On the Relaxation Mechanisms of 6-Azauracil

The nonadiabatic photochemistry of 6-azauracil has been studied by means of the CASPT2//CASSCF protocol and double-zeta plus polarization ANO basis sets. Minimum energy states, transition states, minimum energy paths, and surface intersections have been computed in order to obtain an accurate description of several potential energy hypersurfaces. It is concluded that, after absorption of ultraviolet radiation (248 nm), two main relaxation mechanisms may occur, via which the lowest (3)(pi pi*) state can be populated. The first one takes place via a conical intersection involving the bright (1)(pi pi*) and the lowest (1)(n pi*) states, ((1)pi pi*/(1)n pi*)(CI), from which a low energy singlet-triplet crossing, ((1)n pi*/(3)pi pi*)(STC), connecting the (1)(n pi*) state to the lowest (3)(pi pi*) triplet state is accessible. The second mechanism arises via a singlet-triplet crossing, ((1)pi pi*/(3)n pi*)(STC), leading to a conical intersection in the triplet manifold, ((3)n pi*/(3)pi pi*)(CI), evolving to the lowest (3)(pi pi*) state. Further radiationless decay to the ground state is possible through a (gs/(3)pi pi*)(STC).

A three-state model for the photophysics of guanine

The nonadiabatic photochemistry of the guanine molecule (2-amino-6-oxopurine) and some of its tautomers has been studied by means of the high-level theoretical ab initio quantum chemistry methods CASSCF and CASPT2. Accurate computations, based by the first time on minimum energy reaction paths, states minima, transition states, reaction barriers, and conical intersections on the potential energy hypersurfaces of the molecules lead to interpret the photochemistry of guanine and derivatives within a three-state model. As in the other purine DNA nucleobase, adenine, the ultrafast subpicosecond fluorescence decay measured in guanine is attributed to the barrierless character of the path leading from the initially populated (1)(pi pi* L-a) spectroscopic state of the molecule toward the low-lying methanamine-like conical intersection (gs/pi pi* L-a)(CI). On the contrary, other tautomers are shown to have a reaction energy barrier along the main relaxation profile. A second, slower decay is attributed to a path involving switches toward two other states, (1)(pi pi* L-b) and, in particular, (1)(n(o)pi*), ultimately leading to conical intersections with the ground state. A common framework for the ultrafast relaxation of the natural nucleobases is obtained in which the predominant role of a pi pi*-type state is confirmed.

Parcelamento do solo, a necessidade de uniformizar alguns padrões de projetos das vias urbanas

Este trabalho faz uma análise da legislação sobre o parcelamento do solo nas diferentes instâncias de Governo. São analisadas as diversidades e contradições das leis municipais de parcelamento do solo de onze prefeituras estrategicamente distribuídas no Estado. A análise foca em particular o tratamento da hierarquia viária; as dimensões dos gabaritos viários; as rampas empregadas; o comprimento máximo dos quarteirões nos loteamentos residenciais em função da testada mínima dos lotes e a concordância vertical nas interseções. São analisados também os requisitos técnicos de projeto geométrico de vias urbanas estabelecidas por Órgãos federais e estaduais. A revisão bibliográfica aborda questões fundamentais na urbanização tais como os pedestres, as interseções e a capacidade das vias urbanas, com o propósito de sustentar a proposição de alterações nos requisitos técnicos preconizados pelas legislações sobre o parcelamento do solo urbano. Suprindo lacuna constatada na legislação municipal sobre o parcelamento do solo e, fundamentado em simulação gráfica com veículo de transporte coletivo urbano, o trabalho apresenta tabela com sugestões para o tratamento de curvas verticais nas interseções das vias urbanas nos loteamentos. Com as informações obtidas da análise da legislação, na pesquisa bibliográfica e dos requisitos técnicos constantes nas normas conhecidas, propõe-se dimensões para vias urbanas, comprimento ideal para quarteirões residenciais, valores de taxas de declividade urbana e formas de executar-se a concordância destas rampas nas interseções. Com os valores planimétricos sugeridos fez-se um parcelamento em gleba fictícia e comparou-se os resultados com outros loteamentos projetados na mesma gleba utilizando-se as prescrições das leis municipais estudadas.

