Organocatalytic enantioselective construction of nitrocyclohexanes containing multiple chiral centres via a cascade reaction

The stereoselective construction of complex molecules with multiple stereogenicity in a single step represents an extremely useful, but challenging approach to complexity in chemical synthesis. The development of organocatalytic cascade processes has proven useful in these studies, but reports where four or more stereocentres are created in a single step from just two achiral reagents are rare. Herein we report the development of a novel asymmetric domino Michael-Michael reaction between nitrohex-4-enoates and nitro-olefins to generate cyclohexanes of high complexity, including one with a quaternary centre, and one with five contiguous stereocentres. This methodology provides access to a range of useful nitrocyclohexane derivatives, including a novel class of a-lycorane-like structures.

Asymmetric organocatalysis and the nitro group functionality

The nitro group is an exceptionally versatile functional group, not only because it is essentially a masked amine, but also because its chemistry can be exploited in a number of useful ways. Asymmetric organocatalysis in particular has capitalized on the use of the nitro group towards the synthesis of a variety of nitrogen- containing targets. Perhaps of greatest interest is that this functional group has been shown to be invaluable within the rapidly expanding field of organocatalytic domino reactions. This review features selected examples of nitro group reactivity in organocatalysis to demonstrate its dynamism and utility.

A conceptual framework for service system interaction

There is a growing research concern on how service ecosystems form and interact. This research thus aims to explore the service ecosystem formation and interaction as well as its underlying nature of value co-creation. This work develops an initial conceptual framework for assessing service system interactions that includes the various stages of value co-creation within ecosystem context. How the conceptual framework will further be developed and future plan are also presented.

Proposta e implementação de uma máquina de workflow para o Projeto CEMT

Este trabalho apresenta um protótipo de uma máquina de workflow, de uso geral, implementado em plataforma de software livre. O protótipo utiliza um servidor web com PHP, em sistema operacional Linux, alguns programas desenvolvidos em C e o banco de dados MySql. O projeto CEMT demanda o uso da tecnologia de workflow, com o objetivo de controlar a execução de cursos a distância. Antes de ser iniciado o desenvolvimento do protótipo, foi feito um estudo sobre algumas máquinas de workflow existentes, com o objetivo de encontrar alguma que tivesse licença livre e pudesse ser utilizada no projeto CEMT, ou colher subsídios para o desenvolvimento de uma máquina de workflow própria. Foram testadas duas máquinas de workflow de licença livre (Openflow e OFBIZ), uma máquina com cópia de demonstração (Reactor) e foram consultadas as documentações fornecidas pelos fabricantes. Além disso foi consultada também a documentação do Domino Workflow, que não disponibilizou cópia de avaliação e cuja licença não é livre. Um dos requisitos do protótipo é a compatibilidade com os padrões de interface recomendados pela WfMC. Esses padrões permitem a interoperabilidade entre softwares de workflow. O primeiro benefício da adoção desses padrões é a interação com o editor gráfico de workflow AW (Amaya Workflow), desenvolvido no Instituto de Informática da UFRGS. Este editor gera definições de processos de workflow no formato da linguagem XPDL (XML Process Definition Language), que alimentam a máquina de workflow. O esquema XPDL foi traduzido para um esquema de banco de dados relacional e foi desenvolvido um compilador que lê um arquivo no formato XPDL e gera comandos SQL de inserção das informações desse arquivo no banco de dados. Foi desenvolvida uma interface web para demonstrar o funcionamento do protótipo. A API definida na Interface 2 da WfMC foi implementada parcialmente. Essa API permite o desenvolvimento independente de outras interfaces de usuário. Foram propostas algumas extensões à Interface 1 e modificações na definição de estados recomendada pela Interface 2 da WfMC. Com isso foi possível aumentar o controle sobre a execução das instâncias de workflow. Foram incluídas as restrições de data e possibilidade de bloqueio na execução de instâncias de atividades. Outras extensões possibilitam um serviço de notificações e atividades em grupo e oferecem novas possibilidades de alocação de atividades. O funcionamento básico do protótipo é descrito e inclui as funcionalidades de carga da definição de processo, instanciação de processo, visualização da lista de trabalho e execução das atividades, entre outras.

