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Linear Alpha Olefins (LAOs) are one of the most important commodities in the chemical industry, which are currently mainly produced via homogenous catalytic processes. Heterogeneous catalysts have always been desirable from an industrial viewpoint due to their advantages of low operation cost, ease of separation, and catalyst reusability. However, the development of highly active, selective, and stable heterogeneous catalysts for the production of LAOs has been a challenge throughout the last 60 years. In this dissertation, we designed and prepared a series of heterogeneous catalysts by incorporating structural moieties of homogenous benchmark catalysts into metal-organic-frameworks (MOFs), aiming to provide a feasible solution to this long-standing challenge. First, we reviewed the background and state of the art of this field and put forward the main objectives of our research. Then, we thoroughly discussed a novel heterogeneous catalyst (Ni-ZIF-8) that we developed for ethylene dimerization to produce 1-butene, focusing on its designed principle, detailed characterizations, catalytic performance evaluation, and reaction mechanisms. Ni-ZIF-8 exhibits an average ethylene turnover frequency greater than 1,000,000 h$^{-1}$ (1-butene selectivity >85%), far exceeding the activities of previously reported heterogeneous and many homogenous catalysts under similar conditions. Compared with homogenous nickel catalysts, Ni-ZIF-8 has significantly higher stability and showed constant activity during four hours of continuous reaction for at least two reaction cycles. The combination of isotopic labeling studies and Density Functional Theory calculations demonstrated that ethylene dimerization on Ni-ZIF-8 follows the Cossee-Arlman mechanism, and that the full exposure and square-planer coordination of the nickel sites account for the observed high activity. After that, we further optimized the Ni-ZIF-8 catalytic system from the perspective of practical applications. We achieved double productivity of 1-butene by optimizing the synthetic conditions and explored its usability and performances under solvent-free conditions. Then, we extended our catalyst design concept to prepare heterogeneous catalysts comprising other metals and MOFs, which provided a suitable platform for studying the effects of the metallic center and coordination environment on the catalytic production of LAOs. Finally, we gave our perspectives on the further development of heterogeneous catalysts for the production of LAOs.

Durante el transcurso de la presente Tesis Doctoral se estudió el proceso de formación por vía electroquímica y la caracterización de nanoestructuras unimetálicas de Pd y Rh, así como también del par bimetálico Rh-Pd, sobre sustratos carbonosos de HOPG y CV. Para ello, se emplearon técnicas electroquímicas convencionales y de caracterización superficial, tales como microscopía STM y AFM ex-situ, SEM, EDX y XPS. Las potenciales propiedades electrocatalíticas para la reacción de hidrógeno fueron analizadas para el sistema bimetálico Rh-Pd/CV. Inicialmente, se analizó la electrodeposición de los metales individuales, Pd y Rh, sobre HOPG y CV. Para ambos sustratos, la deposición metálica siguió un mecanismo de nucleación y crecimiento 3D controlado por difusión. Los depósitos logrados fueron caracterizados por AFM corroborando el mecanismo propuesto. En todos los casos, se pudieron analizar los sitios activos preferenciales para la nucleación, morfología y el tamaño de los cristales generados. Para el sistema Pd/HOPG, fue posible obtener, dependiendo de las condiciones de polarización empleadas, estructuras unidimensionales sobre los bordes de escalón del sustrato. Además, se logró demostrar la deposición espontánea de Rh sobre HOPG activado. Las imágenes de AFM mostraron cristales de diversos tamaños y formas, generando principalmente grandes aglomerados con el incremento del tiempo de inmersión. El análisis EDX confirmó la presencia de C y Rh en la superficie del sustrato. Seguidamente, fue posible generar estructuras bimetálicas Rh-Pd/CV, mediante la deposición secuencial de los metales, aplicando escalones potenciostáticos, a partir de electrolitos conteniendo los cationes