Mesoporous silica nanoparticle supported PdIr bimetal catalyst for selective hydrogenation, and the significant promotional effect of Ir

NASA Astrophysics Data System (ADS)

Yang, Hui; Huang, Chao; Yang, Fan; Yang, Xu; Du, Li; Liao, Shijun

2015-12-01

A mesoporous silica nanoparticle (MSN) supported bimetal catalyst, PdIr/MSN, was prepared by a facile impregnation and hydrogen reduction method. The strong promotional effect of Ir was observed and thoroughly investigated. At the optimal molar ratio of Ir to Pd (NIr/NPd = 0.1), the activity of PdIr0.1/MSN was up to eight times and 28 times higher than that of monometallic Pd/MSN and Ir/MSN, respectively. The catalysts were characterized comprehensively by X-ray diffraction, transmission electron microscopy, X-ray photoelectron spectroscopy, and hydrogen temperature programmed reduction, which revealed that the promotional effect of Ir may be due to the enhanced dispersion of active components on the MSN, and to the intensified Pd-Ir electronic interaction caused by the addition of Ir.

The influence of nano-architectured CeOx supports in RhPd/CeO₂ for the catalytic ethanol steam reforming reaction

DOE PAGES

Divins, N. J.; Senanayake, S. D.; Casanovas, A.; ...

2015-01-19

The ethanol steam reforming (ESR) reaction has been tested over RhPd supported on polycrystalline ceria in comparison to structured supports composed of nanoshaped CeO₂ cubes and CeO₂ rods tailored towards the production of hydrogen. At 650-700 K the hydrogen yield follows the trend RhPd/CeO₂-cubes > RhPd/CeO₂ -rods > RhPd/CeO₂- polycrystalline, whereas at temperatures higher than 800 K the catalytic performance of all samples is similar and close to the thermodynamic equilibrium. The improved performance of RhPd/CeO₂-cubes and RhPd/CeO₂ -rods for ESR at low temperature is mainly ascribed to higher water-gas shift activity and a strong interaction between the bimetallic -more » oxide support interaction. STEM analysis shows the existence of RhPd alloyed nanoparticles in all samples, with no apparent relationship between ESR performance and RhPd particle size. X-ray diffraction under operating conditions shows metal reorganization on {100} and {110} ceria crystallographic planes during catalyst activation and ESR, but not on {111} ceria crystallographic planes. The RhPd reconstructing and tuned activation over ceria nanocubes and nanorods is considered the main reason for better catalytic activity with respect to conventional catalysts based on polycrystalline ceria« less

Charge partitioning and anomalous hole doping in Rh-doped Sr2IrO4

NASA Astrophysics Data System (ADS)

Chikara, S.; Fabbris, G.; Terzic, J.; Cao, G.; Khomskii, D.; Haskel, D.

2017-02-01

The simultaneous presence of sizable spin-orbit interactions and electron correlations in iridium oxides has led to predictions of novel ground states including Dirac semimetals, Kitaev spin liquids, and superconductivity. Electron and hole doping studies of spin-orbit assisted Mott insulator Sr2Ir O4 are being intensively pursued due to extensive parallels with the La2CuO4 parent compound of cuprate superconductors. In particular, the mechanism of charge doping associated with replacement of Ir with Rh ions remains controversial with profound consequences for the interpretation of electronic structure and transport data. Using x-ray absorption near edge structure measurements at the Rh L, K, and Ir L edges we observe anomalous evolution of charge partitioning between Rh and Ir with Rh doping. The partitioning of charge between Rh and Ir sites progresses in a way that holes are initially doped into the Jeff=1 /2 band at low x only to be removed from it at higher x values. This anomalous hole doping naturally explains the reentrant insulating phase in the phase diagram of Sr2Ir1 -xRhxO4 and ought to be considered when searching for superconductivity and other emergent phenomena in iridates doped with 4 d elements.

Highly Active and Stable MgAl2O4 Supported Rh and Ir Catalysts for Methane Steam Reforming: A Combined Experimental and Theoretical Study

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

Mei, Donghai; Glezakou, Vassiliki Alexandra; Lebarbier, Vanessa MC

2014-07-01

In this work we present a combined experimental and theoretical investigation of stable MgAl2O4 spinel-supported Rh and Ir catalysts for the steam methane reforming (SMR) reaction. Firstly, catalytic performance for a series of noble metal catalysts supported on MgAl2O4 spinel was evaluated for SMR at 600-850°C. Turnover rate at 850°C follows the order: Pd > Pt > Ir > Rh > Ru > Ni. However, Rh and Ir were found to have the best combination of activity and stability for methane steam reforming in the presence of simulated biomass-derived syngas. It was found that highly dispersed ~2 nm Rh andmore » ~1 nm Ir clusters were formed on the MgAl2O4 spinel support. Scanning Transition Electron Microscopy (STEM) images show that excellent dispersion was maintained even under challenging high temperature conditions (e.g. at 850°C in the presence of steam) while Ir and Rh catalysts supported on Al2O3 were observed to sinter at increased rates under the same conditions. These observations were further confirmed by ab initio molecular dynamics (AIMD) simulations which find that ~1 nm Rh and Ir particles (50-atom cluster) bind strongly to the MgAl2O4 surfaces via a redox process leading to a strong metal-support interaction, thus helping anchor the metal clusters and reduce the tendency to sinter. Density functional theory (DFT) calculations suggest that these supported smaller Rh and Ir particles have a lower work function than larger more bulk-like ones, which enables them to activate both water and methane more effectively than larger particles, yet have a minimal influence on the relative stability of coke precursors. In addition, theoretical mechanistic studies were used to probe the relationship between structure and reactivity. Consistent with the experimental observations, our theoretical modeling results also suggest that the small spinel-supported Ir particle catalyst is more active than the counterpart of Rh catalyst for SMR. This work was financially supported

X-ray Absorption Spectroscopy Study of the Effect of Rh doping in Sr2IrO4

PubMed Central

Sohn, C. H.; Cho, Deok-Yong; Kuo, C.-T.; Sandilands, L. J.; Qi, T. F.; Cao, G.; Noh, T. W.

2016-01-01

We investigate the effect of Rh doping in Sr2IrO4 using X-ray absorption spectroscopy (XAS). We observed appearance of new electron-addition states with increasing Rh concentration (x in Sr2Ir1−xRhxO4) in accordance with the concept of hole doping. The intensity of the hole-induced state is however weak, suggesting weakness of charge transfer (CT) effect and Mott insulating ground states. Also, Ir Jeff = 1/2 upper Hubbard band shifts to lower energy as x increases up to x = 0.23. Combined with optical spectroscopy, these results suggest a hybridisation-related mechanism, in which Rh doping can weaken the (Ir Jeff = 1/2)–(O 2p) orbital hybridisation in the in-planar Rh-O-Ir bond networks. PMID:27025538

Formation of an incoherent metallic state in Rh-doped Sr2IrO4

NASA Astrophysics Data System (ADS)

Louat, A.; Bert, F.; Serrier-Garcia, L.; Bertran, F.; Le Fèvre, P.; Rault, J.; Brouet, V.

2018-04-01

Sr2IrO4 is the archetype of the spin-orbit Mott insulator, but the nature of the metallic states that may emerge from this type of insulator is still not very well known. We study with angle-resolved photoemission the insulator-to-metal transition observed in Sr2Ir1 -xRhxO4 when Ir is substituted by Rh (0.02 Rh doping is that Ir and Rh, which are formally isovalent, adopt different charge states, a rather unusual and inhomogeneous situation. We show that the evolution to the metallic state can be essentially understood as a shift of the Fermi level into the lower Hubbard band of Sr2IrO4 . The Mott gap appears quite insensitive to the introduction of up to ˜20 % holes in this band. The metallic phase, which forms for x >0.07 , is not a Fermi liquid. It is characterized by the absence of quasiparticles, unrenormalized band dispersion compared to calculations, and an ˜30 -meV pseudogap on the entire Fermi surface.

Catalytic hydrodechlorination of trichloroethylene in a novel NaOH/2-propanol/methanol/water system on ceria-supported Pd and Rh catalysts.

PubMed

Cobo, Martha; Becerra, Jorge; Castelblanco, Miguel; Cifuentes, Bernay; Conesa, Juan A

2015-08-01

The catalytic hydrodechlorination (HDC) of high concentrations of trichloroethylene (TCE) (4.9 mol%, 11.6 vol%) was studied over 1%Pd, 1%Rh and 0.5%Pd-0.5%Rh catalysts supported on CeO2 under conditions of room temperature and pressure. For this, a one-phase system of NaOH/2-propanol/methanol/water was designed with molar percentages of 13.2/17.5/36.9/27.6, respectively. In this system, the alcohols delivered the hydrogen required for the reaction through in-situ dehydrogenation reactions. PdRh/CeO2 was the most active catalyst for the degradation of TCE among the evaluated materials, degrading 85% of the trichloroethylene, with alcohol dehydrogenation rates of 89% for 2-propanol and 83% for methanol after 1 h of reaction. Fresh and used catalysts were characterized by Transmission Electron Microscopy (TEM), X-ray Photoelectron Spectroscopy (XPS), and Thermogravimetric analysis (TGA). These results showed important differences of the active phase in each catalyst sample. Rh/CeO2 had particle sizes smaller than 1 nm and the active metal was partially oxidized (Rh(0)/Rh(+δ) ratio of 0.43). This configuration showed to be suitable for alcohols dehydrogenation. On the contrary, Pd/CeO2 showed a Pd completed oxidized and with a mean particle size of 1.7 nm, which seemed to be unfavorable for both, alcohols dehydrogenation and TCE HDC. On PdRh/CeO2, active metals presented a mean particle size of 2.7 nm and more reduced metallic species, with ratios of Rh(0)/Rh(+δ) = 0.67 and Pd(0)/Pd(+δ) = 0.28, which showed to be suitable features for the TCE HDC. On the other hand, TGA results suggested some deposition of NaCl residues over the catalyst surfaces. Thus, the new reaction system using PdRh/CeO2 allowed for the degradation of high concentrations of the chlorinated compound by using in situ hydrogen liquid donors in a reaction at room temperature and pressure. Copyright © 2015 Elsevier Ltd. All rights reserved.

Competition of Dzyaloshinskii-Moriya and Higher-Order Exchange Interactions in Rh /Fe Atomic Bilayers on Ir(111)

NASA Astrophysics Data System (ADS)

Romming, Niklas; Pralow, Henning; Kubetzka, André; Hoffmann, Markus; von Malottki, Stephan; Meyer, Sebastian; Dupé, Bertrand; Wiesendanger, Roland; von Bergmann, Kirsten; Heinze, Stefan

2018-05-01

Using spin-polarized scanning tunneling microscopy and density functional theory we demonstrate the occurrence of a novel type of noncollinear spin structure in Rh /Fe atomic bilayers on Ir(111). We find that higher-order exchange interactions depend sensitively on the stacking sequence. For fcc-Rh /Fe /Ir (111 ) , frustrated exchange interactions are dominant and lead to the formation of a spin spiral ground state with a period of about 1.5 nm. For hcp-Rh /Fe /Ir (111 ) , higher-order exchange interactions favor an up-up-down-down (↑↑↓↓) state. However, the Dzyaloshinskii-Moriya interaction at the Fe /Ir interface leads to a small angle of about 4° between adjacent magnetic moments resulting in a canted ↑↑↓↓ ground state.

Confining the nucleation and overgrowth of Rh to the {111} facets of Pd nanocrystal seeds: the roles of capping agent and surface diffusion.

PubMed

Xie, Shuifen; Peng, Hsin-Chieh; Lu, Ning; Wang, Jinguo; Kim, Moon J; Xie, Zhaoxiong; Xia, Younan

2013-11-06

This article describes a systematic study of the spatially confined growth of Rh atoms on Pd nanocrystal seeds, with a focus on the blocking effect of a surface capping agent and the surface diffusion of adatoms. We initially used Pd cuboctahedrons as the seeds to illustrate the concept and to demonstrate the capabilities of our approach. Because the Pd{100} facets were selectively capped by a layer of chemisorbed Br(–) or I(–) ions, we were able to confine the nucleation and deposition of Rh atoms solely on the {111} facets of a Pd seed. When the synthesis was conducted at a relatively low temperature, the deposition of Rh atoms followed an island growth mode because of the high Rh–Rh interatomic binding energy. We also facilitated the surface diffusion of deposited Rh atoms by increasing the reaction temperature and decreasing the injection rate for the Rh precursor. Under these conditions, the deposition of Rh on the Pd{111} facets was switched to a layered growth mode. We further successfully extended this approach to a variety of other types of Pd polyhedral seeds that contained Pd{111} and Pd{100} facets in different proportions on the surface. As expected, a series of Pd–Rh bimetallic nanocrystals with distinctive elemental distributions were obtained. We could remove the Pd cores through selective chemical etching to generate Rh hollow nanoframes with different types and degrees of porosity. This study clearly demonstrates the importance of facet capping, surface diffusion, and reaction kinetics in controlling the morphologies of bimetallic nanocrystals during a seed-mediated process. It also provides a new direction for the rational design and synthesis of nanocrystals with spatially controlled distributions of elements for a variety of applications.

Synthesis, Crystal Chemistry, and Physical Properties of Ternary Intermetallic Compounds An2T2X( An=Pu, Am; X=ln, Sn; T=Co, Ir, Ni, Pd, Pt, Rh)

NASA Astrophysics Data System (ADS)

Pereira, L. C. J.; Wastin, F.; Winand, J. M.; Kanellakopoulos, B.; Rebizant, J.; Spirlet, J. C.; Almeida, M.

1997-11-01

The synthesis, structural, and physical characterization of nine new ternary intermetallic compounds belonging to the isostructural An2T2Xfamily with the transuranium Pu and Am elements, namely, Pu 2Ni 2In, Pu 2Pd 2In, Pu 2Pt 2In, Pu 2Rh 2In, Pu 2Ni 2Sn, Pu 2Pd 2Sn, Pu 2Pt 2Sn, Am 2Ni 2Sn, and Am 2Pd 2Sn, are reported. From these compounds only Pu 2Rh 2In, Am 2Ni 2Sn, and Am 2Pd 2Sn melt incongruently. All of these compounds crystallize in a tetragonal U 3Si 2-type structure, with the space group P4/ mbm, ( Z=2) as most of the U and Np 2-2-1 compounds already found. In this structure, Anatoms occupy the 4 h( x1, x1+0.5, 0.5), Tthe 4 g( x2, x2+0.5, 0), and Xthe 2 a(0, 0, 0) positions. The average values of x1and x2are, respectively, 0.17 and 0.37. Single-crystal X-ray data were refined to R/ RW=0.045/0.066, 0.043/0.072, 0.066/0.080, 0.070/0.098, 0.029/0.048, 0.055/0.080, 0.073/0.096, 0.048/0.086, 0.048/0.065 for Pu 2Ni 2In, Pu 2Pd 2In, Pu 2Pt 2In, Pu 2Rh 2In, Pu 2Ni 2Sn, Pu 2Pd 2Sn, Pu 2Pt 2Sn, Am 2Ni 2Sn, and Am 2Pd 2Sn, respectively, for seven variables. The variation of the lattice parameters and the range of stability of the 2-2-1 phase are discussed in terms of the substitution of different An(actinide), T(transition metal), and X( p-electron) elements in their crystal structure. The possible role of spin fluctuations in the low-temperature behavior of the Pu samples is indicated by magnetic and electrical resistivity measurements.

First principles study of surface stability and segregation of PdRuRh ternary metal alloy system

NASA Astrophysics Data System (ADS)

Aspera, Susan Meñez; Arevalo, Ryan Lacdao; Nakanishi, Hiroshi; Kasai, Hideaki

2018-05-01

The recognized importance on the studies of alloyed materials is due to the high possibility of forming designer materials that caters to different applications. In any reaction and application, the stability and configuration of the alloy combination are important. In this study, we analyzed the surface stability and segregation of ternary metal alloy system PdRuRh through first principles calculation using density functional theory (DFT). We considered the possibility of forming phases as observed in the binary combinations of elements, i.e., completely miscible, and separating phases. With that, the model we analyzed for the ternary metal alloy slabs considers forming complete atomic miscibility, segregation of each component, and segregation of one component with mixing of the two other. Our results show that for the ternary combination of Pd, Rh and Ru, the Pd atoms have high tendency to segregate at the surface, while due to the high tendency of Ru and Rh to mix, core formation of a mixed RuRh is possible. Also, we determined that the trend of stability in the binary alloy system is a good determinant of stability in the ternary alloy system.

Absence of Local Fluctuating Dimers in Superconducting Ir 1-x(Pt,Rh) xTe 2

DOE PAGES

Yu, Runze; Banerjee, S.; Lei, H. C.; ...

2018-06-01

The compound IrTe2 is known to exhibit a transition to a modulated state featuring Ir-Ir dimers, with large associated atomic displacements. Partial substitution of Pt or Rh for Ir destabilizes the modulated structure and induces superconductivity. It has been proposed that quantum critical dimer fluctuations might be associated with the superconductivity. Here we test for such local dimer correlations and demonstrate their absence. X-ray pair distribution function approach reveals that the local structure of Ir 0.95Pt 0.05Te 2 and Ir 0.8Rh 0.2Te 2 dichalcogenide superconductors with compositions just past the dimer/superconductor boundary is explained well by a dimer-free model downmore » to 10 K, ruling out the possibility of there being nanoscale dimer fluctuations in this regime. This is inconsistent with the proposed quantum-critical-point-like interplay of the dimer state and superconductivity, and precludes scenarios for dimer fluctuations mediated superconducting pairing.« less

Absence of Local Fluctuating Dimers in Superconducting Ir 1-x(Pt,Rh) xTe 2

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

Yu, Runze; Banerjee, S.; Lei, H. C.

The compound IrTe2 is known to exhibit a transition to a modulated state featuring Ir-Ir dimers, with large associated atomic displacements. Partial substitution of Pt or Rh for Ir destabilizes the modulated structure and induces superconductivity. It has been proposed that quantum critical dimer fluctuations might be associated with the superconductivity. Here we test for such local dimer correlations and demonstrate their absence. X-ray pair distribution function approach reveals that the local structure of Ir 0.95Pt 0.05Te 2 and Ir 0.8Rh 0.2Te 2 dichalcogenide superconductors with compositions just past the dimer/superconductor boundary is explained well by a dimer-free model downmore » to 10 K, ruling out the possibility of there being nanoscale dimer fluctuations in this regime. This is inconsistent with the proposed quantum-critical-point-like interplay of the dimer state and superconductivity, and precludes scenarios for dimer fluctuations mediated superconducting pairing.« less

Absence of local fluctuating dimers in superconducting Ir1 -x(Pt,Rh ) xTe2

NASA Astrophysics Data System (ADS)

Yu, Runze; Banerjee, S.; Lei, H. C.; Sinclair, Ryan; Abeykoon, M.; Zhou, H. D.; Petrovic, C.; Guguchia, Z.; Bozin, E. S.

2018-05-01

The compound IrTe2 is known to exhibit a transition to a modulated state featuring Ir-Ir dimers, with large associated atomic displacements. Partial substitution of Pt or Rh for Ir destabilizes the modulated structure and induces superconductivity. It has been proposed that quantum critical dimer fluctuations might be associated with the superconductivity. Here we test for such local dimer correlations and demonstrate their absence. X-ray pair distribution function approach reveals that the local structure of Ir0 :95Pt0 :05Te2 and Ir0 :8Rh0 :2Te2 dichalcogenide superconductors with compositions just past the dimer/superconductor boundary is explained well by a dimer-free model down to 10 K, ruling out the possibility of there being nanoscale dimer fluctuations in this regime. This is inconsistent with the proposed quantum-critical-point-like interplay of the dimer state and superconductivity, and precludes scenarios for dimer fluctuations mediated superconducting pairing.

Realization of Ru-C Eutectic Point for Evaluation of W-Re and IrRh/Ir Thermocouples

NASA Astrophysics Data System (ADS)

Ogura, H.; Masuyama, S.; Izuchi, M.; Yamazawa, K.; Arai, M.

2015-03-01

Tungsten-rhenium (W-Re) thermocouples are widely used in industry for measurements at high temperatures, up to . Since the electromotive force (emf) of a W-Re thermocouple is known to change during exposure at high temperatures, evaluation of the emf stability is essential for measuring temperature precisely and for realizing precise temperature control used to ensure the quality of products subject to annealing processes. To evaluate precisely the thermoelectric stability around , two Ru-C cells (crucible and Ru-C eutectic alloy) were constructed in our laboratory. The key feature of the cells is that their dimensions are large to ensure there is sufficient immersion available to evaluate the homogeneity characteristics of the thermocouples. By using one of the Ru-C cells, the drift and inhomogeneity of Type C (tungsten-5 % rhenium vs tungsten-26 % rhenium) thermocouples during an exposure to high temperature around were evaluated. Furthermore, to explore possible applications of the eutectic point to other types of high-temperature thermocouples, the drift of an IrRh/Ir thermocouple (iridium-40 % rhodium vs iridium) was also evaluated using another Ru-C cell. The tests with W-Re and IrRh/Ir thermocouples demonstrate that the newly developed Ru-C cells can be used to successfully realize melting plateaux repeatedly. This enables the long-term drift measurements essential for the evaluation and improvement of high-temperature thermocouples. The results obtained in this study will also be useful for evaluating the uncertainty of thermocouple calibrations at around.

A novel IrNi@PdIr/C core-shell electrocatalyst with enhanced activity and durability for the hydrogen oxidation reaction in alkaline anion exchange membrane fuel cells.

PubMed

Qin, Bowen; Yu, Hongmei; Jia, Jia; Jun, Chi; Gao, Xueqiang; Yao, Dewei; Sun, Xinye; Song, Wei; Yi, Baolian; Shao, Zhigang

2018-03-08

Herein, a novel non-platinum core-shell catalyst, namely, IrNi@PdIr/C was prepared via a galvanic replacement reaction; it exhibits enhanced hydrogen oxidation activity and excellent stability under alkaline conditions. Electrochemical experiments demonstrated that the mass and specific activities at 50 mV of IrNi@PdIr/C are 2.1 and 2.2 times that of commercial Pt/C in 0.1 M KOH at 298 K, respectively. Moreover, accelerated degradation tests have shown that the electrochemically active surface area (ECSA) of IrNi@PdIr/C reduces by only 5.1%, which is almost 4 times less than that of commercial Pt/C and the mass activity at 50 mV of IrNi@PdIr/C after 2000 potential cycles is still 1.8 times higher than that of aged Pt/C. XRD and XPS analysis suggest that the enhanced HOR activity is attributed to the weakening of the hydrogen binding to the PdIr overlayers induced by the IrNi core. The better stability to potential cycling can be associated with the PdIr shell, which inhibits oxide formation. These results suggest that IrNi@PdIr/C is a promising non-platinum anode catalyst for alkaline anion exchange membrane fuel cells.

Structure symmetry determination and magnetic evolution in Sr 2Ir 1–xRh xO 4

DOE PAGES

Ye, Feng; Wang, Xiaoping; Hoffmann, Christina; ...

2015-11-23

We use single-crystal neutron diffraction to determine the crystal structure symmetry and to study the magnetic evolution in the rhodium doped iridates Sr 2Ir 1–xRh xO 4 (0 ≤ x ≤ 0.16). Throughout this doping range, the crystal structure retains a tetragonal symmetry (space group I4 1/a) with two distinct magnetic Ir sites in the unit cell forming staggered IrO 6 rotation. Upon Rh doping, the magnetic order is suppressed and the magnetic moment of Ir4+ is reduced from 0.21 μ B/Ir for x = 0 to 0.18 μ B/Ir for x = 0.12. As a result, the magnetic structuremore » at x = 0.12 is different from that of the parent compound while the moments remain in the basal plane.« less

Simultaneous leaching of Pt, Pd and Rh from automotive catalytic converters in chloride-containing solutions

NASA Astrophysics Data System (ADS)

Hasani, M.; Khodadadi, A.; Koleini, S. M. J.; Saeedi, A. H.; Meléndez, A. M.

2017-01-01

Dissolution of platinum group metals (PGM; herein Pt, Pd and Rh) in different chloride-based leaching systems from spent auto catalysts was performed. Response surface methodology and a five-level-five-factor central composite design were used to evaluate the effects of 1) temperature, 2) liquid-to-solid ratio, 3) stirring speed, 4) acid concentration and 5) particle size on extraction yield of PGM by aqua regia. Analysis of variance was used to determine the optimum conditions and most significant factors affecting the overall metal extraction. In the optimum conditions, leaching of Pt, Pd and Rh was 91.58%, 93.49% and 60.15%, respectively. The effect of different oxidizing agents on the PGM dissolution in chloride medium was studied comparatively in the following leaching systems: a) aqua regia/sulfuric acid mixture, b) hydrogen peroxide in sulfuric acid (piranha solution), c) sodium hypochlorite and d) copper(II). Dissolution of Rh is increased in both aqua regia and hydrogen peroxide/hydrochloric acid solutions by adding sulfuric acid.

[Determination of ru, rh and Pd in 30% trialkyl phosphine oxide (TRPO)-kerosene by inductively coupled plasma-atomic emission spectrum (ICP-AES)].

PubMed

Wang, Jian-Chen; Zhang, Lin

2013-07-01

The determination method of Ru, Rh and Pd in 30% TRPO-kerosene ICP-AES was studied by using aqueous calibration reference solution and choosing ethanol as diluent. The effects of the contents of 30% TRPO-kerosene and aqueous solution and the concentration of HNO3 in 30% TRPO-kerosene on the intensities of Ru, Rh and Pd were described. The optimized condition for preparing samples and calibration solutions was chosen as follows: The contents of 30% TRPO-kerosene and aqueous phase were 10% (V/V) and 5% (V/V) respectively and the concentration of HNO3 30% TRPO-kerosene was 0.20 mol x L(-1). The determination method of Au, Ru and Pd was set up according to the above condition. The detection limit, precision and recovery ratio of Ru, Rh and Pd are well. The method is not only used in determination of Au, Ru and Pd in 30% TRPO-kerosene, but also used in other organic phases.

Measurement of excitation functions of helion-induced reactions on enriched Ru targets for production of medically important 103Pd and 101mRh and some other radionuclides.

PubMed

Skakun, Ye; Qaim, S M

2008-05-01

Excitation functions were determined by the stacked-foil and induced radioactivity measurement technique for the reactions (100)Ru(alpha,n)(103)Pd, (101)Ru(alpha,2n)(103)Pd, (101)Ru((3)He,n)(103)Pd, and (102)Ru((3)He,2n)(103)Pd, producing the therapeutic radionuclide (103)Pd, and for the reactions (101)Ru((3)He,x)(101 m)Rh(Cum) and (102)Ru((3)He,x)(101 m)Rh(Cum), producing the medically interesting radionuclide (101 m)Rh. Data were also measured for the reactions (101)Ru((3)He,pn+d)(102 m,g)Rh, (102)Ru((3)He,p2n+dn+t)(102 m,g)Rh, (101)Ru((3)He,x)(101 g)Rh(Cum), (102)Ru((3)He,x)(101 g)Rh(Cum), (101)Ru((3)He,3n)(101)Pd, (102)Ru((3)He,4n)(101)Pd, (101)Ru((3)He,4n)(100)Pd, and (101)Ru((3)He,p3n+d2n+tn)(100)Rh, producing other palladium and rhodium isotopes/isomers. The energy ranges covered were up to 25 MeV for alpha-particles and up to 34 MeV for (3)He ions. The radioactivity of the radionuclide (103)Pd induced in thin metallic foils of the enriched ruthenium isotopes was measured by high-resolution X-ray spectrometry and the radioactivities of other radionuclides by gamma-ray spectrometry. The integral thick target yields of the radionuclide (103)Pd calculated from the excitation functions of the first four of the above-named reactions amount to 960, 1050, 50, and 725 kBq/microAh, respectively, at the maximum investigated energies of the incident particles. The integral thick target yields of the radionuclide (101 m)Rh amount to 16.1 and 2.9 MBq/microAh for (101)Ru and (102)Ru targets, respectively, at 34 MeV energy of incident (3)He ions. The integral yields of the other observed radionuclides were also deduced from the excitation functions of the above-mentioned respective nuclear reactions. The excitation functions and integral yields of some rare reaction products were also determined. The experimental excitation functions of some reactions are compared with the predictions of nuclear model calculations. In general, good agreement was obtained.

Partitioning of Ru, Rh, Pd, Re, Ir and Pt between liquid metal and silicate at high pressures and high temperatures - Implications for the origin of highly siderophile element concentrations in the Earth's mantle

NASA Astrophysics Data System (ADS)

Mann, Ute; Frost, Daniel J.; Rubie, David C.; Becker, Harry; Audétat, Andreas

2012-05-01

The apparent overabundance of the highly siderophile elements (HSEs: Pt-group elements, Re and Au) in the mantles of Earth, Moon and Mars has not been satisfactorily explained. Although late accretion of a chondritic component seems to provide the most plausible explanation, metal-silicate equilibration in a magma ocean cannot be ruled out due to a lack of HSE partitioning data suitable for extrapolations to the relevant high pressure and high temperature conditions. We provide a new data set of partition coefficients simultaneously determined for Ru, Rh, Pd, Re, Ir and Pt over a range of 3.5-18 GPa and 2423-2773 K. In multianvil experiments, molten peridotite was equilibrated in MgO single crystal capsules with liquid Fe-alloy that contained bulk HSE concentrations of 53.2-98.9 wt% (XFe = 0.03-0.67) such that oxygen fugacities of IW - 1.5 to IW + 1.6 (i.e. logarithmic units relative to the iron-wüstite buffer) were established at run conditions. To analyse trace concentrations of the HSEs in the silicate melt with LA-ICP-MS, two silicate glass standards (1-119 ppm Ru, Rh, Pd, Re, Ir, Pt) were produced and evaluated for this study. Using an asymmetric regular solution model we have corrected experimental partition coefficients to account for the differences between HSE metal activities in the multicomponent Fe-alloys and infinite dilution. Based on the experimental data, the P and T dependence of the partition coefficients (D) was parameterized. The partition coefficients of all HSEs studied decrease with increasing pressure and to a greater extent with increasing temperature. Except for Pt, the decrease with pressure is stronger below ˜6 GPa and much weaker in the range 6-18 GPa. This change might result from pressure induced coordination changes in the silicate liquid. Extrapolating the D values over a large range of potential P-T conditions in a terrestrial magma ocean (peridotite liquidus at P ⩽ 60-80 GPa) we conclude that the P-T-induced decrease of D

Thermodynamical study of boron doped CeX{sub 3} (X=Pd, Rh)

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

Sharma, Ramesh; Dwivedi, Shalini; Sharma, Yamini, E-mail: sharma.yamini62@gmail.com

2016-05-06

The structural, electronic, thermal, and optical properties of cubic non magnetic CeX{sub 3}(X=Pd, Rh) compounds which crystallize in the Au{sub 3}Cu structure have been studied using the projected augmented wave (PAW) method within the density functional theory (DFT) with generalized gradient approximation (GGA) for exchange correlation potential. In this paper we have calculated the band structure which are interpreted using the density of states. The optical properties such as extinction coefficients clearly illustrate the changes in CeX{sub 3} due to intercalation of boron. Lattice instability is observed in CePd{sub 3}B from the calculated dynamical properties.

Spin-orbit tuned metal-insulator transitions in single-crystal Sr₂Ir 1–xRh xO₄ (0≤x≤1)

DOE PAGES

Qi, T. F.; Korneta, O. B.; Li, L.; ...

2012-09-06

Sr₂IrO₄ is a magnetic insulator driven by spin-orbit interaction (SOI) whereas the isoelectronic and isostructural Sr₂RhO₄ is a paramagnetic metal. The contrasting ground states have been shown to result from the critical role of the strong SOI in the iridate. Our investigation of structural, transport, magnetic, and thermal properties reveals that substituting 4d Rh⁴⁺ (4d⁵) ions for 5d Ir⁴⁺ (5d⁵) ions in Sr₂IrO₄ directly reduces the SOI and rebalances the competing energies so profoundly that it generates a rich phase diagram for Sr₂Ir 1–xRh xO₄ featuring two major effects: (1) Light Rh doping (0 ≤ x ≤ 0.16) prompts amore » simultaneous and precipitous drop in both the electrical resistivity and the magnetic ordering temperature TC, which is suppressed to zero at x = 0.16 from 240 K at x = 0. (2) However, with heavier Rh doping [0.24 < x < 0.85 (±0.05)] disorder scattering leads to localized states and a return to an insulating state with spin frustration and exotic magnetic behavior that only disappears near x = 1. The intricacy of Sr₂Ir 1–xRh xO₄ is further highlighted by comparison with Sr₂Ir 1–xRu xO₄ where Ru⁴⁺ (4d⁴) drives a direct crossover from the insulating to metallic states.« less

A density functional theory study of self-regenerating catalysts LaFe(1-x)M(x)O(3-y) (M = Pd, Rh, Pt).

PubMed

Hamada, Ikutaro; Uozumi, Akifumi; Morikawa, Yoshitada; Yanase, Akira; Katayama-Yoshida, Hiroshi

2011-11-23

Periodic density functional theory was used to investigate the stability and electronic structures of precious-metal atoms in the vicinity of LaFe(1-x)M(x)O(3) (M = Pd, Rh, Pt) perovskite catalyst surfaces. It was found that the surface segregation of Pd and Pt is significantly stabilized by the introduction of O vacancies, whereas the solid-solution phase is favorable for Rh, suggesting an important role of O vacancies in the self-regeneration of Pd and Pt. On the basis of the results, we propose a possible scenario for the self-regeneration of the precious metal in the perovskite catalyst.

Unconventional superconductivity and quantum criticality in the heavy fermions CeIrSi3 and CeRhSi3

NASA Astrophysics Data System (ADS)

Landaeta, J. F.; Subero, D.; Catalá, D.; Taylor, S. V.; Kimura, N.; Settai, R.; Īnuki, Y.; Sigrist, M.; Bonalde, I.

2018-03-01

In most strongly correlated electron systems superconductivity appears nearby a magnetic quantum critical point (QCP) which is believed to cause unconventional behaviors. In order to explore this physics, we present here a study of the heavy-fermion superconductors CeIrSi3 and CeRhSi3 carried out using a newly developed system for high-resolution magnetic penetration-depth measurements under pressure. Superconductivity in CeIrSi3 shows a change from an excitation spectrum with a line-nodal gap to one which is entirely gapful when pressure is close but not yet at the QCP. In contrast, CeRhSi3 does not possess a T =0 quantum phase transition and the superconducting phase remains for all accessible pressures with a nodal gap. Combining both results suggests that in these compounds unconventional superconducting behaviors are rather connected with the coexisting antiferromagnetic order. This study provides another viewpoint on the interplay of superconductivity, magnetism, and quantum criticality in CeIrSi3 and CeRhSi3 and maybe in other heavy fermions.

Systematics of the temperature-dependent interplane resistivity in Ba(Fe 1-xM x)₂As₂ (M=Co, Rh, Ni, and Pd)

DOE PAGES

Tanatar, M. A.; Ni, N.; Thaler, A.; ...

2011-07-27

Temperature-dependent interplane resistivity ρ c(T) was measured systematically as a function of transition-metal substitution in the iron-arsenide superconductors Ba(Fe 1-xM x)₂As₂, M=Ni, Pd, Rh. The data are compared with the behavior found in Ba(Fe 1-xCo x)₂As₂, revealing resistive signatures of pseudogap. In all compounds we find resistivity crossover at a characteristic pseudogap temperature T* from nonmetallic to metallic temperature dependence on cooling. Suppression of T* proceeds very similarly in cases of Ni and Pd doping and much faster than in similar cases of Co and Rh doping. In cases of Co and Rh doping an additional minimum in the temperature-dependentmore » ρ c emerges for high dopings, when superconductivity is completely suppressed. These features are consistent with the existence of a charge gap covering part of the Fermi surface. The part of the Fermi surface affected by this gap is notably larger for Ni- and Pd-doped compositions than in Co- and Rh-doped compounds.« less

Roadside Accumulation of Pt, Pd, Rh and Other Trace Elements From Automobiles: Catalytic Converter Attrition and Platinum-Group Element Mobility in the Roadside Environment.

NASA Astrophysics Data System (ADS)

Ely, J. C.; Dahlheimer, S. R.; Neal, C. R.

2003-12-01

Elemental abundances of Pt, Pd and Rh have been documented across the industrialized world in roadside environments due to attrition of automotive catalytic converters (Zereini and Alt, 2000, Anthropogenic PGE Emissions, Springer, 308pp; Ely et al., 2001, EnvSci&Tech, 35:3816-3822; Whiteley and Murray, 2003, SciTotEnv, in press). In our ongoing study, the highest reported roadside Pt abundance 1.8 ppm has been found immediately adjacent to the road at a field site in South Bend, IN, USA. Furthermore, initial studies show positive correlations of Pt, Pd and Rh with some trace elements (Ni, Cu, Zn and Pb), which has been confirmed by further analysis for these and other elements (Ce, Cr). It has been demonstrated that elements such as Ce are present in catalytic converters at concentrations of 100's ppm to 3-wt.%. These elements are also being attrited with Pt, Pd and Rh and aerially transported and deposited. Our field site was established next to US-933 adjacent to the Notre Dame campus. Areas were cleared of the top 2-4 cm of soil (removing surficial Pt, Pd and Rh) at 1, 5, 10 and 50 meters from the roadside. Within 3 months the 1-meter site contained 67% of the initial Rh and Pt concentrations and 100% of the initial Pd concentration. The sites at 5, 10 and 50 meters showed similar results, in some cases exceeding the initial concentrations. After 6 months the concentrations of Pt, Pd and Rh were all within error of the initial concentrations, indicating steady state abundances had probably been reached. Grass samples from each site showed that washed vs. unwashed samples were within error of each other, and there may be a slight enrichment (approx. 1 ppb) in the grasses of Pd and Pt, but this enrichment was independent of distance from the road. The steady-state situation suggests that the PGEs are being removed from the immediate roadside environment, which requires that the metals are being oxidized and/or complexed in such a way to facilitate transport. The

Population pharmacokinetic/pharmacodynamic (PK/PD) modelling of the hypothalamic–pituitary–gonadal axis following treatment with GnRH analogues

PubMed Central

Tornøe, Christoffer W; Agersø, Henrik; Senderovitz, Thomas; Nielsen, Henrik A; Madsen, Henrik; Karlsson, Mats O; Jonsson, E Niclas

2007-01-01

Aims To develop a population pharmacokinetic/pharmacodynamic (PK/PD) model of the hypothalamic–pituitary–gonadal (HPG) axis describing the changes in luteinizing hormone (LH) and testosterone concentrations following treatment with the gonadotropin-releasing hormone (GnRH) agonist triptorelin and the GnRH receptor blocker degarelix. Methods Fifty-eight healthy subjects received single subcutaneous or intramuscular injections of 3.75 mg of triptorelin and 170 prostate cancer patients received multiple subcutaneous doses of degarelix of between 120 and 320 mg. All subjects were pooled for the population PK/PD data analysis. A systematic population PK/PD model-building framework using stochastic differential equations was applied to the data to identify nonlinear dynamic dependencies and to deconvolve the functional feedback interactions of the HPG axis. Results In our final PK/PD model of the HPG axis, the half-life of LH was estimated to be 1.3 h and that of testosterone 7.69 h, which corresponds well with literature values. The estimated potency of LH with respect to testosterone secretion was 5.18 IU l−1, with a maximal stimulation of 77.5 times basal testosterone production. The estimated maximal triptorelin stimulation of the basal LH pool release was 1330 times above basal concentrations, with a potency of 0.047 ng ml−1. The LH pool release was decreased by a maximum of 94.2% by degarelix with an estimated potency of 1.49 ng ml−1. Conclusions Our model of the HPG axis was able to account for the different dynamic responses observed after administration of both GnRH agonists and GnRH receptor blockers, suggesting that the model adequately characterizes the underlying physiology of the endocrine system. PMID:17096678

A first-principles study on the interaction of biogas with noble metal (Rh, Pt, Pd) decorated nitrogen doped graphene as a gas sensor: A DFT study

NASA Astrophysics Data System (ADS)

Zhao, Chunjiang; Wu, Huarui

2018-03-01

Density functional theory calculations are carried out to investigate the adsorption characteristics of methane (CH4), carbon dioxide (CO2), hydrogen (H2), hydrogen sulfide (H2S), nitrogen (N2), and oxygen (O2) on the surface of pyridine-like nitrogen doped graphene (PNG) as well as noble metal (Rh, Pt, Pd) decorated PNG to elaborate their potentials as gas sensors. The adsorption intensities of biogas on noble metal (Rh, Pt, Pd) decorated PNG are in the order of O2> H2S> N2> CH4> CO2> H2, which are corresponded to the order of their sensitivity on surface. Compared with biogas adsorption on pristine PNG, there exist higher adsorption ability, higher charge transfer and higher orbital hybridization upon adsorption on noble metal (Rh, Pt, Pd) decorated PNG. Consequently, the noble metal (Rh, Pt, Pd) decorated PNG can transform the existence of CH4, CO2, H2, H2S, N2, and O2 molecules into electrical signal and they could potentially be used as ideal sensors for detection of biogas in ambient situation.

Oxidative leaching process with cupric ion in hydrochloric acid media for recovery of Pd and Rh from spent catalytic converters.

PubMed

Nogueira, C A; Paiva, A P; Oliveira, P C; Costa, M C; da Costa, A M Rosa

2014-08-15

The recycling of platinum-group metals from wastes such as autocatalytic converters is getting growing attention due to the scarcity of these precious metals and the market pressure originated by increase of demand in current and emerging applications. Hydrometallurgical treatment of such wastes is an alternative way to the most usual pyrometallurgical processes based on smelter operations. This paper focuses on the development of a leaching process using cupric chloride as oxidising agent, in HCl media, for recovery of palladium and rhodium from a spent catalyst. The chloride media allows the adequate conditions for oxidising and solubilising the metals, as demonstrated by equilibrium calculations based on thermodynamic data. The experimental study of the leaching process revealed that Pd solubilisation is clearly easier than that of Rh. The factors temperature, time, and HCl and Cu(2+) concentrations were significant regarding Pd and Rh leaching, the latter requiring higher factor values to achieve the same results. Leaching yields of 95% Pd and 86% Rh were achieved under optimised conditions (T = 80 °C, t = 4h, [HCl] = 6M, [Cu(2+)] = 0.3M). Copyright © 2014 Elsevier B.V. All rights reserved.

A two-state computational investigation of methane C--H and ethane C--C oxidative addition to [CpM(PH3)]n+ (M = Co, Rh, Ir; n = 0, 1).

PubMed

Petit, Alban; Richard, Philippe; Cacelli, Ivo; Poli, Rinaldo

2006-01-11

Reductive elimination of methane from methyl hydride half-sandwich phosphane complexes of the Group 9 metals has been investigated by DFT calculations on the model system [CpM(PH(3))(CH(3))(H)] (M = Co, Rh, Ir). For each metal, the unsaturated product has a triplet ground state; thus, spin crossover occurs during the reaction. All relevant stationary points on the two potential energy surfaces (PES) and the minimum energy crossing point (MECP) were optimized. Spin crossover occurs very near the sigma-CH(4) complex local minimum for the Co system, whereas the heavier Rh and Ir systems remain in the singlet state until the CH(4) molecule is almost completely expelled from the metal coordination sphere. No local sigma-CH(4) minimum was found for the Ir system. The energetic profiles agree with the nonexistence of the Co(III) methyl hydride complex and with the greater thermal stability of the Ir complex relative to the Rh complex. Reductive elimination of methane from the related oxidized complexes [CpM(PH(3))(CH(3))(H)](+) (M = Rh, Ir) proceeds entirely on the spin doublet PES, because the 15-electron [CpM(PH(3))](+) products have a doublet ground state. This process is thermodynamically favored by about 25 kcal mol(-1) relative to the corresponding neutral system. It is essentially barrierless for the Rh system and has a relatively small barrier (ca. 7.5 kcal mol(-1)) for the Ir system. In both cases, the reaction involves a sigma-CH(4) intermediate. Reductive elimination of ethane from [CpM(PH(3))(CH(3))(2)](+) (M = Rh, Ir) shows a similar thermodynamic profile, but is kinetically quite different from methane elimination from [CpM(PH(3))(CH(3))(H)](+): the reductive elimination barrier is much greater and does not involve a sigma-complex intermediate. The large difference in the calculated activation barriers (ca. 12.0 and ca. 30.5 kcal mol(-1) for the Rh and Ir systems, respectively) agrees with the experimental observation, for related systems, of oxidatively

Self-enhanced N-(aminobutyl)-N-(ethylisoluminol) derivative-based electrochemiluminescence immunosensor for sensitive laminin detection using PdIr cubes as a mimic peroxidase

NASA Astrophysics Data System (ADS)

Jiang, Xinya; Wang, Huijun; Wang, Haijun; Zhuo, Ying; Yuan, Ruo; Chai, Yaqin

2016-04-01

Herein, a self-enhanced N-(aminobutyl)-N-(ethylisoluminol) (ABEI) derivative-based electrochemiluminescence (ECL) immunosensor was constructed for the determination of laminin (LN) using PdIr cubes as a mimic peroxidase for signal amplification. Initially, PdIr cubes with efficient peroxidase mimicking properties, large specific surface areas, and good stability and uniformity were synthesized. Then, l-cysteine (l-Cys) and ABEI were immobilized on the PdIr cubes to form the self-enhanced ECL nanocomplex (PdIr-l-Cys-ABEI). In this nanocomplex, PdIr cubes, whose catalytic constant is higher than that of horseradish peroxidase (HRP), could effectively catalyze H2O2 decomposition and thus enhance the ECL intensity of ABEI. Moreover, PdIr cubes can be easily modified with functional groups, which make them adaptable to desired supported platforms. On the other hand, l-Cys as a coreactant of ABEI could effectively enhance the luminous efficiency due to the intramolecular ECL reaction which could reduce the energy loss between l-Cys and ABEI by giving a shorter electron transfer distance. The developed strategy combined an ABEI derivative as a self-enhanced ECL luminophore and PdIr cubes as a mimic peroxidase, resulting in a significantly enhanced ECL signal output. Also, the strategy showed high sensitivity and selectivity for LN, which suggested that our new approach could be potentially applied in monitoring different proteins.

A multi-frequency EPR and ENDOR study of Rh and Ir complexes in alkali and silver halides

NASA Astrophysics Data System (ADS)

Callens, F.; Vrielinck, H.; Matthys, P.

2003-01-01

Aliovalent Rh and Ir cations have been frequently used to influence the photographic properties of silver halide emulsions. The doping introduces several types of related defects with distinct trapping and recombination properties. EPR and ENDOR are, in principle, ideally suited for the determination of the microscopic structure of the individual centres but it will be demonstrated that well-chosen, sometimes sophisticated multi-frequency experiments are necessary in order to (partially) reach this goal. Model studies on single crystals of AgCl and NaCl also appeared indispensable for the unravelling of the spectra. In the review of Rh-centres in NaCl and AgCl special attention is paid to methods that allow to detect cation vacancies near Rh2+ complexes. An alternative explanation for the high temperature behaviour of the [RhCl6](4-) complexes in AgCl is presented.

Ternary lithium stannides Li xT 3Sn 7-x ( T=Rh, Ir)

NASA Astrophysics Data System (ADS)

Sreeraj, Puravankara; Kurowski, Daniel; Hoffmann, Rolf-Dieter; Wu, Zhiyun; Pöttgen, Rainer

2005-11-01

The ternary stannides Li xRh 3Sn 7-x ( x=0.45, 0.64, 0.80) and Li xIr 3Sn 7-x ( x=0.62 and 0.66) were synthesized from the elements in sealed tantalum tubes in a water-cooled sample chamber of an induction furnace. The samples were characterized by X-ray diffraction on powders and single crystals. The stannides adopt the cubic Ir 3Ge 7-type structure (space group Im3¯m, Z=4). In this structure type the tin atoms occupy the Wyckoff positions 12 d and 16 f and form two interpenetrating frameworks consisting of cubes and square antiprisms. The rhodium and iridium atoms center the square antiprisms and are arranged in pairs. With increasing lithium substitution the lattice parameter of Ir 3Sn 7 (936.7) decreases via 932.2 pm ( x=0.62) to 931.2 pm ( x=0.66), while the Ir-Ir distance remains almost the same (290 pm). A similar trend is observed for the rhodium compounds. The lithium atoms substitute Sn on both framework sites. However, the 16 f site shows a substantially larger preference for Li occupation. This is in contrast to the isotypic magnesium based compounds.

Regulation of GnRH I receptor gene expression by the GnRH agonist triptorelin, estradiol, and progesterone in the gonadotroph-derived cell line alphaT3-1.

PubMed

Weiss, J M; Polack, S; Treeck, O; Diedrich, K; Ortmann, O

2006-08-01

The secretion of luteinizing hormone (LH) and the GnRH receptor (GnRH-R) concentration are modulated by ovarian steroids and GnRH. To elucidate whether this regulation is due to alterations at the transcriptional level, we examined the GnRH I-R mRNA expression in the gonadotroph-derived cell line alphaT3-1 treated with different estradiol and progesterone paradigms and the GnRH I agonist triptorelin. alphaT3-1 cells were treated with different steroid paradigms: 1 nM estradiol or 100 nM progesterone for 48 h alone or in combination. Cells were exposed to 10 nM or 100 pM triptorelin for 30 min, 3 h, 9 h, or, in pulsatile way, with a 5-min pulse per hour. The GnRH I-R mRNA was determined by Northern blot analysis. GnRH I-R mRNA from cells treated with continuous triptorelin decreased in a time- and concentration-dependent manner. Pulsatile triptorelin increased GnRH I-R gene expression. Progesterone alone further enhanced this effect, whereas estradiol and its combination with progesterone diminished it. Continuous combined treatment with estradiol and progesterone lead to a significant decrease of GnRH I-R mRNA by 30% and by 35% for estradiol alone. The addition of 10 nM triptorelin for 30 min or 3 h could not influence that steroid effect. In conclusion, estradiol and progesterone exclusively decreased GnRH I-R mRNA in alphaT3-1 cells no matter whether they are treated additionally with the GnRH I agonist triptorelin. The enhanced sensitivity of gonadotrophs and GnRH I-R upregulation by estradiol is not due to increased GnRH I gene expression because GnRH I-R mRNA is downregulated by estradiol and progesterone. Other pathways of the GnRH I-R signal transduction might be involved.

Determination of Pd, Pt and Rh in vehicles escape fumes by GF-AAS and ICP-OES.

PubMed

Goncalves, Antonio; Domínguez, José R; Alvarado, José

2008-04-15

Automotive exhaust gases from vehicles using catalytic converters were filtered through cellulose filter papers to collect suspended particles expulsed along with the engine's escape fumes. A specially designed sample collector was used for supporting the filter papers during collection. The collector was manufactured from a new car's exhaust pipe. A cellulose circular paper filter, 11 cm diameter, was attached to one end of the pipe and kept centered by pressing it against the borders of the pipe by means of a perforated aluminum cap, slightly wider than the pipe, used to cover this end of the collector. Filter papers loaded with the solid particles were acid-digested using a modified domestic microwave oven to bring the solid material into solution. The resulting solutions were analyzed for Pt by graphite furnace atomic absorption spectrometry (GF-AAS) and for Pd and Rh by inductively coupled plasma (ICP-OES). Results indicate that concentration of these analytes in the particulate is higher for new vehicles, having new catalytic converters, than for old ones. Maximum Pd, Pt and Rh in the samples analyzed were found to be 5.36, 12.60 and 1.03 microg g(-1), respectively.

Compositional effects in Ru, Pd, Pt, and Rh-doped mesoporous tantalum oxide catalysts for ammonia synthesis.

PubMed

Yue, Chaoyang; Qiu, Longhui; Trudeau, Michel; Antonelli, David

2007-06-11

A series of early metal-promoted Ru-, Pd-, Pt-, and Rh-doped mesoporous tantalum oxide catalysts were synthesized using a variety of dopant ratios and dopant precursors, and the effects of these parameters on the catalytic activity of NH3 synthesis from H2 and N2 were explored. Previous studies on this system supported an unprecedented mechanism in which N-N cleavage occurred at the Ta sites rather than on Ru. The results of the present study showed, for all systems, that Ba is a better promoter than Cs or La and that the nitrate is a superior precursor for Ba than the isopropoxide or the hydroxide. 15N-labeling studies showed that residual nitrate functions as the major ammonia source in the first hour but that it does not account for the ammonia produced after the nitrate is completely consumed. Ru3(CO)12 proved to be a better Ru precursor than RuCl(3).3H2O, and an almost linear increase in activity with increasing Ru loading level was observed at 350 degrees C (623 K). However, at 175 degrees C (448 K), the increase in Ru had no effect on the reaction rate. Pd functioned with comparable rates to Ru, while Pt and Rh functioned far less efficiently. The surprising activities for the Pd-doped catalysts, coupled with XPS evidence for low-valent Ta in this catalyst system, support a mechanism in which cleavage of the N-N triple bond occurs on Ta rather than the precious metal because the Ea value for N-N cleavage on Pd is 2.5 times greater than that for Ru, and the 9.3 kJ mol-1 Ea value measured previously for the Ru system suggests that N-N cleavage cannot occur at the Ru surface.

Ferromagnetism and Crystalline Electric Field Effects in Cubic UX2Zn20 (X=Co, Rh, Ir)

NASA Astrophysics Data System (ADS)

Bauer, E. D.; Ronning, F.; Silhanek, A.; Harrison, N.; Thompson, J. D.; Sarrao, J. L.; Movshovich, R.; Hundley, M. F.; Jaime, M.; Daniel, E.; Booth, C. H.

2006-03-01

The properties of a new class of cubic UX2Zn20 (X=Co, Rh, Ir) heavy fermion compounds have been investigated by means of magnetic susceptibility, specific heat, electrical resistivity, and x-ray absorption spectroscopy. Both UCo2Zn20 and URh2Zn20 show peaks in C(T) and χ(T) at ˜5-10 K suggesting the presence of crystalline electric field (CEF) effects in these materials, i.e., a localized 5f^2 configuration of uranium. In addition, measurements in high magnetic fields up to 40 T are consistent with a CEF model of a nonmagnetic ground state and a magnetic first excited state separated by ˜ 20 K. In contrast, UIr2Zn20 exhibits a first-order ferromagnetic transition at Tc=2.75 K with a saturation moment μsat=0.5 μB in the ferromagnetic state. All compounds in this series are heavy fermion materials with enhanced electronic specific heat coefficients γ˜ 150-300 mJ/molK^2. The physical properties of UX2Zn20 (X=Co, Rh, Ir) will be discussed.

Nano sponge Mn₂O ₃ as a new adsorbent for the preconcentration of Pd(II) and Rh(III) ions in sea water, wastewater, rock, street sediment and catalytic converter samples prior to FAAS determinations.

PubMed

Yavuz, Emre; Tokalıoğlu, Serife; Sahan, Halil; Patat, Saban

2014-10-01

In this study, a nano sponge Mn2O3 adsorbent was synthesized and was used for the first time. Various parameters affecting the recovery values of Pd(II) and Rh(III) were examined. The tolerance limits (≥ 90 %) for both Pd(II) and Rh(III) ions were found to be 75,000 mg L(-1) Na(I), 75,000 mg L(-1) K(I), 50,000 mg L(-1) Mg(II) and 50,000 mg L(-1) Ca(II). A 30s contact time was enough for both adsorption and elution. A preconcentration factor of 100 was obtained by using 100mg of the nano sponge Mn2O3. The reusability of the adsorbent was 120 times. Adsorption capacities for Pd(II) and Rh(III) were found to be 42 and 6.2 mg g(-1), respectively. The detection limits were 1.0 µg L(-1) for Pd(II) and 0.37 µg L(-1) for Rh(III) and the relative standard deviations (RSD, %) were found to be ≤ 2.5%. The method was validated by analyzing the standard reference material, SRM 2556 (Used Auto Catalyst Pellets) and spiked real samples. The optimized method was applied for the preconcentration of Pd(II) and Rh(III) ions in water (sea water and wastewater), rock, street sediment and catalytic converter samples. Copyright © 2014 Elsevier B.V. All rights reserved.

Reduction Reaction Activity on Pt-Monolayer-Shell PdIr/Ni-core Catalysts

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

Song, Liang; Vukmirovic, Miomir B.; Adzic, Radoslav R.

Platinum monolayer oxygen reduction reaction catalysts present promising way of reducing the Pt content without scarifying its fuel cell performance. We present a facile way of preparing Pt monolayer shell PdIr-based core catalysts, which showed much higher activity for oxygen reduction reaction than that of TKK 46.6% Pt/C catalyst. Among tested samples, PtMLPd2Ir/Ni/C performs the best with Pt and Platinum Group Metal mass activity around 9 and 0.25 times higher of that of TKK 46.6% Pt/C. In addition, accelerated aging test indicates its excellent durability.

Reduction Reaction Activity on Pt-Monolayer-Shell PdIr/Ni-core Catalysts

DOE PAGES

Song, Liang; Vukmirovic, Miomir B.; Adzic, Radoslav R.

2018-05-14

Platinum monolayer oxygen reduction reaction catalysts present promising way of reducing the Pt content without scarifying its fuel cell performance. We present a facile way of preparing Pt monolayer shell PdIr-based core catalysts, which showed much higher activity for oxygen reduction reaction than that of TKK 46.6% Pt/C catalyst. Among tested samples, PtMLPd2Ir/Ni/C performs the best with Pt and Platinum Group Metal mass activity around 9 and 0.25 times higher of that of TKK 46.6% Pt/C. In addition, accelerated aging test indicates its excellent durability.

Ligand effects on the hydrogenation of biomass-inspired substrates with bifunctional Ru, Ir, and Rh complexes.

PubMed

Jansen, Eveline; Jongbloed, Linda S; Tromp, Dorette S; Lutz, Martin; de Bruin, Bas; Elsevier, Cornelis J

2013-09-01

We herein report on the application and structural investigation of a new set of complexes that contain bidentate N-heterocyclic carbenes (NHCs) and primary amine moieties of the type [M(arene)Cl(L)] [M=Ru, Ir, or Rh; arene=p-cymene or pentamethylcyclopentadienyl; L=1-(2-aminophenyl)-3-(n-alkyl)imidazol-2-ylidine]. These complexes were tested and compared in the hydrogenation of acetophenone with hydrogen. Structural variations in the chelate ring size of the heteroditopic ligand revealed that smaller chelate ring sizes in combination with ring conjugation in the ligand are beneficial for the activity of this type of catalyst, favoring an inner-sphere coordination pathway. Additionally, increasing the steric bulk of the alkyl substituent on the NHC aided the reaction, showing almost no induction period and formation of a more active catalyst for the n-butyl complex relative to complexes with smaller Me and Et substituents. As is common in hydrogenation reactions, the activity of the complexes decreases in the order Ru>Ir>Rh. The application of [Ru(p-cym)Cl(L)]PF6 , which outperforms its reported analogues, has been successfully extended to the hydrogenation of more challenging biomass-inspired substrates. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Kondo lattice and antiferromagnetic behavior in quaternary CeTAl 4Si 2 (T = Rh, Ir) single crystals

DOE PAGES

Maurya, Arvind; Kulkarni, Ruta; Thamizhavel, Arumugam; ...

2016-02-26

Here, we have explored in detail the anisotropic magnetic properties of CeRhAl 4Si 2 and CeIrAl 4Si 2, which undergo two antiferromagnetic transitions, at T N1 = 12.6 and 15.5 K, followed by a second transition at T N2 = 9.4 and 13.8 K, respectively, with the [001]-axis as the relatively easy axis of magnetization. The electrical resistivity at ambient and applied pressure provides evidence of Kondo interaction in both compounds, further supported by a reduced value of the entropy associated with the magnetic ordering. The Sommerfeld coefficient γ is inferred to be 195.6 and 49.4 mJ/(mol K 2) formore » CeRhAl 4Si 2 and CeIrAl 4Si 2, respectively, classifying these materials as moderate heavy-fermion compounds. The crystal electric field energy levels are derived from the peak seen in the Schottky heat capacity. Furthermore, we have also performed electronic structure calculations by using the local spin density approximation + U [LSDA+U] approach, which provide physical insights on the observed magnetic behavior of these two compounds.« less

Molecular structures and excited states of CpM(CO)(2) (Cp = eta(5)-C(5)H(5); M = Rh, Ir) and [Cl(2)Rh(CO)(2)](-). Theoretical evidence for a competitive charge transfer mechanism.

PubMed

Hu, Zhenming; Boyd, Russell J; Nakatsuji, Hiroshi

2002-03-20

Molecular structures and excited states of CpM(CO)(2) (Cp = eta(5)-C(5)H(5); M = Rh, Ir) and [Cl(2)Rh(CO)(2)](-) complexes have been investigated using the B3LYP and the symmetry-adapted cluster (SAC)/SAC-configuration interaction (SAC-CI) theoretical methods. All the dicarbonyl complexes have singlet ground electronic states with large singlet-triplet separations. Thermal dissociations of CO from the parent dicarbonyls are energetically unfavorable. CO thermal dissociation is an activation process for [Cl(2)Rh(CO)(2)](-) while it is a repulsive potential for CpM(CO)(2). The natures of the main excited states of CpM(CO)(2) and [Cl(2)Rh(CO)(2)](-) are found to be quite different. For [Cl(2)Rh(CO)(2)](-), all the strong transitions are identified to be metal to ligand CO charge transfer (MLCT) excitations. A significant feature of the excited states of CpM(CO)(2) is that both MLCT excitation and a ligand Cp to metal and CO charge transfer excitation are strongly mixed in the higher energy states with the latter having the largest oscillator strength. A competitive charge transfer excited state has therefore been identified theoretically for CpRh(CO)(2) and CpIr(CO)(2). The wavelength dependence of the quantum efficiencies for the photoreactions of CpM(CO)(2) reported by Lees et al. can be explained by the existence of two different types of excited states. The origin of the low quantum efficiencies for the C-H/S-H bond activations of CpM(CO)(2) can be attributed to the smaller proportion of the MLCT excitation in the higher energy states.

GRAVIMETRIC DETERMINATION OF PLATINIUM, PALLADIUM, RUTHENIUM, RHODIUM AS TlPtS$sub 3$, TlPd$sub 2$S$sub 3$, TlRu$sub 2$S$sub 6$, TlRh$sub 2$S$sub 4$ (in Russian)

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

Rudnev, N.A.; Malofeeva, G.I.

1963-07-01

Gravimetric methods were developed for the determination of microamounts of Ru, Rh, Pt, and Pd as TlRu/sub 2/S/sub 6/, TlRh/sub 2/S/sub 4/ TlPtS/sub 3/, and TlPd/sub 2/S/sub 3/. The methods are simpl e, rapid, and satisfactorily accurate. (auth)

Magnetic structure of the antiferromagnetic Kondo lattice compounds CeRhAl 4Si 2 and CeIrAl 4Si 2

DOE PAGES

Ghimire, N. J.; Calder, S.; Janoschek, M.; ...

2015-06-01

In this article, we have investigated the magnetic ground state of the antiferromagnetic Kondo-lattice compounds CeMAl 4Si 2(M = Rh, Ir) using neutron powder diffraction. Although both of these compounds show two magnetic transitions T N1 and T N2 in the bulk properties measurements, evidence for magnetic long-range order was only found below the lower transition T N2. Analysis of the diffraction profiles reveals a commensurate antiferromagnetic structure with a propagation vector k = (0, 0, 1/2). The magnetic moment in the ordered state of CeRhAl 4Si 2 and CeIrAl 4Si 2 were determined to be 1.14(2) and 1.41(3) μB/Ce,more » respectively, and are parallel to the crystallographic c-axis in agreement with magnetic susceptibility measurements.« less

Crystal growth, structure determination and magnetism of a new m=3, n=1 member of the A3 n+3 mA' nB3 m+ nO 9 m+6 n family of oxides: 12R-Ba 12Rh 9.25Ir 1.75O 33

NASA Astrophysics Data System (ADS)

Stitzer, Katharine E.; El Abed, Ahmed; Darriet, Jacques; zur Loye, Hans-Conrad

2004-04-01

Single crystals of a new Ba-Rh-Ir-O oxide were grown from a molten potassium carbonate flux. The new compound, Ba 12Rh 9.25Ir 1.75O 33, is structurally related to the 2H-hexagonal perovskite structure and contains pseudo one-dimensional chains of alternating units of ten face-sharing (Rh/Ir)O 6 octahedra and one (Rh/Ir)O 6 trigonal prism. The magnetic susceptibility of Ba 12Rh 9.25Ir 1.75O 33 is featureless, indicating the absence of magnetic order. The oxide is a semiconductor with a room temperature resistance of 280 Ω.

Platinum-group elements (Rh, Pt, Pd) and Au distribution in snow samples from the Kola Peninsula, NW Russia

NASA Astrophysics Data System (ADS)

Gregurek, Dean; Melcher, Frank; Niskavaara, Heikki; Pavlov, Vladimir A.; Reimann, Clemens; Stumpfl, Eugen F.

In April 1996 snowpack samples were collected from the surroundings of the ore roasting and dressing plant at Zapoljarnij and the nickel smelters at Nikel and Monchegorsk, Kola Peninsula, NW Russia. In the laboratory, filter residues of snowpack samples (fraction>0.45 μm) from 15 localities (close to the nickel processing centres) were chemically for precious metals (Rh, Pt, Pd, Au) and Te by graphite furnace atomic absorption spectrometry (GFAAS) analysis, and for Cu and Ni by ICP-MS. Values up to 2770 ng/l Pd, 650 ng/l Pt and 186 ng/l Au were found in the filter residues. Additionally, platinum-group elements (PGE) and Au contents in ore samples from Noril'sk , as well as in technogenic products ("Cu-Ni-feinstein" and copper concentrate) processed at the Monchegorsk smelter complex, were analysed using flameless atomic absorption spectroscopy (FAAS) for comparison with results obtained from snow. Rh, Pt, Pd and Au distribution data show the presence of two ore components (Noril'sk and Pechenga). Concentrations of these metals decrease with distance from the industrial sources and with the prevailing wind direction (generally north-south). Microscopic investigations and electron microprobe analysis of polished sections of snow filter residues (>0.45 μm) also reveal differences between particles from the two sources. To avoid confusion the term "Noril'sk" is used throughout the paper to denote material and/or data from the Noril'sk area and its sub-district, Noril'sk while Pechenga relates to the local ore.

