Towards to the trans-bromination of 2-styrylpyridine with a palladacycle intermediary and structure analysis for trans-1,2-dibromo-2-styrylpyridine

The simple halogenation of alkynes in conventional organic reactions gives a blend of cis and trans isomers. It is proposed then, a synthesis of stereospecific halogenation of alkynes in trans position, using palladacycle as intermediaries. The recrystallization of the compound obtained by bromination of 2-Styrylpyridine, with cyclepalladium intermediary results in a single crystal, which is subjected to X-ray diffraction. The crystal packing is established through weak interactions of three types. The first one is of the type pi x pi interactions, from symmetry operation, between the centroids. The second one is of the type C-X center dot center dot center dot pi interactions. And the last type is an anomalous intermolecular interaction between halogens, C-X center dot center dot center dot X-C, with bond distances smaller than the sum of the van der Waals radii. The conformation on the C=C bond is trans and the dihedral angle between the aromatic rings is (with esd approximate) 18.1(3)degrees. (C) 2010 Elsevier B.V. All rights reserved.

Fast and Simple Nuclear Magnetic Resonance Method To Measure Conjugated Linoleic Acid in Beef

Conjugated linoleic acids (CLAs) are a group of linoleic acid isomers that are naturally found in food products originating from ruminants (meat and dairy). These acids have received special attention in recent years due to their potential human health benefits. Research efforts have been proposed to increase the CLA content in beef to improve public health. However, because there are more than 30 million beef cattle used each year by the American food industry, it will be necessary to ensure their content in a large number of samples. Therefore, it is important to have an inexpensive and rapid analytical method to measure CLA content in food products. Because gas chromatography (GC), a current popular method for measuring CLAs, is slow, this paper describes a nuclear magnetic resonance spectroscopy ((1)H NMR) method that is potentially >10 times faster than the GC method. Analyses show a correlation coefficient of 0.97, indicating the capacity of NMR to quantify the CLA content in beef samples. Furthermore, the method proposed herein is simple and does not require sophisticated sample preparation.

Microwave-assisted digestion procedures for biological samples with diluted nitric acid: Identification of reaction products

Microwave-assisted sample preparation using diluted nitric acid solutions is an alternative procedure for digesting organic samples. The efficiency of this procedure depends on the chemical properties of the samples and in this work it was evaluated by the determination of crude protein amount. fat and original carbon. Soybeans grains, bovine blood. bovine muscle and bovine viscera were digested in a cavity-microwave oven using oxidant mixtures in different acid concentrations. The digestion efficiency was evaluated based on the determination of residual carbon content and element recoveries using inductively coupled plasma optical emission spectrometry (ICP OES). In order to determine the main residual organic compounds, the digests were characterized by nuclear magnetic resonance (1 H NMR). Subsequently, studies concerning separation of nitrobenzoic acid isomers were performed by ion pair reversed phase liquid chromatography using a C18 stationary phase, water:acetonitrile:methanol (75:20:5, v/v/v) +0.05% (v/v) TFA as mobile phase and ultraviolet detection at 254 nm. Sample preparation based on diluted acids proved to be feasible and a recommendable alternative for organic sample digestion, reducing both the reagent volumes and the variability of the residues as a result of the process of decomposition. It was shown that biological matt-ices containing amino acids, proteins and lipids in their composition produced nitrobenzoic acid isomers and other organic compounds after cleavage of chemical bonds. (C) 2009 Elsevier B.V. All rights reserved.

