. MUG-OBS is a free falling instrument rated down to 6000 m. The installation of the sensor is monitored by acoustic commands from the surface and a health bulletin with data checking is recovered by acoustic during the installation. The major innovation is that it is possible to recover the data any time on demand (regularly every 6-months or after a crisis) using one of the 6 data-shuttles released from the surface by acoustic command using a one day fast cruise boat of opportunity. Since sensors stayed at the same location for 3 years, it is a perfect tool to monitor large seismic events, background seismic activity and aftershock distribution. Clock, drift measurement and GPS localization is automatic when the shuttle reaches the surface. For remote areas, shuttles released automatically and a seismic events bulletin is transmitted. Selected data can be recovered by two-way Iridium satellite communication. After a period of 3 years the main station is self-recovered by acoustic.

Luminescent Rhenium(I) and Iridium(III) Polypyridine Complexes as Biological Probes, Imaging Reagents, and Photocytotoxic Agents.

PubMed

Lo, Kenneth Kam-Wing

2015-12-15

Although the interactions of transition metal complexes with biological molecules have been extensively studied, the use of luminescent transition metal complexes as intracellular sensors and bioimaging reagents has not been a focus of research until recently. The main advantages of luminescent transition metal complexes are their high photostability, long-lived phosphorescence that allows time-resolved detection, and large Stokes shifts that can minimize the possible self-quenching effect. Also, by the use of transition metal complexes, the degree of cellular uptake can be readily determined using inductively coupled plasma mass spectrometry. For more than a decade, we have been interested in the development of luminescent transition metal complexes as covalent labels and noncovalent probes for biological molecules. We argue that many transition metal polypyridine complexes display triplet charge transfer ((3)CT) emission that is highly sensitive to the local environment of the complexes. Hence, the biological labeling and binding interactions can be readily reflected by changes in the photophysical properties of the complexes. In this laboratory, we have modified luminescent tricarbonylrhenium(I) and bis-cyclometalated iridium(III) polypyridine complexes of general formula [Re(bpy-R(1))(CO)3(py-R(2))](+) and [Ir(ppy-R(3))2(bpy-R(4))](+), respectively, with reactive functional groups and used them to label the amine and sulfhydryl groups of biomolecules such as oligonucleotides, amino acids, peptides, and proteins. Additionally, using a range of biological substrates such as biotin, estradiol, and indole, we have designed luminescent rhenium(I) and iridium(III) polypyridine complexes as noncovalent probes for biological receptors. The interesting results generated from these studies have prompted us to investigate the possible applications of luminescent transition metal complexes in intracellular systems. Thus, in the past few years, we have developed an interest in the cytotoxic activity, cellular uptake, and bioimaging applications of these complexes. Additionally, we and other research groups have demonstrated that many transition metal complexes have facile cellular uptake and organelle-localization properties and that their cytotoxic activity can be readily controlled. For example, complexes that can target the nucleus, nucleolus, mitochondria, lysosomes, endoplasmic reticulum, and Golgi apparatus have been identified. We anticipate that this selective localization property can be utilized in the development of intracellular sensors and bioimaging reagents. Thus, we have functionalized luminescent rhenium(I) and iridium(III) polypyridine complexes with various pendants, including molecule-binding moieties, sugar molecules, bioorthogonal functional groups, and polymeric chains such as poly(ethylene glycol) and polyethylenimine, and examined their potentials as biological reagents. This Account describes our design of luminescent rhenium(I) and iridium(III) polypyridine complexes and explains how they can serve as a new generation of biological reagents for diagnostic and therapeutic applications.

Diffusion on Cu surfaces

NASA Technical Reports Server (NTRS)

Karimi, Majid

1993-01-01

Understanding surface diffusion is essential in understanding surface phenomena, such as crystal growth, thin film growth, corrosion, physisorption, and chemisorption. Because of its importance, various experimental and theoretical efforts have been directed to understand this phenomena. The Field Ion Microscope (FIM) has been the major experimental tool for studying surface diffusion. FIM have been employed by various research groups to study surface diffusion of adatoms. Because of limitations of the FIM, such studies are only limited to a few surfaces: nickel, platinum, aluminum, iridium, tungsten, and rhodium. From the theoretical standpoint, various atomistic simulations are performed to study surface diffusion. In most of these calculations the Embedded Atom Method (EAM) along with the molecular static (MS) simulation are utilized. The EAM is a semi-empirical approach for modeling the interatomic interactions. The MS simulation is a technique for minimizing the total energy of a system of particles with respect to the positions of its particles. One of the objectives of this work is to develop the EAM functions for Cu and use them in conjunction with the molecular static (MS) simulation to study diffusion of a Cu atom on a perfect as well as stepped Cu(100) surfaces. This will provide a test of the validity of the EAM functions on Cu(100) surface and near the stepped environments. In particular, we construct a terrace-ledge-kink (TLK) model and calculate the migration energies of an atom on a terrace, near a ledge site, near a kink site, and going over a descending step. We have also calculated formation energies of an atom on the bare surface, a vacancy in the surface, a stepped surface, and a stepped-kink surface. Our results are compared with the available experimental and theoretical results.

40 CFR 421.261 - Specialized definitions.

Code of Federal Regulations, 2014 CFR

2014-07-01

... apply to this subpart. (b) The term precious metals shall mean gold, platinum, palladium, rhodium, iridium, osmium, and ruthenium. (c) The term Combined Metals, shall mean the total of gold, platinum and...

40 CFR 421.261 - Specialized definitions.

Code of Federal Regulations, 2013 CFR

2013-07-01

... apply to this subpart. (b) The term precious metals shall mean gold, platinum, palladium, rhodium, iridium, osmium, and ruthenium. (c) The term Combined Metals, shall mean the total of gold, platinum and...

40 CFR 421.261 - Specialized definitions.

Code of Federal Regulations, 2011 CFR

2011-07-01

... apply to this subpart. (b) The term precious metals shall mean gold, platinum, palladium, rhodium, iridium, osmium, and ruthenium. (c) The term Combined Metals, shall mean the total of gold, platinum and...

40 CFR 421.261 - Specialized definitions.

Code of Federal Regulations, 2012 CFR

2012-07-01

... apply to this subpart. (b) The term precious metals shall mean gold, platinum, palladium, rhodium, iridium, osmium, and ruthenium. (c) The term Combined Metals, shall mean the total of gold, platinum and...

Short-term survival of ammonites in New Jersey after the end-Cretaceous bolide impact

USGS Publications Warehouse

Landman, Neil H.; Garb, Matthew P.; Rovelli, Remy; Ebel, Denton S.; Edwards, Lucy E.

2012-01-01

A section containing the Cretaceous/Paleogene (= Cretaceous/Tertiary) boundary in Monmouth County, New Jersey, preserves a record of ammonites extending from the end of the Cretaceous into possibly the beginning of the Danian. The section includes the upper part of the Tinton Formation and lower part of the Hornerstown Formation. The top of the Tinton Formation is represented by a richly fossiliferous unit (the Pinna Layer) that contains many bivalves in life position as well as ammonite jaws preserved inside body chambers. Ammonites include Pachydiscus (Neodesmoceras) mokotibensis, Sphenodiscus lobatus, Eubaculites carinatus, E. latecarinatus; Discoscaphites iris, D. sphaeroidalis; D. minardi, and D. jerseyensis. The Pinna Layer probably represents a relatively short interval of time lasting tens to hundreds of years; it is conformably overlain by the Burrowed Unit, which contains a single fragment of Discoscaphites sp. and several fragments of E. latecarinatus, as well as several isolated specimens of ammonite jaws including two of Eubaculites. Examination of the mode of preservation of the ammonites and jaws suggests that they were fossilized during deposition of the Burrowed Unit and were not reworked from older deposits. Based on the ammonites and dinoflagellates in the Pinna Layer and the Burrowed Unit, these strata traditionally would be assigned to the uppermost Maastrichtian, corresponding to calcareous nannofossil Subzone CC26b. However, a weak iridium anomaly (500–600 pg/g) is present at the base of the Pinna Layer, which presumably represents the record of the bolide impact. Correlation with the iridium layer at the Global Stratotype Section and Point at El Kef, Tunisia, would, therefore, imply that these assemblages are actually Danian, provided that the iridium anomaly is in place and the ammonites and dinoflagellates are not reworked. If the iridium anomaly is in place, or even if it has migrated downward from the top of the Pinna Layer, the ammonites would have survived the impact at this site for a brief interval of time lasting from a few days to hundreds of years.

A Yellow-Emitting Homoleptic Iridium(III) Complex Constructed from a Multifunctional Spiro Ligand for Highly Efficient Phosphorescent Organic Light-Emitting Diodes.

PubMed

Ren, Bao-Yi; Guo, Run-Da; Zhong, Dao-Kun; Ou, Chang-Jin; Xiong, Gang; Zhao, Xiang-Hua; Sun, Ya-Guang; Jurow, Matthew; Kang, Jun; Zhao, Yi; Li, Sheng-Biao; You, Li-Xin; Wang, Lin-Wang; Liu, Yi; Huang, Wei

2017-07-17

To suppress concentration quenching and to improve charge-carrier injection/transport in the emission layer (EML) of phosphorescent organic light-emitting diodes (PhOLEDs), a facial homoleptic iridium(III) complex emitter with amorphous characteristics was designed and prepared in one step from a multifunctional spiro ligand containing spiro[fluorene-9,9'-xanthene] (SFX) unit. Single-crystal X-ray analysis of the resulting fac-Ir(SFXpy) 3 complex revealed an enlarged Ir···Ir distance and negligible intermolecular π-π interactions between the spiro ligands. The emitter exhibits yellow emission and almost equal energy levels compared to the commercial phosphor iridium(III) bis(4-phenylthieno[3,2-c]pyridinato-N,C 2 ')acetylacetonate (PO-01). Dry-processed devices using a common host, 4,4'-bis(N-carbazolyl)-1,1'-biphenyl, and the fac-Ir(SFXpy) 3 emitter at a doping concentration of 15 wt % exhibited a peak performance of 46.2 cd A -1 , 36.3 lm W -1 , and 12.1% for the current efficiency (CE), power efficiency (PE), and external quantum efficiency (EQE), respectively. Compared to control devices using PO-01 as the dopant, the fac-Ir(SFXpy) 3 -based devices remained superior in the doping range between 8 and 15 wt %. The current densities went up with increasing doping concentration at the same driving voltage, while the roll-offs remain relatively low even at high doping levels. The superior performance of the new emitter-based devices was ascribed to key roles of the spiro ligand for suppressing aggregation and assisting charge-carrier injection/transport. Benefiting from the amorphous stability of the emitter, the wet-processed device also exhibited respectful CE, PE, and EQE of 32.2 cd A -1 , 22.1 lm W -1 , and 11.3%, respectively, while the EQE roll-off was as low as 1.7% at the luminance of 1000 cd m -2 . The three-dimensional geometry and binary-conjugation features render SFX the ideal multifunctional module for suppressing concentration quenching, facilitating charge-carrier injection/transport, and improving the amorphous stability of iridium(III)-based phosphorescent emitters.

Probing the mer- to fac-isomerization of tris-cyclometallated homo- and heteroleptic (C,N)3 iridium(III) complexes.

PubMed

McDonald, Aidan R; Lutz, Martin; von Chrzanowski, Lars S; van Klink, Gerard P M; Spek, Anthony L; van Koten, Gerard

2008-08-04

We have developed techniques which allow for covalent tethering, via a "hetero" cyclometallating ligand, of heteroleptic tris-cyclometallated iridium(III) complexes to polymeric supports (for application in light-emitting diode technologies). This involved the selective synthesis and thorough characterization of heteroleptic [Ir(C,N) 2(C',N')] tris-cyclometallated iridium(III) complexes. Furthermore, the synthesis and characterization of heteroleptic [Ir(C,N) 2OR] complexes is presented. Under standard thermal conditions for the synthesis of the facial ( fac) isomer of tris-cyclometallated complexes, it was not possible to synthesize pure heteroleptic complexes of the form [Ir(C,N) 2(C',N')]. Instead, a mixture of homo- and heteroleptic complexes was acquired. It was found that a stepwise procedure involving the synthesis of a pure meridonial ( mer) isomer followed by photochemical isomerization of this mer to the fac isomer was necessary to synthesize pure fac-[Ir(C,N) 2(C',N')] complexes. Under thermal isomerization conditions, the conversion of mer-[Ir(C,N) 2(C',N')] to fac-[Ir(C,N) 2(C',N')] was also not a clean reaction, with again a mixture of homo- and heteroleptic complexes acquired. An investigation into the thermal mer to fac isomerization of both homo- and heteroleptic tris-cyclometallated complexes is presented. It was found that the process is an alcohol-catalyzed reaction with the formation of an iridium alkoxide [Ir(C,N) 2OR] intermediate in the isomerization process. This catalyzed reaction can be carried out between 50 and 100 degrees C, the first such example of low-temperature mer-fac thermal isomerization. We have synthesized analogous complexes and have shown that they do indeed react so as to give fac-tris-cyclometallated products. A detailed explanation of the intermediates (and all of their stereoisomers, in particular when systems of the generic formula [M(a,b) 2(a',b')] are synthesized) formed in the mer to fac isomerization process is presented, including how the formed intermediates react further, and the stereoisomeric products they yield.

Neural electrode resilience against dielectric damage may be improved by use of highly doped silicon as a conductive material.

PubMed

Caldwell, Ryan; Sharma, Rohit; Takmakov, Pavel; Street, Matthew G; Solzbacher, Florian; Tathireddy, Prashant; Rieth, Loren

2018-01-01

Dielectric damage occurring in vivo to neural electrodes, leading to conductive material exposure and impedance reduction over time, limits the functional lifetime and clinical viability of neuroprosthetics. We used silicon micromachined Utah Electrode Arrays (UEAs) with iridium oxide (IrO x ) tip metallization and parylene C dielectric encapsulation to understand the factors affecting device resilience and drive improvements. In vitro impedance measurements and finite element analyses were conducted to evaluate how exposed surface area of silicon and IrO x affect UEA properties. Through an aggressive in vitro reactive accelerated aging (RAA) protocol, in vivo parylene degradation was simulated on UEAs to explore agreement with our models. Electrochemical properties of silicon and other common electrode materials were compared to help inform material choice in future neural electrode designs. Exposure of silicon on UEAs was found to primarily affect impedance at frequencies >1kHz, while characteristics at 1 kHz and below were largely unchanged. Post-RAA impedance reduction of UEAs was mitigated in cases where dielectric damage was more likely to expose silicon instead of IrO x . Silicon was found to have a per-area electrochemical impedance >10×higher than many common electrode materials regardless of doping level and resistivity, making it best suited for use as a low-shunting conductor. Non-semiconductor electrode materials commonly used in neural electrode design are more susceptible to shunting neural interface signals through dielectric defects, compared to highly doped silicon. Strategic use of silicon and similar materials may increase neural electrode robustness against encapsulation failures. Copyright © 2017 Elsevier B.V. All rights reserved.

Acoustic levitation with self-adaptive flexible reflectors.

PubMed

Hong, Z Y; Xie, W J; Wei, B

2011-07-01

Two kinds of flexible reflectors are proposed and examined in this paper to improve the stability of single-axis acoustic levitator, especially in the case of levitating high-density and high-temperature samples. One kind is those with a deformable reflecting surface, and the other kind is those with an elastic support, both of which are self-adaptive to the change of acoustic radiation pressure. High-density materials such as iridium (density 22.6 gcm(-3)) are stably levitated at room temperature with a soft reflector made of colloid as well as a rigid reflector supported by a spring. In addition, the containerless melting and solidification of binary In-Bi eutectic alloy (melting point 345.8 K) and ternary Ag-Cu-Ge eutectic alloy (melting point 812 K) are successfully achieved by applying the elastically supported reflector with the assistance of a laser beam.

Acoustic levitation with self-adaptive flexible reflectors

NASA Astrophysics Data System (ADS)

Hong, Z. Y.; Xie, W. J.; Wei, B.

2011-07-01

Two kinds of flexible reflectors are proposed and examined in this paper to improve the stability of single-axis acoustic levitator, especially in the case of levitating high-density and high-temperature samples. One kind is those with a deformable reflecting surface, and the other kind is those with an elastic support, both of which are self-adaptive to the change of acoustic radiation pressure. High-density materials such as iridium (density 22.6 gcm-3) are stably levitated at room temperature with a soft reflector made of colloid as well as a rigid reflector supported by a spring. In addition, the containerless melting and solidification of binary In-Bi eutectic alloy (melting point 345.8 K) and ternary Ag-Cu-Ge eutectic alloy (melting point 812 K) are successfully achieved by applying the elastically supported reflector with the assistance of a laser beam.

Synthesis of pentafluorides

DOEpatents

Asprey, L.B.; Paine, R.T. Jr.

