966 resultados para transition metal sulfides


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A series of metal-matrix composites were formed by extrusion freeform, fabrication of a sinterable aluminum alloy in combination with silicon carbide particles and whiskers, carbon fibers, alumina particles, and hollow flyash cenospheres. Silicon carbide particles were most successful in that the composites retained high density with up to 20 vol% of reinforcement and the strength approximately doubles over the strength of the metal matrix alone. Comparison with simple models suggests that this unexpectedly high degree of reinforcement can be attributed to the concentration of small silicon carbide particles around the larger metal powder. This fabrication method also allows composites to be formed with hollow spheres that cannot be formed by other powder or melt methods.

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Crystal structures have been determined for free Escherichia coli hypoxanthine phosphoribosyltransferase (HPRT) (2.9 Angstrom resolution) and for the enzyme in complex with the reaction products, inosine 5'-monophosphate (IMP) and guanosine 5-monophosphate (GMP) (2.8 Angstrom resolution). Of the known 6-oxopurine phosphoribosyltransferase (PRTase) structures, E. coli HPRT is most similar in structure to that of Tritrichomonas foetus HGXPRT, with a rmsd for 150 Calpha atoms of 1.0 Angstrom. Comparison of the free and product bound structures shows that the side chain of Phe156 and the polypeptide backbone in this vicinity move to bind IMP or GMP. A nonproline cis peptide bond, also found in some other 6-oxopurine PRTases, is observed between Leu46 and Arg47 in both the free and complexed structures. For catalysis to occur, the 6-oxopurine PRTases have a requirement for divalent metal ion, Usually Mg2+ in vivo. In the free structure, a Mg2+, is coordinated to the side chains of Glu103 and Asp104. This interaction may be important for stabilization of the enzyme before catalysis. E. coli HPRT is unique among the known 6-oxopurine PRTases in that it exhibits a marked preference for hypoxanthine as substrate over both xanthine and guanine. The structures suggest that its substrate specificity is due to the modes of binding of the bases. In E. coli HPRT, the carbonyl oxygen of Asp 163 would likely form a hydrogen bond with the 2-exocyclic nitrogen of guanine (in the HPRT-guanine-PRib-PP-Mg2+ complex). However, hypoxanthine does not have a 2-exocyclic atom and the HPRT-IMP structure suggests that hypoxanthine is likely to occupy a different position in the purine-binding pocket.

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Experiments to investigate the transition process in hypervelocity boundary layers were performed in the T4 free-piston shock tunnel. An array of thin-film heat-transfer gauges was used to detect the location and extent of the transitional region on a 1500 mm long x 120 turn wide flat plate, which formed one of the walls of a duct. The experiments were performed in a Mach 6 flow of air with 6- and 12-MJ/kg nozzle-supply enthalpies at unit Reynolds numbers ranging from 1.6 x 10(6) to 4.9 x 10(6) m(-1). The results show that the characteristics typical of transition taking place through the initiation, growth, and merger of turbulent spots are evident in the heat-transfer signals. A 2-mm-high excrescence located 440 turn from the leading edge was found to be capable of generating a turbulent wedge within an otherwise laminar boundary layer at a unit Reynolds number of 2.6 x 10(6) m(-1) at the 6-MJ/kg condition. A tripping strip, located 100 mm from the leading edge and consisting of a line 37 teeth of 2 rum height equally spaced and spanning the test surface, was also found to be capable of advancing the transition location at the same condition and at the higher enthalpy condition.

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This paper analyzes a dual economy consisting of urban market areas and less developed rural areas with or without local markets. Urban areas have better opportunities for earnings and education than rural areas. Rural families choose whether to move to urban areas at costs that differ from location to location. As per capita output grows relative to the moving cost, urbanization proceeds, leading to lower fertility, more investments in human and physical capital per child relative to output per worker, and faster economic growth. These impacts are stronger if rural areas have no access to markets.