O processo de humanização: as bases constitutivas da subjetividade

Iniciando-se por uma descrição longitudinal, seguida de interpretação "a posteriori", obteve-se categorias relativas a cada dimensão do psiquismo. Estas, em seu caráter de transversalidade, foram tomadas como esteios para as explicações acerca da passagem do sujeito da condição biológica à condição de sujeito falante. O norteamento dessa análise teve como ponto de partida a postulação acerca dessas dimensões, dos aspectos relativos as mesmas, e dos efetores referentes por essa passagem, cujo início tem a esses aspectos que respondem lugar quando a mãe se dispõe a apontar para o sujeito o limite entre o núcleo filogenético e as transformações sócio-histórica. A partir dessa delimitação, ocorre a assimilação de características, tipicamente humanas para, enfim, serem fixados pela lei paterna, os limites do “tornar-se humano”. Nesse ínterim, são observadas ocorrências relativas as dimensões mencionadas. Tratando-se de permanência de conteúdos mantidos fora do campo da simbolização, e excluídos da matriz imaginária, tem-se então a caracterização do real ~elo seu mecanismo específico: a foraclusão. Ainda se situa a pulsão no seu caráter impensável e inominável. Já as ações resultantes do recalcamento originário concorrem para a formação de marcas não-simbolizáveis que, como faceta do imaginário, se vinculam às informações do núcleo filogenético referentes aos protofantasmas, aqui considerado corno outra faceta desta dimensão. No que concerne ao simbólico, registra-se a significação como fundante da condição humana, resultante do recalcamento propriamente dito. Sendo assim, a humanização enquanto explicada pelo conceito de recalcamento, conforme evidencia a metapsicologia freudiana, não açambarça todas as nuances relativas ao humano; visto englobar apenas aquilo que é imaginado corno fantasma ou aquilo que e apresentado simbolicamente. Por isso, a utilização do conceito de foraclusão, da perspectiva lacaniana, justifica-se pelo fato de oferecer uma visão mais completa dessa dinâmica. Desse modo, se pode incluir no escopo do "tornar-se humano", aqueles elementos não passíveis de simbolização, bem como aqueles da realidade pulsional que não se apresentam no texto do fantasma; mas que, ao se constituírem como um "pano-de-fundo", possibilitam que a conteúdos simbólicos e imaginários viabilizem a socialização. De resto, a socialização é um processo que, originado do simbólico, se assenta no imaginário tomado como base. Para isto, o real, em seu efeito marginal, possibilita o retorno ao simbólico. A partir daí, se verifica a utilização dos elementos culturais, que são descobertos em função daquilo que a atividade fantasmática suscita.

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

Petrologia do plúton granitico serra verde, porção lestre do domínio seridó

The study area is located at the eastern-central portion of the Seridó Belt, on the interface between the Seridó Group Metasediments and the crystalline basement rocks of the Caicó Complex (RN). Petrographic and geochemical data allow us to define aspects related to the genesis and evolution of the Serra Verde Pluton magmas, which composes the goal of this dissertation The Serra Verde Pluton is a stock with outcropping area of about 25 km², which is intrusive into metasedimentary sequence and the basement gneisses. The pluton intrusion is sintectonic to the Brasiliano event, elongated along the NE direction, developing a cornue geometry. The rock is a monzogranite mainly composed by K-feldspar, plagioclase and quartz, which usually compose more than 85% of the modal analisys. The main mafic mineral is the biotite, while amphibole, sphene, epidote, opaque minerals, allanite, zircon and apatite occur as accessory minerals. It features still a latemagmatic paragenesis composed by chlorite, granular epidote, carbonates and muscovite, developed through the percolation of late CO2 and H2O rich fluids. Chemically, the Serra Verde Pluton rocks may be classified as metaluminous, of calc-alkaline affiliation, sometimes showing trondhjemític characteristics, with high Na2O (>4,5%), Sr (>400ppm) and Ba (>800ppm) and low K2O (≤3,0%), MgO (<1,0%), TiO2 (<0,5%), Rb (<90ppm), Y (≤16ppm) and Zr (≤13ppm). Micropetrographic evidences (mineral assembly and microtextures) indicate that the magma evolution occurred in moderated to high fO2 conditions, above the FMQ buffer. Thermo-barometric data obtained by minor elements geochemistry and the CIPW data, suggest a final/minimal pressure crystallization for the Serra Verde Pluton samples of about 3 to 5 kbar, liquidus temperature around 800o C, solidus temperature between 680o and 660o C. This data is compatible with those observed by many authors for the Neoproterozoic granites of the Seridó Belt. The group of analyzed data (Petrographic, microtextural and geochemical), suggests that the dominant process of the generation and evolution of the Serra Verde Granite magma was the fractional crystallization, probably from basement quartz-dioritic and tonalitic orthogneisses source