1975-12-30

The reactions of uranium, molybdenum, rhenium, osmium and iridium hexafluorides with hydrogen gas in the presence of ultraviolet radiation or with silicon powder in an anhydrous HF slurry provide especially useful, high yield syntheses of pure pentafluorides.

Atomic structure of self-organizing iridium induced nanowires on Ge(001)

NASA Astrophysics Data System (ADS)

Kabanov, N. S.; Heimbuch, R.; Zandvliet, H. J. W.; Saletsky, A. M.; Klavsyuk, A. L.

2017-05-01

The atomic structure of self-organizing iridium (Ir) induced nanowires on Ge(001) is studied by density functional theory (DFT) calculations and variable-temperature scanning tunneling microscopy. The Ir induced nanowires are aligned in a direction perpendicular to the Ge(001) substrate dimer rows, have a width of two atoms and are completely kink-less. Density functional theory calculations show that the Ir atoms prefer to dive into the Ge(001) substrate and push up the neighboring Ge substrate atoms. The nanowires are composed of Ge atoms and not Ir atoms as previously assumed. The regions in the vicinity of the nanowires are very dynamic, even at temperatures as low as 77 K. Time-resolved scanning tunneling microscopy measurements reveal that this dynamics is caused by buckled Ge substrate dimers that flip back and forth between their two buckled configurations.

Reversible hydrogen storage using CO2 and a proton-switchable iridium catalyst in aqueous media under mild temperatures and pressures.

PubMed

Hull, Jonathan F; Himeda, Yuichiro; Wang, Wan-Hui; Hashiguchi, Brian; Periana, Roy; Szalda, David J; Muckerman, James T; Fujita, Etsuko

2012-03-18

Green plants convert CO(2) to sugar for energy storage via photosynthesis. We report a novel catalyst that uses CO(2) and hydrogen to store energy in formic acid. Using a homogeneous iridium catalyst with a proton-responsive ligand, we show the first reversible and recyclable hydrogen storage system that operates under mild conditions using CO(2), formate and formic acid. This system is energy-efficient and green because it operates near ambient conditions, uses water as a solvent, produces high-pressure CO-free hydrogen, and uses pH to control hydrogen production or consumption. The extraordinary and switchable catalytic activity is attributed to the multifunctional ligand, which acts as a proton-relay and strong π-donor, and is rationalized by theoretical and experimental studies.

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.

The Sixth Spectrum of Iridium (Ir VI): Determination of the 5d4, 5d36s and 5d36p Configurations

NASA Astrophysics Data System (ADS)

Azarov, V. I.; Gayasov, R. R.; Gayasov, R. R.; Joshi, Y. N.; Churilov, S. S.

The spectrum of five times ionized iridium, Ir VI, was investigated in the 420-1520 Å wavelength region. The analysis has led to the determination of the 5d4, 5d36s and 5d36p configurations. Thirty of thirty four theoretically possible 5d4 levels, 27 of 38 possible 5d36s levels and 96 of 110 possible 5d36p levels have been established. The levels are based on 711 classified spectral lines. The level structure of the configurations has been theoretically interpreted using the orthogonal operators technique. The energy parameters have been determined by a least squares fit to the observed levels. Calculated energy values and LS-compositions, obtained from the fitted parameter values are given.

Highly siderophile elements were stripped from Earth’s mantle by iron sulfide segregation

NASA Astrophysics Data System (ADS)

Rubie, David C.; Laurenz, Vera; Jacobson, Seth A.; Morbidelli, Alessandro; Palme, Herbert; Vogel, Antje K.; Frost, Daniel J.

2016-09-01

Highly siderophile elements (HSEs) are strongly depleted in the bulk silicate Earth (BSE) but are present in near-chondritic relative abundances. The conventional explanation is that the HSEs were stripped from the mantle by the segregation of metal during core formation but were added back in near-chondritic proportions by late accretion, after core formation had ceased. Here we show that metal-silicate equilibration and segregation during Earth’s core formation actually increased HSE mantle concentrations because HSE partition coefficients are relatively low at the high pressures of core formation within Earth. The pervasive exsolution and segregation of iron sulfide liquid from silicate liquid (the “Hadean matte”) stripped magma oceans of HSEs during cooling and crystallization, before late accretion, and resulted in slightly suprachondritic palladium/iridium and ruthenium/iridium ratios.

Iridium-Coated Rhenium Radiation-Cooled Rockets

NASA Technical Reports Server (NTRS)

Reed, Brian D.; Biaglow, James A.; Schneider, Steven J.

1997-01-01

Radiation-cooled rockets are used for a range of low-thrust propulsion functions, including apogee insertion, attitude control, and repositioning of satellites, reaction control of launch vehicles, and primary propulsion for planetary space- craft. The key to high performance and long lifetimes for radiation-cooled rockets is the chamber temperature capability. The material system that is currently used for radiation-cooled rockets, a niobium alloy (C103) with a fused silica coating, has a maximum operating temperature of 1370 C. Temperature limitations of C103 rockets force the use of fuel film cooling, which degrades rocket performance and, in some cases, imposes a plume contamination issue from unburned fuel. A material system composed of a rhenium (Re) substrate and an iridium (Ir) coating has demonstrated operation at high temperatures (2200 C) and for long lifetimes (hours). The added thermal margin afforded by iridium-coated rhenium (Ir/Re) allows reduction or elimination of fuel film cooling. This, in turn, leads to higher performance and cleaner spacecraft environments. There are ongoing government- and industry-sponsored efforts to develop flight Ir/ Re engines, with the primary focus on 440-N, apogee insertion engines. Complementing these Ir/Re engine development efforts is a program to address specific concerns and fundamental characterization of the Ir/Re material system, including (1) development of Ir/Re rocket fabrication methods, (2) establishment of critical Re mechanical properly data, (3) development of reliable joining methods, and (4) characterization of Ir/Re life-limiting mechanisms.

Highly efficient D2 generation by dehydrogenation of formic acid in D2O through H+/D+ exchange on an iridium catalyst: application to the synthesis of deuterated compounds by transfer deuterogenation.

PubMed

Wang, Wan-Hui; Hull, Jonathan F; Muckerman, James T; Fujita, Etsuko; Hirose, Takuji; Himeda, Yuichiro

2012-07-23

Deuterated compounds have received increasing attention in both academia and industrial fields. However, preparations of these compounds are limited for both economic and practical reasons. Herein, convenient generation of deuterium gas (D(2)) and the preparation of deuterated compounds on a laboratory scale are demonstrated by using a half-sandwich iridium complex with 4,4'-dihydroxy-2,2'-bipyridine. The "umpolung" (i.e., reversal of polarity) of a hydrogen atom of water was achieved in consecutive reactions, that is, a cationic H(+)/D(+) exchange reaction and anionic hydride or deuteride transfer, under mild conditions. Selective D(2) evolution (purity up to 89 %) was achieved by using HCO(2)H as an electron source and D(2)O as a deuterium source; a rhodium analogue provided HD gas (98 %) under similar conditions. Furthermore, pressurized D(2) (98 %) without CO gas was generated by using DCO(2)D in D(2)O in a glass autoclave. Transfer deuterogenation of ketones gave α-deuterated alcohols with almost quantitative yields and high deuterium content by using HCO(2)H in D(2)O. Mechanistic studies show that the H(+)/D(+) exchange reaction in the iridium hydride complex was much faster than β-elimination and hydride (deuteride) transfer. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Management of Ir-192 Disused Sealed Sources with Long-Lived Radioactive Contaminants

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dellamano, Jose Claudio; Ferreira, Robson de Jesus; Potiens, Ademar Jose Jr.

2015-07-01

Iridium-192 sealed sources are the most widely used sealed source in industrial applications in Brazil. They are not recyclable and in the end of the useful life, they are discarded as radioactive waste. The recommended management strategy of this waste is decay in storage and disposal as exempt waste because the half-life is only 73.8 days. Presently, thousands of Ir- 192 sources are under storage waiting release. Surprisingly, sources that were under storage for more than ten years and for which no measurable contact dose rate was expected still present significant remaining radioactivity. The examination of the gamma spectra ofmore » these sources showed the presence of Co-60 and the gamma emission lines from the Ir-192m2 isomer, the metastable isotope with half-life of 241 years, which is also formed by the irradiation of natural iridium. The aim of the study reported in this paper is to characterize the Ir-192 disused sources under interim storage at the Radioactive Waste Management Department, considering the presence of minor contaminants in the irradiated iridium and the fraction of the total initial activity of the sources that is attributable to that metastable isotope. The radioactive inventories at the end of the irradiation and after the decay period were predicted using the Scale 6.0 code and the results were compared with activity measurements of the disused sources by gamma spectrometry. (authors)« less

Topological Transformation of a Metal–Organic Framework Triggered by Ligand Exchange

DOE PAGES

Miera, Greco Gonzalez; Gomez, Antonio Bermejo; Chupas, Peter J.; ...

2017-04-06

Metal-organic frameworks (MOFs) have shown to be unsuspectedly dynamic. Here we describe the topological interconversion of a new framework in the bio-MOF-100 family (dia-c) into the known isomer (lcs) by doubling the pore volume, which occurs during post-synthesis modifications. During this transformation, re-assembling of the MOF building blocks into a completely different framework occurs, involving breaking/forming of metal-ligand bonds. MOF crystallinity and local structure are retained, as determined by powder X-ray diffraction (PXRD) and pair distribution function (PDF) analyses, respectively. We have exploited the inherent dynamism of bio-MOF-100 by coupling chemical decorations of the framework using solvent-assisted ligand exchange (SALE)more » to the topological change. Following this method and starting from the pristine dense dia-c phase, open lcs-bio-MOF-100 was prepared and functionalized in-situ with an iridium complex (IrL). Alternatively, the dia-c MOF could be modified with wide-ranging amounts of IrL up to ca. 50 mol%, as determined by solution 1H Nuclear Magnetic Resonance (NMR) spectroscopy, by tuning the concentration of the solutions used and with no evidence for isomer interconversion. The single-site nature of the iridium complexes within the MOFs was assessed by X-ray absorption spectroscopy (XAS) and PDF analyses. As a result, ligand exchanges occurred quantitatively at room temperature, with no need of excess of the iridium metallolinker.« less

Real-Time Verification of a High-Dose-Rate Iridium 192 Source Position Using a Modified C-Arm Fluoroscope

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nose, Takayuki, E-mail: nose-takayuki@nms.ac.jp; Chatani, Masashi; Otani, Yuki

Purpose: High-dose-rate (HDR) brachytherapy misdeliveries can occur at any institution, and they can cause disastrous results. Even a patient's death has been reported. Misdeliveries could be avoided with real-time verification methods. In 1996, we developed a modified C-arm fluoroscopic verification of an HDR Iridium 192 source position prevent these misdeliveries. This method provided excellent image quality sufficient to detect errors, and it has been in clinical use at our institutions for 20 years. The purpose of the current study is to introduce the mechanisms and validity of our straightforward C-arm fluoroscopic verification method. Methods and Materials: Conventional X-ray fluoroscopic images aremore » degraded by spurious signals and quantum noise from Iridium 192 photons, which make source verification impractical. To improve image quality, we quadrupled the C-arm fluoroscopic X-ray dose per pulse. The pulse rate was reduced by a factor of 4 to keep the average exposure compliant with Japanese medical regulations. The images were then displayed with quarter-frame rates. Results: Sufficient quality was obtained to enable observation of the source position relative to both the applicators and the anatomy. With this method, 2 errors were detected among 2031 treatment sessions for 370 patients within a 6-year period. Conclusions: With the use of a modified C-arm fluoroscopic verification method, treatment errors that were otherwise overlooked were detected in real time. This method should be given consideration for widespread use.« less

Iodine 125 source in interstitial tumor therapy. Clinical and biological considerations.

PubMed

Kim, J H; Hilaris, B

1975-01-01

Our clinical experience with interstitial tumor therapy is presented in 2 groups of patients: 98 patients with metastatic carcinoma in neck lymph nodes implanted with iodine 125, iridium 192 or radon 222 encapsulated sources, and 105 patients with primary unresectable lung tumors, which were implanted either with radon 222 or iodine 125 seeds. The local tumor control rates with iodine 125, radon 222 and iridium 192 were 78 per cent (38/49), 65 per cent (15/23) and 58 per cent (7/12), while the local complication rates were 17 per cent, 35 per cent and 43 per cent, respectively. An analysis of the tumor control rate as a function of the implanted tumor dose shows that the iodine 125 implants with a delivery of the minimal effective tumor dose of 16,000 rads have a higher therapeutic effect than either radon 222 or iridium 192. The results of the patients with unresectable lung tumors similarly show that the implants with iodine 125 sources are superior to those with radon 222. The advantages could stem from the better spatial dose distribution, and from radiobiologic considerations associated with low dose rates, continous irradiation, and possibly gains in RBE. There present clinical data clearly demonstrate that iodine 125 seeds have a higher therapeutic ratio than radon 222 seeds. There are, in addition, distinct physical advantages making iodine 125 an attractive substitute for radon 222 for the interstitial implantation of malignant tumors.

Real-Time Verification of a High-Dose-Rate Iridium 192 Source Position Using a Modified C-Arm Fluoroscope.

PubMed

Nose, Takayuki; Chatani, Masashi; Otani, Yuki; Teshima, Teruki; Kumita, Shinichirou

2017-03-15

High-dose-rate (HDR) brachytherapy misdeliveries can occur at any institution, and they can cause disastrous results. Even a patient's death has been reported. Misdeliveries could be avoided with real-time verification methods. In 1996, we developed a modified C-arm fluoroscopic verification of an HDR Iridium 192 source position prevent these misdeliveries. This method provided excellent image quality sufficient to detect errors, and it has been in clinical use at our institutions for 20 years. The purpose of the current study is to introduce the mechanisms and validity of our straightforward C-arm fluoroscopic verification method. Conventional X-ray fluoroscopic images are degraded by spurious signals and quantum noise from Iridium 192 photons, which make source verification impractical. To improve image quality, we quadrupled the C-arm fluoroscopic X-ray dose per pulse. The pulse rate was reduced by a factor of 4 to keep the average exposure compliant with Japanese medical regulations. The images were then displayed with quarter-frame rates. Sufficient quality was obtained to enable observation of the source position relative to both the applicators and the anatomy. With this method, 2 errors were detected among 2031 treatment sessions for 370 patients within a 6-year period. With the use of a modified C-arm fluoroscopic verification method, treatment errors that were otherwise overlooked were detected in real time. This method should be given consideration for widespread use. Copyright © 2016 Elsevier Inc. All rights reserved.

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

Topological Transformation of a Metal–Organic Framework Triggered by Ligand Exchange

DOE Office of Scientific and Technical Information (OSTI.GOV)

Miera, Greco Gonzalez; Gomez, Antonio Bermejo; Chupas, Peter J.

Metal-organic frameworks (MOFs) have shown to be unsuspectedly dynamic. Here we describe the topological interconversion of a new framework in the bio-MOF-100 family (dia-c) into the known isomer (lcs) by doubling the pore volume, which occurs during post-synthesis modifications. During this transformation, re-assembling of the MOF building blocks into a completely different framework occurs, involving breaking/forming of metal-ligand bonds. MOF crystallinity and local structure are retained, as determined by powder X-ray diffraction (PXRD) and pair distribution function (PDF) analyses, respectively. We have exploited the inherent dynamism of bio-MOF-100 by coupling chemical decorations of the framework using solvent-assisted ligand exchange (SALE)more » to the topological change. Following this method and starting from the pristine dense dia-c phase, open lcs-bio-MOF-100 was prepared and functionalized in-situ with an iridium complex (IrL). Alternatively, the dia-c MOF could be modified with wide-ranging amounts of IrL up to ca. 50 mol%, as determined by solution 1H Nuclear Magnetic Resonance (NMR) spectroscopy, by tuning the concentration of the solutions used and with no evidence for isomer interconversion. The single-site nature of the iridium complexes within the MOFs was assessed by X-ray absorption spectroscopy (XAS) and PDF analyses. As a result, ligand exchanges occurred quantitatively at room temperature, with no need of excess of the iridium metallolinker.« less

Characterization of the Sukinda and Nausahi ultramafic complexes, Orissa, India by platinum-group element geochemistry

USGS Publications Warehouse

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

1985-01-01

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

Summer Biomedical Engineering Institute 1972

NASA Technical Reports Server (NTRS)

Deloatch, E. M.

1973-01-01

The five problems studied for biomedical applications of NASA technology are reported. The studies reported are: design modification of electrophoretic equipment, operating room environment control, hematological viscometry, handling system for iridium, and indirect blood pressure measuring device.

48 CFR 252.208-7000 - Intent to furnish precious metals as Government-furnished material.

Code of Federal Regulations, 2012 CFR

2012-10-01

... Offeror shall cite the type (silver, gold, platinum, palladium, iridium, rhodium, and ruthenium) and... metal* Quantity Deliverable item (NSN and nomenclature)!!rs *If platinum or palladium, specify whether...