Transversalidade e políticas públicas para mulheres no Brasil: percursos de uma pré-política

Esta dissertação discute a transversalidade como instrumento estratégico para a gestão de políticas públicas para as mulheres no Brasil. Parte de uma reconstituição histórica, que leva em conta o surgimento das políticas para as mulheres com a redemocratização do país, e os caminhos percorridos para desenvolvê-las em governos locais e no nacional. Destaca o papel de organismos governamentais específicos de políticas para as mulheres, bem como de atores internacionais, que pautam a transversalidade como estratégia para a promoção da igualdade de gênero nas políticas de instituições governamentais e não governamentais. A discussão conceitual sobre transversalidade é seguida de análise sobre os fatores que a influenciam na prática, uma lacuna da literatura ainda incipiente sobre o tema. Os fatores foram identificados a partir de entrevistas-conversas com gestoras e gestores envolvidos com o Pacto Nacional pelo Enfrentamento à Violência contra as Mulheres, criado em 2007. Conclui-se que, entre constrangimentos e oportunidades trabalhadas a partir do cotidiano entre gestores de diferentes políticas setoriais, a transversalidade pode contribuir para o avanço das políticas para as mulheres no Brasil, mas está distante do que se propõe normativamente a seu respeito.

Sistemas de gestão para resultados no setor público: intersecções entre política, governança e desempenho nas prefeituras de Rio de Janeiro e São Paulo

A gestão para resultados (GpR) tem adquirido importância crescente nos municípios brasileiros, assumindo diferentes funções no interior das organizações públicas. No entanto, implementação de sistemas de GpR no setor público pode vir acompanhada de novos problemas oriundos da complexidade da mensuração de resultados em ambientes expostos ao escrutínio social e político. Nesse contexto, o objetivo deste trabalho é analisar de forma crítica os sistemas de GpR implantados nas prefeituras de Rio de Janeiro e São Paulo, visando a estabelecer, com base na teoria, conexões entre as diferentes funções exercidas pelos sistemas de GpR e as disfunções vivenciadas pelos gestores públicos no cotidiano. Para tanto, foram mapeadas, com base na teoria, as diferentes funções desempenhadas pelos sistemas de GpR e separadas em três macrocategorias: desempenho, governança e política. A partir dessa categorização, foram delimitadas as possíveis disfunções da GpR relacionadas com as intersecções dessas diferentes macrocategorias. Com base nas categorias teóricas estabelecidas, foram coletados dados sobre a GpR nas duas prefeituras, com destaque para a entrevista de 12 gestores e 3 representantes da sociedade civil. Os achados de pesquisa permitiram demonstrar que a Prefeitura do Rio de Janeiro implementou um sistema de GpR voltado principalmente para a melhoria do desempenho, ao passo que São Paulo focou nas funções relacionadas à macrocategoria da governança. Em relação às disfunções, o Rio de Janeiro apresentou indícios de definição tecnocrátia das metas e gaming interno, ao passo que a Prefeitura de São Paulo esteve marcada por gaming externo, miopia e lock-in. Os resultados permitiram identificar ainda outras variáveis relevantes para o estudo das disfunções da GpR, como a cultura política, o envolvimento do prefeito no sistema, a entrada na agenda do tema da GpR, o grau de institucionalização do sistema de GpR. Os resultados demonstram que as diferentes funções assumidas por esses sistemas estão correlacionadas com as disfunções. O capítulo final explora essas possibilidades de correlações.

On invariant Rings of Sylow subgroups of finite classical groups

In this thesis we study the invariant rings for the Sylow p-subgroups of the nite classical groups. We have successfully constructed presentations for the invariant rings for the Sylow p-subgroups of the unitary groups GU(3; Fq2) and GU(4; Fq2 ), the symplectic group Sp(4; Fq) and the orthogonal group O+(4; Fq) with q odd. In all cases, we obtained a minimal generating set which is also a SAGBI basis. Moreover, we computed the relations among the generators and showed that the invariant ring for these groups are a complete intersection. This shows that, even though the invariant rings of the Sylow p-subgroups of the general linear group are polynomial, the same is not true for Sylow p-subgroups of general classical groups. We also constructed the generators for the invariant elds for the Sylow p-subgroups of GU(n; Fq2 ), Sp(2n; Fq), O+(2n; Fq), O-(2n + 2; Fq) and O(2n + 1; Fq), for every n and q. This is an important step in order to obtain the generators and relations for the invariant rings of all these groups.

Estudo da circulação hidrodinâmica e da dispersão de óleo na zona costeira entre Macau e Galinhos RN

This paper presents a study on coastal hydrodynamics and the spread of an oil spill in waters off Macau and Galinhos, on the east coast of the state of Rio Grande do Norte in Northeast Brazil. This area has a very marked coastal dynamic owing to the complexity of its geomorphological features, developed in a regime of semidiurnal mesotides involving reefs, spits, estuaries, mangroves, lakes and dunes. The region also plays an important role in the socioeconomic development of the state, given that the production of oil, natural gas, salt and shrimp is concentrated there. The series of oil platforms is interconnected by a pipeline system that carries oil to the local terminal. This pipeline could leak at any moment, causing immense ecological damage. To gauge the risks of an oil leak and resulting contamination of the coastal region, two hydrodynamic scenarios were simulated. The results obtained were used to implement a contaminant transport model with the creation of various oil leak scenarios modeled at different volumes (from small to large) and intensities (sporadic and continuous), at points considered critical for the model (on two platforms and at two pipeline intersections), under different wind (summer and winter) and tidal (high and low at new, full and quarter moon phases) conditions. The use of hydrodynamic circulation computer models as a tool for representing a real project design has been increasingly frequent in recent years, given that they enable the realistic simulation of the hydrodynamic circulation pattern in bodies of water and an analysis of the impacts caused by contaminants released into the water. This study used the computer models contained in SisBAHIA®, in continuous development in the area of Coastal Engineering and Oceanography at COPPE/UFRJ