Distribution trends and influence of 4d transition metal elements (Ru, Rh and Pd) doping on mechanical properties and martensitic transformation temperature of B2-ZrCu phase

NASA Astrophysics Data System (ADS)

Guo, Fuda; Zhan, Yongzhong

2017-12-01

The prediction for distribution trends and effect of three 4d transition metal elements (Ru, Rh and Pd) on mechanical properties and martensitic transformation temperature of B2-ZrCu phase were investigated by first-principles calculations. The convex surface of formation energy suggests that the alloying elements prefer to occupy the Cu sites in B2-ZrCu phase and the dopants studied in present are able to strengthen the phase stability. The calculated results of substitutional formation energy suggest that the distribution trend of dopants in B2-ZrCu phase is Ru > Rh > Pd below the dopant concentration 9 at. %, and the distribution trend is Rh > Pd > Ru from 9 at. % to 12.5 at. %. The elastic constants and mechanical properties including bulk modulus and shear modulus were calculated and discussed. The brittleness/ductility characteristic was investigated using the B/G ratio, Poisson's ratio v and Cauchy pressure Cp. The martensitic transformation temperature (Ms) and melting point (Tm) were predicted by using two cubic elastic moduli (C‧ and C44). The prediction results suggest that only the Ms of Zr8Cu7Pd is higher than the parent. The martensitic transformation temperatures of other compounds decrease with the addition of 4d transition metal dopants. Finally, the electronic structures and electron density different were discussed to reveal the bonding characteristics.

Functional toxicity and tolerance patterns of bioavailable Pd(II), Pt(II), and Rh(III) on suspended Saccharomyces cerevisiae cells assayed in tandem by a respirometric biosensor.

PubMed

Frazzoli, Chiara; Dragone, Roberto; Mantovani, Alberto; Massimi, Cristiana; Campanella, Luigi

2007-12-01

Toxicological implications of exposure to bioavailable platinum group metals, here Pd, Pt, and Rh, are still to be clarified. This study obtained by a biosensor-based method preliminary information on potential effects on cellular metabolism as well as on possible tolerance mechanisms. Aerobic respiration was taken as the toxicological end point to perform tandem tests, namely functional toxicity test and tolerance test. Cells were suspended in the absence of essential constituents for growth. The dose-response curves obtained by exposure (2 h) to the metals (nanogram per gram range) suggested the same mechanisms of action, with Rh showing the greatest curve steepness and the lowest EC50 value. Conservative (95% lower confidence interval) EC10 values were 187, 85 and 51 ng g(-1) for Pt, Pd, and Rh respectively. Tolerance patterns were tested during the same runs. The full tolerance obtained after 12 h of exposure to each metal suggested mitochondrial inhibition of aerobic respiration as a target effect. The hazard rating of the metals in the tolerance test changed in the Rh EC50 range, where Rh showed the lowest toxicity. The observed tolerance might suggest a protective mechanism such as metallothionein induction at concentrations around the EC50 values. The performance of the bioassay was satisfactory, in terms of the limit of detection, repeatability, reproducibility, roboustness, sensibility, and stability; the method's critical uncertainty sources were identified for improvements.

Non-selective rapid electro-oxidation of persistent, refractory VOCs in industrial wastewater using a highly catalytic and dimensionally stable IrPd/Ti composite electrode.

PubMed

Cho, Wan-Cheol; Poo, Kyung-Min; Mohamed, Hend Omar; Kim, Tae-Nam; Kim, Yul-Seong; Hwang, Moon Hyun; Jung, Do-Won; Chae, Kyu-Jung

2018-05-11

Volatile organic compounds (VOCs) are highly toxic contaminants commonly dissolved in industrial wastewater. Therefore, treatment of VOC-containing wastewater requires a robust and rapid reaction because liquid VOCs can become volatile secondary pollutants. In this study, electro-oxidation with catalytic composite dimensionally stable anodes (DSAs)-a promising process for degrading organic pollutants-was applied to remove various VOCs (chloroform, benzene, toluene, and trichloroethylene). Excellent treatment efficiency of VOCs was demonstrated. To evaluate the VOC removal rate of each DSA, a titanium plate, a frequently used substratum, was coated with four different highly electrocatalytic composite materials (platinum group metals), Ir, IrPt, IrRu, and IrPd. Ir was used as a base catalyst to maintain the electrochemical stability of the anode. Current density and electrolyte concentration were evaluated over various ranges (20-45 mA/cm 2 and 0.01-0.15 mol/L as NaCl, respectively) to determine the optimum operating condition. Results indicated that chloroform was the most refractory VOC tested due to its robust chemical bond strength. Moreover, the optimum current density and electrolyte concentration were 25 mA/cm 2 and 0.05 M, respectively, representing the most cost-effective condition. Four DSAs were examined (Ir/Ti, IrPt/Ti, IrRu/Ti, and IrPd/Ti). The IrPd/Ti anode was the most suitable for treatment of VOCs presenting the highest chloroform removal performance of 78.8%, energy consumption of 0.38 kWh per unit mass (g) of oxidized chloroform, and the least volatilized fraction of 4.4%. IrPd/Ti was the most suitable anode material for VOC treatment because of its unique structure, high wettability, and high surface area. Copyright © 2018 Elsevier Ltd. All rights reserved.

The Disposition of Pt, Pd, Ir, Os, and Ru in Marine Sediments and the K/T Boundary

NASA Technical Reports Server (NTRS)

Lee, Cin-Ty; Wasserburg, Gerald; Kyte, Frank

2003-01-01

The marine record of platinum group elements (PGEs) and Os isotopic compositions provides information on different inputs of PGEs into the oceans. Some studies based on a smaller subset of the PGEs suggest that the PGEs may suffer post-depositional mobility during diagenesis. In some K/T boundary clays, Kyte and others showed that the relative abundances of Pt, Pd, Ir, and Os can differ significantly from chondritic, which is the signature expected from fallout of the meteorite impact. In some K/T boundary sections, elevated Ir concentrations are observed as far as 1 meter from the cm-thick boundary clay containing the meteoritic ejecta. The purpose of this study was to characterize Pt, Pd, Ir, Os, and Ru abundances in zones including the K/T boundary. We determined PGE abundances of boundary clays at two hemipelagic sites (Stevns Klint, Denmark and Caravaca, Spain) in which previous studies by Kyte and others showed that the Ir anomaly is confined to within a few cm. We also analyzed two pelagic Pacific sites: a boundary clay from the north Pacific (Hole 465A) characterized by a 0.5 m thick Ir anomaly and a transect across the K/T boundary from the south Pacific (Hole 596) where the Ir anomaly spans 2 m. The Stevns Klint, Caravaca, and north Pacific sites are characterized by abundant marls and limestones in the section, whereas the south Pacific site is dominated by clays. Samples were spiked with isotopic tracers, mixed with a flux, S and Ni, and equilibrated by fusion. PGEs were extracted from the Ni and analyzed on a Finnigan Element ICP-MS. We find that the narrow Caravaca and Stevns Klint boundary clays have relative PGE abundance patterns indistinguishable from chondritic values. The two Pacific sites were found to have nearly identical PGE patterns but have ratios at the peak, which differ from chondritic values as found earlier by Evans et al. The Pacific sites were found to have nearly identical PGE patterns but are extremely depleted in OS (Os/Ir = 0

Physical properties of the Ce 2 M Al 7 Ge 4 heavy-fermion compounds ( M = Co , Ir , Ni , Pd )

DOE PAGES

Ghimire, N. J.; Cary, S. K.; Eley, S.; ...

2016-05-23

Here, we report the synthesis, crystal structure, and characterization by means of single-crystal x-ray diffraction, neutron powder diffraction, and magnetic, thermal, and transport measurements of the new heavy-fermion compounds Ce 2MAl 7Ge 4 (M=Co,Ir,Ni,Pd). These compounds crystallize in a noncentrosymmetric tetragonal space group Pmore » $$\\bar{4}$$2 1m, consisting of layers of square nets of Ce atoms separated by Ge-Al and M-Al-Ge blocks. Ce 2CoAl 7Ge 4,Ce 2IrAl 7Ge 4, and Ce 2NiAl 7Ge 4 order magnetically below TM=1.8, 1.6, and 0.8 K, respectively. There is no evidence of magnetic ordering in Ce 2PdAl 7Ge 4 down to 0.4 K. Furthermore, the small amount of entropy released in the magnetic state of Ce 2MAl 7Ge 4 (M = Co, Ir, Ni) and the reduced specific heat jump at T M suggest a strong Kondo interaction in these materials. Ce 2PdAl 7Ge 4 shows non-Fermi liquid behavior, possibly due to the presence of a nearby quantum critical point.« less

Long-time variation in magnetic structure of Ce(Ir xRh 1– x) 3Si 2: A new interpretation of time variation

DOE PAGES

Motoya, Kiyoichiro; Hagihala, Masato; Univ. of Tokyo, Chiba; ...

2017-02-03

Here, to clarify the key factor for the slow magnetic transitions in CeIr 3Si 2 and other materials, magnetization and neutron scattering measurements have been carried out on the system Ce(Ir xRh 1–x) 3Si 2. In this system, a magnetic phase transition is accomplished through slow and fast processes. The fractions of these processes vary with the chemical composition x. A new interpretation of magnetic phase transitions, which includes the coexistence of two processes, is presented.

Green synthesis of Pd nanoparticles at Apricot kernel shell substrate using Salvia hydrangea extract: Catalytic activity for reduction of organic dyes.

PubMed

Khodadadi, Bahar; Bordbar, Maryam; Nasrollahzadeh, Mahmoud

2017-03-15

For the first time the extract of the plant of Salvia hydrangea was used to green synthesis of Pd nanoparticles (NPs) supported on Apricot kernel shell as an environmentally benign support. The Pd NPs/Apricot kernel shell as an effective catalyst was prepared through reduction of Pd 2+ ions using Salvia hydrangea extract as the reducing and capping agent and Pd NPs immobilization on Apricot kernel shell surface in the absence of any stabilizer or surfactant. According to FT-IR analysis, the hydroxyl groups of phenolics in Salvia hydrangea extract as bioreductant agents are directly responsible for the reduction of Pd 2+ ions and formation of Pd NPs. The as-prepared catalyst was characterized by Fourier transform infrared (FT-IR) and UV-Vis spectroscopy, field emission scanning electron microscopy (FESEM) equipped with an energy dispersive X-ray spectroscopy (EDS), Elemental mapping, X-ray diffraction analysis (XRD) and transmittance electron microscopy (TEM). The synthesized catalyst was used in the reduction of 4-nitrophenol (4-NP), Methyl Orange (MO), Methylene Blue (MB), Rhodamine B (RhB), and Congo Red (CR) at room temperature. The Pd NPs/Apricot kernel shell showed excellent catalytic activity in the reduction of these organic dyes. In addition, it was found that Pd NPs/Apricot kernel shell can be recovered and reused several times without significant loss of catalytic activity. Copyright © 2016 Elsevier Inc. All rights reserved.

Bulk electronic structure of non-centrosymmetric EuTGe 3 (T=Co, Ni, Rh, Ir) studied by hard x-ray photoelectron spectroscopy

DOE PAGES

Utsumi, Yuki; Kasinathan, Deepa; Swatek, Przemys?aw; ...

2018-03-15

Non-centrosymmetric EuTGe 3 ( T = Co, Ni, Rh, and Ir) possesses magnetic Eu 2+ ions, and antiferromagnetic ordering appears at low temperatures. Transition-metal substitution leads to changes in the unit-cell volume and in the magnetic ordering. However, the magnetic ordering temperature does not scale with the volume change, and the Eu valence is expected to remain divalent. Here we study the bulk electronic structure of non-centrosymmetric Eu T Ge 3 ( T = Co, Ni, Rh, and Ir) by hard x-ray photoelectron spectroscopy. The Eu 3d core-level spectrum confirms the robust Eu 2+ valence state against the transition-metal substitutionmore » with a small contribution from Eu 3+ . The estimated Eu mean valence is around 2.1 in these compounds, as confirmed by multiplet calculations. In contrast, the Ge 2p spectrum shifts to higher binding energy upon cha nging the transition metal from 3d to 4d to 5d elements, hinting at a change in the Ge- T bonding strength. The valence bands of the different compounds are found to be well reproduced by ab initio band structure calculations.« less

Bulk electronic structure of non-centrosymmetric EuTGe 3 (T=Co, Ni, Rh, Ir) studied by hard x-ray photoelectron spectroscopy

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

Utsumi, Yuki; Kasinathan, Deepa; Swatek, Przemys?aw

Non-centrosymmetric EuTGe 3 ( T = Co, Ni, Rh, and Ir) possesses magnetic Eu 2+ ions, and antiferromagnetic ordering appears at low temperatures. Transition-metal substitution leads to changes in the unit-cell volume and in the magnetic ordering. However, the magnetic ordering temperature does not scale with the volume change, and the Eu valence is expected to remain divalent. Here we study the bulk electronic structure of non-centrosymmetric Eu T Ge 3 ( T = Co, Ni, Rh, and Ir) by hard x-ray photoelectron spectroscopy. The Eu 3d core-level spectrum confirms the robust Eu 2+ valence state against the transition-metal substitutionmore » with a small contribution from Eu 3+ . The estimated Eu mean valence is around 2.1 in these compounds, as confirmed by multiplet calculations. In contrast, the Ge 2p spectrum shifts to higher binding energy upon cha nging the transition metal from 3d to 4d to 5d elements, hinting at a change in the Ge- T bonding strength. The valence bands of the different compounds are found to be well reproduced by ab initio band structure calculations.« less

Immune-Related Adverse Events Associated with Anti-PD-1/PD-L1 Treatment for Malignancies: A Meta-Analysis

PubMed Central

Wang, Peng-Fei; Chen, Yang; Song, Si-Ying; Wang, Ting-Jian; Ji, Wen-Jun; Li, Shou-Wei; Liu, Ning; Yan, Chang-Xiang

2017-01-01

Background: Treatment of cancers with programmed cell death protein 1 (PD-1) pathway inhibitors can lead to immune-related adverse events (irAEs), which could be serious and even fetal. Therefore, clinicians should be aware of the characteristics of irAEs associated with the use of such drugs. Methods: The MEDLINE, EMBASE, and Cochrane databases were searched to find potential studies using the following strategies: anti-PD-1/PD-L1 treatment; irAEs; and cancer. R© package Meta was used to pool incidence. Results: Forty-six studies representing 12,808 oncologic patients treated with anti-PD-1/PD-L1 agents were included in the meta-analysis. The anti-PD-1/PD-L1 agents included nivolumab, pembrolizumab, atezolizumab, durvalumab, avelumab, and BMS-936559. The tumor types were melanomas, Hodgkin lymphomas, urothelial carcinomas, breast cancers, non-small cell lung cancers, renal cell carcinomas (RCC), colorectal cancers, and others. We described irAEs according to organ systems, namely, the skin (pruritus, rash, maculopapular rash, vitiligo, and dermatitis), endocrine system (hypothyroidism, hyperthyroidism, hypophysitis, thyroiditis, and adrenal insufficiency), digestive system (colitis, diarrhea, pancreatitis, and increased AST/ALT/bilirubin), respiratory system (pneumonitis, lung infiltration, and interstitial lung disease), and urinary system (increased creatinine, nephritis, and renal failure). In patients treated with the PD-1 signaling inhibitors, the overall incidence of irAEs was 26.82% (95% CI, 21.73–32.61; I2, 92.80) in any grade and 6.10% (95% CI, 4.85–7.64; I2, 52.00) in severe grade, respectively. The development of irAEs was unrelated to the dose of anti-PD-1/PD-L1 agents. The incidence of particular irAEs varied when different cancers were treated with different drugs. The incidence of death due to irAEs was around 0.17%. Conclusion: The occurrence of irAEs was organ-specific and related to drug and tumor types. PMID:29093678

Effect of L1{sub 2} ordering in antiferromagnetic Ir-Mn epitaxial layer on exchange bias of FePd films

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

Chang, Y. C.; Duh, J. G., E-mail: pmami.hsiao@gmail.com, E-mail: lin.yg@nsrrc.org.tw, E-mail: jgd@mx.nthu.edu.tw; Hsiao, S. N., E-mail: pmami.hsiao@gmail.com, E-mail: lin.yg@nsrrc.org.tw, E-mail: jgd@mx.nthu.edu.tw

2015-05-07

Two series of samples of single-layer IrMn and IrMn/FePd bilayer films, deposited on a single-crystal MgO substrate at different IrMn deposition temperatures (T{sub s} = 300–700 °C), were investigated using magnetron sputtering. L1{sub 2} ordering was revealed for the 30 nm-thick IrMn epitaxial (001) films with T{sub s} ≥ 400 °C, determined by synchrotron radiation x-ray diffractometry (XRD). XRD results also provide evidence of the epitaxial growth of the IrMn films on MgO substrate. Increasing T{sub s} from 400 to 700 °C monotonically increases the ordering parameter of L1{sub 2} phases from 0.17 to 0.81. An in-plane exchange bias field (H{sub eb}) of 22 Oe is obtained in amore » 10 nm-thick FePd film that is deposited on the disordered IrMn films. As the L1{sub 2} ordering of the IrMn layers increases, the H{sub eb} gradually decreases to 0 Oe, meaning that the exchange bias behavior vanishes. The increased surface roughness, revealed by atomic force microscopy, of the epitaxial IrMn layers with increasing T{sub s} cannot be the main cause of the decrease in H{sub eb} due to the compensated surface spins regardless of the disordered and ordered (001) IrMn layers. The change of antiferromagnetic structure from the A1 to the L1{sub 2} phase was correlated with the evolution of H{sub eb}.« less

Unusual ground states in {R_5T_4X_{10}} (R  =  rare earth; T  =  Rh, Ir; and X  =  Si, Ge, Sn): a review

NASA Astrophysics Data System (ADS)

Ramakrishnan, S.; van Smaalen, Sander

2017-11-01

Rare earth compounds of the type R_5T_4X10 (R  =  rare earth; T  =  Rh, Ir, and X  =  Si, Ge, Sn) display a variety of phase transitions towards exotic states, including charge density waves (CDW), local moment magnetism, antiferromagnetism in the heavy fermion state, superconductivity and giant positive magnetoresistance. They support strongly correlated electron systems. In particular, R 5Ir4 Si10 (R  =  Dy-Lu) exhibit strong coupling CDWs with high transition temperatures, and superconductivity or magnetic ordering at lower temperatures. R_5T4 Ge10 (R  =  Gd-Tm T  =  Co, Rh, Ir) show multiple magnetic transitions with large magnetoresistance below the magnetic transitions. Finally, the light rare earth series R_5T4 Sn10 (R  =  Ce, Pr, Nd; T  =  Rh, Ir) display heavy fermion behaviour (for Ce and Pr) or possess giant positive magnetoresistance (for Nd) at low temperatures. This review provides a comprehensive overview of compounds, crystal structures and phase transitions. This is followed by an in-depth discussion of the mechanisms of the phase transitions and the properties of the ordered states.

Durable pd-based alloy and hydrogen generation membrane thereof

DOEpatents

Benn, Raymond C.; Opalka, Susanne M.; Vanderspurt, Thomas Henry

2010-02-02

A durable Pd-based alloy is used for a H.sub.2-selective membrane in a hydrogen generator, as in the fuel processor of a fuel cell plant. The Pd-based alloy includes Cu as a binary element, and further includes "X", where "X" comprises at least one metal from group "M" that is BCC and acts to stabilize the .beta. BCC phase for stability during operating temperatures. The metal from group "M" is selected from the group consisting of Fe, Cr, Nb, Ta, V, Mo, and W, with Nb and Ta being most preferred. "X" may further comprise at least one metal from a group "N" that is non-BCC, preferably FCC, that enhances other properties of the membrane, such as ductility. The metal from group "N" is selected from the group consisting of Ag, Au, Re, Ru, Rh, Y, Ce, Ni, Ir, Pt, Co, La and In. The at. % of Pd in the binary Pd--Cu alloy ranges from about 35 at. % to about 55 at. %, and the at. % of "X" in the higher order alloy, based on said binary alloy, is in the range of about 1 at. % to about 15 at. %. The metals are selected according to a novel process.

Bulk electronic structure of non-centrosymmetric Eu T Ge3 (T =Co , Ni, Rh, Ir) studied by hard x-ray photoelectron spectroscopy

NASA Astrophysics Data System (ADS)

Utsumi, Yuki; Kasinathan, Deepa; Swatek, Przemysław; Bednarchuk, Oleksandr; Kaczorowski, Dariusz; Ablett, James M.; Rueff, Jean-Pascal

2018-03-01

Non-centrosymmetric Eu T Ge3 (T = Co, Ni, Rh, and Ir) possesses magnetic Eu2 + ions, and antiferromagnetic ordering appears at low temperatures. Transition-metal substitution leads to changes in the unit-cell volume and in the magnetic ordering. However, the magnetic ordering temperature does not scale with the volume change, and the Eu valence is expected to remain divalent. Here we study the bulk electronic structure of non-centrosymmetric Eu T Ge3 (T = Co, Ni, Rh, and Ir) by hard x-ray photoelectron spectroscopy. The Eu 3 d core-level spectrum confirms the robust Eu2 + valence state against the transition-metal substitution with a small contribution from Eu3 +. The estimated Eu mean valence is around 2.1 in these compounds, as confirmed by multiplet calculations. In contrast, the Ge 2 p spectrum shifts to higher binding energy upon changing the transition metal from 3 d to 4 d to 5 d elements, hinting at a change in the Ge-T bonding strength. The valence bands of the different compounds are found to be well reproduced by ab initio band structure calculations.

Genetic Pd, Pt, Au, Ag, and Rh mineralogy in Noril'sk sulfide ores

NASA Astrophysics Data System (ADS)

Spiridonov, E. M.; Kulagov, E. A.; Serova, A. A.; Kulikova, I. M.; Korotaeva, N. N.; Sereda, E. V.; Tushentsova, I. N.; Belyakov, S. N.; Zhukov, N. N.

2015-09-01

The undeformed ore-bearing intrusions of the Noril'sk ore field (NOF) cut through volcanic rocks of the Late Permian-Early Triassic trap association folded in brachysynclines. Due to the nonuniform load on the roof of intrusive bodies, most sulfide melts were squeezed, up to the tops of ore-bearing intrusions; readily fusible Ni-Fe-Cu sulfide melts were almost completely squeezed. In our opinion, not only one but two stages of mineralization developed at the Noril'sk deposits: (i) syntrap magmatic and (ii) epigenetic post-trap metamorphic-hydrothermal. All platinum-group minerals (PGM) and minerals of gold are metasomatic in the Noril'sk ores. They replaced sulfide solid solutions and exsolution structures. All types of PGM and Au minerals occur in the ores, varying in composition from pyrrhotite to chalcopyrite, talnakhite, mooihoekite, and rich in galena; they are localized in the inner and outer contact zones and differ only in the quantitative proportions of ore minerals. The aureoles of PGM and Au-Ag minerals are wider than the contours of sulfide bodies and coincide with halos of fluid impact on orebodies and adjacent host rocks. The pneumatolytic PGM and Au-Ag minerals are correlated in abundance with the dimensions of sulfide bodies. Their amounts are maximal in veins of late fusible ore composed of eutectic PbS ss and iss intergrowths, as well as at their contacts. The Pd and Pt contents in eutectic sulfide ores of NOF are the world's highest. In the process of noble-metal mineral formation, the fluids supply Pd, Pt, Au, As, Sb, Sn, Bi, and a part of Te, whereas Fe, Ni, Cu, Pb, Ag, Rh, a part of Te and Pd are leached from the replaced sulfide minerals. The pneumatolytic PGM of the early stage comprises Pd and Pt intermetallic compounds enriched in Au along with Pd-Pt-Fe-Ni-Cu-Sn-Pb(As) and (Pd,Pt,Au)(Sn,Sb,Bi,Te,As) solid solutions. Pneumatolytic PGM and Au minerals of the middle stage are products of solid-phase transformation and recrystallization of

[Bifunctional chelates of Rh-105, Au-199, and other metallic radionuclides as potential radiotherapeutic agents

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

Not Available

1991-12-31

Progress during this period is reported under the following headings: Diethylenetriamine based and related bifunctional chelating agents and their complexation with Rh-105, Au-198, Pd-109, cu-67, In-111, and Co-57; studies of Pd-109, Rh-105 and Tc-99m with bifunctional chelates based on phenylenediamine; establishment of an appropriate protein assay method for conjugated proteins; studies of new bifunctional Bi, Tri and tetradentate amine oxime ligands with Rh-105; IgG and antibody B72.3 conjugation studies by HPLC Techniques with bifunctional metal chelates; and progress on ligand systems for Au(III).

(Bifunctional chelates of Rh-105, Au-199, and other metallic radionuclides as potential radiotherapeutic agents)

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

Not Available

1991-01-01

Progress during this period is reported under the following headings: Diethylenetriamine based and related bifunctional chelating agents and their complexation with Rh-105, Au-198, Pd-109, cu-67, In-111, and Co-57; studies of Pd-109, Rh-105 and Tc-99m with bifunctional chelates based on phenylenediamine; establishment of an appropriate protein assay method for conjugated proteins; studies of new bifunctional Bi, Tri and tetradentate amine oxime ligands with Rh-105; IgG and antibody B72.3 conjugation studies by HPLC Techniques with bifunctional metal chelates; and progress on ligand systems for Au(III).

Sc–Zr–Nb–Rh–Pd and Sc–Zr–Nb–Ta–Rh–Pd High-Entropy Alloy Superconductors on a CsCl-Type Lattice

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

Stolze, Karoline; Tao, Jing; von Rohr, Fabian O.

We have synthesized previously unreported High-Entropy Alloys (HEAs) in the pentanary (ScZrNb) 1-x[RhPd] x and hexanary (ScZrNbTa) 1-x[RhPd] x systems. The materials have CsCl-type structures and mixed site occupancies. Both HEAs are type-II superconductors with strongly varying critical temperatures (T cs) depending on the valence electron count (VEC); the T cs increase monotonically with decreasing VEC within each series, and do not follow the trends seen for either crystalline or amorphous transition metal superconductors. The (ScZrNb) 0.65[RhPd] 0.35 HEA with the highest T c, ~9.3 K, also exhibits the largest µ 0H c2(0) = 10.7 T. The pentanary and hexanarymore » HEAs have higher superconducting transition tempera-tures than their simple binary intermetallic relatives with the CsCl-type structure and a surprisingly ductile mechanical behavior. The presence of niobium, even at the 20% level, has a positive impact on the T c. Nevertheless, niobium-free (ScZr) 0.50[RhPd] 0.50, as mother-compound of both superconducting HEAs found here, is itself superconducting, proving that superconductivity is an intrinsic feature of the bulk material.« less

Sc–Zr–Nb–Rh–Pd and Sc–Zr–Nb–Ta–Rh–Pd High-Entropy Alloy Superconductors on a CsCl-Type Lattice

DOE PAGES

Stolze, Karoline; Tao, Jing; von Rohr, Fabian O.; ...

2018-01-17

We have synthesized previously unreported High-Entropy Alloys (HEAs) in the pentanary (ScZrNb) 1-x[RhPd] x and hexanary (ScZrNbTa) 1-x[RhPd] x systems. The materials have CsCl-type structures and mixed site occupancies. Both HEAs are type-II superconductors with strongly varying critical temperatures (T cs) depending on the valence electron count (VEC); the T cs increase monotonically with decreasing VEC within each series, and do not follow the trends seen for either crystalline or amorphous transition metal superconductors. The (ScZrNb) 0.65[RhPd] 0.35 HEA with the highest T c, ~9.3 K, also exhibits the largest µ 0H c2(0) = 10.7 T. The pentanary and hexanarymore » HEAs have higher superconducting transition tempera-tures than their simple binary intermetallic relatives with the CsCl-type structure and a surprisingly ductile mechanical behavior. The presence of niobium, even at the 20% level, has a positive impact on the T c. Nevertheless, niobium-free (ScZr) 0.50[RhPd] 0.50, as mother-compound of both superconducting HEAs found here, is itself superconducting, proving that superconductivity is an intrinsic feature of the bulk material.« less

Iron-Rhodium and Iron-Iridium Mixed-Metal Nitrido-Carbonyl Clusters. Synthesis, Characterization, Redox Properties, and Solid-State Structure of the Octahedral Clusters [Fe(5)RhN(CO)(15)](2)(-), [Fe(5)IrN(CO)(15)](2)(-), and [Fe(4)Rh(2)N(CO)(15)](-). Infrared and Nuclear Magnetic Resonance Spectroscopic Studies on the Interstitial Nitride.

PubMed

Della Pergola, Roberto; Cinquantini, Arnaldo; Diana, Eliano; Garlaschelli, Luigi; Laschi, Franco; Luzzini, Paola; Manassero, Mario; Repossi, Andrea; Sansoni, Mirella; Stanghellini, Pier Luigi; Zanello, Piero

1997-08-13

The cluster [Fe(5)RhN(CO)(15)](2)(-) was synthesized in 40% yield from [Fe(4)N(CO)(12)](-) and [Rh(CO)(4)](-) in refluxing tetrahydrofuran, whereas the analogous anion [Fe(5)IrN(CO)(15)](2)(-) was prepared in CH(3)CN at room temperature from [Fe(6)N(CO)(15)](3)(-) and [Ir(C(8)H(14))(2)Cl](2); the yields are higher than 60%. The monoanion [Fe(4)Rh(2)N(CO)(15)](-) was obtained in 70% yield from [Fe(5)RhN(CO)(15)](2)(-) and hydrated RhCl(3). The solid-state structures of the three anions were determined on their [PPh(4)](+) salts: the six metal atoms are arranged in octahedral cages and are coordinated to 3 edge-bridging and 12 terminal carbonyl ligands and to a &mgr;(6)-N ligand. The Rh and Ir atoms have less terminal COs than Fe, in order to equalize the excess electrons at the d(9) metal centers. The two rhodium atoms in [Fe(4)Rh(2)N(CO)(15)](-) are directly bound. The (15)N NMR spectra of the three compounds have been recorded; the signals of the nitride ligands were found at delta = 514 ppm for the dianions and 470 ppm for [Fe(4)Rh(2)N(CO)(15)](-); any group 9 atom shifts the resonance of nitrogen to higher fields. The coupling constants J((15)N-(103)Rh) are 8-9 Hz. The vibrational patterns of the metal cores have been interpreted on the basis of an idealized M(6) octahedral arrangement, subsequently modified by the perturbations given by different atomic masses and M-M stretching force constants. The motions of the nitrogen are related to the idealized symmetry of the cage; the M-N force constant values depend on the type of metal and on the charge of the anion. The dianions [Fe(5)MN(CO)(15)](2)(-) can be electrochemically oxidized at -20 degrees C to their short-lived monoanions, which can be characterized by EPR spectroscopy. In contrast, the cluster [Fe(4)Rh(2)N(CO)(15)](-) undergoes a single-step 2-electron reduction to the partially stable trianion [Fe(4)Rh(2)N(CO)(15)](3)(-), which was also characterized by EPR spectroscopy. The Fe-Rh nitride clusters are

Probing the electronic properties of ternary AnM3n−1B2n (n = 1: A = Ca, Sr; M = Rh, Ir and n = 3: A = Ca, Sr; M = Rh) phases: observation of superconductivity

PubMed Central

Takeya, Hiroyuki; ElMassalami, Mohammed; Terrazos, Luis A; Rapp, Raul E; Capaz, Rodrigo B; Fujii, Hiroki; Takano, Yoshihiko; Doerr, Mathias; Granovsky, Sergey A

2013-01-01

We follow the evolution of the electronic properties of the titled homologous series when n as well as the atomic type of A and M are varied where for n = 1, A = Ca, Sr and M = Rh, Ir while for n = 3, A = Ca, Sr and M = Rh. The crystal structure of n = 1 members is known to be CaRh2B2-type (Fddd), while that of n = 3 is Ca3Rh8B6-type (Fmmm); the latter can be visualized as a stacking of structural fragments from AM3B2 (P6/mmm) and AM2B2. The metallic properties of the n = 1 and 3 members are distinctly different: on the one hand, the n = 1 members are characterized by a linear coefficient of the electronic specific heat γ ≈ 3 mJ mol−1 K−2, a Debye temperature θD ≈ 300 K, a normal conductivity down to 2 K and a relatively strong linear magnetoresistivity for fields up to 150 kOe. The n = 3 family, on the other hand, exhibits γ ≈ 18 mJ mol−1 K−2, θD ≈ 330 K, a weak linear magnetoresistivity and an onset of superconductivity (for Ca3Rh8B6, Tc = 4.0 K and Hc2 = 14.5 kOe, while for Sr3Rh8 B6, Tc = 3.4 K and Hc2 ≈ 4.0 kOe). These remarkable differences are consistent with the findings of the electronic band structures and density of state (DOS) calculations. In particular, satisfactory agreement between the measured and calculated γ was obtained. Furthermore, the Fermi level, EF, of Ca3Rh8B6 lies at almost the top of a pronounced local DOS peak, while that of CaRh2B2 lies at a local valley: this is the main reason behind the differences between the, e.g., superconducting properties. Finally, although all atoms contribute to the DOS at EF, the contribution of the Rh atoms is the strongest. PMID:27877576

PALLADIUM, PLATINUM, RHODIUM, RUTHENIUM AND IRIDIUM IN PERIDOTITES AND CHROMITITES FROM OPHIOLITE COMPLEXES IN NEWFOUNDLAND.

USGS Publications Warehouse

Page, Norman J; Talkington, Raymond W.

1984-01-01

Samples of spinel lherzolite, harzburgite, dunite, and chromitite from the Bay of Islands, Lewis Hills, Table Mountain, Advocate, North Arm Mountain, White Hills Periodite Point Rousse, Great Bend and Betts Cove ophiolite complexes in Newfoundland were analyzed for the platinum-group elements (PGE) Pd, Pt, Rh, Ru and Ir. The ranges of concentration (in ppb) observed for all rocks are: less than 0. 5 to 77 (Pd), less than 1 to 120 (Pt), less than 0. 5 to 20 (Rh), less than 100 to 250 (Ru) and less than 20 to 83 (Ir). Chondrite-normalized PGE ratios suggest differences between rock types and between complexes. Samples of chromitite and dunite show relative enrichment in Ru and Ir and relative depletion in Pt and Pd.

Electronic absorption and MCD spectra of M sub 2 (TMB) sub 4 sup 2+ , M = Rh and Ir. A valence-bond description of the upper electronic excited states

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

Smith, D.C.; Miskowski, V.M.; Gray, H.B.

1990-05-09

Electronic absorption and magnetic circular dichroism (MCD) spectra of Rh{sub 2}(TMB){sub 4}{sup 2+} and Ir{sub 2}(TMB){sub 4}{sup 2+} are reported along with polarized single-crystal absorption spectra of (Ir{sub 2}(TMB){sub 4})(B(C{sub 6}H{sub 5}){sub 4}){sub 2} {times} CH{sub 3}C{sub 6}H{sub 5} (TMB = 2,5-diisocyano-2,5-dimethylhexane). Interpretation of the spectra is based on a valence-bond model that accommodates highly perturbed dimer transitions as well as monomer-like dimer excitations. In this model, half of the dimer electronic excited states possess ionic character; these states involve metal-to-metal charge transfer (MMCT). The most prominent of the weak features ({approximately} 430 nm) is assigned to the transition tomore » {sup 1}A{sub 1g} (a single-center d{sub z{sup 2}} {yields} p{sub z} excitation). High-energy features ({lambda} < 300 nm) in the spectra of Rh{sub 2}(TMB){sub 4}{sup 2+} and Ir{sub 2}(TMB){sub 4}{sup 2+} are assigned to MMCT arising from d{sub xzyz} {yields} p{sub z} excitations.« less

Polystyrene Oxygen Optodes Doped with Ir(III) and Pd(II) meso-Tetrakis(pentafluorophenyl)porphyrin Using an LED-Based High-Sensitivity Phosphorimeter.

PubMed

Filho, Alexandre F De Moraes; Gewehr, Pedro M; Maia, Joaquim M; Jakubiak, Douglas R

2018-06-15

This paper presents a gaseous oxygen detection system based on time-resolved phosphorimetry (time-domain), which is used to investigate O2 optical transducers. The primary sensing elements were formed by incorporating iridium(III) and palladium(II) meso -tetrakis(pentafluorophenyl)porphyrin complexes (IrTFPP-CO-Cl and PdTFPP) in polystyrene (PS) solid matrices. Probe excitation was obtained using a violet light-emitting diode (LED) (low power), and the resulting phosphorescence was detected by a high-sensitivity compact photomultiplier tube. The detection system performance and the preparation of the transducers are presented along with their optical properties, phosphorescence lifetimes, calibration curves and photostability. The developed lifetime measuring system showed a good signal-to-noise ratio, and reliable results were obtained from the optodes, even when exposed to moderate levels of O2. The new IrTFPP-CO-Cl membranes exhibited room temperature phosphorescence and moderate sensitivity: <τ0>/<τ21%> ratio of ≈6. A typically high degree of dynamic phosphorescence quenching was observed for the traditional indicator PdTFPP: <τ0>/<τ21%> ratio of ≈36. Pulsed-source time-resolved phosphorimetry combined with a high-sensitivity photodetector can offer potential advantages such as: (i) major dynamic range, (ii) extended temporal resolution (Δτ/Δ[O2]) and (iii) high operational stability. IrTFPP-CO-Cl immobilized in polystyrene is a promising alternative for O2 detection, offering adequate photostability and potentially mid-range sensitivity over Pt(II) and Pd(II) metalloporphyrins.

Probing the electronic properties of ternary A n M3n-1B2n (n = 1: A = Ca, Sr; M = Rh, Ir and n = 3: A = Ca, Sr; M = Rh) phases: observation of superconductivity.

PubMed

Takeya, Hiroyuki; ElMassalami, Mohammed; Terrazos, Luis A; Rapp, Raul E; Capaz, Rodrigo B; Fujii, Hiroki; Takano, Yoshihiko; Doerr, Mathias; Granovsky, Sergey A

2013-06-01

We follow the evolution of the electronic properties of the titled homologous series when n as well as the atomic type of A and M are varied where for n = 1, A = Ca, Sr and M = Rh, Ir while for n = 3, A = Ca, Sr and M = Rh. The crystal structure of n = 1 members is known to be CaRh 2 B 2 -type ( Fddd ), while that of n = 3 is Ca 3 Rh 8 B 6 -type ( Fmmm ); the latter can be visualized as a stacking of structural fragments from AM 3 B 2 ( P 6/ mmm ) and AM 2 B 2 . The metallic properties of the n = 1 and 3 members are distinctly different: on the one hand, the n = 1 members are characterized by a linear coefficient of the electronic specific heat γ ≈ 3 mJ mol -1 K -2 , a Debye temperature θ D ≈ 300 K, a normal conductivity down to 2 K and a relatively strong linear magnetoresistivity for fields up to 150 kOe. The n = 3 family, on the other hand, exhibits γ ≈ 18 mJ mol -1 K -2 , θ D ≈ 330 K, a weak linear magnetoresistivity and an onset of superconductivity (for Ca 3 Rh 8 B 6 , T c = 4.0 K and H c2 = 14.5 kOe, while for Sr 3 Rh 8 B 6 , T c = 3.4 K and H c2 ≈ 4.0 kOe). These remarkable differences are consistent with the findings of the electronic band structures and density of state (DOS) calculations. In particular, satisfactory agreement between the measured and calculated γ was obtained. Furthermore, the Fermi level, E F , of Ca 3 Rh 8 B 6 lies at almost the top of a pronounced local DOS peak, while that of CaRh 2 B 2 lies at a local valley: this is the main reason behind the differences between the, e.g., superconducting properties. Finally, although all atoms contribute to the DOS at E F , the contribution of the Rh atoms is the strongest.

Hydrogen sorption characteristics of nanostructured Pd–10Rh processed by cryomilling

DOE PAGES

Yang, Nancy; Yee, Joshua K.; Zhang, Zhihui; ...

2014-10-03

Palladium and its alloys are model systems for studying solid-state storage of hydrogen. Mechanical milling is commonly used to process complex powder systems for solid-state hydrogen storage; however, milling can also be used to evolve nanostructured powder to modify hydrogen sorption characteristics. In the present study, cryomilling (mechanical attrition milling in a cryogenic liquid) is used to produce nanostructured palladium-rhodium alloy powder. Characterization of the cryomilled Pd-10Rh using electron microscopy, X-ray diffraction, and surface area analysis reveals that (i) particle morphology evolves from spherical to flattened disk-like particles; while the (ii) crystallite size decreases from several microns to less thanmore » 100 nm and (iii) dislocation density increases with increased cryomilling time. Hydrogen absorption and desorption isotherms as well as the time scales for absorption were measured for cryomilled Pd-10Rh, and correlated with observed microstructural changes induced by the cryomilling process. In short, as the microstructure of the Pd-10Rh alloy is refined by cryomilling: (i) the maximum hydrogen concentration in the α-phase increases, (ii) the pressure plateau becomes flatter, and (iii) the equilibrium hydrogen capacity at 760 Torr increases. In addition, the rate of hydrogen absorption was reduced by an order of magnitude compared to non-cryomilled (atomized) powder.« less

Spectroscopic determination of crystal-field levels in CeRh2Si2 and CeRu2Si2 and of the 4f0 contributions in CeM2Si2 (M=Cu, Ru, Rh, Pd, and Au)

NASA Astrophysics Data System (ADS)

Willers, T.; Adroja, D. T.; Rainford, B. D.; Hu, Z.; Hollmann, N.; Körner, P. O.; Chin, Y.-Y.; Schmitz, D.; Hsieh, H. H.; Lin, H.-J.; Chen, C. T.; Bauer, E. D.; Sarrao, J. L.; McClellan, K. J.; Byler, D.; Geibel, C.; Steglich, F.; Aoki, H.; Lejay, P.; Tanaka, A.; Tjeng, L. H.; Severing, A.

2012-01-01

We have determined the ground-state wave functions and crystal-field-level schemes of CeRh2Si2 and CeRu2Si2 using linear polarized soft x-ray-absorption spectroscopy (XAS) and inelastic neutron scattering. We find large crystal-field splittings and ground-state wave functions which are made of mainly Jz = |±5/2> with some amount of |∓3/2> in both the compounds. The 4f0 contribution to the ground state of several members of the CeM2Si2 family with M=(Cu, Ru, Rh, Pd, and Au) has been determined with XAS, and the comparison reveals a trend concerning the delocalization of the f electrons. Absolute numbers are extracted from scaling to results from hard x-ray photoelectron spectroscopy on CeRu2Si2 by Yano [Phys. Rev. BPRBMDO1098-012110.1103/PhysRevB.77.035118 77, 035118 (2008)].

Synthesis and spectral studies of platinum metal complexes of benzoin thiosemicarbazone

NASA Astrophysics Data System (ADS)

Offiong, Offiong E.

1994-11-01

The platinum metal chelates of benzoin thiosemicarbazone obtained with Ru(III), Rh(III), Ir(III), Pd(II) and Pt(II) were prepared from their corresponding halide salts. The complexes were characterized by elemental analysis, conductance measurement, IR, Raman, 1H-NMR, 13C-NMR and UV-visible spectra studies. Various ligand field parameters and nephelauxetic parameters were also calculated. The mode of bonding and the geometry of the ligand environment around the metal ion have been discussed in the light of the available data obtained. Complexes of Ru(III), Rh(III) and Ir(III) are six-coordinate octahedral, while Pd(II) and Pt(II) halide complexes are four-coordinated with halides bridging.

Divergent roles of growth factors in the GnRH regulation of puberty in mice

PubMed Central

DiVall, Sara A.; Williams, Tameeka R.; Carver, Sarah E.; Koch, Linda; Brüning, Jens C.; Kahn, C. Ronald; Wondisford, Fredric; Radovick, Sally; Wolfe, Andrew

2010-01-01

Pubertal onset, initiated by pulsatile gonadotropin-releasing hormone (GnRH), only occurs in a favorable, anabolic hormonal milieu. Anabolic factors that may signal nutritional status to the hypothalamus include the growth factors insulin and IGF-1. It is unclear which hypothalamic neuronal subpopulation these factors affect to ultimately regulate GnRH neuron function in puberty and reproduction. We examined the direct role of the GnRH neuron in growth factor regulation of reproduction using the Cre/lox system. Mice with the IR or IGF-1R deleted specifically in GnRH neurons were generated. Male and female mice with the IR deleted in GnRH neurons displayed normal pubertal timing and fertility, but male and female mice with the IGF-1R deleted in GnRH neurons experienced delayed pubertal development with normal fertility. With IGF-1 administration, puberty was advanced in control females, but not in females with the IGF-1R deleted in GnRH neurons, in control males, or in knockout males. These mice exhibited developmental differences in GnRH neuronal morphology but normal number and distribution of neurons. These studies define the role of IGF-1R signaling in the coordination of somatic development with reproductive maturation and provide insight into the mechanisms regulating pubertal timing in anabolic states. PMID:20628204

Unconventional and conventional quantum criticalities in CeRh0.58Ir0.42In5

NASA Astrophysics Data System (ADS)

Luo, Yongkang; Lu, Xin; Dioguardi, Aadm P.; Rosa, Priscila F. S.; Bauer, Eric D.; Si, Qimiao; Thompson, Joe D.

2018-03-01

An appropriate description of the state of matter that appears as a second order phase transition is tuned toward zero temperature, viz. quantum-critical point (QCP), poses fundamental and still not fully answered questions. Experiments are needed both to test basic conclusions and to guide further refinement of theoretical models. Here, charge and entropy transport properties as well as AC specific heat of the heavy-fermion compound CeRh0.58Ir0.42In5, measured as a function of pressure, reveal two qualitatively different QCPs in a single material driven by a single non-symmetry-breaking tuning parameter. A discontinuous sign-change jump in thermopower suggests an unconventional QCP at pc1 accompanied by an abrupt Fermi-surface reconstruction that is followed by a conventional spin-density-wave critical point at pc2 across which the Fermi surface evolves smoothly to a heavy Fermi-liquid state. These experiments are consistent with some theoretical predictions, including the sequence of critical points and the temperature dependence of the thermopower in their vicinity.

Ternary electrocatalysts for oxidizing ethanol to carbon dioxide: making ir capable of splitting C-C bond.

PubMed

Li, Meng; Cullen, David A; Sasaki, Kotaro; Marinkovic, Nebojsa S; More, Karren; Adzic, Radoslav R

2013-01-09

Splitting the C-C bond is the main obstacle to electrooxidation of ethanol (EOR) to CO(2). We recently demonstrated that the ternary PtRhSnO(2) electrocatalyst can accomplish that reaction at room temperature with Rh having a unique capability to split the C-C bond. In this article, we report the finding that Ir can be induced to split the C-C bond as a component of the ternary catalyst. We characterized and compared the properties of several carbon-supported nanoparticle (NP) electrocatalysts comprising a SnO(2) NP core decorated with multimetallic nanoislands (MM' = PtIr, PtRh, IrRh, PtIrRh) prepared using a seeded growth approach. An array of characterization techniques were employed to establish the composition and architecture of the synthesized MM'/SnO(2) NPs, while electrochemical and in situ infrared reflection absorption spectroscopy studies elucidated trends in activity and the nature of the reaction intermediates and products. Both EOR reactivity and selectivity toward CO(2) formation of several of these MM'/SnO(2)/C electrocatalysts are significantly higher compared to conventional Pt/C and Pt/SnO(2)/C catalysts. We demonstrate that the PtIr/SnO(2)/C catalyst with high Ir content shows outstanding catalytic properties with the most negative EOR onset potential and reasonably good selectivity toward ethanol complete oxidation to CO(2).

Sulfide petrology and highly siderophile element geochemistry of abyssal peridotites: a coupled study of samples from the Kane Fracture Zone (45°W 23°20N, MARK area, Atlantic Ocean)

NASA Astrophysics Data System (ADS)

Luguet, Ambre; Lorand, Jean-Pierre; Seyler, Monique

2003-04-01

Nineteen samples from the Kane Fracture Zone have been studied for sulfide mineralogy and analyzed for S, Se, platinum-group elements (PGE), and Au to assess the effect of refertilization processes on the PGE systematics of abyssal peridotites. The lherzolites show broadly chondritic PGE ratios and sulfide modal abundances (0.01 to 0.03 wt%) consistent with partial melting models, although the few pyroxene-hosted sulfide inclusions and in situ LAM-ICPMS analyses provide evidence for in situ mobilization of a Cu-Ni-rich sulfide partial melt. The most refractory harzburgites (spinel Cr# > 29) are almost devoid of magmatic sulfides and show uniformly low Pd N/Ir N (<0.5) for variable Pt N/Ir N (0.8 to 1.2). The compatible behavior of Os, Ir, Ru, Rh, and Pt reflects the presence of primary Os-Ru alloys. Some harzburgites displaying petrographic evidence for refertilization by incremental melts en route to the surface are enriched in sulfides (up to 0.1 wt%). Some of these sulfides are concentrated in small veinlets of clinopyroxene and spinel crystallized from these melts. These S-rich harzburgites display superchondritic Pd N/Ir N (up to 2.04) positively correlated with sulfide modal contents. It is concluded that refertilization processes resulting in precipitation of metasomatic sulfides may significantly enhance Pd concentrations of abyssal peridotites while marginally affecting Pt (Pt N/Ir N ≤ 1.24) and Rh (Rh N/Ir N ≤ 1.23) as well. When the effects of such processes are screened out, our database suggests PGE relative abundances in the DMM (Depleted MORB Mantle; MORB: Mid-Ocean Ridge) within the uncertainty range of chondritic meteorites, without evidence of superchondritic Pt/Ir and/or Rh/Ir ratios.

Developmental Programming: Reproductive Endocrinopathies in the Adult Female Sheep After Prenatal Testosterone Treatment Are Reflected in Altered Ontogeny of GnRH Afferents

PubMed Central

Hershey, John; Mytinger, Andrea; Foster, Douglas L.; Padmanabhan, Vasantha

2011-01-01

The GnRH system represents a useful model of long-term neural plasticity. An unexplored facet of this plasticity relates to the ontogeny of GnRH neural afferents during critical periods when the hypothalamic-pituitary-gonadal axis is highly susceptible to perturbation by sex steroids. Sheep treated with testosterone (T) in utero exhibit profound reproductive neuroendocrine dysfunctions during their lifespan. The current study tested the hypothesis that these changes are associated with alterations in the normal ontogeny of GnRH afferents and glial associations. Adult pregnant sheep (n = 50) were treated with vehicle [control (CONT)] or T daily from gestational day (GD)30 to GD90. CONT and T fetuses (n = 4–6/treatment per age group) were removed by cesarean section on GD90 and GD140 and the brains frozen at −80°C. Brains were also collected from CONT and T females at 20–23 wk (prepubertal), 10 months (normal onset of puberty and oligo-anovulation), and 21 months (oligo-anovulation in T females). Tissue was analyzed for GnRH immunoreactivity (ir), total GnRH afferents (Synapsin-I ir), glutamate [vesicular glutamate transporter-2 (VGLUT2)-ir], and γ-aminobutyric acid [GABA, vesicular GABA transporter (VGAT)-ir] afferents and glial associations (glial fibrillary acidic protein-ir) with GnRH neurons using optical sectioning techniques. The results revealed that: 1) GnRH soma size was slightly reduced by T, 2) the total (Synapsin-I) GnRH afferents onto both somas and dendrites increased significantly with age and was reduced by T, 3) numbers of both VGAT and VGLUT inputs increased significantly with age and were also reduced by T, and 4) glial associations with GnRH neurons were reduced (<10%) by T. Together, these findings reveal a previously unknown developmental plasticity in the GnRH system of the sheep. The altered developmental trajectory of GnRH afferents after T reinforces the notion that prenatal programming plays an important role in the normal

Infrared spectroscopy investigation of Fe-promoted Rh catalysts supported on Titania and Ceria for CO hydrogenation

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

Magee, Joseph W.; Palomino, Robert M.; White, Michael G.

2016-07-04

The nature of the promotional effect of Fe addition to Rh/TiO 2 and Rh/CeO 2 catalysts for CO hydrogenation was investigated using FT-IR spectroscopy in an ultrahigh vacuum compatible transmission IR cell. CO adsorption experiments on Rh and FeRh showed vibrational signatures characteristic of linear and bridge bound CO on Rh0 as well as geminal-dicarbonyl species associated with Rh +. Compared to TiO 2, the CeO 2-supported catalysts show increased dispersion, reflected by decreased particle size, and a lower signal for linear versus geminal-dicarbonyl bonded CO. The absorption frequencies for CO on Rh/CeO 2 are also redshifted relative to Rh/TiOmore » 2, which results from a weaker Rh–CO interaction, likely due to the increased reducibility of the CeO 2 support. Upon addition of Fe, a new spectral feature is observed and attributed to CO bound to Rh in close contact with Fe, likely as a surface alloy. CO hydrogenation on (Fe)Rh catalysts on both supports was also studied. Compared to bare Rh, Fe containing catalysts promote formate and methoxy species on the surface at lower temperature (180 °C), which suggests an enhancement in methanol selectivity by Fe addition. Furthermore, at higher temperatures (220 °C), the spectral features appear similar, further confirming the role of Fe as a disrupter of large Rh o crystallites and regulator of CO dissociation and CH 4 formation.« less

Fourier Transform Infrared Spectroscopy: Part II. Advantages of FT-IR.

ERIC Educational Resources Information Center

Perkins, W. D.

1987-01-01

This is Part II in a series on Fourier transform infrared spectroscopy (FT-IR). Described are various advantages of FT-IR spectroscopy including energy advantages, wavenumber accuracy, constant resolution, polarization effects, and stepping at grating changes. (RH)

Tunable resistivity due to kinetic arrest of antiferro-ferromagnetic transition in FeRh0.46Pd0.54

NASA Astrophysics Data System (ADS)

Saha, Pampi; Rawat, R.

2018-05-01

We show a large negative magnetoresistance (MR) of ≈10% near room temperature in FeRh0.46Pd0.54, which increases to more than 60% at low temperatures. The magnitude of resistivity and, hence, MR depend on the history of the sample in HT (magnetic field-temperature) space, e.g., resistivity at 5 K changes by more than 70% with thermal cycling. These results are explained due to slow kinetics of the transformation from austenite antiferromagnetic (AF) to martensite ferromagnetic (FM) state with the decrease in temperature. As a result, AF to FM transformation remains incomplete on experimental time scales and non-ergodic AF phase co-exists with a low temperature equilibrium FM phase. In the present system, the kinetics of the transition is shown to dominate up to 150 K, which is significantly high in comparison to other kinetically arrested systems.

Durable Clinical Benefit in Metastatic Renal Cell Carcinoma Patients Who Discontinue PD-1/PD-L1 Therapy for Immune-Related Adverse Events.

PubMed

Martini, Dylan J; Hamieh, Lana; McKay, Rana R; Harshman, Lauren C; Brandao, Raphael; Norton, Craig K; Steinharter, John A; Krajewski, Katherine M; Gao, Xin; Schutz, Fabio A; McGregor, Bradley; Bossé, Dominick; Lalani, Aly-Khan A; De Velasco, Guillermo; Michaelson, M Dror; McDermott, David F; Choueiri, Toni K

2018-04-01

The current standard of care for treatment of metastatic renal cell carcinoma (mRCC) patients is PD-1/PD-L1 inhibitors until progression or toxicity. Here, we characterize the clinical outcomes for 19 mRCC patients who experienced an initial clinical response (any degree of tumor shrinkage), but after immune-related adverse events (irAE) discontinued all systemic therapy. Clinical baseline characteristics, outcomes, and survival data were collected. The primary endpoint was time to progression from the date of treatment cessation (TTP). Most patients had clear cell histology and received anti-PD-1/PD-L1 therapy as second-line or later treatment. Median time on PD-1/PD-L1 therapy was 5.5 months (range, 0.7-46.5) and median TTP was 18.4 months (95% CI, 4.7-54.3) per Kaplan-Meier estimation. The irAEs included arthropathies, ophthalmopathies, myositis, pneumonitis, and diarrhea. We demonstrate that 68.4% of patients ( n = 13) experienced durable clinical benefit off treatment (TTP of at least 6 months), with 36% ( n = 7) of patients remaining off subsequent treatment for over a year after their last dose of anti-PD-1/PD-L1. Three patients with tumor growth found in a follow-up visit, underwent subsequent surgical intervention, and remain off systemic treatment. Nine patients (47.4%) have ongoing irAEs. Our results show that patients who benefitted clinically from anti-PD-1/PD-L1 therapy can experience sustained beneficial responses, not needing further therapies after the initial discontinuation of treatment due to irAEs. Investigation of biomarkers indicating sustained benefit to checkpoint blockers are needed. Cancer Immunol Res; 6(4); 402-8. ©2018 AACR . ©2018 American Association for Cancer Research.

AFLOWLIB.ORG: a Distributed Materials Properties Repository from High-throughput Ab initio Calculations

DTIC Science & Technology

2011-11-15

uncle) fcc (uncle) hcp (uncle) phase-diagram Ag Al Al Au Au Bi Bi Ca Ca Cd Cd Ce Ce Co Co Cr Cr Cu Cu Fe Fe Ga Ga Gd Gd Ge Ge Hf...Hf Hg Hg In In Ir Ir La La Li Li Mg Mg Mn Mn Mo Mo Na Na Nb Nb Ni Ni Os Os Pb Pb Pd Pd Pt Pt Rb Rb Re Re Rh Rh Ru Ru Sb Sb Sc...2 S. Curtarolo, A. N. Kolmogorov, and F. H. Cocks, High-throughput ab initio analysis of the Bi-In, Bi- Mg , Bi-Sb, In- Mg , In-Sb, and Mg -Sb systems

Superelectrophilic tetrakis(carbonyl)palladium(II)- and -platinum(II) undecafluorodiantimonate(V), [Pd(CO)4][Sb(2)F(11)]2 and [Pt(CO)4][Sb(2)F(11)]2: syntheses, physical and spectroscopic properties, their crystal, molecular, and extended structures, and density functional calculations: an experimental, computational, and comparative study .

PubMed

Willner, H; Bodenbinder, M; Bröchler, R; Hwang, G; Rettig, S J; Trotter, J; von Ahsen, B; Westphal, U; Jonas, V; Thiel, W; Aubke, F

2001-01-31

The salts [M(CO)(4)][Sb(2)F(11)](2), M = Pd, Pt, are prepared by reductive carbonylation of Pd[Pd(SO(3)F)(6)], Pt(SO(3)F)(4) or PtF(6) in liquid SbF(5), or HF-SbF(5). The resulting moisture-sensitive, colorless solids are thermally stable up to 140 degrees C (M = Pd) or 200 degrees C (M = Pt). Their thermal decompositions are studied by differential scanning calorimetry (DSC). Single crystals of both salts are suitable for an X-ray diffraction study at 180 K. Both isostructural salts crystallize in the monoclinic space group P2(1)/c (No. 14). The unit cell volume of [Pt(CO)(4)][Sb(2)F(11)](2) is smaller than that of [Pd(CO)(4)][Sb(2)F(11)](2) by about 0.4%. The cations [M(CO)(4)](2+), M = Pd, Pt, are square planar with only very slight angular and out-of-plane deviations from D(4)(h)() symmetry. The interatomic distances and bond angles for both cations are essentially identical. The [Sb(2)F(11)](-) anions in [M(CO)(4)][Sb(2)F(11)](2,) M = Pd, Pt, are not symmetry-related, and both pairs differ in their Sb-F-Sb bridge angles and their dihedral angles. There are in each salt four to five secondary interionic C- -F contacts per CO group. Of these, two contacts per CO group are significantly shorter than the sum of the van der Waals radii by 0.58 - 0.37 A. In addition, structural, and spectroscopic details of recently synthesized [Rh(CO)(4)][Al(2)Cl(7)] are reported. The cations [Rh(CO)(4)](+) and [M(CO)(4)](2+), M = Pd, Pt, are characterized by IR and Raman spectroscopy. Of the 16 vibrational modes (13 observable, 3 inactive) 10 (Pd, Pt) or 9 (Rh), respectively, are found experimentally. The vibrational assignments are supported by DFT calculations, which provide in addition to band positions also intensities of IR bands and Raman signals as well as internal force constants for the cations. (13)C NMR measurements complete the characterization of the square planar metal carbonyl cations. The extensive characterization of [M(CO)(4)][Sb(2)F(11)](2), M = Pd, Pt, reported

Synthesis, crystal structure and electronic structure of the binary phase Rh2Cd5

NASA Astrophysics Data System (ADS)

Koley, Biplab; Chatterjee, S.; Jana, Partha P.

2017-02-01

A new phase in the Rh-Cd binary system - Rh2Cd5 has been identified and characterized by single crystal X-ray diffraction and Energy dispersive X-ray analysis. The stoichiometric compound Rh2Cd5 crystallizes with a unit cell containing 14 atoms, in the orthorhombic space group Pbam (55). The crystal structure of Rh2Cd5 can be described as a defect form of the In3Pd5 structure with ordered vacancies, formed of two 2D atomic layers with the stacking sequence: ABAB. The A type layers consist of (3.6.3.6)-Kagomé nets of Cd atoms while the B type layers consist of (35) (37)- nets of both Cd and Rh atoms. The stability of this line phase is investigated by first principle electronic structure calculations on the model of ordered Rh2Cd5.

Inflammatory gastrointestinal diseases associated with PD-1 blockade antibodies.

PubMed

Collins, M; Michot, J M; Danlos, F X; Mussini, C; Soularue, E; Mateus, C; Loirat, D; Buisson, A; Rosa, I; Lambotte, O; Laghouati, S; Chaput, N; Coutzac, C; Voisin, A L; Soria, J C; Marabelle, A; Champiat, S; Robert, C; Carbonnel, F

2017-11-01

Immune check-point blockade agents have shown clinical activity in cancer patients but are associated with immune-related adverse events that could limit their development. The aim of this study was to describe the gastrointestinal immune-related adverse events (GI-irAE) in patients with cancer treated with anti-PD-1. this is a retrospective study of consecutive adult patients who had a suspected GI-irAE due to anti-PD-1 antibodies between 2013 and 2016. Patients were recruited through a pharmacovigilance registry. Patients' data were reviewed by a multidisciplinary committee that included gastroenterologists, oncologists and a pathologist. Quantitative variables are described by median (range), qualitative variable by frequency (percentage). Forty-four patients were addressed to a Gastroenterology unit for a suspected GI-IrAE. Twenty patients had a confirmed GI-irAE related to anti-PD-1, which occurred 4.2 months (0.2; 22.1) after the initiation of anti-PD-1. GI-IrAE incidence rate under anti-PD-1 treatment was estimated to be 1.5%. Among patients with GI-IrAE, main symptoms were diarrhoea (n = 16, 80%), abdominal pain (n = 13, 65%), nausea and vomiting (n = 11, 55%), intestinal obstruction (n = 1, 5%), and haematochezia (n = 2, 10%). No patient had colectomy. Four distinct categories of GI-irAE were observed: acute colitis (n = 8, 40%), microscopic colitis (n = 7, 35%), upper gastrointestinal tract inflammation (n = 4, 20%) and pseudo-obstruction (n = 1, 5%). Response rates to corticosteroids were 87.5% (7/8) in acute colitis, 57% (4/7) in microscopic colitis and 75% (3/4) in upper gastrointestinal tract inflammation. Median time to resolution was 36 days (6-172) in acute colitis, and 98 days (42-226) in microscopic colitis. This study suggests that GI-irAE are different and less frequent with anti PD-1 than with anti CTLA-4. © The Author 2017. Published by Oxford University Press on behalf of the European Society for

Expanding the family of heterobimetallic Bi-Rh paddlewheel carboxylate complexes via equatorial carboxylate exchange.

PubMed

Sunderland, Travis L; Berry, John F

2016-01-07

Five novel homoleptic heterobimetallic bismuth(II)-rhodium(II) carboxylate complexes--BiRh(TPA)4 (1), BiRh(but)4 (2), BiRh(piv)4 (3), BiRh(esp)2 (4), and BiRh(OAc)4 (5)--were synthesized in good yields by equatorial ligand substitution starting from BiRh(TFA)4 (TPA = triphenylacetate, but = butyrate, piv = pivalate, esp = α,α,α',α'-tetramethyl-1,3-benzenedipropionate, OAc = acetate, and TFA = trifluoroacetate). We report here (1)H and (13)C{(1)H} NMR spectra and cyclic voltammograms for complexes , and IR spectra for all complexes. Irreversible redox waves appear between -1.4 to -1.5 V for [BiRh](3+/4+) couples and 1.3 to 1.5 V vs. Fc/Fc(+) for [BiRh](4+/5+) couples for complexes indicating a wide range of stability for the compounds. The X-ray crystal structure of reveals a Bi-Rh distance of 2.53 Å.

Combinatorial high-throughput optical screening of high performance Pd alloy cathode for hybrid Li-air battery.

PubMed

Jun, Young Jin; Park, Sung Hyeon; Woo, Seong Ihl

2014-12-08

Combinatorial high-throughput optical screening method was developed to find the optimum composition of highly active Pd-based catalysts at the cathode of the hybrid Li-air battery. Pd alone, which is one-third the cost of Pt, has difficulty in replacing Pt; therefore, the integration of other metals was investigated to improve its performance toward oxygen reduction reaction (ORR). Among the binary Pd-based catalysts, the composition of Pd-Ir derived catalysts had higher performance toward ORR compared to other Pd-based binary combinations. The composition at 88:12 at. % (Pd: Ir) showed the highest activity toward ORR at the cathode of the hybrid Li-air battery. The prepared Pd(88)Ir(12)/C catalyst showed a current density of -2.58 mA cm(-2) at 0.8 V (vs RHE), which was around 30% higher compared to that of Pd/C (-1.97 mA cm(-2)). When the prepared Pd(88)Ir(12)/C catalyst was applied to the hybrid Li-air battery, the polarization of the cell was reduced and the energy efficiency of the cell was about 30% higher than that of the cell with Pd/C.

