Electronic, vibrational and related properties of group IV metal oxides by ab initio calculations

We present our theoretical results for the structural, electronic, vibrational and optical properties of MO(2) (M = Sn, Zr, Hf and Ti) obtained by first-principles calculations. Relativistic effects are demonstrated to be important for a realistic description of the detailed structure of the electronic frequency-dependent dielectric function, as well as of the carrier effective masses. Based on our results, we found that the main contribution of the high values calculated for the oxides dielectric constants arises from the vibrational properties of these oxides, and the vibrational static dielectric constant values diminish with increasing pressure. (c) 2008 Elsevier B.V. All rights reserved.

ASSOCIATED A-TYPE SUBALKALINE AND HIGH-K CALC-ALKALINE GRANITES IN THE ITU GRANITE PROVINCE, SOUTHEASTERN BRAZIL: PETROLOGICAL AND TECTONIC SIGNIFICANCE

The 590-580 Ma Itu Granite Province (IGP) is a roughly linear belt of post-orogenic granite plutons similar to 60 km wide extending for some 350 km along the southern edge of the Apia-Guaxupe Terrane in southeastern Brazil. Typical components are subalkaline A-type granites (some with rapakivi texture) that crystallized at varied, but mostly strongly oxidizing conditions, and contrast with a coeval association of also oxidized high-K calc-alkaline granites in terms of major (e. g., lower Ca/Fe) and trace elements (higher Nb, Y, Zr). Mantle-derived magmas (such as those forming the LILE-rich Piracaia Monzodiorite, with epsilon(Nd(t)) = -7 to -10, (87)Sr/(86)Sr((t)) = 0.7045-0.7055) are inferred to derive from enriched subcontinental lithosphere modified during previous subduction, and may have played a role in the generation of the A-type granites, adding melts or fluids or both to the lower crust from which the latter were generated. The IGP is interpreted as a reflection of crust uplift and increased heat flux during ascent of hot, less dense asthenosphere after continental collision, probably reflecting breakoff of an oceanic slab coeval to the right-lateral accretion of a terrane related to the Mantiqueira Orogenic System.

The Cariris Velhos tectonic event in Northeast Brazil

The Borborema Province in northeastern South America is a typical Brasiliano-Pan-African branching system of Neoproterozoic orogens that forms part of the Western Gondwana assembly. The province is positioned between the Sao Luis-West Africa craton to the north and the Sao Francisco (Congo-Kasai) craton to the south. For this province the main characteristics are (a) its subdivision into five major tectonic domains, bounded mostly by long shear zones, as follows: Medio Coreau, Ceara Central, Rio Grande do Norte, Transversal, and Southern; (b) the alternation of supracrustal belts with reworked basement inliers (Archean nuclei + Paleoproterozoic belts); and (c) the diversity of granitic plutonism, from Neoproterozoic to Early Cambrian ages, that affect supracrustal rocks as well as basement inliers. Recently, orogenic rock assemblages of early Tonian (1000-920 Ma) orogenic evolution have been recognized, which are restricted to the Transversal and Southern domains of the Province. Within the Transversal Zone, the Alto Pajeu terrane locally includes some remnants of oceanic crust along with island arc and continental arc rock assemblages, but the dominant supracrustal rocks are mature and immature pelitic metasedimentary and metavolcaniclastic rocks. Contiguous and parallel to the Alto Pajeu terrane, the Riacho Gravata subterrane consists mainly of low-grade metamorphic successions of metarhythmites, some of which are clearly turbiditic in origin, metaconglomerates, and sporadic marbles, along with interbedded metarhyolitic and metadacitic volcanic or metavolcaniclastic rocks. Both terrane and subterrane are cut by syn-contractional intrusive sheets of dominantly peraluminous high-K calc-alkaline, granititic to granodioritic metaplutonic rocks. The geochemical patterns of both supracrustal and intrusive rocks show similarities with associations of mature continental arc volcano-sedimentary sequences, but some subordinate intra-plate characteristics are also found. In both the Alto Pajeu and Riacho Gravata terranes, TIMS and SHRIMP U-Pb isotopic data from zircons from both metavolcanic and metaplutonic rocks yield ages between 1.0 and 0.92 Ga, which define the time span for an event of orogenic character, the Cariris Velhos event. Less extensive occurrences of rocks of Cariris Velhos age are recognized mainly in the southernmost domains of the Province, as for example in the Polo Redondo-Maranco terrane, where arc-affinity migmatite-granitic and meta-volcano-sedimentary rocks show U-Pb ages (SHRIMP data) around 0.98-0.97 Ga. For all these domains, Sm-Nd data exhibit Tom model ages between 1.9 and 1.1 Ga with corresponding slightly negative to slightly positive epsilon(Nd)(t) values. These domains, along with the Borborema Province as a whole, were significantly affected by tectonic and magmatic events of the Brasiliano Cycle (0.7-0.5 Ga), so that it is possible that there are some other early Tonian rock assemblages which were completely masked and hidden by these later Brasiliano events. Cariris Velhos processes are younger than the majority of orogenic systems at the end of Mesoproterozoic Era and beginning of Neoproterozoic throughout the world, e.g. Irumide belt, Kibaride belt and Namaqua-Natal belt, and considerably younger than those of the youngest orogenic process (Ottawan) in the Grenvillian System. Therefore, they were probably not associated with the proposed assembly of Rodinia. We suggest, instead, that Cariris Velhos magmatism and tectonism could have been related to a continental margin magmatic arc, with possible back-arc associations, and that this margin may have been a short-lived (<100 m.y.) leading edge of the newly assembled Rodinia supercontinent. (C) 2009 Elsevier Ltd. All rights reserved.