individuales. La caracterización por AFM mostró cristales cuasi-hemisféricos distribuidos uniformemente sobre la superficie y el análisis XPS detectó la presencia de ambos metales, constituyendo una estructura tipo core-shell. Finalmente, se analizó cualitativa y cuantitativamente, el efecto electrocatalítico de las nanoestructuras bimetálicas de Rh-Pd generadas frente a la reacción del electrodo de hidrógeno (HER). El modelo Volmer-Heyrovsky-Tafel (VHT) fue utilizado para obtener el conjunto de parámetros cinéticos, simulando perfectamente el comportamiento de esta reacción en un amplio rango de sobrepotenciales. / During the curse of the present Doctoral Thesis, the electrochemical formation process and the characterization of Pd and Rh metallic nanostructures, as well as the Rh-Pd bimetallic pair, were studied on HOPG and CV carbonaceous substrates. For this purpose, conventional electrochemical and surface characterization techniques, such as ex-situ STM and AFM, SEM, EDX and XPS were used. The potential electrocatalytic properties for the hydrogen reaction were analyzed for the Rh-Pd/CV bimetallic system. Initially, the electrodeposition of the individual metals, Pd and Rh, on HOPG and CV was performed. For both substrates, the metal deposition followed a diffusion-controlled 3D nucleation and growth mechanism. The obtained deposits were characterized by AFM corroborating the proposed mechanism. In all the cases, it was possible to analyze the preferential active sites for nucleation, the morphology and the size of the generated crystals. For the Pd/HOPG system, it could also be obtained one-dimensional structures on the step edges of the substrate, depending on the polarization conditions employed. It was also demonstrated the spontaneous deposition of rhodium on activated HOPG. AFM images showed crystals of different sizes and shapes, generating mainly large agglomerates with increasing immersion time. The EDX analysis confirmed the presence of C and Rh on the substrate surface. Afterwards, it was possible to generate Rh-Pd/CV bimetallic nanostructures by the sequential deposition of the metals, applying potentiostatic steps, from electrolytes containing the individual cations. The AFM characterization showed quasi-hemispherical crystals uniformly distributed on the surface and the XPS analysis confirmed the presence of both metals, constituting a core-shell type structure. Finally, the electrocatalytic effect of the Rh-Pd bimetallic nanostructures, towards the hydrogen electrode reaction (HER), was qualitatively and quantitatively analyzed. The Volmer-Heyrovsky-Tafel (VHT) model was used to obtain the set of kinetic parameters, perfectly simulating the behaviour of this reaction in a wide range of overpotentials.

Estudar a solidão por meio de um ponto de vista psicológico junguiano, o qual entende os fenômenos da psique como plurais, relacionados a aspectos pessoais e coletivos foi o objetivo principal deste trabalho. A partir do conceito junguiano de imagem, ou seja, perspectivas a respeito de qualquer ideia, conceito, sentimento ou percepção que são formados sobre o mundo, buscou-se analisar o que há nas imagens sobre a solidão presentes na contemporaneidade. Estudos nas ciências sociais e o filme Her contribuíram como fontes de imagens para a análise da solidão. O filme apresentou imagens com grande sensibilidade, plasticidade e potencial arquetípico capazes de aprofundar a ampliar o tema. A solidão também foi estudada como elemento importante no processo de desenvolvimento psíquico, como na formação da consciência, na diferenciação gradual da psique do bebê em relação à psique materna e no caminho de individuação, os quais representam movimentos estruturantes que têm seus fundamentos nos processos de separação e diferenciação. Três perspectivas mitológicas foram apresentadas como bases arquetípicas capazes de fornecer luz para a compreensão da solidão: o casamento sagrado de Eros e Psiquê, o mito de Narciso e a concepção de Dioniso e sua relação com o conceito de communitas. Reflexões sobre a interação dessas três perspectivas com a contemporaneidade foram realizadas. A conclusão da pesquisa é de que a solidão representa uma potencialidade de contato com a alma, de interiorização, envolvimento