Adsorption of Rh(III) complexes from chloride solutions obtained by leaching chlorinated spent automotive catalysts on ion-exchange resin Diaion WA21J.

PubMed

Shen, Shaobo; Pan, Tonglin; Liu, Xinqiang; Yuan, Lei; Wang, Jinchao; Zhang, Yongjian; Guo, Zhanchen

2010-07-15

It was found that Rh, Pd and Pt contained in the spent ceramic automotive catalysts could be effectively extracted by dry chlorination with chlorine. In order to concentrate Rh(III) ions contained in the chloride solutions obtained, thermodynamic and kinetics studies for adsorption of Rh(III) complexes from the chloride solutions on an anionic exchange resin Diaion WA21J were carried out. Rh, Pd, Pt, Al, Fe, Si, Zn and Pb from the chloride solution could be adsorbed on the resin. The distribution coefficients (K(d)) of Rh(III) decreased with the increase in initial Rh(III) concentration or in adsorption temperature. The isothermal adsorption of Rh(III) was found to fit Langmuir, Freundlich and Dubinin-Kaganer-Radushkevich models under the adsorption conditions. The maximum monolayer adsorption capacities Q(max) based on Langmuir adsorption isotherms were 6.39, 6.61 and 5.81 mg/g for temperatures 18, 28 and 40 degrees C, respectively. The apparent adsorption energy of Rh was about -7.6 kJ/mol and thus Rh(III) adsorption was a physical type. The experimental data obtained could be better simulated by pseudo-first-order kinetic model and the activation energy obtained was 6.54 J/mol. The adsorption rate of Rh(III) was controlled by intraparticle diffusion in most of time of adsorption process. 2010 Elsevier B.V. All rights reserved.

Metal-insulator transition and superconductivity in the spinel-type Cu(Ir1-xRhx)2S4 system

NASA Astrophysics Data System (ADS)

Matsumoto, Nobuhiro; Endoh, Ryo; Nagata, Shoichi; Furubayashi, Takao; Matsumoto, Takehiko

1999-08-01

The normal thiospinel CuIr2S4 exhibits a temperature-induced metal-insulator (M-I) transition around 226 K with structural transformation, showing hysteresis on heating and cooling. It has been verified that d electrons of Ir atom on the octahedral B sites have a significant role for the M-I transition. On the other hand, CuRh2S4 is a superconductor with the transition temperature Tc=4.70 K, which is well understood on the basis of the BCS theory. It is important to investigate the effect on the M-I transition by substitution of Rh for Ir. We have systematically studied structural transformation and electrical and magnetic properties of Cu(Ir1-xRhx)2S4. The features of the M-I transition change with Rh concentration x. A phase diagram of temperature versus x will be proposed for the Cu(Ir1-xRhx)2S4 system. The sharp M-I transition temperature varies drastically from 226 to 93 K with x from 0.00 to 0.17 and disappears around x=0.20. In a region of 0.00<=x<=0.20, the magnetic susceptibility begins decreasing at a constant onset temperature 226 K on cooling process and shows rather broad temperature variation, even though the metallic state is kept in the resistivity. The sharp M-I transition can take place after the suppression of magnitude in the susceptibility has sufficiently developed far below 226 K. These experimental results are discussed with emphasis on the intrinsic difference between Cu(Ir1-xRhx)2S4 and CuIr2(S1-xSex)4 systems. Furthermore, we will mention the superconductivity for both systems of Cu(Ir1-xRhx)2S4 with high-Rh concentration region and Cu1-xNixRh2S4.

High-pressure synthesis and structural, physical properties of CaIr1-xPtxO3 and CaIr1-xRhxO3

NASA Astrophysics Data System (ADS)

Hirai, S.; Bromiley, G. D.; Klemme, S.; Irifune, T.; Ohfuji, H.; Attfield, P.; Nishiyama, N.

2010-12-01

Since the discovery of the perovskite to post-perovskite transition in MgSiO3 in a laser-heated DAC, wide attention has been focussed on the post-perovskite phase of MgSiO3. This is because the post-perovskite phase is likely to play a key role in Earth’s lowermost mantle, and because the perovskite to post-perovskite transition can explain many features of the D” seismic discontinuity. While it is meaningful to conduct further studies of MgSiO3, the post-perovskite phase of MgSiO3 cannot be quenched to ambient pressure/temperature conditions. Thus, further studies must be conducted using analogue compounds of MgSiO3 post-perovskite, which are quenchable to ambient pressure/temperature conditions. The post-perovskite phase of MgSiO3 crystallizes in a layered structure with CaIrO3-structure. Therefore, it is useful to investigate compounds with CaIrO3-structure. There are only four quenchable oxides with CaIrO3-structure reported to date: CaIrO3, CaPtO3, CaRhO3 and CaRuO3. CaIrO3 can be synthesized at ambient pressure, whilst the other three oxides can only be obtained at high pressure/temperature conditions using a multi-anvil apparatus. Further studies on these materials have revealed structural phase transitions at high P-T and a metal-insulator transition by hole doping. In the case of CaIrO3, The post-perovskite phase of CaIrO3 synthesized at 2GPa, 1373K transforms into a perovskite phase at 2GPa, 1673K. In other words, the perovskite phase can be synthesized at temperatures higher than those needed for synthesizing the post-perovskite phase. This is also the case for CaRhO3 (6GPa, 1873K) and CaRuO3 (23GPa, 1343K), while CaPtO3 remained post-perovskite at higher temperatures. We have succeeded in synthesizing solid solutions between CaIrO3, CaPtO3 and CaRhO3. We have found the systematic change in structural and physical properties of post-perovskite oxides, with composition and P-T, which broadens the future opportunity for studying post-perovskite systems

Phase Structure and Site Preference Behavior of Ternary Alloying Additions to PdTi and PtTi Shape-Memory Alloys

NASA Technical Reports Server (NTRS)

Bozzolo, Guillermo; Mosca, Hugo O.; Noebe, Ronald D.

2006-01-01

The phasc structure and concentration dependence of the lattice parameter and energy of formation of ternary Pd-'I-X and Pt-Ti-X alloys for a large number of ternary alloying additions X (X = Na, Mg, Al, Si, Sc. V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Tc, Ru, Rh, Ag, Cd, Hf, Ta, W, Re, Os, Ir) are investigated with an atomistic modeling approach. In addition, a detailed description of the site preference behavior of such additions showing that the elements can be grouped according to their absolute preference for a specific site, regardless of concentration, or preference for available sites in the deficient sublattice is provided.

Isotope dilution inductively coupled plasma quadrupole mass spectrometry in connection with a chromatographic separation for ultra trace determinations of platinum group elements (Pt, Pd, Ru, Ir) in environmental samples.

PubMed

Müller, M; Heumann, K G

2000-09-01

An isotope dilution inductively coupled plasma quadrupole mass spectrometric (ID-ICP-QMS) method was developed for the simultaneous determination of the platinum group elements Pt, Pd, Ru, and Ir in environmental samples. Spike solutions, enriched with the isotopes 194Pt, 108Pd, 99Ru, and 191Ir, were used for the isotope dilution step. Interfering elements were eliminated by chromatographic separation using an anion-exchange resin. Samples were dissolved with aqua regia in a high pressure asher. Additional dissolution of possible silicate portions by hydrofluoric acid was usually not necessary. Detection limits of 0.15 ng x g(-1), 0.075 ng x g(-1), and 0.015 ng x g(-1) were achieved for Pt, Pd, Ru, and Ir, respectively, using sample weights of only 0.2 g. The reliability of the ID-ICP-QMS method was demonstrated by analyzing a Canadian geological reference material and by participating in an interlaboratory study for the determination of platinum and palladium in a homogenized road dust sample. Surface soil, sampled at different distances from a highway, showed concentrations in the range of 0.1-87 ng x g(-1). An exponential decrease of the platinum and palladium concentration with increasing distance and a small anthropogenic contribution to the natural background concentration of ruthenium and iridium was found in these samples.

Repeated doses of GnRH antagonist at midcycle in artificial frozen embryo transfer cycles may not affect pregnancy outcomes.

PubMed

Palmerola, Katherine L; Hsu, Jennifer Y; Grossman, Lisa C; Sauer, Mark V; Lobo, Roger A

2017-04-01

No significant differences in outcomes have been found between protocols of endometrial preparation for frozen embryo transfer (FET), though gonadotropin releasing hormone (GnRH) antagonists may have detrimental effects on the endometrium. We conducted a retrospective cohort noninferiority study at a single academic center of women receiving multiple doses of mid-cycle GnRH antagonist (GAnt) to those receiving GnRH agonist (GAg) to determine if there are detrimental effects of GnRH antagonists. 1047 FET cycles were identified, detailed data was available in 840 cycles: 610 GAg and 230 GAnt cycles. Patients undergoing GAnt cycles were older (40 ± 6.6 versus 37 ± 5.1 years, p < 0.0001), more often used donor oocyte (36% versus 18.6%, p < 0.0001), and more often exhibited diminished ovarian reserve (49.1% versus 36.2%, p = 0.0009). Clinical pregnancy rates (CPRs) per transfer and implantation rates (IRs) were similar for GAnt and GAg cycles. There was a trend for higher pregnancy and IRs with GAg cycles in younger women (CPR 38.8% versus 26.7%, p = 0.16; IR 36% versus 23.3%, p = 0.07). Stratifying by diagnosis, CPR and IR were similar in GAnt and GAg cycles. A GAnt protocol of endometrial preparation for FET is not inferior to a GAg protocol regardless of patient age, use of donor oocyte, or infertility diagnosis.

Rh Incompatibility

MedlinePlus

... type is called Rh. Rh factor is a protein on red blood cells. Most people are Rh-positive; they have Rh factor. Rh-negative people don't have it. Rh factor is inherited though genes. When you're pregnant, blood from your baby can cross into your ...

Geochemical behaviour of palladium in soils and Pd/PdO model substances in the presence of the organic complexing agents L-methionine and citric acid.

PubMed

Zereini, Fathi; Wiseman, Clare L S; Vang, My; Albers, Peter; Schneider, Wolfgang; Schindl, Roland; Leopold, Kerstin

2016-01-01

Risk assessments of platinum group metal (PGE) emissions, notably those of platinum (Pt), palladium (Pd) and rhodium (Rh), have been mostly based on data regarding the metallic forms used in vehicular exhaust converters, known to be virtually biologically inert and immobile. To adequately assess the potential impacts of PGE, however, data on the chemical behaviour of these metals under ambient conditions post-emission is needed. Complexing agents with a high affinity for metals in the environment are hypothesized to contribute to an increased bioaccessibility of PGE. The purpose of this study is to examine the modulating effects of the organic complexing agents, L-methionine and citric acid, on the geochemical behavior of Pd in soils and model substances (Pd black and PdO). Batch experimental tests were conducted with soils and model substances to examine the impacts of the concentration of complexing agents, pH and length of extraction period on Pd solubility and its chemical transformation. Particle surface chemistry was examined using X-ray photoelectron spectroscopy (XPS) on samples treated with solutions under various conditions, including low and high O2 levels. Pd was observed to be more soluble in the presence of organic complexing agents, compared to Pt and Rh. Pd in soils was more readily solubilized with organic complexing agents compared to the model substances. After 7 days of extraction, L-methionine (0.1 M) treated soil and Pd black samples, for instance, had mean soluble Pd fractions of 12.4 ± 5.9% and 0.554 ± 0.024%, respectively. Surface chemistry analyses (XPS) confirmed the oxidation of metallic Pd surfaces when treated with organic complexing agents. The type of organic complexing agent used for experimental purposes was observed to be the most important factor influencing solubility, followed by solution pH and time of extraction. The results demonstrate that metallic Pd can be transformed into more bioaccessible species in the presence of

Immune-related adverse events associated with PD-1 and PD-L1 inhibitors for nonsmall cell lung cancer

PubMed Central

Sun, Xiaoying; Roudi, Raheleh; Chen, Shangya; Fan, Bin; Li, Hong Jin; Zhou, Min; Li, Xin; Li, Bin

2017-01-01

Abstract Introduction: Nonsmall cell lung cancer accounts for approximately 80% of all lung cancers, and approximately 75% of cases are diagnosed in the middle and late stages of disease. Unfortunately, limited treatment does not improve the prognosis of advanced disease. Monoclonal antibodies targeting programmed cell death protein-1 (PD-1) and programmed death-ligand 1 (PD-L1) represent a new treatment paradigm for nonsmall cell lung cancer. Nevertheless, the immune-related adverse events (irAEs) associated with PD-1 and PD-L1 inhibitors are unique, and early recognition and treatment of these events are essential. Methods and Analysis: A systematic literature search will be performed using the EMBASE, MEDLINE, and Cochrane databases to identify relevant articles published in any language. Randomized clinical trials, case series, and case reports of PD-1 and PD-L1 inhibitors in the treatment of nonsmall cell lung cancer will be included. All meta-analyses will be performed using RevMan software. The quality of the studies will be evaluated using the guidelines listed in the Cochrane Handbook. If the necessary data are available, then subgroup analyses will be performed for high-, median-, and low-dose cohorts. The Preferred Reporting Items for Systematic Reviews and Meta-Analyses statements will be followed until the findings of the systematic review and meta-analysis are reported. Conclusions: This will be the first systematic review and meta-analysis to describe previously reported irAEs related to PD-1 and PD-L1 inhibitors in the treatment of nonsmall cell lung cancer. PMID:29095271

Tunable Catalysis of Water to Peroxide with Anionic, Cationic, and Neutral Atomic Au, Ag, Pd, Rh, and Os

NASA Astrophysics Data System (ADS)

Suggs, K.; Kiros, F.; Tesfamichael, A.; Felfli, Z.; Msezane, A. Z.

2015-05-01

Fundamental anionic, cationic, and neutral atomic metal predictions utilizing density functional theory calculations validate the recent discovery identifying the interplay between Regge resonances and Ramsauer-Townsend minima obtained through complex angular momentum analysis as the fundamental atomic mechanism underlying nanoscale catalysis. Here we investigate the optimization of the catalytic behavior of Au, Ag, Pd, Rh, and Os atomic systems via polarization effects and conclude that anionic atomic systems are optimal and therefore ideal for catalyzing the oxidation of water to peroxide, with anionic Os being the best candidate. The discovery that cationic systems increase the transition energy barrier in the synthesis of peroxide could be important as inhibitors in controlling and regulating catalysis. These findings usher in a fundamental and comprehensive atomic theoretical framework for the generation of tunable catalytic systems. The ultimate aim is to design giant atomic catalysts and sensors, in the context of the recently synthesized tri-metal Ag@Au@Pt and bimetal Ag@Au nanoparticles for greatly enhanced plasmonic properties and improved chemical stability for chemical and biological sensing. Research was supported by U.S. DOE Office of Basic Energy Sciences.

Ferromagnetism of Pd-Fe (abstract)

NASA Astrophysics Data System (ADS)

Griffith, G.; Carnegie, D. W., Jr.; Claus, H.

1984-03-01

We present new low field ac susceptibility measurements on Pd1-xFex alloys (0.002≤X<0.01). The Curie temperature TC, determined from these measurements, are significantly lower than those previously obtained in higher magnetic fields [G. J. Nieuwenhuys, Adv. Phys. 24, 515 (1975)]. We also found that for a given sample, TC depends very sensitively on its heat treatment. As an example, for an alloy with 0.4 at. % Fe, TC can be varied between 4 and 10 K. In other alloys, like PdNi or RhNi similar changes in TC are due to changes in the degree of atomic short-range order [S. Crane, D. W. Carnegie, Jr., and H. Claus, J. Appl. Phys. 53, 2179 (1982)]. However, for PdFe we show evidence that the changes in TC are due to absorption of small amounts of oxygen, the samples with the highest amount of oxygen having the highest TC. It thus seems that oxygen has the opposite effect from hydrogen on the exchange enhanced susceptibility of Pd [J. A. Mydosh, Phys. Rev. Lett. 33, 1562 (1974)].

Magnitude of the magnetic exchange interaction in the heavy-fermion antiferromagnet CeRhIn 5

DOE PAGES

Das, Pinaki; Lin, S. -Z.; Ghimire, N. J.; ...

2014-12-08

We have used high-resolution neutron spectroscopy experiments to determine the complete spin wave spectrum of the heavy-fermion antiferromagnet CeRhIn₅. The spin wave dispersion can be quantitatively reproduced with a simple frustrated J₁-J₂ model that also naturally explains the magnetic spin-spiral ground state of CeRhIn₅ and yields a dominant in-plane nearest-neighbor magnetic exchange constant J₀=0.74(3) meV. Our results lead the way to a quantitative understanding of the rich low-temperature phase diagram of the prominent CeTIn₅ (T = Co, Rh, Ir) class of heavy-fermion materials.

Thermodynamic assessment of the rhodium-ruthenium-oxygen (Rh-Ru-O) system

NASA Astrophysics Data System (ADS)

Gossé, S.; Bordier, S.; Guéneau, C.; Brackx, E.; Domenger, R.; Rogez, J.

2018-03-01

Ruthenium (Ru) and rhodium (Rh) are abundant platinum-group metals formed during burn-up of nuclear fuels. Under normal operating conditions, Rh and Ru accumulate and predominantly form metallic precipitates with other fission products like Mo, Pd and Tc. In the framework of vitrification of high-level nuclear waste, these fission products are poorly soluble in molten glasses. They precipitate as metallic particles and oxide phases. Moreover, these Ru and Rh rich phases strongly depend on temperature and the oxygen fugacity of the glass melt. In case of severe accidental conditions with air ingress, oxidation of the Ru and Rh is possible. At low temperatures (T < 1422 K for rhodium sesquioxide and T < 1815 K for ruthenium dioxide), the formed oxides are relatively stable. On the other hand, at high temperatures (T > 1422 K for rhodium sesquioxide and T > 1815 K for ruthenium dioxide), they may decompose into (Rh)-FCC or (Ru)-HCP metallic phases and radiotoxic volatile gaseous species. A thermodynamic assessment of the Rh-Ru-O system will enable the prediction of: (1) the metallic and oxide phases that form during the vitrification of high-level nuclear wastes and (2) the release of volatile gaseous species during a severe accident. The Calphad method developed herein employs a thermodynamic approach in the investigation of the thermochemistry of rhodium and ruthenium at high temperatures. Current literature on the thermodynamic properties and phase diagram data enables preliminary thermodynamic assessments of the Rh-O and Ru-O systems. Additionally, select compositions in the ternary Rh-Ru-O system underwent experimental tests to complement data found in literature and to establish the phase equilibria in the ternary system.

Near infrared photoimmunotherapy with avelumab, an anti-programmed death-ligand 1 (PD-L1) antibody.

PubMed

Nagaya, Tadanobu; Nakamura, Yuko; Sato, Kazuhide; Harada, Toshiko; Choyke, Peter L; Hodge, James W; Schlom, Jeffrey; Kobayashi, Hisataka

2017-01-31

Near Infrared-Photoimmunotherapy (NIR-PIT) is a highly selective tumor treatment that employs an antibody-photo-absorber conjugate (APC). Programmed cell death protein-1 ligand (PD-L1) is emerging as a molecular target. Here, we describe the efficacy of NIR-PIT, using fully human IgG1 anti-PD-L1 monoclonal antibody (mAb), avelumab, conjugated to the photo-absorber, IR700DX, in a PD-L1 expressing H441 cell line, papillary adenocarcinoma of lung. Avelumab-IR700 showed specific binding and cell-specific killing was observed after exposure of the cells to NIR in vitro. In the in vivo study, avelumab-IR700 showed high tumor accumulation and high tumor-background ratio. Tumor-bearing mice were separated into 4 groups: (1) no treatment; (2) 100 μg of avelumab-IR700 i.v.; (3) NIR light exposure only, NIR light was administered; (4) 100 μg of avelumab-IR700 i.v., NIR light was administered. Tumor growth was significantly inhibited by NIR-PIT treatment compared with the other groups (p < 0.001), and significantly prolonged survival was achieved (p < 0.01 vs other groups). In conclusion, the anti-PD-L1 antibody, avelumab, is suitable as an APC for NIR-PIT. Furthermore, NIR-PIT with avelumab-IR700 is a promising candidate of the treatment of PD-L1-expressing tumors that could be readily translated to humans.

Near infrared photoimmunotherapy with avelumab, an anti-programmed death-ligand 1 (PD-L1) antibody

PubMed Central

Nagaya, Tadanobu; Nakamura, Yuko; Sato, Kazuhide; Harada, Toshiko; Choyke, Peter L.; Hodge, James W.; Schlom, Jeffrey; Kobayashi, Hisataka

2017-01-01

Near Infrared-Photoimmunotherapy (NIR-PIT) is a highly selective tumor treatment that employs an antibody-photo-absorber conjugate (APC). Programmed cell death protein-1 ligand (PD-L1) is emerging as a molecular target. Here, we describe the efficacy of NIR-PIT, using fully human IgG1 anti-PD-L1 monoclonal antibody (mAb), avelumab, conjugated to the photo-absorber, IR700DX, in a PD-L1 expressing H441 cell line, papillary adenocarcinoma of lung. Avelumab-IR700 showed specific binding and cell-specific killing was observed after exposure of the cells to NIR in vitro. In the in vivo study, avelumab-IR700 showed high tumor accumulation and high tumor-background ratio. Tumor-bearing mice were separated into 4 groups: (1) no treatment; (2) 100 μg of avelumab-IR700 i.v.; (3) NIR light exposure only, NIR light was administered; (4) 100 μg of avelumab-IR700 i.v., NIR light was administered. Tumor growth was significantly inhibited by NIR-PIT treatment compared with the other groups (p < 0.001), and significantly prolonged survival was achieved (p < 0.01 vs other groups). In conclusion, the anti-PD-L1 antibody, avelumab, is suitable as an APC for NIR-PIT. Furthermore, NIR-PIT with avelumab-IR700 is a promising candidate of the treatment of PD-L1-expressing tumors that could be readily translated to humans. PMID:27716622

Synthesis, crystal structures, and characterization of double complex salts [Au(en)2][Rh(NO2)6]·2H2O and [Au(en)2][Rh(NO2)6

NASA Astrophysics Data System (ADS)

Plyusnin, Pavel E.; Makotchenko, Evgenia V.; Shubin, Yury V.; Baidina, Iraida A.; Korolkov, Ilya V.; Sheludyakova, Liliya A.; Korenev, Sergey V.

2015-11-01

Double complex salts of rhodium(III) and gold(III) of the composition [Au(en)2][Rh(NO2)6]·2H2O (1) and [Au(en)2][Rh(NO2)6] (2) have been prepared. Crystal structures of the compounds have been determined by single crystal X-ray diffraction. The compounds have been characterized by PXRD, IR, far-IR, CHN and DTA. The complexes have a layered structures. The presence of water in 1 makes the structure of the hydrated DCS less dense as compared to the anhydrous one. The environment of the cation and the anion in the two structures is the same, oxygen atoms of the nitro groups are involved in hydrogen bonds N-H⋯O, N⋯O distances being approximately the same. The structures of 1 and 2 are notable in having shortened contacts between the gold atoms and the oxygen atoms of the nitro groups of the neighboring complex anions. The thermal behavior of the complexes in a hydrogen atmosphere was investigated. The final product of thermolysis prepared at the temperature 600°C is a two-phase mixture of pure metallic gold and the solid solution Rh0.93Au0.07.

Chemical composition and reactivity of water on hexagonal Pt-group metal surfaces.

PubMed

Shavorskiy, A; Gladys, M J; Held, G

2008-10-28

The dissociation behaviour and valence-electronic structure of water adsorbed on clean and oxygen-covered Ru{0001}, Rh{111}, Pd{111}, Ir{111} and Pt{111} surfaces has been studied by high-resolution X-ray photoelectron spectroscopy with the aim of identifying similarities and trends within the Pt-group metals. On average, we find higher reactivity for the 4d metals (Ru, Rh, Pd) as compared to 5d (Ir, Pt), which is correlated with characteristic shifts in the 1b(1) and 3a(1) molecular orbitals of water. Small amounts of oxygen (< 0.2 ML) induce dissociation of water on all five surfaces, for higher coverages (> 0.25 ML) only intact water is observed. Under UHV conditions these higher coverages can only be reached on the 4d metals, the 5d metals are, therefore, not passivated.

Anti-PD-L1 Treatment Induced Central Diabetes Insipidus.

PubMed

Zhao, Chen; Tella, Sri Harsha; Del Rivero, Jaydira; Kommalapati, Anuhya; Ebenuwa, Ifechukwude; Gulley, James; Strauss, Julius; Brownell, Isaac

2018-02-01

Immune checkpoint inhibitors, including anti-programmed cell death protein 1 (PD-1), anti-programmed cell death protein ligand 1 (PD-L1), and anti-cytotoxic T-lymphocyte antigen 4 (anti-CTLA4) monoclonal antibodies, have been widely used in cancer treatment. They are known to cause immune-related adverse events (irAEs), which resemble autoimmune diseases. Anterior pituitary hypophysitis with secondary hypopituitarism is a frequently reported irAE, especially in patients receiving anti-CTLA4 treatment. In contrast, posterior pituitary involvement, such as central diabetes insipidus (DI), is relatively rare and is unreported in patients undergoing PD-1/PD-L1 blockade. We describe a case of a 73-year-old man with Merkel cell carcinoma who received the anti-PD-L1 monoclonal antibody avelumab and achieved partial response. The patient developed nocturia, polydipsia, and polyuria 3 months after starting avelumab. Further laboratory testing revealed central DI. Avelumab was held and he received desmopressin for the management of central DI. Within 6 weeks after discontinuation of avelumab, the patient's symptoms resolved and he was eventually taken off desmopressin. The patient remained off avelumab and there were no signs or symptoms of DI 2 months after the discontinuation of desmopressin. To our knowledge, this is the first report of central DI associated with anti-PD-L1 immunotherapy. The patient's endocrinopathy was successfully managed by holding treatment with the immune checkpoint inhibitor. This case highlights the importance of early screening and appropriate management of hormonal irAEs in subjects undergoing treatment with immune checkpoint inhibitors to minimize morbidity and mortality. Copyright © 2017 Endocrine Society

Hydrogen in thin Pd-based layers deposited on reticulated vitreous carbon-A new system for electrochemical capacitors

NASA Astrophysics Data System (ADS)

Łukaszewski, M.; Żurowski, A.; Czerwiński, A.

Reticulated vitreous carbon (RVC) has been used as a matrix for electrodeposition of thin layers of Pd and Pd-rich Pd-Rh alloys. It was found that RVC substrate does not affect qualitatively hydrogen absorption behavior of Pd-based deposits. Similarly to thin Pd or Pd alloy layers deposited on Au wires, the α-β phase transition controls the overall rate of hydrogen absorption and desorption into/from Pd-based/RVC electrodes. The possibility of the application of these materials as phase charging-discharging systems was investigated. The values of specific pseudocapacitance, specific power and specific energy were comparable with those for supercapacitors utilizing various redox reactions.

Formation of gallium vacancies and their effects on the nanostructure of Pd/Ir/Au ohmic contact to p-type GaN.

PubMed

Kim, Kyong Nam; Kim, Tae Hyung; Seo, Jin Seok; Kim, Ki Seok; Bae, Jeong Woon; Yeom, Geun Young

2013-12-01

The properties of Pd/Ir/Au ohmic metallization on p-type GaN have been investigated. Contacts annealed at 400 degrees C in O2 atmosphere demonstrated excellent ohmic characteristics with a specific contact resistivity of 1.5 x 10(-5) Omega-cm2. This is attributed to the formation of Ga vacancies at the contact metal-semiconductor interfacial region due to the out-diffusion of Ga atoms. The out-diffusion of Ga atoms was confirmed by X-ray photoelectron spectroscopy depth profiles, high-resolution transmission electron microscopy, and electron energy loss spectroscopy using a scanning transmission electron microscope.

Ir catalysts: Preventing CH3COOH formation in ethanol oxidation

NASA Astrophysics Data System (ADS)

Miao, Bei; Wu, Zhipeng; Xu, Han; Zhang, Minhua; Chen, Yifei; Wang, Lichang

2017-11-01

Current catalysts used for ethanol oxidation reaction (EOR) cannot effectively prevent CH3COOH formation, and thus become a major hindrance for direct ethanol fuel cell applications. We report an Ir catalyst that shows great promise for a complete EOR based on density functional theory calculations using PBE functional. The reaction barrier on Ir(1 0 0) was found to be 2.10 eV for CH3COOH formation, which is much higher than currently used Pd and Pt, and 0.57 eV for Csbnd C bond cleavage in CHCO species, which are comparable to Pd and Pt. The result suggests future directions for studying optimal complete EOR catalysts.

Synthesis, crystal structure and electronic structure of the binary phase Rh{sub 2}Cd{sub 5}

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

Koley, Biplab; Chatterjee, S.; Jana, Partha P., E-mail: ppj@chem.iitkgp.ernet.in

2017-02-15

A new phase in the Rh-Cd binary system - Rh{sub 2}Cd{sub 5} has been identified and characterized by single crystal X-ray diffraction and Energy dispersive X-ray analysis. The stoichiometric compound Rh{sub 2}Cd{sub 5} crystallizes with a unit cell containing 14 atoms, in the orthorhombic space group Pbam (55). The crystal structure of Rh{sub 2}Cd{sub 5} can be described as a defect form of the In{sub 3}Pd{sub 5} structure with ordered vacancies, formed of two 2D atomic layers with the stacking sequence: ABAB. The A type layers consist of (3.6.3.6)-Kagomé nets of Cd atoms while the B type layers consist ofmore » (3{sup 5}) (3{sup 7})- nets of both Cd and Rh atoms. The stability of this line phase is investigated by first principle electronic structure calculations on the model of ordered Rh{sub 2}Cd{sub 5}. - Graphical abstract: (3.6.3.6)-Kagomé nets of cadmium atoms (top) and (3{sup 5}) (3{sup 7})- nets of both cadmium and rhodium atoms (bottom) in the structure of Rh{sub 2}Cd{sub 5}.« less

Cluster pattern analysis of energy deposition sites for the brachytherapy sources 103Pd, 125I, 192Ir, 137Cs, and 60Co.

PubMed

Villegas, Fernanda; Tilly, Nina; Bäckström, Gloria; Ahnesjö, Anders

2014-09-21

Analysing the pattern of energy depositions may help elucidate differences in the severity of radiation-induced DNA strand breakage for different radiation qualities. It is often claimed that energy deposition (ED) sites from photon radiation form a uniform random pattern, but there is indication of differences in RBE values among different photon sources used in brachytherapy. The aim of this work is to analyse the spatial patterns of EDs from 103Pd, 125I, 192Ir, 137Cs sources commonly used in brachytherapy and a 60Co source as a reference radiation. The results suggest that there is both a non-uniform and a uniform random component to the frequency distribution of distances to the nearest neighbour ED. The closest neighbouring EDs show high spatial correlation for all investigated radiation qualities, whilst the uniform random component dominates for neighbours with longer distances for the three higher mean photon energy sources (192Ir, 137Cs, and 60Co). The two lower energy photon emitters (103Pd and 125I) present a very small uniform random component. The ratio of frequencies of clusters with respect to 60Co differs up to 15% for the lower energy sources and less than 2% for the higher energy sources when the maximum distance between each pair of EDs is 2 nm. At distances relevant to DNA damage, cluster patterns can be differentiated between the lower and higher energy sources. This may be part of the explanation to the reported difference in RBE values with initial DSB yields as an endpoint for these brachytherapy sources.

Cluster pattern analysis of energy deposition sites for the brachytherapy sources 103Pd, 125I, 192Ir, 137Cs, and 60Co

NASA Astrophysics Data System (ADS)

Villegas, Fernanda; Tilly, Nina; Bäckström, Gloria; Ahnesjö, Anders

2014-09-01

Analysing the pattern of energy depositions may help elucidate differences in the severity of radiation-induced DNA strand breakage for different radiation qualities. It is often claimed that energy deposition (ED) sites from photon radiation form a uniform random pattern, but there is indication of differences in RBE values among different photon sources used in brachytherapy. The aim of this work is to analyse the spatial patterns of EDs from 103Pd, 125I, 192Ir, 137Cs sources commonly used in brachytherapy and a 60Co source as a reference radiation. The results suggest that there is both a non-uniform and a uniform random component to the frequency distribution of distances to the nearest neighbour ED. The closest neighbouring EDs show high spatial correlation for all investigated radiation qualities, whilst the uniform random component dominates for neighbours with longer distances for the three higher mean photon energy sources (192Ir, 137Cs, and 60Co). The two lower energy photon emitters (103Pd and 125I) present a very small uniform random component. The ratio of frequencies of clusters with respect to 60Co differs up to 15% for the lower energy sources and less than 2% for the higher energy sources when the maximum distance between each pair of EDs is 2 nm. At distances relevant to DNA damage, cluster patterns can be differentiated between the lower and higher energy sources. This may be part of the explanation to the reported difference in RBE values with initial DSB yields as an endpoint for these brachytherapy sources.

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.

Platinum-Group Elements in Soils and Street Dust of the Southeastern Administrative District of Moscow

NASA Astrophysics Data System (ADS)

Ladonin, D. V.

2018-03-01

The contents of five platinum-group metals (Ru, Rh, Pd, Ir, and Pt) in soils and street dust of the Southeastern administrative district (SEAD) of Moscow have been determined. The contents of these elements in soils may considerably exceed their natural abundances in the lithosphere and are characterized by considerable variability and asymmetric frequency distribution. A close correlation between Rh, Pd, and Pt contents in soils and street dust has been shown. The data on the contents of the elements and the ratios between them suggest that motor vehicles are the major source of pollution of soils and street dust in the studied district.

Density-functional theory study of the initial oxygen incorporation in Pd(111)

NASA Astrophysics Data System (ADS)

Todorova, Mira; Reuter, Karsten; Scheffler, Matthias

2005-05-01

Pd(111) has recently been shown to exhibit a propensity to form a subnanometer thin surface oxide film already well before a full monolayer coverage of adsorbed O atoms is reached on the surface. Aiming at an atomic-scale understanding of this finding, we study the initial oxygen incorporation into the Pd(111) surface using density-functional theory. We find that oxygen incorporation into the sub-surface region starts at essentially the same coverage as formation of the surface oxide. This implies that the role of sub-surface oxygen should be considered as that of a metastable precursor in the oxidation process of the surface. The mechanisms found to play a role towards the ensuing stabilization of an ordered oxidic structure with a mixed on-surface/sub-surface site occupation follow a clear trend over the late 4d transition metal series, as seen by comparing our data to previously published studies concerned with oxide formation at the basal surface of Ru, Rh, and Ag. The formation of a linearly aligned O-TM-O trilayered structure (TM=Ru,Rh,Pd,Ag) , together with an efficient coupling to the underlying substrate seem to be key ingredients in this respect.

Predominant Suppression of FSHβ-immunoreactivity after Long-Term Treatment of Intact and Castrate Adult Male Rats with the GnRH Agonist Deslorelin

PubMed Central

Smith, Arik W.; Asa, Cheryl S.; Edwards, Brian S.; Murdoch, William J.; Skinner, Donal C.

2017-01-01

GnRH agonists are used to treat gonadal steroid-dependent disorders in humans and contracept animals. These agonists are thought to work by desensitizing gonadotropes to GnRH, thereby suppressing FSH and LH secretion. It is not known whether changes occur in the cellular composition of the pituitary gland following chronic GnRH agonist exposure. Adult male Sprague-Dawley rats were treated with a sham, deslorelin, or deslorelin plus testosterone implant for 41.0±0.6 days. In a second experiment, rats were castrated and treated with deslorelin and/or testosterone. Pituitary sections were labeled immunocytochemically for FSHβ and LHβ, or αGSU. Deslorelin suppressed testis weight by two thirds and reduced plasma FSH and LH in intact rats. Deslorelin decreased the percentage of gonadotropes but the effect was specific to the FSHβ-ir cells. Testosterone did not reverse the deslorelin-induced reduction in the overall gonadotrope population. However, in the presence of testosterone, the proportion of gonadotropes that was FSHβ-ir increased in the remaining gonadotropes. There was no effect of treatment on the total LHβ-ir cell population although the loss of FSHβ in bi-hormonal cells increased the proportion of mono-hormonal LHβ-ir gonadotropes. The castration-induced plasma LH and FSH increases were suppressed by deslorelin, testosterone or both. Castration increased both LH-ir and FSH-ir without increasing the overall gonadotrope population; thus increasing the proportion of bi-hormonal cells. Deslorelin suppressed these increases. Testosterone increased FSH-ir in deslorelin-treated castrate rats. Deslorelin did not affect αGSU immunoreactivity, suggesting that the gonadotrope population per se is not eliminated by deslorelin but the ability of gonadotropes to synthesize FSHβ is compromised. We hypothesize that the FSH dominant suppression may be central to the long-term contraceptive efficacy of deslorelin in the male. PMID:22172059

Green light inhibits GnRH-I expression by stimulating the melatonin-GnIH pathway in the chick brain.

PubMed

Zhang, L; Chen, F; Cao, J; Dong, Y; Wang, Z; Hu, M; Chen, Y

2017-05-01

To study the mechanism by which monochromatic light affects gonadotrophin-releasing hormone (GnRH) expression in chicken hypothalamus, a total of 192 newly-hatched chicks were divided into intact, sham-operated and pinealectomy groups and exposed to white (WL), red (RL), green (GL) and blue (BL) lights using a light-emitting diode system for 2 weeks. In the GL intact group, the mRNA and protein levels of GnRH-I in the hypothalamus, the mean cell area and mean cell optical density (OD) of GnRH-I-immunoreactive (-ir) cells of the nucleus commissurae pallii were decreased by 13.2%-34.5%, 5.7%-39.1% and 9.9%-17.3% compared to those in the chicks exposed to the WL, RL and BL, respectively. GL decreased these factors related to GnRH-I expression and the effect of GL was not observed in pinealectomised birds. However, the mRNA and protein levels of hypothalamic gonadotrophin-inhibitory hormone (GnIH) and GnIH receptor (GnIHR), the mean cell area and mean cell OD of the GnIH-ir cells of the paraventricularis magnocellularis, and the plasma melatonin concentration in the chicks exposed to GL were increased by 18.6%-49.2%, 21.1%-60.0% and 8.6%-30.6% compared to the WL, RL and BL intact groups, respectively. The plasma melatonin concentration showed a negative correlation with GnRH-I protein and a positive correlation with GnIH and GnIHR proteins. Protein expression of both GnRH-I and GnIHR showed a negative correlation in the hypothalamus. After pinealectomy, GnRH-I expression increased, whereas plasma melatonin concentration, GnIH and GnIHR expression decreased, and there were no significant differences among the WL, RL, GL and BL groups. Double-labelled immunofluorescence showed that GnIH axon terminals were near GnRH-I neurones, some GnRH-I neurones coexpressed with GnIHR and GnIH neurones coexpressed with melatonin receptor subtype quinone reductase 2. These results demonstrate that green light inhibits GnRH-I expression by increasing melatonin secretion and stimulating

Cutaneous, gastrointestinal, hepatic, endocrine, and renal side-effects of anti-PD-1 therapy.

PubMed

Hofmann, Lars; Forschner, Andrea; Loquai, Carmen; Goldinger, Simone M; Zimmer, Lisa; Ugurel, Selma; Schmidgen, Maria I; Gutzmer, Ralf; Utikal, Jochen S; Göppner, Daniela; Hassel, Jessica C; Meier, Friedegund; Tietze, Julia K; Thomas, Ioannis; Weishaupt, Carsten; Leverkus, Martin; Wahl, Renate; Dietrich, Ursula; Garbe, Claus; Kirchberger, Michael C; Eigentler, Thomas; Berking, Carola; Gesierich, Anja; Krackhardt, Angela M; Schadendorf, Dirk; Schuler, Gerold; Dummer, Reinhard; Heinzerling, Lucie M

2016-06-01

Anti-programmed cell death receptor-1 (PD-1) antibodies represent an effective treatment option for metastatic melanoma as well as for other cancer entities. They act via blockade of the PD-1 receptor, an inhibitor of the T-cell effector mechanisms that limit immune responses against tumours. As reported for ipilimumab, the anti-PD-1 antibodies pembrolizumab and nivolumab can induce immune-related adverse events (irAEs). These side-effects affect skin, gastrointestinal tract, liver, endocrine system and other organ systems. Since life-threatening and fatal irAEs have been reported, adequate diagnosis and management are essential. In total, 496 patients with metastatic melanoma from 15 skin cancer centers were treated with pembrolizumab or nivolumab; 242 side-effects were described in 138 patients. In 116 of the 138 patients, side-effects affected the skin, gastrointestinal tract, liver, endocrine, and renal system. Rare side-effects included diabetes mellitus, lichen planus, and pancreas insufficiency due to pancreatitis. Anti-PD1 antibodies can induce a plethora of irAEs. The knowledge of them will allow prompt diagnosis and improve the management resulting in decreased morbidity. Copyright © 2016 Elsevier Ltd. All rights reserved.

Anti-PD-L1 atezolizumab-Induced Autoimmune Diabetes: a Case Report and Review of the Literature.

PubMed

Hickmott, Laura; De La Peña, Hugo; Turner, Helen; Ahmed, Fathelrahman; Protheroe, Andrew; Grossman, Ashley; Gupta, Avinash

2017-04-01

Programmed cell death-1 and programmed death ligand 1 (PD-1/PD-L1) inhibitors trigger an immune-mediated anti-tumour response by promoting the activation of cytotoxic T lymphocytes. Although proven to be highly effective in the treatment of several malignancies they can induce significant immune-related adverse events (irAEs) including endocrinopathies, most commonly hypophysitis and thyroid dysfunction, and rarely autoimmune diabetes. Here we present the first case report of a patient with a primary diagnosis of urothelial cancer developing PD-L1 inhibitor-induced autoimmune diabetes. A euglycemic 57 year old male presented to clinic with dehydration after the fifth cycle of treatment with the novel PD-L1 inhibitor atezolizumab. Blood tests demonstrated rapid onset hyperglycaemia (BM 24 mmol/L), ketosis and a low C-peptide level (0.65 ng/mL) confirming the diagnosis of type 1 diabetes. He responded well to insulin therapy and was discharged with stable blood glucose levels. Due to the widening use of PD-1/PD-L1 inhibitors in cancer treatment clinicians need to be aware of this rare yet treatable irAE. Given the morbidity and mortality associated with undiagnosed autoimmune diabetes we recommend routine HbA1c and plasma glucose testing in all patients prior to and during treatment with PD-1/PD-L1 inhibitors until more evidence has accumulated on identifying those patients with a pre-treatment risk of such irAEs.

Monoclinic 122-Type BaIr2Ge2 with a Channel Framework: A Structural Connection between Clathrate and Layered Compounds

DOE PAGES

Gui, Xin; Chang, Tay-Rong; Kong, Tai; ...

2017-07-18

A new 122-type phase, monoclinic BaIr2Ge2 is successfully synthesized by arc melting; X-ray diffraction and scanning electron microscopy are used to purify the phase and determine its crystal structure. BaIr2Ge2 adopts a clathrate-like channel framework structure of the monoclinic BaRh2Si2-type, with space group P21/c. Structural comparisons of clathrate, ThCr2Si2, CaBe2Ge2, and BaRh2Si2 structure types indicate that BaIr2Ge2 can be considered as an intermediate between clathrate and layered compounds. Magnetic measurements show it to be diamagnetic and non-superconducting down to 1.8 K. Different from many layered or clathrate compounds, monoclinic BaIr2Ge2 displays a metallic resistivity. Electronic structure calculations performed for BaIr2Ge2more » support its observed structural stability and physical properties.« less

Monoclinic 122-Type BaIr2Ge2 with a Channel Framework: A Structural Connection between Clathrate and Layered Compounds

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

Gui, Xin; Chang, Tay-Rong; Kong, Tai

A new 122-type phase, monoclinic BaIr2Ge2 is successfully synthesized by arc melting; X-ray diffraction and scanning electron microscopy are used to purify the phase and determine its crystal structure. BaIr2Ge2 adopts a clathrate-like channel framework structure of the monoclinic BaRh2Si2-type, with space group P21/c. Structural comparisons of clathrate, ThCr2Si2, CaBe2Ge2, and BaRh2Si2 structure types indicate that BaIr2Ge2 can be considered as an intermediate between clathrate and layered compounds. Magnetic measurements show it to be diamagnetic and non-superconducting down to 1.8 K. Different from many layered or clathrate compounds, monoclinic BaIr2Ge2 displays a metallic resistivity. Electronic structure calculations performed for BaIr2Ge2more » support its observed structural stability and physical properties.« less

Superconductivity in pressurized CeRhG e3 and related noncentrosymmetric compounds

NASA Astrophysics Data System (ADS)

Wang, Honghong; Guo, Jing; Bauer, Eric D.; Sidorov, Vladimir A.; Zhao, Hengcan; Zhang, Jiahao; Zhou, Yazhou; Wang, Zhe; Cai, Shu; Yang, Ke; Li, Aiguo; Li, Xiaodong; Li, Yanchun; Sun, Peijie; Yang, Yi-feng; Wu, Qi; Xiang, Tao; Thompson, J. D.; Sun, Liling

2018-02-01

We report the discovery of superconductivity in pressurized CeRhG e3 , a nonsuperconducting member of the isostructural family of noncentrosymmetric heavy-fermion compounds Ce T X3 (T =Co , Rh, Ir and X =Si , Ge). Superconductivity appears in CeRhG e3 at a pressure of 19.6 GPa and the transition temperature TC reaches a maximum value of 1.3 K at 21.5 GPa. This finding provides an opportunity to establish systematic correlations between superconductivity and material properties within this family. Though ambient-pressure unit-cell volumes and critical pressures for superconductivity vary substantially across the series, all family members reach a maximum TCmax at a common (±1.7%) critical cell volume Vcrit, and TCmax at Vcrit increases with increasing spin-orbit coupling strength of the d electrons. These correlations show that substantial Kondo and spin-orbit couplings favor superconductivity in this family, the latter reflecting the role of broken centrosymmetry.

Transport characteristics of mammalian Rh and Rh glycoproteins expressed in heterologous systems.

PubMed

Westhoff, C M; Wylie, D E

2006-01-01

The development and use of heterologous expression systems is critical for deciphering the function of mammalian Rh and Rh-glycoproteins. The studies here use Xenopus oocytes, well known for their ability to readily traffic and express difficult membrane proteins, and S. cerevisiae wild-type strains and mutants that are defective in ammonium transport. Data obtained in both of these expression systems revealed that mammalian Rh-glycoprotein-mediated transport (RhAG, RhBG, and RhCG) is an electroneutral process that is driven by the NH4+ concentration and the transmembrane H+ gradient, effectively exchanging NH4+ for H+ in a process that results in transport of net NH3. Homology modeling and functional studies suggest that the more recently evolved erythrocyte blood group proteins, RhCE and RhD, may not function directly in ammonia transport and may be evolving a new function in the RBC membrane. The relationship of Rh and Rh-glycoproteins to the Amt/Mep ammonium transporters is substantiated with functional transport data and structural modeling.

Socially regulated reproductive development: analysis of GnRH-1 and kisspeptin neuronal systems in cooperatively breeding naked mole-rats (Heterocephalus glaber).

PubMed

Zhou, Shuzhi; Holmes, Melissa M; Forger, Nancy G; Goldman, Bruce D; Lovern, Matthew B; Caraty, Alain; Kalló, Imre; Faulkes, Christopher G; Coen, Clive W

2013-09-01

In naked mole-rat (NMR) colonies, breeding is monopolized by the queen and her consorts. Subordinates experience gonadal development if separated from the queen. To elucidate the neuroendocrine factors underlying reproductive suppression/development in NMRs, we quantified plasma gonadal steroids and GnRH-1- and kisspeptin-immunoreactive (ir) neurons in subordinate adults and in those allowed to develop into breeders, with or without subsequent gonadectomy. In males and females, respectively, plasma testosterone and progesterone are higher in breeders than in subordinates. No such distinction occurs for plasma estradiol; its presence after gonadectomy and its positive correlation with adrenal estradiol suggest an adrenal source. Numbers of GnRH-1-ir cell bodies do not differ between gonad-intact breeders and subordinates within or between the sexes. As in phylogenetically related guinea pigs, kisspeptin-ir processes pervade the internal and external zones of the median eminence. Their distribution is consistent with actions on GnRH-1 neurons at perikaryal and/or terminal levels. In previously investigated species, numbers of kisspeptin-ir cell bodies vary from substantial to negligible according to sex and/or reproductive state. NMRs are exceptional: irrespective of sex, reproductive state, or presence of gonads, substantial numbers of kisspeptin-ir cell bodies are detected in the rostral periventricular region of the third ventricle (RP3V) and in the anterior periventricular (PVa), arcuate, and dorsomedial hypothalamic nuclei. Nevertheless, the greater number in the RP3V/PVa of female breeders compared with female subordinates or male breeders suggests that emergence from a hypogonadotrophic state in females may involve kisspeptin-related mechanisms similar to those underlying puberty or seasonal breeding in other species. Copyright © 2013 Wiley Periodicals, Inc.

The MNS glycophorin variant GP.Mur affects differential erythroid expression of Rh/RhAG transcripts.

PubMed

Hsu, K; Kuo, M-S; Yao, C-C; Cheng, H-C; Lin, H-J; Chan, Y-S; Lin, M

2017-10-01

The band 3 macrocomplex (also known as the ankyrin-associated complex) on the red cell membrane comprises two interacting subcomplexes: a band 3/glycophorin A subcomplex, and a Rh/RhAG subcomplex. Glycophorin B (GPB) is a component of the Rh/RhAG subcomplex that is also structurally associated with glycophorin A (GPA). Expression of glycophorin B-A-B hybrid GP.Mur enhances band 3 expression and is associated with lower levels of Rh-associated glycoprotein (RhAG) and Rh polypeptides. The goal of this study was to determine whether GP.Mur influenced erythroid Rh/RhAG expression at the transcript level. GP.Mur was serologically determined in healthy participants from Taitung County, Taiwan. RNA was extracted from the reticulocyte-enriched fraction of peripheral blood, followed by reverse transcription and quantitative PCR for RhAG, RhD and RhCcEe. Quantification by real-time PCR revealed significantly fewer RhAG and RhCcEe transcripts in the reticulocytes from subjects with homozygous GYP*Mur. Independent from GYP.Mur, both RhAG and RhD transcript levels were threefold or higher than that of RhCcEe. Also, in GYP.Mur and the control samples alike, direct quantitative associations were observed between the transcript levels of RhAG and RhD, but not between that of RhAG and RhCcEe. Erythroid RhD and RhCcEe were differentially expressed at the transcript levels, which could be related to their different degrees of interaction or sensitivity to RhAG. Further, the reduction or absence of glycophorin B in GYP.Mur erythroid cells affected transcript expressions of RhAG and RhCcEe. Thus, GPB and GP.Mur differentially influenced Rh/RhAG expressions prior to protein translation. © 2017 International Society of Blood Transfusion.

Investigation of energy band alignments and interfacial properties of rutile NMO2/TiO2 (NM = Ru, Rh, Os, and Ir) by first-principles calculations.

PubMed

Yang, Chen; Zhao, Zong-Yan

2017-11-08

In the field of photocatalysis, constructing hetero-structures is an efficient strategy to improve quantum efficiency. However, a lattice mismatch often induces unfavorable interfacial states that can act as recombination centers for photo-generated electron-hole pairs. If the hetero-structure's components have the same crystal structure, this disadvantage can be easily avoided. Conversely, in the process of loading a noble metal co-catalyst onto the TiO 2 surface, a transition layer of noble metal oxides is often formed between the TiO 2 layer and the noble metal layer. In this article, interfacial properties of hetero-structures composed of a noble metal dioxide and TiO 2 with a rutile crystal structure have been systematically investigated using first-principles calculations. In particular, the Schottky barrier height, band bending, and energy band alignments are studied to provide evidence for practical applications. In all cases, no interfacial states exist in the forbidden band of TiO 2 , and the interfacial formation energy is very small. A strong internal electric field generated by interfacial electron transfer leads to an efficient separation of photo-generated carriers and band bending. Because of the differences in the atomic properties of the components, RuO 2 /TiO 2 and OsO 2 /TiO 2 hetero-structures demonstrate band dividing, while RhO 2 /TiO 2 and IrO 2 /TiO 2 hetero-structures have a pseudo-gap near the Fermi energy level. Furthermore, NMO 2 /TiO 2 hetero-structures show upward band bending. Conversely, RuO 2 /TiO 2 and OsO 2 /TiO 2 hetero-structures present a relatively strong infrared light absorption, while RhO 2 /TiO 2 and IrO 2 /TiO 2 hetero-structures show an obvious absorption edge in the visible light region. Overall, considering all aspects of their properties, RuO 2 /TiO 2 and OsO 2 /TiO 2 hetero-structures are more suitable than others for improving the photocatalytic performance of TiO 2 . These findings will provide useful information

Preparation and catalytic activities for H{sub 2}O{sub 2} decomposition of Rh/Au bimetallic nanoparticles

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

Zhang, Haijun, E-mail: zhanghaijun@wust.edu.cn; The State Key Laboratory of Refractory and Metallurgy, Wuhan University of Science and Technology, Wuhan 430081; Deng, Xiangong

2016-07-15

Graphical abstract: PVP-protected Rh/Au bimetallic nanoparticles (BNPs) were prepared by using hydrogen sacrificial reduction method, the activity of Rh80Au20 BNPs were about 3.6 times higher than that of Rh NPs. - Highlights: • Rh/Au bimetallic nanoparticles (BNPs) of 3∼5 nm in diameter were prepared. • Activity for H{sub 2}O{sub 2} decomposition of BNPs is 3.6 times higher than that of Rh NPs. • The high activity of BNPs was caused by the existence of charged Rh atoms. • The apparent activation energy for H{sub 2}O{sub 2} decomposition over the BNPs was calculated. - Abstract: PVP-protected Rh/Au bimetallic nanoparticles (BNPs) weremore » prepared by using hydrogen sacrificial reduction method and characterized by UV–vis, XRD, FT-IR, XPS, TEM, HR-TEM and DF-STEM, the effects of composition on their particle sizes and catalytic activities for H{sub 2}O{sub 2} decomposition were also studied. The as-prepared Rh/Au BNPs possessed a high catalytic activity for the H{sub 2}O{sub 2} decomposition, and the activity of the Rh{sub 80}Au{sub 20} BNPs with average size of 2.7 nm were about 3.6 times higher than that of Rh monometallic nanoparticles (MNPs) even the Rh MNPs possess a smaller particle size of 1.7 nm. In contrast, Au MNPs with size of 2.7 nm show no any activity. Density functional theory (DFT) calculation as well as XPS results showed that charged Rh and Au atoms formed via electronic charge transfer effects could be responsible for the high catalytic activity of the BNPs.« less

Gonadotropin-Releasing Hormone (GnRH) Receptor Structure and GnRH Binding

PubMed Central

Flanagan, Colleen A.; Manilall, Ashmeetha

2017-01-01

Gonadotropin-releasing hormone (GnRH) regulates reproduction. The human GnRH receptor lacks a cytoplasmic carboxy-terminal tail but has amino acid sequence motifs characteristic of rhodopsin-like, class A, G protein-coupled receptors (GPCRs). This review will consider how recent descriptions of X-ray crystallographic structures of GPCRs in inactive and active conformations may contribute to understanding GnRH receptor structure, mechanism of activation and ligand binding. The structures confirmed that ligands bind to variable extracellular surfaces, whereas the seven membrane-spanning α-helices convey the activation signal to the cytoplasmic receptor surface, which binds and activates heterotrimeric G proteins. Forty non-covalent interactions that bridge topologically equivalent residues in different transmembrane (TM) helices are conserved in class A GPCR structures, regardless of activation state. Conformation-independent interhelical contacts account for a conserved receptor protein structure and their importance in the GnRH receptor structure is supported by decreased expression of receptors with mutations of residues in the network. Many of the GnRH receptor mutations associated with congenital hypogonadotropic hypogonadism, including the Glu2.53(90) Lys mutation, involve amino acids that constitute the conserved network. Half of the ~250 intramolecular interactions in GPCRs differ between inactive and active structures. Conformation-specific interhelical contacts depend on amino acids changing partners during activation. Conserved inactive conformation-specific contacts prevent receptor activation by stabilizing proximity of TM helices 3 and 6 and a closed G protein-binding site. Mutations of GnRH receptor residues involved in these interactions, such as Arg3.50(139) of the DRY/S motif or Tyr7.53(323) of the N/DPxxY motif, increase or decrease receptor expression and efficiency of receptor coupling to G protein signaling, consistent with the native residues

Pd-catalytic in situ generation of H2O2 from H2 and O2 produced by water electrolysis for the efficient electro-fenton degradation of rhodamine B.

PubMed

Yuan, Songhu; Fan, Ye; Zhang, Yucheng; Tong, Man; Liao, Peng

2011-10-01

A novel electro-Fenton process was developed for wastewater treatment using a modified divided electrolytic system in which H2O2 was generated in situ from electro-generated H2 and O2 in the presence of Pd/C catalyst. Appropriate pH conditions were obtained by the excessive H+ produced at the anode. The performance of the novel process was assessed by Rhodamine B (RhB) degradation in an aqueous solution. Experimental results showed that the accumulation of H2O2 occurred when the pH decreased and time elapsed. The maximum concentration of H2O2 reached 53.1 mg/L within 120 min at pH 2 and a current of 100 mA. Upon the formation of the Fenton reagent by the addition of Fe2+, RhB degraded completely within 30 min at pH 2 with a pseudo first order rate constant of 0.109 ± 0.009 min(-1). An insignificant decline in H2O2 generation and RhB degradation was found after six repetitions. RhB degradation was achieved by the chemisorption of H2O2 on the Pd/C surface, which subsequently decomposed into •OH upon catalysis by Pd0 and Fe2+. The catalytic decomposition of H2O2 to •OH by Fe2+ was more powerful than that by Pd0, which was responsible for the high efficiency of this novel electro-Fenton process.

Yolk-like Fe3O4@C-Au@void@TiO2-Pd hierarchical microspheres with visible light-assisted enhanced photocatalytic degradation of dye

NASA Astrophysics Data System (ADS)

Chen, Suqing; Liang, Huading; Shen, Mao; Jin, Yanxian

2018-04-01

In this paper, we present the design and implementation of a type of yolk-like Fe3O4@C-Au@void@TiO2-Pd hierarchical microspheres with visible light-assisted enhanced photocatalytic degradation of dye and rapid magnetic separation. The resulting composite microspheres exhibited yolk-like hierarchical structures with a 236.3 m2 g-1 surface area and a high-saturation magnetization of 31.5 emu g-1. As an example of applications, the photodegradation of Rhodamine B (RhB) in the presence of NaBH4 was investigated under simulated sunlight irradiation. The results show that the photocatalytic activity of the yolk-like Fe3O4@C-Au@void@TiO2-Pd microcomposites in the RhB photodegradation is higher than the Fe3O4@C-Au@void@TiO2 and Fe3O4@C@TiO2 microcomposites, as they can degrade RhB with 40 min of irradiation time. In addition, by magnetic separation, the as-prepared yolk-like Fe3O4@C-Au@void@TiO2-Pd hierarchical microcomposites can be completely separated and reused for four times.

Antibacterial activity of Pd(II) complexes with salicylaldehyde-amino acids Schiff bases ligands.

PubMed

Rîmbu, Cristina; Danac, Ramona; Pui, Aurel

2014-01-01

Palladium(II) complexes with Schiff bases ligands derived from salicylaldehyde and amino acids (Ala, Gly, Met, Ser, Val) have been synthesized and characterized by Fourier transform (FT)-IR, UV-Vis and (1)H-NMR spectroscopy. The electrospray mass spectrometry (ES-MS) spectrometry confirms the formation of palladium(II) complexes in 1/2 (M/L) molar ratio. All the Pd(II) complexes 1, [Pd(SalAla)2]Cl2; 2, [Pd(SalGly)2]Cl2; 3, [Pd(SalMet)2]Cl2; 4, [Pd(SalSer)2]Cl2; 5, [Pd(SalVal)2]Cl2; have shown antibacterial activity against Gram-positive bacteria Staphylococcus aureus and Gram-negative bacteria Escherichia coli.

Geochemistry and mineralogy of Pd in the magnetitite layer within the upper gabbro of the Mesoarchean Nuasahi Massif (Orissa, India)

NASA Astrophysics Data System (ADS)

Prichard, Hazel M.; Mondal, Sisir K.; Mukherjee, Ria; Fisher, Peter C.; Giles, Nicolas

2018-04-01

Palladium concentrations of 1-3 ppm with an average Pt/Pd ratio of 0.15 have been located for the first time in a magnetitite layer in the Nuasahi Massif in Orissa India. This layer occurs at a high stratigraphic level in the complex and is nearly 4-km long and 5-12-m thick. The sections of the Pd-rich zone identified to date extend over a distance of 1 km at the southern end of the layer. Several phases of mineralization are evident. The first, primary assemblage of platinum-group minerals (PGM) contains Pd-sulfides (vysotskite), Pd-Pb alloys (zvyagintsevite), and a Pd-In alloy, a mineral probably new to mineralogy. These PGM are confined to central magnetite grains in the magnetitites. The magnetite grains with exsolved fine laths of ilmenite at centers are referred to as central magnetite grains. These central magnetite grains are commonly surrounded by blebs of ilmenite and magnetite that contain the majority of the PGM. These are dominated by Pd-antimonides, variably altered to Pd-oxides, and other PGM including PtAs2 (sperrylite), RuS2 (laurite), and IrRhAsS (irarsite/hollingwothite). Many of these PGM also occur in the interstitial silicates, with rare occurrences in the central magnetite grains. We propose that the platinum-group elements (PGE) crystallized during a minor sulfide saturation event that occurred as the magnetitites crystallized. This event produced the minor Cu-sulfides in these magnetitites. Later introduction of antimony and arsenic, during the alteration event that produced the blebby ilmenite and magnetite, led to the more primary PGM being succeeded by the main PGM assemblage, dominated by Pd-antimonides. These are associated with secondary Cu minerals and sperrylite. Subsequent oxidation during weathering in the hot wet Indian climate produced the Pd-oxides. The Nuasahi Massif is a sill-like Archean layered ultramafic-mafic intrusion genetically linked to high-Mg siliceous basalt or boninites and is characterized by unusually thick

Expression of the GnRH and GnRH receptor (GnRH-R) genes in the hypothalamus and of the GnRH-R gene in the anterior pituitary gland of anestrous and luteal phase ewes.

PubMed

Ciechanowska, Magdalena; Lapot, Magdalena; Malewski, Tadeusz; Mateusiak, Krystyna; Misztal, Tomasz; Przekop, Franciszek

2008-11-01

Data exists showing that seasonal changes in the innervations of GnRH cells in the hypothalamus and functions of some neural systems affecting GnRH neurons are associated with GnRH release in ewes. Consequently, we put the question as to how the expression of GnRH gene and GnRH-R gene in the hypothalamus and GnRH-R gene in the anterior pituitary gland is reflected with LH secretion in anestrous and luteal phase ewes. Analysis of GnRH gene expression by RT-PCR in anestrous ewes indicated comparable levels of GnRH mRNA in the preoptic area, anterior and ventromedial hypothalamus. GnRH-R mRNA at different concentrations was found throughout the preoptic area, anterior and ventromedial hypothalamus, stalk/median eminence and in the anterior pituitary gland. The highest GnRH-R mRNA levels were detected in the stalk/median eminence and in the anterior pituitary gland. During the luteal phase of the estrous cycle in ewes, the levels of GnRH mRNA and GnRH-R mRNA in all structures were significantly higher than in anestrous ewes. Also LH concentrations in blood plasma of luteal phase ewes were significantly higher than those of anestrous ewes. In conclusion, results from this study suggest that low expression of the GnRH and GnRH-R genes in the hypothalamus and of the GnRH-R gene in the anterior pituitary gland, amongst others, may be responsible for a decrease in LH secretion and the anovulatory state in ewes during the long photoperiod.

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

USGS Publications Warehouse

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

2007-01-01

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

On the Structure Sensitivity of Dimethyl Ether Electro-oxidation on Eight FCC Metals: A First-Principles Study

DOE PAGES

Herron, Jeffrey A.; Ferrin, Peter; Mavrikakis, Manos

2015-09-24

The electro-oxidation of dimethyl ether (DME) was investigated using periodic, self-consistent density functional theory (DFT) calculations on the (111) and (100) facets of eight fcc metals: Au, Ag, Cu, Pt, Pd, Ni, Ir, and Rh. The goal of this study is to understand the experimentally observed structure sensitivity of this reaction on Pt, and to predict trends in structure sensitivity of this reaction across the other seven metals studied. The main conclusion is that the enhanced activity of Pt(100) originates from more facile C–O bond breaking and removal of surface poisoning species, including CO and CH. When comparing C–O bondmore » breaking energetics, we do not find a universal trend where these elementary steps are always more exergonic on the (100) facet. However, we find that, at a given potential, DME can be dehydrogenated (prior to breaking the C–O bond) to a greater extent on the (100) facet. Additionally, we find that the reaction energy for C–O bond breaking in CHxOCHy-type species becomes increasingly exergonic as the species becomes increasingly dehydrogenated. Together, the more facile dehydrogenation on the (100) facets provides more favorable routes to C–O bond activation. Though we calculate a lower onset potential on Au(100), Ag(100), Cu(100), Pt(100), and Pd(100) than their respective (111) facets, the calculated onset potential for Ni(100), Ir(100), and Rh(100) are actually higher than for their respective (111) facets. Lastly, by constructing theoretical volcano plots, we conclude that Au(100), Ag(100), Cu(100), Pt(100), and Pd(100) should be more active than their respective (111) facets, while Ni(100), Rh(100), and Ir(100) will show the opposite trend.« less

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

PubMed

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

2016-02-01

In this study, a batch leaching test was executed to evaluate the toxicity associated with chemicals contained in motherboards. The leaching solutions used were distilled water, nitric acid, acetic acid and synthetic acid rain solution. A total of 21 elements including Ag, As, Au, Br, Cd, Co, Cr, Cu, Hf, Ir, Mn, Ni, Os, Pb, Pd, Pt, Rd, Rh, Se, U and Zn were analyzed. In this study, the pH values of all the leachates fell within the range of 2.33-4.88. The highest concentrations of metals were obtained from the acid rain solution, whilst the maximum value of bromine was achieved with solution of acetic acid. Appreciable concentrations of platinum group elements were detected with concentrations around 3.45, 1.43, 1.21 and 22.19 µg L(-1) for Ir, Pd, Pt and Rh, respectively. The different leaching of the motherboards revealed the predominant presence of the toxic substances in the leached from the e-waste. Copyright © 2015 Elsevier Ltd. All rights reserved.

