Dissertations / Theses on the topic 'ONMS system'

This report describes the development of a system for controlling documents. The report starts with a problem description which the company wants an intranet-based solution for. The report then continues to describe the development phase for the different parts of the system which results in a complete system. The company that wanted this system is called Orbit One and is located in Ronneby, Sweden. They have had a problem with old documents circulating in different versions and in different binders. Now thanks to their new system they can access their documents easy and on demand through their intranet.

This thesis describes work carried out on several chemical aspects of fused 1,2,3-triazin-4-ones. In the first section several sUbstituted l,2,3-benzotriazinones were prepared with a view to observing their rate of deazoniation. It ,was envisaged that a kinetic analysis of this reaction would aid the elucidation of the nature of a hitherto controversial reaction intermediate. The rate constants obtained were used to construct Hammett plots and hence calculate the reaction constants. Several pieces of evidence were obtained that suggested the intermediate was of a diradical nature. Unfortunately, this could not be substantiated by Chemically Induced Dynamic Nuclear Polarisation spectroscopy. The second section involved devising a new synthetic route for the preparation of l,2,3-thieno[ 3,4-d]triazinones since the one existing preparation gave polysubstituted products. A simple thienotriazinone was obtained which was used to study the reaction conditions required to cause its deazoniation. It was envisaged that for this reaction to occur, a potentially undesirable sulphurE[intermediate must be surmounted. As anticipated the thieno[3,4-d]triazinone did not deazoniate under the normal conditions.The synthetic route used to prepare the thieno[3,4-d]triazinone also afforded an intermediate aminonitrile. An investigation into the versatility of this compound as a potential precursor to other fused heterocycles was undertaken. Several fused thienopyrimidines were obtained. The final section of this work was dedicated to devising a synthetic route for the preparation of pyrroloand furanotriazinones. Unfortunately these compounds were not obtained due to difficulties of instability and excessive water solubility encountered in the synthesis, several useful intermediates were, however, successfully prepared.

The aim of the project was to investigate the use of mercury mediated cyclisation reactions resulting in the generation of 2,3-dihydropyran-4//-one and 3(2//)-furanone systems. Chapter one discusses the general synthesis of dihydropyranones and furanones. The chapter continues and focuses upon the use of a mercury-mediated cyclisation strategy in the synthesis of 2,3-dihydropyran-4-ones and 3(2//)-mranones. Finally the chapter describes efforts to utilise a mercury-mediated cyclisation strategy to synthesise useful synthetic intermediates. Chapter two is focused upon protein phosphorylation inhibitors, and begins by discussing the processes of protein phosphorylation and compounds which inhibit the process. The chapter focuses on fostriecin and phospholine compounds, and discusses efforts to synthesise key fragments of the compounds using a mercury-mediated cyclisation protocol. Chapter three describes histone deacetylase inhibitors, and their mode of action. The use of computational models to predict and rationalise inhibitor activity is discussed. A small selection of HDAC inhibitors are used to demonstrate the Autodock system in predicting inhibitory activity. A previously unknown compound is synthesized, and inhibitory properties compared to those predicted by the Autodock system. Chapter four discusses efforts to synthesise the spiroketal subunit of (-)-calyculin A. Initially a mercury-mediated cyclisation strategy is presented, detailing the preparation of two key fragments which are combined to form a key scaffold used in the cyclisation strategy. The chapter then describes the use of auxiliary fragments in attempts to generate the spiroketal fragment.

Brazil has majority share of hydroelectric power in its generation matrix electricity, depending on the rainy seasons and settlement of multiannual reservoirs to ensure safety in the generation and distribution system power national power. In this context, time series analysis can provide information useful for planning and more efficient operation of the reservoirs, identifying possible trends in the flow of data or precipitation of the integrated stations hydroelectric plants. The trend analysis in hydrological series is held traditionally using non-parametric tests such as the Mann-Kendall test, and You can treat both monotonic trends or abrupt as in various ways. Such tests, although not require information about the distribution of data, require data to be independent, which rarely occurs in series hydrologic variables. Thus, new tests have arisen in the trend analysis, with objective of taking the autocorrelation of the series under consideration. This paper proposes trend analysis of historical streamflow series of major basins contribute to the National Interconnected System (SIN), obtained from data National Electric System Operator (ONS). The analysis will aim check importance of considering the autocorrelation of the data to detect trends, analyzing the first series without considering the autocorrelation - the nonparametric method Traditional Mann-Kendall with Sen estimator - and then applying filters Pre-Whitening and Trend-Free Pre-Whitening. The tests were implemented through the MatLab program to analyze the average natural flow monthly provided by the ONS. The spatial distribution of trends found It was presented through maps created the Free Software QGIS. The results found for the ONS posts corroborated the theory that the autocorrelation influences the detection of trends. Keywords: autocorrelation, trend analysis, hydropower se
O Brasil possui participaÃÃo majoritÃria de energia hidroelÃtrica em sua matriz de geraÃÃo de energia elÃtrica, dependendo das estaÃÃes chuvosas e da regularizaÃÃo plurianual dos reservatÃrios para garantir a seguranÃa na geraÃÃo e distribuiÃÃo de energia do sistema elÃtrico nacional. Nesse contexto, a anÃlise de sÃries temporais pode oferecer informaÃÃes Ãteis para o planejamento e a operaÃÃo mais eficientes dos reservatÃrios, identificando possÃveis tendÃncias nos dados de vazÃo ou de precipitaÃÃo dos postos integrados Ãs usinas hidrelÃtricas. A anÃlise de tendÃncias em sÃries hidrolÃgicas à realizada tradicionalmente atravÃs de testes nÃo-paramÃtricos, como o teste de Mann-Kendall, e pode tratar tanto de tendÃncias monotÃnicas, quanto de abruptas ou de formas diversas. Esses testes, apesar de nÃo requererem informaÃÃes sobre a distribuiÃÃo dos dados, requerem que os dados sejam independentes, o que raramente ocorre nas sÃries de variÃveis hidrolÃgicas. Assim, novos testes surgiram na anÃlise de tendÃncias, com o objetivo de levar a autocorrelaÃÃo das sÃries em consideraÃÃo. O presente trabalho propÃe a anÃlise de tendÃncias das sÃries histÃricas de vazÃes das principais bacias que contribuem para o Sistema Interligado Nacional (SIN), obtidas a partir de dados do Operador Nacional do Sistema ElÃtrico (ONS). A anÃlise terà por objetivo verificar a importÃncia da consideraÃÃo da autocorrelaÃÃo dos dados na detecÃÃo de tendÃncias, analisando as sÃries primeiramente sem considerar a autocorrelaÃÃo - pelo mÃtodo nÃoparamÃtrico tradicional de Mann-Kendall com estimador de Sen - e, em seguida, aplicando os filtros do Pre-Whitening e do Trend-Free Pre-Whitening. Os testes foram implementados atravÃs do programa MatLab, para anÃlise das vazÃes naturais mÃdias mensais disponibilizadas pelo ONS. A distribuiÃÃo espacial das tendÃncias encontradas foi apresentada atravÃs de mapas criados no software livre QGIS. Os resultados encontrados para os postos do ONS corroboraram a teoria de que a autocorrelaÃÃo influencia na detecÃÃo de tendÃncias.