48 CFR 252.208-7000 - Intent to furnish precious metals as Government-furnished material.

Code of Federal Regulations, 2013 CFR

2013-10-01

... Offeror shall cite the type (silver, gold, platinum, palladium, iridium, rhodium, and ruthenium) and... metal* Quantity Deliverable item (NSN and nomenclature)!!rs *If platinum or palladium, specify whether...

48 CFR 252.208-7000 - Intent to furnish precious metals as Government-furnished material.

Code of Federal Regulations, 2011 CFR

2011-10-01

... Offeror shall cite the type (silver, gold, platinum, palladium, iridium, rhodium, and ruthenium) and... metal* Quantity Deliverable item (NSN and nomenclature)!!rs *If platinum or palladium, specify whether...

48 CFR 252.208-7000 - Intent to furnish precious metals as Government-furnished material.

Code of Federal Regulations, 2014 CFR

2014-10-01

... Offeror shall cite the type (silver, gold, platinum, palladium, iridium, rhodium, and ruthenium) and... metal* Quantity Deliverable item (NSN and nomenclature)!!rs *If platinum or palladium, specify whether...

Surface characteristics and electrochemical corrosion behavior of NiTi alloy coated with IrO2.

PubMed

Li, M; Wang, Y B; Zhang, X; Li, Q H; Liu, Q; Cheng, Y; Zheng, Y F; Xi, T F; Wei, S C

2013-01-01

The aim of this work is to investigate the surface characteristics and corrosion behavior of NiTi (50.6 at.% Ni) shape memory alloy coated by a ceramic-like and highly biocompatible material, iridium oxide (IrO2). IrO2 coatings were prepared by thermal decomposition of H2IrCl6 · 6H2O precursor solution at the temperature of 300 °C, 400 °C and 500 °C, respectively. The surface morphology and microstructure of the coatings were investigated by scanning electron microscope (SEM) and glancing angle X-ray diffraction (GAXRD). X-ray photoelectron spectroscopy (XPS) was employed to determine the surface elemental composition. Corrosion resistance property of the coated samples was studied in a simulated body fluid at 37±1 °C by electrochemical method. It was found that the morphology and microstructure of the coatings were closely related to the oxidizing temperatures. A relatively smooth, intact and amorphous coating was obtained when the H2IrCl6·6H2O precursor solution (0.03 mol/L) was thermally decomposed at 300 °C for 0.5 h. Compared with the bare NiTi alloy, IrO2 coated samples exhibited better corrosion resistance behavior to some extent. Copyright © 2012 Elsevier B.V. All rights reserved.

White-light phosphorescence emission from a single molecule: application to OLED.

PubMed

Bolink, Henk J; De Angelis, Filippo; Baranoff, Etienne; Klein, Cédric; Fantacci, Simona; Coronado, Eugenio; Sessolo, Michele; Kalyanasundaram, K; Grätzel, Michael; Nazeeruddin, Md K

2009-08-21

A simple mononuclear cyclometallated iridium(iii) complex exhibits white photo- and electro- luminescence in the wavelength range from 440 to 800 nm, which originates from a single emitting excited state of mixed character.

Novel Strategy for Photopatterning Emissive Polymer Brushes for Organic Light Emitting Diode Applications

PubMed Central

2017-01-01

A light-mediated methodology to grow patterned, emissive polymer brushes with micron feature resolution is reported and applied to organic light emitting diode (OLED) displays. Light is used for both initiator functionalization of indium tin oxide and subsequent atom transfer radical polymerization of methacrylate-based fluorescent and phosphorescent iridium monomers. The iridium centers play key roles in photocatalyzing and mediating polymer growth while also emitting light in the final OLED structure. The scope of the presented procedure enables the synthesis of a library of polymers with emissive colors spanning the visible spectrum where the dopant incorporation, position of brush growth, and brush thickness are readily controlled. The chain-ends of the polymer brushes remain intact, affording subsequent chain extension and formation of well-defined diblock architectures. This high level of structure and function control allows for the facile preparation of random ternary copolymers and red–green–blue arrays to yield white emission. PMID:28691078

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sanner, Robert D.; Cherepy, Nerine J.; Young, Jr., Victor G.

In this study, we describe the synthesis and crystal structures of four iridium compounds containing the 2-(4,6-difluorophenyl)pyridyl ligand. Cleavage of dichloro-bridged iridium(III) dimers with phosphorus ligands leads to (46dfppy)2Ir(L)(Cl) where L = PPh 3 or P(OPh) 3. Treatment of the chloro compounds with cyanide forms the cyano complexes (46dfppy) 2Ir(L)(CN). All complexes exhibit a trans effect in their molecular structures due to the phosphorus ligands, with the phosphite having a greater effect than the phosphine. With L = PPh 3, blue photoluminescence with CIE coordinates (x = 0.16, y = 0.24), quantum yield of 0.66 ± 0.15 and 4.5 ±more » 0.5 μs decay time is measured. For L = P(OPh) 3, blue photoluminescence with CIE coordinates (x = 0.16, y = 0.21), quantum yield of 0.65 ± 0.15 and 2.9 ± 0.3 μs decay time is measured.« less

Elastic, magnetic and electronic properties of iridium phosphide Ir 2P

DOE PAGES

Wang, Pei; Wang, Yonggang; Wang, Liping; ...

2016-02-24

Cubic (space group: Fm3¯m) iridium phosphide, Ir 2P, has been synthesized at high pressure and high temperature. Angle-dispersive synchrotron X-ray diffraction measurements on Ir 2P powder using a diamond-anvil cell at room temperature and high pressures (up to 40.6 GPa) yielded a bulk modulus of B 0 = 306(6) GPa and its pressure derivative B 0'= 6.4(5). Such a high bulk modulus attributed to the short and strongly covalent Ir-P bonds as revealed by first – principles calculations and three-dimensionally distributed [IrP 4] tetrahedron network. Indentation testing on a well–sintered polycrystalline sample yielded the hardness of 11.8(4) GPa. Relatively lowmore » shear modulus of ~64 GPa from theoretical calculations suggests a complicated overall bonding in Ir 2P with metallic, ionic, and covalent characteristics. Additionally, a spin glass behavior is indicated by magnetic susceptibility measurements.« less

Relation of Field-Aligned Currents Measured by the Network of Iridium® Spacecraft to Solar Wind and Substorms

NASA Astrophysics Data System (ADS)

McPherron, R. L.; Anderson, B. J.; Chu, Xiangning

2018-03-01

The strength of field-aligned currents coupling the magnetosphere to the ionosphere was obtained by the Active Magnetosphere and Planetary Electrodynamics Response Experiment (AMPERE) using the network of Iridium® spacecraft. The distribution of current was integrated giving total current in and out of the ionosphere on the dayside and nightside of the Earth in both hemispheres. The onset of auroral zone negative bays and midlatitude positive bays corresponds to an increase in nightside upward current. The total outward current tends toward saturation with increasing solar wind driver strength. The optimum solar wind coupling function for AL index predicts 73% of the variance in nightside upward current. The dayside and nightside predictors of upward current rise to a peak at 30-45 min and decay slowly over 2.5 hr. Nightside response is delayed relative to dayside.

Organic Light-Emitting Diodes Using Multifunctional Phosphorescent Dendrimers with Iridium-Complex Core and Charge-Transporting Dendrons

NASA Astrophysics Data System (ADS)

Tsuzuki, Toshimitsu; Shirasawa, Nobuhiko; Suzuki, Toshiyasu; Tokito, Shizuo

2005-06-01

We report a novel class of light-emitting materials for use in organic light-emitting diodes (OLEDs): multifunctional phosphorescent dendrimers that have a phosphorescent core and dendrons based on charge-transporting building blocks. We synthesized first-generation and second-generation dendrimers consisting of a fac-tris(2-phenylpyridine)iridium [Ir(ppy)3] core and hole-transporting phenylcarbazole-based dendrons. Smooth amorphous films of these dendrimers were formed by spin-coating them from solutions. The OLEDs using the dendrimer exhibited bright green or yellowish-green emission from the Ir(ppy)3 core. The OLEDs using the film containing a mixture of the dendrimer and an electron-transporting material exhibited higher efficiency than those using the neat dendrimer film. The external quantum efficiency of OLEDs using the film containing a mixture of the first-generation dendrimer and an electron-transporting material was as high as 7.6%.

Catalytic Decomposition of Hydroxylammonium Nitrate Ionic Liquid: Enhancement of NO Formation.

PubMed

Chambreau, Steven D; Popolan-Vaida, Denisia M; Vaghjiani, Ghanshyam L; Leone, Stephen R

2017-05-18

Hydroxylammonium nitrate (HAN) is a promising candidate to replace highly toxic hydrazine in monopropellant thruster space applications. The reactivity of HAN aerosols on heated copper and iridium targets was investigated using tunable vacuum ultraviolet photoionization time-of-flight aerosol mass spectrometry. The reaction products were identified by their mass-to-charge ratios and their ionization energies. Products include NH 3 , H 2 O, NO, hydroxylamine (HA), HNO 3 , and a small amount of NO 2 at high temperature. No N 2 O was detected under these experimental conditions, despite the fact that N 2 O is one of the expected products according to the generally accepted thermal decomposition mechanism of HAN. Upon introduction of iridium catalyst, a significant enhancement of the NO/HA ratio was observed. This observation indicates that the formation of NO via decomposition of HA is an important pathway in the catalytic decomposition of HAN.

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

Novel Strategy for Photopatterning Emissive Polymer Brushes for Organic Light Emitting Diode Applications.

PubMed

Page, Zachariah A; Narupai, Benjaporn; Pester, Christian W; Bou Zerdan, Raghida; Sokolov, Anatoliy; Laitar, David S; Mukhopadhyay, Sukrit; Sprague, Scott; McGrath, Alaina J; Kramer, John W; Trefonas, Peter; Hawker, Craig J

2017-06-28

A light-mediated methodology to grow patterned, emissive polymer brushes with micron feature resolution is reported and applied to organic light emitting diode (OLED) displays. Light is used for both initiator functionalization of indium tin oxide and subsequent atom transfer radical polymerization of methacrylate-based fluorescent and phosphorescent iridium monomers. The iridium centers play key roles in photocatalyzing and mediating polymer growth while also emitting light in the final OLED structure. The scope of the presented procedure enables the synthesis of a library of polymers with emissive colors spanning the visible spectrum where the dopant incorporation, position of brush growth, and brush thickness are readily controlled. The chain-ends of the polymer brushes remain intact, affording subsequent chain extension and formation of well-defined diblock architectures. This high level of structure and function control allows for the facile preparation of random ternary copolymers and red-green-blue arrays to yield white emission.

Rigid biimidazole ancillary ligands as an avenue to bright deep blue cationic iridium(iii) complexes.

PubMed

Henwood, Adam F; Evariste, Sloane; Slawin, Alexandra M Z; Zysman-Colman, Eli

2014-01-01

Herein we report the synthesis and optoelectronic characterisation of three deep blue-emitting cationic iridium complexes, of the form [Ir(dFppy)(2)(N^N)]PF(6), bearing biimidazole-type N^N ancillary ligands (dFppyH = 2-(2,4-difluorophenyl)pyridine). Complex 1 contains the parent biimidazole, biim, while 2 contains a dimethylated analog, dMebiim, and 3 contains an ortho-xylyl-tethered biimidzole, o-xylbiim. We explore a strategy of tethering the biimidazole in order to rigidify the complex and increase the photoluminescent quantum yield, culminating in deep blue (λ(max): 457 nm in MeOH at 298 K) ligand-centered emission with a very high photoluminescent quantum yield of 68% and microsecond emission lifetime. Density functional theory calculations elucidate the origin of such disparate excited state kinetics across this series, especially in light of virtually identical optoelectronic properties observed for these compounds.

Iridium Clusters Encapsulated in Carbon Nanospheres as Nanocatalysts for Methylation of (Bio)Alcohols.

PubMed

Liu, Qiang; Xu, Guoqiang; Wang, Zhendong; Liu, Xiaoran; Wang, Xicheng; Dong, Linlin; Mu, Xindong; Liu, Huizhou

2017-12-08

C-H methylation is an attractive chemical transformation for C-C bonds construction in organic chemistry, yet efficient methylation of readily available (bio)alcohols in water using methanol as sustainable C1 feedstock is limited. Herein, iridium nanocatalysts encapsulated in yolk-shell-structured mesoporous carbon nanospheres (Ir@YSMCNs) were synthesized for this transformation. Monodispersed Ir clusters (ca. 1.0 nm) were encapsulated in situ and spatially isolated within YSMCNs by a silica-assisted sol-gel emulsion strategy. A selection of (bio)alcohols (19 examples) was selectively methylated in aqueous phase with good-to-high yields over the developed Ir@YSMCNs. The improved catalytic efficiencies in terms of activity and selectivity together with the good stability and recyclability were contributable to the ultrasmall Ir clusters with oxidation chemical state as a consequence of the confinement effect of YSMCNs with interconnected nanostructures. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Catalytic dehydroaromatization of n-alkanes by pincer-ligated iridium complexes

NASA Astrophysics Data System (ADS)

Ahuja, Ritu; Punji, Benudhar; Findlater, Michael; Supplee, Carolyn; Schinski, William; Brookhart, Maurice; Goldman, Alan S.

2011-02-01

Aromatic hydrocarbons are among the most important building blocks in the chemical industry. Benzene, toluene and xylenes are obtained from the high temperature thermolysis of alkanes. Higher alkylaromatics are generally derived from arene-olefin coupling, which gives branched products—that is, secondary alkyl arenes—with olefins higher than ethylene. The dehydrogenation of acyclic alkanes to give alkylaromatics can be achieved using heterogeneous catalysts at high temperatures, but with low yields and low selectivity. We present here the first catalytic conversion of n-alkanes to alkylaromatics using homogeneous or molecular catalysts—specifically ‘pincer’-ligated iridium complexes—and olefinic hydrogen acceptors. For example, the reaction of n-octane affords up to 86% yield of aromatic product, primarily o-xylene and secondarily ethylbenzene. In the case of n-decane and n-dodecane, the resulting alkylarenes are exclusively unbranched (that is, n-alkyl-substituted), with selectivity for the corresponding o-(n-alkyl)toluene.

Smart responsive phosphorescent materials for data recording and security protection.

PubMed

Sun, Huibin; Liu, Shujuan; Lin, Wenpeng; Zhang, Kenneth Yin; Lv, Wen; Huang, Xiao; Huo, Fengwei; Yang, Huiran; Jenkins, Gareth; Zhao, Qiang; Huang, Wei

2014-04-07

Smart luminescent materials that are responsive to external stimuli have received considerable interest. Here we report ionic iridium (III) complexes simultaneously exhibiting mechanochromic, vapochromic and electrochromic phosphorescence. These complexes share the same phosphorescent iridium (III) cation with a N-H moiety in the N^N ligand and contain different anions, including hexafluorophosphate, tetrafluoroborate, iodide, bromide and chloride. The anionic counterions cause a variation in the emission colours of the complexes from yellow to green by forming hydrogen bonds with the N-H proton. The electronic effect of the N-H moiety is sensitive towards mechanical grinding, solvent vapour and electric field, resulting in mechanochromic, vapochromic and electrochromic phosphorescence. On the basis of these findings, we construct a data-recording device and demonstrate data encryption and decryption via fluorescence lifetime imaging and time-gated luminescence imaging techniques. Our results suggest that rationally designed phosphorescent complexes may be promising candidates for advanced data recording and security protection.

A rapid and practical strategy for the determination of platinum, palladium, ruthenium, rhodium, iridium and gold in large amounts of ultrabasic rock by inductively coupled plasma optical emission spectrometry combined with ultrasound extraction

NASA Astrophysics Data System (ADS)

Zhang, Gai; Tian, Min

2015-04-01

This proposed method regulated the determination of platinum, palladium, ruthenium, rhodium, iridium and gold in platinum-group ores by nickel sulfide fire assay—inductively coupled plasma optical emission spectrometry (ICP-OES) combined with ultrasound extraction for the first time. The quantitative limits were 0.013-0.023μg/g. The samples were fused to separate the platinum-group elements from matrix. The nickel sulfide button was then dissolved with hydrochloric acid and the insoluble platinum-group sulfide residue was dissolved with aqua regia by ultrasound bath and finally determined by ICP-OES. The proposed method has been applied into the determination of platinum-group element and gold in large amounts of ultrabasic rocks from the Great Dyke of Zimbabwe.

Intermolecular interactions and aggregation of fac-tris(2-phenylpyridinato-C2,N)iridium(III) in nonpolar solvents.