Thermoluminescence properties of natural zoisite mineral under gamma-irradiations and high temperature annealing

Natural silicate mineral of zoisite, Ca(2)Al(3)(SiO(4))(Si(2)O(7))O(OH), has been investigated concerning gamma-radiation, UV-radiation and high temperature annealing effects on thermoluminescence (TL). X-ray diffraction (XRD) measurement confirmed zoisite structure and X-ray fluorescence (XRF) analysis revealed besides Si, Al and Ca that are the main crystal components, other oxides of Fe, Mg, Cr, Na, K, Sr, Ti, Ba and Mn which are present in more than 0.05 wt%. The TL glow curve of natural sample contains (130-150), (340-370) and (435-475)degrees C peaks. Their shapes indicated a possibility that they are result of composition of two or more peaks strongly superposed, a fact confirmed by deconvolution method. Once pre-annealed at 600 degrees C for 1 h, the shape of the glow curves change and the zoisite acquires high sensitivity. Several peaks between 100 and 400 degrees C appear superposed, and the high temperature peak around 435 degrees C cannot be seen. The ultraviolet radiation, on the other hand, produces one TL peak around 130 degrees C and the second one around 200 degrees C and no more. (C) 2010 Elsevier B.V. All rights reserved.

High specific surface area LaFeCo perovskites-Synthesis by nanocasting and catalytic behavior in the reduction of NO with CO

LaFe(1-x)CO(x)O(3) perovskites were conventionally or nanocasting synthesized. The nanocasting involved the preparation of a micro-mesoporous carbon mould using a Silica Aerosil 200 and a carbon source. Then, perovskites were carbon cast at 800 degrees C. The solids were characterized by XRD, N(2) sorption, FTIR, TGA/DTG, SEM and TEM. N(2) sorption evidenced that the nanocast perovskites did not show significant intraparticle porosity in despite of their enhanced (30-50 m(2)/g) specific surface area (SSA). Nevertheless, TEM images, XRD and Rietveld refinement data showed that the solids are constituted at least by 97 wt% of perovskite phase and by agglomerates smaller than 100 nm constituted by crystallites of about 6 nm. TGA/DTG results demonstrated carbon oxidation during the perovskite formation, thus eliminating the template effect and facilitating the occurrence of sintering, which limited the SSA increase. The nanocast perovskites were more active in the reduction of NO than the uncast ones, behavior that was attributed to the increase in their SSA that allows the exposure of a higher number of accessible active sites. However, the perovskite composition and the presence of impurities can reduce the effect of the improvement of the textural properties. The nanocast perovskites also showed high thermal and catalytic stability, corroborating their potential as catalysts for the studied reaction. (C) 2009 Elsevier B.V. All rights reserved.

An investigation of the activation process of high temperature shift catalyst

The aim of this work is to address the activation process of a high temperature shift (HTS) catalyst, composed of Fe2O3/Cr2O3/CuO, by analyzing it before activation (HTS-V) and after activation (HTS-A) using complementary characterization techniques. The textural and morphological characterizations were done by transmission electron rnicroscopy (TEM) and nitrogen physisorption at 77 K; crystallographic structure was confirmed by X-ray diffraction (XRD); electronic structure was analyzed by X-ray absorption spectroscopy (XAS) and the chemical composition of the catalyst`s surface was obtained by X-ray photoelectron spectroscopy (XPS). The investigation pointed out that the HTS-V catalyst presents good textural and morphological properties, which are not deeply affected by the activation process (sample HTS-A). The iron oxide phase in the HTS-V catalyst is hematite whereas in HTS-A catalyst is magnetite with Fe2+/Fe3+ ratio close to the expected value (0.5). For both samples, the Cr ions seem to be incorporated in the iron oxide lattice with higher concentration at particle surface. In the HTS-V catalyst, the Cu ions have oxidation number II and occupy in average distorted octahedral sites; after the activation, the Cu ions are partially reduced, suggesting that the reduction of the Cu species is complex. (C) 2007 Elsevier B.V. All rights reserved.

Effects of a high fat diet on liver mitochondria: increased ATP-sensitive K(+) channel activity and reactive oxygen species generation

High fat diets are extensively associated with health complications within the spectrum of the metabolic syndrome. Some of the most prevalent of these pathologies, often observed early in the development of high-fat dietary complications, are non-alcoholic fatty liver diseases. Mitochondrial bioenergetics and redox state changes are also widely associated with alterations within the metabolic syndrome. We investigated the mitochondrial effects of a high fat diet leading to non-alcoholic fatty liver disease in mice. We found that the diet does not substantially alter respiratory rates, ADP/O ratios or membrane potentials of isolated liver mitochondria. However, H(2)O(2) release using different substrates and ATP-sensitive K(+) transport activities are increased in mitochondria from animals on high fat diets. The increase in H(2)O(2) release rates was observed with different respiratory substrates and was not altered by modulators of mitochondrial ATP-sensitive K(+) channels, indicating it was not related to an observed increase in K(+) transport. Altogether, we demonstrate that mitochondria from animals with diet-induced steatosis do not present significant bioenergetic changes, but display altered ion transport and increased oxidant generation. This is the first evidence, to our knowledge, that ATP-sensitive K(+) transport in mitochondria can be modulated by diet.