Native Multicast plays an important role in distributing and managing delivery of some of the most popular Internet applications, such as IPTV and media delivery. However, due to patchy support and the existence of multiple approaches for Native Multicast, the support for Native Multicast is fragmented into isolated areas termed Multicast Islands. This renders Native Multicast unfit to be used as an Internet wide application. Instead, Application Layer Multicast, which does not have such network requirements but is more expensive in terms of bandwidth and overhead, can be used to connect the native multicast islands. This thesis proposes Opportunistic Native Multicast (ONM) which employs Application LayerMulticast (ALM), on top of a DHT-based P2P overlay network, and Automatic Multicast Tunnelling (AMT) to connect these islands. ALM will be used for discovery and initiating the AMT tunnels. The tunnels will encapsulate the traffic going between islands' Primary Nodes (PNs). AMT was used for its added benefits such as security and being better at traffic shaping and Quality Of Service (QoS). While different approaches for connecting multicast islands exists, the system proposed in the thesis was designed with the following characteristics in mind: scalability, availability, interoperability, self-adaptation and efficiency. Importantly, by utilising AMT tunnels, this approach has unique properties that improve network security and management.

COSTA, C. G. F. Desigualdade, pobreza e governança: uma agenda para Timor-Leste. 2014. 209 f. Tese (Doutorado em Desenvolvimento e Meio Ambiente) - Centro de Ciências, Universidade Federal do Ceará, Fortaleza, 2014.
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The theme of this thesis - "INEQUALITY, POVERTY AND GOVERNANCE: AN AGENDA FOR EAST TIMOR" - stems from an interest to assess the influence of key-actors - NGOs, national governments and the United Nations System - in policy development, in developing countries that emerge from serious conflicts; in particular we search for solutions to deal with the problem of how to evaluate governance, policies and the development path in countries without reliable and structured data. This research animes to contribute to the debate on the influence of NGOs, national governments and the United Nations System on issues concerning governance, sustainable development and environment issues in developing countries that emerge from conflict featuring unconsolidated democracies; We analysed the case of East Timor, between 1999 and 2012, on issues related to social, gender and income inequality and a variety of global issues like climate change and poverty levels, based on the Millennium Development Goals (MDGs). The theoretical and methodological basis of this study was Melucci (1991). Notwithstanding this study is stakeholder-oriented based on inter- and transdisciplinary research, on multi-level and participatory governance theories and political philosophy, with focus on horizontal and environmental policy integration and processes as well as questions of legitimacy, accountability and sustainability based on the analysis of secondary sources (text, numbers, images, etc.) and collection of primary empirical data in the field, in 2012, for policy analysis in different contexts - a necessary step due to the fragility and often lack of reliable data and audited information. We analysed official documents and reports such key UN-resolutions, the Timor-Leste National Development Plan (NDP), the Millennium Development Goals Reports (MDGs), Human Development Reports (HDR), Evolution of the Human Development Index (HDI), scientific articles and several technical reports released by development agencies such as ABD, FAO, UNDP and others. We observed a huge discrepancy between rhetoric and practice concerning the key-actors participation as well as noticeable flaws in policy conduction at various levels. Transparency levels are incredibly low and it permeates all levels of the government. The impression one gets is that there was an interest in promoting the pacification process to enable foreign companies to extract oil at low risk, while issues related to governance, accountability and transparency were neglected. It is argued that such challenges were less a matter of rules and regulations then basic approaches, attitudes and power relations. It is possible that these key-actors, in general, did not succeed in find ways to change their approach during the years of stabilization; with little or no progress on issues related to human development, poverty and inequality reduction. Instead of fostering the development of a viable and autonomous civil society its results have demonstrated the depletion of a model of development that on one hand was efficient on the pacification process while on the other hand have failed in the promotion of opportunities, governance and sustainable development. Finally, we conclude that socioeconomic peculiarities and policies adopted in developing countries that emerge from serious conflicts should not be seeing as specific procedural and institutional factors replicable from stabilized societies, it is necessary to draw up a better database and a set of analysis tools based on the peculiar conditions of developing countries emerging from different forms of conflict focusing on mechanisms that promote good governance, transparency and accountability. As final considerations, to support Timor-Leste’s sustainable development policies, we point out the need to relativize the implementation of criteria considered necessary for good governance, establish a hierarchy over time and across priorities in development programs and projects, which must be guided by the specificities of particular contexts. This research contributed to the debate on the influence of NGOs, national governments and the United Nations System on issues concerning governance, sustainable development and environmental related issues in developing countries that emerge from conflict featuring unconsolidated democracies; We analysed the case of East Timor, between 1999 and 2012, on issues related to social, gender and income inequality and a variety of global issues like climate change and poverty levels, based on the Millennium Development Goals (MDGs). The theoretical and methodological basis of this study was Melucci (1992). This study is stakeholder-oriented based on inter- and transdisciplinary