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Extracellular copper regulates the DNA binding activity of the CopY repressor of Enterococcus hirae and thereby controls expression of the copper homeostatic genes encoded by the cop operon. CopY has a CxCxxxxCxC metal binding motif. CopZ, a copper chaperone belonging to a family of metallochaperones characterized by a MxCxxC metal binding motif, transfers copper to CopY. The copper binding stoichiometries of CopZ and CopY were determined by in vitro metal reconstitutions. The stoichiometries were found to be one copper(l) per CopZ and two copper(l) per CopY monomer. X-ray absorption studies suggested a mixture of two- and three-coordinate copper in Cu(1)CopZ, but a purely three-coordinate copper coordination with a Cu-Cu interaction for Cu(1)(2)CopY. The latter coordination is consistent with the formation of a compact binuclear Cu(l)-thiolate core in the CxCxxxxCxC binding motif of CopY. Displacement of zinc, by copper. from CopY was monitored with 2,4-pyridylazoresorcinol. Two copper(l) ions were required to release the single zinc(II) ion bound per CopY monomer. The specificity of copper transfer between CopZ and CopY was dependent on electrostatic interactions. Relative copper binding affinities of the proteins were investigated using the chelator, diethyldithiocarbamic acid (DDC). These data suggest that CopY has a higher affinity for copper than CopZ. However, this affinity difference is not the sole factor in the copper exchange: a charge-based interaction between the two proteins is required for the transfer reaction to proceed. Gain-of-function mutation of a CopZ homologue demonstrated the necessity of four lysine residues on the chaperone for the interaction with CopY. Taken together, these results suggest a mechanism for copper exchange between CopZ and CopY.

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Quantitative laser ablation (LA)-ICP-MS analyses of fluid inclusions, trace element chemistry of sulfides, stable isotope (S), and Pb isotopes have been used to discriminate the formation of two contrasting mineralization styles and to evaluate the origin of the Cu and Au at Mt Morgan. The Mt Morgan Au-Cu deposit is hosted by Devonian felsic volcanic rocks that have been intruded by multiple phases of the Mt Morgan Tonalite, a low-K, low-Al2O3 tonalite-trondhjemite-dacite (TTD) complex. An early, barren massive sulfide mineralization with stringer veins is conforming to VHMS sub-seafloor replacement processes, whereas the high-grade Au-Cu. ore is associated with a later quartz-chalcopyrite-pyrite stock work mineralization that is related to intrusive phases of the Tonalite complex. LA-ICP-MS fluid inclusion analyses reveal high As (avg. 8850 ppm) and Sb (avg. 140 ppm) for the Au-Cu mineralization and 5 to 10 times higher Cu concentration than in the fluids associated with the massive pyrite mineralization. Overall, the hydrothermal system of Mt Morgan is characterized by low average fluid salinities in both mineralization styles (45-80% seawater salinity) and temperatures of 210 to 270 degreesC estimated from fluid inclusions. Laser Raman Spectroscopic analysis indicates a consistent and uniform array Of CO2-bearing fluids. Comparison with active submarine hydrothermal vents shows an enrichment of the Mt Morgan fluids in base metals. Therefore, a seawater-dominated fluid is assumed for the barren massive sulfide mineralization, whereas magmatic volatile contributions are implied for the intrusive related mineralization. Condensation of magmatic vapor into a seawater-dominated environment explains the CO2 occurrence, the low salinities, and the enriched base and precious metal fluid composition that is associated with the Au-Cu. mineralization. The sulfur isotope signature of pyrite and chalcopyrite is composed of fractionated Devonian seawater and oxidized magmatic fluids or remobilized sulfur from existing sulfides. Pb isotopes indicate that Au and Cu. originated from the Mt Morgan intrusions and a particular volcanic strata that shows elevated Cu background. (C) 2002 Elsevier Science B.V. All rights reserved.

