Polyaniline/layered zirconium phosphate nanocomposites: Secondary-like doped polyaniline obtained by the layer-by-layer technique

In the present work, nanocomposites of polyaniline (PANI) and layered alpha-Zr(HPO4)(2).H2O (alpha-ZrP) were prepared using two different approaches: (i) the in situ aniline polymerization in the presence of the layered inorganic material and (ii) the layer-by-layer (LBL) assembly using an aqueous solution of the polycation emeraldine salt (ES-PANI) and a dispersion of exfoliated negative slabs of alpha-ZrP. These materials were characterized spectroscopically using mainly resonance Raman scattering at four exciting radiations and electronic absorption in the UV-VIS-NIR region. Structural and textural characterizations were carried out using powder X-ray diffraction (XRD) and scanning electron microscopy (SEM). The polymer obtained by the in situ aniline polymerization is located primarily in the external surface of the inorganic material although aniline monomers were intercalated between alpha-ZrP interlayer regions before oxidative polymerization. Through resonance Raman spectroscopy, it was observed that the formed polymer has semiquinone units (ES-PANI) and also azo bonds (-N = N-), showing that this method results in a polymer with a different structure from the usual ""head-to-tail"" ES-PANI. The LBL assembly of pre-formed ES-PANI and exfoliated alpha-ZrP particles produces homogeneous films with reproducible deposition from layer to layer, up to 20 bilayers. Resonance Raman (lambda(0) = 632.8 nm) spectrum of PANI/ZrP LBL film shows an enhancement in the intensity of the polaronic band at 1333 cm(-1) (nu C-N center dot+) and the decrease of the band intensity at 1485 cm(-1) compared to bulk ES-PANI. Its UV-VIS-NIR spectrum presents an absorption tail in the NIR region assigned to delocalized free charge carrier. These spectroscopic features are characteristic of highly conductive secondary doped PANI suggesting that polymeric chains in PANI/ZrP LBL film have a more extended conformation than in bulk ES-PANI.

Ethanol oxidation reaction on PtCeO(2)/C electrocatalysts prepared by the polymeric precursor method

This paper presents a study of the electrocatalysis of ethanol oxidation reactions in an acidic medium on Pt-CeO(2)/C (20 wt.% of Pt-CeO(2) on carbon XC-72R), prepared in different mass ratios by the polymeric precursor method. The mass ratios between Pt and CeO(2) (3:1, 2:1, 1:1, 1:2, 1:3) were confirmed by Energy Dispersive X-ray Analysis (EDAX). X-ray diffraction (XRD) structural characterization data shows that the Pt-CeO(2)/C catalysts are composed of nanosized polycrystalline non-alloyed deposits, from which reflections corresponding to the fcc (Pt) and fluorite (CeO(2)) structures were clearly observed. The mean crystallite sizes calculated from XRD data revealed that, independent of the mass ratio, a value close to 3 nm was obtained for the CeO(2) particles. For Pt, the mean crystallite sizes were dependent on the ratio of this metal in the catalysts. Low platinum ratios resulted in small crystallites. and high Pt proportions resulted in larger crystallites. The size distributions of the catalysts particles, determined by XRD, were confirmed by Transmission Electron Microscope (TEM) imaging. Cyclic voltammetry and chronoamperometic experiments were used to evaluate the electrocatalytic performance of the different materials. In all cases, except Pt-CeO(2)/C 1:1, the Pt-Ceo(2)/C catalysts exhibited improved performance when compared with Pt/C. The best result was obtained for the Pt-CeO(2)/C 1:3 catalyst, which gave better results than the Pt-Ru/C (Etek) catalyst. (C) 2009 Elsevier B.V. All rights reserved.

Entre a ação legislativa e o constrangimento político: o Conselho Municipal do Distrito Federal (1921-1930)

Este trabalho tem como objetivo central analisar a dinâmica política da capital federal, através da atuação do Conselho Municipal do Distrito Federal, nos anos de 1920. Partindo da ideia de que a década em questão foi assinalada por profundas transformaçõe s e efervescência política, busca - se perceber como o Legislativo carioca operou, politicamente, nos anos em tela. Além de elucidar a relação estabelecida entre os principais poderes municipais no período – os intendentes e os prefeitos – identificamos o co ntexto político - partidário da época; destacamos os principais posicionamentos assumidos pelo Conselho frente determinadas conjunturas - chave da política nacional e lançamos luz sobre a heterogeneidade do Legislativo local nos anos vinte. Para cumprir este propósito esta pesquisa se estrutura a partir dos Anais do Conselho Municipal, do Boletim da Prefeitura, do Regimento Interno do Conselho e da Imprensa carioca, através do jornal Correio da Manhã.