research, on multi-level and participatory governance theories and political philosophy, with focus on horizontal and environmental policy integration and processes as well as questions of legitimacy, accountability and sustainability. based on the analysis of secondary sources (text, numbers, images, etc.) and collection of primary empirical data in the field, in 2012, for policy analysis in different contexts - a necessary step due to the fragility and often lack of reliable data and audited information. We analysed official documents and reports such key UN-resolutions, the Timor-Leste National Development Plan (NDP), the Millennium Development Goals Reports (MDGs), Human Development Reports (HDR), Evolution of the Human Development Index (HDI), scientific articles and several technical reports released by development agencies such as ABD, FAO, UNDP and others. We observed a huge discrepancy between rhetoric and practice concerning the key-actors participation as well as noticeable flaws in policy conduction at various levels. Corruption levels are high and permeates all levels of the government. The impression one gets is that there was an interest in promoting the pacification process to enable oil companies to extract oil at low risk, while issues related to governance, accountability and transparency were neglected. It is argued that such challenges were less a matter of rules and regulations then basic approaches, attitudes and power relations. It is possible that these key-actors, in general, have not changed their approach during the years of stabilization; with little or no progress on issues related to human development, poverty and inequality reduction. Instead of fostering the development of a viable and autonomous civil society its results have demonstrated the depletion of a model of development that on one hand was efficient on the pacification procces but that on the other hand have failed in the promotion of opportunities, governance and sustainable development. Finally, we conclude that socioeconomic peculiarities and policies adopted in developing countries that emerge from serious conflicts should not be seing as specific procedural and institutional factors replicable from stabilized societies, it is necessary to draw up a better database and a set of analysis tools based on the peculiar conditions of developing countries emerging from different forms of conflict focusing on mechanisms that promote good governance, transparency and accountability. As final considerations, to support Timor-Lestes´s sustainable development policies, we point out the need to relativize the implementation of criteria considered necessary for good governance, establish a hierarchy over time and across priorities in development programs and projects, which must be guided by the specificities of particular contexts.
O tema desta tese - "Desigualdade, pobreza e governança: uma agenda para Timor-Leste" - decorre do interesse em avaliar a influência de atores-chave - ONGs, governos nacionais e do Sistema das Nações Unidas - no desenvolvimento de políticas, em países em desenvolvimento que emergem de conflitos graves; em particular, procurar soluções para lidar com o problema de como avaliar políticas de governança, e trajetórias de desenvolvimento em países sem base de dados confiáveis e estruturados. Esta pesquisa buscou contribuir para o debate sobre a influência das ONGs, governos nacionais e do Sistema das Nações Unidas sobre questões relacionadas a governança, desenvolvimento sustentável e questões ambientais em países em desenvolvimento que emergem de conflitos configurando democracias não-consolidadas; Analisamos o caso de Timor-Leste entre 1999 e 2012 com relação a questões socioeconômicas, desigualdade de gênero de renda e uma variedade de questões globais como mudanças climáticas e níveis de pobreza, com base nos Objetivos de Desenvolvimento do Milênio (ODM). A base teórica e metodológica deste estudo foi Melucci (1991). Entretanto, este estudo é "stakeholder-orientado", baseado em investigação interdisciplinar e transdisciplinar, em multi-nível com base em teorias de governança participativa e filosofia política, com foco na integração horizontal de processos de ordem política e ambiental, bem como questões de legitimidade, prestação de contas e sustentabilidade com base na análise de fontes secundárias (texto, números, imagens, etc.) e de recolha de dados empíricos primárias no campo em Timor-Leste, em 2012, para a análise de políticas em diferentes contextos - um passo necessário devido à fragilidade e muitas vezes a falta de dados confiáveis e informações auditadas. Foram analisados documentos oficiais e relatórios-chaves baseados em resoluções da ONU, o Plano de Timor-Leste Desenvolvimento Nacional (PDN), os Relatórios sobre os Objetivos de Desenvolvimento do Milênio (ODM), Relatórios de Desenvolvimento Humano (HDR), Evolução do Índice de Desenvolvimento Humano (IDH), artigos científicos e vários relatórios técnicos divulgados por agências de desenvolvimento, como a ABD, FAO, PNUD e outros. Foi observado uma enorme discrepância entre a retórica e a prática relativa à participação atores-chave, bem como falhas visíveis na condução política em vários níveis. Os níveis de transparência são reduzidos e, isso permeia todas as áreas do governo. A impressão que se tem é que houve interesse em promover o processo de pacificação para permitir que as companhias estrangeiras pudessem extrair petróleo com baixo risco, enquanto que as questões relacionadas à governança, à responsabilidade e à transparência foram negligenciadas. Argumenta-se que esses desafios foram menos uma questão de regras e regulamentos do que abordagens básicas, atitudes e relações de poder. É possível que estes atores-chave, em geral, não tenham conseguido mudar suas abordagens durante os anos de estabilização, com rarefeito progresso em questões relacionadas com o desenvolvimento humano, e a redução da pobreza e desigualdade. Ao invés de fomentar o desenvolvimento de uma sociedade civil viável e autônoma, os resultados têm demonstrado o esgotamento de um modelo de desenvolvimento que, se por um lado eficiente na pacificação falhou na promoção de oportunidades, governança e desenvolvimento sustentável. Por fim, concluímos que peculiaridades socioeconômicas e políticas adotadas em países em desenvolvimento, que emergem de conflitos graves, não devem ser vistas como fatores processuais e institucionais replicáveis