A comparative DFT study on the dehydrogenation of methanol on Rh(100) and Rh(110)

NASA Astrophysics Data System (ADS)

Zhang, Minhua; Wu, Xingyu; Yu, Yingzhe

2018-04-01

Numerous density functional theory calculations have been performed to investigate the complete mechanisms of methanol dehydrogenation on Rh(100) and Rh(110) surfaces. The adsorption properties of relevant species were discussed in details. In addition, a comprehensive reaction network including four reaction pathways was built and analyzed. It is found that the initial Osbnd H bond scission of CH3OH seems to be more favorable than Csbnd H bond cleavage on both Rh(100) and Rh(110) surfaces from the perspective of activation barriers. It is also concluded that path1 (CH3OH → CH3O → CH2O → CHO → CO) is the predominant pathway on both Rh(100) and Rh (110) surfaces. On the whole, in most of the dehydrogenation reactions investigated, the energy barriers on Rh(100) are lower than those on Rh (110). Remarkable differences in the activity and predominant reaction pathway on Rh(100), Rh(110) and Rh(111) indicate that the dehydrogenation of methanol might be structure-sensitive.

Comparison of GnRH agonist, GnRH antagonist, and GnRH antagonist mild protocol of controlled ovarian hyperstimulation in good prognosis patients.

PubMed

Stimpfel, Martin; Vrtacnik-Bokal, Eda; Pozlep, Barbara; Virant-Klun, Irma

2015-01-01

The reports on how to stimulate the ovaries for oocyte retrieval in good prognosis patients are contradictory and often favor one type of controlled ovarian hyperstimulation (COH). For this reason, we retrospectively analyzed data from IVF/ICSI cycles carried out at our IVF Unit in good prognosis patients (aged <38 years, first and second attempts of IVF/ICSI, more than 3 oocytes retrieved) to elucidate which type of COH is optimal at our condition. The included patients were undergoing COH using GnRH agonist, GnRH antagonist or GnRH antagonist mild protocol in combination with gonadotrophins. We found significant differences in the average number of retrieved oocytes, immature oocytes, fertilized oocytes, embryos, transferred embryos, embryos frozen per cycle, and cycles with embryo freezing between studied COH protocols. Although there were no differences in live birth rate (LBR), miscarriages, and ectopic pregnancies between compared protocols, pregnancy rate was significantly higher in GnRH antagonist mild protocol in comparison with both GnRH antagonist and GnRH agonist protocols and cumulative LBR per cycle was significantly higher in GnRH antagonist mild protocol in comparison to GnRH agonist protocol. Our data show that GnRH antagonist mild protocol of COH could be the best method of choice in good prognosis patients.

Isonitrile radionuclide complexes for labelling and imaging agents

DOEpatents

Jones, Alun G.; Davison, Alan; Abrams, Michael J.

1984-06-04

A coordination complex of an isonitrile ligand and radionuclide such as Tc, Ru, Co, Pt, Fe, Os, Ir, W, Re, Cr, Mo, Mn, Ni, Rh, Pd, Nb and Ta, is useful as a diagnostic agent for labelling liposomes or vesicles, and selected living cells containing lipid membranes, such as blood clots, myocardial tissue, gall bladder tissue, etc.

The relationship between pulsatile GnRH secretion and cAMP production in immortalized GnRH neurons.

PubMed

Frattarelli, John L; Krsmanovic, Lazar Z; Catt, Kevin J

2011-06-01

In perifused immortalized GnRH neurons (GT1-7), simultaneous measurements of GnRH and cAMP revealed that the secretory profiles for both GnRH and cAMP are pulsatile. An analysis of GnRH and cAMP pulses in 16 independent experiments revealed that 25% of pulses coincide. Inversion of the peak and nadir levels was found in 33% and random relationship between GnRH and cAMP found in 42% of analyzed pulses. The random relation between GnRH and cAMP pulse resets to synchronous after an inverse relation between pulses occurred during the major GnRH release, indicating that GnRH acts as a switching mechanism to synchronize cAMP and GnRH release in perifused GT1-7 neurons. Activation of GnRH receptors with increasing agonist concentrations caused a biphasic change in cAMP levels. Low nanomolar concentrations increased cAMP production, but at high concentrations the initial increase was followed by a rapid decline to below the basal level. Blockade of the GnRH receptors by peptide and nonpeptide antagonists generated monotonic nonpulsatile increases in both GnRH and cAMP production. These findings indicate that cAMP positively regulates GnRH secretion but does not participate in the mechanism of pulsatile GnRH release.

Chirality in distorted square planar Pd(O,N)2 compounds.

PubMed

Brunner, Henri; Bodensteiner, Michael; Tsuno, Takashi

2013-10-01

Salicylidenimine palladium(II) complexes trans-Pd(O,N)2 adopt step and bowl arrangements. A stereochemical analysis subdivides 52 compounds into 41 step and 11 bowl types. Step complexes with chiral N-substituents and all the bowl complexes induce chiral distortions in the square planar system, resulting in Δ/Λ configuration of the Pd(O,N)2 unit. In complexes with enantiomerically pure N-substituents ligand chirality entails a specific square chirality and only one diastereomer assembles in the lattice. Dimeric Pd(O,N)2 complexes with bridging N-substituents in trans-arrangement are inherently chiral. For dimers different chirality patterns for the Pd(O,N)2 square are observed. The crystals contain racemates of enantiomers. In complex two independent molecules form a tight pair. The (RC) configuration of the ligand induces the same Δ chirality in the Pd(O,N)2 units of both molecules with varying square chirality due to the different crystallographic location of the independent molecules. In complexes and atrop isomerism induces specific configurations in the Pd(O,N)2 bowl systems. The square chirality is largest for complex [(Diop)Rh(PPh3 )Cl)], a catalyst for enantioselective hydrogenation. In the lattice of two diastereomers with the same (RC ,RC) configuration in the ligand Diop but opposite Δ and Λ square configurations co-crystallize, a rare phenomenon in stereochemistry. © 2013 Wiley Periodicals, Inc.

Interpreting intensities in vibrational sum frequency generation (SFG) spectroscopy: CO adsorption on Pd surfaces

NASA Astrophysics Data System (ADS)

Morkel, M.; Unterhalt, H.; Klüner, T.; Rupprechter, G.; Freund, H.-J.

2005-07-01

The lineshape and intensity of SFG signals of CO adsorbed on supported Pd nanoparticles and Pd(1 1 1) are analyzed. For CO/Pd(1 1 1) nearly symmetric lorentzian lineshapes were observed. Applying two different visible wavelengths for excitation, asymmetric lineshapes observed for the CO/Pd/Al 2O 3/NiAl(1 1 0) system are explained by a lower resonant and a higher non-resonant SFG signal and a change in the phase between resonant and non-resonant signals, most likely originating from an interband transition in the NiAl substrate. The relative intensity of different CO species (hollow, bridge, on-top) was modeled by DFT calculations of IR transition moments and Raman activities. While the (experimental) sensitivity of SFG towards different CO species strongly varies, the calculated IR and Raman activities are rather similar. The inability to exactly reproduce experimental SFG intensities suggests a strong coverage dependence of Raman activities or that non-linear effects occur that can currently not be properly accounted for.

Search for unconventional superconductors among the YTE 2Si2 compounds (TE  =  Cr, Co, Ni, Rh, Pd, Pt)

NASA Astrophysics Data System (ADS)

Pikul, A. P.; Samsel–Czekała, M.; Chajewski, G.; Romanova, T.; Hackemer, A.; Gorzelniak, R.; Wiśniewski, P.; Kaczorowski, D.

2017-05-01

Motivated by the recent discovery of exotic superconductivity in YFe2Ge2 we undertook reinvestigation of formation and physical properties of yttrium-based 1:2:2 silicides. Here we report on syntheses and crystal structures of the YTE 2Si2 compounds with TE  =  Cr, Co, Ni, Rh, Pd and Pt, and their low-temperature physical properties measurements, supplemented by results of fully relativistic full-potential local-orbital minimum basis band structure calculations. We confirm that most of the members of that family crystallize in a tetragonal ThCr2Si2-type structure (space group I4/mmm) and have three-dimensional Fermi surface, while only one of them (YPt2Si2) forms with a closely-related primitive CaBe2Ge2-type unit cell (space group P4/nmm) and possess quasi-two-dimensional Fermi surface sheets. Physical measurements indicated that BCS-like superconductivity is observed only in YPt2Si2 (T c  =  1.54 K) and YPd2Si2 (T c  =  0.43 K), while no superconducting phase transition was found in other systems at least down to 0.35 K. Thermal analysis showed no polymorphism in both superconducting phases. No clear relation between the superconductivity and the crystal structure (and dimensionality of the Fermi surface) was observed.

From stable divalent to valence-fluctuating behaviour in Eu(Rh1-xIrx)2Si2 single crystals

NASA Astrophysics Data System (ADS)

Seiro, Silvia; Geibel, Christoph

2011-09-01

We have succeeded in growing high-quality single crystals of the valence-fluctuating system EuIr2Si2, the divalent Eu system EuRh2Si2 and the substitutional alloy Eu(Rh1-xIrx)2Si2 across the range 0 < x < 1, which we characterized by means of x-ray diffraction, energy-dispersive x-ray spectroscopy, specific heat, magnetization and resistivity measurements. On increasing x, the divalent Eu ground state subsists up to x = 0.25 with a slight increase in Néel temperature, while for 0.3≤x < 0.7 a sharp hysteretic change in susceptibility and resistivity marks the first-order valence transition. For x≳0.7 the broad feature observed in the physical properties is characteristic of the continuous valence evolution beyond the critical end point of the valence transition line, and the resistivity is reminiscent of Kondo-like behaviour while the Sommerfeld coefficient indicates a mass renormalization of at least a factor of 8. The resulting phase diagram is similar to those reported for polycrystalline Eu(Pd1-xAux)2Si2 and EuNi2(Si1-xGex)2, confirming its generic character for Eu systems, and markedly different to those of homologue Ce and Yb systems, which present a continuous suppression of the antiferromagnetism accompanied by a very smooth evolution of the valence. We discuss these differences and suggest them to be related to the large polarization energy of the Eu half-filled 4f shell. We further argue that the changes in the rare earth valence between RRh2Si2 and RIr2Si2 (R = Ce, Eu, Yb) are governed by a purely electronic effect and not by a volume effect.

Giant magnetoresistance in perpendicularly magnetized synthetic antiferromagnetic coupling with Ir spacer

NASA Astrophysics Data System (ADS)

Fukushima, A.; Taniguchi, T.; Sugihara, A.; Yakushiji, K.; Kubota, H.; Yuasa, S.

2018-05-01

Perpendicularly magnetized magnetic tunnel junction (p-MTJ) is a key element for developing high-density spin-transfer torque switching magnetoresistive random access memory. Recently, a large exchange coupling (IEC) in the synthetic antiferromagnetic reference layer with Ir interlayer was observed in p-MTJs. The evaluation of the IEC is, however, difficult due to the electrostatic breakdown of MTJs. This study demonstrates the evaluation of the IEC with Ir interlayer in giant magnetoresistive (GMR) nanopillar. We fabricated three kinds of perpendicularly magnetized GMR elements; bottom-free structures with Cu or Ir spacer, and top-free structure with Ir spacer. The magnetoresistance (RH) loops of all samples show sharp changes of the magnetoresistance at the magnetic fields over ±10 kOe, indicating the existence of the large IECs. In particular, a sharp change of the magnetoresistance at the field over ±20 kOe was found for the element with Cu of 2 nm thickness.

Steam reforming of fast pyrolysis-derived aqueous phase oxygenates over Co, Ni, and Rh metals supported on MgAl 2O 4

DOE PAGES

Xing, Rong; Dagle, Vanessa Lebarbier; Flake, Matthew; ...

2016-02-03

In this paper we examine the feasibility of steam reforming the mixed oxygenate aqueous fraction derived from fast pyrolysis bio-oils. Catalysts selective towards hydrogen formation and resistant to carbon formation utilizing feeds with relatively low steam-to-carbon (S/C) ratios are desired. Rh (5 wt%), Pt (5 wt%), Ru (5 wt%), Ir (5 wt%), Ni (15 wt%), and Co (15 wt%) metals supported on MgAl2O4 were evaluated for catalytic performance at 500 °C and 1 atm using a complex feed mixture comprising acids, polyols, cycloalkanes, and phenolic compounds. The Rh catalyst was found to be the most active and resistant to carbonmore » formation. The Ni and Co catalysts were found to be more active than the other noble metal catalysts investigated (Pt, Ru, and Ir).« less

Lack of association between Rh status, Rh immune globulin in pregnancy and autism.

PubMed

Miles, Judith H; Takahashi, T Nicole

2007-07-01

Though causes of autism are considered largely genetic, considerable concern remains that exposure to Rh immune globulin (RhIg), which until 2001 in the United States contained the preservative thimerosal, can cause autism. To determine whether mothers of children with autism are more likely to be Rh negative (Rh(-)) or to have received RhIg preserved with thimerosal, which is 49.6% ethyl mercury, we surveyed families of children with an autism spectrum disorder (ASD) ascertained through a University-based autism clinic considered free of ascertainment biases related to type of autism or severity. Between 2004 and 2006, 305 mothers of 321 children with an ASD agreed to participate in a telephone interview. Analysis of complete records including the blood group status and RhIg exposure of 214 families showed that Rh(-) status is no higher in mothers of children with autism than in the general population, exposure to antepartum RhIg, preserved with thimerosal is no higher for children with autism and pregnancies are no more likely to be Rh incompatible. This was also true for autism subgroups defined by behavioral phenotype, gender, IQ, regressive onset, head circumference, dysmorphology, birth status, essential, or complex phenotype. These findings support the consensus that exposure to ethylmercury in thimerosal is not the cause of the increased prevalence of autism. These data are important not only for parents in this country but also for the international health community where thimerosal continues to be used to preserve multi-dose vials which in turn makes vaccines affordable. (c) 2007 Wiley-Liss, Inc.

A novel electrocatalytic approach for effective degradation of Rh-B in water using carbon nanotubes and agarose.

PubMed

Liu, Haiyang; Ren, Miao; Zhang, Zhaocheng; Qu, Jiao; Ma, Ying; Lu, Nan

2018-05-01

Carbon nanotubes (CNTs)/agarose (AG) membrane on the ITO (indium tin oxide) conductive glass, with high efficiency of electrocatalytic degradation for rhodamine B (Rh-B) in water, was prepared using an easy and green method. The prepared CNTs/AG membrane was characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), energy dispersive spectra (EDS), infrared spectroscopy (IR), and electrochemical impedance spectroscopy (EIS). The results revealed that CNTs were dispersed in the AG membrane. Additionally, the electrocatalytic activities for Rh-B were conducted on the electrochemical workstation with a three-electrode system. Both initial pH and potential played an important role in the process of electrocatalytic degradation. At pH 3 and potential reaching 4 V, the removal rate of Rh-B (10 mg/L) in water achieved 96% within 20 min. The stability of the prepared CNTs/AG membrane was also investigated. Besides, the toxicities of the main intermediates from the electrocatalytic degradation for Rh-B were calculated using the ECOSAR program and EPIWIN software, and results indicated that the toxicities of some intermediates were higher than those of the parent pollutant (Rh-B). These findings provided a light-spot to simplify the preparation of efficient working electrode and emphasized the possible potential risks from intermediates at the same time.

Platinum-group element geochemistry of zoned ultramafic intrusive suites, Klamath Mountains, California and Oregon.

USGS Publications Warehouse

Gray, F.; Page, N.J.; Carlson, C.A.; Wilson, S.A.; Carlson, R.R.

1986-01-01

Analyses for platinum-group elements of the varied rock suites of three Alaskan-type ultramafic to mafic multi-intrusive bodies are reported. Ir and Ru are less than analytical sensitivities of 100 and 20 ppb; Rh is less than or near 1 ppb. Average Pd assays vary among the rocks within intrusive complexes and between the three complexes (6.3, 13.7, 36.4 ppb); average Pt assays vary little among the same samples (27.9, 60.9, 34.0 ppb). Statistically adjusted Pt/(Pt + Pd) ratios increase in each suite from gabbro through clinopyroxenite to olivine-rich rocks, possibly owing to Pd fractionation.-G.J.N.

Platinum-group element, Gold, Silver and Base Metal distribution in compositionally zoned sulfide droplets from the Medvezky Creek Mine, Noril'sk, Russia

USGS Publications Warehouse

Barnes, S.-J.; Cox, R.A.; Zientek, M.L.

2006-01-01

Concentrations of Ag, Au, Cd, Co, Re, Zn and Platinum-group elements (PGE) have been determined in sulfide minerals from zoned sulfide droplets of the Noril'sk 1 Medvezky Creek Mine. The aims of the study were; to establish whether these elements are located in the major sulfide minerals (pentlandite, pyrrhotite, chalcopyrite and cubanite), to establish whether the elements show a preference for a particular sulfide mineral and to investigate the model, which suggests that the zonation in the droplets is caused by the crystal fractionation of monosulfide solid solution (mss). Nickel, Cu, Ag, Re, Os, Ir, Ru, Rh and Pd, were found to be largely located in the major sulfide minerals. In contrast, less than 25% of the Au, Cd, Pt and Zn in the rock was found to be present in these sulfides. Osmium, Ir, Ru, Rh and Re were found to be concentrated in pyrrhotite and pentlandite. Palladium and Co was found to be concentrated in pentlandite. Silver, Cd and Zn concentrations are highest in chalcopyrite and cubanite. Gold and platinum showed no preference for any of the major sulfide minerals. The enrichment of Os, Ir, Ru, Rh and Re in pyrrhotite and pentlandite (exsolution products of mss) and the low levels of these elements in the cubanite and chalcopyrite (exsolution products of intermediate solid solution, iss) support the mss crystal fractionation model, because Os, Ir, Ru, Rh and Re are compatible with mss. The enrichment of Ag, Cd and Zn in chalcopyrite and cubanite also supports the mss fractionation model these minerals are derived from the fractionated liquid and these elements are incompatible with mss and thus should be enriched in the fractionated liquid. Gold and Pt do not partition into either iss or mss and become sufficiently enriched in the final fractionated liquid to crystallize among the iss and mss grains as tellurides, bismithides and alloys. During pentlandite exsolution Pd appears to have diffused from the Cu-rich portion of the droplet into

A new biosensor for noninvasive determination of fetal RHD status in maternal blood of RhD negative pregnant women.

PubMed

Dündar Yenilmez, Ebru; Kökbaş, Umut; Kartlaşmış, Kezban; Kayrın, Levent; Tuli, Abdullah

2018-01-01

Prenatal detection of the fetal RHD status can be useful in the management of RhD incompatibility to identify fetuses at risk of hemolytic disease. Hemolytic disease causes morbidity and mortality of the fetus in the neonatal period. The routine use of antenatal and postnatal anti-D prophylaxis has reduced the incidence of hemolytic disease of the fetus and newborn. This study describe the detection of fetal RhD antigens in blood of RhD negative pregnant women using a nanopolymer coated electrochemical biosensor for medical diagnosis. Cell free fetal DNA in maternal plasma was also used to genotyping fetal RHD status using multiplex real-time PCR. Twenty-six RhD negative pregnant women in different gestational ages were included in the study. RhD positive fetal antibodies detected with a developed biosensor in maternal blood of RhD negative mothers. The electrochemical measurements were performed on a PalmSens potentiostat, and corundum ceramic based screen printed gold electrode combined with the reference Ag/AgCl electrode, and the auxiliary Au/Pd (98/2%) electrode. Fetal RHD genotyping performed using fluorescence-based multiplex real-time PCR exons 5 and 7 of the RHD gene. The fetal RHD status of 26 RhD negative cases were detected 21 as RhD positive and 5 as RhD negative with electrochemical biosensor. Fetal RHD status confirmed with extracted fetal DNA in maternal plasma using multiplex real-time PCR RHD genotyping and by serological test after delivery. The new method for fetal RhD detection in early pregnancy is useful and can be carry out rapidly in clinical diagnosis. Using automated biosensors are reproducible, quick and results can be generated within a few minutes compared to noninvasive fetal RHD genotyping from maternal plasma with real-time PCR-based techniques. We suggest the biosensor techniques could become an alternative part of fetal RHD genotyping from maternal plasma as a prenatal screening in the management of RhD incompatibility.

Improvement of sulfur resistance of Pd/Ce-Zr-Al-O catalysts for CO oxidation

NASA Astrophysics Data System (ADS)

Shin, Haebin; Baek, Minsung; Ro, Youngsoo; Song, Changyeol; Lee, Kwan-Young; Song, In Kyu

2018-01-01

Two kinds of mesoporous ceria-zirconia-alumina supports were prepared by a single-step epoxide-driven sol-gel method (SGCZA) and by a co-precipitation method (PCZA). Palladium catalysts supported on these materials were then prepared by a wet impregnation method (Pd/SGCZA and Pd/PCZA). The prepared catalysts were applied to the CO oxidation reaction before and after sulfur aging. XRD and N2 adsorption-desorption analyses revealed that these two catalysts retained different physicochemical properties. Pd/SGCZA had higher surface area and larger pore volume than Pd/PCZA before and after sulfur aging. TPR (Temperature-programmed reduction), CO chemisorption, FT-IR, and XPS analyses showed that the catalysts were differently influenced by sulfur species. Pd/SGCZA formed less sulfate and retained higher palladium dispersion than Pd/PCZA after sulfur aging. In the CO oxidation, Pd/PCZA showed better activity than Pd/SGCZA before sulfur aging. However, Pd/SGCZA showed higher CO conversion than Pd/PCZA after sulfur aging. We concluded that Pd/SGCZA was less poisoned by sulfur species than Pd/PCZA.

Inert anode containing base metal and noble metal useful for the electrolytic production of aluminum

DOEpatents

Ray, Siba P.; Liu, Xinghua

2000-01-01

An inert anode for production of metals such as aluminum is disclosed. The inert anode comprises a base metal selected from Cu and Ag, and at least one noble metal selected from Ag, Pd, Pt, Au, Rh, Ru, Ir and Os. The inert anode may optionally be formed of sintered particles having interior portions containing more base metal than noble metal and exterior portions containing more noble metal than base metal. In a preferred embodiment, the base metal comprises Cu, and the noble metal comprises Ag, Pd or a combination thereof.

The behavior of Pt, Pd, Cu and Ni in the Se-sulfide system between 1050 and 700 °C and the role of Se in platinum-group elements fractionation in sulfide melts

NASA Astrophysics Data System (ADS)

Helmy, Hassan M.; Fonseca, Raúl O. C.

2017-11-01

The behavior of Pt, Pd, Ni and Cu in Se-sulfide system and the role of Se in platinum-group elements (PGE) fractionation have been experimentally investigated at temperatures between 1050 and 700 °C in evacuated silica tubes. At 1050 °C, Se partially partitions into a vapor phase. At 980 °C, monosulfide solid solution (mss) and sulfide melt are the only stable phases. No Pt or Pd-bearing discrete selenide phases form down to 700 °C. Instead cooperite (PtS) forms at 900 °C. Both mss and sulfide melt can accommodate wt.% levels of Se over the whole temperature range covered by the experiments. The addition of Se in the sulfide system leads to an increase in the activity coefficients of Ni and Pd in sulfide melt. This is reflected by an increase in the partition coefficients of Ni and Pd between mss and sulfide melt. The Pt-Se activity coefficient in sulfide melt is lower than that of Pt-S. Owing to selenium's high solubility in sulfides, there never become oversaturated in Se to the extent that discrete selenides form. As such, base metal sulfides are expected to control the geochemical behavior of Se in natural systems. Interestingly, partition coefficients for the platinum-group elements (Os, Ir, Ru, Pt, Rh, Pd) between mss and sulfide melt are undistinguishable regardless of whether Se is present or not. These results imply that Se plays little role in the fractionation of PGE as sulfide melt cools down and crystallize. Furthermore, our experimental results provide evidence that Se is volatile at magmatic temperature and is likely to be degassed like sulfur.

Low-energy vibrations of the group 10 metal monocarbonyl MCO (M = Ni, Pd, and Pt): rotational spectroscopy and force field analysis.

PubMed

Okabayashi, Toshiaki; Yamamoto, Takuya; Okabayashi, Emi Y; Tanimoto, Mitsutoshi

2011-03-17

The rotational spectra of NiCO and PdCO in the ground and ν(2) excited vibrational states were observed by employing a source-modulated microwave spectrometer. The NiCO and PdCO molecules were generated in a free space cell by the sputtering reaction of nickel and palladium sheets, respectively, lining the inner surface of a stainless steel cathode with a dc glow plasma of CO and Ar. The molecular constants of NiCO and PdCO were determined by least-squares analysis. By force field analysis for the molecular constants of not only NiCO and PdCO but also of PtCO as previously reported, the harmonic force constants were determined for these three group 10 metal monocarbonyls. The vibrational wavenumbers derived for the lower M-C stretching vibrations were in good agreement with those obtained from the IR spectra in noble gas matrices and those predicted by several quantum chemical calculations published in the past. The bending vibrational wavenumbers derived by the force field analysis were also consistent with most quantum chemical calculations previously reported, but showed systematic discrepancies from the matrix IR values by about 40 cm(-1), even after reassignment (ν(2) band → 2ν(2) band) of the matrix IR spectra of PdCO and PtCO.

Differential co-localization with choline acetyltransferase in nervus terminalis suggests functional differences for GnRH isoforms in bonnethead sharks (Sphyrna tiburo)

PubMed Central

Moeller, John F.; Meredith, Michael

2010-01-01

The nervus terminalis (NT) is a vertebrate cranial nerve whose function in adults is unknown. In bonnethead sharks the nerve is anatomically independent of the olfactory system, with two major cell populations within one or more ganglia along its exposed length. Most cells are immunoreactive for either gonadotropin-releasing hormone (GnRH) or RFamide-like peptides. To define further the cell populations and connectivity, we used double-label immuno-cytochemistry with antisera to different isoforms of GnRH and to choline acetyltransferase (ChAT). The labeling patterns of two GnRH antisera revealed different populations of GnRH immunoreactive (ir) cell-profiles in the NT ganglion. One antiserum labeled a large group of cells and fibers, which likely contain mammalian GnRH (GnRH-I) as described in previous studies, and which were ChAT immunoreactive. The other antiserum labeled large club-like structures, which were anuclear, and a sparse number of fibers, but with no clear labeling of cell bodies in the ganglion. These club structures were choline acetyltrasferase (ChAT) negative, and preabsorption control tests suggest they may contain chicken-GnRH-II (GnRH-II) or dogfish GnRH. The second major NT ganglion cell-type was immunoreactive for RF-amides, which regulate GnRH release in other vertebrates, and may provide an intraganglionic influence on GnRH release. The immunocytochemical and anatomical differences between the two GnRH immunoreactive profile types indicate possible functional differences for these isoforms in the NT. The club-like structures may be sites of GnRH release into the general circulation since these structures were observed near blood vessels and resembled structures seen in the median eminence of rats. PMID:20950589

Differential co-localization with choline acetyltransferase in nervus terminalis suggests functional differences for GnRH isoforms in bonnethead sharks (Sphyrna tiburo).

PubMed

Moeller, John F; Meredith, Michael

2010-12-17

The nervus terminalis (NT) is a vertebrate cranial nerve whose function in adults is unknown. In bonnethead sharks, the nerve is anatomically independent of the olfactory system, with two major cell populations within one or more ganglia along its exposed length. Most cells are immunoreactive for either gonadotropin-releasing hormone (GnRH) or RF-amide-like peptides. To define further the cell populations and connectivity, we used double-label immunocytochemistry with antisera to different isoforms of GnRH and to choline acetyltransferase (ChAT). The labeling patterns of two GnRH antisera revealed different populations of GnRH-immunoreactive (ir) cell profiles in the NT ganglion. One antiserum labeled a large group of cells and fibers, which likely contain mammalian GnRH (GnRH-I) as described in previous studies and which were ChAT immunoreactive. The other antiserum labeled large club-like structures, which were anuclear, and a sparse number of fibers, but with no clear labeling of cell bodies in the ganglion. These club structures were choline acetyltrasferase (ChAT)-negative, and preabsorption control tests suggest they may contain chicken-GnRH-II (GnRH-II) or dogfish GnRH. The second major NT ganglion cell-type was immunoreactive for RF-amides, which regulate GnRH release in other vertebrates, and may provide an intraganglionic influence on GnRH release. The immunocytochemical and anatomical differences between the two GnRH-immunoreactive profile types indicate possible functional differences for these isoforms in the NT. The club-like structures may be sites of GnRH release into the general circulation since these structures were observed near blood vessels and resembled structures seen in the median eminence of rats. Copyright © 2010 Elsevier B.V. All rights reserved.

Preparation and evaluation of self-microemulsions for improved bioavailability of ginsenoside-Rh1 and Rh2.

PubMed

Yang, Feifei; Zhou, Jing; Hu, Xiao; Yu, Stephanie Kyoungchun; Liu, Chunyu; Pan, Ruile; Chang, Qi; Liu, Xinmin; Liao, Yonghong

2017-10-01

Due to intestinal cytochrome P450 (CYP450)-mediated metabolism and P-glycoprotein (P-gp) efflux, poor oral bioavailability hinders ginsenoside-Rh1 (Rh1) and ginsenoside-Rh2 (Rh2) from clinical application. In this study, Rh1 and Rh2 were incorporated into two self-microemulsions (SME-1 and SME-2) to improve oral bioavailability. SME-1 contained both CYP450 and P-gp inhibitory excipients while SME-2 only consisted of P-gp inhibitory excipients. Results for release, cellular uptake, transport, and lymph node distribution demonstrated no significant difference between either self-microemulsions in vivo, but were elevated significantly in comparison to the free drug. The pharmaceutical profiles in vivo showed that the bioavailability of Rh1 in SME-1 (33.25%) was significantly higher than that in either SME-2 (21.28%) or free drug (12.92%). There was no significant difference in bioavailability for Rh2 between SME-1 (48.69%) or SME-2 (41.73%), although they both had remarkable increase in comparison to free drug (15.02%). We confirmed that SME containing CYP450 and P-gp inhibitory excipient could distinctively improve the oral availabilities of Rh1 compared to free drug or SME containing P-gp inhibitory excipient. No notable increase was observed between either SME for Rh2, suggesting that Rh2 undergoes P-gp-mediated efflux, but may not undergo distinct CYP450-mediated metabolism.

Methods of reforming hydrocarbon fuels using hexaaluminate catalysts

DOEpatents

Gardner, Todd H [Morgantown, WV; Berry, David A [Morgantown, WV; Shekhawat, Dushyant [Morgantown, WV

2012-03-27

A metal substituted hexaaluminate catalyst for reforming hydrocarbon fuels to synthesis gas of the general formula AB.sub.yAl.sub.12-yO.sub.19-.delta., A being selected from alkali metals, alkaline earth metals and lanthanide metals or mixtures thereof. A dopant or surface modifier selected from a transitions metal, a spinel of an oxygen-ion conductor is incorporated. The dopant may be Ca, Cs, K, La, Sr, Ba, Li, Mg, Ce, Co, Fe, Ir, Rh, Ni, Ru, Cu, Pe, Os, Pd, Cr, Mn, W, Re, Sn, Gd, V, Ti, Ag, Au, and mixtures thereof. The oxygen-ion conductor may be a perovskite selected from M'RhO.sub.3, M'PtO.sub.3, M'PdO.sub.3, M'IrO.sub.3, M'RuO.sub.3 wherein M'=Mg, Sr, Ba, La, Ca; a spinel selected from MRh.sub.2O.sub.4, MPt.sub.2O.sub.4, MPd.sub.2O.sub.4, MIr.sub.2O.sub.4, MRu.sub.2O.sub.4 wherein M=Mg, Sr, Ba, La, Ca and mixtures thereof; a florite is selected from M''O.sub.2.

High-throughput screening of small-molecule adsorption in MOF-74

NASA Astrophysics Data System (ADS)

Thonhauser, T.; Canepa, P.

2014-03-01

Using high-throughput screening coupled with state-of-the-art van der Waals density functional theory, we investigate the adsorption properties of four important molecules, H2, CO2, CH4, and H2O in MOF-74-  with  = Be, Mg, Al, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Sr, Zr, Nb, Ru, Rh, Pd, La, W, Os, Ir, and Pt. We show that high-throughput techniques can aid in speeding up the development and refinement of effective materials for hydrogen storage, carbon capture, and gas separation. The exploration of the configurational adsorption space allows us to extract crucial information concerning, for example, the competition of water with CO2 for the adsorption binding sites. We find that only a few noble metals--Rh, Pd, Os, Ir, and Pt--favor the adsorption of CO2 and hence are potential candidates for effective carbon-capture materials. Our findings further reveal significant differences in the binding characteristics of H2, CO2, CH4, and H2O within the MOF structure, indicating that molecular blends can be successfully separated by these nano-porous materials. Supported by DOE DE-FG02-08ER46491.

Platinum-group element contents of Karelian kimberlites: Implications for the PGE budget of the sub-continental lithospheric mantle

NASA Astrophysics Data System (ADS)

Maier, W. D.; O'Brien, H.; Peltonen, P.; Barnes, Sarah-Jane

2017-11-01

We present high-precision isotope dilution data for Os, Ir, Ru, Pt, Pd and Re in Group I and Group II kimberlites from the Karelian craton, as well as 2 samples of the Premier Group I kimberlite pipe from the Kaapvaal craton. The samples have, on average, 1.38 ppb Pt and 1.33 ppb Pd, with Pt/Pd around unity. These PGE levels are markedly lower, by as much as 80%, than those reported previously for kimberlites from South Africa, Brazil and India, but overlap with PGE results reported recently from Canadian kimberlites. Primitive-mantle-normalised chalcophile element patterns are relatively flat from Os to Pt, but Cu, Ni and, somewhat less so, Au are enriched relative to the PGE (e.g., Cu/Pd > 25.000). Pd/Ir ratios are 3,6 on average, lower than in most other mantle melts. The PGE systematics can be largely explained by two components, (i) harzburgite/lherzolite detritus of the SCLM with relatively high IPGE (Os-Ir-Ru)/PPGE (Rh-Pt-Pd) ratios, and (ii) a melt component that has high PPGE/IPGE ratios. By using the concentrations of iridium in the kimberlites as a proxy for the proportion of mantle detritus in the magma, we estimate that the analysed kimberlites contain 3-27% entrained and partially dissolved detritus from the sub-continental lithospheric mantle, consistent with previous estimates of kimberlites elsewhere (Tappe S. et al., 2016, Chem. Geol. 10.1016/j.chemgeo.2016.08.019).

Preparation and Thermoelectric Characteristics of ITO/PtRh:PtRh Thin Film Thermocouple

NASA Astrophysics Data System (ADS)

Zhao, Xiaohui; Wang, Hongmin; Zhao, Zixiang; Zhang, Wanli; Jiang, Hongchuan

2017-12-01

Thin film thermocouples (TFTCs) can provide more precise in situ temperature measurement for aerospace propulsion systems without disturbance of gas flow and surface temperature distribution of the hot components. ITO /PtRh:PtRh TFTC with multilayer structure was deposited on alumina ceramic substrate by magnetron sputtering. After annealing, the TFTC was statically calibrated for multiple cycles with temperature up to 1000 °C. The TFTC with excellent stability and repeatability was realized for the negligible variation of EMF in different calibration cycles. It is believed that owing to oxygen diffusion barriers by the oxidation of top PtRh layer and Schottky barriers formed at the grain boundaries of ITO, the variation of the carrier concentration of ITO film is minimized. Meanwhile, the life time of TFTC is more than 30 h in harsh environment. This makes ITO/PtRh:PtRh TFTC a promising candidate for precise surface temperature measurement of hot components of aeroengines.

Preparation and Thermoelectric Characteristics of ITO/PtRh:PtRh Thin Film Thermocouple.

PubMed

Zhao, Xiaohui; Wang, Hongmin; Zhao, Zixiang; Zhang, Wanli; Jiang, Hongchuan

2017-12-15

Thin film thermocouples (TFTCs) can provide more precise in situ temperature measurement for aerospace propulsion systems without disturbance of gas flow and surface temperature distribution of the hot components. ITO/PtRh:PtRh TFTC with multilayer structure was deposited on alumina ceramic substrate by magnetron sputtering. After annealing, the TFTC was statically calibrated for multiple cycles with temperature up to 1000 °C. The TFTC with excellent stability and repeatability was realized for the negligible variation of EMF in different calibration cycles. It is believed that owing to oxygen diffusion barriers by the oxidation of top PtRh layer and Schottky barriers formed at the grain boundaries of ITO, the variation of the carrier concentration of ITO film is minimized. Meanwhile, the life time of TFTC is more than 30 h in harsh environment. This makes ITO/PtRh:PtRh TFTC a promising candidate for precise surface temperature measurement of hot components of aeroengines.

18FDG-PET predicts pharmacodynamic response to OSI-906, a dual IGF-1R/IR inhibitor, in preclinical mouse models of lung cancer.

PubMed

McKinley, Eliot T; Bugaj, Joseph E; Zhao, Ping; Guleryuz, Saffet; Mantis, Christine; Gokhale, Prafulla C; Wild, Robert; Manning, H Charles

2011-05-15

To evaluate 2-deoxy-2-[(18)F]fluoro-d-glucose positron emission tomography imaging ((18)FDG-PET) as a predictive, noninvasive, pharmacodynamic (PD) biomarker of response following administration of a small-molecule insulin-like growth factor-1 receptor and insulin receptor (IGF-1R/IR) inhibitor, OSI-906. In vitro uptake studies of (3)H-2-deoxy glucose following OSI-906 exposure were conducted evaluating correlation of dose with inhibition of IGF-1R/IR as well as markers of downstream pathways and glucose metabolism. Similarly, in vivo PD effects were evaluated in human tumor cell line xenografts propagated in athymic nude mice by (18)FDG-PET at 2, 4, and 24 hours following a single treatment of OSI-906 for the correlation of inhibition of receptor targets and downstream markers. Uptake of (3)H-2-deoxy glucose and (18)FDG was significantly diminished following OSI-906 exposure in sensitive tumor cells and subcutaneous xenografts (NCI-H292) but not in an insensitive model lacking IGF-1R expression (NCI-H441). Diminished PD (18)FDG-PET, collected immediately following the initial treatment agreed with inhibition of pIGF-1R/pIR, reduced PI3K (phosphoinositide 3-kinase) and MAPK (mitogen activated protein kinase) pathway activity, and predicted tumor growth arrest as measured by high-resolution ultrasound imaging. (18)FDG-PET seems to serve as a rapid, noninvasive PD marker of IGF-1R/IR inhibition following a single dose of OSI-906 and should be explored clinically as a predictive clinical biomarker in patients undergoing IGF-1R/IR-directed cancer therapy. ©2011 AACR.

PdCo/Pd-Hexacyanocobaltate Hybrid Nanoflowers: Cyanogel-Bridged One-Pot Synthesis and Their Enhanced Catalytic Performance

NASA Astrophysics Data System (ADS)

Liu, Zhen-Yuan; Fu, Geng-Tao; Zhang, Lu; Yang, Xiao-Yu; Liu, Zhen-Qi; Sun, Dong-Mei; Xu, Lin; Tang, Ya-Wen

2016-08-01

Elaborate architectural manipulation of nanohybrids with multi-components into controllable 3D hierarchical structures is of great significance for both fundamental scientific interest and realization of various functionalities, yet remains a great challenge because different materials with distinct physical/chemical properties could hardly be incorporated simultaneously into the synthesis process. Here, we develop a novel one-pot cyanogel-bridged synthetic approach for the generation of 3D flower-like metal/Prussian blue analogue nanohybrids, namely PdCo/Pd-hexacyanocobaltate for the first time. The judicious introduction of polyethylene glycol (PEG) and the formation of cyanogel are prerequisite for the successful fabrication of such fascinating hierarchical nanostructures. Due to the unique 3D hierarchical structure and the synergistic effect between hybrid components, the as-prepared hybrid nanoflowers exhibit a remarkable catalytic activity and durability toward the reduction of Rhodamine B (RhB) by NaBH4. We expect that the obtained hybrid nanoflowers may hold great promises in water remediation field and beyond. Furthermore, the facile synthetic strategy presented here for synthesizing functional hybrid materials can be extendable for the synthesis of various functional hybrid nanomaterials owing to its versatility and feasibility.

PdCo/Pd-Hexacyanocobaltate Hybrid Nanoflowers: Cyanogel-Bridged One-Pot Synthesis and Their Enhanced Catalytic Performance.

PubMed

Liu, Zhen-Yuan; Fu, Geng-Tao; Zhang, Lu; Yang, Xiao-Yu; Liu, Zhen-Qi; Sun, Dong-Mei; Xu, Lin; Tang, Ya-Wen

2016-08-30

Elaborate architectural manipulation of nanohybrids with multi-components into controllable 3D hierarchical structures is of great significance for both fundamental scientific interest and realization of various functionalities, yet remains a great challenge because different materials with distinct physical/chemical properties could hardly be incorporated simultaneously into the synthesis process. Here, we develop a novel one-pot cyanogel-bridged synthetic approach for the generation of 3D flower-like metal/Prussian blue analogue nanohybrids, namely PdCo/Pd-hexacyanocobaltate for the first time. The judicious introduction of polyethylene glycol (PEG) and the formation of cyanogel are prerequisite for the successful fabrication of such fascinating hierarchical nanostructures. Due to the unique 3D hierarchical structure and the synergistic effect between hybrid components, the as-prepared hybrid nanoflowers exhibit a remarkable catalytic activity and durability toward the reduction of Rhodamine B (RhB) by NaBH4. We expect that the obtained hybrid nanoflowers may hold great promises in water remediation field and beyond. Furthermore, the facile synthetic strategy presented here for synthesizing functional hybrid materials can be extendable for the synthesis of various functional hybrid nanomaterials owing to its versatility and feasibility.

PdCo/Pd-Hexacyanocobaltate Hybrid Nanoflowers: Cyanogel-Bridged One-Pot Synthesis and Their Enhanced Catalytic Performance

PubMed Central

Liu, Zhen-Yuan; Fu, Geng-Tao; Zhang, Lu; Yang, Xiao-Yu; Liu, Zhen-Qi; Sun, Dong-Mei; Xu, Lin; Tang, Ya-Wen

2016-01-01

Elaborate architectural manipulation of nanohybrids with multi-components into controllable 3D hierarchical structures is of great significance for both fundamental scientific interest and realization of various functionalities, yet remains a great challenge because different materials with distinct physical/chemical properties could hardly be incorporated simultaneously into the synthesis process. Here, we develop a novel one-pot cyanogel-bridged synthetic approach for the generation of 3D flower-like metal/Prussian blue analogue nanohybrids, namely PdCo/Pd-hexacyanocobaltate for the first time. The judicious introduction of polyethylene glycol (PEG) and the formation of cyanogel are prerequisite for the successful fabrication of such fascinating hierarchical nanostructures. Due to the unique 3D hierarchical structure and the synergistic effect between hybrid components, the as-prepared hybrid nanoflowers exhibit a remarkable catalytic activity and durability toward the reduction of Rhodamine B (RhB) by NaBH4. We expect that the obtained hybrid nanoflowers may hold great promises in water remediation field and beyond. Furthermore, the facile synthetic strategy presented here for synthesizing functional hybrid materials can be extendable for the synthesis of various functional hybrid nanomaterials owing to its versatility and feasibility. PMID:27573057

X-ray spectroscopy for chemistry in the 2-4 keV energy regime at the XMaS beamline: ionic liquids, Rh and Pd catalysts in gas and liquid environments, and Cl contamination in γ-Al2O3.

PubMed

Thompson, Paul B J; Nguyen, Bao N; Nicholls, Rachel; Bourne, Richard A; Brazier, John B; Lovelock, Kevin R J; Brown, Simon D; Wermeille, Didier; Bikondoa, Oier; Lucas, Christopher A; Hase, Thomas P A; Newton, Mark A

2015-11-01

The 2-4 keV energy range provides a rich window into many facets of materials science and chemistry. Within this window, P, S, Cl, K and Ca K-edges may be found along with the L-edges of industrially important elements from Y through to Sn. Yet, compared with those that cater for energies above ca. 4-5 keV, there are relatively few resources available for X-ray spectroscopy below these energies. In addition, in situ or operando studies become to varying degrees more challenging than at higher X-ray energies due to restrictions imposed by the lower energies of the X-rays upon the design and construction of appropriate sample environments. The XMaS beamline at the ESRF has recently made efforts to extend its operational energy range to include this softer end of the X-ray spectrum. In this report the resulting performance of this resource for X-ray spectroscopy is detailed with specific attention drawn to: understanding electrostatic and charge transfer effects at the S K-edge in ionic liquids; quantification of dilution limits at the Cl K- and Rh L3-edges and structural equilibria in solution; in vacuum deposition and reduction of [Rh(I)(CO)2Cl]2 to γ-Al2O3; contamination of γ-Al2O3 by Cl and its potential role in determining the chemical character of supported Rh catalysts; and the development of chlorinated Pd catalysts in `green' solvent systems. Sample environments thus far developed are also presented, characterized and their overall performance evaluated.

Zr 2Ir 6B with an eightfold superstructure of the cubic perovskite-like boride ZrIr 3B 0.5: Synthesis, crystal structure and bonding analysis

NASA Astrophysics Data System (ADS)

Hermus, Martin; Fokwa, Boniface P. T.

2010-04-01

Single phase powder samples and single crystals of Zr 2Ir 6B were successfully synthesized by arc-melting the elements in a water-cooled copper crucible under an argon atmosphere. Superstructure reflections were observed both on powder and on single crystal diffraction data, leading to an eightfold superstructure of ZrIr 3B x phase. The new phase, which has a metallic luster, crystallizes in space group Fm3¯m (no. 225) with the lattice parameters a=7.9903(4) Å, V=510.14(4) Å 3. Its crystal structure was refined on the basis of powder as well as single crystal data. The single crystal refinement converged to R1=0.0239 and w R2=0.0624 for all 88 unique reflections and 6 parameters. Zr 2Ir 6B is isotypic to Ti 2Rh 6B and its structure can be described as a defect double perovskite, A2BB' O6, where the A site is occupied by zirconium, the B site by boron, the O site by iridium but the B' site is vacant, leading to the formation of empty and boron-filled octahedral Ir 6 clusters. According to the result of tight-binding electronic structure calculations, Ir-B and Ir-Zr interactions are mainly responsible for the structural stability of the phase. According to COHP bonding analysis, the strongest bonding occurs for the Ir-B contacts, and the Ir-Ir bonding within the empty clusters is two times stronger than that in the BIr 6 octahedra.

Adsorption of Pd(II) complexes from chloride solutions obtained by leaching chlorinated spent automotive catalysts on ion exchange resin Diaion WA21J.

PubMed

Shen, Shaobo; Pan, Tonglin; Liu, Xinqiang; Yuan, Lei; Zhang, Yongjian; Wang, Jinchao; Guo, Zhanchen

2010-05-01

It was found that Rh, Pd and Pt contained in the spent ceramic automotive catalysts could be effectively extracted by dry chlorination with chlorine. In order to concentrate Pd(II) contained in the chloride solution obtained from the dry chlorination process, thermodynamic and kinetics studies for adsorption of Pd(II) complexes from the chloride solutions on anionic exchange resin Diaion WA21J were carried out. It was found that Pd, Pt, Rh, Al, Fe, Si, Zn and Pb from the chloride solution could be adsorbed on the resin. The isothermal adsorption of Pd(II) was found to fit Freundlich, Langmuir and Dubinin-Kaganer-Radushkevich models under the adsorption conditions. The adsorption of Pd(II) on the resin was favorable according to the values of 1/n and R(L) from Freundlich and Langmuir adsorption isotherms, respectively. The maximum monolayer adsorption capacities Q(max) based on Langmuir adsorption isotherms were 5.70, 4.84 and 4.05 mg/g and the corresponding value X(m) based on Dubinin-Kaganer-Radushkevich were 5.55, 4.69 and 4.01 mg/g at temperatures 18 degrees C, 28 degrees C and 40 degrees C, respectively. The apparent adsorption energies (E(ad)) based on Dubinin-Kaganer-Radushkevich isotherm were -15.43, -16.22 and -23.57 kJ/mol for the temperatures 18 degrees C, 28 degrees C and 40 degrees C, respectively. Chemical adsorption was a main mechanism involved in the adsorption process. Pd(II) adsorption on the resin could be accelerated by increasing the adsorption temperature. The adsorption of Pd(II) from the chloride solution on the resin underwent pseudo-first order kinetic process and the apparent adsorption activation energy E(a) was 15.0 kJ/mol. The intra-particle diffusion was a main rate controlling step in the Pd(II) adsorption process under the adsorption conditions. Copyright 2010 Elsevier Inc. All rights reserved.

GnRH and GnRH receptors in the pathophysiology of the human female reproductive system.

PubMed

Maggi, Roberto; Cariboni, Anna Maria; Marelli, Marina Montagnani; Moretti, Roberta Manuela; Andrè, Valentina; Marzagalli, Monica; Limonta, Patrizia

2016-04-01

Human reproduction depends on an intact hypothalamic-pituitary-gonadal (HPG) axis. Hypothalamic gonadotrophin-releasing hormone (GnRH) has been recognized, since its identification in 1971, as the central regulator of the production and release of the pituitary gonadotrophins that, in turn, regulate the gonadal functions and the production of sex steroids. The characteristic peculiar development, distribution and episodic activity of GnRH-producing neurons have solicited an interdisciplinary interest on the etiopathogenesis of several reproductive diseases. The more recent identification of a GnRH/GnRH receptor (GnRHR) system in both the human endometrium and ovary has widened the spectrum of action of the peptide and of its analogues beyond its hypothalamic function. An analysis of research and review articles published in international journals until June 2015 has been carried out to comprehensively summarize both the well established and the most recent knowledge on the physiopathology of the GnRH system in the central and peripheral control of female reproductive functions and diseases. This review focuses on the role of GnRH neurons in the control of the reproductive axis. New knowledge is accumulating on the genetic programme that drives GnRH neuron development to ameliorate the diagnosis and treatment of GnRH deficiency and consequent delayed or absent puberty. Moreover, a better understanding of the mechanisms controlling the episodic release of GnRH during the onset of puberty and the ovulatory cycle has enabled the pharmacological use of GnRH itself or its synthetic analogues (agonists and antagonists) to either stimulate or to block the gonadotrophin secretion and modulate the functions of the reproductive axis in several reproductive diseases and in assisted reproduction technology. Several inputs from other neuronal populations, as well as metabolic, somatic and age-related signals, may greatly affect the functions of the GnRH pulse generator during

Reactions of Pd(II) and Pt(II) Complexes With Tetraethylthiouram Disulfide

PubMed Central

Cervantes, G.; Molins, E.; Miravitlles, C.

1997-01-01

The reactions of tetraethylthiouram disulfide (DTS), an inhibitor of the nephrotoxicity of Pt(II) drugs, an efficient agent in the treatment of chronic alcoholism, in the treatment of HIV infections, AIDS and heavy metal toxicity, and a fungicide and herbicide, with K2[PtCl4], in ratio 1:1 and 1:2, gave the compounds [PtCl2DTS] and [Pt(S2CNEt2)2] respectively. The reaction of the complexes K2[PdCl4], Pd(AcO)2 and [PdCl2(PhCN)2], where PhCN = Benzonitrile, with tetraethylthiouram disulfide in ratio 1:1 or 1:2, yielded orange crystals identified as [Pd(S2CNEt2)2]. The crystals were suitable for study by X-ray diffraction. The -S-S- bridge in the tetraethylthiouram disulfude molecule was broken and the two molecules of the thiocarbamate derivative were bound to the Pd(II) by the equivalents sulfur atoms. All the compounds were characterized by IR, 1H and 13C NMR spectroscopies. PMID:18475812

Role of enzyme-treated cells in RBC antibody screening using the gel test: a study of anti-RH1, -RH2, and -RH3 antibodies.

PubMed

Conne, Jocelyne; Schneider, Philippe; Tissot, Jean-Daniel

2007-01-01

The role of enzyme-treated cells (ETCs) in red blood cell (RBC) antibody screening has been the subject of controversy, and its place in the clinical routine remains to be determined. In this work, plasma samples containing anti-RH1 (anti-D; N = 10), anti-RH2 (anti-C; N = 10), or anti-RH3 (anti-E; N = 10) antibodies were studied. The samples were diluted in nonbuffered or buffered normal saline, as well as in a pool of AB plasma samples. Titers and scores were determined by means of the gel test, using the indirect antiglobulin test (IAT) as well as ETCs, with R(0)r, r'r, or r''r test cells. Our results showed that compared to the IAT, ETCs allowed a clearer detection of anti-RH2 and anti-RH3, but not of anti-RH1 antibodies. Based on our study, it is not clear whether the ETC phase of the gel test should be maintained for RBC antibody screening. 2007 Wiley-Liss, Inc.

GnRH signalling pathways and GnRH-induced homologous desensitization in a gonadotrope cell line (alphaT3-1).

PubMed

Poulin, B; Rich, N; Mas, J L; Kordon, C; Enjalbert, A; Drouva, S V

1998-07-25

Exposure of the gonadotrope cells to gonadotropin-releasing hormone (GnRH) reduces their responsiveness to a new GnRH stimulation (homologous desensitization). The time frame as well as the mechanisms underlying this phenomenon are yet unclear. We studied in a gonadotrope cell line (alphaT3-1) the effects of short as well as long term GnRH pretreatments on the GnRH-induced phospholipases-C (PLC), -A2 (PLA2) and -D (PLD) activities, by measuring the production of IP3, total inositol phosphates (IPs), arachidonic acid (AA) and phosphatidylethanol (PEt) respectively. We demonstrated that although rapid desensitization of GnRH-induced IP3 formation did not occur in these cells, persistent stimulation of cells with GnRH or its analogue resulted in a time-dependent attenuation of GnRH-elicited IPs formation. GnRH-induced IPs desensitization was potentiated after direct activation of PKC by the phorbol ester TPA, suggesting the involvement of distinct mechanisms in the uncoupling exerted by either GnRH or TPA on GnRH-stimulated PI hydrolysis. The levels of individual phosphoinositides remained unchanged under any desensitization condition applied. Interestingly, while the GnRH-induced PLA2 activity was rapidly desensitized (2.5 min) after GnRH pretreatments, the neuropeptide-evoked PLD activation was affected at later times, indicating an important time-dependent contribution of these enzymatic activities in the sequential events underlying the GnRH-induced homologous desensitization processes in the gonadotropes. Under GnRH desensitization conditions, TPA was still able to induce PLD activation and to further potentiate the GnRH-evoked PLD activity. AlphaT3-1 cells possess several PKC isoforms which, except PKCzeta, were differentially down-regulated by TPA (PKCalpha, betaII, delta, epsilon, eta) or GnRH (PKCbetaII, delta, epsilon, eta). In spite of the presence of PKC inhibitors or down-regulation of PKC isoforms by TPA, the desensitizing effect of the neuropeptide on

A chimeric switch-receptor targeting PD1 augments the efficacy of second generation CAR T-Cells in advanced solid tumors

PubMed Central

Liu, Xiaojun; Ranganathan, Raghuveer; Jiang, Shuguang; Fang, Chongyun; Sun, Jing; Kim, Soyeon; Newick, Kheng; Lo, Albert; June, Carl H.; Zhao, Yangbing; Moon, Edmund K.

2015-01-01

Chimeric antigen receptor (CAR)-modified adoptive T-cell therapy (ATC) has been successfully applied to the treatment of hematologic malignancies, but faces many challenges in solid tumors. One major obstacle is the immune-suppressive effects induced in both naturally-occurring and genetically-modified tumor infiltrating lymphocytes (TILs) by inhibitory receptors (IRs), namely PD1. We hypothesized that interfering with PD1 signaling would augment CAR T cell activity against solid tumors. To address this possibility, we introduced a genetically-engineered switch receptor construct, comprising the truncated extracellular domain of PD1 and the transmembrane and cytoplasmic signaling domains of CD28, into CAR T-cells. We tested the effect of this supplement, “PD1CD28”, on human CAR T-cells targeting aggressive models of human solid tumors expressing relevant tumor antigens. Treatment of mice bearing large, established solid tumors with PD1CD28 CAR T-cells led to significant regression in tumor volume due to enhanced CAR TIL infiltrate, decreased susceptibility to tumor-induced hypofunction, and attenuation of IR expression compared to treatments with CAR T-cells alone or PD1 antibodies. Taken together, our findings suggest that the application of PD1CD28 to boost CAR T-cell activity is efficacious against solid tumors via a variety of mechanisms, prompting clinical investigation of this potentially promising treatment modality. PMID:26979791

Gonadotropin-Releasing hormones in the brain and pituitary of the white sucker

USGS Publications Warehouse

Robinson, T. Craig; Tobet, Stuart A.; Chase, Cindy; Waldron, Travis; Sower, Stacia A.

2000-01-01

The present study investigated GnRH forms within the brain of a representative of the order Cypriniformes, the white sucker, Catostomus commersoni, using HPLC, RIA, andimmunocytochemistry. Several immunoreactive (ir) GnRH forms were identified in the brain of the white sucker by chromatography and radioimmunoassay, including ir-salmon GnRH, ir-lamprey GnRH-I and -III, and ir-chicken GnRH-II. Results from immunocytochemical studies were consistent with multiple GnRH forms distributed in different patterns, particularly for fibers. Neuronal perikarya containing ir-salmon GnRH and ir-lamprey-like GnRH were found laterally within the preoptic area and rostralhypothalamus. Cells containing exclusively ir-salmon GnRH appeared slightly more rostrally, but in the same region. Fibers containing ir-salmon GnRH and ir-lamprey-like GnRH were seen throughout the caudal telencephalon and extended into thediencephalon, toward the pituitary. Fibers containing ir-chicken-II-like GnRH were also seen in the caudal telencephalon, but were concentrated more dorsally in the diencephalon. Within the pituitary, fibers containing ir-salmon GnRH and ir-lamprey-like GnRH entered the neurohypophysis, but differed in their destinations. Fibers containing ir-salmon GnRH remained within the neurohypophysis, while fibers containing ir-lamprey-like GnRH targeted adenohypophyseal tissue. These findings are consistent with the hypothesis that multiple GnRH forms with multiple functions exist within the brain and pituitary of teleosts and provide further evidence of a lamprey-like GnRH within an early evolved teleost species.

RhD Specific Antibodies Are Not Detectable in HLA-DRB1*1501 Mice Challenged with Human RhD Positive Erythrocytes

PubMed Central

Bernardo, Lidice; Denomme, Gregory A.; Shah, Kunjlata; Lazarus, Alan H.

2014-01-01

The ability to study the immune response to the RhD antigen in the prevention of hemolytic disease of the fetus and newborn has been hampered by the lack of a mouse model of RhD immunization. However, the ability of transgenic mice expressing human HLA DRB1*1501 to respond to immunization with purified RhD has allowed this question to be revisited. In this work we aimed at inducing anti-RhD antibodies by administering human RhD+ RBCs to mice transgenic for the human HLA DRB1*1501 as well as to several standard inbred and outbred laboratory strains including C57BL/6, DBA1/J, CFW(SW), CD1(ICR), and NSA(CF-1). DRB1*1501 mice were additionally immunized with putative extracellular immunogenic RhD peptides. DRB1*1501 mice immunized with RhD+ erythrocytes developed an erythrocyte-reactive antibody response. Antibodies specific for RhD could not however be detected by flow cytometry. Despite this, DRB1*1501 mice were capable of recognizing immunogenic sequences of Rh as injection with Rh peptides induced antibodies reactive with RhD sequences, consistent with the presence of B cell repertoires capable of recognizing RhD. We conclude that while HLA DRB1*1501 transgenic mice may have the capability of responding to immunogenic sequences within RhD, an immune response to human RBC expressing RhD is not directly observed. PMID:25628657

Palladium, platinum, rhodium, iridium and ruthenium in chromite- rich rocks from the Samail ophiolite, Oman.

USGS Publications Warehouse

Page, N.J.; Pallister, J.S.; Brown, M.A.; Smewing, J.D.; Haffty, J.

1982-01-01

30 samples of chromitite and chromite-rich rocks from two stratigraphic sections, 250 km apart, through the basal ultramafic member of the Samail ophiolite were spectrographically analysed for platinum-group elements (PGE) and for Co, Cu, Ni and V. These data are reported as are Cr/(Cr + Al), Mg/(Mg + Fe) and wt.% TiO2 for most samples. The chromitite occurs as pods or lenses in rocks of mantle origin or as discontinuous layers at the base of the overlying cumulus sequence. PGE abundances in both sections are similar, with average contents in chromite-rich rocks: Pd 8 ppb, Pt 14 ppb, Rh 6 ppb, Ir 48 ppb and Ru 135 ppb. The PGE data, combined with major-element and petrographic data on the chromitite, suggest: 1) relatively larger Ir and Ru contents and highest total PGE in the middle part of each section; 2) PGE concentrations and ratios do not correlate with coexisting silicate and chromite abundances or chromite compositions; 3) Pd/PGE, on average, increases upward in each section; 4) Samail PGE concentrations, particularly Rh, Pt and Pd, are lower than the average values for chromite-rich rocks in stratiform intrusions. 2) suggests that PGEs occur in discrete alloy or sulphide phases rather than in the major oxides or silicates, and 4) suggests that chromite-rich rocks from the oceanic upper mantle are depleted in PGE with respect to chondrites. L.C.C.

New lifetime measurements in Pd 109 and the onset of deformation at N = 60

DOE PAGES

Bucher, B.; Mach, H.; Aprahamian, A.; ...

2015-12-14

We measured several new subnanosecond lifetimes in 109Pd using the fast-timing βγ γ (t ) method. Fission fragments of the A = 109 mass chain were produced by bombarding natural uranium with 30 MeV protons at the Jyväskylä Ion Guide Isotope Separator On-Line (IGISOL) facility. We obtained lifetimes for excited states in 109Pd populated following β decay of 109Rh. The new lifetimes provide some insight into the evolution of nuclear structure in this mass region. In particular, the distinct structure of the two low-lying 7/2+ states occurring systematically across the Pd isotopic chain is supported by the new lifetime measurements.more » Finally, the available nuclear data indicate a sudden increase in deformation at N = 60 which is related to the strong p-n interaction between πg 9/2 and νg 7/2 valence nucleons expected in this region.« less

Human vaccination against RH5 induces neutralizing antimalarial antibodies that inhibit RH5 invasion complex interactions

PubMed Central

Payne, Ruth O.; Silk, Sarah E.; Elias, Sean C.; Diouf, Ababacar; Galaway, Francis; de Graaf, Hans; Brendish, Nathan J.; Poulton, Ian D.; Griffiths, Oliver J.; Edwards, Nick J.; Jin, Jing; Labbé, Geneviève M.; Alanine, Daniel G.W.; Siani, Loredana; Di Marco, Stefania; Roberts, Rachel; Green, Nicky; Berrie, Eleanor; Ishizuka, Andrew S.; Nielsen, Carolyn M.; Bardelli, Martino; Partey, Frederica D.; Ofori, Michael F.; Barfod, Lea; Wambua, Juliana; Murungi, Linda M.; Osier, Faith H.; Biswas, Sumi; McCarthy, James S.; Minassian, Angela M.; Ashfield, Rebecca; Viebig, Nicola K.; Nugent, Fay L.; Douglas, Alexander D.; Wright, Gavin J.; Faust, Saul N.; Hill, Adrian V.S.; Long, Carole A.; Lawrie, Alison M.; Draper, Simon J.

2017-01-01

The development of a highly effective vaccine remains a key strategic goal to aid the control and eventual eradication of Plasmodium falciparum malaria. In recent years, the reticulocyte-binding protein homolog 5 (RH5) has emerged as the most promising blood-stage P. falciparum candidate antigen to date, capable of conferring protection against stringent challenge in Aotus monkeys. We report on the first clinical trial to our knowledge to assess the RH5 antigen — a dose-escalation phase Ia study in 24 healthy, malaria-naive adult volunteers. We utilized established viral vectors, the replication-deficient chimpanzee adenovirus serotype 63 (ChAd63), and the attenuated orthopoxvirus modified vaccinia virus Ankara (MVA), encoding RH5 from the 3D7 clone of P. falciparum. Vaccines were administered i.m. in a heterologous prime-boost regimen using an 8-week interval and were well tolerated. Vaccine-induced anti-RH5 serum antibodies exhibited cross-strain functional growth inhibition activity (GIA) in vitro, targeted linear and conformational epitopes within RH5, and inhibited key interactions within the RH5 invasion complex. This is the first time to our knowledge that substantial RH5-specific responses have been induced by immunization in humans, with levels greatly exceeding the serum antibody responses observed in African adults following years of natural malaria exposure. These data support the progression of RH5-based vaccines to human efficacy testing. PMID:29093263

Multicenter Evaluation of the Tolerability of Combined Treatment With PD-1 and CTLA-4 Immune Checkpoint Inhibitors and Palliative Radiation Therapy

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

Bang, Andrew; Division of Radiation Oncology, University of Ottawa, Ottawa, Ontario; Wilhite, Tyler J.