Títulos de dívida corporativa de empresas brasileiras: investir em emissões do mercado interno ou externo?

O objetivo deste trabalho é analisar a diferença de rentabilidade entre emissões de títulos de dívida corporativa de empresas brasileiras nos mercados local e externo. Sob a ótica do investidor interessado em comprar esses títulos, busca-se responder se, protegendo-se contra oscilações de fatores como câmbio e juros e controlando pelo prazo de vencimento, seria mais rentável em média adquirir um título local (debênture) ou externo (bond) de um mesmo emissor. Para isso, analisamos 177 emissões de debêntures e 119 emissões de bonds de 31 companhias não financeiras brasileiras no período entre janeiro de 2004 e abril de 2013. Regressões em painel com efeitos fixos para controlar pelas características de cada emissor verificam que, em média, o título do mercado externo paga de 164 a 197 bps a mais que o do mercado local, e que tal diferença é estatisticamente significante. A diferença deve-se à maior oferta e variedade de títulos de dívida corporativa no mercado externo, à existência de uma demanda cativa de investidores institucionais por debêntures no mercado local e à falta de integração entre os mercados. A participação de pessoas físicas no mercado externo também é identificada como fator relevante, assim como o possível maior custo de estruturação de dívida cobrado por bancos de investimento no mercado doméstico. Dentre as hipóteses formuladas para o motivo dessa diferença de rentabilidade não ser arbitrada, destacam-se o desconhecimento dos investidores e obstáculos operacionais, como custos de transação, impossibilidade de operação no mercado internacional e de venda a descoberto no mercado local. Tal fato causa ainda uma supervalorização das debêntures pela atuação dos investidores mais otimistas. A alta sensibilidade dos investidores institucionais locais à volatilidade dos retornos, também aparece como fator relevante.

Títulos de dívida corporativa de empresas brasileiras: investir em emissões do mercado interno ou externo?

O objetivo deste trabalho é analisar a diferença de rentabilidade entre emissões de títulos de dívida corporativa de empresas brasileiras nos mercados local e externo. Sob a ótica do investidor interessado em comprar esses títulos, busca-se responder se, protegendo-se contra oscilações de fatores como câmbio e juros e controlando pelo prazo de vencimento, seria mais rentável em média adquirir um título local ou externo de um mesmo emissor. Para isso, analisamos 177 emissões de debêntures e 119 emissões de títulos no exterior de 31 companhias não financeiras brasileiras no período entre janeiro de 2004 e abril de 2013. Regressões em painel com efeitos fixos para controlar pelas características de cada emissor verificam que, em média, o título no mercado externo paga de 164 a 197 bps a mais que o do mercado local, e que tal diferença é estatisticamente significante.

Affine processes, arbitrage-Free Term structures of legendre polynomials,and option pricing

Multivariate Affine term structure models have been increasingly used for pricing derivatives in fixed income markets. In these models, uncertainty of the term structure is driven by a state vector, while the short rate is an affine function of this vector. The model is characterized by a specific form for the stochastic differential equation (SDE) for the evolution of the state vector. This SDE presents restrictions on its drift term which rule out arbitrages in the market. In this paper we solve the following inverse problem: Suppose the term structure of interest rates is modeled by a linear combination of Legendre polynomials with random coefficients. Is there any SDE for these coefficients which rules out arbitrages? This problem is of particular empirical interest because the Legendre model is an example of factor model with clear interpretation for each factor, in which regards movements of the term structure. Moreover, the Affine structure of the Legendre model implies knowledge of its conditional characteristic function. From the econometric perspective, we propose arbitrage-free Legendre models to describe the evolution of the term structure. From the pricing perspective, we follow Duffie et al. (2000) in exploring Legendre conditional characteristic functions to obtain a computational tractable method to price fixed income derivatives. Closing the article, the empirical section presents precise evidence on the reward of implementing arbitrage-free parametric term structure models: The ability of obtaining a good approximation for the state vector by simply using cross sectional data.