de sociedades estabilizadas, é necessário elaborar uma melhor base de dados e um conjunto de ferramentas de análise com base nas condições peculiares dos países em desenvolvimento que emergem de diferentes formas de conflito com foco em mecanismos que promovam a boa governança, transparência e prestação de contas. Como considerações finais, para apoiar políticas de desenvolvimento sustentável em Timor-Leste e em países similares, destacamos a necessidade de relativizar a implementação de critérios considerados necessários para a boa governança, estabelecer uma hierarquia ao longo do tempo, em função das prioridades, em programas e projetos de desenvolvimento, que devem ser guiados pelas especificidades de contextos particulares. Esta pesquisa contribuiu para o debate sobre a influência das ONGs, governos nacionais e do Sistema das Nações Unidas sobre questões relacionadas a governança, desenvolvimento sustentável e questões ambientais em países em desenvolvimento que emergem de conflitos configurando democracias não-consolidadas; Analisamos o caso de Timor Leste entre 1999 e 2012 com relação a questões socioeconômicas, desigualdade de gênero de renda e uma variedade de questões globais como mudanças climáticas e níveis de pobreza, com base nos Objetivos de Desenvolvimento do Milênio (ODM). A base teórica e metodológica deste estudo foi Melucci (1992). Entretanto, este estudo é "stakeholder-orientado",baseado em investigação interdisciplinar e transdisciplinar, em multi-nível com base em teorias de governança participativa e filosofia política, com foco na integração horizontal de processos de ordem política e ambiental, bem como questões de legitimidade, prestação de contas e sustentabilidade. com base na análise de fontes secundárias (texto, números, imagens, etc.) e de recolha de dados empíricos primárias no campo em Timor-Leste, em 2012, para a análise de políticas em diferentes contextos - um passo necessário devido à fragilidade e muitas vezes a falta de dados confiáveis e informações auditadas. Foram analisados ​documentos oficiais e relatórios-chaves baseados em resoluções da ONU, o Plano de Timor-Leste Desenvolvimento Nacional (PDN), os Relatórios sobre os Objetivos de Desenvolvimento do Milênio (ODM), Relatórios de Desenvolvimento Humano (HDR), Evolução do Índice de Desenvolvimento Humano (IDH), artigos científicos e vários relatórios técnicos divulgados por agências de desenvolvimento, como a ABD, FAO, PNUD e outros. Foi observado uma enorme discrepância entre a retórica e a prática relativa à participação atores-chave, bem como falhas visíveis na condução política em vários níveis. Os níveis de corrupção são elevados e permeia todas as áreas do governo. A impressão que se tem é que houve interesse em promover o processo de pacificação para permitir que as companhias petrolíferas pudessem extrair petróleo com baixo risco, enquanto que as questões relacionadas à governança, à responsabilidade e à transparência foram negligenciadas. Argumenta-se que esses desafios foram menos uma questão de regras e regulamentos do que abordagens básicas, atitudes e relações de poder. É possível que estes atores-chave, em geral, não tenham mudado sua abordagem durante os anos de estabilização; com pouco ou nenhum progresso em questões relacionadas com o desenvolvimento humano, a pobreza e a redução da desigualdade. Ao invés de fomentar o desenvolvimento de uma sociedade civil viável e autônoma, os resultados têm demonstrado o esgotamento de um modelo de desenvolvimento que, se por um lado eficiente na pacificação falhou na promoção de oportunidades, governança e desenvolvimento sustentável. Por fim, concluímos que peculiaridades socioeconômicas e políticas adotadas em países em desenvolvimento que emergem de conflitos graves não devem ser vistas como fatores processuais e institucionais replicáveis de sociedades estabilizadas, é necessário elaborar uma melhor base de dados e um conjunto de ferramentas de análise com base nas condições peculiares dos países em desenvolvimento que emergem de diferentes formas de conflito com foco em mecanismos que promovam a boa governança, transparência e prestação de contas. Como considerações finais, para apoiar políticas de desenvolvimento sustentável em Timor-Leste, destacamos a necessidade de relativizar a implementação de critérios considerados necessários para a boa governança, estabelecer uma hierarquia ao longo do tempo, em função das prioridades, em programas e projetos de desenvolvimento, que devem ser guiados pelas especificidades da contextos particulares.

Aquí hem aplicat el Princeton Ocean Model als embassaments de Sau i Boadella, situats a Catalunya, Espanya. Les simulacions s'han realitzat a l'estació d'estiu, quan la columna d'aigua està estratificada de forma contínua, i sota un règim de brisa amb velocitats de fins a 4 m/s. Basant-nos en aquestes simulacions hem analitzat el camp d'ones internes i comparat els resultats numèrics amb dades experimentals disponibles. El model reprodueix adequadament tots els modes observats en l'espectre de la velocitat i temperatura mesurades i ajuda a identificar els diferents modes. Les simulacions mostren la importància dels modes rotacionals en el camp d'ones internes dels embassaments estratificats. En el període estudiat, el radi de Rossby per l'embassament de Sau és de l'ordre de 100 m, que és varies vegades més petit que la amplitud de l'àrea lacustre de l'embassament, i el número de Rossby és de l'ordre de 0.1, corroborant la importancia de l'efecte de Coriolis.
We applied the Princeton Ocean Model to the Sau and Boadella reservoirs, located in Catalonia, Spain. Simulations were done for the summer season, when the water column is continuously stratified, and under a breeze regime with velocities of up to 4 m/s. Based on these simulations we analyzed the internal wave field and compared the numerical results with available field data. The model adequately reproduces all significant modes observed on the spectra of measured velocity and temperature and helps to identify the different modes. The simulations show the importance of rotational modes for the internal wave field of the stratified reservoirs. Under the studied wind regime, the Rossby radius for the Sau Reservoir is of the order of 100 m, that is, several times smaller than the amplitude of the lacustrine zone of the reservoir, and the Rossby number is of order of 0.1, which corroborates the importance of the Coriolis effect.