PubMed

Takayasu, Satoshi; Suzuki, Takayoshi; Shinozaki, Kazuteru

2013-08-15

The intermolecular interaction and aggregation of the neutral complex fac-tris(2-phenylpyridinato-C(2),N)iridium(III) (fac-Ir(ppy)3) in solution was investigated. Intermolecular interactions were found to effectively decrease the luminescence lifetime via self-quenching with increasing fac-Ir(ppy)3 concentrations. A Stern-Volmer plot for quenching in acetonitrile was linear, due to bimolecular self-quenching, but curved in toluene as the result of excimer formation. (1)H NMR spectra demonstrated a monomer-aggregate equilibrium which resulted in spectral shifts depending on solvent polarity. X-ray crystallography provided structural information concerning the aggregate, which is based on a tetramer consisting of two Δ-fac-Ir(ppy)3-Λ-fac-Ir(ppy)3 pairs. Offset π-π stacking of ppy ligands and electrostatic dipole-dipole interactions between complex molecules play an important role in the formation of these molecular pairs.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Göries, D., E-mail: dennis.goeries@desy.de; Roedig, P.; Stübe, N.

We report about the development and implementation of a new setup for time-resolved X-ray absorption fine structure spectroscopy at beamline P11 utilizing the outstanding source properties of the low-emittance PETRA III synchrotron storage ring in Hamburg. Using a high intensity micrometer-sized X-ray beam in combination with two positional feedback systems, measurements were performed on the transition metal complex fac-Tris[2-phenylpyridinato-C2,N]iridium(III) also referred to as fac-Ir(ppy){sub 3}. This compound is a representative of the phosphorescent iridium(III) complexes, which play an important role in organic light emitting diode (OLED) technology. The experiment could directly prove the anticipated photoinduced charge transfer reaction. Our resultsmore » further reveal that the temporal resolution of the experiment is limited by the PETRA III X-ray bunch length of ∼103 ps full width at half maximum (FWHM).« less

Nanosized IrO2 electrocatalysts for oxygen evolution reaction in an SPE electrolyzer

NASA Astrophysics Data System (ADS)

Cruz, J. C.; Baglio, V.; Siracusano, S.; Ornelas, R.; Ortiz-Frade, L.; Arriaga, L. G.; Antonucci, V.; Aricò, A. S.

2011-04-01

Nanosized IrO2 electrocatalysts ( d 7-9 nm) with specific surface area up to 100 m2 g-1 were synthesized and characterized for the oxygen evolution reaction in a solid polymer electrolyte (SPE) electrolyzer. The catalysts were prepared by a colloidal method in aqueous solution and a subsequent thermal treatment. An iridium hydroxide hydrate precursor was obtained at 100 °C, which was, successively, calcined at different temperatures from 200 to 500 °C. The physico-chemical characterization was carried out by X-ray diffraction (XRD), thermogravimetry-differential scanning calorimetry (TG-DSC) and transmission electron microscopy (TEM). IrO2 catalysts were sprayed onto a Nafion 115 membrane up to a loading of 3 mg cm-2. A Pt catalyst was used at the cathode compartment with a loading of 0.6 mg cm-2. The electrochemical activity for water electrolysis of the membrane-electrode assemblies (MEAs) was investigated in a single cell SPE electrolyzer by steady-state polarization curves, impedance spectroscopy and chrono-amperometric measurements. A maximum current density of 1.3 A cm-2 was obtained at 1.8 V and 80 °C for the IrO2 catalyst calcined at 400 °C for 1 h. A stable performance was recorded in single cell for this anode catalyst at 80 °C. The suitable catalytic activity and stability of the most performing catalyst were interpreted in terms of proper combination between nanostructure and suitable morphology.

Interface Modification of Bernal- and Rhombohedral-Stacked Trilayer-Graphene/Metal Electrode on Resistive Switching of Silver Electrochemical Metallization Cells.

PubMed

Wang, Jer-Chyi; Chan, Ya-Ting; Chen, Wei-Fan; Wu, Ming-Chung; Lai, Chao-Sung

2017-10-25

Bernal- and rhombohedral-stacked trilayer graphene (B- and r-TLG) on nickel (Ni) and iridium (Ir) films acting as bottom electrodes (BEs) of silver electrochemical metallization cells (Ag-EMCs) have been investigated in this study. Prior to the fabrication of the EMC devices, Raman mapping and atomic force microscopy are applied to identify the B- and r-TLG sheets, with the latter revealing a significant D peak and a rough surface for the Ir film. The Ag-EMCs with the stacked BE of r-TLG on the Ir film show a conductive mechanism of Schottky emission at the positive top electrode bias for both high- and low-resistance states that can be examined by the resistance change with the device area and are modulated by pulse bias operation. Thus, an effective electron barrier height of 0.262 eV at the r-TLG and Ir interface is obtained because of the conspicuous energy gap of r-TLG on the Ir film and the van der Waals (vdW) gap between the r-TLG and Ir contact metal. With the use of Ni instead of Ir contact metal, the Ag-EMCs with TLG BE demonstrate +0.3 V/-0.75 V operation voltages, more than 10 4 s data retention at 115 °C and 250 times endurance testing, making the TLG sheets suitable for low-power nonvolatile memory applications on flexible substrates.

Fabrication of Amperometric Glucose Sensor Using Glucose Oxidase-Cellulose Nanofiber Aqueous Solution.

PubMed

Yasuzawa, Mikito; Omura, Yuya; Hiura, Kentaro; Li, Jiang; Fuchiwaki, Yusuke; Tanaka, Masato

2015-01-01

Cellulose nanofiber aqueous solution, which remained virtually transparent for more than one week, was prepared by using the clear upper layer of diluted cellulose nanofiber solution produced by wet jet milling. Glucose oxidase (GOx) was easily dissolved in this solution and GOx-immobilized electrode was easily fabricated by simple repetitious drops of GOx-cellulose solution on the surface of a platinum-iridium electrode. Glucose sensor properties of the obtained electrodes were examined in phosphate buffer solution of pH 7.4 at 40°C. The obtained electrode provided a glucose sensor response with significantly high response speed and good linear relationship between glucose concentration and response current. After an initial decrease of response sensitivity for a few days, relatively constant sensitivity was obtained for about 20 days. Nevertheless, the influence of electroactive compounds such as ascorbic acid, uric acid and acetoaminophen were not negletable.

An integrated micro-manipulation and biosensing platform built in glass-based LTPS TFT technology

NASA Astrophysics Data System (ADS)

Chen, Lei-Guang; Wu, Dong-Yi; S-C Lu, Michael

2012-09-01

The glass-based low-temperature polycrystalline-silicon (LTPS) thin-film transistor (TFT) process, widely known for making liquid crystal displays, is utilized in this work to realize a fully integrated, microbead-based micro-manipulation and biosensing platform. The operation utilizes arrays of microelectrodes made of transparent iridium tin oxide (ITO) to move the immobilized polystyrene microbeads to the sensor surface by dielectrophoresis (DEP). Detection of remaining microbeads after a specific antigen/antibody reaction is accomplished by photo-detectors under the transparent electrodes. It was found that microbeads can be driven successfully by the 30 × 30 µm2 microelectrodes separated by 10 µm with no more than 6 Vp-p, which is compatible with the operating range of thin-film transistors. Microbeads immobilized with antimouse immunoglobulin (IgG) and prostate-specific antigen (PSA) antibody were successfully detected after specific binding, illustrating the potential of LTPS TFT microarrays for more versatile biosensing applications.

High-aspect ratio zone plate fabrication for hard x-ray nanoimaging

NASA Astrophysics Data System (ADS)

Parfeniukas, Karolis; Giakoumidis, Stylianos; Akan, Rabia; Vogt, Ulrich

2017-08-01

We present our results in fabricating Fresnel zone plate optics for the NanoMAX beamline at the fourth-generation synchrotron radiation facility MAX IV, to be used in the energy range of 6-10 keV. The results and challenges of tungsten nanofabrication are discussed, and an alternative approach using metal-assisted chemical etching (MACE) of silicon is showcased. We successfully manufactured diffraction-limited zone plates in tungsten with 30 nm outermost zone width and an aspect ratio of 21:1. These optics were used for nanoimaging experiments at NanoMAX. However, we found it challenging to further improve resolution and diffraction efficiency using tungsten. High efficiency is desirable to fully utilize the advantage of increased coherence on the optics at MAX IV. Therefore, we started to investigate MACE of silicon for the nanofabrication of high-resolution and high-efficiency zone plates. The first type of structures we propose use the silicon directly as the phase-shifting material. We have achieved 6 μm deep dense vertical structures with 100 nm linewidth. The second type of optics use iridium as the phase material. The structures in the silicon substrate act as a mold for iridium coating via atomic layer deposition (ALD). A semi-dense pattern is used with line-to-space ratio of 1:3 for a so-called frequency-doubled zone plate. This way, it is possible to produce smaller structures with the tradeoff of the additional ALD step. We have fabricated 45 nm-wide and 3.6 μm-tall silicon/iridium structures.

Bioselective synthesis of gold nanoparticles from diluted mixed Au, Ir, and Rh ion solution by Anabaena cylindrica

NASA Astrophysics Data System (ADS)

Rochert, Anna S.; Rösken, Liz M.; Fischer, Christian B.; Schönleber, Andreas; Ecker, Dennis; van Smaalen, Sander; Geimer, Stefan; Wehner, Stefan

2017-11-01

Over the last years, an environmentally friendly and economically efficient way of nanoparticle production has been found in the biosynthesis of metal nanoparticles by bacteria and cyanobacteria. In this study, Anabaena cylindrica, a non-toxic cyanobacterium, is deployed in a diluted ionic aqueous mixture of equal concentrations of gold, iridium, and rhodium, of 0.1 mM each, for the selective biosynthesis of metal nanoparticles (NPs). To analyze the cyanobacterial metal uptake, X-ray powder diffraction (XRD), transmission electron microscopy (TEM), and inductively coupled plasma mass spectrometry (ICP-MS) were applied. Only gold can be found in crystalline and nanoparticle form inside the cells of A. cylindrica, and it is the only metal for which ICP-MS analyses show a rapid decrease of the concentration in the culture medium. A slight decrease of rhodium and none of iridium was observed in the evaluated timeline of 51 h. The average diameter size of the emerging gold nanoparticles increased over the first few days, but is found to be below 10 nm even after more than 2 days. A new evaluation method was used to determine the spatially resolved distribution of the nanoparticles inside the cyanobacterial cells. This new method was also used to analyze TEM images from earlier studies of A. cylindrica and Anabaena sp., both incubated with an overall concentration of 0.8 mM Au3+ to compare the metal uptake. A. cylindrica was found to be highly selective towards the formation of gold nanoparticles in the presence of rhodium and iridium.

Dehydrogenation of n-Alkanes by Solid-Phase Molecular Pincer-Iridium Catalysts. High Yields of α-Olefin Product.

PubMed

Kumar, Akshai; Zhou, Tian; Emge, Thomas J; Mironov, Oleg; Saxton, Robert J; Krogh-Jespersen, Karsten; Goldman, Alan S

2015-08-12

We report the transfer-dehydrogenation of gas-phase alkanes catalyzed by solid-phase, molecular, pincer-ligated iridium catalysts, using ethylene or propene as hydrogen acceptor. Iridium complexes of sterically unhindered pincer ligands such as (iPr4)PCP, in the solid phase, are found to give extremely high rates and turnover numbers for n-alkane dehydrogenation, and yields of terminal dehydrogenation product (α-olefin) that are much higher than those previously reported for solution-phase experiments. These results are explained by mechanistic studies and DFT calculations which jointly lead to the conclusion that olefin isomerization, which limits yields of α-olefin from pincer-Ir catalyzed alkane dehydrogenation, proceeds via two mechanistically distinct pathways in the case of ((iPr4)PCP)Ir. The more conventional pathway involves 2,1-insertion of the α-olefin into an Ir-H bond of ((iPr4)PCP)IrH2, followed by 3,2-β-H elimination. The use of ethylene as hydrogen acceptor, or high pressures of propene, precludes this pathway by rapid hydrogenation of these small olefins by the dihydride. The second isomerization pathway proceeds via α-olefin C-H addition to (pincer)Ir to give an allyl intermediate as was previously reported for ((tBu4)PCP)Ir. The improved understanding of the factors controlling rates and selectivity has led to solution-phase systems that afford improved yields of α-olefin, and provides a framework required for the future development of more active and selective catalytic systems.

10 CFR 20.2206 - Reports of individual monitoring.

Code of Federal Regulations, 2011 CFR

2011-01-01

... quantitites: Radionuclide Quantity of radionuclide 1 in curies Cesium-137 1 Cobalt-60 1 Gold-198 100 Iodine-131 1 Iridium-192 10 Krypton-85 1,000 Promethium-147 10 Techetium-99m 1,000 1 The Commission may...

10 CFR 20.2206 - Reports of individual monitoring.

Code of Federal Regulations, 2013 CFR

2013-01-01

... quantitites: Radionuclide Quantity of radionuclide 1 in curies Cesium-137 1 Cobalt-60 1 Gold-198 100 Iodine-131 1 Iridium-192 10 Krypton-85 1,000 Promethium-147 10 Techetium-99m 1,000 1 The Commission may...

Iridium 191-m generator

DOEpatents

Treves, S.; Cheng, C.C.

1988-03-08

Potassium osmate, of the formula K[sub 2]OsO[sub 2](OH)[sub 4], is used to make a column for the generation of Ir-191 m, which is used in first pass angiography to detect cardiac defects in patients. 2 figs.

Inmarsat affiliate to operate medium-altitude satellite system

NASA Astrophysics Data System (ADS)

1994-05-01

Inmarsat will form an affiliated company to develop its $2.4-billion Inmarsat-P program as a competitor to Motorola's Iridium and Loral's Globestar in the exploding mobile communications market. Various aspects of the program are briefly discussed.

Iridium-catalyzed direct synthesis of tryptamine derivatives from indoles: exploiting n-protected β-amino alcohols as alkylating agents.

PubMed

Bartolucci, Silvia; Mari, Michele; Bedini, Annalida; Piersanti, Giovanni; Spadoni, Gilberto

2015-03-20

The selective C3-alkylation of indoles with N-protected ethanolamines involving the "borrowing hydrogen" strategy is described. This method provides convenient and sustainable access to several tryptamine derivatives.

Electrocatalyst compositions

DOEpatents

Mallouk, Thomas E.; Chan, Benny C.; Reddington, Erik; Sapienza, Anthony; Chen, Guoying; Smotkin, Eugene; Gurau, Bogdan; Viswanathan, Rameshkrishnan; Liu, Renxuan

2001-09-04

Compositions for use as catalysts in electrochemical reactions are described. The compositions are alloys prepared from two or more elemental metals selected from platinum, molybdenum, osmium, ruthenium, rhodium, and iridium. Also described are electrode compositions including such alloys and electrochemical reaction devices including such catalysts.

40 CFR 421.261 - Specialized definitions.

Code of Federal Regulations, 2010 CFR

2010-07-01

... apply to this subpart. (b) The term precious metals shall mean gold, platinum, palladium, rhodium, iridium, osmium, and ruthenium. (c) The term Combined Metals, shall mean the total of gold, platinum and... AND STANDARDS NONFERROUS METALS MANUFACTURING POINT SOURCE CATEGORY Secondary Precious Metals...

Selective extinction of marine plankton at the end of the Mesozoic era: The fossil and stable isotope record

NASA Technical Reports Server (NTRS)

Herman, Y.; Bhattacharya, S. K.

1988-01-01

Floral, faunal and stable isotope evidence in a continuous sequence of latest Cretaceous and earliest Tertiary shallow water marine deposits in the Mangyshlak Peninsula, USSR suggest severe environmental changes at the Cretaceous/Tertiary (K/T) boundary. Time frame is provided by nanno, micro and macrofossils as well as by magnetic stratigraphy and an iridium spike. Oxygen isotopic analyses of the bulk sediments, composed of nanno and microplankton skeletal remains, show a sharp positive spike at the K/T boundary. This shift is primarily attributed to severe cooling possibly accompanied by increased salinities of the surface mixed layer. Floral and faunal extinctions were selective, affecting approximately 90 percent of the warm water calcareous phyto and zooplankton genera in the Tethyan-Paratethyan regions. These highly diverse taxa with many endemic representatives were at the peak of their evolutionary development. Geologic evidence indicates that the terminal Cretaceous temperature decline was coeval with widespread and intense volcanic activity which reached a peak at the close of the Mesozoic Era. Increased acidity temporarily prohibited calcite nucleation of the surface dwelling warm-water plankton. Superimposed upon decreased alkalinity, severe and rapid climatic changes caused the extinction of calcareous phyto and zooplankton.

40 CFR 266.70 - Applicability and requirements.

Code of Federal Regulations, 2010 CFR

2010-07-01

... (CONTINUED) STANDARDS FOR THE MANAGEMENT OF SPECIFIC HAZARDOUS WASTES AND SPECIFIC TYPES OF HAZARDOUS WASTE... requirements. (a) The regulations of this subpart apply to recyclable materials that are reclaimed to recover economically significant amounts of gold, silver, platinum, palladium, iridium, osmium, rhodium, ruthenium, or...