e intimidade, mas um cuidado inadequado pode resultar em um isolamento que promove estagnação psíquica. É um elemento necessário ao desenvolvimento psicológico, o qual precisa de relacionamento com outros elementos psíquicos como o amor, e que necessita ser recebido na contemporaneidade com mais respeito, paciência e delicadeza. A elaboração da solidão permite a consciência da singularidade e é essencial para a alteridade / To study loneliness through a Junguian psychological point of view, which understands the phenomenas of the psyche as plurals and related to personal and collective aspects was the main objective of this work. From the Jungian concept of image, i.e. perspectives about any idea, concept, feeling or perception that are formed concerning to the world, it sought to analyze what images about loneliness are present in contemporary times. Studies in the social sciences and the film Her contributed as sources of images for the analysis of loneliness. The film showed images with great sensitivity, plasticity and potential archetypal capable to further enlarge and deepen the subject. Loneliness was also studied as an important element in the psychic development process, as in the formation of conscience, the gradual differentiation of the baby\'s psyche in relation to maternal psyche and individuation path, which represent structural movements that have their foundations in the processes of separation and differentiation. Three mythological perspectives were presented as archetypal bases capable to shed some light to the understanding of loneliness: the sacred marriage of Eros and Psyche, the myth of Narcissus and the idea of Dionysus and its relationship with the concept of communitas. Reflections on the interaction of these three perspectives with contemporaneity were held. The conclusion of the research is that loneliness is a potentiality that provides contact with the soul, like internalization, involvement and intimacy, but its improper care may result in an isolation that promotes psychic stagnation. It is a necessary element to the psychological development, which needs to relate with other psychic elements like love, and needs to be received in the contemporary world with more respect, patience and delicacy. The preparation for loneliness allows the consciousness of uniqueness and is essential for otherness

Estudar a solidão por meio de um ponto de vista psicológico junguiano, o qual entende os fenômenos da psique como plurais, relacionados a aspectos pessoais e coletivos foi o objetivo principal deste trabalho. A partir do conceito junguiano de imagem, ou seja, perspectivas a respeito de qualquer ideia, conceito, sentimento ou percepção que são formados sobre o mundo, buscou-se analisar o que há nas imagens sobre a solidão presentes na contemporaneidade. Estudos nas ciências sociais e o filme Her contribuíram como fontes de imagens para a análise da solidão. O filme apresentou imagens com grande sensibilidade, plasticidade e potencial arquetípico capazes de aprofundar a ampliar o tema. A solidão também foi estudada como elemento importante no processo de desenvolvimento psíquico, como na formação da consciência, na diferenciação gradual da psique do bebê em relação à psique materna e no caminho de individuação, os quais representam movimentos estruturantes que têm seus fundamentos nos processos de separação e diferenciação. Três perspectivas mitológicas foram apresentadas como bases arquetípicas capazes de fornecer luz para a compreensão da solidão: o casamento sagrado de Eros e Psiquê, o mito de Narciso e a concepção de Dioniso e sua relação com o conceito de communitas. Reflexões sobre a interação dessas três perspectivas com a contemporaneidade foram realizadas. A conclusão da pesquisa é de que a solidão representa uma potencialidade de contato com a alma, de interiorização, envolvimento e intimidade, mas um cuidado inadequado pode resultar em um isolamento que promove estagnação psíquica. É um elemento necessário ao desenvolvimento psicológico, o qual precisa de relacionamento com outros elementos psíquicos como o amor, e que necessita ser recebido na contemporaneidade com mais respeito, paciência e delicadeza. A elaboração da solidão permite a consciência da singularidade e é