Arquitetura crustal da bacia de Almada no contexto das bacias da margem lesste da América do Sul

A Bacia de Almada, localizada no estado da Bahia, compartilha características similares com as outras bacias da margem leste do Brasil, quando é analisada segundo aspectos como os processos sedimentares e o regime de esforço dominante durante a sua formação. Observa-se uma diferença marcante em relação as outras bacias quando é analisada sob a ótica da composição da crosta transicional, uma vez que não se registra atividade vulcânica durante a fase rifte. A aquisição de um extenso levantamento sísmico 3D, com cabos de 6 km de comprimento e 9.2 segundos de tempo de registro (tempo sísmico duplo), resultaram em imagens sísmicas de boa qualidade das estruturas profundas do rifte. Adicionalmente, estudos de modelagem gravimétrica foram integrados com a análise sísmica para corroborar o modelo geológico. A Bacia de Almada é parte dos sistemas de rifte continentais, desenvolvidos durante o Berriasiano até o Aptiano, que antecederam a quebra do continente do Gondwana, evoluindo posteriormente para uma margem passiva divergente. O processo do rifteamento desenvolveu cinco sub-bacias de orientação NNE-SSO, desde posições terrestres até marinhas profundas, produzindo um arcabouço estrutural complexo. Os perfis da sísmica profunda mostram o afinamento progressivo da crosta continental até espessuras da ordem de 5 km, abaixo da sub-bacia mais oriental, com fatores de estiramento crustal próximo a 7 antes do desenvolvimento de crosta oceânica propriamente dita. As imagens sísmicas de boa qualidade permitem também o reconhecimento de sistemas de falhas lístricas que se iniciam na crosta superior, evoluem atravessando a crosta e conectando as sub-bacias para finalizar em um descolamento horizontal na crosta inferior estratificada. Adicionalmente, a bacia apresenta um perfil assimétrico, compatível com mecanismos de cisalhamento simples. As margens vulcânicas (VM) e não vulcânicas (NVM), são os extremos da análise composicional das margens divergentes continentais. Na Bacia de Almada não se reconhecem os elementos arquiteturais típicos das VM, tais como são as grandes províncias ígneas, caracterizadas por cunhas de refletores que mergulham em direção ao mar e por intenso vulcanismo pré- e sin-rifte nas bacias. Embora a margem divergente do Atlântico Sul seja interpretada tradicionalmente como vulcânica, o segmento do rifte ao sul do Estado da Bahia apresenta características não-vulcânicas, devido à ausência destes elementos arquiteturais e aos resultados obtidos nas perfurações geológicas que eventualmente alcançam a seqüência rifte e embasamento. Regionalmente a margem divergente sul-americana é majoritariamente vulcânica, embora a abundância e a influência do magmatísmo contemporâneo ao rifte seja muito variável. Ao longo da margem continental, desde a Bacia Austral no sul da Argentina, até a Bacia de Pernambuco no nordeste do Brasil, podem ser reconhecidos segmentos de caráter vulcânico forte, médio e não vulcânico. Nos exemplos clássicos de margens não vulcânicas, como a margem da Ibéria, a crosta transicional é altamente afinada podendo apresentar evidências de exumação de manto. Na Bacia de Almada, a crosta transicional apresenta importante estiramento embora não haja evidências concretas de exumação de manto. Os mecanismos responsáveis pela geração e intrusão dos grandes volumes de magma registrados nas margens divergentes são ainda sujeitos a intenso debate. Ao longo da margem divergente sul-americana há evidências da presença dos mecanismos genéticos de estiramento litosférico e impacto de plumas. Alternativamente estes dois mecanismos parecem ter tido um papel importante na evolução tectônica da margem sudeste e sul, diferenciando-as da margem continental onde foi implantada a Bacia de Almada.

Electron tunneling in proteins and water

The subject of this thesis is electronic coupling in donor-bridge-acceptor systems. In Chapter 2, ET properties of cyanide-bridged dinuclear ruthenium complexes were investigated. The strong interaction between the mixed-valent ruthenium centers leads to intense metal-to-metal charge transfer bands (MMCT). Hush analysis of the MMCT absorption bands yields the electronic-coupling strength between the metal centers (H_(AB)) and the total reorganization energy (λ). Comparison of ET kinetics to calculated rates shows that classical ET models fail to account for the observed kinetics and nuclear tunneling must be considered.