Um modelo de leilões com conteúdo local: análise e modelagem dos leilões de concessão de blocos exploratórios de petróleo e gás promovidos pela ANP no Brasil

Os leilões para concessão de blocos de petróleo no Brasil utilizam uma equação para formar a pontuação que define o vencedor. Cada participante deve submeter ao leiloeiro um lance composto por três atributos: Bônus de Assinatura (BA), Programa Exploratório Mínimo (PEM) e Conteúdo Local (CL). Cada atributo possui um peso na equação e a nota final de cada participante também depende dos lances ofertados pelos outros participantes. Apesar de leilões de petróleo serem muito estudados na economia, o leilão multi-atributos, do tipo máxima pontuação, ainda é pouco analisado, principalmente como mecanismo de alocação de direitos minerários. Este trabalho destaca a inserção do CL como atributo que transforma a estrutura, do que poderia ser um leilão simples de primeiro preço, em um leilão multi-atributos de máxima pontuação. Demonstra-se como o CL, através da curva de custos do projeto, está relacionado também ao Bônus de Assinatura, outro importante atributo da equação. Para compreender o impacto do fenômeno da inserção do CL, foram criados três casos de leilões hipotéticos, onde, dentre outras simplificações, o programa exploratório mínimo foi fixado para todas as empresas envolvidas. No caso base (Sem CL), simula-se a estrutura de um leilão de primeiro preço, onde apenas o BA define o vencedor do leilão. Já no caso forçado (CLO=CLR), há inserção do atributo CL, sendo o participante obrigado a cumprir o CL ofertado. Por fim, o caso completo (Com Multa) permite que o participante preveja a aplicação de multa por descumprimento do CL ofertado e, caso haja benefício econômico, descumpra efetivamente o CL ofertado. Considerando estes casos, argumenta-se que, apesar do o lucro das empresas e a eficiência do leilão não serem alterados, a inclusão do conteúdo local na estrutura do leilão pode ter reflexos consideráveis na receita do governo.

Coordenação e governança no Programa Territórios da Cidadania: uma análise multi-level a partir do Vale do Ribeira-SP

Poverty in Brazil has been gradually reduced. Among the main reasons, there are public policies for universalization of rights. On the other hand, the municipalities' Human Development Index indicates scenarios of growing inequality. In other words, some regions, basically of rural character, were left behind in that process of development. In 2008, the “Territórios da Cidadania” (Territories of Citizenship) Program was launched by the federal government, under high expectations. It was proposed to develop those regions and to prioritize the arrival of ongoing federal public policies where they were most demanded. The program has shown an innovative arrangement which included dozens of ministries and other federal agencies, state governments, municipalities and collegialities to the palliative management and control of the territory. In this structure, both new and existing jurisdictions came to support the program coordination. This arrangement was classified as an example of multi-level governance, whose theory has been an efficient instrument to understand the intra- and intergovernmental relations under which the program took place. The program lasted only three years. In Vale do Ribeira Territory – SP, few community leaderships acknowledge it, although not having further information about its actions and effects. Against this background, the approach of this research aims to study the program coordination and governance structure (from Vale Territory, considered as the most local level, until the federal government), based on the hypothesis that, beyond the local contingencies in Vale do Ribeira, the layout and implementation of the Territories of Citizenship Program as they were formulated possess fundamental structural issues that hinder its goals of reducing poverty and inequality through promoting the development of the territory. Complementing the research, its specific goal was to raise the program layout and background in order to understand how the relations, predicted or not in its structure, were formulated and how they were developed, with special attention to Vale do Ribeira-SP. Generally speaking, it was concluded that the coordination and governance arrangement of the Territories of Citizenship Program failed for not having developed qualified solutions to deal with the challenges of the federalist Brazilian structure, party politics, sectorized public actions, or even the territory contingencies and specificities. The complexity of the program, the poverty problem proposed to be faced, and the territorial strategy of development charged a high cost of coordination, which was not accomplished by the proposal of centralization in the federal government with internal decentralization of the coordination. As the presidency changed in 2011, the program could not present results that were able to justify the arguments for its continuation, therefore it was paralyzed, lost its priority status, and the resources previously invested were redirected.