essencial para a alteridade / To study loneliness through a Junguian psychological point of view, which understands the phenomenas of the psyche as plurals and related to personal and collective aspects was the main objective of this work. From the Jungian concept of image, i.e. perspectives about any idea, concept, feeling or perception that are formed concerning to the world, it sought to analyze what images about loneliness are present in contemporary times. Studies in the social sciences and the film Her contributed as sources of images for the analysis of loneliness. The film showed images with great sensitivity, plasticity and potential archetypal capable to further enlarge and deepen the subject. Loneliness was also studied as an important element in the psychic development process, as in the formation of conscience, the gradual differentiation of the baby\'s psyche in relation to maternal psyche and individuation path, which represent structural movements that have their foundations in the processes of separation and differentiation. Three mythological perspectives were presented as archetypal bases capable to shed some light to the understanding of loneliness: the sacred marriage of Eros and Psyche, the myth of Narcissus and the idea of Dionysus and its relationship with the concept of communitas. Reflections on the interaction of these three perspectives with contemporaneity were held. The conclusion of the research is that loneliness is a potentiality that provides contact with the soul, like internalization, involvement and intimacy, but its improper care may result in an isolation that promotes psychic stagnation. It is a necessary element to the psychological development, which needs to relate with other psychic elements like love, and needs to be received in the contemporary world with more respect, patience and delicacy. The preparation for loneliness allows the consciousness of uniqueness and is essential for otherness

Ziel dieser Studie war es, die Häufigkeit der Expression von EGFR, HER-2 sowie COX-2 im Zervixkarzinom zu eruieren. Dabei galt es herauszufinden, ob Unterschiede hinsichtlich des Nachweises dieser drei, möglicherweise therapeutisch relevanten Moleküle zwischen den primären, nicht vortherapierten und operierten Karzinomen und den multimodal vorbehandelten Rezidiven gab. In der vorliegenden retrospektiven Arbeit wurden 45 TMMR-operierte Primärtumoren und 28 LEER-operierte Rezidivtumoren der Universitätsfrauenklinik Leipzig (Triersches Institut) einbezogen und zusätzlich hinsichtlich der prognostischen Überlebensanalyse durch das Tumorstadium, Lymphknotenmetastasen und Rezidivauftreten sowie histologischer Charakteristika untersucht. Dazu wurden Tissue - Microarrays angefertigt mit anschließender immunhistochemischer Untersuchung dieser. Die Ergebnisse zeigten, dass die TMMR-Operation die Überlebensprognose signifikant verbessert, denn lediglich bei den LEER-therapierten Rezidivtumoren erlitten die Patientinnen sowohl Fernmetastasen als auch erneute Rezidive. Weder die Expression der drei untersuchten Moleküle noch die histopathologischen Parameter haben eine prognostische Relevanz. Es gibt keine signifikanten Zusammenhänge zwischen der Häufigkeit der Expression von EGFR, HER-2 sowie COX-2 und Primär-, bzw. Rezidivtumoren, sodass diese Moleküle keine Targets für eine individualisierte, zielgerichtete Therapie beim Zervixkarzinom darstellen.

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The Outline of the development and history of a board game. The Mapping of the contemporary situation in the field of board games. Cultural, social and psychological aspects of playing board games. Defence of the stand that board games are not marginal subject beside modern sorts of amusement e.g. computer games. The Classification of modern board games with regard to their dominant cultural background and origin. The sociological survey on board games and motivation to their playing in the subculture of players 10-15years old. The Analysis of the survey and a search of basic categories of associated motivations for positive relation to board games and their playing. More detailed view on reasons why people do not want to play board games. The Analysis of players' fellowship. The practical application of board games (like general educative tool, a tool in the scope of teambuilding and human resources or else expert diagnostics and therapy). Keywords a subculture of players, a modern classification of a game, a board game, a table game, the history of board games

