A dramatic isotope effect in the reaction of ClSiH with trimethylsilane-1-d: experimental evidence for intermediate complexes in silylene Si-H(D) insertion reactions

A kinetic isotope effect (kD/kH) of 7.4 has been found for the reaction of chlorosilylene with trimethysilane (Me3SiD vs Me3SiH). Such a value can be accounted for by theoretical modelling, but only if an internal rearrangement of the initially form complex is included in the mechanism. This provides the first concrete evidence for such complexes.

Transcription profiling in human platelets reveals LRRFIP1 as a novel protein regulating platelet function

Within the healthy population, there is substantial, heritable, and interindividual variability in the platelet response. We explored whether a proportion of this variability could be accounted for by interindividual variation in gene expression. Through a correlative analysis of genome-wide platelet RNA expression data from 37 subjects representing the normal range of platelet responsiveness within a cohort of 500 subjects, we identified 63 genes in which transcript levels correlated with variation in the platelet response to adenosine diphosphate and/or the collagen-mimetic peptide, cross-linked collagen-related peptide. Many of these encode proteins with no reported function in platelets. An association study of 6 of the 63 genes in 4235 cases and 6379 controls showed a putative association with myocardial infarction for COMMD7 (COMM domain-containing protein 7) and a major deviation from the null hypo thesis for LRRFIP1 [leucine-rich repeat (in FLII) interacting protein 1]. Morpholino-based silencing in Danio rerio identified a modest role for commd7 and a significant effect for lrrfip1 as positive regulators of thrombus formation. Proteomic analysis of human platelet LRRFIP1-interacting proteins indicated that LRRFIP1 functions as a component of the platelet cytoskeleton, where it interacts with the actin-remodeling proteins Flightless-1 and Drebrin. Taken together, these data reveal novel proteins regulating the platelet response.

Multistep π dimerization of tetrakis(n-decyl)heptathienoacene radical cations: a combined experimental and theoretical study

Radical cations of a heptathienoacene a,b-substituted with four n-decyl side groups (D4T7C+) form exceptionally stable p-dimer dications already at ambient temperature (Chem. Comm. 2011, 47, 12622). This extraordinary p-dimerization process is investigated here with a focus on the ultimate[D4T7C+]2 p-dimer dication and yet-unreported transitoryspecies formed during and after the oxidation. To this end, we use a joint experimental and theoretical approach that combines cyclic voltammetry, in situ spectrochemistry and spectroelectrochemistry, EPR spectroscopy, and DFT calculations. The impact of temperature, thienoacene concentration, and the nature and concentration of counteranions on the p-dimerization process is also investigated in detail. Two different transitory species were detected in the course of the one-electron oxidation: 1) a different transient conformation of the ultimate [D4T7C+]2 p-dimer dications, the stability of which is strongly affected by the applied experimental conditions, and 2) intermediate [D4T7]2C+ p-dimer radical cations formed prior to the fully oxidized [D4T7]2C+ p-dimer dications. Thus, this comprehensive work demonstrates the formation of peculiar supramolecular species of heptathienoacene radical cations, the stability, nature, and structure of which have been successfully analyzed. We therefore believe that this study leads to a deeper fundamental understanding of the mechanism of dimer formation between conjugated aromatic systems.

Estudo tomográfico convencional e computadorizado da região posterior da mandíbula

Em uma amostra constituída de oito mandíbulas humanas secas, foram selecionados quatro sítios na região de segundo pré-molar a primeiro molar, dos de cada lado. Um come de gutta-percha foi fixado com adesivo instantâneo na face lingual da mandíbula, na região de cada sítio. Para simular a presença de tecidos moles, as mandíbulas foram incluídas em parafina. Para a correta seleção dos sítios de exame, a tomografia hipocicloidal, foi utilizazda uma incidência radiográfica oclusa total dee cada mandíbula, cuja imagem foi capturada par ao monitor. Sobre a mesma foram selecionados os sítos para a obtenção de cortes ortorradiais de tomografia hipocicloidal, com espessura de 2 mm, através do equipamento IS2000 COMM-CATR. A tomografia computadoriza helicoidal foi obtida através do equipamento Twin FlashR e as reconstruções ortorradiais, cada uma com 2 mm de espessura, foram realizadas com o softtware Denta CTr. A mandíbulas foram seccionadas nos sítios propostos e todas as imagens, digitalizadas através de scanner. As imagens de tomografia hipocicloidal foram redimensionadas de acordo com a magnificação de 26%. Dois examinadores previamente calibrados realizaram medidas de distâncias e horizontais das imagens digitais apresentadas no monitor, sob condições ideiais de visualizaação. As comparações intra e interexaminador não mostraram variabilidade significativas. As medidas obtidas pelos dois métodos foram comparadas ao padrão-ouro e as diferenças encontradas foram menores que 0,1 mm. Tais resultados permitem concluir que, na presente amostra, tanto a tomografia computadoriza helicoidal quando a tomografia hipocicloidal permite obtenção segura das medidas verticais e horizontais propostas na região posterior mandíbula.