Esta investigación analiza los procesos de organización y emergencia indígena en los países centro-andinos (Bolivia, Ecuador, Perú) de la región
latinoamericana. En concreto, determina aquellos factores que determinan la aparición
de movimientos indígenas en Bolivia y Ecuador (de diferente intensidad) así como su
inhibición en Perú a pesar de que los tres países comparten características socio-
económicas comunes y trayectorias histórico-políticas paralelas - incidiendo en la
dinámica que politiza las identidades étnicas en las tres últimas décadas. Al margen de
ello, especifica el impacto que los movimientos indígenas contemporáneos tienen en:
los sistemas políticos actuales y su desempeño en la arena electoral; los procesos de
democratización en marcha en la zona y los desafíos que suponen para éste y las
iniciativas de reforma del estado.
This research analyzes the indigenous organization process in center-andean
countries (Bolivia, Ecuador, Perú) and reveals those factors which cause indigenous
movements (in Bolivia and Ecuador) and those ones which impede this phenomenon in
Perú - although these countries have common trends in economical, political and
historical spheres - with special attention to the political dynamic of ethnic identities
during the last three decades. Also these pages detail the impact of the indigenous
movements in: political systems and their performance in electoral arena;
democratization processes and the challenges that these movements put into them and
over state reform initiatives.

Doutoramento em Bioquímica
Os polissacarídeos são os componentes maioritários dos grãos de café verde e torrado e da bebida de café. Os mais abundantes são as galactomananas, seguindo-se as arabinogalactanas. Durante o processo de torra, as galactomananas e arabinogalactanas sofrem modificações estruturais, as quais estão longe de estar completamente elucidadas devido à sua diversidade e à complexidade estrutural dos compostos formados. Durante o processo de torra, as galactomananas e arabinogalactanas reagem com proteínas, ácidos clorogénicos e sacarose, originando compostos castanhos de alto peso molecular contendo nitrogénio, designados de melanoidinas. As melanoidinas do café apresentam diversas atividades biológicas e efeitos benéficos para a saúde. No entanto, a sua estrutura exata e os mecanismos envolvidos na sua formação permanecem desconhecidos, bem como a relação estrutura-atividade biológica. A utilização de sistemas modelo e a análise por espectrometria de massa permitem obter uma visão global e, simultaneamente, detalhada das modificações estruturais nos polissacarídeos do café promovidas pela torra, contribuindo para a elucidação das estruturas e mecanismos de formação das melanoidinas. Com base nesta tese, oligossacarídeos estruturalmente relacionados com a cadeia principal das galactomananas, (β1→4)-Dmanotriose (Man3), e as cadeias laterais das arabinogalactanas, (α1→5)-Larabinotriose (Ara3), isoladamente ou em misturas com ácido 5-Ocafeoilquínico (5-CQA), o ácido clorogénico mais abundante nos grãos de café verde, e péptidos compostos por tirosina e leucina, usados como modelos das proteínas, foram sujeitos a tratamento térmico a seco, mimetizando o processo de torra. A oxidação induzida por radicais hidroxilo (HO•) foi também estudada, uma vez que estes radicais parecem estar envolvidos na modificação dos polissacarídeos durante a torra. A identificação das modificações estruturais induzidas por tratamento térmico e oxidativo dos compostos modelo foi feita por estratégias analíticas baseadas principalmente em espectrometria de massa, mas também em cromatografia líquida. A cromatografia de gás foi usada na análise de açúcares neutros e ligações glicosídicas. Para validar as conclusões obtidas com os compostos modelo, foram também analisadas amostras de polissacarídeos do café obtidas a partir de resíduo de café e café instantâneo. Os resultados obtidos a partir dos oligossacarídeos modelo quando submetidos a tratamento térmico (seco), assim como à oxidação induzida por HO• (em solução), indicam a ocorrência de despolimerização, o que está de acordo com estudos anteriores que reportam a despolimerização das galactomananas e arabinogalactanas do café durante a torra. Foram ainda identificados outros compostos resultantes da quebra do anel de açúcares formados durante o tratamento térmico e oxidativo da Ara3. Por outro lado, o tratamento térmico a seco dos oligossacarídeos modelo (individualmente ou quando misturados) promoveu a formação de oligossacarídeos com um maior grau de polimerização, e também polissacarídeos com novos tipos de ligações glicosídicas, evidenciando a ocorrência de polimerização através reações de transglicosilação não enzimática induzidas por tratamento térmico a seco. As reações de transglicosilação induzidas por tratamento térmico a seco podem ocorrer entre resíduos de açúcares provenientes da mesma origem, mas também de origens diferentes com formação de estruturas híbridas, contendo arabinose e manose como observado nos casos dos compostos modelo usados. Os resultados obtidos a partir de amostras do resíduo de café e de café instantâneo sugerem a presença de polissacarídeos híbridos nestas amostras de café processado, corroborando a ocorrência de transglicosilação durante o processo de torra. Além disso, o estudo de misturas contendo diferentes proporções de cada oligossacarídeo modelo, mimetizando regiões do grão de café com composição distinta em polissacarídeos, sujeitos a diferentes períodos de tratamento térmico, permitiu inferir que diferentes estruturas híbridas e não híbridas podem ser formadas a partir das arabinogalactanas e galactomananas, dependendo da sua distribuição nas paredes celulares do grão e das condições de torra. Estes resultados podem explicar a heterogeneidade de estruturas de melanoidinas formadas durante a torra do café. Os resultados obtidos a partir de misturas modelo contendo um oligossacarídeo (Ara3 ou Man3) e 5-CQA sujeitas a tratamento térmico a seco, assim como de amostras provenientes do resíduo de café, mostraram a formação de compostos híbridos compostos por moléculas de CQA ligadas covalentemente a um número variável de resíduos de açúcar. Além disso, os resultados obtidos a partir da mistura contendo Man3 e 5-CQA mostraram que o CQA atua como catalisador das reações de transglicosilação. Por outro lado, nas misturas modelo contendo um péptido, mesmo contendo também 5-CQA e sujeitas ao mesmo tratamento, observou-se uma diminuição na extensão das reações transglicosilação. Este resultado pode explicar a baixa extensão das reações de transglicosilação não enzimáticas durante a torra nas regiões do grão de café mais ricas em proteínas, apesar dos polissacarídeos serem os componentes maioritários dos grãos de café. A diminuição das reações de transglicosilação na presença de péptidos/proteínas pode dever-se ao facto de os resíduos de açúcares redutores reagirem preferencialmente com os grupos amina de péptidos/proteínas por reação de Maillard, diminuindo o número de resíduos de açúcares redutores disponíveis para as reações de transglicosilação. Além dos compostos já descritos, uma diversidade de outros compostos foram formados a partir dos sistemas modelo, nomeadamente derivados de desidratação formados durante o tratamento térmico a seco. Em conclusão, a tipificação das modificações estruturais promovidas pela torra nos polissacarídeos do café abre o caminho para a compreensão dos mecanismos de formação das melanoidinas e da relação estrutura-atividade destes compostos.
