204 resultados para Hydrogénolyse de Tsuji
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INTRODUÇÃO: O médico atualizado pode oferecer o melhor cuidado ao paciente e evitar consequências negativas que a defasagem científica pode acarretar. OBJETIVOS: Identificar os meios de atualização utilizados pelos psiquiatras brasileiros; avaliar seus conhecimentos sobre Medicina Baseada em Evidências (MBE) e sua utilização na educação permanente. MÉTODO: Estudo transversal realizado no XXIV Congresso Brasileiro de Psiquiatria. Os participantes (n = 188) responderam um questionário anônimo autoaplicado, com 28 perguntas sobre características sociodemográficas, fontes e periodicidade de atualização, e conhecimentos sobre MBE. RESULTADOS: Para atualização de conhecimentos, 98,3% utilizavam os congressos brasileiros; 97,9% as revistas nacionais; 93,9% os livros-texto; 89,9% as revistas das indústrias farmacêuticas; 63,5% os consensos brasileiros; 63,3% a base de dados Medline; 56,7% as revistas internacionais; e 35% a Biblioteca Cochrane. Os fatores estatisticamente significativos associados com bom conhecimento sobre MBE foram estar graduados há menos de dez anos (p < 0,001), usar o Medline (p < 0,009) e a Biblioteca Cochrane (p < 0,03) como fonte de busca de literatura médica. CONCLUSÕES: Os psiquiatras fazem pouco uso da melhor fonte de evidência para educação médica permanente e continuada, havendo, assim, menor benefício aos pacientes na tomada de decisão clínica.
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A Aprendizagem Baseada em Problemas (ABP) contribui para a busca ativa de informações e habilidades necessárias à formação profissional no internato. Frequentemente, a postura passiva de internos e a conduta de preceptores não contribuem satisfatoriamente para a construção ativa do conhecimento. Este estudo avaliou a percepção dos estudantes de Medicina da Famema e seus preceptores sobre a continuidade do processo ativo de aprendizagem na construção do conhecimento nas atividades do internato. Efetuou-se uma pesquisa qualitativa, sendo realizados grupos focais com internos e entrevistas com preceptores do internato para obtenção de dados, analisados pela técnica de análise de conteúdo. Obtiveram-se três categorias empíricas comuns entre estudantes e preceptores – a ação pedagógica dos preceptores na construção dos conhecimentos dos internos: do comprometimento à interlocução com os sujeitos; a influência dos cenários, dos pacientes e das ações pedagógicas na construção do processo de ensino e aprendizagem no internato; e a ABP e o internato na Famema: o reflexo do processo pedagógico ativo na construção dos conhecimentos e na formação dos estudantes –, que demonstraram a dificuldade de continuar o processo ativo de aprendizagem.