The Beatles: ensaio sobre a ética do amor

The thesis intends to discuss the ethics by the way of love. So, it uses as a mention the musical work and the set of attitudes of the group that changed the way of thinking across the 20th Century mass-comm, entering a new way of thinking about the World: The Beatles. Analyzing the lyrics and the writing of the songs was searched the comprehension of he intrinsic love message at the Ethics it expresses. At the musical art of The Beatles political messages had been announced in a time that the World sought a Ethic way beyond the several declared war and the Cold War. Taking the Edgar Morin works as a base, O método 6, Ética (2005), it sought to understand the idea who permeates the human relations: the good, the possible, the necessary. Another works used as a cognitive base were Meus demônios (2003), Cultura de massas no Século XX: neurose (2005), Cultura de massas no Século XX (2006), The Beatles Anthology (2000) and Many years from now (2000). Holding the Ethics idea showed by Morin were established imaginary lines that perpass the behavior of the group known in the entire World understood till nowadays as tolerance, comprehension, peace, love and endurance messengers. The Beatles operate during the sixties a musical reborn, which allowed to the people the discussion and the reflexion about the World and the human being new behavior,endurance but acting with tolerance. Permeating the basic study, we find the Beatles way, the group origin, the fast walk till success, the spiritual choice, who guide their behavior and the end of the band. The music used as a masscomp instrument passes by the condition of a simple way of communicating. It deeply action feeds feelings, allows transcendence and is showed as target of human being transformation. The Ethics in music passes by the ideological barriers and becomes to comprehension with a clear synthony for the man, cause the polyphony and the new musical order establish the messages worldwide

Temperature effect on seed germination in Canna indica L. (Cannaceae)

Comm indica L. is an herbaceous species with ornamental and medicinal value, having seeds with a hard seed coat. This study aimed to test the influence of constant temperatures ranging from 5 to 45 C, at 5 C intervals, on the germination of scarified seeds. Data obtained were analyzed through the model of enthalpy of activation in order to obtain the optimum temperature range for germination. The species showed seed germinability in a wide temperature range (10-40 degrees C) being the optimal temperature range between 13.84 and 34.41 degrees C, determined by the enthalpy of activation.

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Um intelectual na trincheira: José Honório Rodrigues, intérprete do Brasil

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A log-Birnbaum-Saunders regression model with asymmetric errors

This paper introduces a skewed log-Birnbaum-Saunders regression model based on the skewed sinh-normal distribution proposed by Leiva et al. [A skewed sinh-normal distribution and its properties and application to air pollution, Comm. Statist. Theory Methods 39 (2010), pp. 426-443]. Some influence methods, such as the local influence and generalized leverage, are presented. Additionally, we derived the normal curvatures of local influence under some perturbation schemes. An empirical application to a real data set is presented in order to illustrate the usefulness of the proposed model.

Synthesis, characterization, optical absorption, luminescence and defect centres in Er3+ and Yb3+ co-doped MgAl2O4 phosphors

The Er3+-Yb3+ co-doped MgAl2O4 phosphor powders have been prepared by the combustion method. The phosphor powders are well characterized by X-ray diffraction (XRD) and energy dispersive (EDX) techniques. The absorption spectrum of Er3+/Er3+-Yb3+ doped/co-doped phosphor powder has been recorded in the UV-Vis-NIR region of the electro-magnetic spectrum. The evidence for indirect pumping under 980 nm excitation of Er3+ from Yb3+ was observed in the MgAl2O4 matrix material. Electron spin resonance (ESR) studies were carried out to identify the defect centres responsible for the thermally stimulated luminescence (TSL) process in MgAl2O4:Er3+ phosphor. Three defect centres were identified in irradiated phosphor by ESR measurements which were carried out at room temperature and these were assigned to an O- ion and F+ centres. O- ion (hole centre) appears to correlate with the low temperature TSL peak at 210 A degrees C and one of the F+ centres (electron centre) is related to the high temperature peak at 460 A degrees C.