In Chapter 3, ET rates were measured in four ruthenium-modified highpotential iron-sulfur proteins (HiPIP), which were modified at position His50, His81, His42 and His18, respectively. ET kinetics for the His50 and His81 mutants are a factor of 300 different, while the donor-acceptor separation is nearly identical. PATHWAY calculations corroborate these measurements and highlight the importance of structural detail of the intervening protein matrix.

In Chapter 4, the distance dependence of ET through water bridges was measured. Photoinduced ET measurements in aqueous glasses at 77 K show that water is a poor medium for ET. Luminescence decay and quantum yield data were analyzed in the context of a quenching model that accounts for the exponential distance dependence of ET, the distance distribution of donors and acceptors embedded in the glass and the excluded volumes generated by the finite sizes of the donors and acceptors.

In Chapter 5, the pH-dependent excited state dynamics of ruthenium-modified amino acids were measured. The [Ru(bpy)_(3)] ^(2+) chromophore was linked to amino acids via an amide linkage. Protonation of the amide oxygen effectively quenches the excited state. In addition. time-resolved and steady-state luminescence data reveal that nonradiative rates are very sensitive to the protonation state and the structure of the amino acid moiety.

Análise de fadiga em pontes rodoviárias de concreto armado

As pontes rodoviárias de concreto armado estão sujeitas às ações dinâmicas variáveis devido ao tráfego de veículos sobre o tabuleiro. Estas ações dinâmicas podem gerar o surgimento das fraturas ou mesmo a sua propagação na estrutura. A correta consideração destes aspectos objetivou o desenvolvimento de um estudo, de forma a avaliar os esforços do tráfego de veículos pesados sobre o tabuleiro. As técnicas para a contagem de ciclos de esforços e a aplicação das regras de dano acumulado foram analisadas através das curvas S-N de diversas normas estudadas. A ponte rodoviária investigada é constituída por quatro vigas longitudinais, três transversinas e por um tabuleiro de concreto armado. O modelo computacional, desenvolvido para a análise dinâmica da ponte, foi concebido com base no emprego de técnicas usuais de discretização através do método dos elementos finitos. O modelo estrutural da obra de arte rodoviária estudada foi simulado com base no emprego de elementos finitos sólidos tridimensionais. Os veículos são representados a partir de sistemas massa-mola-amortecedor. O tráfego dessas viaturas é considerado mediante a simulação de comboios semi-infinitos, deslocando-se com velocidade constante sobre o tabuleiro da ponte. As conclusões deste trabalho versam acerca da vida útil de serviço dos elementos estruturais de pontes rodoviárias de concreto armado submetidas às ações dinâmicas provenientes do tráfego de veículos pesados sobre o tabuleiro.

Collective behavior of asperities as a model for friction and adhesion

Understanding friction and adhesion in static and sliding contact of surfaces is important in numerous physical phenomena and technological applications. Most surfaces are rough at the microscale, and thus the real area of contact is only a fraction of the nominal area. The macroscopic frictional and adhesive response is determined by the collective behavior of the population of evolving and interacting microscopic contacts. This collective behavior can be very different from the behavior of individual contacts. It is thus important to understand how the macroscopic response emerges from the microscopic one. In this thesis, we develop a theoretical and computational framework to study the collective behavior. Our philosophy is to assume a simple behavior of a single asperity and study the collective response of an ensemble. Our work bridges the existing well-developed studies of single asperities with phenomenological laws that describe macroscopic rate-and-state behavior of frictional interfaces. We find that many aspects of the macroscopic behavior are robust with respect to the microscopic response. This explains why qualitatively similar frictional features are seen for a diverse range of materials. We first show that the collective response of an ensemble of one-dimensional independent viscoelastic elements interacting through a mean field reproduces many qualitative features of static and sliding friction evolution. The resulting macroscopic behavior is different from the microscopic one: for example, even if each contact is velocity-strengthening, the macroscopic behavior can be velocity-weakening. The framework is then extended to incorporate three-dimensional rough surfaces, long- range elastic interactions between contacts, and time-dependent material behaviors such as viscoelasticity and viscoplasticity. Interestingly, the mean field behavior dominates and the elastic interactions, though important from a quantitative perspective, do not change the qualitative macroscopic response. Finally, we examine the effect of adhesion on the frictional response as well as develop a force threshold model for adhesion and mode I interfacial cracks.

