Methanol and ethanol electro-oxidation on Pt-SnO(2) and Pt-Ta(2)O(5) sol-gel-modified boron-doped diamond surfaces

The search for more efficient anode catalyst than platinum to be used in direct alcohol fuel cell systems is an important challenge. In this study, boron-doped diamond film surfaces were modified with Pt, Pt-SnO(2) and Pt-Ta(2)O(5) nano-crystalline deposits by the sol-gel method to study the methanol and ethanol electro-oxidation reactions in acidic medium. Electrochemical experiments carried out in steady-state conditions demonstrate that the addition of SnO(2) to Pt produces a very reactive electrocatalyst that possibly adsorbs and/or dissociate ethanol more efficiently than pure Pt changing the onset potential of the reaction by 190 mV toward less positive potentials. Furthermore, the addition of Ta(2)O(5) to Pt enhances the catalytic activity toward the methanol oxidation resulting in a negative shift of the onset potential of 170 mV. These synergic effects indicate that the addition of these co-catalysts inhibits the poisoning effect caused by strongly adsorbed intermediary species. Since the SnO(2) catalyst was more efficient for ethanol oxidation, it could probably facilitate the cleavage of the C-C bond of the adsorbed intermediate fragments of the reaction. (C) 2009 Elsevier B.V. All rights reserved.

Síntese e análise estrutural de novos ciclopaladatos e síntese de N-heterociclos a partir de ciclopaladatos e alenos

Os compostos de paládio vêm apresentado uma vasta linha de aplicação, tanto como catalisadores como precursores em reações de síntese orgânica. Dentre esses compostos, os ciclopaladatos, que são compostos cíclicos com uma ligação Pd-heteroátomo, permite a formação de novas estruturas cíclicas contendo algum heteroátomo, como nitrogênio, oxigênio ou enxofre. Neste trabalho foram sintetizadas aminas propargílicas capazes de se coordenar a sais de paládio, formando novos ciclopaladatos através da reação de cloropaladação. Esses compostos se encontram na forma de dímeros e podem apresentar-se como diferentes isômeros. Estudos espectroscópicos, tais como RMN de 1H, 13C e raios-X de monocristais foram realizados para a elucidação estrutural desses novos compostos. Além dos isômeros geométricos clássicos (cisóide e transóide) foram observados pela primeira vez a formação de atropoisômeros. Esses ciclopaladatos, contendo nitrogênio ligado ao paládio, foram testados frente a alenos diferentemente substituídos, mostrando que ocorre a inserção do aleno na ligação Pd-C e, seguido da depaladação, ocorre a formação de novos compostos heterocíclicos a seis membros. Alguns ciclopaladatos, quando em solução, podem apresentar certa instabilidade, ocorrendo a decomposição do ciclopaladato com a regeneração do alcino precursor do respectivo ciclopaladato. Assim, estudou-se a reação de decomposição de diferentes ciclopaladatos, chamada de retrocloropaladação, utilizando a técnica de RMN de 1H em diferentes intervalos de tempo.

Um estudo sobre os determinantes do prêmio de risco da dívida pública no Brasil

O objetivo deste trabalho é identificar os determinantes do prêmio de risco da dívida pública no Brasil, uma vez que a redução deste permitirá que as taxas de juros na economia brasileira sejam compatíveis com um maior crescimento econômico. Os resultados empíricos obtidos não rejeitam as hipóteses dos modelos de Dornbusch (1983), e sua posterior extensão ao caso italiano por Cottarelli, C. e Mecagni, M. (1990), e de Romer (2000), de que uma melhora dos fundamentos econômicos reduz o prêmio de risco da dívida pública. Em particular, concluímos que as variáveis relacionadas a indicadores fiscais explicam os movimentos da medida de prêmio de risco utilizada, o spread over treasury do C-bond.