PERIODIC PERTURBATION of QUADRATIC SYSTEMS WITH TWO INFINITE HETEROCLINIC CYCLES

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Time-periodic perturbation of a Lienard equation with an unbounded homoclinic loop

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Periodic perturbations of quadratic planar polynomial vector fields

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Differential geometry of intersection curves in R(4) of three implicit surfaces

We present algorithms for computing the differential geometry properties of intersection Curves of three implicit surfaces in R(4), using the implicit function theorem and generalizing the method of X. Ye and T. Maekawa for 4-dimension. We derive t, n, b(1), b(2) vectors and curvatures (k(1), k(2), k(3)) for transversal intersections of the intersection problem. (C) 2008 Elsevier B.V. All rights reserved.

Litoestratigrafia e deformação cenzóica na região de Icapuí, Ceará, e implicações para a estruturação de campos de petróleo na borda ocidental da bacia Potiguar(NE do Brasil)

This thesis deals with the sedimentological/stratigraphic and structural evolution of the sedimentary rocks that occur in the NW continental border of the Potiguar Basin. These rocks are well exposed along coastal cliffs between the localities of Lagoa do Mato and Icapuí, Ceará State (NE Brazil). The sedimentological/stratigraphic study involved, at the outcrop scale, detailed facies descriptions, profile mapping of the vertical succession of different beds, and columnar sections displaying inferred lateral relationships. The approach was complemented by granulometric and petrographic analyses, including the characterization of heavy mineral assemblages. The data set allowed to recognize two kinds of lithological units, a carbonate one of very restricted occurrence at the base of the cliffs, and three younger, distinct siliciclastic units, that predominate along the cliffs, in vertical and lateral extent. The carbonate rocks were correlated to the late Cretaceous Jandaíra Formation, which is covered by the siliciclastic Barreiras Formation. The Barreiras Formation occurs in two distinct structural settings, the usual one with nondeformed, subhorizontal strata, or as tilted beds, affected by strong deformation. Two lithofacies were recognized, vertically arranged or in fault contacts. The lower facies is characterized by silty-argillaceous sandstones with low-angle cross bedding; the upper facies comprises medium to coarse grained sandstones, with conglomeratic layers. The Tibau Formation (medium to coarse-grained sandstones with argillite intercalations) occurs at the NW side of the studied area, laterally interlayered with the Barreiras Formation. Eolic sediments correlated to the Potengi Formation overly the former units, either displaying an angular unconformity, or simply an erosional contact (stratigraphic unconformity). Outstanding structural features, identified in the Barreiras Formation, led to characterize a neocenozoic stress field, which generated faults and folds and/or reactivated older structures in the subjacent late cretaceous (to paleogene, in the offshore basin) section. The structures recognized in the Barreiras Formation comprise two distinct assemblages, namely a main extensional deformation between the localities of Ponta Grossa and Redonda, and a contractional style (succeeded by oblique extensional structures) at Vila Nova. In the first case, the structural assemblage is dominated by N-S (N±20°Az) steep to gently-dipping extensional faults, displaying a domino-style or listric geometry with associated roll-over structures. This deformation pattern is explained by an E-W/WNW extension, contemporaneous with deposition of the upper facies of the Barreiras Formation, during the time interval Miocene to Pleistocene. Strong rotation of blocks and faults generated low-angle distensional faults and, locally, subvertical bedding, allowing to estimate very high strain states, with extension estimates varying between 40% up to 200%. Numerous detachment zones, parallel to bedding, help to acommodate this intense deformation. The detachment surfaces and a large number of faults display mesoscopic features analoguous to the ones of ductile shear zones, with development of S-C fabrics, shear bands, sigmoidal clasts and others, pointing to a hydroplastic deformation regime in these cases. Local occurrences of the Jandaíra limestone are controled by extensional faults that exhume the pre-Barreiras section, including an earlier event with N-S extension. Finally, WNWtrending extensional shear zones and faults are compatible with the Holocene stress field along the present continental margin. In the Vila Nova region, close to Icapuí, gentle normal folds with fold hinges shallowly pluging to SSW affect the lower facies of the Barreiras Formation, displaying an incipient dissolution cleavage associated with an extension lineation at high rake (a S>L fabric). Deposition of the upper facies siliciclastics is controlled by pull-apart graben structures, bordered by N-NE-trending sinistral-normal shear zones and faults, characterizing an structural inversion. Microstructures are compatible with tectonic deformation of the sedimentary pile, burried at shallow depths. The observed features point to high pore fluid pressures during deformation of the sediments, producing hydroplastic structures through mechanisms of granular flow. Such structures are overprinted by microfractures and microfaults (an essentially brittle regime), tracking the change to microfracturing and frictional shear mechanisms accompanying progressive dewatering and sediment lithification. Correlation of the structures observed at the surface with those present at depth was tested through geophysical data (Ground Penetrating Radar, seismics and a magnetic map). EW and NE-trending lineaments are observed in the magnetic map. The seismic sections display several examples of positive flower structures which affect the base of the cretaceous sediments; at higher stratigraphic levels, normal components/slips are compatible with the negative structural inversion characterized at the surface. Such correlations assisted in proposing a structural model compatible with the regional tectonic framework. The strong neogenepleistocene deformation is necessarily propagated in the subsurface, affecting the late cretaceous section (Açu and Jandaíra formations), wich host the hydrocarbon reservoirs in this portion of the Potiguar Basin. The proposed structural model is related to the dextral transcurrent/transform deformation along the Equatorial Margin, associated with transpressive terminations of E-W fault zones, or at their intersections with NE-trending lineaments, such as the Ponta Grossa-Fazenda Belém one (the LPGFB, itself controlled by a Brasiliano-age strike-slip shear zone). In a first step (and possibly during the late Cretaceous to Paleogene), this lineament was activated under a sinistral transpressional regime (antithetic to the main dextral deformation in the E-W zones), giving way to the folds in the lower facies of the Barreiras Formation, as well as the positive flower structures mapped through the seismic sections, at depth. This stage was succeeded (or was penecontemporaneous) by the extensional structures related to a (also sinistral) transtensional movement stage, associated to volcanism (Macau, Messejana) and thermal doming processes during the Neogene-Pleistocene time interval. This structural model has direct implications to hydrocarbon exploration and exploitation activities at this sector of the Potiguar Basin and its offshore continuation. The structure of the reservoirs at depth (Açu Formation sandstones of the post-rift section) may be controlled (or at least, strongly influenced) by the deformation geometry and kinematics characterized at the surface. In addition, the deformation event recognized in the Barreiras Formation has an age close to the one postulated for the oil maturation and migration in the basin, between the Oligocene to the Miocene. In this way, the described structural cenario represents a valid model to understand the conditions of hydrocarbon transport and acummulation through space openings, trap formation and destruction. This model is potentially applicable to the NW region of the Potiguar Basin and other sectors with a similar structural setting, along the brazilian Equatorial Atlantic Margin