Purpose: To analyze immune-related adverse events (ir-AEs) in patients treated with radiation and immune checkpoint blockade. Methods and Materials: We retrospectively reviewed records from patients with metastatic non-small cell lung cancer, melanoma, or renal cell cancer who received at least 1 cycle of a CTLA-4 or PD-1 inhibitor and radiation. Immune-related adverse events, defined using Common Terminology Criteria for Adverse Events version 4.0, were tabulated in relation to treatment variables, and associations with sequencing and timing were assessed. Results: We identified 133 patients, of whom 28 received a CTLA-4 inhibitor alone, 88 received a PD-1 inhibitor alone, and 17 received bothmore » classes of inhibitors either sequentially (n=13) or concurrently (n=4). Fifty-six patients received radiation within 14 days of an immune checkpoint inhibitor. Forty-six patients experienced at least 1 ir-AE (34.6%). Patients receiving both CTLA-4 and PD-1 inhibitors experienced more any-grade ir-AEs as compared with either individually (71% vs 29%, P=.0008). Any-grade ir-AEs occurred in 39% of patients in whom radiation was administered within 14 days of immunotherapy, compared with 23% of other patients (P=.06) and more often in patients who received higher equivalent dose in 2-Gy fractions (EQD2) EQD2 (P=.01). However, most toxicities were mild. There were no associations between site irradiated and specific ir-AEs. Conclusions: Our data suggest the combination of focal palliative radiation and CTLA-4 and/or PD-1 inhibitors is well tolerated, with manageable ir-AEs that did not seem to be associated with the particular site irradiated. Although conclusions are limited by the heterogeneity of patients and treatments, and future confirmatory studies are needed, this information can help guide clinical practice for patients receiving immune checkpoint therapy who require palliative radiation therapy.« less

Experimental determination of the Fermi surface of Sr3Ir4Sn13

NASA Astrophysics Data System (ADS)

Chen, Xiaoye; Goh, Swee K.; Tompsett, David A.; Yu, Wing Chi; Klintberg, Lina; Friedemann, Sven; Tan, Hong'En; Yang, Jinhu; Chen, Bin; Imai, M.; Yoshimura, Kazuyoshi; Gamza, Monika B.; Grosche, F. Malte; Sutherland, Michael L.

2016-06-01

The stannide family of materials A3T4 Sn13 (A =La ,Sr ,Ca ; T =Ir ,Rh ) is interesting due to the interplay between a tunable lattice instability and phonon-mediated superconductivity with Tc˜5 -7 K . In Sr3Ir4Sn13, a structural transition temperature T˜147 K associated with this instability has been reported, which is believed to result from a superlattice distortion of the high-temperature phase on cooling. Here we report an experimental study of the electronic structure of a member of this material family, Sr3Ir4Sn13, through measurements of quantum oscillations and comparison with density functional theory calculations. Our measurements reveal good agreement with theory using the lattice parameters consistent with a body-centered-cubic lattice of symmetry I 4 ¯3 d of the low-temperature phase. The study of the fermiology of Sr3Ir4Sn13 that we present here should help inform models of multiband superconductivity in the superconducting stannides.

Synthesis and characterization of Pd(0), PdS, and Pd-PdO core-shell nanoparticles by solventless thermolysis of a Pd-thiolate cluster

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

Jose, Deepa; Jagirdar, Balaji R., E-mail: jagirdar@ipc.iisc.ernet.i

2010-09-15

Colloids of palladium nanoparticles have been prepared by the solvated metal atom dispersion (SMAD) method. The as-prepared Pd colloid consists of particles with an average diameter of 2.8{+-}0.1 nm. Digestive ripening of the as-prepared Pd colloid, a process involving refluxing the as-prepared colloid at or near the boiling point of the solvent in the presence of a passivating agent, dodecanethiol resulted in a previously reported Pd-thiolate cluster, [Pd(SC{sub 12}H{sub 25}){sub 2}]{sub 6} but did not render the expected narrowing down of the particle size distribution. Solventless thermolysis of the Pd-thiolate complex resulted in various Pd systems such as Pd(0), PdS,more » and Pd-PdO core-shell nanoparticles thus demonstrating its versatility. These Pd nanostructures have been characterized using high-resolution electron microscopy and powder X-ray diffraction methods. - Graphical abstract: Solventless thermolysis of a single palladium-thiolate cluster affords various Pd systems such as Pd(0), Pd-PdO core-shell, and PdS nanoparticles demonstrating the versatility of the precursor and the methodology.« less

Down-regulation of pituitary receptors for luteinizing hormone-releasing hormone (LH-RH) in rats by LH-RH antagonist Cetrorelix.

PubMed Central

Halmos, G; Schally, A V; Pinski, J; Vadillo-Buenfil, M; Groot, K

1996-01-01

Antagonists of luteinizing hormone-releasing hormone (LH-RH), unlike the LH-RH agonists, suppress gonadotropins and sex steroid secretion immediately after administration, without initial stimulatory effects. [Ac-D-Nal(2)1,D-Ph(4Cl)2,D-Pal(3)3,D-Cit6,D-Ala10]LH-R H (SB-75; Cetrorelix) is a modern, potent antagonistic analog of LH-RH. In this study, the binding characteristics of receptors for LH-RH in membrane fractions from rat anterior pituitaries were investigated after a single injection of Cetrorelix at a dose of 100 microg per rat. To determine whether the treatment with Cetrorelix can affect the concentration of measurable LH-RH binding sites, we applied an in vitro method to desaturate LH-RH receptors by chaotropic agents such as manganous chloride (MnCl2) and ammonium thiocyanate (NH4SCN). Our results show that the percentages of occupied LH-RH receptors at 1, 3, and 6 h after administration of Cetrorelix were approximately 28%, 14%, and 10%, respectively, of total receptors. At later time intervals, we could not detect occupied LH-RH binding sites. Ligand competition assays, following in vitro desaturation, demonstrated that rat pituitary LH-RH receptors were significantly (P < 0.01) down-regulated for at least 72 h after administration of Cetrorelix. The lowest receptor concentration was found 3-6 h after Cetrorelix treatment and a recovery in receptor number began within approximately 24 h. The down-regulation of LH-RH binding sites induced by Cetrorelix was accompanied by serum LH and testosterone suppression. Higher LH-RH receptor concentrations coincided with elevated serum hormone levels at later time intervals. Our results indicate that administration of LH-RH antagonist Cetrorelix produces a marked down-regulation of pituitary receptors for LH-RH and not merely an occupancy of binding sites. PMID:8637885

Lattice dynamics and metastability of fcc metals in the hcp structure and the crucial role of spin-orbit coupling in platinum

NASA Astrophysics Data System (ADS)

Schönecker, Stephan; Li, Xiaoqing; Richter, Manuel; Vitos, Levente

2018-06-01

We investigate the lattice dynamical properties of Ni, Cu, Rh, Pd, Ag, Ir, Pt, and Au in the nonequilibrium hcp structure by means of density-functional simulations, wherein spin-orbit coupling (SOC) was considered for Ir, Pt, and Au. The determined dynamical properties reveal that all eight elements possess a metastable hcp phase at zero temperature and pressure. The hcp Ni, Cu, Rh, Pd, and Au previously observed in nanostructures support this finding. We make evident that the inclusion of SOC is mandatory for an accurate description of the phonon dispersion relations and dynamical stability of hcp Pt. The underlying sensitivity of the interatomic force constants is ascribed to a SOC-induced splitting of degenerate band states accompanied by a pronounced reduction of electronic density of states at the Fermi level. To give further insight into the importance of SOC in Pt, we (i) focus on phase stability and examine a lattice transformation related to optical phonons in the hcp phase and (ii) focus on the generalized stacking fault energy (GSFE) of the fcc phase pertinent to crystal plasticity. We show that the intrinsic stable and unstable fault energies of the GSFE scale as in other common fcc metals, provided that the spin-orbit interaction is taken into account.

Metastability and structural polymorphism in noble metals: the role of composition and metal atom coordination in mono- and bimetallic nanoclusters.

PubMed

Sanchez, Sergio I; Small, Matthew W; Bozin, Emil S; Wen, Jian-Guo; Zuo, Jian-Min; Nuzzo, Ralph G

2013-02-26

This study examines structural variations found in the atomic ordering of different transition metal nanoparticles synthesized via a common, kinetically controlled protocol: reduction of an aqueous solution of metal precursor salt(s) with NaBH₄ at 273 K in the presence of a capping polymer ligand. These noble metal nanoparticles were characterized at the atomic scale using spherical aberration-corrected scanning transmission electron microscopy (C(s)-STEM). It was found for monometallic samples that the third row, face-centered-cubic (fcc), transition metal [(3M)-Ir, Pt, and Au] particles exhibited more coherently ordered geometries than their second row, fcc, transition metal [(2M)-Rh, Pd, and Ag] analogues. The former exhibit growth habits favoring crystalline phases with specific facet structures while the latter samples are dominated by more disordered atomic arrangements that include complex systems of facets and twinning. Atomic pair distribution function (PDF) measurements further confirmed these observations, establishing that the 3M clusters exhibit longer ranged ordering than their 2M counterparts. The assembly of intracolumn bimetallic nanoparticles (Au-Ag, Pt-Pd, and Ir-Rh) using the same experimental conditions showed a strong tendency for the 3M atoms to template long-ranged, crystalline growth of 2M metal atoms extending up to over 8 nm beyond the 3M core.

Noninvasive fetal RhCE genotyping from maternal blood.

PubMed

Geifman-Holtzman, O; Grotegut, C A; Gaughan, J P; Holtzman, E J; Floro, C; Hernandez, E

2009-01-01

The successful prevention of RhD disease has brought attention to other red blood cells' antigens causing alloimmunisation including RhC/c and RhE/e. Prenatal diagnosis of fetal Rh genotype from maternal blood is in clinical use in Europe but not in the USA. To estimate the collective reported diagnostic accuracy of fetal RhCE genotyping from peripheral maternal blood and compare the results of genotyping when fetal cells and free fetal DNA (FfDNA) are used. English-written literature describing fetal RhCE determination from maternal blood using fetal cells or FfDNA was performed using medical subject headings and text words. The sources included Pubmed (1966-2007), Ovid (1966-2007), CINAHL, The Cochrane Library, ACP Journal Club and OCLC. Key words were prenatal diagnosis, fetal RhCE, fetal DNA in maternal blood and alloimmunisation. A study was considered eligible if it described fetal RhCE type determination using maternal peripheral blood reported in the English literature. Abstracts were excluded. From each study, we determined the number of samples tested, fetal RhCE genotype, the source of the fetal DNA, gestational age, presence of alloimmunisation and confirmation of fetal RhCE type. Exclusions and inclusions were noted. We calculated composite estimates of accuracy using a weighted random effects model. We assessed the papers against an international quality, STARD checklist which is standards for reporting studies of diagnostic accuracy. We identified 20 protocols in six English-written publications reporting fetal RhC/c (seven protocols) and/or E/e (13 protocols) genotyping using DNA obtained from maternal blood for a total of 369 samples. For RhC/c, 176 samples were tested and for RhE/e, 193 samples were tested. Accuracy was determined for each study and for all studies. The combined accuracy of fetal genotype was 96.3% for RhC/c and 98.2% for RhE/e. Only a few samples of the sorted cells were found to be a source for accurate diagnosis, but plasma was

Dissecting the steps of CO2 reduction: 2. The interaction of CO and CO2 with Pd/γ-Al2O3: an in situ FTIR study

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

Szanyi, Janos; Kwak, Ja Hun

2014-08-07

Alumina supported Pd catalysts with metal loadings of 0.5, 2.5 and 10 wt% were investigated by in situ FTIR spectroscopy in order to understand the nature of adsorbed species formed during their exposure to CO2 and CO. Exposing the annealed samples to CO2 at 295 K resulted in the formation of alumina support-bound surface species only: linear adsorbed CO2, bidentate carbonates and bicarbonates. Room temperature exposure of all three samples to CO produced IR features characteristic of both ionic and metallic Pd, as well as bands we observed upon CO2 adsorption (alumina support-bound species). Low temperature (100 K) adsorption ofmore » CO on the three samples provided information about the state of Pd after oxidation and reduction. Oxidized samples contained exclusively ionic Pd, while mostly metallic Pd was present in the reduced samples. Subsequent annealing of the CO-saturated samples revealed the facile (low temperature) reduction of PdOx species by adsorbed CO. This process was evidenced by the variations in IR bands characteristic of ionic and metallic Pd-bound CO, as well as by the appearance of IR bands associated with CO2 adsorption as a function of annealing temperature. Samples containing oxidized Pd species (oxidized, annealed or reduced) always produced CO2 upon their exposure to CO, while CO2-related surface entities were observed on samples having only fully reduced (metallic) Pd. Acknowledgements: The catalyst preparation was supported by a Laboratory Directed Research and Development (LDRD) project. This work was supported by the US Department of Energy Basic Energy Sciences, Division of Chemical Sciences, Geosciences & Biosciences. Pacific Northwest National Laboratory is operated by Battelle for the US Department of Energy. JHK also acknowledges the support of this work by the 2013 Research Fund of UNIST (Ulsan National Institute of Science and Technology, Ulsan, Korea).« less

Formation and electronic properties of palladium hydrides and palladium-rhodium dihydride alloys under pressure.

PubMed

Yang, Xiao; Li, Huijian; Ahuja, Rajeev; Kang, Taewon; Luo, Wei

2017-06-14

We present the formation possibility for Pd-hydrides and Pd-Rh hydrides system by density functional theory (DFT) in high pressure upto 50 GPa. Calculation confirmed that PdH 2 in face-centered cubic (fcc) structure is not stable under compression that will decomposition to fcc-PdH and H 2 . But it can be formed under high pressure while the palladium is involved in the reaction. We also indicate a probably reason why PdH 2 can not be synthesised in experiment due to PdH is most favourite to be formed in Pd and H 2 environment from ambient to higher pressure. With Rh doped, the Pd-Rh dihydrides are stabilized in fcc structure for 25% and 75% doping and in tetragonal structure for 50% doping, and can be formed from Pd, Rh and H 2 at high pressure. The electronic structural study on fcc type Pd x Rh 1-x H 2 indicates the electronic and structural transition from metallic to semi-metallic as Pd increased from x = 0 to 1.

18FDG-PET predicts pharmacodynamic response to OSI-906, a dual IGF-1R/IR inhibitor, in preclinical mouse models of lung cancer

PubMed Central

McKinley, Eliot T.; Bugaj, Joseph E.; Zhao, Ping; Guleryuz, Saffet; Mantis, Christine; Gokhale, Prafulla C.; Wild, Robert; Manning, H. Charles

2011-01-01

Purpose To evaluate 2-deoxy-2-[18F]fluoro-D-glucose positron emission tomography imaging (18FDG-PET) as a predictive, non-invasive, pharmacodynamic (PD) biomarker of response following administration of a small-molecule IGF-1R/IR inhibitor, OSI-906. Experimental Design In vitro uptake studies of 3H-2-deoxy glucose following OSI-906 exposure were performed evaluating correlation of dose with inhibition of IGF-1R/IR as well as markers of downstream pathways and glucose metabolism. Similarly, in vivo PD effects were evaluated in human tumor cell line xenografts propagated in athymic nude mice by 18FDG-PET at 2, 4, and 24 hours following a single treatment of OSI-906 for the correlation of inhibition of receptor targets and downstream markers. Results Uptake of 3H-2-deoxy glucose and 18FDG was significantly diminished following OSI-906 exposure in sensitive tumor cells and subcutaneous xenografts (NCIH292) but not in an insensitive model lacking IGF-1R expression (NCI-H441). Diminished pharmacodynamic 18FDG-PET collected immediately following the initial treatment agreed with inhibition of pIGF-1R/pIR, reduced PI3K and MAPK pathway activity, and predicted tumor growth arrest as measured by high-resolution ultrasound imaging. Conclusion 18FDG-PET appears to serve as a rapid, non-invasive, PD marker of IGF-1R/IR inhibition following a single dose of OSI-906 and should be explored clinically as a predictive clinical biomarker in patients undergoing IGF-1R/IR-directed cancer therapy. PMID:21257723

Origins of gonadotropin-releasing hormone (GnRH) in vertebrates: identification of a novel GnRH in a basal vertebrate, the sea lamprey.

PubMed

Kavanaugh, Scott I; Nozaki, Masumi; Sower, Stacia A

2008-08-01

We cloned a cDNA encoding a novel (GnRH), named lamprey GnRH-II, from the sea lamprey, a basal vertebrate. The deduced amino acid sequence of the newly identified lamprey GnRH-II is QHWSHGWFPG. The architecture of the precursor is similar to that reported for other GnRH precursors consisting of a signal peptide, decapeptide, a downstream processing site, and a GnRH-associated peptide; however, the gene for lamprey GnRH-II does not have introns in comparison with the gene organization for all other vertebrate GnRHs. Lamprey GnRH-II precursor transcript was widely expressed in a variety of tissues. In situ hybridization of the brain showed expression and localization of the transcript in the hypothalamus, medulla, and olfactory regions, whereas immunohistochemistry using a specific antiserum showed only GnRH-II cell bodies and processes in the preoptic nucleus/hypothalamus areas. Lamprey GnRH-II was shown to stimulate the hypothalamic-pituitary axis using in vivo and in vitro studies. Lamprey GnRH-II was also shown to activate the inositol phosphate signaling system in COS-7 cells transiently transfected with the lamprey GnRH receptor. These studies provide evidence for a novel lamprey GnRH that has a role as a third hypothalamic GnRH. In summary, the newly discovered lamprey GnRH-II offers a new paradigm of the origin of the vertebrate GnRH family. We hypothesize that due to a genome/gene duplication event, an ancestral gene gave rise to two lineages of GnRHs: the gnathostome GnRH and lamprey GnRH-II.

Green synthesis of Pd NPs from Pimpinella tirupatiensis plant extract and their application in photocatalytic activity dye degradation

NASA Astrophysics Data System (ADS)

Narasaiah, Palajonna; Mandal, Badal Kumar; Sarada, N. C.

2017-11-01

The present report the synthesis of palladium nanoparticles through the green method route offers few advantages over the common chemical and physical procedures, as it is an easy and fast, eco-friendly and does not involve any costly chemicals as well as hazardous chemicals. In this study, we reported synthesis of Pd NPs by using the Pimpinella tirupatiensis plant Extract (PTPE). The synthesized Pd NPs was characterization using different technique such as UV-Visible for the formation of Pd NPs. FT-IR spectroscopy was performed to detect the bio-active molecules liable for reduction and capping of biogenic Pd NPs. Crystallinity of Pd NPs conformed by powder - XRD. In the present study performed photo catalytic activity of synthesized Pd NPs using organic dye such as Congo red (CR). Hence, this study concludes the PTPE aqueous extract produced Pd NPs can be act as promising material for the degradation of organic pollutants.

What Factors Control Platinum-Group Element (PGE) Abundances in Basalts From the Ontong Java Plateau?

NASA Astrophysics Data System (ADS)

Chazey, W. J.; Neal, C. R.

2002-12-01

Eleven samples encompassing four sites drilled by Ocean Drilling Program Leg 192 to the Ontong Java Plateau (OJP) were analyzed for major, trace and platinum-group (PGEs: Ir, Ru, Rh, Pt, and Pd) elements. Based on major and trace element chemistry, these are divided into two groups: a primitive group, which was newly discovered on Leg 192, and Kwaimbaita-type basalts, which are ubiquitous on the OJP (cf. Tejada et al., 2002, J. Pet. 43:449). The primitive group is relatively enriched in MgO, Ni, and Cr and relatively depleted in incompatible elements compared to the Kwaimbaita-type basalts. Petrography indicates that the fractionating phases during emplacement of both types of basalts were olivine and Cr-spinel +/- plagioclase +/- cpx. Normalized PGE profiles are fractionated, but exhibit a flattening between Ru and Ir and occasionally an enrichment in Ir. It has been shown that chromite can preferentially incorporate Os and Ru (Kd ?150) over Ir (Kd ?100), which may account for the Ir and Ru systematics. We do not consider sulfide to be a factor in fractionating the PGEs because it is either absent or present as a trace phase in these basalts and the OJP basalts are sulfur undersaturated (Michael and Cornell, 1996, EOS 77:714). Additionally, the primitive samples from the OJP also have Cu/Pd ratios (4500-8000) that are roughly similar to primitive mantle (7300), and have a generally flat transition from Pd to Y on a primitive mantle-normalized plot. It is unlikely that these samples reached sulfur saturation. The Kwaimbaita-type basalts have slightly elevated Cu/Pd ratios (9000-14000). While there are subtle differences between the PGE profiles of basalts from the Leg 192 drill cores compared to OJP basalts from subaerial outcrops in the Solomon Islands (e.g., the former have general lower Pt/Rh and higher Rh/Ru ratios), it is apparent that silicate and oxide phases are controlling the PGE profiles and abundances. For example, the six samples analyzed from Site

Surface enrichment of Pt in stable Pt-Ir nano-alloy particles on MgAl 2 O 4 spinel in oxidizing atmosphere

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

Li, Wei-Zhen; Nie, Lei; Cheng, Yingwen

With the capability of MgAl2O4 spinel {111} nano-facets in stabilizing small Rh, Ir and Pt particles, bimetallic Ir-Pt catalysts on the same support were investigated, aiming at further lowering the catalyst cost by substituting expensive Pt with cheaper Ir in the bulk. Small Pt-Ir nano-alloy particles (< 2nm) were successfully stabilized on the spinel {111} nano-facets as expected. Interestingly, methanol oxidative dehydrogenation (ODH) rate on the surface Pt atoms increases with oxidizing aging but decreases upon reducing treatment, where Ir is almost inactive under the same reaction conditions. Up to three times enhancement in Pt exposure was achieved when themore » sample was oxidized at 800 °C in air for 1 week and subsequently reduced by H2 for 2 h, demonstrating successful surface enrichment of Pt on Pt-Ir nano-alloy particles. A dynamic stabilization mechanism involving wetting\

Hydrodeoxygenation of phenol to benzene and cyclohexane on Rh(111) and Rh(211) surfaces: Insights from density functional theory

DOE PAGES

Garcia-Pintos, Delfina; Voss, Johannes; Jensen, Anker D.; ...

2016-07-22

Herein we describe the C–O cleavage of phenol and cyclohexanol over Rh(111) and Rh(211) surfaces using density functional theory calculations. Our analysis is complemented by a microkinetic model of the reactions, which indicates that the C–O bond cleavage of cyclohexanol is easier than that of phenol and that Rh(211) is more active than Rh(111) for both reactions. This indicates that phenol will react mainly following a pathway of initial hydrogenation to cyclohexanol followed by hydrodeoxygenation to cyclohexane. In conclusion, we show that there is a general relationship between the transition state and the final state of both C–O cleavage reactions,more » and that this relationship is the same for Rh(111) and Rh(211).« less

PD-1/PD-L1, but not PD-1/PD-L2, interactions regulate the severity of experimental autoimmune encephalomyelitis.

PubMed

Carter, Laura L; Leach, Michael W; Azoitei, Mihai L; Cui, Junqing; Pelker, Jeffrey W; Jussif, Jason; Benoit, Steve; Ireland, Gretchen; Luxenberg, Deborah; Askew, G Roger; Milarski, Kim L; Groves, Christopher; Brown, Tom; Carito, Brenda A; Percival, Karen; Carreno, Beatriz M; Collins, Mary; Marusic, Suzana

2007-01-01

Interactions between PD-1 and its two differentially expressed ligands, PD-L1 and PD-L2, attenuate T cell activation and effector function. To determine the role of these molecules in autoimmune disease of the CNS, PD-1-/-, PD-L1-/- and PD-L2-/- mice were generated and immunized to induce experimental autoimmune encephalomyelitis (EAE). PD-1-/- and PD-L1-/- mice developed more severe EAE than wild type and PD-L2-/- mice. Consistent with this, PD-1-/- and PD-L1-/- cells produced elevated levels of the pro-inflammatory cytokines IFN-gamma, TNF, IL-6 and IL-17. These results demonstrate that interactions between PD-1/PD-L1, but not PD-1/PDL-2, are crucial in attenuating T cell responses in EAE.

Comparison of Two Porcine Collagen Membranes Combined with rhBMP-2 and rhBMP-9 on Osteoblast Behavior In Vitro.

PubMed

Fujioka-Kobayashi, Masako; Schaler, Benoit; Shirakata, Yoshinori; Nakamura, Toshiaki; Noguchi, Kazuyuki; Zhang, Yufeng; Miron, Richard J

To investigate the bone-inducing properties of two types of collagen membranes in combination with recombinant human bone morphogenetic protein (rhBMP)-2 and rhBMP-9 on osteoblast behavior. Porcine pericardium collagen membranes (PPCM) and porcine dermis-derived collagen membranes (PDCM) were coated with either rhBMP-2 or rhBMP-9. The adsorption and release abilities were first investigated via enzyme-linked immunosorbent assay up to 10 days. Moreover, murine bone stromal ST2 cell adhesion, proliferation, and osteoblast differentiation were assessed by MTS assay; real-time polymerase chain reaction for genes encoding runt-related transcription factor 2 (Runx2); alkaline phosphatase (ALP); and osteocalcin, ALP assay, and alizarin red staining. Both rhBMP-2 and rhBMP-9 adsorbed to collagen membranes and were gradually released over time up to 10 days. PPCM showed significantly less cell attachment, whereas PDCM demonstrated comparable cell attachment with the control tissue culture plastic at 8 hours. While both rhBMPs were shown not to affect cell proliferation, collagen membranes combined with rhBMP-9 significantly increased ALP activity at 7 days and ALP mRNA levels at either 3 or 14 days compared with the control tissue culture plastic. Furthermore, rhBMP-9 increased osteocalcin mRNA levels and alizarin red staining at 14 days compared with the control tissue culture plastic. The results from this study suggest that both porcine-derived collagen membranes combined with rhBMP-9 accelerated the osteopromotive potential of ST2 cells. Interestingly, rhBMP-9 demonstrated additional osteogenic differentiation compared with rhBMP-2 and may serve as a suitable growth factor for future clinical use.

INVESTIGATIONS ON THE OCCURRENCE OF Rh SUBSTANCES IN AMNIOTIC FLUID

PubMed Central

Witebsky, Ernest; Mohn, James F.

1945-01-01

1. Rh substances are found in amniotic fluid. Not all anti-Rh sera seem to be suitable for the detection of Rh substances in amniotic fluid. Careful selection of Rh antisera, as well as quantitative considerations, determine success or failure of their demonstration. 2. The baby's Rh type and not the mother's determines the occurrence of Rh substances in amniotic fluid. 3. There are Rh secretors and Rh non-secretors. At least four out of five individuals are secretors. 4. The secretion of Rh substance into the amniotic fluid would seem to be entirely independent of the secretion of the blood group specific substances. 5. The majority of Rh-positive amniotic fluids seem to contain both Rh1 and Rh2 substances. However, in certain instances fluids belonging to the pure Rh1 type or pure Rh2 type were found. 6. Three cases of erythroblastosis were described. All three came from Rh-negative mothers with Rh-positive babies. The amniotic fluids of all three failed to reveal the presence of Rh substances. PMID:19871489

Platinum-group minerals in the LG and MG chromitites of the eastern Bushveld Complex, South Africa

NASA Astrophysics Data System (ADS)

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

2016-01-01

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

Determination of boron in blood, urine and bone by electrothermal atomic absorption spectrometry using zirconium and citric acid as modifiers

NASA Astrophysics Data System (ADS)

Burguera, Marcela; Burguera, José Luis; Rondón, Carlos; Carrero, Pablo

2001-10-01

A comparative study of various potential chemical modifiers (Au, Ba, Be, Ca, Cr, Ir, La, Lu, Mg, Ni, Pd, Pt, Rh, Ru, Sr, V, W, and Zr), and different 'coating' treatments (Zr, W, and W+Rh) of the pyrolytic graphite platform of a longitudinally heated graphite tube atomizer for thermal stabilization and determination of boron was undertaken. The use of Au, Ba, Be, Cr, Ir, Pt, Rh, Ru, Sr and V as modifiers, and of W+Rh coating produced erratic, and noisy signals, while the addition of La, Ni and Pd as modifiers, and the W coating had positive effects, but with too high background absorption signals, rendering their use unsuitable for boron determination even in aqueous solutions. The atomic absorption signal for boron was increased and stabilized when the platform was coated with Zr, and by the addition of Ca, Mg, Lu, W or Zr as modifiers. Only the addition of 10 μg of Zr as a modifier onto Zr-treated platforms allowed the use of a higher pyrolysis temperature without analyte losses. The memory effect was minimized by incorporating a cleaning step with 10 μl of 50 g l -1 NH 4F HF after every three boron measurements. The addition of 10 μl of 15 g l -1 citric acid together with Zr onto Zr-treated platforms significantly improved the characteristic mass to m0=282 pg, which is adequate for biological samples such as urine and bone, although the sensitivity was still inadequate for the determination of boron in blood of subjects without supplementary diet. Under optimized conditions, the detection limit (3σ) was 60 μg l -1. The amount of boron found in whole blood, urine and femur head samples from patients with osteoporosis was in agreement with values previously reported in the literature.

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

PubMed

Boulyga, Sergei F; Heumann, Klaus G

2005-10-01

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

The Forgotten Nitroaromatic Phosphines as Weakly Donating P-ligands: An N-Aryl-benzimidazolyl Series in RhCl(CO) Complexes.

PubMed

Zhu, Chongwei; Gras, Emmanuel; Duhayon, Carine; Lacassin, Francis; Cui, Xiuling; Chauvin, Remi

2017-11-02

The coordination chemistry of a priori weakly σ-donating nitroaromatic phosphines is addressed through a series of nitro-substituted (N-phenyl-benzimidazol-1-yl)diphenylphosphines in Rh I complexes. From a set of seven such phosphines L=L xyz (') (x, y, z=0 or 1=number of NO 2 substituents at the 5, 6 and N-Ph para positions, respectively), including the non-nitrated parent L 000 and its dicationic N-methyl counterpart L 000 ', three LRhCl(COD) and seven L 2 RhCl(CO) complexes have been obtained in 72-95 % yield. Despite of a cis orientation of the L and CO ligands, the C=O IR stretching frequency ν CO varies in the expected sense, from 1967±1 cm -1 for L xy0 to 1978±1 cm -1 for L xy1 , and 2005 cm -1 for L 000 '. The 103 Rh NMR chemical shift δ Rh varies from -288 ppm for L 000 to -316±1 ppm for L 10z or L 01z , and -436 ppm for L 000 '. The ν CO and δ Rh probes thus reveal moderate but systematic variations, and act as "orthogonal" spectroscopic indicators of the presence of nitro groups on the N-Ph group and the benzimidazole core, respectively. For the dicationic ligand L 000 ', a tight electrostatic sandwiching of the Rh-Cl bond by the benzimidazole moities is evidenced by X-ray crystallography (RhCl δ- ⋅⋅⋅CN 2 + ≈3.01 Å). Along with the LRhCl(CO) complexes, dinuclear side-products (μ-CO)(RhClL) 2 were also obtained in low spectroscopic yield: for the dinitro ligand L=L 011 , a unique 1:6.7 clathrate structure, with dichloromethane as solvate, is also revealed by X-ray crystallography. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Check for chirality in {sup 102}Rh

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

Tonev, D.; Goutev, N.; Yavahchova, M. S.

2012-10-20

Excited states in {sup 102}Rh, populated by the fusion-evaporation reaction {sup 94}Zr({sup 11}B,3n){sup 102}Rh at a beam energy of 36 MeV, were studied using the INGA spectrometer at IUAC, New Delhi. The angular correlations and the electromagnetic character of some of the gamma-ray transitions observed were investigated in details. A new chiral candidate sister band was found in the level-scheme of {sup 102}Rh. Lifetimes of exited states in {sup 102}Rh were measured by means of the Doppler-shift attenuation technique. The experimental results do not support the presence of static chirality in {sup 102}Rh.

Metal Carbon Eutectics to Extend the Use of the Fixed-Point Technique in Precision IR Thermometry

NASA Astrophysics Data System (ADS)

Battuello, M.; Girard, F.; Florio, M.

2008-06-01

The high-temperature extension of the fixed-point technique for primary calibration of precision infrared (IR) thermometers was investigated both through mathematical simulations and laboratory investigations. Simulations were performed with Co C (1,324°C) and Pd C (1, 492°C) eutectic fixed points, and a precision IR thermometer was calibrated from the In point (156.5985°C) up to the Co C point. Mathematical simulations suggested the possibility of directly deriving the transition temperature of the Co C and Pd C points by extrapolating the calibration derived from fixed-point measurements from In to the Cu point. Both temperatures, as a result of the low uncertainty associated with the In Cu calibration and the high number of fixed points involved in the calibration process, can be derived with an uncertainty of 0.11°C for Co C and 0.18°C for Pd C. A transition temperature of 1,324.3°C for Co C was determined from the experimental verification, a value higher than, but compatible with, the one proposed by the thermometry community for inclusion as a secondary reference point for ITS-90 dissemination, i.e., 1,324.0°C.

PD-1/PD-L1 in disease.

PubMed

Kuol, Nyanbol; Stojanovska, Lily; Nurgali, Kulmira; Apostolopoulos, Vasso

2018-02-01

Expression of PD-1 on T/B cells regulates peripheral tolerance and autoimmunity. Binding of PD-1 to its ligand, PD-L1, leads to protection against self-reactivity. In contrary, tumor cells have evolved immune escape mechanisms whereby overexpression of PD-L1 induces anergy and/or apoptosis of PD-1 positive T cells by interfering with T cell receptor signal transduction. PD-L1 and PD-1 blockade using antibodies are in human clinical trials as an alternative cancer treatment modality. Areas covered: We describe the role of PD-1/PD-L1 in disease in the context of autoimmunity, neurological disorders, stroke and cancer. For immunotherapy/vaccines to be successful, the expression of PD-L1/PD-1 on immune cells should be considered, and the combination of checkpoint inhibitors and vaccines may pave the way for successful outcomes to disease.

First Principles Calculations of Transition Metal Binary Alloys: Phase Stability and Surface Effects

NASA Astrophysics Data System (ADS)

Aspera, Susan Meñez; Arevalo, Ryan Lacdao; Shimizu, Koji; Kishida, Ryo; Kojima, Kazuki; Linh, Nguyen Hoang; Nakanishi, Hiroshi; Kasai, Hideaki

2017-06-01

The phase stability and surface effects on binary transition metal nano-alloy systems were investigated using density functional theory-based first principles calculations. In this study, we evaluated the cohesive and alloying energies of six binary metal alloy bulk systems that sample each type of alloys according to miscibility, i.e., Au-Ag and Pd-Ag for the solid solution-type alloys (SS), Pd-Ir and Pd-Rh for the high-temperature solid solution-type alloys (HTSS), and Au-Ir and Ag-Rh for the phase-separation (PS)-type alloys. Our results and analysis show consistency with experimental observations on the type of materials in the bulk phase. Varying the lattice parameter was also shown to have an effect on the stability of the bulk mixed alloy system. It was observed, particularly for the PS- and HTSS-type materials, that mixing gains energy from the increasing lattice constant. We furthermore evaluated the surface effects, which is an important factor to consider for nanoparticle-sized alloys, through analysis of the (001) and (111) surface facets. We found that the stability of the surface depends on the optimization of atomic positions and segregation of atoms near/at the surface, particularly for the HTSS and the PS types of metal alloys. Furthermore, the increase in energy for mixing atoms at the interface of the atomic boundaries of PS- and HTSS-type materials is low enough to overcome by the gain in energy through entropy. These, therefore, are the main proponents for the possibility of mixing alloys near the surface.

Highly-efficient photocatalytic degradation of methylene blue by PoPD-modified TiO 2 nanocomposites due to photosensitization-synergetic effect of TiO2 with PoPD.

PubMed

Yang, Chuanxi; Dong, Wenping; Cui, Guanwei; Zhao, Yingqiang; Shi, Xifeng; Xia, Xinyuan; Tang, Bo; Wang, Weiliang

2017-06-21

Poly-o-phenylenediamine modified TiO 2 nanocomposites were successfully synthesized via an 'in situ' oxidative polymerization method. The modified nanocomposites were characterized by BET, XRD, TEM, FT-IR, TGA, XPS, EA and UV-Vis DRS. The photocatalytic degradation of methylene blue was chosen as a model reaction to evaluate the photocatalytic activities of TiO 2 and PoPD/TiO 2 . The results indicated that PoPD/TiO 2 nanocomposites exhibited good photocatalytic activity and stability. The photocatalytic activity of PoPD/TiO 2 increased as the initial pH increased because of electrostatic adsorption between the photocatalyst and MB as well as the generation of ·OH, whereas it exhibited an earlier increasing and later decreasing trend as the concentration of the photocatalyst increased owing to the absorption of visible light. The photocatalytic stability of the PoPD/TiO 2 nanocomposite was dependent on the stability of its structure. Based on radical trapping experiments and ESR measurements, the origin of oxidizing ability of PoPD/TiO 2 nanocomposites on photocatalytic degradation of MB was proposed, which taking into account of ·OH and ·O 2 - were the first and second important ROS, respectively. The possible photocatalytic mechanism and photocatalytic activity enhanced mechanism has been proposed, taking into account the photosensitization effect and synergetic effect of TiO 2 with PoPD.

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

Not Available

The following are reported: theoretical calculations (configuration interaction, relativistic effective core potentials, polyatomics, CASSCF); proposed theoretical studies (clusters of Cu, Ag, Au, Ni, Pt, Pd, Rh, Ir, Os, Ru; transition metal cluster ions; transition metal carbide clusters; bimetallic mixed transition metal clusters); reactivity studies on transition metal clusters (reactivity with H{sub 2}, C{sub 2}H{sub 4}, hydrocarbons; NO and CO chemisorption on surfaces). Computer facilities and codes to be used, are described. 192 refs, 13 figs.

Role of gonadotropin-releasing hormone (GnRH) in ovarian cancer

PubMed Central

Gründker, Carsten; Emons, Günter

2003-01-01

The expression of GnRH (GnRH-I, LHRH) and its receptor as a part of an autocrine regulatory system of cell proliferation has been demonstrated in a number of human malignant tumors, including cancers of the ovary. The proliferation of human ovarian cancer cell lines is time- and dose-dependently reduced by GnRH and its superagonistic analogs. The classical GnRH receptor signal-transduction mechanisms, known to operate in the pituitary, are not involved in the mediation of antiproliferative effects of GnRH analogs in these cancer cells. The GnRH receptor rather interacts with the mitogenic signal transduction of growth-factor receptors and related oncogene products associated with tyrosine kinase activity via activation of a phosphotyrosine phosphatase resulting in downregulation of cancer cell proliferation. In addition GnRH activates nucleus factor κB (NFκB) and protects the cancer cells from apoptosis. Furthermore GnRH induces activation of the c-Jun N-terminal kinase/activator protein-1 (JNK/AP-1) pathway independent of the known AP-1 activators, protein kinase (PKC) or mitogen activated protein kinase (MAPK/ERK). Recently it was shown that human ovarian cancer cells express a putative second GnRH receptor specific for GnRH type II (GnRH-II). The proliferation of these cells is dose- and time-dependently reduced by GnRH-II in a greater extent than by GnRH-I (GnRH, LHRH) superagonists. In previous studies we have demonstrated that in ovarian cancer cell lines except for the EFO-27 cell line GnRH-I antagonist Cetrorelix has comparable antiproliferative effects as GnRH-I agonists indicating that the dichotomy of GnRH-I agonists and antagonists might not apply to the GnRH-I system in cancer cells. After GnRH-I receptor knock down the antiproliferative effects of GnRH-I agonist Triptorelin were abrogated while the effects of GnRH-I antagonist Cetrorelix and GnRH-II were still existing. In addition, in the ovarian cancer cell line EFO-27 GnRH-I receptor but not

Radiosondes Corrected for Inaccuracy in RH Measurements

DOE Data Explorer

Miloshevich, Larry

2008-01-15

Corrections for inaccuracy in Vaisala radiosonde RH measurements have been applied to ARM SGP radiosonde soundings. The magnitude of the corrections can vary considerably between soundings. The radiosonde measurement accuracy, and therefore the correction magnitude, is a function of atmospheric conditions, mainly T, RH, and dRH/dt (humidity gradient). The corrections are also very sensitive to the RH sensor type, and there are 3 Vaisala sensor types represented in this dataset (RS80-H, RS90, and RS92). Depending on the sensor type and the radiosonde production date, one or more of the following three corrections were applied to the RH data: Temperature-Dependence correction (TD), Contamination-Dry Bias correction (C), Time Lag correction (TL). The estimated absolute accuracy of NIGHTTIME corrected and uncorrected Vaisala RH measurements, as determined by comparison to simultaneous reference-quality measurements from Holger Voemel's (CU/CIRES) cryogenic frostpoint hygrometer (CFH), is given by Miloshevich et al. (2006).

Synthesis, characterization and single crystal structures of chiral Schiff base and its tetranuclear palladium complex with Pdsbnd Osbnd Pd bridging and Pdsbnd Pd bonds

NASA Astrophysics Data System (ADS)

Rajegowda, H. R.; Kumar, P. Raghavendra; Hosamani, Amar; Butcher, R. J.; Naveen, S.; Lokanath, N. K.

2018-03-01

A new chiral Schiff base ligand 2-{N-[(2S)-(1-hydroxy-3-phenylpropan-2-yl]ethanimidoyl} phenol ((S)sbnd H2L) was obtained by acid catalyzed condensation of (2S)-(-)-2-amino-3-phenyl-1-propanol with 2‧-hydroxyacetophenone. The palladium complex was prepared by treating a solution of (S)sbnd H2L in acetone with a solution of Na2PdCl4 in water in 1:1 M ratio. The new ligand and its complex were characterized by FT-IR, 1H, 13C{1H} NMR spectroscopy, polarimetry and elemental analysis and their molecular structures were determined by single crystal X-ray diffraction. Both the compounds crystallizes in monoclinic system in the space group P21. There exists an intra [Osbnd H ⋯N (1.62(5) Å)] and intermolecular [Osbnd H ⋯O (1.53(5) Å) and Csbnd H ⋯O (2.59 Å)] hydrogen bonding and secondary interactions in the crystal of (S)sbnd H2L. The structure of the palladium complex was found very interesting wherein the ligand coordinated to metal center as tridentate dianionic (O-, N, O-) fashion, (S)-L, resulting in a tetranuclear palladium cluster, [Pd4((S)-L)4]. In these supramolecular structures phenolate oxygen coordinated to Pd(II) ion as Pdsbnd O terminal bonds [1.934(12) - 1.977(11) Å] and the alkoxide oxygen coordinated as Pdsbnd Osbnd Pd bridging bonds [1.993(11) - 2.012(12) Å]. The Pdsbnd N bond lengths found were in the range of 1.949(13) to 1.919(12) Å. There exists two asymmetric tetranuclear complex molecules in its crystal lattice. There exists very strong metal-metal bond interaction, Pd(2)sbnd Pd(3) [3.0410(18) Å] and Pd(6)sbnd Pd(7) [3.0517(19) Å] respectively in the two asymmetric units.

A Reactive Oxide Overlayer on Rh Nanoparticles during CO Oxidation and Its Size Dependence Studied by in Situ Ambient Pressure XPS

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

Grass, Michael E.; Zhang, Yawen; Butcher, Derek R.

2008-09-15

CO oxidation is one of the most studied heterogeneous reactions, being scientifically and industrially important, particularly for removal of CO from exhaust streams and preferential oxidation for hydrogen purification in fuel cell applications. The precious metals Ru, Rh, Pd, Pt, and Au are most commonly used for this reaction because of their high activity and stability. Despite the wealth of experimental and theoretical data, it remains unclear what is the active surface for CO oxidation under catalytic conditions for these metals. In this communication, we utilize in situ synchrotron ambient pressure X-ray photoelectron spectroscopy (APXPS) to monitor the oxidation statemore » at the surface of Rh nanoparticles during CO oxidation and demonstrate that the active catalyst is a surface oxide, the formation of which is dependent on particle size. The amount of oxide formed and the reaction rate both increase with decreasing particle size.« less

rhIGF-1 Treatment Increases Bone Mineral Density and Trabecular Bone Structure in Children with PAPP-A2 Deficiency.

PubMed

Hawkins-Carranza, Federico G; Muñoz-Calvo, María T; Martos-Moreno, Gabriel Á; Allo-Miguel, Gonzalo; Del Río, Luis; Pozo, Jesús; Chowen, Julie A; Pérez-Jurado, Luis A; Argente, Jesús

2018-01-01

Our objective was to determine changes in bone mineral density (BMD), trabecular bone score (TBS), and body composition after 2 years of therapy with recombinant human insulin-like growth factor-1 (rhIGF-1) in 2 prepubertal children with a complete lack of circulating PAPP-A2 due to a homozygous mutation in PAPP-A2 (p.D643fs25*) resulting in a premature stop codon. Body composition, BMD, and bone structure were determined by dual-energy X-ray absorptiometry at baseline and after 1 and 2 years of rhIGF-1 treatment. Height increased from 132 to 145.5 cm (patient 1) and from 111.5 to 124.5 cm (patient 2). Bone mineral content increased from 933.40 to 1,057.97 and 1,152.77 g in patient 1, and from 696.12 to 773.26 and 911.51 g in patient 2, after 1 and 2 years, respectively. Whole-body BMD also increased after 2 years of rhIGF-1 from baseline 0.788 to 0.869 g/cm2 in patient 1 and from 0.763 to 0.829 g/cm2 in patient 2. After 2 years of treatment, both children had an improvement in TBS. During therapy, a slight increase in body fat mass was seen, with a concomitant increase in lean mass. No adverse effects were reported. Two years of rhIGF-1 improved growth, with a tendency to improve bone mass and bone microstructure and to modulate body composition. © 2018 S. Karger AG, Basel.

Design of Co/Pd multilayer system with antiferromagnetic-to-ferromagnetic phase transition

NASA Astrophysics Data System (ADS)

Thiele, Jan-Ulrich

2009-03-01

Among the known magnetic material systems there are only very few examples of materials that undergo a temperature dependent antiferromagnetic-to-ferromagnetic phase transition, and of these only the chemically ordered alloy FeRh exhibits this transition near room temperature [1, 2]. Here we present a perpendicular anisotropy multilayer structure that mimics FeRh. The basic idea is to use two stacks of Co/Pd multilayers with large perpendicular magnetic anisotropy and high Curie temperature, TC, separated by a layer providing antiferromagnetic coupling, and a CoNi/Pd multilayer with perpendicular anisotropy with a lower TC, interlayer, in the range of the desired AF-FM transition temperature, TAF-FM. At room temperature this system behaves as two antiferromagnetically coupled layers with a low perpendicular remanent magnetic moment. As the temperature is raised to approach TC, interlayer the magnetization of the interlayer is gradually reduced to zero, and consequently its coupling strength is reduced. Eventually, the effective coupling between the two high-KU, high-TC layers becomes dominated by their dipolar fields, resulting in a parallel alignment of their moments and a net remanent magnetic moment equal to the sum of the moments of the two high-TC layers [2]. [4pt] [1] J. S. Kouvel and C. C. Hartelius, J. Appl. Phys. 33 (1962) p1343 [0pt] [2] J.-U. Thiele, E. E. Fullerton, S. Maat, Appl. Phys. Lett. 82 (2003) p2859 [0pt] [3] J.-U. Thiele. T. Hauet. O. Hellwig, Appl. Phys. Lett. 92 (2008) 242502.

Structure-function relationship exists for ginsenosides in reducing cell proliferation and inducing apoptosis in the human leukemia (THP-1) cell line.

PubMed

Popovich, David G; Kitts, David D

2002-10-01

Ginsenosides of the 20(S)-protopanaxadiol and 20(S)-protopanaxatriol classifications including the aglycones, protopanaxadiol (PD), protopanaxatriol (PT), and ginsenosides Rh2 and Rh1 were shown to posses characteristic effects on the proliferation of human leukemia cells (THP-1). A similar efficacy was not apparent for ginsenoside Rg3. The concentrations to inhibit 50% of cells (LC50) for PD, Rh2, PT, and Rh1 were 13, 15, 19, and 210 microg/mL, respectively. PD and PT induced DNA fragmentation at the LC50 after 72 h of treatment, compared to Rh2, Rh1, dexamethasone, and untreated cells. Cell-cycle analysis confirmed apoptosis with PD and PT treatment of THP-1 cells resulting in a buildup of sub-G1 cells after 24, 48, and 72 h of treatment. Rh2 and dexamethasone treatments also increased apoptotic cells after 24 h, whereas Rh1 did not. After 48 and 72 h, Rh2, Rh1, and dexamethasone similarly increased apoptosis, but these effects were significantly (P<0.05) lower than those observed for both PD and PT treatments. Furthermore, treatments that produced the largest buildup of apoptotic cells were also found to have the largest release of lactate dehydrogenase. It can be concluded from these studies that the presence of sugars in PD and PT aglycone structures reduces the potency to induce apoptosis, and alternately alter membrane integrity. These cytotoxic effects were different to THP-1 cells than dexamethasone.

Conformational space comparison of GnRH and lGnRH-III using molecular dynamics, cluster analysis and Monte Carlo thermodynamic integration.

PubMed

Watts, C R; Mezei, M; Murphy, R F; Lovas, S

2001-04-01

The conformational space available to GnRH and lGnRH-III was compared using 5.2 ns constant temperature and pressure molecular dynamics simulations with explicit TIP3P solvation and the AMBER v. 5.0 force field. Cluster analysis of both trajectories resulted in two groups of conformations. Results of free energy calculations, in agreement with previous experimental data, indicate that a conformation with a turn from residues 5 through 8 is preferred for GnRH in an aqueous environment. By contrast, a conformation with a helix from residues 2 through 7 with a bend from residues 6 through 10 is preferred for lGnRH-III in an aqueous environment. The side chains of His2 and Trp3 in lGnRH-III occupy different regions of phase space and participate in weakly polar interactions different from those in GnRH. The unique conformational properties of lGnRH-III may account for its specific anti cancer activity.

Feeding of Rh and Ag isomers in fast-neutron-induced reactions

DOE PAGES

Fotiades, Nikolaos; Devlin, Matthew James; Nelson, Ronald Owen; ...

2016-10-17

In (n,n') reactions on stable Ir and Au isotopes in the mass A=190 region, the experimentally established feeding of the isomers relative to the feeding of the corresponding ground states increases with increasing neutron energy, up to the neutron energy where the (n,2n) reaction channel opens up, and then decreases. In order to check for similar behavior in the mass A=100 region, the feeding of isomers and ground states in fast-neutron-induced reactions on stable isotopes in this mass region was studied. This is of especial interest for Rh which can be used as a radiochemical detector. Here, excited states weremore » studied using the (n,n'γ), (n,2nγ), and (n,3nγ) reactions on 103Rh and 109Ag. A germanium detector array for γ-ray detection and the broad-spectrum pulsed neutron source of the Los Alamos Neutron Science Center's Weapons Neutron Research facility were used for the measurement. The energy of the incident neutrons was determined using the time-of-flight technique. Absolute partial γ-ray cross sections were measured for 57 transitions feeding isomers and ground states in 101,102,103Rh and 107,108,109Ag. The feeding of the isomers was found to be very similar in the corresponding reaction channels and it is compared to the feeding determined for the ground states. In conclusion, the opening of reaction channels at higher neutron energies removes angular momentum from the residual nucleus and reduces the population of the higher-spin isomers relative to the feeding of the lower-spin ground states. Similar behavior was observed in the mass A=190 region in the feeding of higher-spin isomers, but the reverse behavior was observed in 176Lu with a lower-spin isomer and a higher-spin ground state.« less

Feeding of Rh and Ag isomers in fast-neutron-induced reactions

NASA Astrophysics Data System (ADS)

Fotiades, N.; Devlin, M.; Nelson, R. O.; Kawano, T.; Carroll, J. J.

2016-10-01

Background: In (n ,n' ) reactions on stable Ir and Au isotopes in the mass A =190 region, the experimentally established feeding of the isomers relative to the feeding of the corresponding ground states increases with increasing neutron energy, up to the neutron energy where the (n ,2 n ) reaction channel opens up, and then decreases. Purpose: In order to check for similar behavior in the mass A =100 region, the feeding of isomers and ground states in fast-neutron-induced reactions on stable isotopes in this mass region was studied. This is of especial interest for Rh which can be used as a radiochemical detector. Methods: Excited states were studied using the (n ,n'γ ), (n ,2 n γ ), and (n ,3 n γ ) reactions on 103Rh and 109Ag. A germanium detector array for γ -ray detection and the broad-spectrum pulsed neutron source of the Los Alamos Neutron Science Center's Weapons Neutron Research facility were used for the measurement. The energy of the incident neutrons was determined using the time-of-flight technique. Results: Absolute partial γ -ray cross sections were measured for 57 transitions feeding isomers and ground states in 101,102,103Rh and 107,108,109Ag. The feeding of the isomers was found to be very similar in the corresponding reaction channels and it is compared to the feeding determined for the ground states. Conclusions: The opening of reaction channels at higher neutron energies removes angular momentum from the residual nucleus and reduces the population of the higher-spin isomers relative to the feeding of the lower-spin ground states. Similar behavior was observed in the mass A =190 region in the feeding of higher-spin isomers, but the reverse behavior was observed in 176Lu with a lower-spin isomer and a higher-spin ground state.

Feeding of Rh and Ag isomers in fast-neutron-induced reactions

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

Fotiades, Nikolaos; Devlin, Matthew James; Nelson, Ronald Owen

In (n,n') reactions on stable Ir and Au isotopes in the mass A=190 region, the experimentally established feeding of the isomers relative to the feeding of the corresponding ground states increases with increasing neutron energy, up to the neutron energy where the (n,2n) reaction channel opens up, and then decreases. In order to check for similar behavior in the mass A=100 region, the feeding of isomers and ground states in fast-neutron-induced reactions on stable isotopes in this mass region was studied. This is of especial interest for Rh which can be used as a radiochemical detector. Here, excited states weremore » studied using the (n,n'γ), (n,2nγ), and (n,3nγ) reactions on 103Rh and 109Ag. A germanium detector array for γ-ray detection and the broad-spectrum pulsed neutron source of the Los Alamos Neutron Science Center's Weapons Neutron Research facility were used for the measurement. The energy of the incident neutrons was determined using the time-of-flight technique. Absolute partial γ-ray cross sections were measured for 57 transitions feeding isomers and ground states in 101,102,103Rh and 107,108,109Ag. The feeding of the isomers was found to be very similar in the corresponding reaction channels and it is compared to the feeding determined for the ground states. In conclusion, the opening of reaction channels at higher neutron energies removes angular momentum from the residual nucleus and reduces the population of the higher-spin isomers relative to the feeding of the lower-spin ground states. Similar behavior was observed in the mass A=190 region in the feeding of higher-spin isomers, but the reverse behavior was observed in 176Lu with a lower-spin isomer and a higher-spin ground state.« less

Theoretical studies of chemisorption and dimer model systems: Moller-Plesset and configuration interaction calculations on PdH, PdC, PdO, PdF, Pd sub 2 , and PdCO

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

Schwerdtfeger, P.; McFeaters, J.S.; Moore, J.J.

1991-01-01

Ab initio SCF studies have been performed to study the molecular properties of several single-bonded palladium compounds, PdH, PdC, PdO, PdF, Pd{sub 2}, and PdCO, which are important in surface and materials science. Electron correlation effects were evaluated by a second- and third-order Moller-Plesset (MP) perturbation theory and a size-consistency-corrected configuration interaction with single and double substitutions (CISC). Relativistic effects were investigated for PdH and PdF. The ground state of PdC has been calculated at the CISC level to be a {sup 3}{Pi} state which is only 0.26 eV below the {sup 3}{Sigma}{sup {minus}} state (previously assigned ground state) andmore » 0.51 eV below the {sup 1}{Sigma}{sup +} state. PdC is predicted to be stable in the gas phase, and the possibility of preparing this compound is investigated. The bonding in CO chemisorbed on palladium is studied by using the model Pd-CO system. The effect of d{sub {pi}}-{pi}{sup *} back-bonding, discussed at the Hartree-Fock and CI level, is compared with results from multiple-scattering {Chi}{alpha} calculations. The C-O stretching frequency shift for CO on palladium was analyzed at various levels of theory, and the results indicated that the decrease in the CO force constant associated with chemisorption is not solely the result of d{sub {pi}}-{pi}{sup *} back-bonding.« less

Highly efficient photocatalytic degradation of methylene blue by PoPD/TiO2 nanocomposite

PubMed Central

Dong, Wenping; Cui, Guanwei; Ren, Zongming

2017-01-01

The poly-o-phenylenediamine (PoPD)/TiO2 nanocomposite was successfully synthesized via ‘in situ’ oxidative polymerization method. The modified photocatalysts were characterized by BET, scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), Fourier-transform infrarad spectra (FT-IR), thermogravimrtic analysis (TGA), X-ray photoelectron spectroscopy (XPS), Ultraviolet-visible diffuse reflectance spectrum (UV-Vis DRS) and Photocurrent Test. The results showed that the PoPD exists on the surface of TiO2, the presence of PoPD does not impact on the lattice structure and grain size of TiO2, and the presence of PoPD enhances the visible response and photoelectric property. The photocatalytic degradation of methylene blue (MB) was chosen as a model reaction to evaluate the photocatalytic activities of TiO2 and PoPD/TiO2. The optimal preparation condition was the molar ratio of oPD to TiO2 = 3:1, HCl concentration = 1.2 mol/L, the molar ratio of APS to oPD = 1:1. The apparent first-order rate constant kapp of PoPD/TiO2 nanocomposite was 0.0098 min-1, which is 6 times higher than TiO2 (0.0016 min-1). Meanwhile, the PoPD/TiO2 nanocomposites showed excellent photocatalytic stability, and the photocatalytic stability was depended on the stability of structure. At last, the photocatalytic mechanism of POPD/TiO2 nanocomposites was also proposed based on the synergetic effect between TiO2 and PoPD. PMID:28329007

High-affinity PD-1 molecules deliver improved interaction with PD-L1 and PD-L2.

PubMed

Li, Yanyan; Liang, Zhaoduan; Tian, Ye; Cai, Wenxuan; Weng, Zhiming; Chen, Lin; Zhang, Huanling; Bao, Yifeng; Zheng, Hongjun; Zeng, Sihai; Bei, Chunhua; Li, Yi

2018-06-11

The inhibitory checkpoint molecule programmed death (PD)-1 plays a vital role in maintaining immune homeostasis upon binding to its ligands, PD-L1 and PD-L2. Several recent studies have demonstrated that soluble PD-1 (sPD-1) can block the interaction between membrane PD-1 and PD-L1 to enhance the anti-tumor capability of T cells. However, the affinity of natural sPD-1 binding to PD-L1 is too low to permit therapeutic applications. Here a PD-1 variant with ~3,000-fold and ~70-fold affinity increase to bind PD-L1 and PD-L2, respectively, was generated through directed molecular evolution and phage display technology. Structural analysis showed that mutations at amino acid positions 124 and 132 of PD-1 played major roles in enhancing the affinity of PD-1 binding to its ligands. The high-affinity PD-1 mutant could compete with the binding of antibodies specific to PD-L1 or PD-L2 on cancer cells or dendritic cells (DCs), and it could enhance the proliferation and IFN-γ release of activated lymphocytes. These features potentially qualify the high-affinity PD-1 variant as a unique candidate for the development of a new class of PD-1 immune checkpoint blockade therapeutics. This article is protected by copyright. All rights reserved. This article is protected by copyright. All rights reserved.

Controllable exchange bias in Fe/metamagnetic FeRh bilayers

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

Suzuki, Ippei; Hamasaki, Yosuke; Itoh, Mitsuru

2014-10-27

We report the studies of tuning the exchange bias at ferromagnetic Fe/metamagnetic FeRh bilayer interfaces. Fe/FeRh(111) bilayers show exchange bias in the antiferromagnetic state of FeRh while no exchange bias occurs at Fe/FeRh(001) interface. The contrasting results are attributed to the spin configurations of FeRh at the interface, i.e., the uncompensated ferromagnetic spin configuration of FeRh appears exclusively for (111) orientation. The exchange bias disappears as the bilayers are warmed above the antiferromagnetic-ferromagnetic transition temperature. The direction of the exchange bias for Fe/FeRh(111) is also found to be perpendicular to the cooling-field direction, in contrast to the commonly observed directionmore » of exchange bias for ferromagnetic/antiferromagnetic interfaces. In view of these results, the exchange bias in Fe/FeRh bilayers with the (111) crystallographic orientation should be useful for the design of rapid writing technology for magnetic information devices.« less

RhNAC2 and RhEXPA4 Are Involved in the Regulation of Dehydration Tolerance during the Expansion of Rose Petals1[C][W][OA

PubMed Central

Dai, Fanwei; Zhang, Changqing; Jiang, Xinqiang; Kang, Mei; Yin, Xia; Lü, Peitao; Zhang, Xiao; Zheng, Yi; Gao, Junping

2012-01-01

Dehydration inhibits petal expansion resulting in abnormal flower opening and results in quality loss during the marketing of cut flowers. We constructed a suppression subtractive hybridization library from rose (Rosa hybrida) flowers containing 3,513 unique expressed sequence tags and analyzed their expression profiles during cycles of dehydration. We found that 54 genes were up-regulated by the first dehydration, restored or even down-regulated by rehydration, and once again up-regulated by the second dehydration. Among them, we identified a putative NAC family transcription factor (RhNAC2). With transactivation activity of its carboxyl-terminal domain in yeast (Saccharomyces cerevisiae) cell and Arabidopsis (Arabidopsis thaliana) protoplast, RhNAC2 belongs to the NAC transcription factor clade related to plant development in Arabidopsis. A putative expansin gene named RhEXPA4 was also dramatically up-regulated by dehydration. Silencing RhNAC2 or RhEXPA4 in rose petals by virus-induced gene silencing significantly decreased the recovery of intact petals and petal discs during rehydration. Overexpression of RhNAC2 or RhEXPA4 in Arabidopsis conferred strong drought tolerance in the transgenic plants. RhEXPA4 expression was repressed in RhNAC2-silenced rose petals, and the amino-terminal binding domain of RhNAC2 bound to the RhEXPA4 promoter. Twenty cell wall-related genes, including seven expansin family members, were up-regulated in Arabidopsis plants overexpressing RhNAC2. These data indicate that RhNAC2 and RhEXPA4 are involved in the regulation of dehydration tolerance during the expansion of rose petals and that RhEXPA4 expression may be regulated by RhNAC2. PMID:23093360

The comparision of effect of microdose GnRH-a flare-up, GnRH antagonist/aromatase inhibitor letrozole and GnRH antagonist/clomiphene citrate protocols on IVF outcomes in poor responder patients.

PubMed

Ozcan Cenksoy, Pinar; Ficicioglu, Cem; Kizilkale, Ozge; Suhha Bostanci, Mehmet; Bakacak, Murat; Yesiladali, Mert; Kaspar, Cigdem

2014-07-01

To compare the effects of microdose GnRH-a flare-up, GnRH antagonist/aromatase inhibitor letrozole and GnRH antagonist/clomiphene citrate protocols on IVF outcomes in poor responder patients. Of 225 patients, 83 patients were in microdose flare-up group (Group 1), 70 patients were in GnRH antagonist/letrozole group (Group 2) and 72 patients were in GnRH antagonist/clomiphene citrate group (Group 3). Demographic and endocrine characteristics, the total number of oocytes retrieved, cancellation rate and clinical pregnancy rate were collected Results: Total dosage of gonadotropins (p=0.002) and serum E2 levels on the day of hCG administration (p=0.010) were significantly higher and duration of stimulations (p=0.03) was significantly longer in group 1. The number of oocytes retrieved was significantly greater in group 1 and 2 when compare to those of group 3 (p=0,000). There was a trend towards increasing cycle cancellation rates with GnRH antagonist/clomiphene citrate and GnRH antagonist/letrozole. Our finding suggest that the results of microdose flare-up protocol are better than other two used treatment protocols, in terms of maximum estradiol levels, number of mature oocytes retrieved, and cancellation rate and it still seems to be superior the ovarian stimulation regime for the poor responder patients.

Elevated GnRH receptor expression plus GnRH agonist treatment inhibits the growth of a subset of papillomavirus 18-immortalized human prostate cells.

PubMed

Morgan, Kevin; Stavrou, Emmanouil; Leighton, Samuel P; Miller, Nicola; Sellar, Robin; Millar, Robert P

2011-06-15

Human metastatic prostate cancer cell growth can be inhibited by GnRH analogs but effects on virus-immortalized prostate cells have not been investigated. Virus-immortalized prostate cells were stably transfected with rat GnRH receptor cDNA and levels of GnRH binding were correlated with GnRH effects on signaling, cell cycle, growth, exosome production, and apoptosis. High levels of cell surface GnRH receptor occurred in transfected papillomavirus-immortalized WPE-1-NB26 epithelial cells but not in non-tumourigenic RWPE-1, myoepithelial WPMY-1 cells, or SV40-immortalized PNT1A. Endogenous cell surface GnRH receptor was undetectable in non-transfected cells or cancer cell lines LNCaP, PC3, and DU145. GnRH receptor levels correlated with induction of inositol phosphates, elevation of intracellular Ca(2+) , cytoskeletal actin reorganization, modulation of ERK activation and cell growth-inhibition with GnRH agonists. Hoechst 33342 DNA staining-cell sorting indicated accumulation of cells in G2 following agonist treatment. Release of exosomes from transfected WPE-1-NB26 was unaffected by agonists, unlike induction observed in HEK293([SCL60]) cells. Increased PARP cleavage and apoptotic body production were undetectable during growth-inhibition in WPE-1-NB26 cells, contrasting with HEK293([SCL60]) . EGF receptor activation inhibited GnRH-induced ERK activation in WPE-1-NB26 but growth-inhibition was not rescued by EGF or PKC inhibitor Ro320432. Growth of cells expressing low levels of GnRH receptor was not affected by agonists. Engineered high-level GnRH receptor activation inhibits growth of a subset of papillomavirus-immortalized prostate cells. Elucidating mechanisms leading to clone-specific differences in cell surface GnRH receptor levels is a valuable next step in developing strategies to exploit prostate cell anti-proliferation using GnRH agonists. Copyright © 2010 Wiley-Liss, Inc.