Ensaios em macroeconometria e finanças

Esta tese de doutorado está composta por quatro ensaios em macroeconometria e finanças com aplicações nas áreas de abertura comercial, custo de bem estar do ciclo de negócios e taxas de juros. No primeiro ensaio analisamos o comportamento da indústria de transformação após as reformas implantadas na década de noventa. Verificamos se o processo de abertura gerou aumentos da produtividade média da indústria de transformação. Adicionalmente, estimamos o mark-up de diferentes setores industriais e testamos se este se modifica após a abertura comercial. Os resultados das estimações indicam a existência de um significativo aumento na produtividade industrial na maior parte dos setores estudados. O canal para este aumento de produtividade, aparentemente, não é o aumento da concorrência, já que não há evidência estatística de redução de mark-up. Este é talvez o resultado mais surpreendente do artigo, o fato de que o mark-up não se modificar significativamente após a abertura comercial. Os setores estimados como não concorrenciais antes da abertura continuaram a ser depois dela. Acesso a insumo importados e uso de novas tecnologias podem ser possíveis canais de aumento de produtividade. Este resultado está em desacordo com Moreira (1999) que constrói diretamente dos dados medidas de mark-up. No segundo ensaio testamos a Hipótese das Expectativas Racionais (HER) para a estrutura a termo brasileira. Examinamos várias combinações de prazos entre 1 dia e 1 ano, seguindo a metodologia adotada pelo Banco Central do Brasil, para o período de Julho de 1996 a Dezembro de 2001. Mostramos que: (i) os coeficientes estimados dos diferenciais de rendimento entre as taxas longa e curta (yield spreads) nas equações de mudança de curto prazo da taxa longa e nas equações de mudança de longo prazo da taxa curta são imprecisos e incapazes de rejeitarem a HER; e (ii) diferenciais de rendimento altamente correlacionados com as previsões de expectativas racionais das futuras mudanças das taxas curtas, mas significativamente mais voláteis que estas últimas, sugerem a rejeição da HER. A hipótese alternativa de reação exagerada (overreaction) do diferencial de rendimento em relação à expectativa das futuras variações da taxa curta parece uma explicação razoável para as evidências, com implicações para a política monetária e para a gestão de investimentos. No terceiro ensaio estudamos o custo de bem-estar dos ciclos de negócios. Robert Lucas (1987) mostrou um resultado surpreendente para a literatura de ciclos de negócios, o custo de bem-estar, por ele calculado, é muito pequeno (US$ 8,50 por ano). Modelamos as preferências por funções com elasticidade de substituição constante e uma forma reduzida para o consumo razoável. Construímos dados seculares para a economia americana e computamos o custo de bem-estar para dois períodos distintos, pré e pós-segunda guerra mundial, usando três formas alternativas de decomposição tendência-ciclo, com foco na decomposição de Beveridge-Nelson. O período pós-guerra foi calmo, com um custo de bem-estar que raramente ultrapassa 1% do consumo per-capita (US$ 200,00 por ano). Para o período pré-guerra há uma alteração drástica nos resultados, se utilizamos a decomposição de Beveridge-Nelson encontramos uma compensação de 5% do consumo per-capita (US$ 1.000,00 por ano) com parâmetros de preferências e desconto intertemporal razoáveis. Mesmo para métodos alternativos, como o modelo com tendência linear, encontramos um custo de bem estar de 2% do consumo per-capita (US$ 400,00 por ano). Deste estudo podemos concluir: (i) olhando para dados pós-guerra, o custo de bem-estar dos ciclos de negócios marginal é pequeno, o que depõe contra a intensificação de políticas anticíclicas, sendo que do ponto de vista do consumidor pré-segunda guerra este custo é considerável; e (ii) o custo de bem-estar dos ciclos de negócios caiu de 5% para 0.3% do consumo per-capita, do período pré para o período pós-guerra, se esta redução é resultado de políticas anticíclicas, estas políticas foram muito bem sucedidas. Por último, no quarto ensaio analisamos o comportamento da taxa de juros livre de risco - cupom cambial - na economia brasileira para o período de 20 de janeiro de 1999 a 30 de julho de 2003. Identificamos os componentes de curto e longo prazo de três medidas de taxa de retorno, as quais foram submetidas aos tratamentos econométricos propostos em Vahid e Engle (1993) e Proietti (1997). Os resultados sugerem a convergência das taxas de retorno para um equilíbrio de longo prazo. Identificamos a dominância do componente de longo prazo na determinação da trajetória do Prêmio do C-BOND e do componente de curto prazo no caso do Prêmio do Swap Cambial. Já para o Prêmio Descoberto de Juros não conseguimos identificar o domínio de qualquer componente. Associando o componente de longo prazo aos fundamentos da economia e os componentes de curto prazo a choques nominais, poderíamos dizer que, em termos relativos, o Prêmio do C-BOND estaria mais fortemente ligado aos fundamentos e o Prêmio do Swap Cambial a choques nominais.