Synthesis, characterisation, luminescence and defect centres in solution combustion synthesised CaZrO3:Tb3+ phosphor

Tb3+ doped CaZrO3 has been prepared by an easy solution combustion synthesis method. The combustion derived powder was investigated by X-ray diffraction, Fourier-transform infrared spectrometry and scanning electron microscopy techniques. A room temperature photoluminescence study showed that the phosphors can be efficiently excited by 251 nm light with a weak emission in the blue and orange region and a strong emission in green light region. CaZrO3:Tb3+ exhibits three thermoluminescence (TL) glow peaks at 126 degrees C, 200 degrees C and 480 degrees C. Electron Spin Resonance (ESR) studies were carried out to study the defect centres induced in the phosphor by gamma irradiation and also to identify the centres responsible for the TL peaks. The room temperature ESR spectrum of irradiated phosphor appears to be a superposition of two distinct centres. One of the centres (centre I) with principal g-value 2.0233 is identified as an O- ion. Centre II with an axial symmetric g-tensor with principal values g(parallel to) = 1.9986 and g(perpendicular to) = 2.0023 is assigned to an F+ centre (singly ionised oxygen vacancy). An additional defect centre is observed during thermal annealing experiments and this centre (assigned to F+ centre) seems to originate from an F centre (oxygen vacancy with two electrons). The F centre and also the F+ centre appear to correlate with the observed high temperature TL peak in CaZrO3:Tb3+ phosphor. (c) 2012 Elsevier B.V. All rights reserved.

Structural and textural studies of NiO impregnation in mesoporous ZrO2-CeO2 for catalysis applications.

The synthesis of zirconia-based ordered mesoporous structures for catalytic applications is a research area under development. These systems are also potential candidates as anodes in intermediate temperature solid oxide fuel cells (it-SOFC) due to an enhancement on their surface area [1-4]. The structural features of mesoporous zirconia-ceria materials in combination with oxygen storage/release capacity (OSC) are crucial for various catalytic reactions. The direct use of hydrocarbons as fuel for the SOFC (instead of pure H2), without the necessity of reforming and purification reactors can improve global efficiency of these systems [4]. The X-ray diffraction data showed that ZrO2-x%CeO2 samples with x>50 are formed by a larger fraction of the cubic phase (spatial group Fm3m), while for x<50 the major crystalline structure is the tetragonal phase (spatial group P42/nmc). The crystallite size of the cubic phase increases with increase in ceria content. The tetragonal crystallite size decreases when ceria content increases. After impregnation, the Rietveld analysis showed a NiO content around 60wt.% for all samples. The lattice parameters for the ZrO2 tetragonal phase are lower for higher ZrO2 contents, while for all samples the cubic NiO and CeO2 parameters do not present changes. The calculated densities are higher for higher ceria content, as expected. The crystallite size of NiO are similar (~20nm) for all samples and 55nm for the NiO standard. Nitrogen adsorption experiments revealed a broader particle size distribution for higher CeO2 content. The superficial area values were around 35m2/g for all samples, the average pore diameter and pore volumes were higher when increasing ceria content. After NiO impregnation the particle size distribution was the same for all samples, with two pore sizes, the first around 3nm and a broader peak around 10nm. The superficial area increased to approximately 45m2/g for all samples, and the pore volume was also higher after impregnation and increased when ceria content increased. These results point up that the impregnation of NiO improves the textural characteristics of the pristine material. The complementary TEM/EDS images present a homogeneous coating of NiO particles over the ZrO2-x%CeO2 support, showing that these samples are excellent for catalysis applications. [1] D. Y. Zhao, J. Feng, Q. Huo, N. Melosh, G. H. Fredrickson, B. F. Chmelka, G. D. Stucky, Science 279, 548-552 (1998). [2] C. Yu, Y. Yu, D. Zhao, Chem. Comm. 575-576 (2000). [3] A. Trovarelli, M. Boaro, E. Rocchini, C. de Leitenburg, G. Dolcetti, J. Alloys Compd. 323-324 (2001) 584-591. [4] S. Larrondo, M. A. Vidal, B. Irigoyen, A. F. Craievich, D. G. Lamas, I. O. Fábregas, et al. Catal. Today 107–108 (2005) 53-59.