Static and dynamic bimolecular fluorescence quenching of porphyrin dendrimers in solution

The fluorescence quenching kinetics of two porphyrin dendrimer series (GnTPPH(2) and GnPZn) by different type of quenchers is reported. The microenvironment surrounding the core in GnPZn was probing by core-quencher interactions using benzimidazole. The dependence of quencher binding constant (K(a) ) on generation indicates the presence of a weak interaction between branches and the core of the porphyrin dendrimer. The similar free volume in dendrimers of third and fourth generation suggests that structural collapse in high generations occurs by packing of the dendrimer peripheral layer. Dynamic fluorescence quenching of the porphyrin core by 1,3-dicyanomethylene-2-methyl-2-pentyl-indan (PDCMI) in GnTPPH(2) is a distance dependent electron transfer process with an exponential attenuation factor beta=0.33 angstrom(-1). The quenching by 1,2-dibromobenzene occurs by diffusion process of the quencher toward to the porphyrin core, and its rate constant is practically independent of dendrimer generation.

Modelo de mensuração de mercado para bens duráveis: o caso de condicionadores de ar para uso residencial

Trata de uma proposta de mensuração de mercado de bens duráveis em nível municipal. O processo de modelagem assume que: a função deve ser determinada a partir do análise do estágio do produto em seu processo de difusão n o mercado, cada município é uma unidade representada p o r variáveis obtidas através d e dados secundários e os dados secundários a serem coletados podem determinados através d o conhecimento d o comportamento de compra do produto. No modelo, os resíduos sã o tratados como ferramenta estratégica mercadológica. É apresentada uma aplicação do modelo para condicionadores de ar

Do encontro das águas ao Atlântico negro: organização, difusão de frames e os limites do ativismo transnacional no movimento negro brasileiro

Meu objetivo nesta tese é compreender o processo de transnacionalização do movimento negro brasileiro e as suas consequências para a luta antirracista no Brasil. Em outras palavras, busco compreender como os negros brasileiros se articulam com os negros do mundo para cumprir seus objetivos. Uma vez que hoje a cultura negra global tem sido compreendida a partir da metáfora do “Atlântico Negro”, que representa um espaço de trocas transnacional que conecta todos os sujeitos da diáspora negra, assumo esta mesma metáfora como ponto de partida para minha reflexão. Entretanto, me interessa refletir sob um dos aspectos do Atlântico Negro, que é a sua dimensão organizacional. Se é pelo Atlântico Negro que hoje circulam um conjunto de conteúdos que são compartilhados pela comunidade negra mundial, tais como idéias e práticas que estão relacionadas a religião, a música, a literatura e as formas de organização, então podemos afirmar que a organização do movimento negro brasileiro se alimenta também destas múltiplas dimensões. Para desenvolver esta linha de argumentação, a tese utiliza o caso do movimento negro brasileiro para analisar o processo de difusão de um frame transnacional racialista que é apropriado pelo movimento negro como base para a elaboração de um diagnóstico, prognóstico e ressonância das ações de combate ao racismo no Brasil e para a definição das estruturas de mobilização e das estratégias de ação do movimento. Contudo, esta apropriação não ocorre sem problemas, pois este frame enfrenta outros frames locais, de caráter não-racialista, o que acarreta severas restrições ao ativismo transnacional na medida em que o próprio movimento negro se vê diante do dilema entre manter o alinhamento com o frame transnacional e aproveita as oportunidades políticas oferecidas pelo racialismo, ou relativiza este frame fazendo algumas concessões em suas propostas e na sua organização, a fim de se adaptar aos frames locais, negociando estas oportunidades a partir das restrições existentes. Para entender esta dinâmica, proponho a metáfora do “Encontro das Águas” amazonense, como um ponto de argumentação complementar ao Atlântico Negro, pois leva em conta os aspectos locais da luta antirracista que se apoiam na mestiçagem como identidade autônoma que não se dilui facilmente na identidade negra. Além de desenvolver estes pontos, a tese contribui para compreender melhor a dialética entre o global e local, bem como as tensões advindas dos frames em disputa.