Catalytic ignition of ionic liquids for propellant applications.

PubMed

Shamshina, Julia L; Smiglak, Marcin; Drab, David M; Parker, T Gannon; Dykes, H Waite H; Di Salvo, Roberto; Reich, Alton J; Rogers, Robin D

2010-12-21

In this proof of concept study, the ionic liquids, 2-hydroxyethylhydrazinium nitrate and 2-hydroxyethylhydrazinium dinitrate, ignited on contact with preheated Shell 405 (iridium supported on alumina) catalyst and energetically decomposed with no additional ignition source, suggesting a possible route to hydrazine replacements.

Novel iridium (III)‑derived organometallic compound for the inhibition of human platelet activation.

PubMed

Shyu, Kou-Gi; Velusamy, Marappan; Hsia, Chih-Wei; Yang, Chih-Hao; Hsia, Chih-Hsuan; Chou, Duen-Suey; Jayakumar, Thanasekaran; Sheu, Joen-Rong; Li, Jiun-Yi

2018-05-01

Since cisplatin achieved clinical success, transition metal platinum (Pt) drugs have been effectively used for the treatment of cancer. Iridium (Ir) compounds are considered to be potential alternatives to Pt compounds, as they possess promising anticancer effects with minor side effects. Platelet activation is associated with the metastasis and progression of cancer, and also with arterial thrombosis. Therefore, it is necessary to develop novel, effective antithrombotic agents. An Ir (III)‑derived complex, [Ir (Cp*) 1‑(2‑pyridyl)‑3‑(3‑methoxyphenyl)imidazo[1,5‑a]pyridine Cl]BF4 (Ir‑3), was developed as a novel antiplatelet drug. Ir‑3 exerted more potent inhibitory activity on platelet aggregation stimulated by collagen compared with other agonists, including thrombin. In collagen‑activated platelets, Ir‑3 also inhibited adenosine trisphosphate release, intracellular Ca+2 mobilization and surface P‑selectin expression, as well as the phosphorylation of phospholipase Cγ2 (PLCγ2), protein kinase C (PKC), protein kinase B (Akt) and c‑Jun N‑terminal kinase (JNK) 1, but not p38 mitogen‑activated protein kinase or extracellular signal‑regulated kinases. Ir‑3 did not markedly affect phorbol 12, 13‑dibutyrate‑stimulated platelet aggregation. Neither the adenylate cyclase inhibitor SQ22536 nor the guanylate cyclase inhibitor 1H‑[1, 2, 4] oxadiazolo [4,3‑a]quinoxalin‑1‑one significantly reversed the Ir‑3‑mediated inhibition of platelet aggregation. Furthermore, Ir‑3 had no considerable diminishing effects on OH radical signals in collagen‑stimulated platelets or Fenton reaction solution. In conclusion, Ir‑3 serves a novel function in the inhibition of platelet aggregation through inhibiting the PLCγ2‑PKC cascade, and the subsequent suppression of Akt and JNK1 activation. Therefore, Ir‑3 may be a potential novel therapeutic agent for the treatment of thromboembolic disorders, or the interplay between platelets and tumor cells which contributes to tumor cell proliferation and progression.

Iridium-catalyzed enantioselective hydrogenation of imines in supercritical carbon dioxide

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kainz, S.; Brinkmann, A.; Leitner, W.

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}]more » 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.« less

Iridium-Knife: Another knife in radiation oncology.

PubMed

Milickovic, Natasa; Tselis, Nikolaos; Karagiannis, Efstratios; Ferentinos, Konstantinos; Zamboglou, Nikolaos

Intratarget dose escalation with superior conformity is a defining feature of three-dimensional (3D) iridium-192 ( 192 Ir) high-dose-rate (HDR) brachytherapy (BRT). In this study, we analyzed the dosimetric characteristics of interstitial 192 Ir HDR BRT for intrathoracic and cerebral malignancies. We examined the dose gradient sharpness of HDR BRT compared with that of linear accelerator-based stereotactic radiosurgery and stereotactic body radiation therapy, usually called X-Knife, to demonstrate that it may as well be called a Knife. Treatment plans for 10 patients with recurrent glioblastoma multiforme or intrathoracic malignancies, five of each entity, treated with X-Knife (stereotactic radiosurgery for glioblastoma multiforme and stereotactic body radiation therapy for intrathoracic malignancies) were replanned for simulated HDR BRT. For 3D BRT planning, we used identical structure sets and dose prescription as for the X-Knife planning. The indices for qualitative treatment plan analysis encompassed planning target volume coverage, conformity, dose falloff gradient, and the maximum dose-volume limits to different organs at risk. Volume coverage in HDR plans was comparable to that calculated for X-Knife plans with no statistically significant difference in terms of conformity. The dose falloff gradient-sharpness-of the HDR plans was considerably steeper compared with the X-Knife plans. Both 3D 192 Ir HDR BRT and X-Knife are effective means for intratarget dose escalation with HDR BRT achieving at least equal conformity and a steeper dose falloff at the target volume margin. In this sense, it can reasonably be argued that 3D 192 Ir HDR BRT deserves also to be called a Knife, namely Iridium-Knife. Copyright © 2017 American Brachytherapy Society. Published by Elsevier Inc. All rights reserved.

Control of intramolecular π-π stacking interaction in cationic iridium complexes via fluorination of pendant phenyl rings.

PubMed

He, Lei; Ma, Dongxin; Duan, Lian; Wei, Yongge; Qiao, Juan; Zhang, Deqiang; Dong, Guifang; Wang, Liduo; Qiu, Yong

2012-04-16

Intramolecular π-π stacking interaction in one kind of phosphorescent cationic iridium complexes has been controlled through fluorination of the pendant phenyl rings on the ancillary ligands. Two blue-green-emitting cationic iridium complexes, [Ir(ppy)(2)(F2phpzpy)]PF(6) (2) and [Ir(ppy)(2)(F5phpzpy)]PF(6) (3), with the pendant phenyl rings on the ancillary ligands substituted with two and five fluorine atoms, respectively, have been synthesized and compared to the parent complex, [Ir(ppy)(2)(phpzpy)]PF(6) (1). Here Hppy is 2-phenylpyridine, F2phpzpy is 2-(1-(3,5-difluorophenyl)-1H-pyrazol-3-yl)pyridine, F5phpzpy is 2-(1-pentafluorophenyl-1H-pyrazol-3-yl)-pyridine, and phpzpy is 2-(1-phenyl-1H-pyrazol-3-yl)pyridine. Single crystal structures reveal that the pendant phenyl rings on the ancillary ligands stack to the phenyl rings of the ppy ligands, with dihedral angles of 21°, 18°, and 5.0° between least-squares planes for complexes 1, 2, and 3, respectively, and centroid-centroid distances of 3.75, 3.65, and 3.52 Å for complexes 1, 2, and 3, respectively, indicating progressively reinforced intramolecular π-π stacking interactions from complexes 1 to 2 and 3. Compared to complex 1, complex 3 with a significantly reinforced intramolecular face-to-face π-π stacking interaction exhibits a significantly enhanced (by 1 order of magnitude) photoluminescent efficiency in solution. Theoretical calculations reveal that in complex 3 it is unfavorable in energy for the pentafluorophenyl ring to swing by a large degree and the intramolecular π-π stacking interaction remains on the lowest triplet state. © 2012 American Chemical Society

A G-quadruplex-selective luminescent iridium(III) complex and its application by long lifetime.

PubMed

Lin, Sheng; Lu, Lihua; Liu, Jin-Biao; Liu, Chenfu; Kang, Tian-Shu; Yang, Chao; Leung, Chung-Hang; Ma, Dik-Lung

2017-05-01

The G-quadruplex motif has been widely used for the construction of analytical detection platforms due to its rich structural polymorphism and flexibility. Luminescent assays are often limited due to the interference from endogenous fluorophores in biological samples. To address this challenge, a novel long lifetime iridium(III) complex 1 was synthesized and used to construct a G-quadruplex-based assay for detecting prostate specific antigen (PSA) in aqueous solution. PSA is a common biomarker in serum and used as a model for demonstration in this work. The PSA assay has achieved a detection limit of 40.8pg·mL -1 , and shows high selectivity towards PSA over other proteins. Additionally, the assay could function in diluted human serum by using time-resolved luminescent spectroscopy, with good linearity from 1 to 10ng·mL -1 of PSA, which is adequate to detect the PSA levels for physiological (<4ng·mL -1 ) and clinical (4-10ng·mL -1 ) applications. The assay was successfully constructed. As revealed from time-resolved method, the long lifetime property of iridium(III) complex 1 plays an important role in distinguishing phosphorescence signals from short-life auto-fluorescence of human serum. Luminescent transition metal complexes offer several advantages over other widely used organic fluorophores, such as long phosphorescence lifetime, large Stokes shift and modular syntheses. In addition, the assay could work effectively in diluted human serum using time-resolved luminescent spectroscopy, it therefore could be potentially developed to monitor PSA in biological samples. This article is part of a Special Issue entitled "G-quadruplex" Guest Editor: Dr. Concetta Giancola and Dr. Daniela Montesarchio. Copyright © 2016 Elsevier B.V. All rights reserved.

Search for the Tunguska event in the Antarctic snow

NASA Technical Reports Server (NTRS)

Rocchia, R.; Deangelis, M.; Doclet, D.; Bonte, PH.; Jehanno, C.; Robin, E.

1988-01-01

The Tunguska explosion in 1908 is supposed to have been produced by the impact of a small celestial body. The absence of any identifiable crater together with the huge energy released by the event suggest that the impactor exploded in midair and that its material was widely spread over the Earth. The short term contribution of such exceptional events to the total accretion rate of extraterrestrial material by the Earth could be significant. Samples were chosen in a core electromechanically drilled in 1984 near South Pole Station. There, the low temperatures, preventing melting all year long, and the nearly regular snow fall rate provide good conditions for a reliable continuous record of any infalling material. In many samples Ir was below the detection limit of the instrumentation. The iridium infall averaged over 45 samples is given. In a few samples the iridium content is significantly higher than the average: the frequency and amplitude of such fluctuations can be explained by the presence on some filters of finite size cosmic particles. No significant systematic increase above the average level is observed in the part of the core corresponding to the Tunguska event. The two major results of this study are: (1) The presence of Tunguska explosion debris in the Antarctic snow is not confirmed; and (2) The estimate of the average iridium infall, is an order of magnitude lower than the Ganapathy's background but is close to the values measured in Antarctic snow and atmospheric samples by Takahashi et al. The results are also consistent with the flux of micrometeoroids deduced from optical and radar observations or derived from the study of Greenland cosmic dust collection but are lower than the flux at mid-latitude measured in paleocene-oligocene sediments from the central part of the Pacific Ocean.

Pentamethylcyclopentadienyl-rhodium and iridium complexes containing (N^N and N^O) bound chloroquine analogue ligands: synthesis, characterization and antimalarial properties.

PubMed

Ekengard, Erik; Kumar, Kamlesh; Fogeron, Thibault; de Kock, Carmen; Smith, Peter J; Haukka, Matti; Monari, Magda; Nordlander, Ebbe

2016-03-07

The synthesis and characterization of twenty new pentamethylcyclopentadienyl-rhodium and iridium complexes containing N^N and N^O-chelating chloroquine analogue ligands are described. The in vitro antimalarial activity of the new ligands as well as the complexes was evaluated against the chloroquine sensitive (CQS) NF54 and the chloroquine resistant (CQR) Dd2 strains of Plasmodium falciparum. The antimalarial activity was found to be good to moderate; although all complexes are less active than artesunate, some of the ligands and complexes showed better activity than chloroquine (CQ). In particular, rhodium complexes were found to be considerably more active than iridium complexes against the CQS NF54 strain. Salicylaldimine Schiff base ligands having electron-withdrawing groups (F, Cl, Br, I and NO2) in para position of the salicyl moiety and their rhodium complexes showed good antiplasmodial activity against both the CQS-NF54 and the CQR-Dd2 strains. The crystal structures of (η(5)-pentamethylcyclopentadienyl){N(1)-(7-chloroquinolin-4-yl)-N(2)-(pyridin-2-ylmethyl)ethane-1,2-diamine)} chlororhodium(III) chloride and (η(5)-pentamethylcyclopentadienyl){(4-chloro-2-(((2-((7-chloroquinolin-4-yl)amino)ethyl)imino)methyl)phenolate)}chlororhodium(III) chloride are reported. The crystallization of the amino-pyridyl complex (η(5)-pentamethylcyclopentadienyl){(N(1)-(7-chloroquinolin-4-yl)-N(2)-(pyridin-2-ylmethyl)ethane-1,2-diamine)}chloroiridium(III) chloride in acetone resulted in the formation of the imino-pyridyl derivative (η(5)-pentamethylcyclopentadienyl){(N1-(7-chloroquinolin-4-yl)-N2-(pyridin-2-ylmethylene)ethane-1,2-diamine)}chloroiridium(III) chloride, the crystal structure of which is also reported.

MUG-OBS - Multiparameter Geophysical Ocean Bottom System : a new instrumental approach to monitor earthquakes.

NASA Astrophysics Data System (ADS)

Hello, Y.; Yegikyan, M.; Charvis, P.; Verfaillie, R.; Philippe, O.

2015-12-01

There are several attempts to monitor real time seismic activity, using regional scale wired nodes, such as Neptune in Canada and in the U.S, Antares in France or DONET in Japan.On another hand there are also initiatives in deploying repeatedly OBS array like during the amphibious Cascadia Initiative (four 1-year deployments), the Japanese Pacific Array (broadband OBSs "ocean-bottom broadband dispersion survey" with 2-years autonomy), the Obsismer program in the French Lesser Antilles (eight 6-months deployments) and the Osisec program in Ecuador (four 6-months deployments). These OBSs are autonomous, they are self-recovered or recovered using an ROV. These systems are costly including ship time, and require to recover the OBS before to start working on data.Among the most recent alternative we developed a 3-years autonomy OBS equipped with a Nanometrics Trillium 120 s, a triaxial accelerometer, a differential, an absolute pressure gauge, and a hydrophone. MUG-OBS is a free falling instrument rated down to 6000 m. The installation of the sensor is monitored by acoustic commands from the surface and a health bulletin with data checking is recovered by acoustic during the installation. The major innovation is that it is possible to recover the data any time on demand (regularly every 6-months or after a seismic crisis) utilizing one of the 6 data-shuttles released from the surface by acoustic command using a one day fast cruise boat of opportunity. Since sensors stayed at the same location for 3 years (when an OBS is redeployed on the same site, it will not land in the same place), it is a perfect tool to monitor slow seismic events, background seismic activity and aftershock distribution. Clock, drift measurement and GPS localization is automatic when the shuttle reaches the surface. A new version is being developed; for remote areas, shuttles released automatically and a seismic events bulletin is transmitted. Selected data can be recovered by two- way Iridium satellite communication. After a period of 3 years the main station is ­self-recovered by acoustic.

Materials characterization of impregnated W and W-Ir cathodes after oxygen poisoning

NASA Astrophysics Data System (ADS)

Polk, James E.; Capece, Angela M.

2015-05-01

Electric thrusters use hollow cathodes as the electron source for generating the plasma discharge and for beam neutralization. These cathodes contain porous tungsten emitters impregnated with BaO material to achieve a lower surface work function and are operated with xenon propellant. Oxygen contaminants in the xenon plasma can poison the emitter surface, resulting in a higher work function and increased operating temperature. This could lead directly to cathode failure by preventing discharge ignition or could accelerate evaporation of the BaO material. Exposures over hundreds of hours to very high levels of oxygen can result in increased temperatures, oxidation of the tungsten substrate, and the formation of surface layers of barium tungstates. In this work, we present results of a cathode test in which impregnated tungsten and tungsten-iridium emitters were operated with 100 ppm of oxygen in the xenon plasma for several hundred hours. The chemical and morphological changes were studied using scanning electron microscopy, energy dispersive spectroscopy, and laser profilometry. The results provide strong evidence that high concentrations of oxygen accelerate the formation of tungstate layers in both types of emitters, a phenomenon not inherent to normal cathode operation. Deposits of pure tungsten were observed on the W-Ir emitter, indicating that tungsten is preferentially removed from the surface and transported in the insert plasma. A W-Ir cathode surface will therefore evolve to a pure W composition, eliminating the work function benefit of W-Ir. However, the W-Ir emitter exhibited less erosion and redeposition at the upstream end than the pure W emitter.

Mineral resource of the month: platinum-group metals

USGS Publications Warehouse

Hilliard, Henry

2003-01-01

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

Measurement of the Ir-191,193(n,2n)Ir-190,192 Reaction Cross Section Between 9.0 and 16.5 MeV

NASA Astrophysics Data System (ADS)

Wildenhain, Elizabeth; Finch, Sean; Tornow, Werner; Krishichayan, F.