The risk premium on brazilian government debt, 1996-2002

The goal of this paper is to identify the determinants of the risk premium on Brazilian government debt. As the risk premium is a component of the interest rate set by the Brazilian central bank, its reduction would make it possible for the central bank to cut interest rates to levels compatible with a higher economic growth environment. The empirical evidence presented in this paper does not reject the hypotheses that fiscal solvency and the size of the public debt affect the risk premium as measured by the spread over treasury bills of the Brazilian C-bond.

A tellurium-based cathepsin B inhibitor: Molecular structure, modelling, molecular docking and biological evaluation

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Theoretical study on the molecular mechanism for the reaction of VO2+ with C2H4

The complex reaction between VO2+ ((1)A(1)/(3)A) and C2H4 (Ag-1(g)/(3)A(1)) to yield VO+ ((1)Delta/(3)Sigma) and CH3CHO ('A'/(3)A) has been studied by means of B3LYP/6-31G* and B3LYP/6-311G(2d,p) calculations. The structures of all reactants, products, intermediates, and transition structures of this reaction have been optimized and characterized at the fundamental singlet and first excited triplet electronic states. Crossing points are localized, and possible spin inversion processes are discussed by means of the intrinsic reaction coordinate approach. Relevant stationary points along the most favorable reaction pathways have been studied at the CCSD/6-311G(2d,p)//B3LYP/6-311G(2d,p) calculation level. The theoretical results allow the development of thermodynamic and kinetic arguments about the reaction pathways of the title process. In the singlet state, the first step is the barrierless obtention of a reactant complex associated with the formation of a V-C bond, while in the triplet state a three-membered ring addition complex with the V bonded to the two C atoms is obtained. Similar behavior is found in the exit channels: the product complexes can be formed from isolated products without barriers. The reactant and product complexes are the most stable stationary points in the singlet and triplet electronic states. From the singlet state reactant complex, two reaction pathways are posssible to reach the triplet state product complex. (i) A mechanism in which a hydrogen transfer process is the first and rate limiting step and the second step is an oxygen transfer between vanadium and carbon atoms with a concomitant change in the spin state. The crossing point between singlet and triplet spin states is not kinetically relevant because it takes place at a later stage occurring in the exit channel. (ii) A mechanism in which the first stage renders a four-membered ring between vanadyl cation and the ethylene fragment and an oxygencarbon bond is formed; on going from this minimum to the second transition structure, associated with a carbon-vanadium bond breaking process, the crossing point between singlet and triplet spin states is reached. The final step is the hydrogen transfer between both carbon atoms to yield the product complex. In this case the spin change opens a lower barrier pathway. The transition structures with larger values of relative energies for both reactive channels of VO2+ ((1)A(1)) + C2H4 (Ag-1) --> VO+ ((3)Sigma) + CH3CHO ((1)A') present similar energies, and the two reaction pathways can be considered as competitive.