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L’application des métaux de transition à la fonctionnalisation directe a ouvert la voie à une nouvelle classe de réactions pour la formation de liens carbone-carbone. De par l'omniprésence des liaisons C–H, l’introduction de nouvelles fonctionnalités chimiques par voie directe et pré-activation minimale s’impose comme une stratégie de synthèse très attrayante. Ainsi, il est envisageable de préparer de manière rapide et efficace des supports complexes menant à des molécules complexes, qui pourraient être utiles dans divers domaines de la chimie. L'objectif principal de la présente thèse vise la fonctionnalisation directe des arènes hétérocycliques et non hétérocycliques et, plus précisément, les techniques d’arylation. Dans un premier temps, nous allons aborder le thème de l’arylation directe tout en mettant l’accent sur les pyridines (Chapitre 1). Ces molécules sont à la base d'une multitude de composés biologiquement actifs et jouent un rôle important dans le domaine des sciences des matériaux, de l’agrochimie et de la synthèse des produits naturels. Dans un deuxième temps, nous discuterons de nos travaux sur l’arylation directe catalysé par un complex de palladium sur des ylures de N-iminopyridinium en soulignant la dérivatisation du sel de pyridinium après une phénylation sp2 (Chapitre 2). L’étude de ce procédé nous a permis de mettre en lumière plusieurs découvertes importantes, que nous expliquerons en détails une à une : l’arylation benzylique directe lorsque des ylures N-iminopyridinium substituées avec un groupement alkyl à la position 2 sont utilisés comme partenaires dans la réaction; les allylations Tsuji-Trost catalysée par un complex de palladium; et l’alkylation directe et sans métal via une catalyse par transfert de phase. Plusieurs défis restent à relever pour le développement de procédés directs utilisant des métaux de transition peu coûteux, d’autant plus que la synthèse par transformation directe des pyridines 2-alcényles, lesquelles sont pertinentes sur le plan pharmacologique, n’a pas encore été rapportée à ce jour. Avec cette problématique en tête, nous avons réussi à mettre au point une alcénylation directe catalysé par un complex de cuivre sur des ylures de N-iminopyridinium. Nous discuterons également d’une nouvelle méthode pour la préparation des iodures de vinyle utilisés dans les couplages. Ces réactions sont non seulement remarquablement chimiosélectives, mais sont aussi applicables à plusieurs substrats (Chapitre 3). En optimisant ce procédé direct, nous avons découvert une façon unique de synthétiser les pyrazolo[1,5-a]pyridines 2-substituées (Chapitre 4). Le mécanisme global met en jeu une séquence tandem de fonctionnalisation-cyclisation directe et un procédé direct en cascade, qui n’avais jamais été rapporté. Cela simplifie ansi la synthèse autrement compliquée de ces substrats en y apportant une solution à un problème de longue date. Dans les deux derniers chapitres, nous examinerons en détail les techniques d’arylation directe qui n'impliquent pas les partenaires de couplage hétérocycliques. Entre autres, au Chapitre 5, nous soulignerons notre découverte d’un umpolung dirigé et catalysé par un complexe de palladium du benzène et de quelques autres dérivés arènes. Il s’agit là du premier cas de fonctionnalisation directe dans laquelle le groupe directeur se trouve sur le partenaire halogène et il s’ajoute à la courte liste d’exemples connus dans la littérature rapportant une arylation directe du benzène. Finalement, au Chapitre 6, nous passerons en revue une nouvelle arylation directe catalysée au fer, qui se veut un procédé peu coûteux, durable et présentant une économie d’atomes. Nous discutons des substrats possibles ainsi des études mécanistiques réalisés.
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Pyrroles are found in various natural products and in the chemical composition of certain drugs because of their interesting biological properties. Lipitor, Tolmetin and Amtolmetin are examples of drugs with 1,2,5-substituted pyrroles in their composition, in which biological activities have been certified. Moreover, pyrroles are used as precursors of semiconductor polymers, oligomers and dendrimers useful for the synthesis of electroluminescent materials used in devices, such as organic light-emitting diodes, field-effect transistors, solar and organic photovoltaic cells. We are interested in conjugated polymers based on pyrrole due to their optical properties, electrochemical and the conductivity produced by electron delocalization along their carbon chains. The overall objective of the work presented in this thesis is the synthesis of new molecules based on pyrrole for studying their electronic and