Improved Road Design for Future Maintenance - Analysis of Road Barrier Repair Costs

The cost of a road construction over its service life is a function of the design, quality of construction, maintenance strategies and maintenance operations. Unfortunately, designers often neglect a very important aspect which is the possibility to perform future maintenance activities. The focus is mainly on other aspects such as investment costs, traffic safety, aesthetic appearance, regional development and environmental effects. This licentiate thesis is a part of a Ph.D. project entitled “Road Design for lower maintenance costs” that aims to examine how the life-cycle costs can be optimized by selection of appropriate geometrical designs for the roads and their components. The result is expected to give a basis for a new method used in the road planning and design process using life-cycle cost analysis with particular emphasis on road maintenance. The project started with a review of literature with the intention to study conditions causing increased needs for road maintenance, the efforts made by the road authorities to satisfy those needs and the improvement potential by consideration of maintenance aspects during planning and design. An investigation was carried out to identify the problems which obstruct due consideration of maintenance aspects during the road planning and design process. This investigation focused mainly on the road planning and design process at the Swedish Road Administration. However, the road planning and design process in Denmark, Finland and Norway were also roughly evaluated to gain a broader knowledge about the research subject. The investigation was carried out in two phases: data collection and data analysis. Data was collected by semi-structured interviews with expert actors involved in planning, design and maintenance and by a review of design-related documents. Data analyses were carried out using a method called “Change Analysis”. This investigation revealed a complex combination of problems which result in inadequate consideration of maintenance aspects. Several urgent needs for changes to eliminate these problems were identified. Another study was carried out to develop a model for calculation of the repair costs for damages of different road barrier types and to analyse how factors such as road type, speed limits, barrier types, barrier placement, type of road section, alignment and seasonal effects affect the barrier damages and the associated repair costs. This study was carried out using a method called the “Case Study Research Method”. Data was collected from 1087 barrier repairs in two regional offices of the Swedish Road Administration, the Central Region and the Western Region. A table was established for both regions containing the repair cost per vehicle kilometre for different combinations of barrier types, road types and speed limits. This table can be used by the designers in the calculation of the life-cycle costs for different road barrier types.

Road Design for Future Maintenance : Life-cycle Cost Analyses for Road Barriers

The cost of a road construction over its service life is a function of design, quality of construction as well as maintenance strategies and operations. An optimal life-cycle cost for a road requires evaluations of the above mentioned components. Unfortunately, road designers often neglect a very important aspect, namely, the possibility to perform future maintenance activities. Focus is mainly directed towards other aspects such as investment costs, traffic safety, aesthetic appearance, regional development and environmental effects. This doctoral thesis presents the results of a research project aimed to increase consideration of road maintenance aspects in the planning and design process. The following subgoals were established: Identify the obstacles that prevent adequate consideration of future maintenance during the road planning and design process; and Examine optimisation of life-cycle costs as an approach towards increased efficiency during the road planning and design process. The research project started with a literature review aimed at evaluating the extent to which maintenance aspects are considered during road planning and design as an improvement potential for maintenance efficiency. Efforts made by road authorities to increase efficiency, especially maintenance efficiency, were evaluated. The results indicated that all the evaluated efforts had one thing in common, namely ignorance of the interrelationship between geometrical road design and maintenance as an effective tool to increase maintenance efficiency. Focus has mainly been on improving operating practises and maintenance procedures. This fact might also explain why some efforts to increase maintenance efficiency have been less successful. An investigation was conducted to identify the problems and difficulties, which obstruct due consideration of maintainability during the road planning and design process. A method called “Change Analysis” was used to analyse data collected during interviews with experts in road design and maintenance. The study indicated a complex combination of problems which result in inadequate consideration of maintenance aspects when planning and designing roads. The identified problems were classified into six categories: insufficient consulting, insufficient knowledge, regulations and specifications without consideration of maintenance aspects, insufficient planning and design activities, inadequate organisation and demands from other authorities. Several urgent needs for changes to eliminate these problems were identified. One of the problems identified in the above mentioned study as an obstacle for due consideration of maintenance aspects during road design was the absence of a model for calculating life-cycle costs for roads. Because of this lack of knowledge, the research project focused on implementing a new approach for calculating and analysing life-cycle costs for roads with emphasis on the relationship between road design and road maintainability. Road barriers were chosen as an example. The ambition is to develop this approach to cover other road components at a later stage. A study was conducted to quantify repair rates for barriers and associated repair costs as one of the major maintenance costs for road barriers. A method called “Case Study Research Method” was used to analyse the effect of several factors on barrier repairs costs, such as barrier type, road type, posted speed and seasonal effect. The analyses were based on documented data associated with 1625 repairs conducted in four different geographical regions in Sweden during 2006. A model for calculation of average repair costs per vehicle kilometres was created. Significant differences in the barrier repair costs were found between the studied barrier types. In another study, the injuries associated with road barrier collisions and the corresponding influencing factors were analysed. The analyses in this study were based on documented data from actual barrier collisions between 2005 and 2008 in Sweden. The result was used to calculate the cost for injuries associated with barrier collisions as a part of the socio-economic cost for road barriers. The results showed significant differences in the number of injuries associated with collisions with different barrier types. To calculate and analyse life-cycle costs for road barriers a new approach was developed based on a method called “Activity-based Life-cycle Costing”. By modelling uncertainties, the presented approach gives a possibility to identify and analyse factors crucial for optimising life-cycle costs. The study showed a great potential to increase road maintenance efficiency through road design. It also showed that road components with low investment costs might not be the best choice when including maintenance and socio-economic aspects. The difficulties and problems faced during the collection of data for calculating life-cycle costs for road barriers indicated a great need for improving current data collecting and archiving procedures. The research focused on Swedish road planning and design. However, the conclusions can be applied to other Nordic countries, where weather conditions and road design practices are similar. The general methodological approaches used in this research project may be applied also to other studies.