Polysaccharides are the major components of green and roasted coffee beans, and coffee brew. The most abundant ones are galactomannans, followed by arabinogalactans. During the roasting process, galactomannans and arabinogalactans undergo structural modifications that are far to be completely elucidated due to their diversity and complexity of the compounds formed. During the roasting process, galactomannans and arabinogalactans react with proteins, chlorogenic acids, and sucrose, originating high molecular weight brown compounds containing nitrogen, known as melanoidins. Several biological activities and beneficial health effects have been attributed to coffee melanoidins. However, their exact structures and the mechanisms involved in their formation remain unknown, as well as the structure-biological activity relationship. The use of model systems and mass spectrometry analysis allow to obtain an overall view and, simultaneously, detailed, of the structural modifications in coffee polysaccharides promoted by roasting, contributing to the elucidation of the structures and formation mechanisms of melanoidins. Based on this thesis, oligosaccharides structurally related to the backbone of galactomannans, (β1→4)-D-mannotriose, and the side chains of arabinogalactans, (α1→5)-Larabinotriose, alone or in mixtures with 5-O-caffeoylquinic acid, the most abundant chlorogenic acid in green coffee beans, and dipeptides composed by tyrosine and leucine, used as models of proteins, were submitted to dry thermal treatments, mimicking the coffee roasting process. The oxidation induced by hydroxyl radicals (HO•) was also studied, since these radicals seem to be involved in the modification of the polysaccharides during roasting. The identification of the structural modifications induced by thermal and oxidative treatment of the model compounds was performed mostly by mass spectrometry-based analytical strategies, but also using liquid chromatography. Gas chromatography was used in the analysis of neutral sugars and glycosidic linkages. To validate the conclusions achieved with the model compounds, coffee polysaccharide samples obtained from spent coffee grounds and instant coffee were also analysed. The results obtained from the model oligosaccharides when submitted to thermal treatment (dry) or oxidation induced by HO• (in solution) indicate the occurrence of depolymerization, which is in line with previous studies reporting the depolymerization of coffee galactomannans and arabinogalactans during roasting. Compounds resulting from sugar ring cleavage were also formed during thermal treatment and oxidative treatment of Ara3. On the other hand, the dry thermal treatment of the model oligosaccharides (alone or when mixed) promoted the formation of oligosaccharides with a higher degree of polymerization, and also polysaccharides with new type of glycosidic linkages, evidencing the occurrence of polymerization via non-enzymatic transglycosylation reactions induced by dry thermal treatment. The transglycosylation reactions induced by dry thermal treatment can occur between sugar residues from the same origin, but also of different origins, with formation of hybrid structures, containing arabinose and mannose in the case of the model compounds used. The results obtained from spent coffee grounds and instant coffee samples suggest the presence of hybrid polysaccharides in these processed coffee samples, corroborating the occurrence of transglycosylation during the roasting process. Furthermore, the study of mixtures containing different proportions of each model oligosaccharide, mimicking coffee bean regions with distinct polysaccharide composition, subjected to different periods of thermal treatment, allowed to infer that different hybrid and non-hybrid structures may be formed from arabinogalactans and galactomannans, depending on their distribution in the bean cell walls and on roasting conditions. These results may explain the heterogeneity of melanoidins structures formed during coffee roasting. The results obtained from model mixtures containing an oligosaccharide (Ara3 or Man3) and 5-CQA and subjected to dry thermal treatment, as well as samples derived from spent coffee grounds, showed the formation of hybrid compounds composed by CQA molecules covalently linked to a variable number of sugar residues. Moreover, the results obtained from the mixture containing Man3 and 5-CQA showed that CQA acts as catalyst of transglycosylation reactions. On the other hand, in the model mixtures containing a peptide, even if containing 5-CQA and subjected to the same treatment, it was observed a decrease in the extent of transglycosylation reactions. This outcome can explain the low extent of non-enzymatic transglycosylation reactions during roasting in coffee bean regions enriched in proteins, although polysaccharides are the major components of the coffee beans. The decrease of transglycosylation reactions in the presence of peptides/proteins can be related with the preferential reactivity of reducing residues with the amino groups of peptides/proteins by Maillard reaction, decreasing the number of reducing residues available to be directly involved in the transglycosylation reactions. In addition to the compounds already described, a diversity of other compounds were formed from model systems, namely dehydrated derivatives formed during dry thermal treatment. In conclusion, the identification of the structural modifications in coffee polysaccharides promoted by roasting pave the way to the understanding of the mechanisms of formation of melanoidins and structure-activity relationship of these compounds.