O câncer de mama permanece como segundo tipo de câncer mais frequente no mundo e o primeiro entre as mulheres. Tumores de mama podem ser categorizados pela expressão de receptores como o HER-2 (receptor de fator de crescimento epidermal 2). A hiperexpressão do receptor HER-2 é observada em cerca de 30% dos carcinomas de mama, e está associada a prognósticos desfavoráveis. Os ácidos graxos poli-insaturados (AGPI) , como os ácidos graxos ômega-3, parecem diminuir o risco de câncer de mama. O ácido docosahexaenoico (DHA), um tipo de AGPI ômega-3 parece ter o maior potencial antitumoral no câncer de mama. Alguns mecanismos de ação foram propostos para a ação do DHA no controle do câncer de mama, no entanto, faltam dados para elucidar os mecanismos moleculares do DHA no tecido mamário normal e cancerígeno. Dessa maneira, o objetivo desse trabalho foi avaliar a ação do DHA na modulação da expressão de genes em linhagem celular normal (HB4a), transformada (HB4aC5.2) e de carcinoma mamário humano (SKBR-3). As linhagens estudadas foram tratadas com 100 ?M de DHA ou controle (etanol) durante 72 horas. Após a extração de RNA realizamos a técnica de expressão gênica global (Microarray) para encontrar os genes diferencialmente expressos, em relação ao tratamento com DHA, em cada linhagem celular estudada. Na linhagem normal (HB4a) observamos 174 genes diferencialmente expressos (p<0,01), sendo 136 hiperexpressos e 38 hipoexpressos, na linhagem celular transformada (HB4aC5.2) encontramos 208 genes diferencialmente expressos (p<0,01), sendo 32 hiperexpressos e 176 hipoexpressos. A linhagem do carcinoma mamário (SKBR-3) apresentou 126 genes diferencialmente expressos (p<0,01), sendo 48 hiperexpressos e 78 hipoexpressos. A análise ontológica destes genes permitiu identificar processos biológicos como: adesão celular, diferenciação celular e metabolismo lipídico. Concluímos que o DHA altera o perfil de expressão gênica de maneiras distintas em linhagem normal, transformada e de carcinoma mamário humano. Além disso, encontramos após o tratamento com DHA genes envolvidos com o metabolismo lipídico nas linhagens que hiperexpressam o receptor HER-2 / Breast cancer remains the second most common cancer in the world and first among women. Breast tumors can be categorized by the expression of receptors such as HER-2. Overexpression of HER-2 receptor is associated with unfavorable prognosis.The polyunsaturated fatty acids (PUFAs) omega- 3 appears to decrease the risk of breast cancer. Docosahexaenoic acid (DHA), a type of omega-3 PUFAs, seems to have greater antitumor potential in breast cancer. However, the gene expression profile resulting from the action of DHA in breast cancer has not been elucidated yet. We aimed to examine the effects of DHA on normal breast cell line (HB4a), transformed cell line (HB4aC5.2) and breast cancer cell line (SKBR-3) and using a microarray approach. Cells were treated with 100?M of DHA for 72 hours. We identified 174, 208 and 126 differentially expressed genes after DHA treatment, in HB4a, HB4aC5.2 and SKBR3, respectively. Notably, the molecular pathways for the differentially expressed genes included those related to lipid metabolism, cell growth, molecular transport and cell-to-cell signaling. Where found genes related to overexpression of HER-2 after treatment with DHA. These genes involved in lipid metabolism and were down-expressed after treatment, suggesting a possible mechanism DHA in breast cancer by lipid metabolism control