Surface enrichment of Pt in stable Pt-Ir nano-alloy particles on MgAl 2O 4 spinel in oxidizing atmosphere

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

Li, Wei -Zhen; Nie, Lei; Cheng, Yingwen

With the capability of MgAl 2O 4 spinel {111} nano-facets in stabilizing small Rh, Ir and Pt particles, bimetallic Ir-Pt catalysts on the same support were investigated in this paper, aiming at further lowering the catalyst cost by substituting expensive Pt with cheaper Ir in the bulk. Small Pt-Ir nano-alloy particles (< 2 nm) were successfully stabilized on the spinel {111} nano-facets as expected. Interestingly, methanol oxidative dehydrogenation (ODH) rate on the surface Pt atoms increases with oxidizing aging but decreases upon reducing treatment, where Ir is almost inactive under the same reaction conditions. Up to three times enhancement inmore » Pt exposure was achieved when the sample was oxidized at 800 °C in air for 1 week and subsequently reduced by H 2 for 2 h, demonstrating successful surface enrichment of Pt on Pt-Ir nano-alloy particles. Finally, a dynamic stabilization mechanism involving wetting/nucleation seems to be responsible for the evolution of surface compositions upon cyclic oxidizing and reducing thermal treatments.« less

Surface enrichment of Pt in stable Pt-Ir nano-alloy particles on MgAl 2O 4 spinel in oxidizing atmosphere

DOE PAGES

Li, Wei -Zhen; Nie, Lei; Cheng, Yingwen; ...

2017-01-13

With the capability of MgAl 2O 4 spinel {111} nano-facets in stabilizing small Rh, Ir and Pt particles, bimetallic Ir-Pt catalysts on the same support were investigated in this paper, aiming at further lowering the catalyst cost by substituting expensive Pt with cheaper Ir in the bulk. Small Pt-Ir nano-alloy particles (< 2 nm) were successfully stabilized on the spinel {111} nano-facets as expected. Interestingly, methanol oxidative dehydrogenation (ODH) rate on the surface Pt atoms increases with oxidizing aging but decreases upon reducing treatment, where Ir is almost inactive under the same reaction conditions. Up to three times enhancement inmore » Pt exposure was achieved when the sample was oxidized at 800 °C in air for 1 week and subsequently reduced by H 2 for 2 h, demonstrating successful surface enrichment of Pt on Pt-Ir nano-alloy particles. Finally, a dynamic stabilization mechanism involving wetting/nucleation seems to be responsible for the evolution of surface compositions upon cyclic oxidizing and reducing thermal treatments.« less

Multimodal Study of the Speciations and Activities of Supported Pd Catalysts During the Hydrogenation of Ethylene

DOE PAGES

Zhao, Shen; Li, Yuanyuan; Liu, Deyu; ...

2017-08-07

In this paper we describe a multimodal exploration of the atomic structure and chemical state of silica-supported palladium nanocluster catalysts during the hydrogenation of ethylene in operando conditions that variously transform the metallic phases between hydride and carbide speciations. The work exploits a microreactor that allows combined multiprobe investigations by high-resolution transmission electron microscopy (HR-TEM), X-ray absorption fine structure (XAFS), and microbeam IR (μ-IR) analyses on the catalyst under operando conditions. The work specifically explores the reaction processes that mediate the interconversion of hydride and carbide phases of the Pd clusters in consequence to changes made in the composition ofmore » the gas-phase reactant feeds, their stability against coarsening, the reversibility of structural/compositional transformations, and the role that oligomeric/waxy byproducts (here forming under hydrogen-limited reactant compositions) might play in modifying activity. The results provide new insights into structural features of the chemistry/mechanisms of Pd catalysis during the selective hydrogenation of acetylene in ethylene—a process simplified here in the use of binary ethylene/hydrogen mixtures. Finally, these explorations, performed in operando conditions, provide new understandings of structure–activity relationships for Pd catalysis in regimes that actively transmute important attributes of electronic and atomic structures.« less

Multimodal Study of the Speciations and Activities of Supported Pd Catalysts During the Hydrogenation of Ethylene

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

Zhao, Shen; Li, Yuanyuan; Liu, Deyu

In this paper we describe a multimodal exploration of the atomic structure and chemical state of silica-supported palladium nanocluster catalysts during the hydrogenation of ethylene in operando conditions that variously transform the metallic phases between hydride and carbide speciations. The work exploits a microreactor that allows combined multiprobe investigations by high-resolution transmission electron microscopy (HR-TEM), X-ray absorption fine structure (XAFS), and microbeam IR (μ-IR) analyses on the catalyst under operando conditions. The work specifically explores the reaction processes that mediate the interconversion of hydride and carbide phases of the Pd clusters in consequence to changes made in the composition ofmore » the gas-phase reactant feeds, their stability against coarsening, the reversibility of structural/compositional transformations, and the role that oligomeric/waxy byproducts (here forming under hydrogen-limited reactant compositions) might play in modifying activity. The results provide new insights into structural features of the chemistry/mechanisms of Pd catalysis during the selective hydrogenation of acetylene in ethylene—a process simplified here in the use of binary ethylene/hydrogen mixtures. Finally, these explorations, performed in operando conditions, provide new understandings of structure–activity relationships for Pd catalysis in regimes that actively transmute important attributes of electronic and atomic structures.« less

Incidence of Maternal Rh Immunization by ABO Compatible and Incompatible Pregnancies

PubMed Central

Ascari, W. Q.; Levine, P.; Pollack, W.

1969-01-01

The incidence of maternal Rh immunization in Rh-negative women following a single ABO compatible Rh-positive pregnancy is about 17%. This incidence was determined by following Rh-negative women through two Rh-incompatible pregnancies and analysing their sera for anti-Rh at the time of delivery of their second observed pregnancy. Maternal Rh immunization occurs almost exclusively after delivery; however, antibodies may not be detectable in the absence of further antigenic stimulation. The incidence of maternal Rh immunization when maternal-foetal ABO incompatibility is also present is 9–13% and 17% for group O and non-group O women respectively. This study emphasizes the need to offer Rh-immune prophylaxis to Rh-negative women having Rh-positive infants whether or not ABO incompatibility exists between the mother and infant. PMID:4179167

Production of Antiserum to LH-Releasing Hormone (LH-RH) Associated with Gonadal Atrophy in Rabbits: Development of Radioimmunoassays for LH-RH

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

ARIMURA, A.; SATO, H.; KUMASAKA, T.

1973-11-01

Repeated injections of synthetic LH -- RH decapeptide, adsorbed on polyvinylpyrrolidone and emulsified with complete Freund's adjuvant, resulted in the production of a specific antiserum to LH-- RH in two of three rabbits. The animals that produced this antiserum showed a reduction of pituitary LH content and marked atrophy of the testes. The antiserum-antibody complex was detected by the complement flxation test. The antiserum was capable of binding /sup 125/I- labeled LH--RH. After iodination of LHRH (using /sup 125/I and either the chloramine T or lactoperoxidase method) separation of the iodination products on CMC yielded three main peaks of radioactivity:more » The first was free iodide, the second was labeled peptide with low immunoreactivity, and the third was immunoreactive peptide. This 3rd peak consisted of two or three subpeaks; the leading subpeak(s) were more readily bound by antiserum than the trailing one(s). Binding of these fractions to antiserum was increased in the presence of small amounts of unlabeled LH--RH (a phenomenon called paradoxical binding or hock effect) but inhibited by larger amounts. Both the augmentation and the inhibition effects were dose-related, allowing the development of two different radioimmunoassay (RIA) systems for LH--RH. An ordinary (coinpetitive) type of RIA was developed in which a small amount (0.31 ng/assay tube) of unlabeled LH-- RH was added to the labeled peptide. This saturated the antiserum's capacity for paradoxical binding, so that further addition of LH-- RH (from 0.04 to 2.5 ng/ tube) inhibited binding of labeled LH--RH. The assay developed using paradoxical binding omitted the premixing of labeled and unlabeled LH--RH; in this assay addition of very small amounts (0.5 to 310 pg) of unlabeled LH--RH to the assay tubes increased the amount of label bound to antiserum and allowed construction of a parabolic curve of positive slope when B/T was plotted against arithmetic dose. The assays seem to be highly

Constitution and thermodynamics of the Mo-Ru, Mo-Pd, Ru-Pd and Mo-Ru-Pd systems

NASA Astrophysics Data System (ADS)

Kleykamp, H.

1989-09-01

The constitution of the Mo-Ru, Mo-Pd and Ru-Pd systems was reinvestigated between 800 and 2000°C. The Mo-Ru system is of the eutectic type, a σ-phase Mo 5Ru 3 exists between 1915 and 1143°C. The Mo-Pd system is characterized by an hcp phase Mo 9Pd 11 and by two peritectic reactions, β- Mo( Pd) + L = Mo9Pd11andMo9Pd11 + L = α- Pd( Mo). Mo 9Pd 11 decomposes eutectoidally at 1370°C. The Ru-Pd system is simple peritectic. The continuous series of the hcp solid solutions between Mo 9Pd 11 and ɛ-Ru(Mo, Pd) in the ternary Mo-Ru-Pd system observed at 1700°C are suppressed below 1370°C near the Mo-Pd boundary system by the formation of a narrow α + β + ɛ three-phase field. Relative partial molar Gibbs energies of Mo, Mo and Ru in the respective binary systems and of Mo in the ternary system were measured by the EMF method with a Zr(Ca)O 2 electrolyte. xsΔ ḠMo∞ quantities were evaluated at 1200 K which give -43 kJ/mol Mo in Ru and -94 kJ/mol Mo in Pd at infinite dilution. Gibbs energies of formation of the Mo-Ru and Mo-Pd systems were calculated.

Spectroscopic study of active phase-support interactions on a RhO{sub x}/CeO{sub 2} catalyst: Evidence for electronic interactions

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

Martinez-Arias, A.; Soria, J.; Conesa, J.C.

The effects of thermal treatments under vacuum, used as a way to generate reduced centers on Rh{sub 2}O{sub 3} and RhO{sub x}/CeO{sub 2}, have been studied by ESR and FTIR, using respectively oxygen and carbon monoxide as probe molecules. The results obtained for the outgassed samples reveal the presence of ceria-rhodia interactions favoring the stabilization of paramagnetic Rh{sup 2+} cations in rhodium oxide clusters on the ceria surface. Subsequent O{sub 2} adsorption leads to the formation of different oxygen-related paramagnetic species located on ceria, on rhodium oxide clusters and at the boundary between both oxides; their contribution to the spectramore » depends on outgassing conditions and O{sub 2} adsorption temperature. The unexpected absence of O{sub 2}{sup -}-Ce{sup 4+} species after O{sub 2} contact at 77 K with RhO{sub x}/CeO{sub 2} outgassed above 573 K evidences the existence of electronic interactions between the RhO{sub x}, and CeO{sub 2} phases, being explained on the basis of electron transfer to the mixed valence RhO{sub x}, phase from the surface-reduced ceria, leading to electron depletion of the latter. This effect is inhibited by CO adsorption, showing the dependence between the electron-accepting properties of the rhodia clusters and the presence of vacant coordination sites at the surface Rh ions. An effect of similar kind may be responsible for shifts observed in the IR bands of rhodium dicarbonyls formed in the RhO{sub x}/CeO{sub 2} system. The latter results suggest the possibility that thermal enhancement of surface reactions in complex systems could depend on electron transfer between adjacent phases and that adsorption on one phase may influence the surface reactivity of another phase by affecting to the electron transfer between them. 34 refs., 8 figs., 2 tabs.« less

GnRH in the Human Female Reproductive Axis.

PubMed

Limonta, Patrizia; Marelli, Marina Montagnani; Moretti, Roberta; Marzagalli, Monica; Fontana, Fabrizio; Maggi, Roberto

2018-01-01

Gonadotropin-releasing hormone (GnRH) is recognized as the central regulator of the functions of the pituitary-gonadal axis. The increasing knowledge on the mechanisms controlling the development and the function of GnRH-producing neurons is leading to a better diagnostic and therapeutic approach for hypogonadotropic hypogonadisms and for alterations of the puberty onset. During female life span, the function of the GnRH pulse generator may be affected by a number of inputs from other neuronal systems, offering alternative strategies for diagnostic and therapeutic interventions. Moreover, the identification of a GnRH/GnRH receptor system in both human ovary and endometrium has widened the spectrum of action of the peptide outside its hypothalamic functions. The pharmacological use of GnRH itself or its synthetic analogs (agonists and antagonists) provides a valid tool to either stimulate or block gonadotropin secretion and to modulate the female fertility in several reproductive disorders and in assisted reproduction technology. The use of GnRH agonists in young female patients undergoing chemotherapy is also considered a promising therapeutic approach to counteract iatrogenic ovarian failure. © 2018 Elsevier Inc. All rights reserved.

Continuous delivery of rhBMP2 and rhVEGF165 at a certain ratio enhances bone formation in mandibular defects over the delivery of rhBMP2 alone--An experimental study in rats.

PubMed

Lohse, N; Moser, N; Backhaus, S; Annen, T; Epple, M; Schliephake, H

2015-12-28

The aim of the present study was to test the hypothesis that different amounts of vascular endothelial growth factor and bone morphogenic protein differentially affect bone formation when applied for repair of non-healing defects in the rat mandible. Porous composite PDLLA/CaCO3 carriers were fabricated as slow release carriers and loaded with rhBMP2 and rhVEGF165 in 10 different dosage combinations using gas foaming with supercritical carbon dioxide. They were implanted in non-healing defects of the mandibles of 132 adult Wistar rats with additional lateral augmentation. Bone formation was assessed both radiographically (bone volume) and by histomorphometry (bone density). The use of carriers with a ratio of delivery of VEGF/BMP between 0.7 and 1.2 was significantly related to the occurrence of significant increases in radiographic bone volume and/or histologic bone density compared to the use of carriers with a ratio of delivery of ≤ 0.5 when all intervals and all outcome parameters were considered. Moreover, simultaneous delivery at this ratio helped to "save" rhBMP2 as both bone volume and bone density after 13 weeks were reached/surpassed using half the dosage required for rhBMP2 alone. It is concluded, that the combined delivery of rhVEGF165 and rhBMP2 for repair of critical size mandibular defects can significantly enhance volume and density of bone formation over delivery of rhBMP2 alone. It appears from the present results that continuous simultaneous delivery of rhVEGF165 and rhBMP2 at a ratio of approximately 1 is favourable for the enhancement of bone formation. Copyright © 2015. Published by Elsevier B.V.

GnRH agonist versus GnRH antagonist in ovarian stimulation: is the emperor naked?

PubMed

Orvieto, R; Rabinson, J; Meltzer, S; Homburg, R; Anteby, E; Zohav, E

2006-01-01

The aim of the study was to evaluate the influence of type of GnRH-analog used during controlled ovarian hyperstimulation (COH) on the outcome of in vitro fertilization (IVF) cycles. All consecutive women aged < or = 35 years admitted to our IVF unit from January 2001 to December 2004 were enrolled in the study. Only patients undergoing up to their third IVF cycle attempt were included. Ovarian stimulation characteristics, number of oocytes retrieved, number of embryos transferred, and clinical pregnancy rate were compared between women given GnRH-agonist or GnRH-antagonist during COH. Four hundred and eighty-seven consecutive IVF cycles were evaluated, 226 in the agonist group and 261 in the antagonist group. A clinical pregnancy was achieved in 93 patients in the agonist group (pregnancy rate 41.2% per cycle) and 66 patients in the antagonist grup (pregnancy rate 25.3%); this difference was statistically significant (p < 0.01). The agonist group also used significantly more gonadotropin ampoules, required longer stimulation, and had higher estradiol levels on the day of human chorionic gonadotropin administration. The midluteal long GhRH-agonist suppressive protocol should be the protocol of choice in young patients in their first three IVF cycle attempts.

Reciprocal Cross Talk between Gonadotropin-Releasing Hormone (GnRH) and Prostaglandin Receptors Regulates GnRH Receptor Expression and Differential Gonadotropin Secretion

PubMed Central

Naor, Zvi; Jabbour, Henry N.; Naidich, Michal; Pawson, Adam J.; Morgan, Kevin; Battersby, Sharon; Millar, Michael R.; Brown, Pamela; Millar, Robert P.

2007-01-01

The asynchronous secretion of gonadotrope LH and FSH under the control of GnRH is crucial for ovarian cyclicity but the underlying mechanism is not fully resolved. Because prostaglandins (PG) are autocrine regulators in many tissues, we determined whether they have this role in gonadotropes. We first demonstrated that GnRH stimulates PG synthesis by induction of cyclooxygenase-2, via the protein kinase C/c-Src/phosphatidylinositol 3′-kinase/MAPK pathway in the LβT2 gonadotrope cell line. We then demonstrated that PGF2α and PGI2, but not PGE2 inhibited GnRH receptor expression by inhibition of phosphoinositide turnover. PGF2α, but not PGI2 or PGE2, reduced GnRH-induction of LHβ gene expression, but not the α-gonadotropin subunit or the FSHβ subunit genes. The prostanoid receptors EP1, EP2, FP, and IP were expressed in rat gonadotropes. Incubations of rat pituitaries with PGF2α, but not PGI2 or PGE2, inhibited GnRH-induced LH secretion, whereas the cyclooxygenase inhibitor, indomethacin, stimulated GnRH-induced LH secretion. None of these treatments had any effect on GnRH-induced FSH secretion. The findings have thus elaborated a novel GnRH signaling pathway mediated by PGF2α-FP and PGI2-IP, which acts through an autocrine/paracrine modality to limit autoregulation of the GnRH receptor and differentially inhibit LH and FSH release. These findings provide a mechanism for asynchronous LH and FSH secretions and suggest the use of combination therapies of GnRH and prostanoid analogs to treat infertility, diseases with unbalanced LH and FSH secretion and in hormone-dependent diseases such as prostatic cancer. PMID:17138645

DFT computations support the σ-complex assisted metathesis (σ-CAM) mechanism for the 1,4-Rh shift of Cp*Rh(III)-(η(1)-β-styryl) complexes.

PubMed

Li, Yougui; He, Gang; Kantchev, Eric Assen B

2014-11-28

DFT calculations support the σ-complex assisted metathesis (σ-CAM) mechanism recently proposed for the first 1,4-Rh shift of a Rh(III) complex rather than the oxidative addition/reductive elimination pathway characteristic of Rh(i). A single, concerted TS (ΔG(‡) = 27-34 kcal mol(-1)) was found and its electronic structure characterized by Bader's AIM analysis. The 4-centered TS is characterized by a enhanced charge separation (Rh and H atoms - positive, both C atoms - negative) relative to the σ-vinyl Rh starting material and the σ-aryl-Rh product. The AIM topological analysis of the electron density reveals a network of interactions: Rh with H as well as both Rh and H with both C(vinyl) and C(aryl) in the TS and confirms the C(vinyl)-Rh agnostic interaction observed experimentally in the σ-aryl-Rh product.

Color vision of the coelacanth (Latimeria chalumnae) and adaptive evolution of rhodopsin (RH1) and rhodopsin-like (RH2) pigments.

PubMed

Yokoyama, S

2000-01-01

The coelacanth, a "living fossil," lives at a depth of about 200 m near the coast of the Comoros archipelago in the Indian Ocean and receives only a narrow range of light at about 480 nm. To see the entire range of "color" the Comoran coelacanth appears to use only rod-specific RH1 and cone-specific RH2 visual pigments, with the optimum light sensitivities (lambda max) at 478 nm and 485 nm, respectively. These blue-shifted lambda max values of RH1 and RH2 pigments are fully explained by independent double amino acid replacements E122Q/A292S and E122Q/M207L, respectively. More generally, currently available mutagenesis experiments identify only 10 amino acid changes that shift the lambda max values of visual pigments more than 5 nm. Among these, D83N, E1220, M207L, and A292S are associated strongly with the adaptive blue shifts in the lambda max values of RH1 and RH2 pigments in vertebrates.

Neuroendocrine control of reproductive aging: roles of GnRH neurons.

PubMed

Yin, Weiling; Gore, Andrea C

2006-03-01

The process of reproductive senescence in many female mammals, including humans, is characterized by a gradual transition from regular reproductive cycles to irregular cycles to eventual acyclicity, and ultimately a loss of fertility. In the present review, the role of the hypothalamic gonadotropin-releasing hormone (GnRH) neurons is considered in this context. GnRH neurons provide the primary driving force upon the other levels of the reproductive axis. With respect to aging, GnRH cells undergo changes in biosynthesis, processing and release of the GnRH decapeptide. GnRH neurons also exhibit morphologic and ultrastructural alterations that appear to underlie these biosynthetic properties. Thus, functional and morphologic changes in the GnRH neurosecretory system may play causal roles in the transition to acyclicity. In addition, GnRH neurons are regulated by numerous inputs from neurotransmitters, neuromodulators and glia. The relationship among GnRH cells and their inputs at the cell body (thereby affecting GnRH biosynthesis) and the neuroterminal (thereby affecting GnRH neurosecretion) is crucial to the function of the GnRH system, with age-related changes in these relationships contributing to the reproductive senescent process. Therefore, the aging hypothalamus is characterized by changes intrinsic to the GnRH cell, as well as its regulatory inputs, which summate to contribute to a loss of reproductive competence in aging females.

Early prepubertal ontogeny of pulsatile gonadotropin-releasing hormone (GnRH) secretion: I. Inhibitory autofeedback control through prolyl endopeptidase degradation of GnRH.

PubMed

Yamanaka, C; Lebrethon, M C; Vandersmissen, E; Gerard, A; Purnelle, G; Lemaitre, M; Wilk, S; Bourguignon, J P

1999-10-01

GnRH[1-5], a subproduct resulting from degradation of GnRH by prolyl endopeptidase (PEP) and endopeptidase 24.15 (EP24.15) was known to account for an inhibitory autofeedback of GnRH secretion through an effect at the N-methyl-D-aspartate (NMDA) receptors. This study aimed at determining the possible role of such a mechanism in the early developmental changes in frequency of pulsatile GnRH secretion. Using retrochiasmatic explants from fetal male rats (day 20-21 of gestation), no GnRH pulses could be observed in vitro, whereas pulses occurred at a mean interval of 86 min from the day of birth onwards. This interval decreased steadily until day 25 (39 min), during the period preceding the onset of puberty. Based on GnRH[1-10] or GnRH[1-9] degradation and GnRH[1-5] generation after incubation with hypothalamic extracts, EP24.15 activity did not change with age, whereas PEP activity was maximal at days 5-10 and decreased subsequently until day 50. These changes were consistent with the ontogenetic variations in PEP messenger RNAs (mRNAs) quantitated using RT-PCR. Using fetal explants, the NMDA-evoked release of GnRH was potentiated in a dose-dependent manner by bacitracin, a competitive PEP inhibitor and the desensitization to the NMDA effect was prevented using 2 mM of bacitracin. At day 5, a higher bacitracin concentration of 20 mM was required for a similar effect. Pulsatile GnRH secretion from fetal explants was not caused to occur using bacitracin or Fmoc-Prolyl-Pyrrolidine-2-nitrile (Fmoc-Pro-PyrrCN), a noncompetitive PEP inhibitor. At postnatal days 5 and 15, a significant acceleration of pulsatility was obtained using 1 microM of Fmoc-Pro-PyrrCN or 2 mM of bacitracin. At 25 and 50 days, a lower bacitracin concentration of 20 microM was effective as well in increasing the frequency of GnRH pulsatility. We conclude that the GnRH inhibitory autofeedback resulting from degradation of the peptide is operational in the fetal hypothalamus but does not explain the

Impaired Insulin Signaling is Associated with Hepatic Mitochondrial Dysfunction in IR+/--IRS-1+/- Double Heterozygous (IR-IRS1dh) Mice.

PubMed

Franko, Andras; Kunze, Alexander; Böse, Marlen; von Kleist-Retzow, Jürgen-Christoph; Paulsson, Mats; Hartmann, Ursula; Wiesner, Rudolf J

2017-05-30

Mitochondria play a pivotal role in energy metabolism, but whether insulin signaling per se could regulate mitochondrial function has not been identified yet. To investigate whether mitochondrial function is regulated by insulin signaling, we analyzed muscle and liver of insulin receptor (IR) +/- -insulin receptor substrate-1 (IRS-1) +/- double heterozygous (IR-IRS1dh) mice, a well described model for insulin resistance. IR-IRS1dh mice were studied at the age of 6 and 12 months and glucose metabolism was determined by glucose and insulin tolerance tests. Mitochondrial enzyme activities, oxygen consumption, and membrane potential were assessed using spectrophotometric, respirometric, and proton motive force analysis, respectively. IR-IRS1dh mice showed elevated serum insulin levels. Hepatic mitochondrial oxygen consumption was reduced in IR-IRS1dh animals at 12 months of age. Furthermore, 6-month-old IR-IRS1dh mice demonstrated enhanced mitochondrial respiration in skeletal muscle, but a tendency of impaired glucose tolerance. On the other hand, 12-month-old IR-IRS1dh mice showed improved glucose tolerance, but normal muscle mitochondrial function. Our data revealed that deficiency in IR/IRS-1 resulted in normal or even elevated skeletal muscle, but impaired hepatic mitochondrial function, suggesting a direct cross-talk between insulin signaling and mitochondria in the liver.

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

NASA Astrophysics Data System (ADS)

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

2015-06-01

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

Methane Oxidation on Pd-Ceria. A DFT Study of the Combustion Mechanism over Pd, PdO and Pd-ceria Sites

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

Mayernick, Adam D.; Janik, Michael J.

2010-12-24

Palladium/ceria exhibits unique catalytic activity for hydrocarbon oxidation; however, the chemical and structural properties of active sites on the palladium–ceria surface are difficult to characterize. Strong interactions between palladium and the ceria support stabilize oxidized Pd δ+ species, which may contribute to the significant activity of Pd/ceria for methane oxidation. We present a density functional theory (DFT + U) investigation into methane oxidation over Pd/ceria and quantify the activity of the Pd xCe 1-xO 2(1 1 1) mixed oxide surface in comparison with the PdO(1 0 0) and Pd(1 1 1) surfaces. The methane activation barrier is lowest over themore » Pd xCe 1-xO 2(1 1 1) surface, even lower than over the Pd(1 1 1) surface or low coordinated stepped or kinked Pd sites. Subsequent reaction steps in complete oxidation, including product desorption and vacancy refilling, are considered to substantiate that methane activation remains the rate-limiting step despite the low barrier over Pd xCe 1-xO 2(1 1 1). The low barrier over the Pd xCe 1-xO 2(1 1 1) surface demonstrates that mixed ceria-noble metal oxides offer the potential for improved hydrocarbon oxidation performance with respect to dispersed noble metal particles on ceria.« less

Hyperprogression during anti-PD-1/PD-L1 therapy in patients with recurrent and/or metastatic head and neck squamous cell carcinoma.

PubMed

Saâda-Bouzid, E; Defaucheux, C; Karabajakian, A; Coloma, V P; Servois, V; Paoletti, X; Even, C; Fayette, J; Guigay, J; Loirat, D; Peyrade, F; Alt, M; Gal, J; Le Tourneau, C

2017-07-01

Pembrolizumab and nivolumab are immune checkpoint inhibitors targeting PD-1 that have recently been approved in pretreated recurrent and/or metastatic head and neck squamous cell carcinoma (R/M HNSCC) patients. In the clinic, some patients seem not only not to benefit from anti-PD-L1/PD-1 agents but rather to experience an acceleration of tumor growth kinetics (TGK). We retrospectively compared TGK on immunotherapy and TGK on last treatment in patients with R/M HNSCC treated with PD-1/PD-L1 inhibitors in four French centers. The TGK ratio (TGKR, ratio of the slope of tumor growth before treatment and the slope of tumor growth on treatment) was calculated. Hyperprogression was defined as a TGKR ≥ 2. From September 2012 to September 2015, 34 patients were identified. Patterns of recurrence included exclusive loco-regional recurrence in 14 patients, exclusive distant metastases in 11 patients, and both in 9 patients. No pseudo-progression was observed. Hyperprogression was observed in 10 patients (29%), including 9 patients with at least a locoregional recurrence, and only 1 patient with exclusively distant metastases. Hyperprogression significantly correlated with a regional recurrence (TGKR ≥ 2: 90% versus TGKR < 2: 37%, P = 0.008), but not with local or distant recurrence. Hyperprogression was associated with a shorter progression-free survival (PFS) according to RECIST (P = 0.003) and irRECIST (P = 0.02), but not with overall survival (P = 0.77). Hyperprogression was observed in 29% of patients with R/M HNSCC treated with anti-PD-L1/PD-1 agents and correlated with a shorter PFS. It occurred in 39% of patients with at least a locoregional recurrence and 9% of patients with exclusively distant metastases. No pseudo-progressions were reported. Mechanisms and causality of hyperprogression should further be assessed through prospective controlled studies. © The Author 2017. Published by Oxford University Press on behalf of the European Society for

Engineering of mesoporous silica nanoparticles for release of ginsenoside CK and Rh2 to enhance their anticancer and anti-inflammatory efficacy: in vitro studies

NASA Astrophysics Data System (ADS)

Singh, Priyanka; Singh, Hina; Castro-Aceituno, Verónica; Ahn, Sungeun; Kim, Yeon Ju; Farh, Mohamed El-Agamy; Yang, Deok Chun

2017-07-01

The current study highlights the fabrication of drug delivery system by utilizing 200 nm mesoporous silica nanoparticles (MSNPs) with 4-nm pore size, as a carrier system for delivery ginsenoside compound K (CK) and Rh2 to enhance their efficacy. The two pharmacologically imperative ginsenosides, CK and Rh2, were loaded to the MSNPs to prepare MSNPs-CK and MSNPs-Rh2, respectively. A fluorescein isothiocyanate (FITC) fluorescent dye was combined in the MSNPs carrier system, in order to trace the cellular uptake of ginsenoside-loaded nanoparticles for in vitro studies. Following purification, the so-prepared MSNPs-CK-FITC and MSNPs-Rh2-FITC were characterized by several analytical techniques, which includes, high-pressure liquid chromatography (HPLC), 1H NMR, field emission transmission electron microscopy (FE-TEM), Fourier transform infrared spectroscopy (FT-IR), x-ray diffraction (XRD), thermogravimetric analysis (TGA), and dynamic light scattering (DLS). In vitro cytotoxicity assay in HaCaT skin cells, A549 lung cancer cells, HepG2 liver carcinoma cells, and HT-29 colon cancer cell lines were tested for MSNPs-CK-FITC and MSNPs-Rh2-FITC. The results demonstrate the excellent biocompatibility of nanoparticles in normal cell lines (HaCaT skin cells) and anticancer efficacy in all the tested cancer cell lines at 10-μM concentration. Additionally, the in vitro anti-inflammatory behavior of MSNPs-CK-FITC and MSNPs-Rh2-FITC were checked in RAW264.7 (murine macrophage) cell lines. The outcomes showed higher anti-inflammatory efficacy of MSNPs-CK-FITC and MSNPs-Rh2-FITC as compared to standard ginsenosides CK and Rh2 in RAW264.7 cell lines. Thus, with 200 nm MSNPs carrier system for the delivery ginsenosides CK and Rh2, a high amount of loading and increasing in vitro pharmacological efficacies of ginsenosides were realized. This study may provide useful insights for designing and improving the applicability of MSNPs for ginsenoside delivery.

A study of Pd/SO4/ZrO2/Al2O3 catalysts in n-hexane isomerization

NASA Astrophysics Data System (ADS)

Dzhikiya, O. V.; Smolikov, M. D.; Kazantsev, K. V.; Yablokova, S. S.; Kireeva, T. V.; Paukshtis, E. A.; Gulyaeva, T. I.; Belyi, A. S.

2017-08-01

The effect of palladium concentration in a range from 0.02 to 1.6 wt.% on characteristics of n-hexane isomerization was studied. The (O2-Hchem) titration and O2 chemisorption study revealed that palladium in Pd/SO4/ZrO2/Al2O3 systems adsorbs hydrogen in a ratio H/Pds = 1.13-1.65 at./at. Investigation of the charge state of the metal by IR spectroscopy of adsorbed CO showed the presence of both the metallic (Pd0) and charged palladium species. Pd/SO4/ZrO2/Al2O3 catalysts with charged palladium atoms exhibit high activity and selectivity in n-hexane isomerization.

Probing the interaction of Rh, Co and bimetallic Rh-Co nanoparticles with the CeO2 support: catalytic materials for alternative energy generation.

PubMed

Varga, E; Pusztai, P; Óvári, L; Oszkó, A; Erdőhelyi, A; Papp, C; Steinrück, H-P; Kónya, Z; Kiss, J

2015-10-28

The interaction of CeO2-supported Rh, Co and bimetallic Rh-Co nanoparticles, which are active catalysts in hydrogen production via steam reforming of ethanol, a process related to renewable energy generation, was studied by X-ray diffraction (XRD), high resolution electron microscopy (HRTEM), X-ray photoelectron spectroscopy (XPS) and low energy ion scattering (LEIS). Furthermore, diffuse reflectance infrared spectroscopy (DRIFTS) of adsorbed CO as a probe molecule was used to characterize the morphology of metal particles. At small loadings (0.1%), Rh is in a much dispersed state on ceria, while at higher contents (1-5%), Rh forms 2-8 nm particles. Between 473-673 K pronounced oxygen transfer from ceria to Rh is observed and at 773 K significant agglomeration of Rh occurs. On reduced ceria, XPS indicates a possible electron transfer from Rh to ceria. The formation of smaller ceria crystallites upon loading with Co was concluded from XRD and HRTEM; for 10% Co, the CeO2 particle size decreased from 27.6 to 10.7 nm. A strong dissolution of Co into ceria and a certain extent of encapsulation by ceria were deduced by XRD, XPS and LEIS. In the bimetallic system, the presence of Rh enhances the reduction of cobalt and ceria. During thermal treatments, reoxidation of Co occurs, and Rh agglomeration as well as oxygen migration from ceria to Rh are hindered in the presence of cobalt.

RH-TRU Waste Inventory Characterization by AK and Proposed WIPP RH-TRU Waste Characterization Objectives

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

Most, W. A.; Kehrman, R.; Gist, C.

2002-02-26

The U.S. Department of Energy (DOE)-Carlsbad Field Office (CBFO) has developed draft documentation to present the proposed Waste Isolation Pilot Plant (WIPP) remote-handled (RH-) transuranic (TRU) waste characterization program to its regulators, the U.S. Environmental Protection Agency and the New Mexico Environment Department. Compliance with Title 40, Code of Federal Regulations, Parts 191 and 194; the WIPP Land Withdrawal Act (PL 102-579); and the WIPP Hazardous Waste Facility Permit, as well as the Certificates of Compliance for the 72-B and 10-160B Casks, requires that specific waste parameter limits be imposed on DOE sites disposing of TRU waste at WIPP. Themore » DOE-CBFO must control the sites' compliance with the limits by specifying allowable characterization methods. As with the established WIPP contact handled TRU waste characterization program, the DOE-CBFO has proposed a Remote-Handled TRU Waste Acceptance Criteria (RH-WAC) document consolidating the requirements from various regulatory drivers and proposed allowable characterization methods. These criteria are consistent with the recommendation of a recent National Academy Sciences/National Research Council to develop an RH-TRU waste characterization approach that removes current self imposed requirements that lack a legal or safety basis. As proposed in the draft RH-WAC and other preliminary documents, the DOE-CBFO RH-TRU waste characterization program proposes the use of acceptable knowledge (AK) as the primary method for obtaining required characterization information. The use of AK involves applying knowledge of the waste in light of the materials or processes used to generate the waste. Documentation, records, or processes providing information about various attributes of a waste stream, such as chemical, physical, and radiological properties, may be used as AK and may be applied to individual waste containers either independently or in conjunction with radiography, visual examination, assay

Low TCR nanocomposite strain gages

NASA Technical Reports Server (NTRS)

Gregory, Otto J. (Inventor); Chen, Ximing (Inventor)

2012-01-01

A high temperature thin film strain gage sensor capable of functioning at temperatures above 1400.degree. C. The sensor contains a substrate, a nanocomposite film comprised of an indium tin oxide alloy, zinc oxide doped with alumina or other oxide semiconductor and a refractory metal selected from the group consisting of Pt, Pd, Rh, Ni, W, Ir, NiCrAlY and NiCoCrAlY deposited onto the substrate to form an active strain element. The strain element being responsive to an applied force.

Superconductivity versus structural phase transition in the closely related Bi 2Rh 3.5S 2 and Bi 2Rh 3S 2

DOE PAGES

Kaluarachchi, Udhara S.; Xie, Weiwei; Lin, Qisheng; ...

2015-05-19

Single crystals of Bi 2Rh 3S 2 and Bi 2Rh 3.5S 2 were synthesized by solution growth, and the crystal structures and thermodynamic and transport properties of both compounds were studied. In the case of Bi 2Rh 3S 2, a structural first-order transition at around 165 K is identified by single-crystal diffraction experiments, with clear signatures visible in resistivity, magnetization, and specific heat data. No superconducting transition for Bi 2Rh 3S 2 was observed down to 0.5 K. In contrast, no structural phase transition at high temperature was observed for Bi 2Rh 3.5S 2; however, bulk superconductivity with a criticalmore » temperature, T c ≈ 1.7 K, was observed. The Sommerfeld coefficient γ and the Debye temperature (Θ D) were found to be 9.41 mJ mol –1K –2 and 209 K, respectively, for Bi 2Rh 3S 2, and 22 mJ mol –1K –2 and 196 K, respectively, for Bi 2Rh 3.5S 2. As a result, the study of the specific heat in the superconducting state of Bi 2Rh 3.5S 2 suggests that Bi 2Rh 3.5S 2 is a weakly coupled, BCS superconductor.« less

C-H activation in Ir(III) and N-demethylation in Pt(II) complexes with mesoionic carbene ligands: examples of monometallic, homobimetallic and heterobimetallic complexes.

PubMed

Maity, Ramananda; Tichter, Tim; van der Meer, Margarethe; Sarkar, Biprajit

2015-11-14

Mononuclear Pt(II) and the first dinuclear Pt(II) complexes along with a cyclometalated heterobimetallic Ir(III)/Pd(II) complex bearing mesoionic carbene donor ligands are presented starting from the same bis-triazolium salt. The mononuclear Pt(II) complex possesses a free triazole moiety which is generated from the corresponding triazolium salt through an N-demethylation reaction, whereas the mononuclear Ir(III) complex features an unreacted triazolium unit.

GnRH Analogues in the Prevention of Ovarian Hyperstimulation Syndrome

PubMed Central

Alama, Pilar; Bellver, Jose; Vidal, Carmen; Giles, Juan

2013-01-01

The GnRH analogue (agonist and antagonist GnRH) changed ovarian stimulation. On the one hand, it improved chances of pregnancy to obtain more oocytes and better embryos. This leads to an ovarian hyper-response, which can be complicated by the ovarian hyperstimulation syndrome (OHSS). On the other hand, the GnRH analogue can prevent the incidence of OHSS: GnRH antagonist protocols, GnRH agonist for triggering final oocyte maturation, either together or separately, coasting, and the GnRH analogue may prove useful for avoiding OHSS in high-risk patients. We review these topics in this article. PMID:23825982

Tailoring Silica-alumina Supported Pt-Pd As Poison Tolerant Catalyst For Aromatics Hydrogenation

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

Yu, Yanzhe; Gutierrez, Oliver Y.; Haller, Gary L.

2013-08-01

The tailoring of the physicochemical and catalytic properties of mono- and bimetallic Pt-Pd catalysts supported on amorphous silica-alumina is studied. Electron energy loss spectroscopy and extended X-ray absorption fine structure analyses indicated that bimetallic Pt-Pd and relatively large monometallic Pd particles were formed, whereas the X-ray absorption near edge structure provided direct evidence for the electronic deficiency of the Pt atoms. The heterogeneous distribution of metal particles was also shown by high resolution transmission electron microscopy. The average structure of the bimetallic particles (Pt-rich core and Pd-rich shell) and the presence of Pd particles led to surface Pd enrichment, whichmore » was independently shown by IR spectra of adsorbed CO. The specific metal distribution, average size, and surface composition of the Pt-Pd particles depend to a large extent on the metal precursors. In the presence of NH3 ligands, Pt-Pd particles with a fairly homogeneous bulk and surface metal distribution were formed. Also high Lewis acid site concentration of the carrier leads to more homogeneous bimetallic particles. All catalysts were active for the hydrogenation of tetralin in the absence and presence of quinoline and dibenzothiophene (DBT). Monometallic Pt catalysts had the highest hydrogenation activity in poison-free and quinoline-containing feed. When DBT was present, bimetallic Pt-Pd catalysts with the most homogenous metal distribution showed the highest activity. The higher resistance of bimetallic catalysts towards sulfur poisoning compared to their monometallic Pt counterparts results from the weakened metal-sulfur bond on the electron deficient Pt atoms. Thus, increasing the fraction of electron deficient Pt on the surface of the bimetallic particles increases the efficiency of the catalyst in the presence of sulfur.« less

Microdose GnRH Agonist Flare-Up versus Ultrashort GnRH Agonist Combined with Fixed GnRH Antagonist in Poor Responders of Assisted Reproductive Techniques Cycles

PubMed Central

Eftekhar, Maryam; Mohammadian, Farnaz; Yousefnejad, Fariba; Khani, Parisa

2013-01-01

Background: This study compares the microdose flare-up protocol to the ultrashort gonadotropinreleasing hormone (GnRH) agonist flare combined with the fixed multidose GnRH antagonist protocol in poor responders undergoing ovarian stimulation. Materials and Methods: In this randomized clinical trial, 120 women who were candidates for assisted reproductive techniques (ART) and had histories of one or more failed in vitro fertilization (IVF) cycles with three or fewer retrieved oocytes were prospectively randomized into two groups. Group I (60 patients) received the microdose flare-up regimen and group II (60 patients) received the ultrashort GnRH agonist combined with fixed GnRH antagonist. Results: There were no significant differences between the groups in the number of used gonadotropin ampoules (p=0.591), duration of stimulation (p=0.610), number of retrieved oocytes (p=0.802), fertilization rate (p=0.456), and the number of transferred embryos (p=0.954). The clinical pregnancy rates were statistically similar in group I (10%) compared with group II (13.3%, p=0.389). Conclusion: According to our results, there is no significant difference between these protocols for improving the ART outcome in poor responders. Additional prospective, randomized studies with more patients is necessary to determine the best protocol (Registration Number: IRCT201105096420N1). PMID:24520450

Microdose GnRH Agonist Flare-Up versus Ultrashort GnRH Agonist Combined with Fixed GnRH Antagonist in Poor Responders of Assisted Reproductive Techniques Cycles.

PubMed

Eftekhar, Maryam; Mohammadian, Farnaz; Yousefnejad, Fariba; Khani, Parisa

2013-01-01

This study compares the microdose flare-up protocol to the ultrashort gonadotropinreleasing hormone (GnRH) agonist flare combined with the fixed multidose GnRH antagonist protocol in poor responders undergoing ovarian stimulation. In this randomized clinical trial, 120 women who were candidates for assisted reproductive techniques (ART) and had histories of one or more failed in vitro fertilization (IVF) cycles with three or fewer retrieved oocytes were prospectively randomized into two groups. Group I (60 patients) received the microdose flare-up regimen and group II (60 patients) received the ultrashort GnRH agonist combined with fixed GnRH antagonist. There were no significant differences between the groups in the number of used gonadotropin ampoules (p=0.591), duration of stimulation (p=0.610), number of retrieved oocytes (p=0.802), fertilization rate (p=0.456), and the number of transferred embryos (p=0.954). The clinical pregnancy rates were statistically similar in group I (10%) compared with group II (13.3%, p=0.389). According to our results, there is no significant difference between these protocols for improving the ART outcome in poor responders. Additional prospective, randomized studies with more patients is necessary to determine the best protocol (Registration Number: IRCT201105096420N1).

Structural, electronic, and thermal properties of indium-filled InxIr4Sb12 skutterudites

NASA Astrophysics Data System (ADS)

Wallace, M. K.; Li, Jun; Subramanian, M. A.

2018-06-01

The "phonon-glass/electron-crystal" approach has been implemented through incorporation of "rattlers" into skutterudite void sites to increase phonon scattering and thus increase the thermoelectric efficiency. Indium filled IrSb3 skutterudites are reported for the first time. Polycrystalline samples of InxIr4Sb12 (0 ≤ x ≤ 0.2) were prepared by solid-state reaction under a gas mixture of 5% H2 and 95% Ar. The solubility limit of InxIr4Sb12 was found to be close to 0.18. Synchrotron X-ray diffraction refinements reveal all InxIr4Sb12 phases crystallized in body-centered cubic structure (space group : Im 3 bar) with ∼8% antimony site vacancy and with indium partially occupying the 16f site. Unlike known rattler filled skutterudites, under synthetic conditions employed, indium filling in IrSb3 significantly increases the electrical resistivity and decreases the Seebeck coefficient (n-type) while reducing the thermal conductivity by ∼30%. The resultant power factor offsets the decrease in total thermal conductivity giving rise to a substantial decrease in ZT. Principal thermoelectric properties of InxM4Sb12 (M = Co, Rh, Ir) phases are compared. As iridium is a 5d transition metal, zero field cooled (ZFC) magnetization were performed to unravel the effect of spin-orbit interaction on the electronic properties. These results serve to advance the understanding of filled skutterudites, and provide additional insight on the less explored smaller "rattlers" and their influence on key thermoelectric properties.

Interfacial and Alloying Effects on Activation of Ethanol from First-Principles

DOE PAGES

An, Wei; Men, Yong; Wang, Jinguo; ...

2017-02-24

Here, we present a first-principles density-functional theory study of ethanol activation at oxide/Rh(111) interface and the alloying effect on mitigating carbon deposition, which are essential to direct ethanol fuel cell (DEFC) anode reaction and steam reforming of ethanol (SRE) reaction. Our calculated results show that charge can transfer from Rh(111) substrate to MO x chain (e.g., MoO 3 and MnO 2), or from MO x chain (e.g., MgO, SnO 2, ZrO 2, and TiO 2) to Rh(111) substrate. The OH-binding strength is increased exponentially with M δ+ charge ranging from 1.4 to 2.2, which renders MnO 2/Rh(111) and MgO/Rh(111) interfacesmore » weaker OH-binding, and thereby enhanced oxidizing functionality of OH* for promoting ethanol oxidation reaction (EOR) at DEFC anode. For efficient C–C bond breaking, a large number of Rh ensemble sizes are critically needed at the interface of MO x/Rh(111). We found that Rh 1Au 3 near surface alloy has the weakest C* and CO* binding, followed by Rh 1Cu 3 and Rh 1Pd 3 near surface alloys, while Rh 1Ir 3 and Rh 1Ru 3 surface alloys have C* and CO* binding strength similar to that of pure Rh metal. The general implication of this study is that by engineering alloyed structure of weakened C* and CO* binding complemented with metal oxides of weakened OH-binding, high-performance DEFC anode or SRE catalysts can be identified.« less

Comparison of Ti/Pd/Ag, Pd/Ti/Pd/Ag and Pd/Ge/Ti/Pd/Ag contacts to n-type GaAs for electronic devices handling high current densities

NASA Astrophysics Data System (ADS)

Huo, Pengyun; Galiana, Beatriz; Rey-Stolle, Ignacio

2017-04-01

In the quest for metal contacts for electronic devices handling high current densities, we report the results of Pd/Ti/Pd/Ag and Pd/Ge/Ti/Pd/Ag contacts to n-GaAs and compare them to Ti/Pd/Ag and AuGe/Ni/Au. These metal systems have been designed with the goal of producing an electrical contact with (a) low metal-semiconductor specific contact resistance, (b) very high sheet conductance, (c) good bondability, (d) long-term durability and (e) cost-effectiveness. The structure of the contacts consists of an interfacial layer (either Pd or Pd/Ge) intended to produce a low metal-semiconductor specific contact resistance; a diffusion barrier (Ti/Pd) and a thick top layer of Ag to provide the desired high sheet conductance, limited cost and good bondability. The results show that both systems can achieve very low metal resistivity (ρ M ˜ 2 × 10-6 Ω cm), reaching values close to that of pure bulk silver. This fact is attributed to the Ti/Pd bilayer acting as an efficient diffusion barrier, and thus the metal sheet resistance can be controlled by the thickness of the deposited silver layer. Moreover, the use of Pd as interfacial layer produces contacts with moderate specific contact resistance (ρ C ˜ 10-4 Ω cm2) whilst the use of Pd/Ge decreases the specific contact resistance to ρ C ˜ 1.5 × 10-7 Ω cm2, as a result of the formation of a Pd4(GaAs, Ge2) compound at the GaAs interface.

Isolation and Quantification of Ginsenoside Rh23, a New Anti-Melanogenic Compound from the Leaves of Panax ginseng.

PubMed

Lee, Dae Young; Kim, Hyoung-Geun; Lee, Yeong-Geun; Kim, Jin Hee; Lee, Jae Won; Choi, Bo-Ram; Jang, In-Bae; Kim, Geum-Soog; Baek, Nam-In

2018-01-29

A new ginsenoside, named ginsenoside Rh23 ( 1 ), and 20- O -β-d-glucopyranosyl-3β,6α,12β,20β,25-pentahydroxydammar-23-ene ( 2 ) were isolated from the leaves of hydroponic Panax ginseng . Compounds were isolated by various column chromatography and their structures were determined based on spectroscopic methods, including high resolution quadrupole/time of flight mass spectrometry (HR-QTOF/MS), nuclear magnetic resonance (NMR) spectroscopy, and infrared (IR) spectroscopy. To determine anti-melanogenic activity, the change in the melanin content in melan-a cells treated with identified compounds was tested. Additionally, we investigated the melanin inhibitory effects of ginsenoside Rh23 on pigmentation in a zebrafish in vivo model. Compound 1 inhibited potent melanogenesis in melan-a cells with 37.0% melanogenesis inhibition at 80 µM and also presented inhibition on the body pigmentation in zebrafish model. Although compound 2 showed slightly lower inhibitory activity than compound 1 , it also showed significantly decreased melanogenesis in melan-a cell and in zebrafish model. These results indicated that compounds isolated from hydroponic P. ginseng may be used as new skin whitening compound through the in vitro and in vivo systems. Furthermore, this study demonstrated the utility of MS-based compound 1 for the quantitative analysis. Ginsenoside Rh23 ( 1 ) was found at a level of 0.31 mg/g in leaves of hydroponic P. ginseng .

Cost-effectiveness of the management of rh-negative pregnant women.

PubMed

Duplantie, Julie; Gonzales, Odilon Martinez; Bois, Antoine; Nshimyumukiza, Léon; Gekas, Jean; Bujold, Emmanuel; Morin, Valérie; Vallée, Maud; Giguère, Yves; Gagné, Christian; Rousseau, François; Reinharz, Daniel

2013-08-01

The purpose of this study was to determine the most cost-effective option to prevent alloimmunization against the Rh factor. A virtual population of Rh-negative pregnant women in Quebec was built to simulate the cost-effectiveness of preventing alloimmunization. The model considered four options: (1) systematic use of anti-D immunoglobulin; (2) fetal Rh(D) genotyping; (3) immunological determination of the father's Rh type; (4) mixed screening: immunological determination of the father's Rh type, followed if positive by fetal Rh(D) genotyping. Two outcomes were considered, in addition to the estimated costs: (1) the number of babies without hemolytic disease, and (2) the number of surviving infants. In a first pregnancy, two options emerged as the most cost-effective options: systematic prophylaxis and immunological Rh typing of the father, with overlapping confidence intervals between them. In a second pregnancy, the results were similar. In all cases (first or second pregnancy or a combination of the two) fetal genotyping was not found to be a cost-effective option. Routine prophylaxis and immunological Rh typing of the father are the most cost-effective options for the prevention of Rh alloimmunization. Considering that immunological typing of the father would probably not be carried out by the majority of clinicians, routine prophylaxis remains the preferred option. However, this could change if the cost of Rh(D) fetal genotyping fell below $140 per sample.

Neonatal Hyperbilirubinemia in infants with G6PD c.563C > TVariant

PubMed Central

2012-01-01

Background There is a strong correlation between glucose-6-phosphate dehydrogenase (G6PD) deficiency and neonatal hyperbilirubinemia with a rare but potential threat of devastating acute bilirubin encephalopathy. G6PD deficiency was observed in 4–14% of hospitalized icteric neonates in Pakistan. G6PD c.563C > T is the most frequently reported variant in this population. The present study was aimed at evaluating the time to onset of hyperbilirubinemia and the postnatal bilirubin trajectory in infants having G6PD c.563C > T. Methods This was a case–control study conducted at The Aga Khan University, Pakistan during the year 2008. We studied 216 icteric male neonates who were re-admitted for phototherapy during the study period. No selection was exercised. Medical records showed that 32 were G6PD deficient while 184 were G6PD normal. Each infant was studied for birth weight, gestational age, age at the time of presentation, presence of cephalhematoma, sepsis and neurological signs, peak bilirubin level, age at peak bilirubin level, days of hospitalization, whether phototherapy or exchange blood transfusion was initiated, and the outcome. During hospital stay, each baby was tested for complete blood count, reticulocyte count, ABO and Rh blood type, direct antiglobulin test and quantitative G6PD estimation [by kinetic determination of G6PDH]. G6PDgenotype was analyzed in 32 deficient infants through PCR-RFLP analysis and gene sequencing. Results G6PD variants c.563C > T and c.131 C > G were observed in 21 (65%) and three (9%) of the 32 G6PD deficient infants, respectively. DNA of eight (25%) newborns remained uncharacterized. In contrast to G6PD normal neonates, infants with c.563C > T variant had significantly lower enzyme activity (mean ± 1SD; 0.3 ± 0.2 U/gHb vs. 14.0 ± 4.5 U/gHb, p < 0.001) experienced higher peak levels of total serum bilirubin (mean ± 1SD; 16.8 ± 5.4 mg/dl vs. 13.8 ± 4.6 mg/dl, p = 0.008) which peaked earlier after

Basal cell carcinoma: PD-L1/PD-1 checkpoint expression and tumor regression after PD-1 blockade.

PubMed

Lipson, Evan J; Lilo, Mohammed T; Ogurtsova, Aleksandra; Esandrio, Jessica; Xu, Haiying; Brothers, Patricia; Schollenberger, Megan; Sharfman, William H; Taube, Janis M

2017-01-01

Monoclonal antibodies that block immune regulatory proteins such as programmed death-1 (PD-1) have demonstrated remarkable efficacy in controlling the growth of multiple tumor types. Unresectable or metastatic basal cell carcinoma, however, has largely gone untested. Because PD-Ligand-1 (PD-L1) expression in other tumor types has been associated with response to anti-PD-1, we investigated the expression of PD-L1 and its association with PD-1 expression in the basal cell carcinoma tumor microenvironment. Among 40 basal cell carcinoma specimens, 9/40 (22%) demonstrated PD-L1 expression on tumor cells, and 33/40 (82%) demonstrated PD-L1 expression on tumor-infiltrating lymphocytes and associated macrophages. PD-L1 was observed in close geographic association to PD-1+ tumor infiltrating lymphocytes. Additionally, we present, here, the first report of an objective anti-tumor response to pembrolizumab (anti-PD-1) in a patient with metastatic PD-L1 (+) basal cell carcinoma, whose disease had previously progressed through hedgehog pathway-directed therapy. The patient remains in a partial response 14 months after initiation of therapy. Taken together, our findings provide a rationale for testing anti-PD-1 therapy in patients with advanced basal cell carcinoma, either as initial treatment or after acquired resistance to hedgehog pathway inhibition.

Effects of Alloyed Metal on the Catalysis Activity of Pt for Ethanol Partial Oxidation: Adsorption and Dehydrogenation on Pt3M (M=Pt, Ru, Sn, Re, Rh, and Pd)

PubMed Central

Xu, Zhen-Feng; Wang, Yixuan

2011-01-01

The adsorption and dehydrogenation reactions of ethanol over bimetallic clusters, Pt3M (M = Pt, Ru, Sn, Re, Rh, and Pd), have been extensively investigated with density functional theory. Both the α-hydrogen and hydroxyl adsorptions on Pt as well as on the alloyed transition metal M sites of PtM were considered as initial reaction steps. The adsorptions of ethanol on Pt and M sites of some PtM via the α-hydrogen were well established. Although the α-hydrogen adsorption on Pt site is weaker than the hydroxyl, the potential energy profiles show that the dehydrogenation via the α-hydrogen path has much lower energy barrier than that via the hydroxyl path. Generally for the α-hydrogen path the adsorption is a rate-determining-step because of rather low dehydrogenation barrier for the α-hydrogen adsorption complex (thermodynamic control), while the hydroxyl path is determined by its dehydrogenation step (kinetic control). The effects of alloyed metal on the catalysis activity of Pt for ethanol partial oxidation, including adsorption energy, energy barrier, electronic structure, and eventually rate constant were discussed. Among all of the alloyed metals only Sn enhances the rate constant of the dehydrogenation via the α-hydrogen path on the Pt site of Pt3Sn as compared with Pt alone, which interprets why the PtSn is the most active to the oxidation of ethanol. PMID:22102920

[Study on rhG-CSF modified with polyethylene glycol].

PubMed

Zhang, Lin-Lin; Zheng, Chun-Yang; Lei, Jian-Du; Ma, Guang-Hui; Su, Zhi-Guo; Wang, Li

2005-11-01

Monomethoxy Polyethylene Glycol(mPEG20000) was activated by N-hydroxysuccinimede and analyzed by infrared spectrum and hydrolysis kinetics. In order to propose the optimized reaction conditions of mono-PEGylated rhG-CSF, orthogonal design of the experiment was investigated. Ion exchange chromatography was used to separate and purify PEGylated rhG-CSF from unPEGylated rhG-CSF. The purity of mono-PEGylated rhG-CSF was analyzed by high performance liquid chromatography (HPLC) to be 97%.

Single crystal study of layered UnRhIn3n+2 materials: Case of the novel U2RhIn8 compound

NASA Astrophysics Data System (ADS)

Bartha, Attila; Kratochvílová, M.; Dušek, M.; Diviš, M.; Custers, J.; Sechovský, V.

2015-05-01

We report on the single crystal properties of the novel U2RhIn8 compound studied in the context of parent URhIn5 and UIn3 systems. The compounds were prepared by In self-flux method. U2RhIn8 adopts the Ho2CoGa8-type structure with lattice parameters a=4.6056(6) Å and c=11.9911(15) Å. The behavior of U2RhIn8 strongly resembles that of the related URhIn5 and UIn3 with respect to magnetization, specific heat and resistivity except for magnetocrystalline anisotropy developing with lowering dimensionality in the series UIn3 vs. U2RhIn8 and URhIn5. U2RhIn8 orders antiferromagnetically below TN=117 K and exhibits a slightly enhanced Sommerfeld coefficient γ=47 mJ mol-1 K-2. Magnetic field leaves the value of Néel temperature for both URhIn5 and U2RhIn8 unaffected up to 9 T. On the other hand, TN is increasing when applying hydrostatic pressure up to 3.2 GPa. The character of uranium 5f electron states of U2RhIn8 was studied by first principles calculations based on the density functional theory. The overall phase diagram of U2RhIn8 is discussed in the context of magnetism in the related URhX5 and UX3 (X=In, Ga) compounds.

Structure functions in decomposing CuRh systems

NASA Astrophysics Data System (ADS)

Prem, M.; Blaschko, O.; Rosta, L.

1997-02-01

The time evolution of a CuRh alloy quenched within the miscibility gap is investigated by small and wide angle neutron scattering techniques. Near fundamental Bragg reflections diffuse satellites arising from a lattice parameter modulation induced by the precipitation pattern are investigated. The results show that in CuRh the precipitation morphology and its time evolution are quite different from decomposition characteristics recently observed in the system AuPt. The results are discussed and related to the larger lattice misfit present in CuRh in comparison to AuPt.

GnRH agonist for final oocyte maturation in GnRH antagonist co-treated IVF/ICSI treatment cycles: Systematic review and meta-analysis

PubMed Central

Youssef, M.A.F.; Abdelmoty, Hatem I.; Ahmed, Mohamed A.S.; Elmohamady, Maged

2015-01-01

Final oocyte maturation in GnRH antagonist co-treated IVF/ICSI cycles can be triggered with HCG or a GnRH agonist. We conducted a systematic review and meta-analysis of randomized controlled trials to evaluate the efficacy and safety of the final oocyte maturation trigger in GnRH antagonist co-treated cycles. Outcome measures were ongoing pregnancy rate (OPR) and ovarian hyperstimulation syndrome (OHSS) incidence. Searches: were conducted in MEDLINE, EMBASE, Science Direct, Cochrane Library, and databases of abstracts. There was a statistically significant difference against the GnRH agonist for OPR in fresh autologous cycles (n = 1024) with an odd ratio (OR) of 0.69 (95% CI: 0.52–0.93). In oocyte-donor cycles (n = 342) there was no evidence of a difference (OR: 0.91; 95% CI: 0.59–1.40). There was a statistically significant difference in favour of GnRH agonist regarding the incidence of OHSS in fresh autologous cycles (OR: 0.06; 95% CI: 0.01–0.33) and donor cycles respectively (OR: 0.06; 95% CI: 0.01–0.27). In conclusion GnRH agonist trigger for final oocyte maturation trigger in GnRH antagonist cycles is safer but less efficient than HCG. PMID:26257931

[Observation on gene polymorphism of Rh blood group in Chinese Han nationality].

PubMed

Lan, Jiong-Cai; Wang, Cong-Rong; Wei, Ya-Ming; Zhou, Hua-You; Cao, Qiong; Zhang, Yin-Ze; Jiang, KuReXi; Wu, Da-Lin; Liu, Zhong

2003-12-01

To observe the gene polymorphism of Rh blood group in unrelated random individuals and families for Chinese Han nationality, polymerase chain reaction-sequence specific primer (PCR-SSP) was used to amplify the Rh C/E gene, RhD gene, exons, intron 2 and 10, insert and Rh Box in 160 blood samples of RhD positive unrelated individuals and 71 samples of RhD negative unrelated individuals and 7 samples of families whose probands were RhD-negative. The results showed that RhD genes of RhD-negative individuals with C antigens were polymorphism, three forms were found for D exon including intact, partial deletion and complete deletion exons. Insert fragments and Rh Box were found in most cases of families whose probands were RhD-negative and its inheritance accorded with the Mendel's Law, and it did not affect the expression of RhD gene. "Normal" RhD exon 4 amplifying product was not found in all of the samples. It was concluded that gene structure of the RhD-negative in Chinese was polymorphism, intact, partial deletion and complete deletion exons were found in the individuals with C antigen and probably existed specific D (nf) Ce haplotype. The function of insert was uncertain. The Rh gene sequences of Chinese Han nationality are different from those of Caucasian and the Rh gene library based on Han nationality should be established.

Impaired Insulin Signaling is Associated with Hepatic Mitochondrial Dysfunction in IR+/−-IRS-1+/− Double Heterozygous (IR-IRS1dh) Mice

PubMed Central

Franko, Andras; Kunze, Alexander; Böse, Marlen; von Kleist-Retzow, Jürgen-Christoph; Paulsson, Mats; Hartmann, Ursula; Wiesner, Rudolf J.

2017-01-01

Mitochondria play a pivotal role in energy metabolism, but whether insulin signaling per se could regulate mitochondrial function has not been identified yet. To investigate whether mitochondrial function is regulated by insulin signaling, we analyzed muscle and liver of insulin receptor (IR)+/−-insulin receptor substrate-1 (IRS-1)+/− double heterozygous (IR-IRS1dh) mice, a well described model for insulin resistance. IR-IRS1dh mice were studied at the age of 6 and 12 months and glucose metabolism was determined by glucose and insulin tolerance tests. Mitochondrial enzyme activities, oxygen consumption, and membrane potential were assessed using spectrophotometric, respirometric, and proton motive force analysis, respectively. IR-IRS1dh mice showed elevated serum insulin levels. Hepatic mitochondrial oxygen consumption was reduced in IR-IRS1dh animals at 12 months of age. Furthermore, 6-month-old IR-IRS1dh mice demonstrated enhanced mitochondrial respiration in skeletal muscle, but a tendency of impaired glucose tolerance. On the other hand, 12-month-old IR-IRS1dh mice showed improved glucose tolerance, but normal muscle mitochondrial function. Our data revealed that deficiency in IR/IRS-1 resulted in normal or even elevated skeletal muscle, but impaired hepatic mitochondrial function, suggesting a direct cross-talk between insulin signaling and mitochondria in the liver. PMID:28556799

Tetra- and Heptametallic Ru(II),Rh(III) Supramolecular Hydrogen Production Photocatalysts

DOE PAGES

Manbeck, Gerald F.; Fujita, Etsuko; Brewer, Karen J.