2017-09-01

Iridium is one of the elements prioritized by Nonproliferation and Homeland Security agencies. In addition, Ir-192 is being used in various medical treatments. Improved data and corresponding evaluations of neutron-induced reactions on the iridium isotopes are required to meet the demands of several applications of societal interest. This study measured the cross section of the Ir-191,193(n, 2n)Ir-190,192 reactions at energies from 9.0 to 16.5 MeV using the activation technique. Natural Ir samples [Ir-191 37.3%, Ir-193 62.7%] were sandwiched between Au-197 monitor foils and irradiated with monoenergetic neutron beams at the tandem facility of the Triangle Universities Nuclear Laboratory (TUNL). Gamma rays from the irradiated samples were counted in TUNL's low background facility using high-efficient HPGe detectors. Measured cross-section data are compared to previous data and to predictions from nuclear data libraries (e.g. ENDF). Research at TUNL funded by the NSF.

Aqueous NMR Signal Enhancement by Reversible Exchange in a Single Step Using Water-Soluble Catalysts

PubMed Central

2016-01-01

Two synthetic strategies are investigated for the preparation of water-soluble iridium-based catalysts for NMR signal amplification by reversible exchange (SABRE). In one approach, PEGylation of a variant N-heterocyclic carbene provided a novel catalyst with excellent water solubility. However, while SABRE-active in ethanol solutions, the catalyst lost activity in >50% water. In a second approach, synthesis of a novel di-iridium complex precursor where the cyclooctadiene (COD) rings have been replaced by CODDA (1,2-dihydroxy-3,7-cyclooctadiene) leads to the creation of a catalyst [IrCl(CODDA)IMes] that can be dissolved and activated in water—enabling aqueous SABRE in a single step, without need for either an organic cosolvent or solvent removal followed by aqueous reconstitution. The potential utility of the CODDA catalyst for aqueous SABRE is demonstrated with the ∼(−)32-fold enhancement of 1H signals of pyridine in water with only 1 atm of parahydrogen. PMID:27350846

Organometallic rhodium(III) and iridium(III) cyclopentadienyl complexes with curcumin and bisdemethoxycurcumin co-ligands.

PubMed

Pettinari, Riccardo; Marchetti, Fabio; Pettinari, Claudio; Condello, Francesca; Petrini, Agnese; Scopelliti, Rosario; Riedel, Tina; Dyson, Paul J

2015-12-21

A series of half-sandwich cyclopentadienyl rhodium(III) and iridium(III) complexes of the type [Cp*M(curc/bdcurc)Cl] and [Cp*M(curc/bdcurc)(PTA)][SO3CF3], in which Cp* = pentamethylcyclopentadienyl, curcH = curcumin and bdcurcH = bisdemethoxycurcumin as O^O-chelating ligands, and PTA = 1,3,5-triaza-7-phosphaadamantane, is described. The X-ray crystal structures of three of the complexes, i.e. [Cp*Rh(curc)(PTA)][SO3CF3] (5), [Cp*Rh(bdcurc)(PTA)][SO3CF3] (6) and [Cp*Ir(bdcurc)(PTA)][SO3CF3] (8), confirm the expected "piano-stool" geometry. With the exception of 5, the complexes are stable under pseudo-physiological conditions and are moderately cytotoxic to human ovarian carcinoma (A2780 and A2780cisR) cells and also to non-tumorigenic human embryonic kidney (HEK293) cells, but lack the cancer cell selectivity observed for related arene ruthenium(II) complexes.

Atomistic characterization of the active-site solvation dynamics of a model photocatalyst

DOE PAGES

van Driel, Tim B.; Kjær, Kasper S.; Hartsock, Robert W.; ...

2016-11-28

The interactions between the reactive excited state of molecular photocatalysts and surrounding solvent dictate reaction mechanisms and pathways, but are not readily accessible to conventional optical spectroscopic techniques. Here we report an investigation of the structural and solvation dynamics following excitation of a model photocatalytic molecular system [Ir 2(dimen) 4] 2+, where dimen is para-diisocyanomenthane. The time-dependent structural changes in this model photocatalyst, as well as the changes in the solvation shell structure, have been measured with ultrafast diffuse X-ray scattering and simulated with Born-Oppenheimer Molecular Dynamics. Both methods provide direct access to the solute–solvent pair distribution function, enabling themore » solvation dynamics around the catalytically active iridium sites to be robustly characterized. Our results provide evidence for the coordination of the iridium atoms by the acetonitrile solvent and demonstrate the viability of using diffuse X-ray scattering at free-electron laser sources for studying the dynamics of photocatalysis.« less

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.

The influence of iridium chemical oxidation state on the performance and durability of oxygen evolution catalysts in PEM electrolysis

NASA Astrophysics Data System (ADS)

Siracusano, S.; Baglio, V.; Grigoriev, S. A.; Merlo, L.; Fateev, V. N.; Aricò, A. S.

2017-10-01

Nanosized Ir-black (3 nm) and Ir-oxide (5 nm) oxygen evolution electrocatalysts showing high performance in polymer electrolyte membrane (PEM) water electrolysis based on Aquivion® short-side chain ionomer membrane are investigated to understand the role of the Ir oxidation state on the electrocatalytic activity and stability. Despite the smaller mean crystallite size, the Ir-black electrocatalyst shows significantly lower initial performance than the Ir-oxide. During operation at high current density, the Ir-black shows a decrease of cell potential with time whereas the Ir-oxide catalyst shows increasing cell potential resulting in a degradation rate of about 10 μV/h, approaching 1000 h. The unusual behaviour of the Ir-black results from the oxidation of metallic Ir to IrOx. The Ir-oxide catalyst shows instead a hydrated structure on the surface and a negative shift of about 0.5 eV for the Ir 4f binding energy after 1000 h electrolysis operation. This corresponds to the formation of a sub-stoichiometric Ir-oxide on the surface. These results indicate that a hydrated IrO2 with high oxidation state on the surface is favourable in decreasing the oxygen evolution overpotential. Modifications of the Ir chemical oxidation state during operation can affect significantly the catalytic activity and durability of the electrolysis system.

DNA-barcode directed capture and electrochemical metabolic analysis of single mammalian cells on a microelectrode array.

PubMed

Douglas, Erik S; Hsiao, Sonny C; Onoe, Hiroaki; Bertozzi, Carolyn R; Francis, Matthew B; Mathies, Richard A

2009-07-21

A microdevice is developed for DNA-barcode directed capture of single cells on an array of pH-sensitive microelectrodes for metabolic analysis. Cells are modified with membrane-bound single-stranded DNA, and specific single-cell capture is directed by the complementary strand bound in the sensor area of the iridium oxide pH microelectrodes within a microfluidic channel. This bifunctional microelectrode array is demonstrated for the pH monitoring and differentiation of primary T cells and Jurkat T lymphoma cells. Single Jurkat cells exhibited an extracellular acidification rate of 11 milli-pH min(-1), while primary T cells exhibited only 2 milli-pH min(-1). This system can be used to capture non-adherent cells specifically and to discriminate between visually similar healthy and cancerous cells in a heterogeneous ensemble based on their altered metabolic properties.

DNA-barcode directed capture and electrochemical metabolic analysis of single mammalian cells on a microelectrode array

PubMed Central

Douglas, Erik S.; Hsiao, Sonny C.; Onoe, Hiroaki; Bertozzi, Carolyn R.; Francis, Matthew B.; Mathies, Richard A.

2010-01-01

A microdevice is developed for DNA-barcode directed capture of single cells on an array of pH-sensitive microelectrodes for metabolic analysis. Cells are modified with membrane-bound single-stranded DNA, and specific single-cell capture is directed by the complementary strand bound in the sensor area of the iridium oxide pH microelectrodes within a microfluidic channel. This bifunctional microelectrode array is demonstrated for the pH monitoring and differentiation of primary T cells and Jurkat T lymphoma cells. Single Jurkat cells exhibited an extracellular acidification rate of 11 milli-pH min−1, while primary T cells exhibited only 2 milli-pH min−1. This system can be used to capture non-adherent cells specifically and to discriminate between visually similar healthy and cancerous cells in a heterogeneous ensemble based on their altered metabolic properties. PMID:19568668

No geochemical evidence for an asteroidal impact at late Devonian mass extinction horizon

NASA Astrophysics Data System (ADS)

McGhee, G. R., Jr.; Gilmore, J. S.; Orth, C. J.; Olsen, E.

1984-04-01

Three sedimentary sequences in New York State (Dunkirk Beach, Walnut Creek Gorge, and Mills Mills) and one sedimentary sequence in Belgium (Sinsin), that cross the Devonian Frasnian-Famennian boundary, were examined for an iridium (Ir) anomaly to determine whether the biotic extinctions at the end of the Cretaceous could have been caused by an asteroidal impact. The sampling at three of the four areas was on 2-cm center points, and 15 to 20 g of sample were collected. The instrumental neutron activation method required 5 g samples, and consequently the distance between samples was less than 1 cm. Though the Devonian samples studied had a high probability of locating an Ir anomaly, none was found. The highest Ir values were between 0.2 and 2 percent of those reported for the marine and terrestrial Ir analyses at the Cretaceous-Tertiary boundary, and Devonian pyrite-rich sediments did not exhibit high Ir concentrations.

CO Adsorption on Reconstructed Ir(100) Surfaces from UHV to mbar Pressure: A LEED, TPD, and PM-IRAS Study

PubMed Central

2016-01-01

Clean and stable surface modifications of an iridium (100) single crystal, i.e., the (1 × 1) phase, the (5 × 1) reconstruction, and the oxygen-terminated (2 × 1)-O surface, were prepared and characterized by low energy electron diffraction (LEED), temperature-programmed desorption (TPD), infrared reflection absorption spectroscopy (IRAS) and polarization modulation IRAS (PM-IRAS). The adsorption of CO in UHV and at elevated (mbar) pressure/temperature was followed both ex situ and in situ on all three surface modifications, with a focus on mbar pressures of CO. The Ir(1 × 1) surface exhibited c(4 × 2)/c(2 × 2) and c(6 × 2) CO structures under low pressure conditions, and remained stable up to 100 mbar and 700 K. For the (2 × 1)-O reconstruction CO adsorption induced a structural change from (2 × 1)-O to (1 × 1), as confirmed by LEED, TPD, and IR. For Ir (2 × 1)-O TPD indicated that CO reacted with surface oxygen forming CO2. The (5 × 1) reconstruction featured a reversible and dynamic behavior upon CO adsorption, with a local lifting of the reconstruction to (1 × 1). After CO desorption, the (5 × 1) structure was restored. All three reconstructions exhibited CO adsorption with on-top geometry, as evidenced by IR. With increasing CO exposure the resonances shifted to higher wavenumber, due to adsorbate–adsorbate and adsorbate–substrate interactions. The largest wavenumber shift (from 2057 to 2100 cm–1) was observed for Ir(5 × 1) upon CO dosing from 1 L to 100 mbar. PMID:27257467

Performance of an autonomously deployable telemetered deep ocean seismic observatory

NASA Astrophysics Data System (ADS)

Berger, Jonathan; Laske, Gabe; Orcutt, John; Babcock, Jeffrey

2016-04-01

We describe a transformative technology that can provide near real-time telemetry of sensor data from the ocean bottom without a moored buoy or a cable to shore. The breakthrough technology that makes this system possible is an autonomous surface vehicle called a Wave Glider developed by Liquid Robotics, which harvests wave and solar energy for motive and electrical power. For navigation, the wave glider is equipped with a small computer, a GPS receiver, a rudder, solar panels and batteries, AIS ship detection receiver, weather station, and an Iridium satellite modem. Wave gliders have demonstrated trans-oceanic range and long-term station keeping capabilities. We present results from several deployments of a prototype system that demonstrate the feasibility of this concept. The system comprises ocean bottom package (OBP) and an ocean surface gateway (OSG). Acoustic communications connect the OBP instruments with OSG while communications between the gateway and land are provided by the Iridium satellite constellation. The most recent deployment of the OBP was off the edge of the Patton Escarpment some 300 km west of San Diego in 4000 m of water. The OSG was launched about 30 km west of San Diego harbor and programmed to navigate to the site of the ocean bottom package. Arriving after 161 hours, the OSG then commenced holding station at the site for the next 68 days. Speeds over-the-ground varied with wind, wave, and surface current conditions but averaged 0.5 m/s while winds varied between 0 m/s and 17 m/s and wave heights between 0.2 m and 5.9 m. Over this period the median total data latency was 260 s and the data loss less that 0.2% when the wave glider was within 1.5 km of the central point. We have also tested a full-scale model of a towable ocean bottom package, which demonstrated that a wave glider could tow and navigate an autonomously deployable ocean bottom package. Taken together, these tests have demonstrated that the concept is viable for long-term deployment as a high-seas seismographic station. The next generation will incorporate a towable OBP and a keel mounted rather than towed acoustic modem on the OSG. The longevity of the bottom package will be limited by its energy supply but at least two years is feasible while telemetering 1 sps data streams continuously plus an average of 1 hour /day of 40 sps data-on-demand. Biofouling is likely to be the limiting factor on the length of operation of a single OSG but a relief unit can be dispatched from a convenient port to take over operations.

Outer-Sphere Direction in Iridium C-H Borylation

PubMed Central

Roosen, Philipp C.; Kallepalli, Venkata A.; Chattopadhyay, Buddhadeb; Singleton, Daniel A.; Maleczka, Robert E.; Smith, Milton R.

2013-01-01

The NHBoc group affords ortho selective C–H borylations in arenes and alkenes. Experimental and computational studies support an outer sphere mechanism where the N–H proton hydrogen bonds to a boryl ligand oxygen. The regioselectivities are unique and complement those of directed ortho metalations. PMID:22703452

Fuel Cells | Hydrogen and Fuel Cells | NREL

Science.gov Websites

Reduction Reaction for Ultrathin Uniform Pt/C Catalyst Layers without Influence from Nafion, Electrochimica Acta (2016) Suppression of Oxygen Reduction Reaction Activity on Pt-Based Electrocatalysts from Ionomer Durability of Iridium Nanoparticles in the Oxygen Evolution Reaction, Journal of the Electrochemical Society

Porous carbon-coated graphite electrodes for energy production from salinity gradient using reverse electrodialysis

NASA Astrophysics Data System (ADS)

Lee, Su-Yoon; Jeong, Ye-Jin; Chae, So-Ryong; Yeon, Kyeong-Ho; Lee, Yunkyu; Kim, Chan-Soo; Jeong, Nam-Jo; Park, Jin-Soo

2016-04-01

Performance of graphite foil electrodes coated by porous carbon black (i.e., Vulcan) was investigated in comparison with metal electrodes for reverse electrodialysis (RED) application. The electrode slurry that was used for fabrication of the porous carbon-coated graphite foil is composed of 7.2 wt% of carbon black (Vulcan X-72), 0.8 wt% of a polymer binder (polyvinylidene fluoride, PVdF), and 92.0 wt% of a mixing solvent (dimethylacetamide, DMAc). Cyclic voltammograms of both the porous carbon (i.e., Vulcan)-coated graphite foil electrode and the graphite foil electrode without Vulcan showed good reversibility in the hexacyanoferrate(III) (i.e., Fe(CN)63-) and hexacyanoferrate(II) (i.e., Fe(CN)64-) redox couple and 1 M Na2SO4 at room temperature. However, anodic and cathodic current of the Vulcan-coated graphite foil electrode was much higher than those of the graphite foil electrode. Using a bench-scale RED stack, the current-voltage polarization curve of the Vulcan-coated graphite electrode was compared to that of metal electrodes such as iridium (Ir) and platinum (Pt). From the results, it was confirmed that resistance of four different electrodes increased with the following order: the Vulcan-coated graphite foil

Waves and the Equilibrium Range at Ocean Weather Station P

DTIC Science & Technology

2013-11-08

spectral moments are computed onboard. The spectra are transmitted via Iridium satellite modem to the Coastal Data Information Program ( CDIP ) at the...Julie Thomas and Grant Cameron ( CDIP -SIO) provided the waverider data telemetry and data archiving. Wind data were provided by the PMEL-NOAA Ocean

Stereoselective Synthesis of Cyclometalated Iridium (III) Complexes: Characterization and Photophysical Properties

PubMed Central

Yang, Liangru; von Zelewsky, Alex; Nguyen, Huong P.; Muller, Gilles; Labat, Gaël; Stoeckli-Evans, Helen

2009-01-01

The stereoselective synthesis of a highly luminescent neutral Ir(III) complex comprising two bidentate chiral, cyclometalating phenylpyridine derivatives, and one acetylacetonate as ligands is described. The final complex and some intermediates were characterized by X-ray structural analysis, NMR-, CD-, and CPL-spectroscopy. PMID:20161195

Simulation of the potentiodynamic and galvanostatic phase formation in melts

NASA Astrophysics Data System (ADS)

Isaev, V. A.; Grishenkova, O. V.; Kosov, A. V.; Semerikova, O. L.; Zaykov, Yu. P.