Pontes e fronteiras entre o eu e o outro: um estudo sobre o amor e a paixão nos segmentos médios da cidade do Rio de Janeiro

O objetivo deste trabalho consiste em realizar uma interpretação de discursos sobre o amor e a paixão buscando compreendê-los sob o prisma do ideal do individualismo, e também de noções importantes na cultura ocidental tais como a liberdade e a igualdade. Os dados etnográficos dessa pesquisa foram obtidos através de entrevistas qualitativas e o universo pesquisado foi composto por indivíduos pertencentes aos segmentos médios cariocas, reunidos através de um sistema de rede de relações. Foram analisadas nove entrevistas em que a experiência amorosa foi compreendida como uma situação de alteridade particularmente significativa na investigação da relação entre o indivíduo moderno e seu contexto social/cultural. A análise dos dados ressalta algumas noções e valores indicados por eles envolvendo o momento do encantamento amoroso assim como suas práticas amorosas, buscando também compreender os sentimentos do amor, da paixão e da amizade. Explora também as questões sobre a fidelidade perpassando as noções de liberdade individual e do individualismo como valores a provocar possíveis tensões entre os indivíduos.

Composite second-order performance improvement in optical fibre CATV transmission system using chirped fibre grating

Theoretically, we analyse the dispersion compensation characteristics of the chirped fibre grating (CFG) in an optical fibre cable television (CATV) system and obtain the analytic expression of the composite second-order (CSO) distortion using the time-domain form of the field envelope wave equation. The obtained result is in good agreement with the numerical simulation result. Experimentally, we verify the result by making use of the tunable characteristics of CFG to change the dispersion compensation amount and obtain an optimal CSO performance in a 125km fibre transmission link. Both the theoretical and experimental results show that the CSO performance can be improved by properly choosing the dispersion compensation amount for a certain fibre transmission link.

Analysis of dispersion compensation for position-dependence in externally modulated CATV lightwave systems by using chirped fiber grating

The dispersion compensation characteristics of the chirped fiber grating (CFG) for different dispersion compensation positions are analyzed in externally modulated cable television (CATV) lightwave system and the analytic expression of the composite second order (CSO) distortion is derived. The analyses give a reasonable explanation for the position-dependent effect of CFG dispersion compensator, which was found in practical systems. Moreover, the theoretical result is also verified by an experiment. It is believed that the theory will be helpful in designing optical CATV fiber links with nodes at proper positions both for intensity amplification and dispersion compensation.

Heterometallic Complexes as Models of Enzymatic Active Sites

This dissertation describes studies on two multinucleating ligand architectures: the first scaffold was designed to support tricopper complexes, while the second platform was developed to support tri- and tetrametallic clusters.

In Chapter 2, the synthesis of yttrium (and lanthanide) complexes supported by a tripodal ligand framework designed to bind three copper centers in close proximity is described. Tricopper complexes were shown to react with dioxygen in a 1:1 [Cu₃]/O₂ stoichiometry to form intermediates in which the O–O bond was fully cleaved, as characterized via UV-Vis spectroscopy and determination of the reaction stoichiometry. Pre-arrangement of the three Cu centers was pivotal to cooperative O₂ activation, as mono-copper complexes reacted differently with dioxgyen. The reactivity of the observed intermediates was studied with various substrates (reductants, O-atom acceptors, H-atom donors, Brønsted acids) to determine their properties. In Chapter 3, the reactivity of the same yttrium-tricopper complex with nitric oxide was explored. Reductive coupling to form a trans-hyponitrite complex (characterized by X-ray crystallography) was observed via cooperative reactivity by an yttrium and a copper center on two distinct tetrametallic units. The hyponitrite complex was observed to release nitrous oxide upon treatment with a Brønsted acid, supporting its viability as an intermediate in nitric oxide reduction to nitrous oxide.

In Chapter 4, a different multinucleating ligand scaffold was employed to synthesize heterometallic triiron clusters containing one oxide and one hydroxide bridges. The effects of the redox-inactive, Lewis acidic heterometals on redox potential was studied by cyclic voltammetry, unveiling a linear correlation between redox potential and heterometal Lewis acidity. Further studies on these complexes showed that the Lewis acidity of the redox-inactive metals also affected the oxygen-atom transfer reactivity of these clusters. Comparisons of this reactivity with manganese systems, collaborative efforts to reassign the structures of related manganese oxo-hydroxo clusters, and synthetic attempts to access related dioxo clusters are also described.

In Appendix A, ongoing efforts to synthesize new clusters supported by the same multinucleating ligand platform are described. Studies of novel approaches towards ligand exchange in tetrametallic clusters and incorporation of new supporting and bridging ligand motifs in trinuclear complexes are presented.