electrochemical properties as well for the synthesis of conjugated polymers. Initially, we performed the synthesis of 1,3,5-tri-(1-alkyl-5-methylpyrrol-2-yl)benzenes, which may serve as precursors for the synthesis of conjugated dendrimers. Their synthesis was made in three steps starting from trimethyl 1,3,5-benzene-tricarboxylate which was converted to 1,3,5-tri-(pent-4-enoyl)benzene using vinylmagnesium bromide in a Grignard reaction catalyzed by copper cyanide. The olefins of 1,3,5-tri-(pent-4-enoyl)benzene were oxidized to produce 1,3,5-tri-(4-oxopentanoyl)benzene using a modified protocol of the Tsuji-Wacker reaction. Subsequent, Paal-Knorr condensation reactions on 1,3,5-tri-(4-oxopentanoyl)benzene with different amines were used to synthesize 1,3,5-tri-(1-alkyl-5-methylpyrrol-2-yl)benzenes with different N-substituents in yields between 44 and 60%. Incomplete reaction of vinylmagnesium bromide with trimethyl 1,3,5-benzenetricarboxylate gave the methyl-3,5-di(pent-4-enoyl)benzoate, which was converted to methyl-3,5-dipyrrolylbenzoate following the reaction of Tsuji- Wacker and Paal-Knorr with yields between 30 and 60%. The photochemical and electrochemical properties of the 1,3,5-tri-(1-alkyl-5-methylpyrrol-2-yl)benzenes and methyl-3,5-dipyrrolylbenzoates were studied in collaboration with the research group of professor William Skene. The results have shown that both types of pyrrole have potential for the synthesis of conjugated polymers and dendrimers used in the manufacture of electroluminescent materials. Following these encouraging results, we performed the synthesis of 6,12-dimethyl-1,5-dipyrrolediazocane. Methyl N-(Boc)-β-alaninate was converted to its corresponding homoallylic ketone, which was oxidized to N-(Boc)aminoheptan-3,6-dione. The Paal-Knorr condensation between N-(Boc)aminoheptan-3,6-dione and aminoheptan-3,6-dione hydrochloride gave 6,12-dimethyl-1,5-dipyrrolediazocane in 17% yield. In sum, we have synthesized and characterized seven new molecules, six of them having photochemical and electrochemical properties interesting for the synthesis of conjugated polymers and dendrimers. The latter offering potential as precursor for the conception of compounds of therapeutic interest.
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Introducción: la contaminación atmosférica no solo tiene efectos sobre el sistema respiratorio sino también sobre el cardiovascular. El objetivo de este estudio es generar evidencia que permita establecer una asociación entre el infarto agudo del miocardio y la concentración de PM10 en el ambiente como un estudio preliminar para un grupo de pacientes en Bogotá. Metodología: la asociación entre la concentración del material particulado (en este caso PM10 medido en la estación más cercana del lugar reportado por el paciente) y el infarto agudo del miocardio se estableció utilizando el diseño case crossover. Se utilizó información de las historias clínicas de los pacientes con infarto agudo del miocardio que ingresaron al Servicio de Urgencias de la FSFB, y las concentraciones de PM10 medido en la estación más cercana al lugar de inicio de los síntomas de síndrome coronario agudo, reportado por el paciente. Resultados: se encontró que la asociación entre la concentración de PM10 y el diagnóstico de infarto agudo del miocardio es estadísticamente significativa teniendo en cuenta tres momentos de control: 2 horas antes del evento, 24 horas antes del evento y 48 horas antes del evento. Discusión: este estudio sugiere que las altas concentraciones de material particulado en el ambiente son un factor de riesgo para el desarrollo de infarto agudo del miocardio especialmente en personas con enfermedad coronaria subyacente. Con esta investigación se demuestra la importancia de generar acciones que disminuyan la contaminación de la ciudad y de esta forma proteger la salud de las personas.
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Las tecnologías de la información han empezado a ser un factor importante a tener en cuenta en cada uno de los procesos que se llevan a cabo en la cadena de suministro. Su implementación y correcto uso otorgan a las empresas ventajas que favorecen el desempeño operacional a lo largo de la cadena. El desarrollo y aplicación de software han contribuido a la integración de los diferentes miembros de la cadena, de tal forma que desde los proveedores hasta el cliente final, perciben beneficios en las variables de desempeño operacional y nivel de satisfacción respectivamente. Por otra parte es importante considerar que su implementación no siempre presenta resultados positivos, por el contrario dicho proceso de implementación puede verse afectado seriamente por barreras que impiden maximizar los beneficios que otorgan las TIC.