Made available in DSpace on 2015-04-20T12:31:16Z (GMT). No. of bitstreams: 1 lesemky.pdf: 1202883 bytes, checksum: f8220049d5a1bd344120a49c3ed2500a (MD5) Previous issue date: 2012-12-12 / Cytokeratin 19 (CK 19) is a molecular marker that express cell replication and differentiation, and HER-2 oncogene (Human Epidermal Growth factor receptor-Type 2) is the second member of the human epidermal growth factor receptor (EGFR) family. Its overexpression can mean aggressiveness and poor prognostic in various kinds of tumors, as breast, lung and prostate. In last few decades the diagnostic of morphological changes of the thyroid gland was increased. When being diagnosed with ultrasound, the thyroid nodule prevalence reaches 20% to 30% in the general population. The aim of this prospective study is verify the presence of these markers in thyroid glands in operated non-coastal Amazon inhabitants, and its relationship with pathologic findings. We selected 34 samples of formalin-fixed, paraffin-embedded thyroid tumor tissues, from patients treated at Hospital Adriano Jorge, Manaus, Amazonas. The patients consisted of six men and 28 women, aged between 25 and 76 years, average 47 years. The tissues corresponded to nine multinodular goiter (MNG), seven colloid goiters (CG), five nodular hyperplasia (NH) four adenomatous goiters (AG), three papillary thyroid microcarcinoma (PTMC) and five papillary thyroid carcinomas (PTC). Immunohistochemistry (IHC) staining with CK 19 and HER-2 were performed using the labeled streptavidin biotin peroxidase complex system (LSAB2, DAKO, USA) on all tissues using monoclonal antibodies BA17 mab mouse (Dako M0772, USA) and SP3 rabbit mab (Spring M3034, USA) and inferential statistical analysis applying (Fisher exact test with 5% significance level). HER-2 IHC was not found in all samples. We found a strong positive reactivity for IHC CK19 in all 3 patients with PTMC, in four with PTC, one with MNG, and one with CG. We found focal positivity for CK 19 in one PTC, two MNG, 4 CG and one AG. Statistical significance was found only between CK 19 and histopathology. The results suggest thats HER-2 oncogene has no predictive or prognostic value in thyroid tissues and CK 19 marker showed affinity for PTC, although it is also found in benign tissues with less intensity. / A citoqueratina 19 (CK 19) é um marcador molecular que expressa diferenciação e replicação celular e o oncogene HER-2 (Human Epidermal Growth factor receptor-Type 2), membro da família Fator de Crescimento Epidérmico Humano (EGFR), uma proteína que quando sobre-expressa pode significar maior ploriferação celular e agressividade em vários tipos de tumores, dentre eles mama, pulmão e próstata. Nas últimas décadas vêm aumentando o diagnóstico de alterações morfológicas da glândula tireoide, sendo que quando diagnosticado à ultrassonografia a prevalência do nódulo tireoideano chega a 20% a 30% na população geral. Objetivamos neste estudo prospectivo verificar a presença destes marcadores em glândulas tireoideas operadas em pacientes habitantes em região amazônica não litorânea, e sua relação com as alterações morfológicas encontradas. Foram selecionadas 34 amostras de tecido tireoidiano preservados em formol e armazenados em parafina, de pacientes operados na Fundação Hospital Adriano Jorge, de Manaus, Amazonas. Os pacientes corresponderam a seis homens e 28 mulheres, com idade entre 25 e 76 anos e média de 47 anos. Os tecidos corresponderam a nove bócios multinodulares (BMN), sete bócios coloides (BC), cinco hiperplasias nodulares (HN) quatro bócios adenomatosos (BA), três microcarcinomas papilíferos (MCP) e cinco carcinomas papilíferos da tireóide (CPT). Exames de imuno-histoquímica em busca dos marcadores CK19 e HER-2 foram realizados em todos os tecidos usando anticorpos monoclonais BA17 (mab rato, Dako M0772, EUA) e SP3 (policlonal em coelho, Spring M3034, EUA) e o método esteptavidina-biotina-peroxidade (Kit LSAB, Dako, EUA) e análise estatística inferencial aplicando o teste Exato de Fisher com nível de significância de 5%. Não foi encontrada positividade para o marcador HER-2 em tecidos tireoidianos malignos ou benignos. Foram encontrados positividade média a forte intensidade para CK19 em todos os três pacientes com MCP, quatro CPT, um BMN e um BC. Foram encontrados positividade focal em um CPT, dois BMN, quatro BC e um BA. A análise estatística demonstrou significância estatística somente entre as variáveis CK 19 e tipo histopatológico. Os resultados da amostra analisada demonstraram que a pesquisa no oncogene HER-2 não apresentou presença deste marcador em nenhum dos tecidos tireoidianos, e o marcador CK 19 foi presente em maior intensidade nos casos de Carcinoma que nos tecidos benignos onde foi encontrado.