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This article analyzes physical symptoms experienced by mid-age Australian women in different stages of the menopause transition. A total of 8,623 women, aged 45 to 50 years in 1996, who participated the mid-age cohort of the Australian Longitudinal Study on Women's Health, completed Survey I in 1996 and Survey 2 in 1998. Women were assigned to I of 6 menopause groups according to their menopausal status at Surveys 1 and 2, and compared on symptoms experienced at Surveys I and 2, adjusted for lifestyle, behavioral and demographic factors. At Survey 1, the most commonly reported symptoms were headaches, back pain, stiff joints, tiredness, and difficulty sleeping. Perimenopausal women were more likely than premenopausal or postmenopausal women to report these symptoms. Hot flushes and night sweats were more common among postmenopausal women. Compared with those who remained premenopausal, women who were in the early stages of menopause or perimenopausal were more likely to report tiredness, stiff joints, difficulty sleeping, and hot flushes at Survey 2. Women who remained perimenopausal were also more likely to report back pain and leaking urine. Compared with premenopausal women, odds ratios for night sweats increased for women in consecutive stages of the menopause transition and remained high in the postmenopausal women.

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Directional solidification of unmodified and strontium modified binary, high-purity aluminium-7 wt% silicon and commercial A356 alloys has been carried out to investigate the mechanism of eutectic solidification. The microstructure of the eutectic growth inter-face was investigated with optical microscopy and Electron Backscattering Diffraction (EBSD). In the commercial alloys, the eutectic solidification inter-face extends in the growth direction and creates a eutectic mushy zone. A planar eutectic growth front is observed in the high-purity alloys. The eutectic aluminium has mainly the same crystallographic orientation as the dendrites in the unmodified alloys and the strontium modified high-purity alloy. A more complex eutectic grain structure is found in the strontium modified commercial alloy. A mechanism involving constitutional undercooling and a columnar to equiaxed transition explains the differences between pure and commercial alloys. It is probably caused by the segregation of iron and magnesium and the activation of nucleants in the commercial alloy. (C) 2002 Acta Materialia Inc. Published by Elsevier Science Ltd. All rights reserved.

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Petrogenetic models for the origin of lamproites are evaluated using new major element, trace element, and Sr, Nd, and Pb isotope data for Holocene lamproites from the Gaussberg volcano in the East Antarctic Shield. Gaussberg lamproites exhibit very unusual Pb isotope compositions (Pb-206/Pb-204 = 17.44-17.55 and Pb-207/Pb-204 = 15.56-15.63), which in common Pb isotope space plot above mantle evolution lines and to the left of the meteorite isochron. Combined with very unradiogenic Nd, such compositions are shown to be inconsistent with an origin by melting of sub-continental lithospheric mantle. Instead, a model is proposed in which late Archaean continent-derived sediment is subducted as K-hollandite and other ultra-high-pressure phases and sequestered in the Transition Zone (or lower mantle) where it is effectively isolated for 2-3 Gyr. The high Pb-207/Pb-204 ratio is thus inherited from ancient continent-derived sediment, and the relatively low Pb-206/Pb-204 ratio is the result of a single stage of U/Pb fractionation by subduction-related U loss during slab dehydration. Sr and Nd isotope ratios, and trace element characteristics (e.g. Nb/Ta ratios) are consistent with sediment subduction and dehydration-related fractionation. Similar models that use variable time of isolation of subducted sediment can be derived for all lamproites. Our interpretation of lamproite sources has important implications for ocean island basalt petrogenesis as well as the preservation of geochemically anomalous reservoirs in the mantle.

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Organic microcavity light-emitting diodes typically exhibit a blueshift of the emitting wavelength with increasing viewing angle. We have modeled the shift of the resonance wavelength for several metal mirrors. Eight metals (Al, Ag, Cr, Ti, Au, Ni, Pt, and Cu) have been considered as top or bottom mirrors, depending on their work functions. The model fully takes into account the dependence of the phase change that occurs on reflection on angle and wavelength for both s and p polarization, as well as on dispersion in the organic layers. Different contributions to the emission wavelength shift are discussed. The influence of the thickness of the bottom mirror and of the choice and thickness of the organic materials inside the cavity has been investigated. Based on the results obtained, guidelines for a choice of materials to reduce blueshift; are given. (C) 2002 Optical Society of America.