Construcao e calibracao de sensores termoeletricos para a medida da radiacao solar

Neste trabalho experimental, apresenta-se várias propostas para a construção de sensores termoelétricos para a medida da radiação solar. 0s sensores construídos segundo estas propostas obedecem 4 configurações geométricas, e têm seus princípios de funcionamento de acordo com dois sistemas: Preto e Branco e de Grande Capacidade Calorífica. 0s materiais utilizados são facilmente encontrados no mercado brasileiro, e a técnica de construção é simples e assegura a reprodutibilidade dos instrumentos. Uma das grandes vantagens oferecidas por alguns destes instrumentos é a possibilidade da utilização de instrumentos auxliares de leitura, baratos e comuns no mercado brasileiro. Enfim, os instrumentos construídos para este trabalho são considerados bons, fornecem um sinal de saída alto e um custo relativamente baixo, quando comparado aos instrumentos importados.

Análise não linear física e geométrica de pórticos espaciais

Apresenta-se uma formulação do tipo incrementaliterativa destinada a análise não linear de pórticos espaciais. Considera-se os efeitos não lineares introduzidos pelas mudanças de configuração geométrica da estrutura e também pela combinação destes efeitos com aqueles inerentes ao comportamento plástico exibido pelo material. As relações cinemáticas empregadas permitem a consideração de deslocamentos arbitrariamente grandes, acompanhadas de pequenas deformações . A modelagem do comportamento plástico do material é efetuada através do conceito de rótula plástica, estabelecido a partir de um critério de plastificação generalizado. Adota-se uma matriz de rigidez geométrica de barra baseada em momentos semitangenciais. Para elementos com extremos plastificados, é deduzida uma matriz de rigidez elasto-plástica. Emprega-se um método numérico do tipo incremental-iterativo, que utiliza como condição básica de controle da análise a constância do trabalho realizado pelos incrementos de cargas, em cada passo incremental (Método de Controle por Trabalho).A formulação permite uma descricão completa do desempenho mecânico da estrutura, inclusive em estágio de deformação pós-crítico em que ocorre regressão do carregamento com aumento de deslocamentos, ou vice-versa. A formulação foi implementada em um programa computacional elaborado em linguagem FORTRAN. Vários exemplos numéricos são apresentados para mostrar a eficiência das procedimentos propostos.