Análise toxicológica in vitro e in vivo de uma fucana antitrombótica da alga marrom Spatoglossum schdöederi

Fucan is a term used to denominate a family of sulfated polysaccharides rich in L-fucose. They are extracted mainly from the extracellular matrix of brown algae and echinoderms. The brown alga Spatoglossum schröederi (Dictyotaceae) has three heterofucans named A, B and C. Our research group have been extracted non anticoagulant heterofucan from S. schröederi which possess antithrombotic activity in vivo. However, their toxicity in vitro and in vivo has not yet been determined. For the results in toxicity in vitro, we observed that the fucan A at 20, 500 and 1000 μg/plate showed no mutagenic activity in Kado test (Microsuspension), when the bacterial strains TA97a, TA98, TA100 and TA102, with and without S9 were used. The comet assay showed that fucan A (from 20 to 1000 μg/mL) did not cause any genotoxic effect on CHO cells. There was no damage to the DNA of these cells, as evidenced by the tail length and tail moment, which were similar to that found for the negative control. The fucan A from S. schröederi was administered at 20 μg/g of rat (dose which it showed high antithrombotic activity) during two months. After that, the animals were killed and examined. The data showed that fucan A did not cause any change in biochemistry and hematological parameters, as well as, in the morphology and size of the rat s organs analyzed. In conclusion, this study indicates that fucan is a compound with potential pharmacological that has no toxicity

Association of an insulin-like growth factor 1 gene microsatellite with phenotypic variation and estimated breeding values of growth traits in Canchim cattle

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Podcast na educação brasileira: natureza, potencialidades e implicações de uma tecnologia da comunicação

This thesis aims to build a panoramic analysis with the intention of providing the theoretical initial a thought articulated educational of podcast, a technology orality distributed demand. This joint search considering the various spheres that educational technology in Brazilian use, both in school and non-school contexts, including scenarios and distance. This study unites questions addressed piecemeal in the area to new perspectives about the podcast, in order to characterize its nature, examining such technology from a perspective of educational technology itself, as well as unveiling its main potentials and implications. The survey was conducted from the combined use of quantitative and qualitative categories, with emphasis on the last one. The method of participant observation was followed by immersion of the researcher in the audience groups of Brazilians podcasts. Data collection with sources held in non-school contexts, from a look at targeted interactions given the blogs of Brazilian productions, as well as from open-ended interviews with producers - made online - besides giving themselves from the hearing itself about five hundred podcasts of Brazil. In the school context, the research focused on a literature review of the literature of the study area. Were added to the corpus described statistics derived mainly from "Podpesquisa 2009," Numerical major survey on the use of podcasts in Brazil. The articulation and analysis of the collected data, we used the concept of Education Paulo Freire (1971, 1987), so that, understanding it as synonymous to communication - understood this concept in Freire - were able to reveal the various ramifications educational podcast Brazilian atmosphere permeated by a dialogic between its participants. Moreover, the ideas of Célestin Freinet (1998) about the cooperation, while education practice, conducted the analyzes productive technology addressed in this work. The philosophical thought of Andrew Feenberg (2003) on the notion of "technologies" buoyed technological design elaborate. Such consideration provided the foundation for the reflections and proposals offered in this study, which, in the characterization of the oral nature of the podcast - especially their version for the deaf - appropriated the placements Luis Antonio Marcuschi (2001) about the relationship between orality and writing. In addition to these references, several other authors were considered, dealing with issues that pervade the theme here delimited, contemplating discussions on topics such as educational interest, online production, inclusive education, among other aspects. At the end, there was the podcast as a technology, while still reproducing social asymmetries Brazilian fairly directed at promoting mitigations hierarchical and open production in digital orality promotes. In view of its technical and educational implications in national use, the technology study has revealed potential relevant to the sophistication of teaching practices with orality, in various contexts, and proved adequate to serve as a motto to the revision of school practices, to even the very role of the school. This, by the prospects unveiled here, can, through the podcast, mitigate their questions reproductivist to constitute themselves as under privileged communication, boosted by critical rescue and sophistication of management through the most basic education component: speech

Técnicas visuais de localização e mapeamento simultâneos sem extração de primitivas geométricas da imagem