2017-06-01

Supramolecular mixed metal complexes combining the trimetallic chromophore [{(bpy) 2Ru(dpp)} 2Ru(dpp)] 6+ (Ru 3) with [Rh(bpy)Cl 2] + or [RhCl 2] + catalytic fragments to form [{(bpy) 2Ru(dpp)} 2Ru(dpp)RhCl 2(bpy)](PF 6) 7 (Ru 3Rh) or [{(bpy) 2Ru(dpp)} 2Ru(dpp)] 2RhCl 2(PF 6) 13 (Ru 3RhRu 3) (bpy = 2,2'-bipyridine and dpp = 2,3-bis(2-pyridyl)pyrazine) catalyze the photochemical reduction of protons to H 2. This first example of a heptametallic Ru,Rh photocatalyst produces over 300 turnovers of H 2 upon photolysis of a solution of acetonitrile, water, triflic acid, and N,N-dimethylaniline as an electron donor. Conversely, the tetrametallic Ru 3Rh produces only 40more » turnovers of H 2 due to differences in the excited state properties and nature of the catalysts upon reduction as ascertained from electrochemical data, transient absorption spectroscopy, and flash-quench experiments. And while the lowest unoccupied molecular orbital of Ru 3Rh is localized on a bridging ligand, it is Rh-centered in Ru 3RhRu 3 facilitating electron collection at Rh in the excited state and reductively quenched state. The Ru → Rh charge separated state of Ru 3RhRu 3 is endergonic with respect to the emissive Ru → dpp 3MLCT excited and cannot be formed by static electron transfer quenching of the 3MLCT state. Instead, a mechanism of subnanosecond charge separation from high lying states is proposed. Multiple reductions of Ru 3 and Ru 3Rh using sodium amalgam were carried out to compare UV–vis absorption spectra of reduced species and to evaluate the stability of highly reduced complexes. Furthermore, the Ru 3 and Ru 3Rh can be reduced by 10 and 13 electrons, respectively, to final states with all bridging ligands doubly reduced and all bpy ligands singly reduced.« less

[PD-L1 expression and PD-1/PD-L1 inhibitors in breast cancer].

PubMed

Monneur, Audrey; Gonçalves, Anthony; Bertucci, François

2018-03-01

The development of immune checkpoints inhibitors represents one of the major recent advances in oncology. Monoclonal antibodies directed against the programmed cell death protein 1 (PD-1) or its ligand (PD-L1) provides durable disease control, particularly in melanoma, lung, kidney, bladder and head and neck cancers. The purpose of this review is to synthesize current data on the expression of PD-L1 in breast cancer and on the preliminary clinical results of PD-1/PD-L1 inhibitors in breast cancer patients. In breast cancer, PD-L1 expression is heterogeneous and is generally associated with the presence of tumor-infiltrating lymphocytes as well as the presence of poor-prognosis factors, such as young age, high grade, ER-negativity, PR-negativity, and HER-2 overexpression, high proliferative index, and aggressive molecular subtypes (triple negative, basal-like, HER-2-overexpressing). Its prognostic value remains controversial when assessed with immunohistochemistry, whereas it seems favorable in triple-negative cancers when assessed at the mRNA level. Early clinical trials with PD-1/PD-L1 inhibitors in breast cancer have shown efficacy in terms of tumor response and/or disease control in refractory metastatic breast cancers, notably in the triple-negative subtype. Many trials are currently underway, both in the metastatic and neo-adjuvant setting. A crucial issue is identification of biomarkers predictive of response to PD-1/PD-L1 inhibitors. Copyright © 2018 Société Française du Cancer. Published by Elsevier Masson SAS. All rights reserved.

Molecular mechanism of PD-1/PD-L1 blockade via anti-PD-L1 antibodies atezolizumab and durvalumab.

PubMed

Lee, Hyun Tae; Lee, Ju Yeon; Lim, Heejin; Lee, Sang Hyung; Moon, Yu Jeong; Pyo, Hyo Jeong; Ryu, Seong Eon; Shin, Woori; Heo, Yong-Seok

2017-07-17

In 2016 and 2017, monoclonal antibodies targeting PD-L1, including atezolizumab, durvalumab, and avelumab, were approved by the FDA for the treatment of multiple advanced cancers. And many other anti-PD-L1 antibodies are under clinical trials. Recently, the crystal structures of PD-L1 in complex with BMS-936559 and avelumab have been determined, revealing details of the antigen-antibody interactions. However, it is still unknown how atezolizumab and durvalumab specifically recognize PD-L1, although this is important for investigating novel binding sites on PD-L1 targeted by other therapeutic antibodies for the design and improvement of anti-PD-L1 agents. Here, we report the crystal structures of PD-L1 in complex with atezolizumab and durvalumab to elucidate the precise epitopes involved and the structural basis for PD-1/PD-L1 blockade by these antibodies. A comprehensive comparison of PD-L1 interactions with anti-PD-L1 antibodies provides a better understanding of the mechanism of PD-L1 blockade as well as new insights into the rational design of improved anti-PD-L1 therapeutics.

Magnetic behavior in heterometallic one-dimensional chains or octanuclear complex regularly aligned with metal-metal bonds as -Rh-Rh-Pt-Cu-Pt

NASA Astrophysics Data System (ADS)

Uemura, Kazuhiro

2018-06-01

Heterometallic one-dimensional chains, [{Rh2(O2CCH3)4}{Pt2Cu(piam)4(NH3)4}]n(PF6)2n (1 and 2, piam = pivalamidate) and [{Rh2(O2CCH3)4}{Pt2Cu(piam)4(NH3)4}2](CF3CO2)2(ClO4)2·2H2O (3), are paramagnetic one-dimensional chains or octanuclear complexes that are either aligned as -Rh-Rh-Pt-Cu-Pt- (1 and 2) or as Pt-Cu-Pt-Rh-Rh-Pt-Cu-Pt (3) with metal-metal bonds. Compounds 1-3 have rare structures, from the standpoint of that the paramagnetic species of Cu atoms are linked by direct metal-metal bonds. Magnetic susceptibility measurements for 1-3 performed at temperatures of 2 K-300 K indicated that the unpaired electrons localize in the Cu 3dx2-y2 orbitals, where S = 1/2 Cu(II) atoms are weakly antiferromagnetically coupled with J = -0.35 cm-1 (1), -0.47 cm-1 (2), and -0.45 cm-1 (3).

BPA Directly Decreases GnRH Neuronal Activity via Noncanonical Pathway.

PubMed

Klenke, Ulrike; Constantin, Stephanie; Wray, Susan

2016-05-01

Peripheral feedback of gonadal estrogen to the hypothalamus is critical for reproduction. Bisphenol A (BPA), an environmental pollutant with estrogenic actions, can disrupt this feedback and lead to infertility in both humans and animals. GnRH neurons are essential for reproduction, serving as an important link between brain, pituitary, and gonads. Because GnRH neurons express several receptors that bind estrogen, they are potential targets for endocrine disruptors. However, to date, direct effects of BPA on GnRH neurons have not been shown. This study investigated the effects of BPA on GnRH neuronal activity using an explant model in which large numbers of primary GnRH neurons are maintained and express many of the receptors found in vivo. Because oscillations in intracellular calcium have been shown to correlate with electrical activity in GnRH neurons, calcium imaging was used to assay the effects of BPA. Exposure to 50μM BPA significantly decreased GnRH calcium activity. Blockage of γ-aminobutyric acid ergic and glutamatergic input did not abrogate the inhibitory BPA effect, suggesting direct regulation of GnRH neurons by BPA. In addition to estrogen receptor-β, single-cell RT-PCR analysis confirmed that GnRH neurons express G protein-coupled receptor 30 (G protein-coupled estrogen receptor 1) and estrogen-related receptor-γ, all potential targets for BPA. Perturbation studies of the signaling pathway revealed that the BPA-mediated inhibition of GnRH neuronal activity occurred independent of estrogen receptors, GPER, or estrogen-related receptor-γ, via a noncanonical pathway. These results provide the first evidence of a direct effect of BPA on GnRH neurons.

BPA Directly Decreases GnRH Neuronal Activity via Noncanonical Pathway

PubMed Central

Klenke, Ulrike; Constantin, Stephanie

2016-01-01

Peripheral feedback of gonadal estrogen to the hypothalamus is critical for reproduction. Bisphenol A (BPA), an environmental pollutant with estrogenic actions, can disrupt this feedback and lead to infertility in both humans and animals. GnRH neurons are essential for reproduction, serving as an important link between brain, pituitary, and gonads. Because GnRH neurons express several receptors that bind estrogen, they are potential targets for endocrine disruptors. However, to date, direct effects of BPA on GnRH neurons have not been shown. This study investigated the effects of BPA on GnRH neuronal activity using an explant model in which large numbers of primary GnRH neurons are maintained and express many of the receptors found in vivo. Because oscillations in intracellular calcium have been shown to correlate with electrical activity in GnRH neurons, calcium imaging was used to assay the effects of BPA. Exposure to 50μM BPA significantly decreased GnRH calcium activity. Blockage of γ-aminobutyric acid ergic and glutamatergic input did not abrogate the inhibitory BPA effect, suggesting direct regulation of GnRH neurons by BPA. In addition to estrogen receptor-β, single-cell RT-PCR analysis confirmed that GnRH neurons express G protein-coupled receptor 30 (G protein-coupled estrogen receptor 1) and estrogen-related receptor-γ, all potential targets for BPA. Perturbation studies of the signaling pathway revealed that the BPA-mediated inhibition of GnRH neuronal activity occurred independent of estrogen receptors, GPER, or estrogen-related receptor-γ, via a noncanonical pathway. These results provide the first evidence of a direct effect of BPA on GnRH neurons. PMID:26934298

Development of a complex of instrumental nuclear-physical methods to detect PGE, Re, Au, and Ag in hard-to-analyze rocks and complex ores

NASA Astrophysics Data System (ADS)

Kolmogorov, Yu. P.; Mezentsev, N. A.; Mironov, A. G.; Parkhomenko, V. S.; Spiridonov, A. M.; Shaporenko, A. D.; Yusupov, T. S.; Zhmodik, S. M.; Zolotarev, K. V.; Anoshin, G. N.

2009-05-01

A system of methods to detect platinum group elements (PGE): Re, Au, and Ag in hard-to-analyze rocks and complex ores has been developed. It applies the SRXRF for Ru, Rh, Pd, and Ag and the INAA method for Os, Ir, Pt and Ag and implies mechanoactivation of probes to study. The results of measurement of standard samples of carbonaceous rocks and ores in order to PGE, gold, and silver confirm the possibility of detecting some of the above-listed elements with a detection limit of 10 ppb.

Low carrier semiconductor like behavior in Lu3Ir4Ge13 single crystal

NASA Astrophysics Data System (ADS)

Kumar, Anil; Matteppanavar, Shidaling; Thamizhavel, A.; Ramakrishnan, S.

2018-04-01

Single crystal of Lu3Ir4Ge13 crystallizing in the Yb3Rh4Sn13-type cubic crystal structure has been grown by Czochralski method in a tetra-arc furnace. In this paper we report on the crystal structure, magnetic and transport properties of Lu3Ir4Ge13. The analysis of the powder x-ray diffraction (XRD) studies revealed that Lu3Ir4Ge13 crystallizes in a cubic structure with the space group Pm-3n, no. 223. The lattice parameter was obtained from the Rietveld refinement of the room temperature XRD data which amounts to 8.904 (3) Å with low R factors. The temperature dependence of the resistivity exhibited semiconductor like behavior till 1.8 K, with a broad hump around 15 - 62 K. This hump was observed in both warming and cooling cycle with a very small hysteresis, it may be due to the existence of structural transition from high - low symmetry. The temperature dependent magnetization data shows the diamagnetic behavior with an anomaly around 70 K, which is well supported by the derivative of resistivity data.

London penetration depth measurements in Ba (Fe 1-xT x) 2As 2(T=Co,Ni,Ru,Rh,Pd,Pt,Co+Cu) superconductors

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

Gordon, Ryan T.

2011-01-01

The London penetration depth has been measured in various doping levels of single crystals of Ba(Fe 1-xT x) 2As 2 (T=Co,Ni,Ru,Rh,Pd,Pt,Co+Cu) superconductors by utilizing a tunnel diode resonator (TDR) apparatus. All in-plane penetration depth measurements exhibit a power law temperature dependence of the form Δλ ab(T) = CT n, indicating the existence of low-temperature, normal state quasiparticles all the way down to the lowest measured temperature, which was typically 500 mK. Several different doping concentrations from the Ba(Fe 1-xT x) 2As 2 (T=Co,Ni) systems have been measured and the doping dependence of the power law exponent, n, is compared tomore » results from measurements of thermal conductivity and specific heat. In addition, a novel method has been developed to allow for the measurement of the zero temperature value of the in-plane penetration depth, λ ab(0), by using TDR frequency shifts. By using this technique, the doping dependence of λ ab(0) has been measured in the Ba(Fe 1-xCo x) 2As 2 series, which has allowed also for the construction of the doping-dependent superfluid phase stiffness, ρ s(T) = [λ(0)/λ(T)] 2. By studying the effects of disorder on these superconductors using heavy ion irradiation, it has been determined that the observed power law temperature dependence likely arises from pair-breaking impurity scattering contributions, which is consistent with the proposed s±-wave symmetry of the superconducting gap in the dirty scattering limit. This hypothesis is supported by the measurement of an exponential temperature dependence of the penetration depth in the intrinsically clean LiFeAs, indicative of a nodeless superconducting gap.« less

Visible-light-assisted SLCs template synthesis of sea anemone-like Pd/PANI nanocomposites with high electrocatalytic activity for methane oxidation in acidic medium

NASA Astrophysics Data System (ADS)

Tan, De-Xin; Wang, Yan-Li

2018-03-01

Sea anemone-like palladium (Pd)/polyaniline (PANI) nanocomposites were synthesized via visible-light-assisted swollen liquid crystals (SLCs) template method. The resulting samples were characterized by transmission electron microscopy (TEM), selected area electron diffraction (SAED), energy dispersive spectrometer (EDS), x-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), ultraviolet-visible (UV–vis) absorption spectroscopy and Fourier transform infrared (FT-IR) spectroscopy, respectively. The electrocatalytic properties of Pd/PANI nanocomposites modified glass carbon electrode (GCE) for methane oxidation were investigated by cycle voltammetry (CV) and chronoamperometry. Those dispersed sea anemone-like Pd/PANI nanocomposites had an average diameter of 320 nm. The obtained Pd nanoparticles with an average diameter of about 45 nm were uniformly distributed in PANI matrix. Sea anemone-like Pd/PANI nanocomposites exhibited excellent electrocatalytic activity and stability for oxidation of methane (CH4).

Fanconi anemia A is a nucleocytoplasmic shuttling molecule required for gonadotropin-releasing hormone (GnRH) transduction of the GnRH receptor.

PubMed

Larder, Rachel; Karali, Dimitra; Nelson, Nancy; Brown, Pamela

2006-12-01

GnRH binds its cognate G protein-coupled GnRH receptor (GnRHR) located on pituitary gonadotropes and drives expression of gonadotropin hormones. There are two gonadotropin hormones, comprised of a common alpha- and hormone-specific beta-subunit, which are required for gonadal function. Recently we identified that Fanconi anemia a (Fanca), a DNA damage repair gene, is differentially expressed within the LbetaT2 gonadotrope cell line in response to stimulation with GnRH. FANCA is mutated in more than 60% of cases of Fanconi anemia (FA), a rare genetically heterogeneous autosomal recessive disorder characterized by bone marrow failure, endocrine tissue cancer susceptibility, and infertility. Here we show that induction of FANCA protein is mediated by the GnRHR and that the protein constitutively adopts a nucleocytoplasmic intracellular distribution pattern. Using inhibitors to block nuclear import and export and a GnRHR antagonist, we demonstrated that GnRH induces nuclear accumulation of FANCA and green fluorescent protein (GFP)-FANCA before exporting back to the cytoplasm using the nuclear export receptor CRM1. Using FANCA point mutations that locate GFP-FANCA to the cytoplasm (H1110P) or functionally uncouple GFP-FANCA (Q1128E) from the wild-type nucleocytoplasmic distribution pattern, we demonstrated that wild-type FANCA was required for GnRH-induced activation of gonadotrope cell markers. Cotransfection of H1110P and Q1128E blocked GnRH activation of the alphaGsu and GnRHR but not the beta-subunit gene promoters. We conclude that nucleocytoplasmic shuttling of FANCA is required for GnRH transduction of the alphaGSU and GnRHR gene promoters and propose that FANCA functions as a GnRH-induced signal transducer.

Fanconi Anemia a Is a Nucleocytoplasmic Shuttling Molecule Required for Gonadotropin-Releasing Hormone (GnRH) Transduction of the GnRH Receptor

PubMed Central

Larder, Rachel; Karali, Dimitra; Nelson, Nancy; Brown, Pamela

2007-01-01

GnRH binds its cognate G protein-coupled GnRH receptor (GnRHR) located on pituitary gonadotropes and drives expression of gonadotropin hormones. There are two gonadotropin hormones, comprised of a common α- and hormone-specific β-subunit, which are required for gonadal function. Recently we identified that Fanconi anemia a (Fanca), a DNA damage repair gene, is differentially expressed within the LβT2 gonadotrope cell line in response to stimulation with GnRH. FANCA is mutated in more than 60% of cases of Fanconi anemia (FA), a rare genetically heterogeneous autosomal recessive disorder characterized by bone marrow failure, endocrine tissue cancer susceptibility, and infertility. Here we show that induction of FANCA protein is mediated by the GnRHR and that the protein constitutively adopts a nucleocytoplasmic intracellular distribution pattern. Using inhibitors to block nuclear import and export and a GnRHR antagonist, we demonstrated that GnRH induces nuclear accumulation of FANCA and green fluorescent protein (GFP)-FANCA before exporting back to the cytoplasm using the nuclear export receptor CRM1. Using FANCA point mutations that locate GFP-FANCA to the cytoplasm (H1110P) or functionally uncouple GFP-FANCA (Q1128E) from the wild-type nucleocytoplasmic distribution pattern, we demonstrated that wild-type FANCA was required for GnRH-induced activation of gonadotrope cell markers. Cotransfection of H1110P and Q1128E blocked GnRH activation of the αGsu and GnRHR but not the β-subunit gene promoters. We conclude that nucleocytoplasmic shuttling of FANCA is required for GnRH transduction of the αGSU and GnRHR gene promoters and propose that FANCA functions as a GnRH-induced signal transducer. PMID:16946016

Functional Reconstitution into Liposomes of Purified Human RhCG Ammonia Channel

PubMed Central

Mouro-Chanteloup, Isabelle; Cochet, Sylvie; Chami, Mohamed; Genetet, Sandrine; Zidi-Yahiaoui, Nedjma; Engel, Andreas; Colin, Yves; Bertrand, Olivier; Ripoche, Pierre

2010-01-01

Background Rh glycoproteins (RhAG, RhBG, RhCG) are members of the Amt/Mep/Rh family which facilitate movement of ammonium across plasma membranes. Changes in ammonium transport activity following expression of Rh glycoproteins have been described in different heterologous systems such as yeasts, oocytes and eukaryotic cell lines. However, in these complex systems, a potential contribution of endogenous proteins to this function cannot be excluded. To demonstrate that Rh glycoproteins by themselves transport NH3, human RhCG was purified to homogeneity and reconstituted into liposomes, giving new insights into its channel functional properties. Methodology/Principal Findings An HA-tag introduced in the second extracellular loop of RhCG was used to purify to homogeneity the HA-tagged RhCG glycoprotein from detergent-solubilized recombinant HEK293E cells. Electron microscopy analysis of negatively stained purified RhCG-HA revealed, after image processing, homogeneous particles of 9 nm diameter with a trimeric protein structure. Reconstitution was performed with sphingomyelin, phosphatidylcholine and phosphatidic acid lipids in the presence of the C12E8 detergent which was subsequently removed by Biobeads. Control of protein incorporation was carried out by freeze-fracture electron microscopy. Particle density in liposomes was a function of the Lipid/Protein ratio. When compared to empty liposomes, ammonium permeability was increased two and three fold in RhCG-proteoliposomes, depending on the Lipid/Protein ratio (1/300 and 1/150, respectively). This strong NH3 transport was reversibly inhibited by mercuric and copper salts and exhibited a low Arrhenius activation energy. Conclusions/Significance This study allowed the determination of ammonia permeability per RhCG monomer, showing that the apparent PunitNH3 (around 1×10−3 µm3.s−1) is close to the permeability measured in HEK293E cells expressing a recombinant human RhCG (1.60×10−3 µm3.s−1), and in human red

New Rh 2 (II,II) Architecture for the Catalytic Reduction of H +

DOE PAGES

White, Travis A.; Witt, Suzanne E.; Li, Zhanyong; ...

2015-09-25

Formamidinate-bridged Rh 2 II,II complexes containing diimine ligands of the formula cis-[Rh 2 II,II(μ-DTolF) 2(NN) 2] 2+ (Rh 2-NN 2), where DTolF = p-ditolylformamidinate and NN = dppn (benzo[i]dipyrido[3,2-a:2',3'-h]quinoxaline), dppz (dipyrido[3,2-a:2',3'-c]phenazine), and phen (1,10-phenanthroline), electrocatalytically reduce H + to H 2 in DMF solutions containing CH 3COOH at a glassy carbon electrode. Cathodic scans in the absence of acid display a Rh III,II/II,II reduction at -0.90 V vs Fc +/Fc followed by NN 0/– reduction at -1.13, -1.36, and -1.65 V for Rh 2-dppn 2, Rh 2-dppz 2, and Rh 2-phen 2, respectively. Upon the addition of acid, Rh 2-dppnmore » 2 and Rh 2-dppz 2 undergo reduction–protonation–reduction at each pyrazine-containing NN ligand prior to the Rh 2 II,II/II,I reduction. The Rh 2 II,I species is thus protonated at one of the metal centers, resulting in the formation of the corresponding Rh 2 II,III-hydride. In the case of Rh 2-phen 2, the reduction of the phen ligand is followed by intramolecular electron transfer to the Rh 2 II,II core in the presence of protons to form a Rh 2 II,III-hydride species. Further reduction and protonation at the Rh 2 core for all three complexes rapidly catalyzes H 2 formation with varied calculated turnover frequencies (TOF) and overpotential values (η): 2.6 × 10 4 s –1 and 0.56 V for Rh 2-dppn, 2.8 × 10 4 s –1 and 0.50 V for Rh 2-dppz 2, and 5.9 × 10 4 s –1 and 0.64 V for Rh 2-phen 2. Bulk electrolysis confirmed H 2 formation, and further CH 3COOH addition regenerates H 2 production, attesting to the robust nature of the architecture. The cis-[Rh 2 II,II(μ-DTolF) 2(NN) 2] 2+ architecture benefits by combining electron-rich formamidinate bridges, a redox-active Rh 2 II,II core, and electron-accepting NN diimine ligands to allow for the electrocatalysis of H + substrate to H 2 fuel.« less

Rh isoimmunization in Sub-Saharan Africa indicates need for universal access to anti-RhD immunoglobulin and effective management of D-negative pregnancies

PubMed Central

Osaro, Erhabor; Charles, Adias Teddy

2010-01-01

Transplacental or fetomaternal hemorrhage (FMH) may occur during pregnancy or at delivery and lead to immunization to the D antigen if the mother is Rh-negative and the baby is Rh-positive. This can result in hemolytic disease of the fetus and newborn (HDFN) in subsequent D-positive pregnancies. The aim of this study is to highlight the challenges associated with the effective management and prevention of Rh alloimmunization among Rh-negative women in Sub-Saharan Africa. In most Sub-Saharan African countries, there is poor and sometimes no alloimmunization prevention following potentially sensitizing events and during medical termination of pregnancy in Rh-negative women. Information about previous pregnancies and termination are often lacking in patients’ medical notes due to poor data management. These issues have made the management of Rh-negative pregnancy a huge challenge. Despite the fact that the prevalence of Rh-negative phenotype is significantly lower among Africans than Caucasians, Rh alloimmunization remains a major factor responsible for perinatal morbidity in Sub-Saharan Africa and may result in the compromise of the woman’s obstetric care due to the unaffordability of anti-D immunoglobulin. There is the urgent need for the implementation of universal access to anti-D immunoglobulin for the Rh-negative pregnant population in Africa. Anti-D immunoglobulin should be available in cases of potentially sensitizing events such as amniocentesis, cordocentesis, antepartum hemorrhage, vaginal bleeding during pregnancy, external cephalic version, abdominal trauma, intrauterine death and stillbirth, in utero therapeutic interventions, miscarriage, and therapeutic termination of pregnancy. There is also the need for the availability of FMH measurements following potentially sensitizing events. The low-cost acid elution method, a modification of the Kleihauer–Betke (KB) test, can become a readily available, affordable, and minimum alternative to flow

Anti-tumor immunotherapy by blockade of the PD-1/PD-L1 pathway with recombinant human PD-1-IgV.

PubMed

Zhang, C; Wu, S; Xue, X; Li, M; Qin, X; Li, W; Han, W; Zhang, Y

2008-01-01

Blockade of the programmed death-1 (PD-1)/PD-ligand 1 (PD-L1) pathway can delay tumor growth and prolong the survival of tumor-bearing mice. The extracellular immunoglobulin (Ig) V domain of PD-1 is important for the interaction between PD-1 and PD-L1, suggesting that PD-1-IgV may be a potential target for anti-tumor immunotherapy. The extracellular sequence of human PD-1-IgV (hPD-1-IgV) was expressed in Escherichia coli and purified. The anti-tumor effect of hPD-1-IgV on tumor-bearing mice was tested. hPD-1-IgV recombinant protein could bind PD-L1 at molecular and cellular levels and enhance Cytotoxic T Lymphocyte (CTL) activity and anti-tumor effect on tumor-bearing mice in vivo. The percentage of CD4(+)CD25(+) T cells in tumor-bearing mice was decreased compared with control mice after administration of the recombinant protein. Our results suggest that inhibition of the interaction between PD-1 and PD-L1 by hPD-1-IgV may be a promising strategy for specific tumor immunotherapy.

Gonadotropin-releasing hormone (Gn-RH) in striped mullet (Mugil cephalus), milkfish (Chanos chanos), and rainbow trout (Salmo gairdneri): comparison with salmon Gn-RH.

PubMed

Sherwood, N M; Harvey, B; Brownstein, M J; Eiden, L E

1984-08-01

Immunoreactive gonadotropin-releasing hormone (Gn-RH) was extracted from brains of striped mullet, milkfish, rainbow trout, and chum salmon with acetone/HCl and petroleum ether. High pressure liquid chromatography and cross-reactivity studies show mullet, milkfish, and trout brains to contain a peptide chromatographically and immunologically identical to synthetic salmon Gn-RH, while the mammalian form of Gn-RH is detectable in none of these fishes. Gn-RH is present in immature 7-month-old and 4-year-old milkfish. A second immunoreactive peptide is separable by HPLC in all the fish studied. This "early-eluting" form of Gn-RH is unlikely to be a precursor; its cross-reactivity with antisera R-42 and #185 suggests that any modification is in the C-terminal region. Several possible roles for this peptide are advanced.

Circadian gene expression regulates pulsatile gonadotropin-releasing hormone (GnRH) secretory patterns in the hypothalamic GnRH-secreting GT1-7 cell line.

PubMed

Chappell, Patrick E; White, Rachel S; Mellon, Pamela L

2003-12-03

Although it has long been established that episodic secretion of gonadotropin-releasing hormone (GnRH) from the hypothalamus is required for normal gonadotropin release, the molecular and cellular mechanisms underlying the synchronous release of GnRH are primarily unknown. We used the GT1-7 mouse hypothalamic cell line as a model for GnRH secretion, because these cells release GnRH in a pulsatile pattern similar to that observed in vivo. To explore possible molecular mechanisms governing secretory timing, we investigated the role of the molecular circadian clock in regulation of GnRH secretion. GT1-7 cells express many known core circadian clock genes, and we demonstrate that oscillations of these components can be induced by stimuli such as serum and the adenylyl cyclase activator forskolin, similar to effects observed in fibroblasts. Strikingly, perturbation of circadian clock function in GT1-7 cells by transient expression of the dominant-negative Clock-Delta19 gene disrupts normal ultradian patterns of GnRH secretion, significantly decreasing mean pulse frequency. Additionally, overexpression of the negative limb clock gene mCry1 in GT1-7 cells substantially increases GnRH pulse amplitude without a commensurate change in pulse frequency, demonstrating that an endogenous biological clock is coupled to the mechanism of neurosecretion in these cells and can regulate multiple secretory parameters. Finally, mice harboring a somatic mutation in the Clock gene are subfertile and exhibit a substantial increase in estrous cycle duration as revealed by examination of vaginal cytology. This effect persists in normal light/dark (LD) cycles, suggesting that a suprachiasmatic nucleus-independent endogenous clock in GnRH neurons is required for eliciting normal pulsatile patterns of GnRH secretion.

Preparation of a Nile Red-Pd-based fluorescent CO probe and its imaging applications in vitro and in vivo.

PubMed

Liu, Keyin; Kong, Xiuqi; Ma, Yanyan; Lin, Weiying

2018-05-01

Carbon monoxide (CO) is a key gaseous signaling molecule in living cells and organisms. This protocol illustrates the synthesis of a highly sensitive Nile Red (NR)-Pd-based fluorescent probe, NR-PdA, and its applications for detecting endogenous CO in tissue culture cells, ex vivo organs, and zebrafish embryos. In the NR-PdA synthesis process, 3-diethylamine phenol reacts with sodium nitrite in the acidic condition to afford 5-(diethylamino)-2-nitrosophenol hydrochloride (compound 1), which is further treated with 1-naphthalenol at a high temperature to provide the NR dye via a cyclization reaction. Finally, NR is reacted with palladium acetate to obtain the desired Pd-based fluorescent probe NR-PdA. NR-PdA possesses excellent two-photon excitation and near-IR emission properties, high stability, low background fluorescence, and a low detection limit. In addition to the chemical synthesis procedures, we provide step-by-step procedures for imaging endogenous CO in RAW 264.7 cells, mouse organs ex vivo, and live zebrafish embryos. The synthesis process for the probe requires ∼4 d, and the biological imaging experiments take ∼14 d.

Tunable Rh 2(II,II) Light Absorbers as Excited State Electron Donors and Acceptors Accessible with Red/Near-IR Irradiation

DOE PAGES

Whittemore, Tyler; Millet, Agustin; Sayre, Hannah; ...

2018-04-04

In this study, a series of dirhodium(II,II) paddlewheeel complexes of the type cis-[Rh 2(μ-DTolF) 2(μ-L) 2][BF 4] 2, where DTolF = N,N'-di(p-tolyl)formamidinate and L = 1,8-naphthyridine (np), 2-(pyridin-2-yl)-1,8-naphthyridine (pynp), 2-(quinolin-2-yl)-1,8-naphthyridine (qnnp), and 2-(1,8-naphthyridin-2-yl)quinoxaline (qxnp), were synthesized and characterized. These molecules feature new tridentate ligands that concomitantly bridge the dirhodium core and cap the axial positions. The complexes absorb light strongly throughout the ultraviolet/visible range and into the near-infrared region and exhibit relatively long-lived triplet excited-state lifetimes. Both the singlet and triplet excited states exhibit metal/ligand-to-ligand charge transfer (ML-LCT) in nature as determined by transient absorption spectroscopy and spectroelectrochemistry measurements. Whenmore » irradiated with low-energy light, these black dyes are capable of undergoing reversible bimolecular electron transfer both to the electron acceptor methyl viologen and from the electron donor p-phenylenediamine. Photoinduced charge transfer in the latter was inaccessible with previous Rh 2(II,II) complexes. Finally, these results underscore the fact that the excited state of this class of molecules can be readily tuned for electron-transfer reactions upon simple synthetic modification and highlight their potential as excellent candidates for p- and n-type semiconductor applications and for improved harvesting of low-energy light to drive useful photochemical reactions.« less

Tunable Rh 2(II,II) Light Absorbers as Excited State Electron Donors and Acceptors Accessible with Red/Near-IR Irradiation

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

Whittemore, Tyler; Millet, Agustin; Sayre, Hannah

In this study, a series of dirhodium(II,II) paddlewheeel complexes of the type cis-[Rh 2(μ-DTolF) 2(μ-L) 2][BF 4] 2, where DTolF = N,N'-di(p-tolyl)formamidinate and L = 1,8-naphthyridine (np), 2-(pyridin-2-yl)-1,8-naphthyridine (pynp), 2-(quinolin-2-yl)-1,8-naphthyridine (qnnp), and 2-(1,8-naphthyridin-2-yl)quinoxaline (qxnp), were synthesized and characterized. These molecules feature new tridentate ligands that concomitantly bridge the dirhodium core and cap the axial positions. The complexes absorb light strongly throughout the ultraviolet/visible range and into the near-infrared region and exhibit relatively long-lived triplet excited-state lifetimes. Both the singlet and triplet excited states exhibit metal/ligand-to-ligand charge transfer (ML-LCT) in nature as determined by transient absorption spectroscopy and spectroelectrochemistry measurements. Whenmore » irradiated with low-energy light, these black dyes are capable of undergoing reversible bimolecular electron transfer both to the electron acceptor methyl viologen and from the electron donor p-phenylenediamine. Photoinduced charge transfer in the latter was inaccessible with previous Rh 2(II,II) complexes. Finally, these results underscore the fact that the excited state of this class of molecules can be readily tuned for electron-transfer reactions upon simple synthetic modification and highlight their potential as excellent candidates for p- and n-type semiconductor applications and for improved harvesting of low-energy light to drive useful photochemical reactions.« less

WinRho: Rh immune globulin prepared by ion exchange for intravenous use.

PubMed Central

Bowman, J M; Friesen, A D; Pollock, J M; Taylor, W E

1980-01-01

An Rh immune globulin [Rh IgG] for intravenous use, WinRho, has been prepared by the Winnipeg Rh Institute by a modification of the ion-exchange column method of Hoppe and colleagues. When administered to Rh-negative male and nonpregnant female volunteers WinRho was found to be nonpyrogenic, nontoxic, safe and protective against Rh alloimmunization. In a clinical trial with 240 microgram given at about 28 weeks' gestation and 120 microgram given after delivery to Rh-negative women at risk of Rh immunization WinRho was effective in preventing Rh immunization. Of the 870 women carrying Rh-positive fetuses who were treated with WinRho during pregnancy and were not tested several months after delivery 14 would have shown evidence of Rh immunization by the time of delivery if WinRho had been ineffective; none showed such evidence. Of the 1122 women carrying Rh-positive fetuses who were retested 4 to 6 months after delivery 83 would have shown evidence of Rh immunization at that time if WinRho had been ineffective; only 1 showed such evidence. The efficiency of yield of anti-D with the modified method of production, the fct that it can be given intravenously (a route that causes the patient less discomfort and immediately results in high anti-D levels) and the lower levels of contaminating IgA and IgM make WinRho the preparation of choice for preventing Rh immunization. PMID:6161687

Rational Design of Emissive NIR-Absorbing Chromophores: Rh(III) Porphyrin-Aza-BODIPY Conjugates with Orthogonal Metal-Carbon Bonds.

PubMed

Zhou, Jinfeng; Gai, Lizhi; Zhou, Zhikuan; Yang, Wu; Mack, John; Xu, Kejing; Zhao, Jianzhang; Zhao, Yue; Qiu, Hailin; Chan, Kin Shing; Shen, Zhen

2016-09-05

The facile synthesis of Group 9 Rh(III) porphyrin-aza-BODIPY conjugates that are linked through an orthogonal Rh-C(aryl) bond is reported. The conjugates combine the advantages of the near-IR (NIR) absorption and intense fluorescence of aza-BODIPY dyes with the long-lived triplet states of transition metal rhodium porphyrins. Only one emission peak centered at about 720 nm is observed, irrespective of the excitation wavelength, demonstrating that the conjugates act as unique molecules rather than as dyads. The generation of a locally excited (LE) state with intramolecular charge-transfer (ICT) character has been demonstrated by solvatochromic effects in the photophysical properties, singlet oxygen quantum yields in polar solvents, and by the results of density functional theory (DFT) calculations. In nonpolar solvents, the Rh(III) conjugates exhibit strong aza-BODIPY-centered fluorescence at around 720 nm (ΦF =17-34 %), and negligible singlet oxygen generation. In polar solvents, enhancements of the singlet-oxygen quantum yield (ΦΔ =19-27 %, λex =690 nm) have been observed. Nanosecond pulsed time-resolved absorption spectroscopy confirms that relatively long-lived triplet excited states are formed. The synthetic methodology outlined herein provides a useful strategy for the assembly of functional materials that are highly desirable for a wide range of applications in material science and biomedical fields. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Gonadotropin-releasing hormone (Gn-RH) in striped mullet (Mugil cephalus), milkfish (Chanos chanos), and rainbow trout (Salmo gairdneri): comparison with salmon Gn-RH

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

Sherwood, N.M.; Harvey, B.; Brownstein, M.J.

Immunoreactive gonadotropin-releasing hormone (Gn-RH) was extracted from brains of striped mullet, milkfish, rainbow trout, and chum salmon with acetone/HCl and petroleum ether. High pressure liquid chromatography and cross-reactivity studies show mullet, milkfish, and trout brains to contain a peptide chromatographically and immunologically identical to synthetic salmon Gn-RH, while the mammalian form of Gn-RH is detectable in none of these fishes. Gn-RH is present in immature 7-month-old and 4-year-old milkfish. A second immunoreactive peptide is separable by HPLC in all the fish studied. This early-eluting form of Gn-RH is unlikely to be a precursor; its cross-reactivity with antisera R-42 and number185more » suggests that any modification is in the C-terminal region. Several possible roles for this peptide are advanced.« less

Molecular definition of red cell Rh haplotypes by tightly linked SphI RFLPs.

PubMed

Huang, C H; Reid, M E; Chen, Y; Coghlan, G; Okubo, Y

1996-01-01

The Rh blood group system of human red cells contains five major antigens D, C/c, and E/e (the latter four designated "non-D") that are specified by eight gene complexes known as Rh haplotypes. In this paper, we report on the mapping of RH locus and identification of a set of SphI RFLPs that are tightly linked with the Rh structural genes. Using exon-specific probes, we have localized the SphI cleavage sites resulting in these DNA markers and derived a comprehensive map for the RH locus. It was found that the SphI fragments encompassing exons 4-7 of the Rh genes occur in four banding patterns or frameworks that correspond to the distribution and segregation of the common Rh haplotypes. This linkage disequilibrium allowed a genotype-phenotype correlation and direct determination of Rh zygosity related to the Rh-positive or Rh-negative status (D/D, D/d, and d/d). Studies on the occurrence of SphI RFLPs in a number of rare Rh variants indicated that Rh phenotypic diversity has taken place on different haplotype backgrounds and has arisen by diverse genetic mechanisms. The molecular definition of Rh haplotypes by SphI RFLP frameworks should provide a useful procedure for genetic counseling and prenatal assessment of Rh alloimmunization.

Origin of primary PGM assemblage in сhromitite from a mantle tectonite at Harold's Grave (Shetland Ophiolite Complex, Scotland)

NASA Astrophysics Data System (ADS)

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

2013-12-01

In this paper we present textural and mineral chemistry data for a PGM inclusion assemblage and whole-rock platinum-group element (PGE) concentrations of chromitite from Harold's Grave, which occurrs in a dunite pod in a mantle tectonite at Unst in the Shetland Ophiolite Complex (SOC), Scotland. The study utilized a number of analytical techniques, including acid digestion and isotope dilution (ID) ICP-MS, hydroseparation and electron microprobe analysis. The chromitite contains a pronounced enrichment of refractory PGE (IPGE: Os, Ir and Ru) over less refractory PGE (PPGE: Rh, Pt and Pd), typical of mantle hosted `ophiolitic' chromitites. A `primary' magmatic PGM assemblage is represented by euhedrally shaped (up to 60 μm in size) single and composite inclusions in chromite. Polyphase PGM grains are dominated by laurite and osmian iridium, with subordinate laurite + osmian iridium + iridian osmium and rare laurite + Ir-Rh alloy + Rh-rich sulphide (possibly prassoite). The compositional variability of associated laurite and Os-rich alloys at Harold's Grave fit the predicted compositions of experiment W-1200-0.37 of Andrews and Brenan (Can Mineral 40: 1705-1716, 2002) providing unequivocal information on conditions of their genesis, with the upper thermal stability of laurite in equilibrium with Os-rich alloys estimated at 1200-1250 °C and f(S2) of 10-0.39-10-0.07.

Structure sensitivity in the kinetics and the dynamics of CO oxidation over stepped Pd(335) studied by the molecular beam infrared chemiluminescence technique: Determination of working sites during the steady-state reaction

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

Uetsuka, H.; Watanabe, K.; Kimpara, H.

Kinetics and dynamics of CO oxidation have been studied on a stepped Pd(335) surface at a steady-state condition and compared with those on flat Pd(111). The infrared (IR) chemiluminescence technique was applied to determine where the active catalytic sites are on the Pd(335) surface. Since the vibrational energy state of the product CO{sub 2} is sensitive to the structures of the reaction sites on Pd surfaces, information about the working reaction sites during the steady-state CO oxidation can be obtained from the IR emission spectra of the product CO{sub 2}. The production rate of CO{sub 2} was higher on Pd(335)more » than on Pd(111), indicating that the steps on the surface enhance the catalytic activity for Co oxidation under the steady-state condition. However, the rate data do not necessarily show the real active sites for the CO + O recombination reaction. At a surface temperature of 850 K, the vibrational Boltzmann temperature (T{sub v}) of the product CO{sub 2} on Pd(335) was quite different from (much lower than) that on Pd(111), although the Pd(335) surface has four-atom wide (111) terraces. The lower T{sub v} value on Pd(335) was similar to that on Pd(110)(1 x 1), indicating that a relatively linear activated CO{sub 2} complex was formed. Therefore, during the steady-state CO oxidation on Pd(335), the reaction does not take place on the (111) terrace sites, but mostly on the step sites at 850 K. On the contrary, as the CO coverage increased at a lower surface temperature and at a high CO/O{sub 2} ratio, the T{sub v} values on Pd(335) tend to approach those on Pd(111), indicating that the contribution of the active sites on the steps is decreased and the working reaction sites shift to the (111) terrace sites.« less

Toxicity of platinum, palladium and rhodium to Daphnia magna in single and binary metal exposure experiments.

PubMed

Zimmermann, Sonja; Wolff, Carolina; Sures, Bernd

2017-05-01

Mainly due to automobile traffic, but also due to other sources, the platinum group elements (PGE) platinum (Pt), palladium (Pd) and rhodium (Rh) are introduced into aquatic biotopes where they accumulate in sediments of lakes and rivers. However, the toxicity of these noble metals to aquatic organisms is not well understood and especially toxicity studies under standardized condition are lacking. Thus, the toxicity of Pt, Pd and Rh to Daphnia magna was tested in single metal exposure experiments according to OECD guideline 202. Immobility and lethality was recorded after 24 h and 48 h of exposure and EC 50 and LC 50 , respectively, were determined. As the nominal exposure concentration of Pd differed significantly from the quantified concentration, the control of the real exposure concentration by chemical analysis is mandatory, especially for Pd. The toxicity decreased in the order Pd > Pt ≫ Rh with e.g. LC 50 (48 h) values of 14 μg/L for Pd, 157 μg/L for Pt and 56,800 μg/L for Rh. The exposure period had a clear effect on the toxicity of Pt, Pd and Rh. For Pt and Rh the endpoint immobility was more sensitive than the endpoint lethality whereas Pd toxicity was similar for both endpoints. The Hill slopes, which are a measure for the steepness of the concentration-response curves, showed no significant discrepancies between the different metals. The binary metal exposure to Pt and Pd revealed a more-than-additive, i.e. a synergistic toxicity using the toxic unit approach. The present study is a start to understand the toxicity of interacting PGE. The modes of action behind the synergistic effect are unclear. Copyright © 2017 Elsevier Ltd. All rights reserved.

Immunohistochemical evidence for the involvement of gonadotropin releasing hormone in neuroleptic and cataleptic effects of haloperidol in mice.

PubMed

Fegade, Harshal A; Umathe, Sudhir N

2016-04-01

Blockade of dopamine D2 receptor by haloperidol is attributed for neuroleptic and cataleptic effects; and also for the release of gonadotropin releasing hormone (GnRH) from the hypothalamus. GnRH agonist is reported to exhibit similar behavioural effects as that of haloperidol, and pre-treatment with GnRH antagonist is shown to attenuate the effects of haloperidol, suggesting a possibility that GnRH might mediate the effects of haloperidol. To substantiate such possibility, the influence of haloperidol on GnRH immunoreactivity (GnRH-ir) in the brain was studied in vehicle/antide pre-treated mice by peroxidase-antiperoxidase method. Initially, an earlier reported antide-haloperidol interaction in rat was confirmed in mice, wherein haloperidol (250μg/kg, i.p.) exhibited suppression of conditioned avoidance response (CAR) on two-way shuttle box, and induced catalepsy in bar test; and pre-treatment with antide (50μg/kg, s.c., GnRH antagonist) attenuated both effects of haloperidol. Immunohistochemical study was carried out to identify GnRH-ir in the brain, isolated 1h after haloperidol treatment to mice pre-treated with vehicle/antide. The morphometric analysis of microphotographs of brain sections revealed that haloperidol treatment increased integrated density units of GnRH-ir in various regions of the limbic system. Considering basal GnRH-ir in vehicle treated group as 100%, the increase in GnRH-ir after haloperidol treatment was by 100.98% in the medial septum; 54.26% in the bed nucleus of the stria terminalis; 1152.85% in the anteroventral periventricular nucleus; 120.79% in the preoptic area-organum vasculosum of the lamina terminalis and 138.82% in the arcuate nucleus. Antide did not influence basal and haloperidol induced increase in GnRH-ir in any of the regions. As significant increase in GnRH-ir after haloperidol treatment was observed in such regions of the brain which are reported to directly or indirectly communicate with the hippocampus and basal

Molecular definition of red cell Rh haplotypes by tightly linked SphI RFLPs

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

Huang, C.H.; Reid, M.E.; Chen, Y.

The Rh blood group system of human red cells contains five major antigens D, C/c, and E/e (the latter four designated {open_quotes}non-D{close_quotes}) that are specified by eight gene complexes known as Rh haplotypes. In this paper, we report on the mapping of the RH locus and identification of a set of SphI RFLPs that are tightly linked with the Rh structural genes. Using exon-specific probes, we have localized the SphI cleavage sites resulting in these DNA markers and derived a comprehensive map for the RH locus. It was found that the SphI fragments encompassing exons 4-7 of the Rh genesmore » occur in four banding patterns or frameworks that correspond to the distribution and segregation of the common Rh haplotypes. This linkage disequilibrium allowed a genotype-phenotype correlation and direct determination of Rh zygosity related to the Rh-positive or Rh-negative status (D/D, D/d, and d/d). Studies on the occurrence of SphI RFLPs in a number of rare Rh variants indicated that Rh phenotypic diversity has taken place on different haplotype backgrounds and has arisen by diverse genetic mechanisms. The molecular definition of Rh haplotypes by SphI RFLP frameworks should provide a useful procedure for genetic counseling and prenatal assessment of Rh alloimmunization. 32 refs., 7 figs., 3 tabs.« less

ABO-Rh blood groups distribution in cardiac syndrome X patients.

PubMed

Kheradmand, Fatemeh; Rasmi, Yousef; Nemati, Mohaddeseh; Mohammadzad, Mir Hossein Seyed

2012-07-01

Data on frequency distribution of ABO-Rh blood groups in cardiac syndrome X (CSX) patients are not available. We aimed to investigate the distribution of ABO-Rh blood groups in these patients. A total of 247 CSX patients' records were reviewed in a cross-sectional study from 2006 to 2010. One hundred forty six patients (59.1%) were female, and the mean patient age was 52 ± 11 years. The frequency of ABO-Rh blood groups was compared to the frequency of these blood groups in the West-Azerbaijan province, Iran; general population. Blood groups distribution among CSX patients showed phenotypes A, B, AB, O and Rh negative as 33.1%, 21.9%, 9.3%, 35.8%, and 7.9%, respectively. According to our results, there were no differences in ABO-Rh blood groups distribution between CSX patients and normal population. These data suggest that ABO-Rh blood groups might be unassociated with CSX.

Effectiveness of anti-PD-1/PD-L1 antibodies in urothelial carcinoma patients with different PD-L1 expression levels: a meta-analysis.

PubMed

Liu, Junqi; Zhang, Chuanfeng; Hu, Jiegang; Tian, Qing; Wang, Xin; Gu, Hao; Zhang, Song; Zhao, Di; Fan, Ruitai

2018-02-23

Urothelial carcinoma ranks the ninth among malignant cancers. We conducted this study to identify which patients could benefit more from the treatment of programmed death-1 (PD-1)/programmed death-ligand1 (PD-L1) inhibitors. We performed literature searches, combined data from qualified literature and performed comparative analyses on the effectiveness of anti-PD-1/PD-L1 antibodies in patients with different PD-L1 expression levels. We divided patients into three groups according to the percentages of PD-L1-positive cells, namely the low- PD-L1 (PD-L1 < 1%), the medium-PD-L1 (PD-L1 ≥ 1 and < 5%) and the high-PD-L1 (PD-L1 ≥ 5%) groups. We found that the high-PD-L1 group responded significantly better than other groups (P = 0.0003, ORs = 0.45, 95%CI: 0.29-071; P = 0.0009, ORs = 0.43, 95%CI: 0.25-0.73, for low-PD-L1 and medium-PD-L1 groups, respectively), while the latter two groups responded similarly (P = 0.90, ORs = 1.06, 95%CI: 0.62-1.83) to both PD-1 and PD-L1 inhibitors. Furthermore, we found that the medium-PD-L1 and high-PD-L1 groups responded similarly to PD-1/ PD-L1 inhibitors (P = 0.65, ORs = 1.11, 95%CI: 0.69-1.77), while the low-PD-L1 group responded better to PD-1 inhibitors than PD-L1 inhibitors (P = 0.046, ORs = 1.92, 95%CI: 0.98-3.89). Our results suggest that PD-L1 positive patients should be defined as those with ≥ 5% or greaterPD-L1-positive cells. PD-1 antibodies performed better only in the low-group patients, likely because they could block the interactions of PD-1 with both PD-L1 and PD-L2.

Recombinant human interleukin-3 (rhIL-3) enhances the mobilization of peripheral blood progenitor cells by recombinant human granulocyte colony-stimulating factor (rhG-CSF) in normal volunteers.

PubMed

Huhn, R D; Yurkow, E J; Tushinski, R; Clarke, L; Sturgill, M G; Hoffman, R; Sheay, W; Cody, R; Philipp, C; Resta, D; George, M

1996-06-01

To identify a precisely timed and safe protocol for progenitor cell mobilization, we studied the effects of rhIL-3 and rhG-CSF administration to normal volunteers. rhG-CSF 5 micrograms/kg/d was administered subcutaneously (s.c.) for 7 consecutive days either alone or preceded by rhIL-3 5 micrograms/kg/d s.c. for 4 consecutive days in sequential or partially overlapping schedules. The combined cytokines were well-tolerated--adverse effects were similar to those of the individual agents. Total white blood cell (WBC) and neutrophil counts rose briskly in response to rhG-CSF, and peak mean values were similar between treatment cohorts. Mean platelet counts were modestly elevated during rhG-CSF treatment only in the cohorts receiving rhIL-3 and rhG-CSF. Mean circulating CD34+ cells peaked on day 5 in the rhG-CSF group (38.9+/-14.3/microliter), day 6 in the sequential rhIL-3/rhG-CSF group (56.4+/-12.4/microliter), and day 6 in the partial overlap group (46.1+/-10.9/microliter). On day 3, mean CD34+ cell counts of the subjects who received sequential treatment were markedly higher than observed in the other groups (p<0.05) and were estimated to have been sufficient for collection of adequate grafts by single 10-L leukapheresis procedures in 60% of subjects. Circulating clonogenic cells (CFU-GM and/or BFU-E) were substantially higher in the sequential group than the rhG-CSF group on days 3-6 but were only minimally elevated above baseline in the partial overlap group. The numbers of circulating CD34+/Lin-/Thy-1+ cells (putative stem cells) were increased substantially, especially in the sequential group. On the basis of this pilot trial, we conclude that priming with rhIL-3 is a safe and well-tolerated method for enhancing the mobilization of human blood progenitors and stem cells by rhG-CSF.

The anticancer immune response of anti-PD-1/PD-L1 and the genetic determinants of response to anti-PD-1/PD-L1 antibodies in cancer patients

PubMed Central

Han, Weidong; Wang, Xian; Fang, Yong; Li, Da; Pan, Hongming; Zhang, Li

2015-01-01

The programmed death-1 (PD-1), a coinhibitory receptor expressed on activated T cells and B cells, is demonstrated to induce an immune-mediated response and play a critical role in tumor initiation and development. The cancer patients harboring PD-1 or PD ligand 1 (PD-L1) protein expression have often a poor prognosis and clinical outcome. Currently, targeting PD-1 pathway as a potential new anticancer strategy is attracting more and more attention in cancer treatment. Several monoclonal antibodies against PD-1 or PD-L1 have been reported to enhance anticancer immune responses and induce tumor cell death. Nonetheless, the precise molecular mechanisms by which PD-1 affects various cancers remain elusive. Moreover, this therapy is not effective for all the cancer patients and only a fraction of patients respond to the antibodies targeting PD-1 or PD-L1, indicating these antibodies may only works in a subset of certain cancers. Thus, understanding the novel function of PD-1 and genetic determinants of response to anti-PD-1 therapy will allow us to develop a more effective and individualized immunotherapeutic strategy for cancer. PMID:26305724

7 CFR 1980.309 - Lender participation in guaranteed RH loans.

Code of Federal Regulations, 2010 CFR

2010-01-01

... 7 Agriculture 14 2010-01-01 2009-01-01 true Lender participation in guaranteed RH loans. 1980.309... Lender participation in guaranteed RH loans. (a) Qualification. The following Lenders are eligible to participate in the RHS guaranteed RH loan program upon presentation of evidence of said approval and execution...

Hg(ii) and Pd(ii) complexes with a new selenoether bridged biscarbene ligand: efficient mono- and bis-arylation of methyl acrylate with a pincer biscarbene Pd(ii) precatalyst.

PubMed

Rishu; Prashanth, Billa; Bawari, Deependra; Mandal, Ushnish; Verma, Aditya; Choudhury, Angshuman Roy; Singh, Sanjay

2017-05-16

Two equivalents of 1-benzyl-3-bromoethylbenzimidazolium bromide couple with Na 2 Se to produce the first selenoether bridged bis-benzimidazolium salt (LH 2 )Br 2 . The nitrate (LH 2 )(NO 3 ) 2 and tetrafluoroborate (LH 2 )(BF 4 ) 2 salts were also synthesized from (LH 2 )Br 2 . The reaction of Hg(OAc) 2 with (LH 2 )Br 2 gave the first pseudo pincer carbene mercury complex, [Hg(L-κ 2 C)][HgBr 4 ] (C1). Different complexes of Pd(ii) with selenoether bridged carbene were obtained using (LH 2 )Br 2 and (LH 2 )(NO 3 ) 2 . Syntheses of these complexes were dependent on the counter anion and the temperature. Thus, the pincer type ionic complex [PdBr(L-κ 3 CSeC)]Br (C2) was isolated at 80 °C and the pseudo pincer type neutral complex cis-[PdBr 2 (L-κ 2 C)] (C3) was isolated at room temperature from (LH 2 )Br 2 and Pd(OAc) 2 in DMSO. The nitrate precursor (LH 2 )(NO 3 ) 2 on palladation with Pd(OAc) 2 afforded [Pd(L-κ 4 C Bz CSeC)]NO 3 (C4) showing an unprecedented intramolecular metallation at the ortho position of the benzyl wingtip of the benzimidazole moiety. The ligand salts and metal complexes have been characterized using HRMS, heteronuclear NMR and IR spectroscopy. Single crystal X-ray structures of the ligand salts (LH 2 )Br 2 and (LH 2 )(BF 4 ) 2 and complexes C1-C4 have also been elucidated. Complex C2 showed good activity for C-C coupling in the mono-Heck reaction of methyl acrylate and arylbromides. Interestingly, the less common bis-arylation was also observed with deactivated arylbromides as the result of double-Heck coupling.

Mechanism of degradation of LH-RH and neurotensin by synaptosomal peptidases.

PubMed

McDermott, J R; Smith, A I; Dodd, P R; Hardy, J A; Edwardson, J A

1983-01-01

The products of degradation of LH-RH and neurotensin by synaptosomes isolated from rat hypothalamus and cortex have been identified. LH-RH is cleaved at Tyr5-Gly6 and Pro9-Gly10 giving rise to LH-RH (1-5), LH-RH (6-10) and LH-RH (1-9). Neurotensin is cleaved at Arg8-Arg9, Pro10-Tyr11 and Ile12-Leu13, giving neurotensin (1-8), neurotensin (1-10), neurotensin (1-12) and neurotensin (9-13) as major products. While most of the peptidase activity is localized in the cytoplasmic fraction, a small but significant proportion is membrane bound. For LH-RH, the specificity of the membrane-bound activity is similar to that in the cytosol fraction; for neurotensin, the membrane fraction preferentially gives rise to the (1-10) and (1-11) peptides. The most potent inhibitors of the LH-RH and neurotensin degrading enzymes in synaptosomes are heavy metal ions (mercury and copper), p-chloromercuribenzoate and 1,10 phenanthroline.

Evolution of two Rh blood group-related genes of the amphioxus species Branchiostoma floridae.

PubMed

Kitano, Takashi; Satou, Masahiro; Saitou, Naruya

2010-04-01

We determined cDNAs of two genes that belong to the Rhesus (Rh) blood group gene family in an amphioxus species (Branchiostoma floridae) and designated them Rh-related-1 (RhR-1) and Rh-related-2 (RhR-2). RhR-1 and RhR-2 consisted of 10 and 11 exons, respectively. 3' UTR sequences of RhR-1 were shorter (220-272 bp) than those of RhR-2 (1,505-1,650 bp). CDS lengths were 1,344 and 1,476 bp for RhR-1 and RhR-2, respectively, and the average nucleotide difference between their CDS regions was 0.33. The corresponding regions of Rh genes from exons 2 to 7 were relatively conserved among the chordate species examined in this study. Length difference numbers were in multiples of three, which implies that codon frames were conserved among them, and the same exon/intron boundary phases were observed in those regions. This region was used for the phylogenetic analyses. RhR-1 and RhR-2 formed a cluster on the phylogenetic tree of the Rh gene family. Gene duplication time of RhR-1 and RhR-2 was estimated to be ca. 500 million years ago. It is likely that the four Rh family genes in vertebrates emerged by gene duplications in the common ancestor of vertebrates, and functional differentiation has occurred after the first gene duplication.

Rh immunization in Manitoba: progress in prevention and management.

PubMed Central

Bowman, J. M.; Pollock, J.

1983-01-01

For two decades the perinatal mortality caused by erythroblastosis has been decreasing in Manitoba. The improved management of Rh-immunized pregnancies has lowered the death rate among affected infants from 10.8% to 3.4%, while the prevention of Rh immunization has reduced its incidence from 9.1 to 2.2 per 1000 total births. In its first 6 years and 8 months Manitoba's antenatal prophylaxis program, in which immunoglobulin is administered to Rh-negative women at 28 weeks' gestation, reduced the incidence of Rh immunization during pregnancy by 93%. In combination with post-abortion and postpartum prophylaxis the antenatal treatment has provided a protection rate of 98.6% among primigravidas at risk. Further improvements are expected. PMID:6409390

PdBI cold dust imaging of two extremely red H – [4.5] > 4 galaxies discovered with SEDS and CANDELS

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

Caputi, K. I.; Popping, G.; Spaans, M.

2014-06-20

We report Plateau de Bure Interferometer (PdBI) 1.1 mm continuum imaging toward two extremely red H – [4.5] > 4 (AB) galaxies at z > 3, which we have previously discovered making use of Spitzer SEDS and Hubble Space Telescope CANDELS ultra-deep images of the Ultra Deep Survey field. One of our objects is detected on the PdBI map with a 4.3σ significance, corresponding to S{sub ν}(1.1 mm)=0.78±0.18 mJy. By combining this detection with the Spitzer 8 and 24 μm photometry for this source, and SCUBA2 flux density upper limits, we infer that this galaxy is a composite active galacticmore » nucleus/star-forming system. The infrared (IR)-derived star formation rate is SFR ≈ 200 ± 100 M {sub ☉} yr{sup –1}, which implies that this galaxy is a higher-redshift analogue of the ordinary ultra-luminous infrared galaxies more commonly found at z ∼ 2-3. In the field of the other target, we find a tentative 3.1σ detection on the PdBI 1.1 mm map, but 3.7 arcsec away of our target position, so it likely corresponds to a different object. In spite of the lower significance, the PdBI detection is supported by a close SCUBA2 3.3σ detection. No counterpart is found on either the deep SEDS or CANDELS maps, so, if real, the PdBI source could be similar in nature to the submillimeter source GN10. We conclude that the analysis of ultra-deep near- and mid-IR images offers an efficient, alternative route to discover new sites of powerful star formation activity at high redshifts.« less

Tumor cells versus host immune cells: whose PD-L1 contributes to PD-1/PD-L1 blockade mediated cancer immunotherapy?

PubMed

Tang, Fei; Zheng, Pan

2018-01-01

Antibody blockade of the PD-1/PD-L1 pathway has elicited durable antitumor responses in the therapy of a broad spectrum of cancers. PD-L1 is constitutively expressed in certain tumors and host immune cells, and its expression can be induced or maintained by many factors. The expression of PD-L1 on tumor tissues has been reported to be positively correlated with the efficacy of anti-PD-1/PD-L1 therapy in patients. However, multiple clinical trials indicate that patients with PD-L1-negative tumors also respond to this blockade therapy, which suggests the potential contribution of PD-L1 from host immune cells. Recently, six articles independently evaluated and verified the contributions of PD-L1 from tumor versus non-tumor cells in various mouse tumor models. These studies confirmed that PD-L1 on either tumor cells or host immune cells contributes to tumor escape, and the relative contributions of PD-L1 on these cells seem to be context-dependent. While both tumor- and host-derived PD-L1 can play critical roles in immune suppression, differences in tumor immunogenicity appear to underlie their relative importance. Notably, these reports highlight the essential roles of PD-L1 from host myeloid cells in negatively regulating T cell activation and limiting T cell trafficking. Therefore, comprehensive evaluating the global PD-L1 expression, rather than monitoring PD-L1 expression on tumor cells alone, should be a more accurate way for predicting responses in PD-1/PD-L1 blockade therapy in cancer patients.

Dynamic evolution of the GnRH receptor gene family in vertebrates.

PubMed

Williams, Barry L; Akazome, Yasuhisa; Oka, Yoshitaka; Eisthen, Heather L

2014-10-25

Elucidating the mechanisms underlying coevolution of ligands and receptors is an important challenge in molecular evolutionary biology. Peptide hormones and their receptors are excellent models for such efforts, given the relative ease of examining evolutionary changes in genes encoding for both molecules. Most vertebrates possess multiple genes for both the decapeptide gonadotropin releasing hormone (GnRH) and for the GnRH receptor. The evolutionary history of the receptor family, including ancestral copy number and timing of duplications and deletions, has been the subject of controversy. We report here for the first time sequences of three distinct GnRH receptor genes in salamanders (axolotls, Ambystoma mexicanum), which are orthologous to three GnRH receptors from ranid frogs. To understand the origin of these genes within the larger evolutionary context of the gene family, we performed phylogenetic analyses and probabilistic protein homology searches of GnRH receptor genes in vertebrates and their near relatives. Our analyses revealed four points that alter previous views about the evolution of the GnRH receptor gene family. First, the "mammalian" pituitary type GnRH receptor, which is the sole GnRH receptor in humans and previously presumed to be highly derived because it lacks the cytoplasmic C-terminal domain typical of most G-protein coupled receptors, is actually an ancient gene that originated in the common ancestor of jawed vertebrates (Gnathostomata). Second, unlike previous studies, we classify vertebrate GnRH receptors into five subfamilies. Third, the order of subfamily origins is the inverse of previous proposed models. Fourth, the number of GnRH receptor genes has been dynamic in vertebrates and their ancestors, with multiple duplications and losses. Our results provide a novel evolutionary framework for generating hypotheses concerning the functional importance of structural characteristics of vertebrate GnRH receptors. We show that five

Expression of PD-1 and PD-L1 in poorly differentiated neuroendocrine carcinomas of the digestive system: a potential target for anti-PD-1/PD-L1 therapy.

PubMed

Roberts, Jordan A; Gonzalez, Raul S; Das, Satya; Berlin, Jordan; Shi, Chanjuan

2017-12-01

Poorly differentiated neuroendocrine carcinoma of the digestive system has a dismal prognosis with limited treatment options. This study aimed to investigate expression of the PD-1/PD-L1 pathway in these tumors. Thirty-seven patients with a poorly differentiated neuroendocrine carcinoma of the digestive system were identified. Their electronic medical records, pathology reports, and pathology slides were reviewed for demographics, clinical history, and pathologic features. Tumor sections were immunohistochemically labeled for PD-1 and PD-L1, and expression of PD-1 and PD-L1 on tumor and tumor-associated immune cells was analyzed and compared between small cell and large cell neuroendocrine carcinomas. The mean age of patients was 61 years old with 18 men and 19 women. The colorectum (n=20) was the most common primary site; other primary sites included the pancreaticobiliary system, esophagus, stomach, duodenum, and ampulla. Expression of PD-1 was detected on tumor cells (n=6, 16%) as well as on tumor-associated immune cells (n=23, 63%). The 6 cases with PD-1 expression on tumor cells also had the expression on immune cells. Expression of PD-L1 was visualized on tumor cells in 5 cases (14%) and on tumor-associated immune cells in 10 cases (27%). There was no difference in PD-1 and PD-L1 expression between small cell and large cell neuroendocrine carcinomas. In conclusion, PD-1/PD-L1 expression is a frequent occurrence in poorly differentiated neuroendocrine carcinomas of the digestive system. Checkpoint blockade targeting the PD-1/PD-L1 pathway may have a potential role in treating patients with this disease. Copyright © 2017 Elsevier Inc. All rights reserved.

Varied distribution of RhD epitopes in the Indian population.