碩士
元智大學
資訊工程學系
95
In the EPON, any failure of OLT or feeder fiber can halt the whole system. Many previous studies proposed dedicated protection architectures for critical components and the redundancy results in high cost for deployment. To achieve high reliability and low-cost, this article proposes a novel fault-tolerant Multi-EPON system with cost-effective shared protection through Bridge ONUs. Under the failures, the Bridge ONU controls the faulty EPON, plays the role of OLT and the transmission of faulty EPONs is restored by relayed to other interconnected adjacent EPONs. Additionally, the minimum hop count relay algorithm and relay window mechanism are also proposed in the Multi-EPON system to help the data for relaying to the central office efficiently. Furthermore, the One-Wait DBA enables the controller of affected PONs to obtain more up-to-date buffer occupancy information from each ONU in order to enhance overall system performance. The simulation results show that the proposed Multi-EPON system can provide high system performance for different failures in terms of throughput, average delay, MAX delay and EF jitter, especially in high traffic load.

碩士
國立臺北科技大學
光電工程系研究所
98
In this thesis, a bi-directional long-reach wavelength division multiplexing Passive Optical Network (WDM-PON), with 10 Gb/s bit rate in downlink and 5 Gb/s bit rate in uplink, are proposed. There are two channels with 0.4 nm channel spacing in downstream and upstream, respectively. The dispersion-compensating Raman amplifier /EDFA hybrid amplifier (DCRA/EDFA) which based on dispersion compensating fiber (DCF) is built in the local exchange. The DCRA/EDFA hybrid amplifier not only boost up the power budget, but also reduce the noise in long-reach transmission, including the chromatic dispersion and the effect of amplified spontaneous emission (ASE). Colorless operation is implemented by an electro-absorption modulator (EAM) to re-modulate the downstream signal in each reflective optical network units (R-ONUs) for uplink signals. In this thesis, the hybrid DCRA/EDFA amplifier is verified to improve the fiber dispersion and reduce the loss through the long reach transmission. Due to this scheme, the fiber link can be extended to 120 km transmission and reduced the number of optical amplifiers. The comparison of different pumping type between the feed-forward and backward pumping in RZ-DPSK downlink signal and RZ-OOK uplink signal are presented. And the power penalty are less than 1dB in at 10-9 bit-error-rate in bi-directional fiber link . The results showed that the feed-forward pumping in hybrid amplifier integrated with colorless technique in long-reach WDM-PON transport system not only can reduce capital expenditures, but also can improve the signal performance. Furthermore, it will provide the better sensitivity in transmission.

碩士
台北醫學院
藥學研究所
90
Abstract A facile synthesis of 2-amino-benzo[e][1,3]thiazin-4-one derivatives was achieved. A methanolic solution of 2-methylsulfanyl-benzo[e][1,3] thizin-4-one was treated with various amine compounds at 25℃. The amine compounds are ammonia water, n-butylamine, n-octylamine, hydroxylamine, 3-aminopropanol, ethylenediamine, N,N-dimethylethyl- enediamine, aminoacetaldehyde dimethylacetal, triethylamine, piperidine, piperazine, N-ethylpiperazine, morpholine, (S)-(+)-2-methanol- pyrrolidine, aniline, and p-phenetidine. The reaction completed in 6 to 48 hours, and the recrystallized products were identified with melting point measurement, IR, MS, 1H and 13C nuclear magnetic resonance spectroscopic analyses. The yields were between 60 to 90%. Initially, six analogues including 4, 5, 8, 9, 11 and 14 were submitted for central nervous system activity assay by using glutamate receptor and gamma-aminobutylamine receptor binding inhibition methods. The glutamate receptor binding inhibition method showed that compounds 9 and 14 demonstrated 20.09% and 19.06% were more active than that 5,5-dihydro-hydantoin demonstrated 5.10%. On the other hand, in the gamma-aminobutylamine-A receptor [3H]muscimol binding assay showed that compound 9 demonstrated 28.41% was more active than that dilantin demonstrated 4.35%. Compounds 5 and 8 were the other action to the gamma-aminobutylamine-A receptor [3H]muscimol binding assay that demonstrated —10.89% and —15.84%.

Les pyrrolodiazépinones ont des activités biologiques intéressantes sur différents récepteurs biologiques, ce qui en font une cible de choix pour développer de nouvelles petites molécules biologiquement actives. Une méthodologie en solution a été développée pour synthétiser des pyrrolo[3,2-e][1,4]diazépin-2-ones, qui utilise la réaction de Pictet-Spengler pour former le cycle diazépinone, comme réaction clé. Il a été démontré que le pyrrolo[3,2-e][1,4]diazépin-2-one mime un tour-γ inverse par l’analyse de cristaux par rayon X. Cette méthodologie a été transposée sur trois types de support, soit la résine de Merrifield, de Wang et un support soluble (TAP). Le système urotensinergétique joue un rôle dans certaines pathologies du système cardiovasculaire, comme l’hypertension artérielle, l’insuffisance cardiaque et l’athérosclérose. Le système urotensinergétique est exprimé dans le système circulatoire, extractoire et le système nerveux central et comprend l’UII, l’URP et le récepteur UT. L’UII et l’URP humains sont composés respectivement des séquences d’acides aminés : H-Glu-Thr-Pro-Asp-c[Cys-Phe-Trp-Lys-Tyr-Cys]-Val-OH et H-Ala-c[Cys-Phe-Trp-LysTyr-Cys]-Val-OH. L’UII est le peptide vasoconstricteur le plus puissant connu à ce jour, dont l’URP est son isoforme. Les deux peptides ont des effets biologiques différents et on peut supposer qu’ils jouent un rôle distinct dans certaines pathologies. Il a été démontré que la partie active de l’UII est composée du tripeptide : Trp-Lys-Tyr. Dans l’URP, il a été démontré que ce tripeptide forme un tour-γ inverse, ce qui fait du récepteur