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Empezando con Chile a comienzos de 1980, los países de América Latina han profundizado la reforma a las telecomunicaciones para crear un entorno regulatorio que incentive la inversión privada, en particular la inversión extranjera. En este artículo, trabajo las tendencias regulatorias en el sector telecomunicaciones de 24 países latinoamericanos y del caribe durante el período 1980-1997 y construyo un índice basado en : autonomía, rendición de cuentas, claridad de las funciones y objetivos, transparencia y participación, y el tipo de mandato legal que crea el ente regulador. El índice muestra que, en promedio, la mayoría de los países llevaron a cabo fuertes reformas regulatorias en la dirección sugerida por expertos e investigadores. El índice también se correlación bien con varias variables políticas, de riesgo, económicas y de telecomunicaciones.
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Revealing the evolution of well-organized social behavior requires understanding a mechanism by which collective behavior is produced. A well-organized group may be produced by two possible mechanisms, namely, a central control and a distributed control. In the second case, local interactions between interchangeable components function at the bottom of the collective behavior. We focused on a simple behavior of an individual ant and analyzed the interactions between a pair of ants. In an experimental set-up, we placed the workers in a hemisphere without a nest, food, and a queen, and recorded their trajectories. The temporal pattern of velocity of each ant was obtained. From this bottom-up approach, we found the characteristic behavior of a single worker and a pair of workers as follows: (1) Activity of each individual has a rhythmic component. (2) Interactions between a pair of individuals result in two types of coupling, namely the anti-phase and the in-phase coupling. The direct physical contacts between the pair of workers might cause a phase shift of the rhythmic components in individual ants. We also build up a simple model based on the coupled oscillators toward the understanding of the whole colony behavior.
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The gamergate (generally called the “queen”) of the Diacamma sp. walks around in the nest and comes into contact with the workers. The gamergate informs the workers of its presence by physical contact. This behavior is called a “patrol.” In previous work, it was reported that the gamergate controls its patrolling time depending on the colony size. How does the gamergate know the colony size, and how does it control the patrolling time? In this article, we propose a simple dynamics to explain this behavior. We assume that the gamergate and the workers have internal states which interact by physical contacts. By numerical simulations, we confirm that the patrol time of the proposed model depends on the size of the colony.
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In order to shed light on the collective behavior of social insects, we analyzed the behavior of ants from single to multi-body. In an experimental set-up, ants are placed in hemisphere without a nest and food. Trajectory of ants is recorded. From this bottom-up approach, we found that collective behavior of ants as follows: 1. Activity of single ant increases and decreases periodically. 2. Spontaneous meeting process is observed between two ants and meeting spot of two ants is localized in hemisphere. 3. Result on division of labor is obtained between two ants.
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To understand the evolution of well-organized social behaviour, we must first understand the mechanism by which collective behaviour establishes. In this study, the mechanisms of collective behaviour in a colony of social insects were studied in terms of the transition probability between active and inactive states, which is linked to mutual interactions. The active and inactive states of the social insects were statistically extracted from the velocity profiles. From the duration distributions of the two states, we found that 1) the durations of active and inactive states follow an exponential law, and 2) pair interactions increase the transition probability from inactive to active states. The regulation of the transition probability by paired interactions suggests that such interactions control the populations of active and inactive workers in the colony.