In Simultaneous Localization and Mapping (SLAM - Simultaneous Localization and Mapping), a robot placed in an unknown location in any environment must be able to create a perspective of this environment (a map) and is situated in the same simultaneously, using only information captured by the robot s sensors and control signals known. Recently, driven by the advance of computing power, work in this area have proposed to use video camera as a sensor and it came so Visual SLAM. This has several approaches and the vast majority of them work basically extracting features of the environment, calculating the necessary correspondence and through these estimate the required parameters. This work presented a monocular visual SLAM system that uses direct image registration to calculate the image reprojection error and optimization methods that minimize this error and thus obtain the parameters for the robot pose and map of the environment directly from the pixels of the images. Thus the steps of extracting and matching features are not needed, enabling our system works well in environments where traditional approaches have difficulty. Moreover, when addressing the problem of SLAM as proposed in this work we avoid a very common problem in traditional approaches, known as error propagation. Worrying about the high computational cost of this approach have been tested several types of optimization methods in order to find a good balance between good estimates and processing time. The results presented in this work show the success of this system in different environments

Síntese e caracterização estrutural do niobato de potássio e estrôncio com estrutura tipo Tetragonal Tungstênio Bronze TTB

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Medidas e análise estatística em sinais bioelétricos sobre pontos de acupuntura

In the 20th century, the acupuncture has spread on occident as a complementary practice of heath care. This fact has motivated the international scientific community to invest in research that seek to understand why acupuncture works. In this work we compare statistically volt age fluctuation of bioelectric signals caught on the skin at an acupuncture point (IG 4) another nearby on acupuncture point. The acquisition of these signals was performed utilizing an electronic interface with a computer, which was based on an instrumentation amplifier designed with adequate specifications to this end. On the collected signals from a sample of 30 volunteers we have calculated major statistics and submitted them to pairing t-test with significance leveI a = O, 05. We have estimated to bioelectric signals the following parameters: standard deviation, asymmetry and curtose. Moreover, we have calculated the self-correlation function matched by on exponential curve we have observed that the signal decays more rapidly from a non-acupoint then from an acupoint. This fact is an indicative of the existence of information in the acupoint

In vivo CYP2E1 phenotyping as a new potential biomarker of occupational and experimental exposure to benzene

Assessing CYP2E1 phenotype in vivo may be important to predict individual susceptibility to those chemicals, including benzene, which are metabolically activated by this isoenzyme. Chlorzoxazone (CHZ), a specific CYP2E1 substrate, is readily hydroxylated to 6-OH-chlorzoxazone (6-OH-CHZ) by liver CYP2E1 and the metabolic ratio 6-OH-CHZ/CHZ in serum (MR) is a specific and sensitive biomarker of CYP2E1 activity in vivo in humans. We used this MR as a potential biomarker of effect in benzene-treated rats and, also, in humans occupationally exposed to low levels of benzene. Male Sprague-Dawley rats (375-400 g b.w.) were treated i.p. for 3 days with either a 0.5 ml solution of benzene (5 mmol/kg b.w.) in corn oil, or 0.5 ml corn oil alone. Twenty-four hours after the last injection, a polyethylene glycol (PEG) solution of CHZ (20 mg/kg b.w.) was injected i.p. in both treated and control animals. After 2, 5.10,15, 20,30,45, 60, 90, 120, 180, and 240 min from injection, 0.2 ml blood was taken from the tip tail and stored at -20 degrees C until analysis. A modified reverse phase HPLC method using a 5 mu m Ultrasphere C18 column equipped with a direct-connection ODS guard column, was used to measure CHZ and its metabolite 6-OH-CHZ in serum. No statistically significant difference in the MR was observed, at any sampling time, between benzene-treated and control rats. The concentration-versus-time area under the curve (AUC), however, was lower (p < 0.05, Mann-Whitney test), whereas the systemic clearance was higher (p < 0.05) in treated than in control rats. Eleven petrochemical workers occupationally exposed to low levels of airborne benzene (mean +/- SD, 25.0 +/- 24.4 mu g/m(3)) and 13 non-exposed controls from the same factory (mean +/- SD, 6.7 +/- 4.0 mu g/m(3)) signed an informed consent form and were administered 500 mg CHZ p.o. Two hours later a venous blood sample was taken for CHZ and 6-OH-CHZ measurements. Despite exposed subjects showed significantly higher levels of t,t-MA and S-PMA, two biomarkers of exposure to benzene, than non-exposed workers, no difference in the MR mean values +/- SD was found between exposed (0.59 +/- 0.29) and non-exposed (0.57 +/- 0.23) subjects. So, benzene was found to modify CHZ disposition, but not CYP2E1 phenotype in benzene-treated rats, nor in workers exposed to benzene, probably due to the levels of exposure being too low. (C) 2009 Elsevier B.V. All rights reserved.