Soliton parameters and chaotic sets

In this work we apply a nonperturbative approach to analyze soliton bifurcation ill the presence of surface tension, which is a reformulation of standard methods based on the reversibility properties of the system. The hypothesis is non-restrictive and the results can be extended to a much wider variety of systems. The usual idea of tracking intersections of unstable manifolds with some invariant set is again used, but reversibility plays an important role establishing in a geometrical point of view some kind of symmetry which, in a classical way, is unknown or nonexistent. Using a computer program we determine soliton solutions and also their bifurcations ill the space of parameters giving a picture of the chaotic structural distribution to phase and amplitude shift phenomena. (C) 2009 Published by Elsevier Ltd.

Otimização amostral de atributos de latossolos considerando aspectos solo-relevo

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

TRICUT: a program to clip triangle meshes using the rapid and triangle libraries and the visualization toolkit

An efficient technique to cut polygonal meshes as a step in the geometric modeling of topographic and geological data has been developed. In boundary represented models of outcropping strata and faulted horizons polygonal meshes often intersect each other. TRICUT determines the line of intersection and re-triangulates the area of contact. Along this line the mesh is split in two or more parts which can be selected for removal. The user interaction takes place in the 3D-model space. The intersection, selection and removal are under graphic control. The visualization of outcropping geological structures in digital terrain models is improved by determining intersections against a slightly shifted terrain model. Thus, the outcrop line becomes a surface which overlaps the terrain in its initial position. The area of this overlapping surface changes with respect to the strike and dip of the structure, the morphology and the offset. Some applications of TRICUT on different real datasets are shown. TRICUT is implemented in C+ + using the Visualization Toolkit in conjunction with the RAPID and TRIANGLE libraries. The program runs under LINUX and UNIX using the MESA OpenGL library. This work gives an example of solving a complex 3D geometric problem by integrating available robust public domain software. (C) 2002 Elsevier B.V. Ltd. All rights reserved.