Modelo de volatilidade estocástica com saltos aplicado a commodities agrícolas

Mensalmente são publicados relatórios pelo Departamento de Agricultura dos Estados Unidos (USDA) onde são divulgados dados de condições das safras, oferta e demanda globais, nível dos estoques, que servem como referência para todos os participantes do mercado de commodities agrícolas. Esse mercado apresenta uma volatilidade acentuada no período de divulgação dos relatórios. Um modelo de volatilidade estocástica com saltos é utilizado para a dinâmica de preços de milho e de soja. Não existe um modelo ‘ideal’ para tal fim, cada um dos existentes têm suas vantagens e desvantagens. O modelo escolhido foi o de Oztukel e Wilmott (1998), que é um modelo de volatilidade estocástica empírica, incrementado com saltos determinísticos. Empiricamente foi demonstrado que um modelo de volatilidade estocástica pode ser bem ajustado ao mercado de commodities, e o processo de jump-diffusion pode representar bem os saltos que o mercado apresenta durante a divulgação dos relatórios. As opções de commodities agrícolas que são negociadas em bolsa são do tipo americanas, então alguns métodos disponíveis poderiam ser utilizados para precificar opções seguindo a dinâmica do modelo proposto. Dado que o modelo escolhido é um modelo multi-fatores, então o método apropriado para a precificação é o proposto por Longstaff e Schwartz (2001) chamado de Monte Carlo por mínimos quadrados (LSM). As opções precificadas pelo modelo são utilizadas em uma estratégia de hedge de uma posição física de milho e de soja, e a eficiência dessa estratégia é comparada com estratégias utilizando-se instrumentos disponíveis no mercado.

Studies in non-Gaussian analysis

This thesis presents general methods in non-Gaussian analysis in infinite dimensional spaces. As main applications we study Poisson and compound Poisson spaces. Given a probability measure μ on a co-nuclear space, we develop an abstract theory based on the generalized Appell systems which are bi-orthogonal. We study its properties as well as the generated Gelfand triples. As an example we consider the important case of Poisson measures. The product and Wick calculus are developed on this context. We provide formulas for the change of the generalized Appell system under a transformation of the measure. The L² structure for the Poisson measure, compound Poisson and Gamma measures are elaborated. We exhibit the chaos decomposition using the Fock isomorphism. We obtain the representation of the creation, annihilation operators. We construct two types of differential geometry on the configuration space over a differentiable manifold. These two geometries are related through the Dirichlet forms for Poisson measures as well as for its perturbations. Finally, we construct the internal geometry on the compound configurations space. In particular, the intrinsic gradient, the divergence and the Laplace-Beltrami operator. As a result, we may define the Dirichlet forms which are associated to a diffusion process. Consequently, we obtain the representation of the Lie algebra of vector fields with compact support. All these results extends directly for the marked Poisson spaces.

MIGRATION MEASUREMENTS FROM PLASTIC PACKAGING: A SIMULATION STUDY ON INFLUENCE OF INITIAL CONCENTRATION PROFILE

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Processos difusivos generalizados

We investigate several diffusion equations which extend the usual one by considering the presence of nonlinear terms or a memory effect on the diffusive term. We also considered a spatial time dependent diffusion coefficient. For these equations we have obtained a new classes of solutions and studied the connection of them with the anomalous diffusion process. We start by considering a nonlinear diffusion equation with a spatial time dependent diffusion coefficient. The solutions obtained for this case generalize the usual one and can be expressed in terms of the q-exponential and q-logarithm functions present in the generalized thermostatistics context (Tsallis formalism). After, a nonlinear external force is considered. For this case the solutions can be also expressed in terms of the q-exponential and q-logarithm functions. However, by a suitable choice of the nonlinear external force, we may have an exponential behavior, suggesting a connection with standard thermostatistics. This fact reveals that these solutions may present an anomalous relaxation process and then, reach an equilibrium state of the kind Boltzmann- Gibbs. Next, we investigate a nonmarkovian linear diffusion equation that presents a kernel leading to the anomalous diffusive process. Particularly, our first choice leads to both a the usual behavior and anomalous behavior obtained through a fractionalderivative equation. The results obtained, within this context, correspond to a change in the waiting-time distribution for jumps in the formalism of random walks. These modifications had direct influence in the solutions, that turned out to be expressed in terms of the Mittag-Leffler or H of Fox functions. In this way, the second moment associated to these distributions led to an anomalous spread of the distribution, in contrast to the usual situation where one finds a linear increase with time

Comparative degradation of ZnO- and SnO(2)-based polycrystalline non-ohmic devices by current pulse stress

The degradation behaviour of SnO(2)-based varistors (SCNCr) due to current pulses (8/20 mu s) is reported here for the first time in comparison with the ZnO-based commercial varistors (ZnO). Puncturing and/or cracking failures were observed in ZnO-based varistors possessing inferior thermo-mechanical properties in comparison with that found in a SCNCr system free of failures. Both systems presented electric degradation related to the increase in the leakage current and decrease in the electric breakdown field, non-linear coefficient and average value of the potential barrier height. However, it was found that a more severe degradation occurred in the ZnO-based varistors concerning their non-ohmic behaviour, while in the SCNCr system, a strong non-ohmic behaviour remained after the degradation. These results indicate that the degradation in the metal oxide varistors is controlled by a defect diffusion process whose rate depends on the mobility, the concentration of meta-stable defects and the amount of electrically active interfaces. The improved behaviour of the SCNCr system is then inferred to be associated with the higher amount of electrically active interfaces (85%) and to a higher energy necessary to activate the diffusion of the specific defects.