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Background Recent studies indicate an increased frequency of mutations in the gene encoding glucocerebrosidase (GBA), a deficiency of which causes Gaucher`s disease, among patients with Parkinson`s disease. We aimed to ascertain the frequency of GBA mutations in an ethnically diverse group of patients with Parkinson`s disease. Methods Sixteen centers participated in our international, collaborative study: five from the Americas, six from Europe, two from Israel, and three from Asia. Each center genotyped a standard DNA panel to permit comparison of the genotyping results across centers. Genotypes and phenotypic data from a total of 5691 patients with Parkinson`s disease (780 Ashkenazi Jews) and 4898 controls (387 Ashkenazi Jews) were analyzed, with multivariate logistic-regression models and the Mantel-Haenszel procedure used to estimate odds ratios across centers. Results All 16 centers could detect two GBA mutations, L444P and N370S. Among Ashkenazi Jewish subjects, either mutation was found in 15% of patients and 3% of controls, and among non-Ashkenazi Jewish subjects, either mutation was found in 3% of patients and less than 1% of controls. GBA was fully sequenced for 1883 non-Ashkenazi Jewish patients, and mutations were identified in 7%, showing that limited mutation screening can miss half the mutant alleles. The odds ratio for any GBA mutation in patients versus controls was 5.43 across centers. As compared with patients who did not carry a GBA mutation, those with a GBA mutation presented earlier with the disease, were more likely to have affected relatives, and were more likely to have atypical clinical manifestations. Conclusions Data collected from 16 centers demonstrate that there is a strong association between GBA mutations and Parkinson`s disease.
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Objectives: Studies of the viscoelastic properties of the vocal folds are normally performed with rheometers that use parallel assigned a fixed value. In tissues subject to variation of thickness plates whose interplate space is usually at between samples, fixed gaps could result in different compressions, compromising the comparison among them. We performed,in experimental study to determine whether different compressions call lead to different results in measurements of dynamic viscosity (DV) of vocal fold samples. Methods: We Measured the DV of vocal fold samples of 10 larynges of cadavers under 3 different compression levels, corresponding to 0.2, 0.5, and 10 N on an 8-mm-diameter parallel-plate rheometer. Results: The DV directly varied with compression. We observed statistically significant differences between the results of 0.2 and 10 N (p = 0.0396) and 0.5 and 10 N (p = 0.0442). Conclusions: The study demonstrated that the level of compression influences the DV measure and Suggests that a defined compression level should be used in rheometric studies of biological tissues.
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Iniciado nos anos de 1960, o segundo estágio do processo de globalização, liderado principalmente pelas empresas multinacionais e suas estratégias de expansão, e suportado pelos avanços da tecnologia de informação e comunicação, resultou em profundas transformações nas estruturas organizacionais, que passaram de modelos hierarquizados em detrimento de modelos mais flexíveis e dinâmicos, mudando a maneira de trabalhar. Este projeto objetivou estudar o impacto decorrente da utilização de estruturas organizacionais baseadas em redes globais e equipes globais virtuais nos profissionais que atuam em bancos de investimento multinacionais. Os impactos foram avaliados através do conceito de descontinuidade, que é entendido como fator ou fatores que contribuem para falta de coesão em situações de coletividade. Foram analisados 15 profissionais, de 4 bancos de investimentos multinacionais, e aplicaram-se entrevistas individuais presenciais formuladas considerando as descontinuidades e itens propostos na literatura (Duarte e Snyder, 1999; Watson-Manheim et al., 2002; Espinosa et al., 2003; Saunders et al., 2004; Jarvenpaa et al., 2004; Zolin et al., 2004; Golden e Veiga, 2005; Chudoba et al., 2005; Dani et al., 2006) para investigação. Os resultados das análises dos dados coletados permitem inferir que os fatores de descontinuidade sugeridos no estudo são relevantes aos profissionais de banco de investimentos multinacionais. Adicionalmente, percebe-se que apesar de coletadas e analisadas individualmente, há correlação entre as descontinuidades analisadas, com incidência conjunta ou simultânea no desempenho das atividades dos profissionais.
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Este trabalho examina a relação entre a volatilidade do fluxo de caixa operacional e o valor da firma, utilizando como amostra empresas brasileiras não financeiras listadas na Bolsa de Valores de São Paulo (Bovespa), no período de 2004 a 2007. O estudo aplica duas metodologias distintas para garantir a robustez dos resultados. Embora os resultados apontem que empresas com menor volatilidade do fluxo de caixa possuem maior valor, os valores encontrados não se mostram significativos.