Astrocytes and human cognition: Modeling information integration and modulation of neuronal activity

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

O princípio da igualdade e as obrigações constitucionais do Estado na tutela penal

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

O efeito vinculante e as garantias constitucionais do processo

Pós-graduação em Direito - FCHS

Resolução de problemas no cenário da matemática discreta

Pós-graduação em Educação Matemática - IGCE

O jogo de dominó como contexto interativo para a construção de conhecimentos por pré-escolares

Vários autores reconhecem a importância de jogar com regras para o desenvolvimento infantil. Poucos estudos têm analisado a construção de conhecimentos no contexto das interações sociais, em jogos específicos. O presente estudo documentou as mudanças no desempenho de crianças pré-escolares jogando dominó, considerando: o seguimento das regras do jogo, o domínio dos conceitos implícitos nelas e as interações entre os participantes. Ao longo de um ano, vinte pré-escolares jogaram quatro tipos de dominó com dificuldades conceituais crescentes. Apesar de não terem tido experiências prévias com este jogo, o percentual de erros por tipo de dominó foi sempre inferior a doze por cento das jogadas e foram corrigidos em proporção semelhante pelas crianças e pelo pesquisador. As interações propiciaram momentos de transmissão e de construção de conhecimentos compartilhados.

Adequação de demandas funcionais de atividades para a participação escolar de crianças com disfu'nções neuromotoras

The school participation is a prerequisite for the construction of knowledge, learning and development. Neurological deficits may affect child's ability to explore the environment and engage in typical activities. Considering the importance of encouraging professionals in the field of education to conduct simple adjustments in school activities of daily life, this study aimed to adapt, with low cost materials, resources of entertainment and educational for children with neuromotor disorders . It was objects of this study eight resources prescribed and designed for three children diagnosed with cerebral palsy: domino, puzzle, memory game, moving magnetized alphabet, crossword, doll body scheme, adaptation of pencils for writing and bracelet sinker.The analysis of these resources occurred in the parameters of conventional design and management skills, followed by identifying the limiting conditions of the motor skills of the cases observed, indicating the materials used in the adaptation and possible uses. This study provides subsidy for implementation of teaching strategies in the care of students with neuromotor disorders.

A crise do subprime e seus efeitos sobre os Estados Unidos e reflexos no Brasil

Between December 2007 and June 2009 the United States witnessed 18 months of recession that became known as the subprime crisis. Beginning in the housing market, the crisis moved into the banking and financial markets and spread throughout the entire economy through a domino effect, affecting the majority of other businesses. A major reflection of this was the large rise in unemployment rates due to business slashing jobs in an attempt to preserve cash. Although the crisis has officially ended, the unemployment rate reached over 10% in 2010 in the United States. American's continue to seek new jobs in a very difficult employment market, while attempting to manage the family household budget. American household income, which decreased either by pay cuts, job loss, and the effects of inflation, leads the majority of Americans to declare that the crisis had not yet ended. The crisis has spread to the world in varying degrees. Brazil was one of the countries least affected due to government policies and the large amount of foreign exchange. Although the crisis has affected Brazil only slightly, we will show how it reached this country and how the government solved this problem. This research paper will explain how the subprime crisis began, how it manifested itself in the U.S. economy and throughout the population. Also, it will show the crisis’ effects in Brazil and show some statements from Americans with their respective views and their experiences relative to the crisis

Sincronia das bolsas de valores

This study aims to analyze various index stock exchanges around the world, with mathematical methods, analyzing the Product Distribution function (PDF), cumulative distribution and correlation. It is thought that the world economy is connected, as if the financial markets were a network, where the fluctuation of a market generates a variation on another and another, creating a pattern, that this change will affect the entire network, thus creating what we might call the domino effect. From this we intend to study, using as a basis the main index of the major stock exchanges around the world the relationship they have with each other, analyzing the influence and correlation that generates this effect, showing that markets are connected and influence each other. We can see this effect in the crisis of 2008, where the U.S. market from one moment to the other was shaken, affecting the whole world in a few days, creating effects that are felt in the present day