Síntese e caracterização da ferrita de MnZn obtida pelo método dos citratos precursores

It was synthesized MnZn ferrite with general formulae Mn1-xZnxFe2O4 (mol%), 0,3 ≤ x ≤ 0,7 by using the citrate precursor method. The precursors decomposition was studied by thermogravimetric analysis (TGA), differential thermogravimetric analysis (DTG), differential thermal analysis (DTA) and Fourier transform infrared (FTIR) of powder calcined at 350ºC/3,5h. X-ray diffraction pattern (XRD) of samples was done from 350 to 1200ºC/2h using various atmospheres. The power calcined at 350ºC/3,5h formed spinel phase. It is necessary atmosphere control to avoid secondary phase such as hematite. From 900 to 1200ºC was obtained 90,66 and 100% of MnZn spinel ferrite phase, respectively. Analysis by dispersive energy scanning (EDS) at 350ºC shows high Mn and Zn dispersion, indicating that the diffusion process was homogeneous. Semi-quantitative analysis by EDS verified that despite the atmosphere control during calcinations at high temperatures (< 800ºC) occurred ZnO evaporation causing stoichiometric deviation. Vibrating sample magnetometer (VSM) measures show soft ferrite material characteristics with Hc from 6,5 x 10-3 to 11,1 x 10-2 T. Saturation magnetization (Ms) and initial permeability (µi) of MnZn spinel phase obtained, respectively, from 14,3 to 83,8 Am2/kg and 14,1 to 62,7 (Am2/kg)T

Ageing behavior in the Cu-10 wt.%Al and Cu-10 wt.%Al-4 wt.%Ag alloys

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

Evolution and population structure of africanized honey bees in Brazil: Evidence from spatial analysis of morphometric data

In recent years, studies based on isoenzymatic patterns of geographic variation have revealed that what is usually called the Africanized honey bee does not constitute a single population. Instead, several local populations exist with various degrees of admixture with European honey bees. In this paper, we evaluated new data on morphometric patterns of Africanized honey bees collected at 42 localities in Brazil, using univariate and multivariate (canonical) trend surface and spatial autocorrelation analyses. The clinal patterns of variation found for genetically independent characters (wing size characters and some wing venation angles) are concordant with previous studies of malate dehydrogenase (MDH) allelic frequencies and support the hypothesis that larger honey bees in southern and southeastern Brazil originated by racial admixture in the initial phases of African honey bee colonization. Geographic variation patterns of Africanized honey bee populations reflect a demic diffusion process in which European genes were gradually lost because of the higher fitness of the African gene pool in Neotropical environmental conditions.

Small-angle X-ray scattering study of the smart thermo-optical behavior of zirconyl aqueous colloids

The smart thermo-optical systems studied here are based on the unusual thermoreversible sol-gel transition of zirconyl chloride aqueous solution modified by sulfuric acid in the molar ratio Zr/SO4:3/1. The transparency to the visible light changes during heating due to light scattering. This feature is related to the aggregates growth that occurs during gelation. These reversible changes can be controlled by the amount of chloride ions in solution. The thermoreversible sol-gel transition temperature increases from 323 to 343 K by decreasing the molar ratio Cl/Zr from 7.0 to 1.3. In this work the effect of the concentration of chloride ions on the structural characteristics of the system has been analyzed by in situ SAXS measurements during the sol-gel transition carried out at 323 and 333 K. The experimental SAXS curves of sols exhibit three regions at small, medium and high scattering vectors characteristics of Guinier, fractal and Porod regimes, respectively. The radius of primary particles, obtained from the crossover between the fractal and Porod regimes, remains almost invariable with the chloride concentration, and the value (4 Angstrom) is consistent with the size of the molecular precursor. During the sol-gel transition the aggregates grow with a fractal structure and the fractal dimensionality decreases from 2.4 to 1.8. This last value is characteristic of a cluster-cluster aggregation controlled by a diffusion process. Furthermore, the time exponent of aggregate growth presents values of 0.33 and 1, typical of diffusional and hydrodynamic motions. A crossover between these two regimes is observed.

Structural and Electronic Properties of Lithiated SnO2. A Periodic DFT Study

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Initial concentration profile influence on migration measurements from plastic packaging: A simulation study

Migration of components from plastic packaging into foodstuffs or into medicines is a very important issue, concerning public health. Using experimental techniques, like gas chromatography-mass spectrometry, these essays measure total migration and specific migration of components from plastic packaging. This work presents an explanation and applications of a numerical technique tool for this measurement, allowing the comprehension of the diffusion process and the estimate of component migration in difficult or impractical measurements. As an application example, the non-uniform influence of initial concentration profile on the migration is presented, demonstrating the necessity of this profile determination for high quality considerations on involved metrology.