2017-02-01

A general scheme is used to consider the initial stages of electrocrystallization under potentiodynamic and galvanostatic conditions. Proposed theoretical models are shown to agree well with the experimental results obtained during the electrodeposition of silver crystals on an iridium microelectrode from nitrate melt containing an excess background electrolyte.

76 FR 75523 - Vessel Monitoring Systems; Approved Mobile Transmitting Units and Communications Service...

Federal Register 2010, 2011, 2012, 2013, 2014

2011-12-02

... communications (email, eforms) and position services. This configuration is enabled through the Iridium Short... relevant features of the enhanced mobile transmitting unit (E-MTU) VMS and communications service providers... communications service providers (including specifications), please contact the VMS Support Center at phone (888...

ULTRAFINE INSOLUBLE IRIDIUM PARTICLES ARE NEGLIGIBLY TRANSLOCATED FROM LUNG EPITHELIUM TO EXTRAPULMONARY ORGANS. (R827354C004)

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...

Rhenium and Iridium Partitioning in Silicate and Magmatic Spinels: Implications for Planetary Magmatism and Mantles

NASA Technical Reports Server (NTRS)

Righter, K.

2001-01-01

Highly siderophile elements Re, Ru and Ir partition strongly into spinel structures with large octahedral sites. New experimental results for both magmatic and silicate spinels will be presented with a few planetary implications. Additional information is contained in the original extended abstract.

Electrochemical characterization of high frequency stimulation electrodes: role of electrode material and stimulation parameters on electrode polarization

NASA Astrophysics Data System (ADS)

Ghazavi, Atefeh; Cogan, Stuart F.

2018-06-01

Objective. With recent interest in kilohertz frequency electrical stimulation for nerve conduction block, understanding the electrochemistry and role of electrode material is important for assessing the safety of these stimulus protocols. Here we describe an approach to determining electrode polarization in response to continuous kilohertz frequency sinusoidal current waveforms. We have also investigated platinum, iridium oxide, and titanium nitride as coatings for high frequency electrodes. The current density distribution at 50 kHz at the electrode–electrolyte interface was also modeled to demonstrate the importance of the primary current distribution in supporting charge injection at high frequencies. Approach. We determined electrode polarization in response to sinusoidal currents with frequencies in the 1–50 kHz range and current amplitudes from 100 to 500 µA and 1–5 mA, depending on the electrode area. The current density distribution at the interface was modeled using the finite element method (FEM). Main results. At low frequencies, 1–5 kHz, polarization on the platinum electrode was significant, exceeding the water oxidation potential for high amplitude (5 mA) waveforms. At frequencies of 20 kHz or higher, the polarization was less than 300 mV from the electrode open circuit potential. The choice of electrode material did not play a significant role in electrode polarization at frequencies higher than 10 kHz. The current density distribution modeled at 50 kHz is non-uniform and this non-uniformity persists throughout charge delivery. Significance. At high frequencies (>10 kHz) electrode double-layer charging is the principal mechanism of charge-injection and selection of the electrode material has little effect on polarization, with platinum, iridium oxide, and titanium nitride exhibiting similar behavior. High frequency stimulation is dominated by a highly nonuniform primary current distribution.

Synthesis and Catalytic Applications of Multi-Walled Carbon Nanotube-Polyamidoamine Dendrimer Hybrids.

PubMed

Desmecht, Antonin; Steenhaut, Timothy; Pennetreau, Florence; Hermans, Sophie; Riant, Olivier

2018-06-20

Polyamidoamine (PAMAM) dendrimers were covalently immobilized on multi-walled carbon nanotubes (MWNT) via two 'grafting to' strategies. We demonstrate the existence of non-covalent interactions between the two components but outline the superiority of our two grafting approaches, namely xanthate and click chemistry. MWNT surfaces were functionalized with activated ester and propargylic moieties prior to their reaction with PAMAM or azido-PAMAM dendrimers, respectively. The grafting of PAMAM generations 0 to 3 was evaluated with X-ray photoelectron spectroscopy (XPS), thermogravimetric analysis (TGA) and transmission electron microscopy (TEM). The versatility of our hybrids was demonstrated by post-functionalization sequences involving copper alkyne-azide cycloaddition (CuAAC). We synthesized homogeneous supported iridium complexes at the extremities of the dendrimers. In addition, our materials were used as template for the encapsulation of Pd nanoparticles (NP), validating our nanocomposites for catalytic applications. The palladium-based catalyst was active for carbonylative coupling during 5 consecutive runs without loss of activity. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Surface Organometallic Chemistry of Supported Iridium(III) as a Probe for Organotransition Metal–Support Interactions in C–H Activation

DOE PAGES

Kaphan, David M.; Klet, Rachel C.; Perras, Frederic A.; ...

2018-05-11

Systematic study of the interactions between organometallic catalysts and metal oxide support materials is essential for the realization of rational design in heterogeneous catalysis. Herein we describe the stoichiometric and catalytic chemistry of a [Cp*(PMe 3)Ir(III)] complex chemisorbed on a variety of acidic metal oxides as a multifaceted probe for stereoelectronic communication between the support and organometallic center. Electrophilic bond activation was explored in the context of stoichiometric hydrogenolysis as well as catalytic H/D exchange. Further information was obtained from the observation of processes related to dynamic exchange between grafted organometallic species and those in solution. The supported organometallic speciesmore » were characterized by a variety of spectroscopic techniques including dynamic nuclear polarization-enhanced solid-state NMR spectroscopy, diffuse reflectance infrared Fourier transform spectroscopy, and X-ray absorption spectroscopy. Finally, strongly acidic modified metal oxides such as sulfated zirconia engender high levels of activity toward electrophilic bond activation of both sp 2 and sp 3 C–H bonds, including the rapid deuteration of methane at room temperature; however, the global trend for the supports studied here does not suggest a direct correlation between activity and surface Brønsted acidity.« less

In vivo operation of the Boston 15-channel wireless subretinal visual prosthesis

NASA Astrophysics Data System (ADS)

Shire, Douglas B.; Doyle, Patrick; Kelly, Shawn K.; Gingerich, Marcus D.; Chen, Jinghua; Cogan, Stuart F.; Drohan, William A.; Mendoza, Oscar; Theogarajan, Luke; Wyatt, John; Rizzo, Joseph F.

2010-02-01

This presentation concerns the engineering development of the Boston visual prosthesis for restoring useful vision to patients blind with degenerative retinal disease. A miniaturized, hermetically-encased, 15-channel wirelessly-operated retinal prosthetic was developed for implantation and pre-clinical studies in Yucatan mini-pig animal models. The prosthesis conforms to the eye and drives a microfabricated polyimide stimulating electrode array having sputtered iridium oxide electrodes. This array is implanted into the subretinal space using a specially-designed ab externo surgical technique; the bulk of the prosthesis is on the surface of the sclera. The implanted device includes a hermetic titanium case containing a 15-channel stimulator chip; secondary power/data receiving coils surround the cornea. Long-term in vitro pulse testing was also performed on the electrodes to ensure their stability over years of operation. Assemblies were first tested in vitro to verify wireless operation of the system in biological saline using a custom RF transmitter circuit and primary coils. Stimulation pulse strength, duration and frequency were programmed wirelessly using a computer with a custom graphical user interface. Operation of the retinal implant was verified in vivo in 3 minipigs for more than three months by measuring stimulus artifacts on the eye surface using contact lens electrodes.

Surface Organometallic Chemistry of Supported Iridium(III) as a Probe for Organotransition Metal–Support Interactions in C–H Activation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kaphan, David M.; Klet, Rachel C.; Perras, Frederic A.

Systematic study of the interactions between organometallic catalysts and metal oxide support materials is essential for the realization of rational design in heterogeneous catalysis. Herein we describe the stoichiometric and catalytic chemistry of a [Cp*(PMe 3)Ir(III)] complex chemisorbed on a variety of acidic metal oxides as a multifaceted probe for stereoelectronic communication between the support and organometallic center. Electrophilic bond activation was explored in the context of stoichiometric hydrogenolysis as well as catalytic H/D exchange. Further information was obtained from the observation of processes related to dynamic exchange between grafted organometallic species and those in solution. The supported organometallic speciesmore » were characterized by a variety of spectroscopic techniques including dynamic nuclear polarization-enhanced solid-state NMR spectroscopy, diffuse reflectance infrared Fourier transform spectroscopy, and X-ray absorption spectroscopy. Finally, strongly acidic modified metal oxides such as sulfated zirconia engender high levels of activity toward electrophilic bond activation of both sp 2 and sp 3 C–H bonds, including the rapid deuteration of methane at room temperature; however, the global trend for the supports studied here does not suggest a direct correlation between activity and surface Brønsted acidity.« less

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.

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.

Room-Temperature C-H Functionalization Sequence under Benchtop Conditions for the Undergraduate Chemistry Laboratory

ERIC Educational Resources Information Center

Chen, Shuming

2018-01-01

An iridium(III)-mediated C-H functionalization sequence involving a concerted cyclometalation-deprotonation/migratory insertion pathway is reported for the undergraduate chemistry laboratory. The air- and water-stable iridacycle intermediates are readily isolated and characterized by NMR spectroscopy. Both steps of the experiment are performed at…

A direct access to heterobimetallic complexes by roll-over cyclometallation.

PubMed

Schön, F; Leist, M; Neuba, A; Lang, J; Braun, C; Sun, Y; Niedner-Schatteburg, G; Bräse, S; Thiel, W R

2017-11-02

Complexes of the type [Cp*Ir(N,N')Cl] + (N,N' = 2-(2-dialkylaminopyrimidin-4-yl)pyrimidine) can undergo roll-over cyclometallation leading to a novel N,N'-donor site. Following this strategy heterobimetallic complexes including iridium(iii) and a Group X metal centre in the oxidation state +II were achieved.

Synthesis and Characterization of Heterobimetallic Iridium-Aluminum and Rhodium-Aluminum Complexes.

PubMed

Brewster, Timothy P; Nguyen, Tan H; Li, Zhongjing; Eckenhoff, William T; Schley, Nathan D; DeYonker, Nathan J

2018-02-05

We demonstrate the synthesis and characterization of a new class of late-transition-metal-aluminum heterobimetallic complexes via a novel synthetic pathway. Complexes of this type are exceedingly rare. Joint experimental and theoretical data sheds light on the electronic effect of ligands containing aluminum moieties on late-transition-metal complexes.

Functionalized polyfluorenes for use in optoelectronic devices

DOEpatents

Chichak, Kelly Scott [Clifton Park, NY; Lewis, Larry Neil [Scotia, NY; Cella, James Anthony [Clifton Park, NY; Shiang, Joseph John [Niskayuna, NY

2011-11-01

The present invention relates to process comprising reacting a polyfluorenes comprising at least one structural group of formula I ##STR00001## with an iridium (III) compound of formula II ##STR00002## The invention also relates to the polyfluorenes, which are products of the reaction, and the use of the polyfluorenes in optoelectronic devices.

A Study to Maximize the Learning Experience in the Physical Chemistry Laboratory

DTIC Science & Technology

1979-01-01

commercial instrument is equipped with a platinum- iridium ring of standard dimen- sions for which the dial has been calibrated to read directly in dynes...a standard procedure with antimony trichloride in chloroform to produce a blue color. The percent transmission of the incident filtered light for each

16 CFR 23.9 - Additional guidance for the use of quality marks.

Code of Federal Regulations, 2013 CFR

2013-01-01

...,” “karat,” “carat,” “silver,” “sterling,” “vermeil,” “platinum,” “iridium,” “palladium,” “ruthenium... those in which the words or terms “gold,” “karat,” “silver,” “vermeil,” “platinum” (or platinum group...

16 CFR 23.9 - Additional guidance for the use of quality marks.

Code of Federal Regulations, 2012 CFR

2012-01-01

...,” “karat,” “carat,” “silver,” “sterling,” “vermeil,” “platinum,” “iridium,” “palladium,” “ruthenium... those in which the words or terms “gold,” “karat,” “silver,” “vermeil,” “platinum” (or platinum group...

16 CFR 23.9 - Additional guidance for the use of quality marks.

Code of Federal Regulations, 2010 CFR

2010-01-01

...,” “karat,” “carat,” “silver,” “sterling,” “vermeil,” “platinum,” “iridium,” “palladium,” “ruthenium... those in which the words or terms “gold,” “karat,” “silver,” “vermeil,” “platinum” (or platinum group...

16 CFR 23.9 - Additional guidance for the use of quality marks.

Code of Federal Regulations, 2014 CFR

2014-01-01

...,” “karat,” “carat,” “silver,” “sterling,” “vermeil,” “platinum,” “iridium,” “palladium,” “ruthenium... those in which the words or terms “gold,” “karat,” “silver,” “vermeil,” “platinum” (or platinum group...

Changes Coming to the International System of Units

ERIC Educational Resources Information Center

Aubrecht, Gordon J., II

2012-01-01

The International System of Units (SI) is a coherent system based originally on measurements of properties of material objects. In more recent times, the adopted definitions depend on setting values of universal constants wherever possible. The last remaining human-made material object on which a standard is based is a platinum-iridium kilogram…

16 CFR 23.9 - Additional guidance for the use of quality marks.

Code of Federal Regulations, 2011 CFR

2011-01-01

...,” “karat,” “carat,” “silver,” “sterling,” “vermeil,” “platinum,” “iridium,” “palladium,” “ruthenium... those in which the words or terms “gold,” “karat,” “silver,” “vermeil,” “platinum” (or platinum group...

Visible Light Photocatalysis of [2+2] Styrene Cycloadditions via Energy Transfer

PubMed Central

Lu, Zhan; Yoon, Tehshik P.

2012-01-01

Hip to be square: Styrenes participate in [2+2] cycloadditions upon irradiation with visible light in the presence of an iridium(III) polypyridyl complex. In contrast to previous reports of visible light photoredox catalysis, the mechanism of this process involves photosensitization by energy transfer and not electron transfer. PMID:22965321

Highly Efficient Solution-Processed Deep-Red Organic Light-Emitting Diodes Based on an Exciplex Host Composed of a Hole Transporter and a Bipolar Host.

PubMed

Huang, Manli; Jiang, Bei; Xie, Guohua; Yang, Chuluo

2017-10-19

With the aim to achieve highly efficient deep-red emission, we introduced an exciplex forming cohost, 4,4',4″-tris(3-methylphenylphenylamino)triphenylamine (m-MTDATA): 2,5-bis(2-(9H-carbazol-9-yl)phenyl)-1,3,4-oxadiazole (o-CzOXD) (1:1). Due to the efficient triplet up-conversion processes upon the exciplex forming cohost, excellent performances of the devices were achieved with deep-red emission. Using the heteroleptic iridium complexes as the guest dopants, the solution-processed deep-red phosphorescent organic light-emitting diodes (PhOLEDs) with the iridium(III) bis(6-(4-(tert-butyl)phenyl)phenanthridine)acetylacetonate [(TP-BQ) 2 Ir(acac)]-based phosphorescent emitter exhibited an electroluminescent peak at 656 nm and a maximum external quantum efficiency (EQE) of 11.9%, which is 6.6 times that of the device based on the guest emitter doped in the polymer-based cohost. The unique exciplex with a typical hole transporter and a bipolar material is ideal and universal for hosting the red PhOLEDs and tremendously improves the device performances.

Iridium Complexes with Proton-Responsive Azole-Type Ligands as Effective Catalysts for CO 2 Hydrogenation

DOE PAGES

Ertem, Mehmed Zahid; Suna, Yuki; Himeda, Yuichiro; ...