Synthesis, crystal structure and theoretical studies of aryltellurenyl tetramethylthiourea(tmtu) iodine complexes: Ph-Te(tmtu)I (1) and beta-naphtyl-Te(tmtu)I (2)

(1) C11H17IN2STe, Mr = 463.83, P2(1)/n, a 7.6582(8), b = 13.8008(9), c = 15.026(3) angstrom, beta = 96.233(12)degrees, Z = 4, R-1 = 0.0318. (2) C15H19IN2STe, Mr = 513.88, P2(1)/n, a = 8.434(5), b = 11.697(5), c = 18.472(5) angstrom, beta = 98.556(5)degrees, Z = 4, R-1 = 0.0236. The synthesis of the aryltellurenyl N,N',-tetramethylthiourea (tmtu) iodide has been performed by ligand exchange with potassium iodide and the corresponding aryltellurenyl(tmtu) bromide. In both structures the tellurium atom is primarily three-coordinated, being bonded to a carbon atom of the organic ring and, in directions nearly perpendicular to the Te-C bond, to one tmtu sulfur atom and one iodine. In addition there are Te...secondary bonds, joining the molecules in centrosymmetric dimers, which in turn are joined through C-H...1 and C-H... S interactions, in (1) and (2), respectively.

Hardness and elastic modulus of carbon-germanium alloys

This work reports on the mechanical properties of germanium-rich amorphous carbon-germanium alloys prepared by RF sputtering of a germanium/graphite target under an argon/hydrogen atmosphere. Nano-hardness, elastic modulus and stress were investigated as a function of the carbon content. The stress, which is reduced by the incorporation of carbon, was related to the film structure and to the difference in the Ge-Ge and Ge-C bond length. Contrary to what was expected, the hardness and elastic modulus of the alloys are lower than the corresponding values for pure amorphous hydrogenated germanium film, which in turn has both properties also smaller than those of crystalline germanium. These properties are analyzed in terms of the structural properties of the films. (C) 2001 Elsevier B.V. B.V All rights reserved.

Experimental and theoretical study of the compound [Pd(dmba)(NCO)(imz)]

The compound [Pd(dmba)(NCO)(imz)] (dmba = N,N-dimethylbenzilamine; NCO = cyanate; imz = imidazole) was studied through experimental and theoretical methods. The complex was synthesized and characterized by IR and NMR spectroscopy. To an appropriate representation of the molecular environment, Gaussian basis sets for the constituent atoms of the compound were built and, after adequate supplementation with polarization and diffuse functions, they were used to study the molecule. Calculations of electronic and vibrational structure of two possible isomers were carried out, showing that the compound, which contains the NCO GROUP trans to the Pd-C bond, is 4.29 kcal/mol more stable than the analogous one, where the imz ligand is trans to the Pd-C bond. The calculated molecular parameters, bond distances, and bond angles showed that the geometry around the metallic center is square-planar with the cyanate being linear. The theoretical infrared spectrum of C(1) symmetry (electronic state (1)A) is in accordance with the experimental one. It also verified the contribution of Pd (4d(xz) + 4d(yz)) and Pd (4d(xy)) in the HOMO and LUMO orbitals, respectively. (c) 2006 Elsevier B.V. All rights reserved.

The valuable role of renucleation rate in ultrananocrystalline diamond growth

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Compostos derivados de benzilcobaloximas: estudo por espectrometria de massas, análise térmica e eletroquímica

Pós-graduação em Química - IQ

Search for gravitational wave ringdowns from perturbed intermediate mass black holes in LIGO-Virgo data from 2005-2010

We report results from a search for gravitational waves produced by perturbed intermediate mass black holes ( IMBH) in data collected by LIGO and Virgo between 2005 and 2010. The search was sensitive to astrophysical sources that produced damped sinusoid gravitational wave signals, also known as ringdowns, with frequency 50 <= f(0)/Hz <= 2000 and decay timescale 0.0001 less than or similar to tau/s less than or similar to 0.1 characteristic of those produced in mergers of IMBH pairs. No significant gravitational wave candidate was detected. We report upper limits on the astrophysical coalescence rates of IMBHs with total binary mass 50 <= M/ M circle dot <= 450 and component mass ratios of either 1: 1 or 4: 1. For systems with total mass 100 <= M/M circle dot <= 150, we report a 90% confidence upper limit on the rate of binary IMBH mergers with nonspinning and equal mass components of 6.9 x 10(-8) Mpc(-3) yr(-1). We also report a rate upper limit for ringdown waveforms from perturbed IMBHs, radiating 1% of their mass as gravitational waves in the fundamental, l = m = 2, oscillation mode, that is nearly three orders of magnitude more stringent than previous results.