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.

Saudosa Maloca, Maloca querida: um estudo morfológico da relação forma/usos do espaço em moradias autoconstruídas e construídas pelo poder público após um ano de ocupação

This study intends to enhance the existing knowledge concerning the patterns of the uses of space for low cost housing in Parnamirim, Rio Grande do Norte, Brazil, by way of comparative morphological studies in spatial arrangements and articulations regarding three distinct, however inter-related, sets of social housing: (1) a development comprising 21 self-built houses erected on public routes and illegal plots within a tract of land originally designed to be an industrial development: (2) architect-designed houses built by the public authority in order to accommodate the previous 21 (plus a few additions) families occupying the self-built dwellings, and (3) modifications performed by dwellers on a total of those 24 houses built by the public authority after an occupation period of one year. The predominant uses of each room within the self-built and modified houses were represented in ground plan, based on empirical observation, surveys with dwellers and the use of analytical procedures of morphologic analysis of nature predominantly geometric (specific) and topology (space syntax analysis). A scale of priorities was identified in relation to the uses of each room, its geometrical arrangement (adjacency, front/back relations etc), and underlying structures (connectivity, depth and spatial integration) in order to establish congruencies and non-congruencies between a social-cultural order embedded in the self-built domestic space and the design logic contained in the houses offered by official agencies. The comparative analysis points towards the convivial existence of two tendencies: one that seems to reinforce a design logic inasmuch as the additions and modifications performed by the dwellers do not alter but even emphasize the original configuration of the designed houses, and another one in which those patterns are subverted in accordance with a logic which, to a lesser or greater degree, coincides with that of the self-built dwellings

Simulação de fluxo de fluidos em meios porosos desordenados uma análise de efeito de escala na estimativa da permeabilidade e do coeficiente de arrasto

The present study provides a methodology that gives a predictive character the computer simulations based on detailed models of the geometry of a porous medium. We using the software FLUENT to investigate the flow of a viscous Newtonian fluid through a random fractal medium which simplifies a two-dimensional disordered porous medium representing a petroleum reservoir. This fractal model is formed by obstacles of various sizes, whose size distribution function follows a power law where exponent is defined as the fractal dimension of fractionation Dff of the model characterizing the process of fragmentation these obstacles. They are randomly disposed in a rectangular channel. The modeling process incorporates modern concepts, scaling laws, to analyze the influence of heterogeneity found in the fields of the porosity and of the permeability in such a way as to characterize the medium in terms of their fractal properties. This procedure allows numerically analyze the measurements of permeability k and the drag coefficient Cd proposed relationships, like power law, for these properties on various modeling schemes. The purpose of this research is to study the variability provided by these heterogeneities where the velocity field and other details of viscous fluid dynamics are obtained by solving numerically the continuity and Navier-Stokes equations at pore level and observe how the fractal dimension of fractionation of the model can affect their hydrodynamic properties. This study were considered two classes of models, models with constant porosity, MPC, and models with varying porosity, MPV. The results have allowed us to find numerical relationship between the permeability, drag coefficient and the fractal dimension of fractionation of the medium. Based on these numerical results we have proposed scaling relations and algebraic expressions involving the relevant parameters of the phenomenon. In this study analytical equations were determined for Dff depending on the geometrical parameters of the models. We also found a relation between the permeability and the drag coefficient which is inversely proportional to one another. As for the difference in behavior it is most striking in the classes of models MPV. That is, the fact that the porosity vary in these models is an additional factor that plays a significant role in flow analysis. Finally, the results proved satisfactory and consistent, which demonstrates the effectiveness of the referred methodology for all applications analyzed in this study.