Design of a timber Howe truss highway bridge

The span of the bridge was assumed as 100 feet. The type of bridge used is the timber Howe Truss. The height of truss was taken as 20 feet between center lines of top and bottom chords. The width was taken as 18 feet center to center of trusses. The truss was divided up into five panels 20 feet long.

It was designed according to the "General Specifications for Steel Highway Bridges" by Ketchum. For the live load for the floor and its supports, a load of 80 pounds per square foot of total floor surface or a 15 ton traction engine with axles 10 feet centers and 6 feet gage, two thirds of load to be carried by rear axles.

For the truss a load of 75 pounds per square foot of floor surface.

For the wind load the bottom lateral bracing is to be designed to resist a lateral wind load of 300 pounds per foot of span; 150 pounds of this to be treated as a moving load.

The top lateral bracing is to be designed to resist a lateral wind force of 150 pounds per foot of span.

The timber to be used in the bridge is to be Douglas fir.

The unit stresses used for timber are those of the American Railway Engineering Association.

Part I. Synchronization of the cell division cycle of HeLa cells in suspension cultures. Part II. Studies on chromosomal proteins of HeLa cells during the cell division cycle

Part I

These studies investigate the potential of single and double treatments with either 5-fluorodeoxyuridine of excess thymidine to induce cell division synchrony in suspension cultures of HeLa cells. The patterns of nucleic acid synthesis and cell proliferation have been analyzed in cultures thus synchronized. Several changes in cell population during long incubation with 5-fluorodeoxyuridine or excess thymidine are also described. These results are subjected to detailed evaluation in terms of the degree and quality of synchrony finally achieved.

Part II

Histones and non-histone proteins associated with interphase and metaphase chromosomes of HeLa cells have been qualitatively and quantitatively analyzed. Histones were fractionated by chromatography on Amberlite CG-50 and further characterized by analytical disc electrophoresis and amino acid analysis of each chromatographic fraction. It is concluded that histones of HeLa cells are comprised of only a small number of major components and that these components are homologous to those of other higher organisms. Of all the histones, arginine-rich histone III alone contains cysteine and can polymerize through formation of intermolecular disulfide bridges between histone III monomers.

A detailed comparison by chromatography and disc electrophoresis established that interphase and metaphase histones are made up of similar components. However, certain quantitative differences in proportions of different histones of interphase and metaphase cells are reported. Indirect evidence indicates that a certain proportion of metaphase histone III is polymerized through intermolecular disulfide links, whereas interphase histone III occurs mainly in the monomeric form.

Metaphase chromosomes are associated with an additional acid-soluble protein fraction which is absent from interphase chromosomes. All of these additional acid-soluble proteins of metaphase chromosomes are shown to be non-histones and it is concluded that the histone/DNA ratio is identical in interphase and metaphase chromosomes. The bulk of acid-soluble non-histone proteins of metaphase chromosomes were found to be polymerized through disulfide bridges; corresponding interphase non-histone proteins displayed no evidence of similar polymerization.

The factors responsible for the condensed configuration and metabolic inactivity of metaphase chromosomes are discussed in light of these findings.

The relationship between histone and DNA synthesis in nondividing differentiated chicken erythrocyte cells and in rapidly dividing undifferentiated HeLa cells is also investigated. Of all the histones, only arginine-rich histones are synthesized in mature erythrocytes. Histone synthesis in HeLa cells was studied in both unsynchronized and synchronized cultures. In HeLa cells, only part of the synthesis of all histone fractions is dependent on concurrent DNA synthesis, whereas all histones are synthesized in varying degrees even in the absence of DNA synthesis.

Analysis of dispersion compensation by chirped fiber grating in directly and externally modulated CATV systems

The dispersion compensation effect of the chirped fiber grating (CFG) is analyzed theoretically, and analytic expressions are derived for composite second-order (CSO) distortion in analog modulated sub-carrier multiplexed (AM-SCM) cable television (CATV) systems with externally and directly modulated transmitters. Simulations are given for the two kinds of modulations and for standard single mode fiber and non-zero dispersion shift fiber (NZDSF) systems. The results show that CFG could be used as a dispersion compensator in directly modulated systems, but its dispersion coefficient should be adjusted much more precisely than the externally modulated system. The requirements for the NZDSF system could be loosened much. It is proposed that directly modulated source may be used as a transmitter in CATV systems combined with tunable CFG dispersion compensator being adjusted precisely, which may be more cost-effective than externally modulation technology. (c) 2006 Elsevier GmbH. All rights reserved.