Methods and results of a search for gravitational waves associated with gamma-ray bursts using the GEO 600, LIGO, and Virgo detectors

In this paper we report on a search for short-duration gravitational wave bursts in the frequency range 64 Hz-1792 Hz associated with gamma-ray bursts (GRBs), using data from GEO 600 and one of the LIGO or Virgo detectors. We introduce the method of a linear search grid to analyze GRB events with large sky localization uncertainties, for example the localizations provided by the Fermi Gamma-ray Burst Monitor (GBM). Coherent searches for gravitational waves (GWs) can be computationally intensive when the GRB sky position is not well localized, due to the corrections required for the difference in arrival time between detectors. Using a linear search grid we are able to reduce the computational cost of the analysis by a factor of O(10) for GBM events. Furthermore, we demonstrate that our analysis pipeline can improve upon the sky localization of GRBs detected by the GBM, if a high-frequency GW signal is observed in coincidence. We use the method of the linear grid in a search for GWs associated with 129 GRBs observed satellite-based gamma-ray experiments between 2006 and 2011. The GRBs in our sample had not been previously analyzed for GW counterparts. A fraction of our GRB events are analyzed using data from GEO 600 while the detector was using squeezed-light states to improve its sensitivity; this is the first search for GWs using data from a squeezed-light interferometric observatory. We find no evidence for GW signals, either with any individual GRB in this sample or with the population as a whole. For each GRB we place lower bounds on the distance to the progenitor, under an assumption of a fixed GW emission energy of 10(-2)M circle dot c(2), with a median exclusion distance of 0.8 Mpc for emission at 500 Hz and 0.3 Mpc at 1 kHz. The reduced computational cost associated with a linear search grid will enable rapid searches for GWs associated with Fermi GBM events once the advanced LIGO and Virgo detectors begin operation.

Search for Gravitational Waves Associated with gamma-ray Bursts Detected by the Interplanetary Network

We present the results of a search for gravitational waves associated with 223 gamma-ray bursts (GRBs) detected by the InterPlanetary Network (IPN) in 2005-2010 during LIGO's fifth and sixth science runs and Virgo's first, second, and third science runs. The IPN satellites provide accurate times of the bursts and sky localizations that vary significantly from degree scale to hundreds of square degrees. We search for both a well-modeled binary coalescence signal, the favored progenitor model for short GRBs, and for generic, unmodeled gravitational wave bursts. Both searches use the event time and sky localization to improve the gravitational wave search sensitivity as compared to corresponding all-time, all-sky searches. We find no evidence of a gravitational wave signal associated with any of the IPN GRBs in the sample, nor do we find evidence for a population of weak gravitational wave signals associated with the GRBs. For all IPN-detected GRBs, for which a sufficient duration of quality gravitational wave data are available, we place lower bounds on the distance to the source in accordance with an optimistic assumption of gravitational wave emission energy of 10(-2)M(circle dot)c(2) at 150 Hz, and find a median of 13 Mpc. For the 27 short-hard GRBs we place 90% confidence exclusion distances to two source models: a binary neutron star coalescence, with a median distance of 12 Mpc, or the coalescence of a neutron star and black hole, with a median distance of 22 Mpc. Finally, we combine this search with previously published results to provide a population statement for GRB searches in first-generation LIGO and Virgo gravitational wave detectors and a resulting examination of prospects for the advanced gravitational wave detectors.