2017-10-06

Pentamethylcyclopentadienyl iridium (Cp*Ir) complexes with bidentate ligands consisting of a pyridine ring and an electron-rich diazole ring were prepared. Their catalytic activity towards CO 2 hydrogenation in 2.0 M KHCO 3 aqueous solutions (pH 8.5) at 50 °C, under 1.0 MPa CO 2/H 2 (1:1) have been reported as an alternative to photo- and electrochemical CO 2 reduction. Bidentate ligands incorporating an electron-rich diazole ring improved the catalytic performance of the Ir complexes compared to the bipyridine ligand. Complexes 2, 4 and 6, possessing both a hydroxy group and an uncoordinated NH group, which are proton-responsive and capable of generatingmore » pendent-bases in basic media, recorded high initial TOF values of 1300 h -1, 1550 h -1 and 2000 h -1, respectively. Here, spectroscopic and computational investigations revealed that the reversible deprotonation changes the electronic properties of the complexes and causes interactions between pendent base and substrate and/or solvent water molecules, resulting in the high catalytic performance in basic media.« less

Efficient blue and green phosphorescent OLEDs with host material containing electronically isolated carbazolyl fragments

NASA Astrophysics Data System (ADS)

Grigalevicius, Saulius; Tavgeniene, Daiva; Krucaite, Gintare; Blazevicius, Dovydas; Griniene, Raimonda; Lai, Yi-Ning; Chiu, Hao-Hsuan; Chang, Chih-Hao

2018-05-01

Dry process-able host materials are well suited to realize high performance phosphorescent organic light-emitting diodes (OLED) with precise deposition of organic layers. We demonstrate in this study high efficiency green and blue phosphorescent OLED devices by employing 3-[bis(9-ethylcarbazol-3-yl)methyl]-9-hexylcarbazole based host material. By doping a typical green emitter of fac tris(2-phenylpyridine)iridium (Ir (ppy)3) in the compound the resultant dry-processed green device exhibited superior performance with low turn on voltage of 3.0 V and with peak efficiencies of 11.4%, 39.9 cd/A and 41.8 lm/W. When blue emitter of bis [2-(4,6-difluorophenyl)pyridinato-C2,N](picolinato)iridium (III) was used, the resultant blue device showed turn on voltage of 2.9 V and peak efficiencies of 9.4%, 21.4 cd/A and 21.7 lm/W. The high efficiencies may be attributed to the host possessing high triplet energy level, effective host-to-guest energy transfer and effective carrier injection balance.

Simple color tuning of phosphorescent dendrimer light emitting diodes

NASA Astrophysics Data System (ADS)

Namdas, Ebinazar B.; Anthopoulos, Thomas D.; Samuel, Ifor D. W.; Frampton, Michael J.; Lo, Shih-Chun; Burn, Paul L.

2005-04-01

A simple way of tuning the emission color in solution processed phosphorescent organic light emitting diodes is demonstrated. For each color a single emissive spin-coated layer consisting of a blend of three materials, a fac-tris(2-phenylpyridyl)iridium (III) cored dendrimer (Ir-G1) as the green emitter, a heteroleptic [bis(2-phenylpyridyl)-2-(2'-benzo[4,5-α]thienyl)pyridyl]iridium (III) cored dendrimer [Ir(ppy)2btp] as the red emitter, and 4,4'-bis(N-carbazolyl) biphenyl (CBP) as the host was employed. By adjusting the relative amount of green and red dendrimers in the blends, the color of the light emission was tuned from green to red. High efficiency two layer devices were achieved by evaporating a layer of electron transporting 1,3,5-tris(2-N-phenylbenzimidazolyl)benzene (TPBI) on top of the spin-coated emissive layer. A brightness of 100cd/m2 was achieved at drive voltages in the range 5.3-7.3 V. The peak external efficiencies at this brightness ranged from 31cd/A(18lm/W) to 7cd/A(4lm/W).

Iridium and trace element measurements from the Cretaceous-Tertiary boundary, site 752, Broken Ridge, Indian Ocean

NASA Technical Reports Server (NTRS)

Schuraytz, B. C.; O'Connell, S.; Sharpton, V. L.

1991-01-01

Fourteen samples spanning a 2.5 m interval that includes the Cretaceous-Tertiary (K/T) boundary from Hole 752B near the crest of Broken Ridge in the eastern Indian Ocean were studied in order to search for anomalous enrichments of iridium (Ir) and shock-metamorphosed quartz grains. No allogenic quartz grains larger than 10 microns were observed, hence the presence of quartz containing diagnostic evidence of shock-metamorphism could not be confirmed. Two Ir anomalies of 2.2 +/- 0.6 and 2.0 +/- 0.4 parts per billion (ppb) were measured in samples of dark green ash-bearing chalk at depths of 357.93 and 358.80 m below seafloor, respectively. These samples containing anomalous enrichments of Ir were taken from approximately 82 cm above and 5 cm below the extinction level of Globotruncanids. Our results are consistent with those of Michel et al., who observe elevated concentrations of Ir at these depths in addition to a larger Ir anomaly associated with the extinction level of Globotruncanids.

Spectroscopic, Electrochemical and DFT Studies of Phosphorescent Homoleptic Cyclometalated Iridium(III) Complexes Based on Substituted 4-Fluorophenylvinyl- and 4-Methoxyphenylvinylquinolines

PubMed Central

Adeloye, Adewale O.; Adekunle, Abolanle S.; Ramasami, Ponnadurai

2017-01-01

This study reports the synthesis and comparative investigation of the substituent effects of a new series of highly luminescent homoleptic tris-cyclometalated iridium(III) complexes of the type [Ir(N˄C)3]. These are based on two ligand type derivatives comprising of 4-fluorophenylvinylquinolines and 4-methoxyphenylvinylquinolines with electron-donating and/or electron-withdrawing groups as aryl substituents at 2-position. The structures of the ligands and their complexes were characterized by means of FT-IR, UV-Vis and NMR spectrometry complemented with photoluminescence and cyclic voltammetry. The photophysical properties of 2-aryl-4-(4-fluorophenylvinyl)quinoline and its corresponding complex were also studied using the density functional theory method. The photoluminescent properties of the ligands and the corresponding complexes showed high fluorescent intensities and quantum yields in solvents of different polarities. The photoluminescence spectra of the complexes in solid film, showed common transmission curves at longer wavelengths maximum (λem = 697 nm) possibly originating from the interference of scattered light of higher-order transmission of monochromators. PMID:28934145

A search for evidence of large body Earth impacts associated with biological crisis zones in the fossil record

NASA Technical Reports Server (NTRS)

Orth, C. J.; Gilmore, J. S.; Knight, J. D.

1985-01-01

The natural history of the Earth, how the present plant and animal species developed, how others completely died out, etc., was studied. The rock strata sampled and studied were at the time of deposition at sea bottom. It was found that, exactly at the stratigraphic level corresponding to the extinction, a thin clay layer was greatly enriched in the the rare element iridium. It was hypothesized that the excess irridium at the boundary came from a large steroid like object that hit the earth, and that the impact of this object threw up a dust cloud dense enough and long lasting enough to bring about the extinction of a wide variety of plants and animals, producing the unique break in in the fossil record, the cretaceous-tertiary boundary. The same iridium and platinum metals enrichement are found in a thin clay layer that corresponds with the boundary as difined by sudden radical changes in plant populations. The irridium enrichement is confirmed at other fresh water origin rites in the Raton Basin.

Cross section of α-induced reactions on iridium isotopes obtained from thick target yield measurement for the astrophysical γ process

NASA Astrophysics Data System (ADS)

Szücs, T.; Kiss, G. G.; Gyürky, Gy.; Halász, Z.; Fülöp, Zs.; Rauscher, T.

2018-01-01

The stellar reaction rates of radiative α-capture reactions on heavy isotopes are of crucial importance for the γ process network calculations. These rates are usually derived from statistical model calculations, which need to be validated, but the experimental database is very scarce. This paper presents the results of α-induced reaction cross section measurements on iridium isotopes carried out at first close to the astrophysically relevant energy region. Thick target yields of 191Ir(α,γ)195Au, 191Ir(α,n)194Au, 193Ir(α,n)196mAu, 193Ir(α,n)196Au reactions have been measured with the activation technique between Eα = 13.4 MeV and 17 MeV. For the first time the thick target yield was determined with X-ray counting. This led to a previously unprecedented sensitivity. From the measured thick target yields, reaction cross sections are derived and compared with statistical model calculations. The recently suggested energy-dependent modification of the α + nucleus optical potential gives a good description of the experimental data.

Iridium Complexes with Proton-Responsive Azole-Type Ligands as Effective Catalysts for CO2 Hydrogenation.

PubMed

Suna, Yuki; Himeda, Yuichiro; Fujita, Etsuko; Muckerman, James T; Ertem, Mehmed Z

2017-11-23

Pentamethylcyclopentadienyl iridium (Cp*Ir) complexes with bidentate ligands consisting of a pyridine ring and an electron-rich diazole ring were prepared. Their catalytic activity toward CO 2 hydrogenation in 2.0 m KHCO 3 aqueous solutions (pH 8.5) at 50 °C, under 1.0 MPa CO 2 /H 2 (1:1) have been reported as an alternative to photo- and electrochemical CO 2 reduction. Bidentate ligands incorporating an electron-rich diazole ring improved the catalytic performance of the Ir complexes compared to the bipyridine ligand. Complexes 2, 4, and 6, possessing both a hydroxy group and an uncoordinated NH group, which are proton-responsive and capable of generating pendent bases in basic media, recorded high initial turnover frequency values of 1300, 1550, and 2000 h -1 , respectively. Spectroscopic and computational investigations revealed that the reversible deprotonation changes the electronic properties of the complexes and causes interactions between pendent base and substrate and/or solvent water molecules, resulting in high catalytic performance in basic media. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Tuning the Selectivity of Catalytic Carbon Dioxide Hydrogenation over Iridium/Cerium Oxide Catalysts with a Strong Metal-Support Interaction.

PubMed

Li, Siwei; Xu, Yao; Chen, Yifu; Li, Weizhen; Lin, Lili; Li, Mengzhu; Deng, Yuchen; Wang, Xiaoping; Ge, Binghui; Yang, Ce; Yao, Siyu; Xie, Jinglin; Li, Yongwang; Liu, Xi; Ma, Ding

2017-08-28

A one-step ligand-free method based on an adsorption-precipitation process was developed to fabricate iridium/cerium oxide (Ir/CeO 2 ) nanocatalysts. Ir species demonstrated a strong metal-support interaction (SMSI) with the CeO 2 substrate. The chemical state of Ir could be finely tuned by altering the loading of the metal. In the carbon dioxide (CO 2 ) hydrogenation reaction it was shown that the chemical state of Ir species-induced by a SMSI-has a major impact on the reaction selectivity. Direct evidence is provided indicating that a single-site catalyst is not a prerequisite for inhibition of methanation and sole production of carbon monoxide (CO) in CO 2 hydrogenation. Instead, modulation of the chemical state of metal species by a strong metal-support interaction is more important for regulation of the observed selectivity (metallic Ir particles select for methane while partially oxidized Ir species select for CO production). The study provides insight into heterogeneous catalysts at nano, sub-nano, and atomic scales. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Spectroscopic, Electrochemical and DFT Studies of Phosphorescent Homoleptic Cyclometalated Iridium(III) Complexes Based on Substituted 4-Fluorophenylvinyl- and 4-Methoxyphenylvinylquinolines.

PubMed

Adeloye, Adewale O; Mphahlele, Malose J; Adekunle, Abolanle S; Rhyman, Lydia; Ramasami, Ponnadurai

2017-09-21

This study reports the synthesis and comparative investigation of the substituent effects of a new series of highly luminescent homoleptic tris-cyclometalated iridium(III) complexes of the type [Ir(N ˄ C)₃]. These are based on two ligand type derivatives comprising of 4-fluorophenylvinylquinolines and 4-methoxyphenylvinylquinolines with electron-donating and/or electron-withdrawing groups as aryl substituents at 2-position. The structures of the ligands and their complexes were characterized by means of FT-IR, UV-Vis and NMR spectrometry complemented with photoluminescence and cyclic voltammetry. The photophysical properties of 2-aryl-4-(4-fluorophenylvinyl)quinoline and its corresponding complex were also studied using the density functional theory method. The photoluminescent properties of the ligands and the corresponding complexes showed high fluorescent intensities and quantum yields in solvents of different polarities. The photoluminescence spectra of the complexes in solid film, showed common transmission curves at longer wavelengths maximum (λ em = 697 nm) possibly originating from the interference of scattered light of higher-order transmission of monochromators.

Mitochondrial imaging in live or fixed tissues using a luminescent iridium complex.

PubMed

Sorvina, Alexandra; Bader, Christie A; Darby, Jack R T; Lock, Mitchell C; Soo, Jia Yin; Johnson, Ian R D; Caporale, Chiara; Voelcker, Nicolas H; Stagni, Stefano; Massi, Massimiliano; Morrison, Janna L; Plush, Sally E; Brooks, Douglas A

2018-05-29

Mitochondrial morphology is important for the function of this critical organelle and, accordingly, altered mitochondrial structure is exhibited in many pathologies. Imaging of mitochondria can therefore provide important information about disease presence and progression. However, mitochondrial imaging is currently limited by the availability of agents that have the capacity to image mitochondrial morphology in both live and fixed samples. This can be particularly problematic in clinical studies or large, multi-centre cohort studies, where tissue archiving by fixation is often more practical. We previously reported the synthesis of an iridium coordination complex [Ir(ppy) 2 (MeTzPyPhCN)] + ; where ppy is a cyclometalated 2-phenylpyridine and TzPyPhCN is the 5-(5-(4-cyanophen-1-yl)pyrid-2-yl)tetrazolate ligand; and showed that this complex (herein referred to as IraZolve-Mito) has a high specificity for mitochondria in live cells. Here we demonstrate that IraZolve-Mito can also effectively stain mitochondria in both live and fixed tissue samples. The staining protocol proposed is versatile, providing a universal procedure for cell biologists and pathologists to visualise mitochondria.

Iridium oxide pH sensor for biomedical applications. Case urea-urease in real urine samples.

PubMed

Prats-Alfonso, Elisabet; Abad, Llibertat; Casañ-Pastor, Nieves; Gonzalo-Ruiz, Javier; Baldrich, Eva

2013-01-15

This work demonstrates the implementation of iridium oxide films (IROF) grown on silicon-based thin-film platinum microelectrodes, their utilization as a pH sensor, and their successful formatting into a urea pH sensor. In this context, Pt electrodes were fabricated on Silicon by using standard photolithography and lift-off procedures and IROF thin films were growth by a dynamic oxidation electrodeposition method (AEIROF). The AEIROF pH sensor reported showed a super-Nerstian (72.9±0.9mV/pH) response between pH 3 and 11, with residual standard deviation of both repeatability and reproducibility below 5%, and resolution of 0.03 pH units. For their application as urea pH sensors, AEIROF electrodes were reversibly modified with urease-coated magnetic microparticles (MP) using a magnet. The urea pH sensor provided fast detection of urea between 78μM and 20mM in saline solution, in sample volumes of just 50μL. The applicability to urea determination in real urine samples is discussed. Copyright © 2012 Elsevier B.V. All rights reserved.

Distinguishing triplet energy transfer and trap-assisted recombination in multi-color organic light-emitting diode with an ultrathin phosphorescent emissive layer

DOE Office of Scientific and Technical Information (OSTI.GOV)

Xue, Qin, E-mail: xueqin19851202@163.com; Liu, Shouyin; Xie, Guohua

2014-03-21

An ultrathin layer of deep-red phosphorescent emitter tris(1-phenylisoquinoline) iridium (III) (Ir(piq){sub 3}) is inserted within different positions of the electron blocking layer fac-tris (1-phenylpyrazolato-N,C{sup 2′})-iridium(III) (Ir(ppz){sub 3}) to distinguish the contribution of the emission from the triplet exciton energy transfer/diffusion from the adjacent blue phosphorescent emitter and the trap-assisted recombination from the narrow band-gap emitter itself. The charge trapping effect of the narrow band-gap deep-red emitter which forms a quantum-well-like structure also plays a role in shaping the electroluminescent characteristics of multi-color organic light-emitting diodes. By accurately controlling the position of the ultrathin sensing layer, it is considerably easy tomore » balance the white emission which is quite challenging for full-color devices with multiple emission zones. There is nearly no energy transfer detectable if 7 nm thick Ir(ppz){sub 3} is inserted between the blue phosphorescent emitter and the ultrathin red emitter.« less

Effect of Trace Levels of Si on Microstructure and Grain Boundary Segregation in DOP-26 Iridium Alloy

NASA Astrophysics Data System (ADS)

Pierce, Dean; Muralidharan, Govindarajan; Heatherly, Lee; Fox, Ethan

2018-03-01

The thermodynamics and kinetics of Silicon (Si) segregation to grain boundaries in Iridium alloy DOP-26 with added trace levels of Si of 6, 11, 29, and 36 wppm was studied by Auger Electron Spectroscopy. The four alloys were annealed at 1500 or 1535 °C for 19 or 76 hours followed by cooling at three different rates. Si enrichment at the grain boundaries (GB) increased with increasing bulk Si content, with the grain boundary Si enrichment factors ranging from 62 to 344, depending on the bulk Si content and the cooling rate. Grain boundary Si contents increased with decreasing cooling rate in all alloys, indicating that Si GB segregation is influenced by both thermodynamic and kinetic factors in the alloys and temperature ranges of the study. A Langmuir-McLean isotherm-based model was successfully used to predict the temperature dependence of GB Si segregation in DOP-26 alloys with Si additions and estimate the temperature independent free energy of Si segregation to grain boundaries in DOP-26.

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

USGS Publications Warehouse

Desborough, George A.; Criddle, Alan J.

1984-01-01

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