948 resultados para ASYMMETRIC ALLYLIC ALKYLATION


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Dissertação para obtenção do Grau de Mestre em Engenharia Química e Bioquímica

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Dissertação para obtenção do Grau de Mestre em Genética Molecular e Biomedicina

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A Work Project, presented as part of the requirements for the Award of a Masters Degree in Finance from the NOVA – School of Business and Economics

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The prediction of asymmetric equilibria with Stackelberg outcomes is clearly the most frequent result in the endogenous timing literature. Several experiments have tried to validate this prediction empirically, but failed to find support for it. By contrast, the experiments find that simultaneous-move outcomes are modal and that behavior in endogenous timing games is quite heterogeneous. This paper generalizes Saloner’s (1987) and Hamilton and Slutsky’s (1990) endogenous timing games by assuming that players are averse to inequality in payoffs. We explore the theoretical implications of inequity aversion and compare them to the empirical evidence. We find that this explanation is able to organize most of the experimental evidence on endogenous timing games. However, inequity aversion is not able to explain delay in Hamilton and Slutsky’s endogenous timing games.

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A thesis submitted in fulfillment of the requirements for the degree of the Masters in Molecular Genetics and Biomedicine

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Ionic Liquids (ILs) belong to a class of compounds with unusual properties: very low vapour pressure; high chemical and thermal stability and the ability to dissolve a wide range of substances. A new field in research is evaluating the possibility to use natural chiral biomolecules for the preparation of chiral ionic liquids (CILs). This important challenge in synthetic chemistry can open new avenues of research in order to avoid some problems related with the intrinsic biodegradability and toxicity associated to conventional ILs. The research work developed aimed for the synthesis of CILs, their characterization and possible applications, based on biological moieties used either as chiral cations or anions, depending on the synthetic manipulation of the derivatives. Overall, a total of 28 organic salts, including CILs were synthesized: 9 based on L-cysteine derivatives, 12 based on L-proline, 3 based on nucleosides and 4 based on nucleotides. All these new CILs were completely characterized and their chemical and physical properties were evaluated. Some CILs based on L-cysteine have been applied for discrimination processes, including resolution of racemates and as a chiral catalyst for asymmetric Aldol condensation. L-proline derived CILs were also studied as chiral catalysts for Michael reaction. In parallel, the interactions of macrocyclic oligosugars called cyclodextrins (CDs) with several ILs were studied. It was possible to improve the solubility of CDs in water and serum. Additionally, fatty acids and steroids showed an increase in water solubility when ILs-CDs systems were used. The development of efficient and selective ILs-CDs systems is indispensable to expand the range of their applications in host-guest interactions, drug delivery systems or catalytic reactions. Novel salts derived from nucleobases were used in order to enhance the fluorescence in aqueous solution. Additionally, preliminary studies regarding ethyl lactate as an alternative solvent for asymmetric organocatalysis were performed.

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Following the European Commission’s 2009 Recommendation on the Regulatory Treatment of Fixed and Mobile Termination Rates in the EU, the Portuguese regulatory authority (ANACOM) decided to reduce termination prices in mobile networks to their long-run incremental cost (LRIC). Nevertheless, no serious quantitative assessment of the potential effects of this decision was carried out. In this paper, we adapt and calibrate the Harbord and Hoernig (2014) model of the UK mobile telephony market to the Portuguese reality, and simulate the likely impact on consumer surplus, profits and welfare of four different regulatory approaches: pure LRIC, reciprocal termination charges with fixed networks, “bill & keep”, and asymmetric termination rates. Our results show that reducing MTRs does increase social welfare, profits and consumer surplus in the fixed market, but mobile subscribers are seriously harmed by this decision.