PubMed

Kulkarni, S S; Gupte, S C; Vasantha, K; Mohanty, D; Ghosh, K

2007-01-01

Inhabited by more than 4000 caste and tribal groups, India has an extremely heterogenous population. For thousands of years many tribal groups have practised endogamy and are practically genetically isolated. Traditionally, polyclonal anti-D reagent has been used for RhD typing; though monoclonal antibodies are increasingly being used. As a result, blood banks find it difficult to assign the RhD status to an increasing number of people. As monoclonal anti-D typing reagents may not detect all RhD antigen epitopes, we studied the RhD antigen epitope heterogeneity in different population groups in India. Red cells of 5315 RhD-positive individuals belonging to different castes and tribes of India were tested with 30 different epitope-specific monoclonal anti-D antibodies. No single monoclonal antibody could detect all RhD-positive red cells detected by polyclonal antisera. The highest proportion of D antigen was detected by LHM 76/55 and BRAD-8 (98%) monoclonal antibodies. We need to determine the correct mix of monoclonal antibodies that will detect nearly all RhD antigens detected by polyclonal anti-D sera. Similarly, before accepting monoclonal anti-D for therapeutic use, it would be necessary to determine the appropriate ones for use in the Indian population.

Selective interactions among Rh, ABO, and sex ratio of newborns.

PubMed

Valenzuela, C Y; Walton, R

1985-01-01

The hypothesis that the Rh and ABO blood systems behave like the HLA system in relation to mother-conception tolerance-rejection mechanisms was tested in 25,501 mother-infant pairs. According to this hypothesis, heterozygotes carrying a paternal gene that is not present in their mothers should be better tolerated than homozygotes. Significantly more BO infants born to AO mothers. AO infants born to BO mothers, Rh(+) heterozygotes born to Rh(-) mothers, and less significantly AO infants born to OO mothers confirm the hypothesis. Fewer homozygotes occurred in Rh(-) infants born to Rh(+) mothers and in O infants born to non-O mothers. Deviations from the Hardy-Weinberg equilibrium found in the ABO system were modified by the Rh and sex of the infant. These data strongly support the hypothesis that at least two feto-maternal systems influence the destiny of pregnancies: the classical known incompatibility system which operates late in pregnancy and a new one which is based on the induction of maternal tolerance early in pregnancy: maternal tolerance seems to be better elicited by heterozygous eggs or embryos carrying a gene not present in the mother. The data also support the hypothesis that the sex ratio is influenced by feto-maternal tolerance-rejection mechanisms associated with the ABO and Rh systems.

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

NASA Astrophysics Data System (ADS)

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

2017-05-01

Assessment of the environmental impact of platinum group elements (PGE) and other trace elements from mining activities is essential to prevent potential environmental risks. This study evaluates the concentrations of PGE in stream sediments of the Hex River, which drains the mining area of the Bushveld Igneous Complex (South Africa), at four sampling points. Major, minor and trace elements (Fe, Ca, Al, Mg, Mn, V, Cr, Zn, Cu, As, Co, Ni, Cd, and Pb) were analyzed by FAAS and ETAAS in suspended particulate matter and different sediment fractions (<63, 63-500 and 500-2000 μm), and Pt, Pd, Rh, and Ir were measured by ICP-MS after removal of interfering elements (cation exchange resin 50W-DOWEX-X8). Procedures were blank-corrected and accuracy checked using reference materials. Nickel, Cr, Pt, Pd, Rh and Ir show concentrations 3-, 13- 18-, 28-, 48- and 44- fold the typical upper continental crust levels, respectively, although lower than concentrations reported for the parent rocks. The highest concentrations were observed closer to the mining area, decreasing with distance and in the <63 μm fraction, probably derived from atmospheric deposition and surface runoff of PGE-rich particles released from mining activities. Thus, mining activities are causing some disturbance of the surface PGE geochemical cycle, increasing the presence of PGE in the fine fraction of river sediments. We propose that indicators such as airborne particulate matter, and soil and river sediment quality, should be added to the protocols for evaluating the sustainability of mining activities.

Mental distress and personality in women undergoing GnRH agonist versus GnRH antagonist protocols for assisted reproductive technology.

PubMed

Stenbæk, D S; Toftager, M; Hjordt, L V; Jensen, P S; Holst, K K; Bryndorf, T; Holland, T; Bogstad, J; Pinborg, A; Hornnes, P; Frokjaer, V G

2015-01-01

Do mental distress and mood fluctuations in women undergoing GnRH agonist and GnRH antagonist protocols for assisted reproductive technology (ART) differ depending on protocol and the personality trait, neuroticism? ART treatment did not induce elevated levels of mental distress in either GnRH antagonist or agonist protocols but neuroticism was positively associated with increased mental distress, independent of protocols. ART treatment may increase mental distress by mechanisms linked to sex hormone fluctuations. General psychological characteristics, such as personality traits indexing negative emotionality, e.g. neuroticism, are likely to affect mental distress during ART treatment. A total of 83 women undergoing their first ART cycle were consecutively randomized 1:1 to GnRH antagonist (n = 42) or GnRH agonist (n = 41) protocol. The study population was a subgroup of a larger ongoing Danish clinical randomized trial and was established as an add-on in the period 2010-2012. Women in the GnRH antagonist protocol received daily injections with recombinant follicle-stimulating hormone, Puregon(®) and subcutaneous injections with GnRH antagonist, Orgalutran(®). Women in the GnRH agonist protocol received nasal administration of the GnRH agonist, Synarela(®) and subcutaneous injections with FSH, Puregon(®). The study design did not allow for a blinding procedure. All women self-reported the Profile of Mood States, the Perceived Stress Scale, the Symptom Checklist-92-Revised, and the Major Depression Inventory questionnaires, at baseline, at ART cycle day 35, on the day of oocyte pick-up, and on the day of hCG testing. Also, a series of Profile of Mood States were reported daily during pharmacological treatment to monitor mood fluctuations. The personality trait Neuroticism was assessed at baseline by the self-reported NEO-PI-R questionnaire. ART did not induce within- or between-protocol changes in any of the applied measures of mental distress. However, the GnRH

Structural evidence of [Rh(Thio) 6] 3+ and [Rh(Thio) 5Cl] 2+ cations in three novel ionic systems based on Co(III) dioximates

NASA Astrophysics Data System (ADS)

Bourosh, Paulina N.; Coropceanu, Eduard B.; Rija, Andrei P.; Bologa, Olga A.; Gdaniec, Maria; Bulhac, Ion I.

2011-07-01

Multicomponent mixed metal ionic-type dioximates, [Со(DH) 2(Thio) 2][Rh(Thio) 6][BF 4] 4 ( 1), [Со(DH) 2(Thio) 2][Rh(Thio) 6][TiF 6] 2·H 2O ( 2) and [Со(NioxH) 2(Thio) 2] 2[Rh(Thio) 5Cl][TiF 6] 2·CH 3OH·3H 2O ( 3), where DH 2 is dimethylglyoxime, NioxH 2 is 1.2-cyclohexanedionedioxime, and Thio is thiourea, were synthesized and their structures were determined by an X-ray method. Compounds 1-3 consist of two different mononuclear coordination cations with cobalt(III) and rhodium(III) as octahedrally coordinated metal centers and fluorine-containing anions as counterions. In the studied systems, Rh(III) mostly binds Thio ligands instead of dioximes, while a typical bis-dioximate in trans geometry is formed by Co(III) with two Thio ligands placed in axial positions. A structural characterization of coordination cations [Rh(Thio) 6] 3+ and [Rh(Thio) 5Cl] 2+ is given for the first time. The interactions and arrangement of the components in crystals 1-3 are discussed.

PD-1 expression and clinical PD-1 blockade in B-cell lymphomas.

PubMed

Xu-Monette, Zijun Y; Zhou, Jianfeng; Young, Ken H

2018-01-04

Programmed cell death protein 1 (PD-1) blockade targeting the PD-1 immune checkpoint has demonstrated unprecedented clinical efficacy in the treatment of advanced cancers including hematologic malignancies. This article reviews the landscape of PD-1/programmed death-ligand 1 (PD-L1) expression and current PD-1 blockade immunotherapy trials in B-cell lymphomas. Most notably, in relapsed/refractory classical Hodgkin lymphoma, which frequently has increased PD-1 + tumor-infiltrating T cells, 9p24.1 genetic alteration, and high PD-L1 expression, anti-PD-1 monotherapy has demonstrated remarkable objective response rates (ORRs) of 65% to 87% and durable disease control in phase 1/2 clinical trials. The median duration of response was 16 months in a phase 2 trial. PD-1 blockade has also shown promise in a phase 1 trial of nivolumab in relapsed/refractory B-cell non-Hodgkin lymphomas, including follicular lymphoma, which often displays abundant PD-1 expression on intratumoral T cells, and diffuse large B-cell lymphoma, which variably expresses PD-1 and PD-L1. In primary mediastinal large B-cell lymphoma, which frequently has 9p24.1 alterations, the ORR was 35% in a phase 2 trial of pembrolizumab. In contrast, the ORR with pembrolizumab was 0% in relapsed chronic lymphocytic leukemia (CLL) and 44% in CLL with Richter transformation in a phase 2 trial. T cells from CLL patients have elevated PD-1 expression; CLL PD-1 + T cells can exhibit a pseudo-exhaustion or a replicative senescence phenotype. PD-1 expression was also found in marginal zone lymphoma but not in mantle cell lymphoma, although currently anti-PD-1 clinical trial data are not available. Mechanisms and predictive biomarkers for PD-1 blockade immunotherapy, treatment-related adverse events, hyperprogression, and combination therapies are discussed in the context of B-cell lymphomas. © 2018 by The American Society of Hematology.

Strontium attenuates rhBMP-2-induced osteogenic differentiation via formation of Sr-rhBMP-2 complex and suppression of Smad-dependent signaling pathway.

PubMed

Zhang, Wenjing; Tian, Yu; He, Hongyan; Chen, Rui; Ma, Yifan; Guo, Han; Yuan, Yuan; Liu, Changsheng

2016-03-01

Strontium (Sr(2+)) has pronounced effects on stimulating bone formation and inhibiting bone resorption in bone regeneration. In this current study, the effect and the underlying mechanism involved of Sr(2+) on the biological activity of bone morphogenetic protein-2 (BMP-2) were studied in detail with pluripotent skeletal muscle myogenic progenitor C2C12 model cell line. The results indicated that Sr(2+) could bind recombinant human BMP-2 (rhBMP-2) rapidly, even in the presence of Ca(2+) and Mg(2+), and inhibited rhBMP-2-induced osteogenic differentiation in vitro and osteogenetic efficiency in vivo. Further studies demonstrated that Sr(2+) treatment undermined the binding capacity of rhBMP-2 with its receptor BMPRIA and thus attenuated Smad 1/5/8 phosphorylation without affecting their dephosphorylation in C2C12 cells. Furthermore, circular dichroism spectroscopy, fluorescence spectroscopy and X-ray photoelectron spectroscopy all revealed that the inhibitory effect of Sr(2+) on the rhBMP-2 osteogenic activity was associated with the formation of Sr-rhBMP-2 complex and ensuing enhancement of β-sheet structure. Our work suggests the activity of rhBMP-2 to induce osteogenic differentiation was decreased by directly interaction with free Sr ions in solution, which should provide guide and assist for development of BMP-2-based materials for bone regeneration. Due to easy denaturation and ensuing the reduced activity of rhBMP-2, preserving/enhancing the capacity of rhBMP-2 to induce osteogenic differentiation is of critical importance in developing the protein-based therapy. Cations as effective elements influence the conformation and thereby the bioactivity of protein. Strontium (Sr(2+)), stimulating bone formation and inhibiting bone resorption, has been incorporated into biomaterials/scaffold to improve the bioactivity for bone-regeneration applications. However, Sr(2+)-induced changes in the conformation and bioactivity of BMP-2 have never been investigated. In this

Microdose Flare-up Gonadotropin-releasing Hormone (GnRH) Agonist Versus GnRH Antagonist Protocols in Poor Ovarian Responders Undergoing Intracytoplasmic Sperm Injection

PubMed Central

Boza, Aysen; Cakar, Erbil; Boza, Barıs; Api, Murat; Kayatas, Semra; Sofuoglu, Kenan

2016-01-01

Background: Microdose flare-up GnRH agonist and GnRH antagonist have become more popular in the management of poor ovarian responders (POR) in recent years; however, the optimal protocol for POR patients undergoing in vitro fertilization has still been a challenge. Methods: In this observational study design, two hundred forty four poor ovarian responders were retrospectively evaluated for their response to GnRH agonist protocol (group-1, n=135) or GnRH antagonist protocol (group-2, n=109). Clinical pregnancy rate was the primary end point and was compared between the groups. Student t-test, Mann Whitney U test and χ2-test were used to compare the groups. The p<0.05 was considered to show a statistically significant result. Results: The mean total gonadotropin doses were 3814±891 IU in group 1 and 3539±877 IU in group 2 (p=0.02). The number of metaphase-II oocytes (3.6±2.4 vs. 2.8±1.9, p=0.005) and implantation rates (27.8% vs. 18.8%, p=0.04) in group 1 and group 2, respectively were significantly different. The fertilization rate in group 1 and group 2 was 73% vs. 68%, respectively (p=0.5) and clinical pregnancy rate was 19.8% vs. 14.4%, respectively (p=0.13). Conclusion: The GnRH agonist microdose flare-up protocol has favorable outcomes with respect to the number of oocytes retrieved and implantation rate; nevertheless, the clinical pregnancy rate was found to be similar in comparison to GnRH antagonist protocol in poor ovarian responders. GnRH antagonist protocol appears to be promising with significantly lower gonadotropin requirement and lower treatment cost in poor ovarian responders. PMID:27478770

Microdose Flare-up Gonadotropin-releasing Hormone (GnRH) Agonist Versus GnRH Antagonist Protocols in Poor Ovarian Responders Undergoing Intracytoplasmic Sperm Injection.

PubMed

Boza, Aysen; Cakar, Erbil; Boza, Barıs; Api, Murat; Kayatas, Semra; Sofuoglu, Kenan

2016-01-01

Microdose flare-up GnRH agonist and GnRH antagonist have become more popular in the management of poor ovarian responders (POR) in recent years; however, the optimal protocol for POR patients undergoing in vitro fertilization has still been a challenge. In this observational study design, two hundred forty four poor ovarian responders were retrospectively evaluated for their response to GnRH agonist protocol (group-1, n=135) or GnRH antagonist protocol (group-2, n=109). Clinical pregnancy rate was the primary end point and was compared between the groups. Student t-test, Mann Whitney U test and χ (2)-test were used to compare the groups. The p<0.05 was considered to show a statistically significant result. The mean total gonadotropin doses were 3814±891 IU in group 1 and 3539±877 IU in group 2 (p=0.02). The number of metaphase-II oocytes (3.6±2.4 vs. 2.8±1.9, p=0.005) and implantation rates (27.8% vs. 18.8%, p=0.04) in group 1 and group 2, respectively were significantly different. The fertilization rate in group 1 and group 2 was 73% vs. 68%, respectively (p=0.5) and clinical pregnancy rate was 19.8% vs. 14.4%, respectively (p=0.13). The GnRH agonist microdose flare-up protocol has favorable outcomes with respect to the number of oocytes retrieved and implantation rate; nevertheless, the clinical pregnancy rate was found to be similar in comparison to GnRH antagonist protocol in poor ovarian responders. GnRH antagonist protocol appears to be promising with significantly lower gonadotropin requirement and lower treatment cost in poor ovarian responders.

Site Preference of Ternary Alloying Additions to AuTi

NASA Technical Reports Server (NTRS)

Bozzolo, Guillermo; Mosca, Hugo O.; Noebe, Ronald D.

2006-01-01

Atomistic modeling of the site substitution behavior of several alloying additions, namely. Na, Mg, Al, Si. Sc, V, Cr, Mn. Fe, Co, Ni, Cu, Zn, Y, Zr. Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, Hf, Ta, W, Re, Os, Ir, and Pt in B2 TiAu is reported. The 30 elements can be grouped according to their absolute preference for a specific site, regardless of concentration, or preference for available sites in the deficient sublattice. Results of large scale simulations are also presented, distinguishing between additions that remain in solution from those that precipitate a second phase.

Assessment of trends in the electrochemical CO 2 reduction and H 2 evolution reactions on metal nanoparticles

DOE PAGES

Alfonso, Dominic R.; Kauffman, Douglas R.

2017-08-14

Here, we used density functional theory to investigate the electrochemical CO 2 reduction and competing hydrogen evolution reaction on model Au, Ag, Cu, Ir, Ni, Pd, Pt, and Rh nanoparticles. On the coinage metal, the free energy of adsorbed COOH, CO, and H intermediates generally becomes more favorable with decreasing particle size. This pattern was also observed on all transition metals with the binding of the intermediates observed to be stronger on almost all of these metals. Comparative studies of the reaction profile reveal that H 2 evolution is the first reaction to be energetically allowed at zero applied bias

Assessment of trends in the electrochemical CO 2 reduction and H 2 evolution reactions on metal nanoparticles

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

Alfonso, Dominic R.; Kauffman, Douglas R.

Here, we used density functional theory to investigate the electrochemical CO 2 reduction and competing hydrogen evolution reaction on model Au, Ag, Cu, Ir, Ni, Pd, Pt, and Rh nanoparticles. On the coinage metal, the free energy of adsorbed COOH, CO, and H intermediates generally becomes more favorable with decreasing particle size. This pattern was also observed on all transition metals with the binding of the intermediates observed to be stronger on almost all of these metals. Comparative studies of the reaction profile reveal that H 2 evolution is the first reaction to be energetically allowed at zero applied bias

Catalytic combustion of methane over commercial catalysts in presence of ammonia and hydrogen sulphide.

PubMed

Hurtado, Paloma; Ordóñez, Salvador; Vega, Aurelio; Díez, Fernando V

2004-05-01

The performance of different commercially available catalysts (supported Pd, Pt, Rh, bimetallic Pd-Pt, and Cr-Cu-Ti oxide catalyst) for the oxidation of methane, alone and in presence of ammonia and hydrogen sulphide is studied in this work. Catalysts performance was evaluated both in terms of activity and resistance to poisoning. The main conclusions are that supported Pd and Rh, present the highest activities for methane oxidation, both alone and in presence of ammonia, whereas they are severely poisoned in presence of H2S. Pt and Cr-Cu-Ti are less active but more sulphur resistant, but their activity is lower than the residual activity of sulphur-deactivated Pd and Rh catalysts. The Pd-Pt catalyst exhibits low activity and it is quickly deactivated in presence of hydrogen sulphide.

Tailored Rh surface facilitates, enhancement of Raman scattering in trimetallic AuPt core/Rh shell composites: Experimental and theoretical evidences

NASA Astrophysics Data System (ADS)

Loganathan, B.; Chandraboss, V. L.; Senthilvelan, S.; Karthikeyan, B.

2016-01-01

We present a detailed analysis of surface-enhanced Raman scattering of 7-azaindole and L-cysteine adsorbed on a tailored Rh surface by using experimental and density functional theoretical (DFT) calculations. DFT with the B3LYP/Lanl2DZ basis set was used for the optimization of the ground state geometries and simulation of the surface-enhanced Raman spectrum of probe molecules adsorbed on Rh6 cluster. 7-azaindole and L-cysteine adsorption at the shell interface was ascertained from first-principles. In addition, characterization of synthesized trimetallic AuPt core/Rh shell colloidal nanocomposites has been analyzed by UV-visible spectroscopy, high-resolution transmission and scanning electron microscopy, selected area electron diffraction pattern analysis, energy-dispersive X-ray spectroscopy, atomic force, confocal Raman microscopy, FT-Raman and surface-enhanced Raman spectroscopic analysis. This analysis serves as the first step in gaining an accurate understanding of specific interactions at the interface of organic and biomolecules and to gain knowledge on the surface composition of trimetallic Au/Pt/Rh colloidal nanocomposites.

X-ray structural study of intermetallic alloys RT{sub 2}Si and RTSi{sub 2} (R=rare earth, T=noble metal)

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

Gribanov, Alexander, E-mail: avgri@mail.r; Chemistry Department of the Moscow State University, Leninskie Gory, GSP-1, 119991 Moscow; Grytsiv, Andriy

Two series of intermetallic alloys, RT{sub 2}Si and RTSi{sub 2}, have been synthesized from stoichiometric compositions. The crystal structures of EuPt{sub 1+x}Si{sub 2-x} (CeNiSi{sub 2}-type), CeIr{sub 2}Si (new structure type), YbPd{sub 2}Si and YbPt{sub 2}Si (both YPd{sub 2}Si-type) have been elucidated from X-ray single crystal CCD data, which were confirmed by XPD experiments. The crystal structures of LaRh{sub 2}Si and LaIr{sub 2}Si (CeIr{sub 2}Si-type), {l_brace}La,Ce,Pr,Nd{r_brace}AgSi{sub 2} (all TbFeSi{sub 2}-type), and EuPt{sub 2}Si (inverse CeNiSi{sub 2}-type) were characterized by XPD data. RT{sub 2}Si/RTSi{sub 2} compounds were neither detected in as-cast alloys Sc{sub 25}Pt{sub 50}Si{sub 25}, Eu{sub 25}Os{sub 25}Si{sub 50} and Eu{submore » 25}Rh{sub 25}Si{sub 50} nor after annealing at 900 {sup o}C. Instead, X-ray single crystal data prompted Eu{sub 2}Os{sub 3}Si{sub 5} (Sc{sub 2}Fe{sub 3}Si{sub 5}-type) and EuRh{sub 2+x}Si{sub 2-x} (x=0.04, ThCr{sub 2}Si{sub 2}-type) as well as a new structure type for Sc{sub 2}Pt{sub 3}Si{sub 2} (own type). - Graphical abstract: Two series of the intermetallic compounds, RT{sub 2}Si and RTSi{sub 2}, have been investigated by X-ray diffraction methods. The new tetragonal CeIr{sub 2}Si-type of the crystal structure was described and the interrelation between orthorhombic CeNiSi{sub 2} and tetragonal CeIr{sub 2}Si had been discussed as a similar packing of the BaAl{sub 4} and AlB{sub 2} slabs.« less

Magnetic properties of Co/Rh (001) multilayers studied by x-ray magnetic-circular dichroism

NASA Astrophysics Data System (ADS)

Tomaz, M. A.; Mayo, E.; Lederman, D.; Hallin, E.; Sham, T. K.; O'brien, W. L.; Harp, G. R.

1998-11-01

The layer-averaged magnetic moments of Co and Rh have been measured in sputter deposited Co/Rh (001) multilayer thin films using the x-ray magnetic circular dichroism. The Rh moments were measured at both the L and M absorption edges, where we find that the Rh moment decreases as a function of increasing Rh layer thickness (tRh). The decline of the layer-averaged Rh moment is well described in terms of a simple dilution, implying that the Rh moment is confined to the interfacial region. We find that the Co moment remains largely unaffected, maintaining a bulklike value of 1.7μB in the region preceding the first antiferromagnetic coupling peak where tRh ranges from 0 to 4 Å. We also find, via application of the dichroism sum rules, that the ratio / for Co increases ~10% for this same region. Finally, we contrast the magnetic behavior of the Co/Rh (001) and Fe/Rh (001) multilayer systems.

Behaviour of Ni-PGE-Au-Cu in mafic-ultramafic volcanic suites of the 2.7 Ga Kambalda Sequence, Kalgoorlie Terrane, Yilgarn Craton

NASA Astrophysics Data System (ADS)

Said, Nuru; Kerrich, Robert; Maier, W. D.; McCuaig, Campbell

2011-05-01

The 2.7 Ga Kambalda Sequence comprises a mafic to ultramafic dominated volcanic rock sequence of the Kalgoorlie Terrane, Yilgarn Craton, Western Australia. The Sequence is divided into Lower and Upper Units separated by the Kambalda Komatiite Formation. Five basalt suites of the Lower Unit are tholeiitic where MgO spans 5-10 wt.% MgO, with minor assimilation-fractional crystallization (AFC), whereas six volcanic suites identified in the Upper Unit are tholeiitic to komatiitic-basalts with MgO 24-5 wt.% having generally greater degrees of AFC. Upper suites plot at Al 2O 3/TiO 2 (17-26) close to the primitive mantle ratio of 21, and Pt + Pd (19-31 ppb), whereas the PGE-depleted Lower basalts plot at generally lower Al 2O 3/TiO 2 (<16) and Pt + Pd (<10 ppb). Most suites have an average Pt/Pd ratio of 1.11, despite large variations in MgO contents, broadly consistent with the Pt/Pd ratio in the primitive mantle. On primitive mantle-normalised PGE plots, Upper suites generally display less fractionated patterns of the IPGE (Os, Ir, Ru and Rh) from the PPGE (Pt and Pd) relative to the Lower basalts. Most suites exhibit patterns with positive slopes reflecting relative enrichment of Pd, Pt, Au and Cu relative to Ni and IPGE. In suites of both Units, the concentrations of Ir and Ru fall with decreasing MgO contents, indicating their broadly compatible behaviour during magmatic evolution that involved AFC. Platinum and Pd behave as incompatible elements in the high-MgO suites, whereas Pt and Pd behave compatibly during crystallisation of the Lower basalt magmas, an interpretation consistent with progressively higher Cu/Pt and Cu/Pd ratios at decreasing MgO contents, and with falling Pt/Ti, collectively due to sulphur saturation induced by AFC as recorded in an antivariance of Pd/Ir with Nb/Th, a monitor of AFC. Collectively, the data suggest that several of the Lower Basalt suites crystallised under sulphide-saturated conditions, whereas most of the Upper Basalt Sequences

Development and characterization of monoclonal antibodies against canine PD-1 and PD-L1.

PubMed

Nemoto, Yuki; Shosu, Kazuha; Okuda, Masaru; Noguchi, Shunsuke; Mizuno, Takuya

2018-04-01

Recent research has focused on immunotherapy, particularly with regard to cancer treatment. Programmed death-1 and programmed death ligand 1 (PD-1/PD-L1) pathway blockade is a central topic of the promising immunotherapy field. In veterinary medicine, observations of the PD-1/PD-L1 pathway, including the relationship between immune cells and diseases, have increased. In this study, monoclonal antibodies specific to canine PD-1 and PD-L1 were developed, and the antibodies against PD-1 and PD-L1 bind to PD-1 and PD-L1 overexpressing cells, respectively. Additionally, each antibody interfered with the interaction between PD-1 and PD-L1. The expression of PD-1 and PD-L1 was detected on activated T cells from canine peripheral blood mononuclear cells (PBMC), and, remarkably, was the first recorded instance of PD-L1 expression on canine immature dendritic cells. Production of IFN-γ by activated T cells increased significantly when incubated with anti-PD-1 antibody alone and with both anti-PD-1 and anti-PD-L1 antibodies, revealing the functional effects of the antibodies. The antibodies will be useful for research on immune systems and may be the first passive immunotherapy approach in canine cancer patients. Copyright © 2018 Elsevier B.V. All rights reserved.

An effective diagnostic strategy for accurate detection of RhD variants including Asian DEL type in apparently RhD-negative blood donors in Korea.

PubMed

Seo, M H; Won, E J; Hong, Y J; Chun, S; Kwon, J R; Choi, Y S; Kim, J N; Lee, S A; Lim, A H; Kim, S H; Park, K U; Cho, D

2016-11-01

The purpose of this study was to provide an effective RHD genotyping strategy for the East Asian blood donors. RhD phenotyping, weak D testing and RhCE phenotyping were performed on 110 samples from members of the RhD-negative club, private organization composed of RhD-negative blood donors, in the GwangJu-Chonnam region of Korea. The RHD promoter, intron 4, and exons 7 and 10 were analysed by real-time PCR. Two nucleotide changes (c.1227 G>A, and c.1222 T>C) in exon 9 were analysed by sequencing. Of 110 RhD-negative club members, 79 (71·8%) showed complete deletion of the RHD gene, 10 (9·1%) showed results consistent with RHD-CE-D hybrid, and 21 (19·1%) showed amplification of RHD promoter, intron 4, and exons 7 and 10. Of the latter group, 16 (14·5%) were in the DEL blood group including c.1227 G>A (N = 14) and c.1222 T>C (N = 2), 2 (1·8%) were weak D, 1(0·9%) was partial D, and 2 (1·8%) were undetermined. The RhD-negative phenotype samples consisted of 58 C-E-c+e+, 19 C-E+c+e+, 3 C-E+c+e-, 21 C+E-c+e-, 6 C+E-c+e+ and 3 C+E-c-e + . Notably, all 58 samples with the C-E-c+e+ phenotype were revealed to have complete deletion of the RHD gene. The C-E-c+e+ phenotype showed 100% positive predictive value for detecting D-negative cases. RHD genotyping is not required in half of D-negative cases. We suggest here an effective RHD genotyping strategy for accurate detection of RhD variants in apparently RhD-negative blood donors in East Asia. © 2016 International Society of Blood Transfusion.

Synthesis Gas Conversion over Rh-Based Catalysts Promoted by Fe and Mn

DOE PAGES

Liu, Yifei; Göeltl, Florian; Ro, Insoo; ...

2017-06-13

Rh/SiO2 catalysts promoted with Fe and Mn are selective for synthesis gas conversion to oxygenates and light hydrocarbons at 523 K and 580 psi. Selective anchoring of Fe and Mn species on Rh nanoparticles was achieved by controlled surface reactions and was evidenced by ultraviolet–visible absorption spectroscopy, scanning transmission electron microscopy, and inductively coupled plasma absorption emission spectroscopy. The interaction between Rh and Fe promotes the selective production of ethanol through hydrogenation of acetaldehyde and enhances the selectivity toward C2 oxygenates, which include ethanol and acetaldehyde. The interaction between Rh and Mn increases the overall reaction rate and the selectivitymore » toward C2+ hydrocarbons. The combination of Fe and Mn on Rh/SiO2 results in trimetallic Rh-Fe-Mn catalysts that surpass the performance of their bimetallic counterparts. The highest selectivities toward ethanol (36.9%) and C2 oxygenates (39.6%) were achieved over the Rh-Fe-Mn ternary system with a molar ratio of 1:0.15:0.10, as opposed to the selectivities obtained over Rh/SiO2, which were 3.5% and 20.4%, respectively. The production of value-added oxygenates and C2+ hydrocarbons over this trimetallic catalyst accounted for 55% of the total products. X-ray photoelectron spectroscopy measurements suggest that significant fractions of the Fe and Mn species exist as metallic iron and manganese oxides on the Rh surface upon reduction. These findings are rationalized by density functional theory (DFT) calculations, which reveal that the exact state of metals on the surfaces is condition-dependent, with Mn present as Mn(I) and Mn(II) oxide on the Rh (211) step edges and Fe present as Fe(I) oxide on the step edge and metallic subsurface iron on both Rh steps and terraces. CO Fourier transform infrared spectroscopy and DFT calculations suggest that the binding of CO to Rh (211) step edges modified by Fe and/or manganese oxide is altered in comparison to

PD-1/PD-L1 pathway inhibitors in advanced prostate cancer.

PubMed

Isaacsson Velho, Pedro; Antonarakis, Emmanuel S

2018-05-01

Pharmacological inhibition of immune checkpoint receptors or their ligands represents a transformative breakthrough in the management of multiple cancers. However, immune checkpoint inhibitors have yet to be FDA-approved for the management of metastatic prostate cancer (PCa), the commonest non-cutaneous malignancy in men. Areas covered: We review our current understanding of the PD-1/PD-L1 pathway in cancer, the use of anti-PD-1/PD-L1 therapeutics in PCa, and potential subgroups of PCa patients who may derive the greatest benefit from these agents (such as men with tumors that have expression of PD-L1 and/or high mutational load). We also review the prior and current clinical trials evaluating the blockade of PD-1/PD-L1 in PCa, highlighting some of the key ongoing studies of greatest relevance to the field. Expert commentary: Clinical trials investigating PD-1/PD-L1 inhibitors should be encouraged in patients with PCa. While it is unlikely that immune checkpoint monotherapies will produce long-lasting responses in a substantial proportion of patients, there is early evidence of activity in some patient subsets. These subgroups may include those with high PD-L1 expression, those with hypermutated or microsatellite-unstable tumors, and those enriched for germline and/or somatic DNA-repair gene mutations (e.g. intraductal/ductal histology, primary Gleason pattern 5, and perhaps AR-V7-positive tumors).

Neutralization of Plasmodium falciparum merozoites by antibodies against PfRH5

PubMed Central

Douglas, Alexander D.; Williams, Andrew R.; Knuepfer, Ellen; Illingworth, Joseph J.; Furze, Julie M.; Crosnier, Cécile; Choudhary, Prateek; Bustamante, Leyla Y.; Zakutansky, Sara E.; Awuah, Dennis K.; Alanine, Daniel G. W.; Theron, Michel; Worth, Andrew; Shimkets, Richard; Rayner, Julian C.; Holder, Anthony A.; Wright, Gavin J.; Draper, Simon J.

2013-01-01

There is intense interest in induction and characterization of strain-transcending neutralizing antibody against antigenically variable human pathogens. We have recently identified the human malaria parasite Plasmodium falciparum reticulocyte-binding protein homologue 5 (PfRH5) as a target of broadly-neutralizing antibodies, but there is little information regarding the functional mechanism(s) of antibody-mediated neutralization. Here, we report that vaccine-induced polyclonal anti-PfRH5 antibodies inhibit the tight attachment of merozoites to erythrocytes, and are capable of blocking the interaction of PfRH5 with its receptor basigin. Furthermore, by developing anti-PfRH5 monoclonal antibodies (mAbs), we provide evidence that i) the ability to block the PfRH5-basigin interaction in vitro is predictive of functional activity, but absence of blockade does not predict absence of functional activity; ii) neutralizing mAbs bind spatially-related epitopes on the folded protein, involving at least two defined regions of the PfRH5 primary sequence; iii) a brief exposure window of PfRH5 is likely to necessitate rapid binding of antibody to neutralize parasites; and iv) intact bivalent IgG contributes to but is not necessary for parasite neutralization. These data provide important insight into the mechanisms of broadly-neutralizing anti-malaria antibodies and further encourage anti-PfRH5 based malaria prevention efforts. PMID:24293631

Spectroscopic and DFT Study of RhIII Chloro Complex Transformation in Alkaline Solutions.

PubMed

Vasilchenko, Danila B; Berdyugin, Semen N; Korenev, Sergey V; O'Kennedy, Sean; Gerber, Wilhelmus J

2017-09-05

The hydrolysis of [RhCl 6 ] 3- in NaOH-water solutions was studied by spectrophotometric methods. The reaction proceeds via successive substitution of chloride with hydroxide to quantitatively form [Rh(OH) 6 ] 3- . Ligand substitution kinetics was studied in an aqueous 0.434-1.085 M NaOH matrix in the temperature range 5.5-15.3 °C. Transformation of [RhCl 6 ] 3- into [RhCl 5 (OH)] 3- was found to be the rate-determining step with activation parameters of ΔH † = 105 ± 4 kJ mol -1 and ΔS † = 59 ± 10 J K -1 mol -1 . The coordinated hydroxo ligand(s) induces rapid ligand substitution to form [Rh(OH) 6 ] 3- . By simulating ligand substitution as a dissociative mechanism, using density functional theory (DFT), we can now explain the relatively fast and slow kinetics of chloride substitution in basic and acidic matrices, respectively. Moreover, the DFT calculated activation energies corroborated experimental data that the kinetic stereochemical sequence of [RhCl 6 ] 3- hydrolysis in an acidic solution proceeds as [RhCl 6 ] 3- → [RhCl 5 (H 2 O)] 2- → cis-[RhCl 4 (H 2 O) 2 ] - . However, DFT calculations predict in a basic solution the trans route of substitution [RhCl 6 ] 3- → [RhCl 5 (OH)] 3- → trans-[RhCl 4 (OH) 2 ] 3- is kinetically favored.

Advantages with prophylactic PEG-rhG-CSF versus rhG-CSF in breast cancer patients receiving multiple cycles of myelosuppressive chemotherapy: an open-label, randomized, multicenter phase III study.

PubMed

Xie, Jie; Cao, Jun; Wang, Jing-Fen; Zhang, Bai-Hong; Zeng, Xiao-Hua; Zheng, Hong; Zhang, Yang; Cai, Li; Wu, Yu-Dong; Yao, Qiang; Zhao, Xiao-Chun; Mao, Wei-Dong; Jiang, Ai-Mei; Chen, Shao-Shui; Yang, Shun-E; Wang, Shu-Sen; Wang, Jian-Hong; Pan, Yue-Yin; Ren, Bi-Yong; Chen, Yan-Ju; Ouyang, Li-Zhi; Lei, Kai-Jian; Gao, Jing-Hua; Huang, Wen-He; Huang, Zhan; Shou, Tao; He, Yan-Ling; Cheng, Jing; Sun, Yang; Li, Wei-Ming; Cui, Shu-de; Wang, Xin; Rao, Zhi-Guo; Ma, Hu; Liu, Wei; Wu, Xue-Yong; Shen, Wei-Xi; Cao, Fei-Lin; Xiao, Ze-Min; Wu, Biao; Tian, Shu-Yan; Meng, Dong; Shen, Peng; Wang, Bi-Yun; Wang, Zhonghua; Zhang, Jian; Wang, Leiping; Hu, Xi-Chun

2018-04-01

PEG-rhG-CSF reduces neutropenia and improves chemotherapy safety. In China's registration trial (CFDA: 2006L01305), we assessed its efficacy and safety against rhG-CSF, and prospectively explored its value over multiple cycles of chemotherapy. In this open-label, randomized, multicenter phase 3 study, breast cancer patients (n = 569) were randomized to receive PEG-rhG-CSF 100 µg/kg, PEG-rhG-CSF 6 mg, or rhG-CSF 5 µg/kg/d after chemotherapy. The primary endpoints were the incidence and duration of grade 3/4 neutropenia during cycle 1. Secondary endpoints included the incidence and duration of grade 3/4 neutropenia during cycles 2-4, the incidence of febrile neutropenia, and the safety. A once-per-cycle PEG-rhG-CSF at either 100 µg/kg or 6 mg was not different from daily injections of rhG-CSF for either incidence or duration of grade 3/4 neutropenia. Interestingly, a substantial difference was noted during cycle 2, and the difference became bigger over cycles 3-4, reaching a statistical significance at cycle 4 in either incidence (P = 0.0309) or duration (P = 0.0289) favoring PEG-rhG-CSF. A significant trend toward a lower incidence of all-grade adverse events was noted at 129 (68.98%), 142 (75.53%), and 160 (82.47%) in the PEG-rhG-CSF 100 µg/kg and 6 mg and rhG-CSF groups, respectively (P = 0.0085). The corresponding incidence of grade 3/4 drug-related adverse events was 2/187 (1.07%), 1/188 (0.53%), and 8/194 (4.12%), respectively (P = 0.0477). Additionally, PFS in metastatic patients preferred PEG-rhG-CSF to rhG-CSF despite no significance observed by Kaplan-Meier analysis (n = 49, P = 0.153). PEG-rhG-CSF is a more convenient and safe formulation and a more effective prophylactic measure in breast cancer patients receiving multiple cycles of chemotherapy.

High temperature Ir segregation in Ir-B ceramics: Effect of oxygen presence on stability of IrB 2 and other Ir-B phases

DOE PAGES

Xie, Zhilin; Terracciano, Anthony C.; Cullen, David A.; ...

2015-05-13

The formation of IrB 2, IrB 1.35, IrB 1.1 and IrB monoboride phases in the Ir–B ceramic nanopowder was confirmed during mechanochemical reaction between metallic Ir and elemental B powders. The Ir–B phases were analysed after 90 h of high energy ball milling and after annealing of the powder for 72 h at 1050°C in vacuo. The iridium monoboride (IrB) orthorhombic phase was synthesised experimentally for the first time and identified by powder X-ray diffraction. Additionally, the ReB 2 type IrB 2 hexagonal phase was also produced for the first time and identified by high resolution transmission electron microscope. Irmore » segregation along disordered domains of the boron lattice was found to occur during high temperature annealing. Furthermore, these nanodomains may have useful catalytic properties.« less

The aging correlation (RH + t): Relative humidity (%) + temperature (deg C)

NASA Technical Reports Server (NTRS)

Cuddihy, E. F.

1986-01-01

An aging correlation between corrosion lifetime, and relative humidity RH (%) and temperature t (C) has been reported in the literature. This aging correlation is a semi-log plot of corrosion lifetime on the log scale versus the interesting summation term RH(%) + t(C) on the linear scale. This empirical correlation was derived from observation of experimental data trends and has been referred to as an experimental law. Using electrical resistivity data of polyvinyl butyral (PVB) measured as a function of relative humidity and temperature, it was found that the electrical resistivity could be expressed as a function of the term RH(%) t(C). Thus, if corrosion is related to leakage current through an organic insulator, which, in turn, is a function of RH and t, then some partial theoretical validity for the correlation is indicated. This article describes the derivation of the term RH(%) t(C) from PVB electrical resistivity data.

Modulating PD-L1 expression in multiple myeloma: an alternative strategy to target the PD-1/PD-L1 pathway.

PubMed

Tremblay-LeMay, Rosemarie; Rastgoo, Nasrin; Chang, Hong

2018-03-27

Even with recent advances in therapy regimen, multiple myeloma patients commonly develop drug resistance and relapse. The relevance of targeting the PD-1/PD-L1 axis has been demonstrated in pre-clinical models. Monotherapy with PD-1 inhibitors produced disappointing results, but combinations with other drugs used in the treatment of multiple myeloma seemed promising, and clinical trials are ongoing. However, there have recently been concerns about the safety of PD-1 and PD-L1 inhibitors combined with immunomodulators in the treatment of multiple myeloma, and several trials have been suspended. There is therefore a need for alternative combinations of drugs or different approaches to target this pathway. Protein expression of PD-L1 on cancer cells, including in multiple myeloma, has been associated with intrinsic aggressive features independent of immune evasion mechanisms, thereby providing a rationale for the adoption of new strategies directly targeting PD-L1 protein expression. Drugs modulating the transcriptional and post-transcriptional regulation of PD-L1 could represent new therapeutic strategies for the treatment of multiple myeloma, help potentiate the action of other drugs or be combined to PD-1/PD-L1 inhibitors in order to avoid the potentially problematic combination with immunomodulators. This review will focus on the pathophysiology of PD-L1 expression in multiple myeloma and drugs that have been shown to modulate this expression.

Electric field control of magnetic properties in FeRh/PMN-PT heterostructures

NASA Astrophysics Data System (ADS)

Xie, Yali; Zhan, Qingfeng; Shang, Tian; Yang, Huali; Liu, Yiwei; Wang, Baomin; Li, Run-Wei

2018-05-01

We investigated electric control of magnetic properties in FeRh/PMN-PT heterostructures. An electric field of 1 kV/cm applied on the PMN-PT substrate could increase the coercivity of FeRh film from 60 to 161 Oe at 360 K where the FeRh antiferromagnetic to ferromagnetic phase transition occurs. The electric field dependent coercive field reveals a butterfly shape, indicating a strain-mediated magnetoelectric coupling across the FeRh/PMN-PT interface. However, the uniaxial magnetic anisotropy of FeRh is almost unchanged with the applied electric field on the PMN-PT substrate, which suggests the change of coercivity in FeRh films is mainly due to the shift of the magnetic transition temperature under the electric field.

[Detection and analysis of anti-Rh blood group antibodies].

PubMed

Wu, Yuan-jun; Wu, Yong; Chen, Bao-chan; Liu, Yan

2008-06-01

To study the prevalence and distribution of anti-Rh blood group antibodies in Chinese population and its clinical significance. Irregular antibodies were screened and identified by Microcolum Gel Coomb's test. For those identified as positive anti-Rh samples, monoclonal antibodies (anti-D, -C, -c, -E and -e) were used to identify the specific antigen and confirm the accuracy of the irregular antibody tests. The titers, Ig-types and 37 Degrees Celsius-reactivity were tested to confirm its clinical significance. For evaluation of the origin of irregular antibodies, histories of pregnancy and transfusion were reviewed. For the newborns who had positive antibodies, their mothers were tested simultaneously to confirm the origin of the antibodies. 47 out of 54 000 (0.087%) patients were identified as positive with Rh blood group antibodies.Of them, 27 cases had history of pregnancy, 13 had transfusion and 1 had the histories of both. 6 newborns had antibodies derived form their mothers. The specificity of the antibody was as follows: 29 with anti-E (61.70%), 8 with anti-D (17.02%), anti-cE 5(10.64%), 4 with anti-c (8.51%) and 1 with anti-C (2.13%). All the 47 Rh blood group antibodies were IgG or IgG+IgM, and were reactive to red blood cells with corresponding antigens at 37 Degrees Celsius, with a highest titer of 1:4 096. The prevalence of Rh antibodies is lower in Chinese population as compared with that in White population.Of all the antibodies, anti-E is most frequently identified and anti-D was declining. Alloimmunization by pregnancy and transfusion is the major cause of Rh antibody production. Rh blood group antibodies derived from mothers are the major cause of Non-ABO-HDN.

Decomposition pathways of C2 oxygenates on Rh-modified tungsten carbide surfaces

DOE PAGES

Kelly, Thomas G.; Ren, Hui; Chen, Jingguang G.

2015-03-27

Ethanol decomposition on tungsten monocarbide (WC) and Rh-modified WC was investigated using ultrahigh vacuum (UHV) surface science experiments and density functional theory (DFT) calculations. DFT calculations indicated that the binding energies of ethanol and its decomposition intermediates on WC(0001) were modified by Rh, with Rh/WC(0001) showing similar values to those on Rh(111). Through temperature-programmed desorption (TPD) experiments on polycrystalline WC and Rh-modified WC, it was shown that the selectivity for ethanol decomposition was different on these surfaces. On WC, the C-O bond of ethanol was preferentially broken to produce ethylene; on Rh-modified WC, the C-C bond was broken to producemore » carbon monoxide and methane. In addition, high-resolution electron energy loss spectroscopy (HREELS) was used to determine likely surface intermediates. On Rh-modified WC, ethanol first formed ethoxy through O-H scission, then reacted through an aldehyde intermediate to form the C1 products.« less

Immunoreactive GnRH Type I Receptors in the Mouse and Sheep Brain

PubMed Central

Albertson, Asher J.; Navratil, Amy; Mignot, Mallory; Dufourny, Laurence; Cherrington, Brian; Skinner, Donal C.

2008-01-01

GnRH has been implicated in an array of functions outside the neuroendocrine reproductive axis. Previous investigations have reported extensive GnRH binding in numerous sites and this has been supported by in situ hybridization studies reporting GnRH receptor mRNA distribution. The present study on mice and sheep supports and extends these earlier investigations by revealing the distribution of cells immunoreactive for the GnRH receptor. In addition to sites previously shown to express GnRH receptors such as the hippocampus, amygdala and the arcuate nucleus, the improved resolution afforded by immunocytochemistry detected cells in the mitral cell lay of the olfactory bulb as well as the central grey of the mesencephalon. In addition, GnRH receptor immunoreactive neurons in the hippocampus and mesencephalon of the sheep were shown to colocalize with estrogen receptor β. Although GnRH may act at some of these sites to regulate reproductive processes, evidence is accumulating to support an extra-reproductive role for this hypothalamic decapeptide. PMID:18439800

Lattice dynamic properties of Rh2XAl (X=Fe and Y) alloys

NASA Astrophysics Data System (ADS)

Al, Selgin; Arikan, Nihat; Demir, Süleyman; Iyigör, Ahmet

2018-02-01

The electronic band structure, elastic and vibrational spectra of Rh2FeAl and Rh2YAl alloys were computed in detail by employing an ab-initio pseudopotential method and a linear-response technique based on the density-functional theory (DFT) scheme within a generalized gradient approximation (GGA). Computed lattice constants, bulk modulus and elastic constants were compared. Rh2YAl exhibited higher ability to resist volume change than Rh2FeAl. The elastic constants, shear modulus, Young modulus, Poisson's ratio, B/G ratio electronic band structure, total and partial density of states, and total magnetic moment of alloys were also presented. Rh2FeAl showed spin up and spin down states whereas Rh2YAl showed none due to being non-magnetic. The calculated total densities of states for both materials suggest that both alloys are metallic in nature. Full phonon spectra of Rh2FeAl and Rh2YA1 alloys in the L21 phase were collected using the ab-initio linear response method. The obtained phonon frequencies were in the positive region indicating that both alloys are dynamically stable.

Structural analysis of the RH-like blood group gene products in nonhuman primates

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

Salvignol, I.; Calvas, P.; Blancher, A.

1995-03-01

Rh-related transcripts present in bone marrow samples from several species of nonhuman primates (chimpanzee, gorilla, gibbon, crab-eating macaque) have been amplified by RT-polymerase chain reaction using primers deduced from the sequence of human RH genes. Nucleotide sequence analysis of the nonhuman transcripts revealed a high degree of similarity to human blood group Rh sequences, suggesting a great conservation of the RH genes throughout evolution. Full-length transcripts, potentially encoding 417 amino acid long proteins homologous to Rh polypeptides, were characterized, as well as mRNA isoforms which harbored nucleotide deletions or insertions and potentially encode truncated proteins. Proteins of 30-40,000 M{sub r},more » immunologically related to human Rh proteins, were detected by western blot analysis with antipeptide antibodies, indicating that Rh-like transcripts are translated into membrane proteins. Comparison of human and nonhuman protein sequences was pivotal in clarifying the molecular basis of the blood group C/c polymorphism, showing that only the Pro103Ser substitution was correlated with C/c polymorphism. In addition, it was shown that a proline residue at position 102 was critical in the expression of C and c epitopes, most likely by providing an appropriate conformation of Rh polypeptides. From these data a phylogenetic reconstruction of the RH locus evolution has been calculated from which an unrooted phylogenetic tree could be proposed, indicating that African ape Rh-like genes would be closer to the human RhD gene than to the human RhCE gene. 55 refs., 4 figs., 1 tab.« less

Electrical resistivity of Co-Ni-Pd and Co-Pd alloys

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

Jen, S.U.; Chen, T.P.; Chang, S.A.

1991-11-15

Three series of ferromagnetic alloys have been made: Co{sub 100{minus}{ital x}}Pd{sub {ital x}}, Co{sub 25}Ni{sub 75{minus}{ital y}}Pd{sub {ital y}} and Co{sub 5{minus}{ital z}}Ni{sub {ital z}}Pd{sub 95}. The electrical resistivity {rho} of these alloys was measured from 4 to 300 K. Their high field ({ital H}{gt}2 T) susceptibility {chi}{sub HF} was obtained with superconducting quantum interference device measurements at 5 K. Comparing the residual resistivity {rho}{sub 0} of Co-Ni and Co-Pd, it is found that the spin-up resistivity {rho}{sub {up arrow}} of Co-Ni follows the Nordheim's rule, while that of Co-Pd peaks at {ital x}=85. This indicates the spin-up {ital d}more » band of Co-Pd is not full for all the {ital x} values. Also, {chi}{sub HF} data reveal the same tendency of the spin-up band. Based on the deviation from Matthiessen's rule of the two-current model, we estimate {alpha}={rho}{sub 0{down arrow}} /{rho}{sub 0{up arrow}}{congruent}2 for the dilute {ital PdCo} alloy, where {rho}{sub 0}={rho}{sub 0{down arrow}} {rho}{sub 0{up arrow}}/({rho}{sub 0{up arrow}}+{rho}{sub 0{down arrow}} ), from the residual resistivity of the ternary Co{sub 5{minus}{ital z}}Ni{sub {ital z}}Pd{sub 95} alloy and from the temperature dependence of {rho}({ital T}) of the binary Co{sub 5}Pd{sub 95} alloy« less

Oral administration of erythrocyte membrane antigen does not suppress anti-Rh(D) antibody responses in humans.

PubMed Central

Barnes, R M; Duguid, J K; Roberts, F M; Risk, J M; Johnson, P M; Finn, R; Hardy, J; Napier, J A; Clarke, C A

1987-01-01

The effects of prior oral administration of erythrocyte membrane preparations (Oral Rh antigen) on the serum anti-Rh(D) antibody response has been evaluated in non-sensitized Rh(D)-negative male volunteers, and in female volunteers sensitized previously by Rh(D)-positive fetal blood during pregnancy. Sixty-one percent (11/18) of males who received oral Rh antigen (either D-positive or D-negative) before intravenous challenge with Rh(D)-positive cells produced detectable antibodies; of these 11, six received oral Rh(D)-negative antigen and five received oral Rh(D)-positive antigen. Seventy-two percent (13/18) of control males, who had received no prior oral Rh antigen, produced antibodies following challenge with Rh(D)-positive cells. Three out of six pre-sensitized females who received oral D-positive or D-negative Rh antigen for 4 weeks, but without intravenous challenge, increased their anti-Rh(D) antibody levels which peaked after 11-18 weeks: two had received Rh(D)-positive antigen, and one Rh(D)-negative antigen. These data indicate that administration of oral Rh antigen before parenteral immunization does not significantly suppress the anti-Rh(D) antibody response. Indeed, oral administration of either Rh(D)-positive or Rh(D)-negative antigen can boost systemic antibody in pre-sensitized females. These results do not support the rationale of treating Rh-sensitized pregnant women with oral Rh antigen. PMID:3113783

Two highly similar DEAD box proteins, OsRH2 and OsRH34, homologous to eukaryotic initiation factor 4AIII, play roles of the exon junction complex in regulating growth and development in rice.

PubMed

Huang, Chun-Kai; Sie, Yi-Syuan; Chen, Yu-Fu; Huang, Tian-Sheng; Lu, Chung-An

2016-04-12

The exon junction complex (EJC), which contains four core components, eukaryotic initiation factor 4AIII (eIF4AIII), MAGO/NASHI (MAGO), Y14/Tsunagi/RNA-binding protein 8A, and Barentsz/Metastatic lymph node 51, is formed in both nucleus and cytoplasm, and plays important roles in gene expression. Genes encoding core EJC components have been found in plants, including rice. Currently, the functional characterizations of MAGO and Y14 homologs have been demonstrated in rice. However, it is still unknown whether eIF4AIII is essential for the functional EJC in rice. This study investigated two DEAD box RNA helicases, OsRH2 and OsRH34, which are homologous to eIF4AIII, in rice. Amino acid sequence analysis indicated that OsRH2 and OsRH34 had 99 % identity and 100 % similarity, and their gene expression patterns were similar in various rice tissues, but the level of OsRH2 mRNA was about 58-fold higher than that of OsRH34 mRNA in seedlings. From bimolecular fluorescence complementation results, OsRH2 and OsRH34 interacted physically with OsMAGO1 and OsY14b, respectively, which indicated that both of OsRH2 and OsRH34 were core components of the EJC in rice. To study the biological roles of OsRH2 and OsRH34 in rice, transgenic rice plants were generated by RNA interference. The phenotypes of three independent OsRH2 and OsRH34 double-knockdown transgenic lines included dwarfism, a short internode distance, reproductive delay, defective embryonic development, and a low seed setting rate. These phenotypes resembled those of mutants with gibberellin-related developmental defects. In addition, the OsRH2 and OsRH34 double-knockdown transgenic lines exhibited the accumulation of unspliced rice UNDEVELOPED TAPETUM 1 mRNA. Rice contains two eIF4AIII paralogous genes, OsRH2 and OsRH34. The abundance of OsRH2 mRNA was about 58-fold higher than that of OsRH34 mRNA in seedlings, suggesting that the OsRH2 is major eIF4AIII in rice. Both OsRH2 and OsRH34 are core components of the EJC

Histological organization of the central nervous system and distribution of a gonadotropin-releasing hormone-like peptide in the blue crab, Portunus pelagicus.

PubMed

Saetan, Jirawat; Senarai, Thanyaporn; Tamtin, Montakan; Weerachatyanukul, Wattana; Chavadej, Jittipan; Hanna, Peter J; Parhar, Ishwar; Sobhon, Prasert; Sretarugsa, Prapee

2013-09-01

We present a detailed histological description of the central nervous system (CNS: brain, subesophageal ganglion, thoracic ganglia, abdominal ganglia) of the blue crab, Portunus pelagicus. Because the presence of gonadotropin-releasing hormone (GnRH) in crustaceans has been disputed, we examine the presence and localization of a GnRH-like peptide in the CNS of the blue crab by using antibodies against lamprey GnRH (lGnRH)-III, octopus GnRH (octGnRH) and tunicate GnRH (tGnRH)-I. These antibodies showed no cross-reactivity with red-pigment-concentrating hormone, adipokinetic hormone, or corazonin. In the brain, strong lGnRH-III immunoreactivity (-ir) was detected in small (7-17 μm diameter) neurons of clusters 8, 9 and 10, in medium-sized (21-36 μm diameter) neurons of clusters 6, 7 and 11 and in the anterior and posterior median protocerebral neuropils, olfactory neuropil, median and lateral antenna I neuropils, tegumentary neuropil and antenna II neuropil. In the subesophageal ganglion, lGnRH-III-ir was detected in medium-sized neurons and in the subesophageal neuropil. In the thoracic and abdominal ganglia, lGnRH-III-ir was detected in medium-sized and small neurons and in the neuropils. OctGnRH-ir was observed in neurons of the same clusters with moderate staining, particularly in the deutocerebrum, whereas tGnRH-I-ir was only detected in medium-sized neurons of cluster 11 in the brain. Thus, anti-lGnRH-III shows greater immunoreactivity in the crab CNS than anti-octGnRH and anti-tGnRH-I. Moreover, our functional bioassay demonstrates that only lGnRH-III has significant stimulatory effects on ovarian growth and maturation. We therefore conclude that, although the true identity of the crab GnRH eludes us, crabs possess a putative GnRH hormone similar to lGnRH-III. The identification and characterization of this molecule is part of our ongoing research.

New Rh 2 (II,II) Complexes for Solar Energy Applications: Panchromatic Absorption and Excited-State Reactivity

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

Whittemore, Tyler J.; Sayre, Hannah J.; Xue, Congcong

In this work, the new heteroleptic paddlewheel complexes cis-[Rh 2(μ-form) 2(μ-np) 2][BF 4] 2, where form = p-ditolylformamidinate (DTolF) or p-difluorobenzylformamidinate (F-form) and np = 1,8-napthyridyine, and cis-Rh 2(μ-form) 2(μ-npCOO) 2 (npCOO – = 1,8-naphthyridine-2-carboxylate), were synthesized and characterized. The complexes absorb strongly throughout the ultraviolet (λ max = 300 nm, ε = 20 300 M –1 cm –1) and visible regions (λ max = 640 nm ε = 3500 M –1 cm –1), making them potentially useful new dyes with panchromatic light absorption for solar energy conversion applications. Ultrafast and nanosecond transient absorption and time-resolved infrared spectroscopies were usedmore » to characterize the identity and dynamics of the excited states, where singlet and triplet Rh 2/form-to-naphthyridine, metal/ligand-to-ligand charge-transfer (ML-LCT) excited states were observed in all four complexes. The npCOO – complexes exhibit red-shifted absorption profiles extending into the near-IR and undergo photoinitiated electron transfer to generate reduced methyl viologen, a species that persists in the presence of a sacrificial donor. The energy of the triplet excited state of each complex was estimated from energy-transfer quenching experiments using a series of organic triplet donors (E( 3ππ*) from 1.83 to 0.78 eV). The singlet reduction (+0.6 V vs Ag/AgCl) potentials, and singlet and triplet oxidation potentials (-1.1 and -0.5 V vs Ag/AgCl, respectively) were determined. Finally, based on the excited-state lifetimes and redox properties, these complexes represent a new class of light absorbers with potential application as dyes for charge injection into semiconductor solar cells and in sensitizer-catalyst assemblies for photocatalysis that operate with irradiation from the ultraviolet to ~800 nm.« less

New Rh 2 (II,II) Complexes for Solar Energy Applications: Panchromatic Absorption and Excited-State Reactivity

DOE PAGES

Whittemore, Tyler J.; Sayre, Hannah J.; Xue, Congcong; ...

2017-10-04

In this work, the new heteroleptic paddlewheel complexes cis-[Rh 2(μ-form) 2(μ-np) 2][BF 4] 2, where form = p-ditolylformamidinate (DTolF) or p-difluorobenzylformamidinate (F-form) and np = 1,8-napthyridyine, and cis-Rh 2(μ-form) 2(μ-npCOO) 2 (npCOO – = 1,8-naphthyridine-2-carboxylate), were synthesized and characterized. The complexes absorb strongly throughout the ultraviolet (λ max = 300 nm, ε = 20 300 M –1 cm –1) and visible regions (λ max = 640 nm ε = 3500 M –1 cm –1), making them potentially useful new dyes with panchromatic light absorption for solar energy conversion applications. Ultrafast and nanosecond transient absorption and time-resolved infrared spectroscopies were usedmore » to characterize the identity and dynamics of the excited states, where singlet and triplet Rh 2/form-to-naphthyridine, metal/ligand-to-ligand charge-transfer (ML-LCT) excited states were observed in all four complexes. The npCOO – complexes exhibit red-shifted absorption profiles extending into the near-IR and undergo photoinitiated electron transfer to generate reduced methyl viologen, a species that persists in the presence of a sacrificial donor. The energy of the triplet excited state of each complex was estimated from energy-transfer quenching experiments using a series of organic triplet donors (E( 3ππ*) from 1.83 to 0.78 eV). The singlet reduction (+0.6 V vs Ag/AgCl) potentials, and singlet and triplet oxidation potentials (-1.1 and -0.5 V vs Ag/AgCl, respectively) were determined. Finally, based on the excited-state lifetimes and redox properties, these complexes represent a new class of light absorbers with potential application as dyes for charge injection into semiconductor solar cells and in sensitizer-catalyst assemblies for photocatalysis that operate with irradiation from the ultraviolet to ~800 nm.« less

Linker-based GnRH-PE chimeric proteins inhibit cancer growth in nude mice.

PubMed

Ben-Yehudah, A; Yarkoni, S; Nechushtan, A; Belostotsky, R; Lorberboum-Galski, H

1999-04-01

Since the number of cancer-related deaths has not decreased in recent years, major efforts are being made to find new drugs for cancer treatment. In this report we introduce the gonadotropin releasing hormone-Pseudomonas exotoxin (GnRH-PE) based chimeric proteins L-GnRH-PE66 and L-GnRH-PE40. These proteins are composed of a GnRH moiety attached to modified forms of Pseudomonas exotoxin via a polylinker (gly4ser)2. The chimeric proteins L-GnRH-PE66 and L-GnRH-PE40 have the ability to target and kill adenocarcinoma cell lines in vitro, whereas non-adenocarcinoma cell lines are not affected. We demonstrate that L-GnRH-PE66 and L-GnRH-PE40 efficiently inhibit cancer growth. Nude mice were injected subcutaneously with the SW-48 adenocarcinoma cell line to produce xenograft tumours. When the tumours were established and visible, the animals were injected with chimeric proteins for 10 days. At the end of this period, a reduction of up to 3-fold in tumor size was obtained in the treated mice, as compared with the control group, which received equivalent amounts of GnRH; the difference was even greater 13 days after termination of treatment. Thus, the chimeric proteins L-GnRH-PE66 and L-GnRH-PE40 are promising candidates for treatment of a variety of adenocarcinomas and their use in humans should be considered.

Nanoamorphous carbon-based photonic crystal infrared emitters

DOEpatents

Norwood, Robert A [Tucson, AZ; Skotheim, Terje [Tucson, AZ

2011-12-13

Provided is a tunable radiation emitting structure comprising: a nanoamorphous carbon structure having a plurality of relief features provided in a periodic spatial configuration, wherein the relief features are separated from each other by adjacent recessed features, and wherein the nanoamorphous carbon comprises a total of from 0 to 60 atomic percent of one or more dopants of the dopant group consisting of: transition metals, lanthanoids, electro-conductive carbides, silicides and nitrides. In one embodiment, a dopant is selected from the group consisting of: Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, La and other lanthanides, Hf, Ta, W, Rh, Os, Ir, Pt, Au, and Hg. In one embodiment, a dopant is selected from the group consisting of: electro-conductive carbides (like Mo.sub.2C), silicides (like MoSi.sub.2) and nitrides (like TiN).

Calibrated Mid-wave Infrared (IR) (MidIR) and Long-wave IR (LWIR) Stokes and Degree-of-Liner Polarization (DOLP)

DTIC Science & Technology

2008-09-01

LWIR long-wave IR MCT mercury cadmium telluride MidIR mid-wave IR NUC nonuniformity corrections ROI regions-of-interest 22 No. of Copies...Calibrated Mid-wave Infrared (IR) (MidIR) and Long-wave IR ( LWIR ) Stokes and Degree-of-Liner Polarization (DOLP) by Kristan P. Gurton and... LWIR ) Stokes and Degree-of-Liner Polarization (DOLP) Kristan P. Gurton and Melvin Felton Computational and Information Sciences Directorate

Amphioxus: beginning of vertebrate and end of invertebrate type GnRH receptor lineage.

PubMed

Tello, Javier A; Sherwood, Nancy M

2009-06-01

In vertebrates, activation of the GnRH receptor is necessary to initiate the reproductive cascade. However, little is known about the characteristics of GnRH receptors before the vertebrates evolved. Recently genome sequencing was completed for amphioxus, Branchiostoma floridae. To understand the GnRH receptors (GnRHR) from this most basal chordate, which is also classified as an invertebrate, we cloned and characterized four GnRHR cDNAs encoded in the amphioxus genome. We found that incubation of GnRH1 (mammalian GnRH) and GnRH2 (chicken GnRH II) with COS7 cells heterologously expressing the amphioxus GnRHRs caused potent intracellular inositol phosphate turnover in two of the receptors. One of the two receptors displayed a clear preference for GnRH1 over GnRH2, a characteristic not previously seen outside the type I mammalian GnRHRs. Phylogenetic analysis grouped the four receptors into two paralogous pairs, with one pair grouping basally with the vertebrate GnRH receptors and the other grouping with the octopus GnRHR-like sequence and the related receptor for insect adipokinetic hormone. Pharmacological studies showed that octopus GnRH-like peptide and adipokinetic hormone induced potent inositol phosphate turnover in one of these other two amphioxus receptors. These data demonstrate the functional conservation of two distinct types of GnRH receptors at the base of chordates. We propose that one receptor type led to vertebrate GnRHRs, whereas the other type, related to the mollusk GnRHR-like receptor, was lost in the vertebrate lineage. This is the first report to suggest that distinct invertebrate and vertebrate GnRHRs are present simultaneously in a basal chordate, amphioxus.