UT une bonne cible biologique pour tester une librairie de pyrrolo[3,2-e][1,4]diazépin-2-ones, reprenant le tripeptide Trp-Lys-Tyr. Dernièrement, l’équipe du professeur David Chatenet a mis au point un peptide, l’urocontrin en remplaçant le segment Trp par un groupement biphénylalanine, qui a démontré un comportement spécifique comme antagoniste du récepteur UT. La Librairie de pyrrolo[3,2-e][1,4]diazépin-2-ones est basée sur la séquence TrpLys-Tyr de l’UII et de l’URP et de la séquence Trp-Lys-Bip de l’urocontrin. La synthèse de la librairie est faite sur la résine de Wang. La chaîne latérale de Tyr est mimée en utilisant la tyramine, Lys et Orn sont utilisés et la chaîne latérale de Trp a été reproduite II en utilisant le biphényle (comme dans l’urocontrin), le 1-naphthyle et le 2-naphthyle, sont introduits en employant les aldéhydes respectifs dans la réaction de Pictet-Spengler, ce qui donne les pyrrolo[3,2-e][1,4]diazépin-2-ones insaturés et les saturés S- et R-. L’évaluation de l’activité biologique des pyrrolo[3,2-e][1,4]diazépin-2-ones obtenues sur le récepteur UT se fait par des tests in vitro et ex vivo. Les tests in vitro consistent en un essai de liaisons sur des cellules CHO exprimant le récepteur UT en employant hUII-125I, comme contrôle radiomarqé. Les tests ex vivo sont effectués sur des aortes de rats pour mesurer la capacité à induire des contractions ou de moduler les contractions induites par hUII et URP. Certains R-pyrrolo[3,2-e][1,4]diazépin-2-ones causent une réduction de 50% du signal radioactivité du hUII-125I. Les pyrrolo[3,2-e][1,4]diazépin-2-ones ne montrent guère d’activité ex vivo, mais ils ont la capacité de moduler les contractions induites par l’hUII et l’URP. Par exemple, l’analogue Lys R-saturé avec le biphényle inhibe toutes les contractions de l’aorte à 14 µM avec un pKb de 5,54 à 4 µM, sans influencer les contractions de l’aorte induites par l’URP. Les pyrrolo[3,2-e][1,4]diazépin-2-ones ont une sélectivité pour le système urotensinergétique et sont inactifs sur le récepteur de l’endotheline-1. Les pyrrolo[3,2-e][1,4]diazépin-2-ones sont les premières petites molécules qui peuvent moduler l’activité biologique de l’UII et URP et offrir un potentiel intéressant comme outil pour étudier le système urotensinergétique.
The pyrrolodiazepinones have interesting biological activities on various biological receptors, which makes them a prime target for developing new biologically active small molecules. A methodology in solution had been developed for synthesizing pyrrolo[3,2-e][1,4]diazepin-2-ones, which utilized the Pictet-Spengler condensation as the key reaction to form the diazepinone ring. Pyrrolo[3,2-e][1,4]diazepin-2-ones were found to mimic an inverse γ-turn conformation by X-ray crystallographic analysis. The methodology was subsequently implemented on three types of support: Merrifield resin, Wang resin and the soluble TAP support. The urotensinergic system plays a role in certain diseases of the cardiovascular system, such as hypertension, heart failure and atherosclerosis. The urotensinergic system is expressed in the circulatory system, excretory and central nervous systems and includes the endogenous ligands urotensin II (UII) and urotensin II-related peptide (URP), and the urotensin receptor UT. The ligands UII and human URP are composed of the respective amino acid sequences: H-Glu-Thr-Pro-Asp-c[Cys-Phe-Trp-Lys-Tyr-Cys]-Val-OH and H-Ala-c[Cys-Phe-Lys-Tyr-Trp-Cys]-Val-OH. The peptide UII is the most potent vasoconstrictor known to date. The two peptides have different biological effects and may exhibit distinct roles in certain diseases. Their common Trp-Lys-Tyr sequence is believed to play an important role in the activity of UII and URP, and has been suggested to adopt an inverse γ-turn conformation. Notably, the laboratory of Professor David Chatenet developed the UT receptor antagonist peptide urocontrin by replacing the Trp residue by biphenylalanine (Bip) in URP. A library of pyrrolo[3,2-e][1,4]diazepin-2-one analogs was thus designed to mimic the inverse γ-turn sequence and targeted against UT. The pyrrolo[3,2-e][1,4]diazepin-2-one library was designed based on the Trp-Lys-Tyr sequence of UII and URP, and Trp-Lys-Bip sequence of urocontrin. The synthesis of the pyrrolo[3,2-e][1,4]diazepin-2-one library was achieved on Wang resin. The side chain of Tyr was mimicked using tyramine, Lys and Orn were used as the basic amino acid component, and the side chain of Trp was replicated using biphenyl (as in urocontrin) 1-naphthyl and 2-naphthyl groups that were introduced by employing their respective aldehydes in a Pictet-Spengler reaction, which furnished unsaturated and saturated S- and R-pyrrolo[3,2-e][1,4]diazepin-2-ones. Evaluation of the biological activity of the pyrrolo[3,2-e][1,4]diazepin-2-ones on the UT receptor was performed in vitro and ex vivo. Tests in vitro measured binding in CHO-cells which expressed UT by employing hUII-125I as radiolabeled control. In rat aorta, ex vivo tests measured capacity to induce contraction, or modulate the contractions induced by hUII and URP. Certain R-pyrrolo[3,2-e][1,4]diazepin-2-ones caused an up to 50% reduction of the radioactive signal of hUII-125I. Pyrrolo[3,2-e][1,4]diazepin-2-ones exhibited little activity ex vivo; however, they modulated contractions induced by hUII and URP. For example, the saturated R-analog possessing lysine and a biphenyl side chain inhibited completely hUII-induced contractions of the aorta at 14 µM with a pKb of 5.54 at 4 µM, without influencing URP-induced contractions. Pyrrolo[3,2-e][1,4]diazepin-2-ones were selective for the urotensinergic system and inactive on the related receptor endothelin-1. Pyrrolo[3,2-e][1,4]diazepin-2-ones represent the first small molecules that can differently modulate the biological activities of UII and URP, and offer interesting potential as tools for studying the urotensinergic system.