Influência na qualidade final de metais retificados através da variação da velocidade de mergulho

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

Hydroalumination of seleno acetylenes: a versatile generation and reactions of alpha-aluminate vinyl selenide intermediates in the highly regio and stereoselective synthesis of telluro(seleno)ketene acetals

The hydroalumination of butylseleno acetylenes with DIBAL-H followed by addition of n-butyllithium generated in situ the (Z)-butylseleno vinyl alanates intermediates which were captured with C(4)H(9)TeBr furnishing the (E)-telluro(seleno)ketene acetals exclusively. The isomers with opposite stereochemistry (Z)-telluro(seleno)ketene acetals were obtained by the reduction of phenylseleno acetylenes with lithium di-(isobutyl)-n-butyl aluminate hydride (Zweifel's reagent) followed by reaction of (E)-phenylseleno vinyl alanates intermediates with C(4)H(9)TeBr. (c) 2008 Elsevier Ltd. All rights reserved.

Interference effects in nonplanar wires with a two-dimensional electron gas

We have studied the universal conductance fluctuations (UCF) due to quantum interface in a two-dimensional electron gas (2DEG) grown on the substrates with pre-patterned, sub-micron wires. The dependence of UCF on the angle between the direction of the magnetic field and the substrate has been investigated. We found, that magnetoresistance traces for different angles are completely uncorrelated. A non-planar character of electron motion is responsible for these angular conductance fluctuations. We compared the experimental results with a simple geometrical model.

Reflexões sobre a construção e evolução de conceitos geométricos nas séries intermediárias do ensino fundamental

This thesis represents a didactic research linked to the Post-graduation Programme in Education of the Universidade Federal do Rio Grande do Norte which aimed to approach the construction of the geometrical concepts of Volume of the Rectangular Parallelepiped, Area and Perimeter of the Rectangle adding a study of the Area of the Circle. The research was developed along with students from the 6th level of the Elementary School, in a public school in Natal/RN. The pedagogical intervention was made up of three moments: application of a diagnostic evaluation, instrument that enabled the creation of the teaching module by showing the level of the geometry knowledge of the students; introduction of a Teaching Module by Activities aiming to propose a reflexive didactic routing directed to the conceptual construction because we believed that such an approach would favor the consolidation of the learning process by becoming significant to the apprentice, and the accomplishment of a Final Evaluation through which we established a comparison of the results obtained before and after the teaching intervention. The data gathered were analyzed qualitatively by means of a study of understanding categories of mathematical concepts, in addition to using descriptive statistics under the quantitative aspect. Based on the theory of Richard Skemp, about categorization of mathematical knowledge, in the levels of Relational and Instrumental Understanding were achieved in contextual situations and varied proportions, thus enabling a contribution in the learning of the geometrical concepts studied along with the students who took part in the research. We believe that this work may contribute with reflections about the learning processes, a concern which remained during all the stages of the research, and also that the technical competence along with the knowledge about the constructivist theory will condition the implementation of a new dynamics to the teaching and learning processes. We hope that the present research work may add some contribution to the teaching practice in the context of the teaching of Mathematics for the intermediate levels of the Elementary School

A dinâmica do pensamento geométrico :aprendendo a enxergar meias verdades e a construir novos significados

This work is a case study to investigate the dynamics of the historians thought as they produce a knowledge about the history of the area measurement systems as forms of historical expressions and representations. We refer to some of the ideas of David Bohm (1989, 1992, 1994, 1996) to support our theoretical understanding about the operation of thought. We chose a period that is recognized by the theorists as the origin of the geometrical thought -embracing the knowledge developed by the Egyptians, Babylonians, Chinese, Hindus, Greeks and Romans- and is referred to as containing a cycle in the development of this knowledge, described as beginning, apogee and decline. We assume this history, as told by the theorists, as a version that we organize and tell with the help of three sets of categories. The first refers to the elements that take part in the measurement practices; the second refers to the historians understanding about the development of the scientific knowledge. This exercise allowed us to extract the theorists main beliefs, that we criticized in the light of the knowledge about Cubação (Dal Pian, 1990). We stress the importance of the methodological approach adopted in this study to the teaching of Geometry and its history