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The goal of this thesis is the investigation and optimization of the synthesis of potential fragrances. This work is projected as collaboration between the University of Applied Sciences in Merseburg and the company Miltitz Aromatics GmbH in Bitterfeld‐Wolfen (Germany). Flavoured compounds can be synthesized in different ways and by various methods. In this work, methods like the phase transfer catalysis and the Cope‐rearrangement were investigated and applied, for getting a high yield and quantity of the desired substances and without any by‐products or side reactions. This involved the study of syntheses with different process parameters such as temperature, solvent, pressure and reaction time. The main focus was on Cope‐rearrangement, which is a common method in the synthesis of new potential fragrance compounds. The substances synthesized in this work have a hepta‐1,5‐diene‐structure and that is why they can easily undergo this [3,3]‐sigma tropic rearrangement. The lead compound of all research was 2,5‐dimethyl‐2‐vinyl‐4‐hexenenitrile (Neronil). Neronil is synthesized by an alkylation of 2‐methyl‐3‐butenenitrile with prenylchloride under basic conditions in a phase‐transfer system. In this work the yield of isolated Neronil is improved from about 35% to 46% by according to the execution conditions of the reaction. Additionally the amount of side product was decreased. This synthesized hexenenitrile involved not only the aforementioned 1,5‐diene‐structure, but also a cyano group, that makes this structure a suitable base for the synthesis of new potential fragrance compounds. It was observed that Neronil can be transferred into 2,5‐dimethyl‐2‐vinyl‐4‐hexenoic acid by a hydrolysis under basic conditions. After five hours the acid can be obtained with a yield of 96%. The following esterification is realized with isobutanol to produce 2,5‐dimethyl‐2‐vinyl‐4‐hexenoic acid isobutyl ester with quantitative conversion. It was observed that the Neronil and the corresponding ester can be converted into the corresponding Cope‐product, with a conversion of 30 % and 80%. Implementing the Cope‐rearrangement, the acid was heated and an unexpected decarboxylated product is formed. To achieve the best verification of reaction development and structure, scrupulous analyses were done using GC‐MS, 1H‐NMR and 13C‐ NMR.

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Economics is a social science which, therefore, focuses on people and on the decisions they make, be it in an individual context, or in group situations. It studies human choices, in face of needs to be fulfilled, and a limited amount of resources to fulfill them. For a long time, there was a convergence between the normative and positive views of human behavior, in that the ideal and predicted decisions of agents in economic models were entangled in one single concept. That is, it was assumed that the best that could be done in each situation was exactly the choice that would prevail. Or, at least, that the facts that economics needed to explain could be understood in the light of models in which individual agents act as if they are able to make ideal decisions. However, in the last decades, the complexity of the environment in which economic decisions are made and the limits on the ability of agents to deal with it have been recognized, and incorporated into models of decision making in what came to be known as the bounded rationality paradigm. This was triggered by the incapacity of the unboundedly rationality paradigm to explain observed phenomena and behavior. This thesis contributes to the literature in three different ways. Chapter 1 is a survey on bounded rationality, which gathers and organizes the contributions to the field since Simon (1955) first recognized the necessity to account for the limits on human rationality. The focus of the survey is on theoretical work rather than the experimental literature which presents evidence of actual behavior that differs from what classic rationality predicts. The general framework is as follows. Given a set of exogenous variables, the economic agent needs to choose an element from the choice set that is avail- able to him, in order to optimize the expected value of an objective function (assuming his preferences are representable by such a function). If this problem is too complex for the agent to deal with, one or more of its elements is simplified. Each bounded rationality theory is categorized according to the most relevant element it simplifes. Chapter 2 proposes a novel theory of bounded rationality. Much in the same fashion as Conlisk (1980) and Gabaix (2014), we assume that thinking is costly in the sense that agents have to pay a cost for performing mental operations. In our model, if they choose not to think, such cost is avoided, but they are left with a single alternative, labeled the default choice. We exemplify the idea with a very simple model of consumer choice and identify the concept of isofin curves, i.e., sets of default choices which generate the same utility net of thinking cost. Then, we apply the idea to a linear symmetric Cournot duopoly, in which the default choice can be interpreted as the most natural quantity to be produced in the market. We find that, as the thinking cost increases, the number of firms thinking in equilibrium decreases. More interestingly, for intermediate levels of thinking cost, an equilibrium in which one of the firms chooses the default quantity and the other best responds to it exists, generating asymmetric choices in a symmetric model. Our model is able to explain well-known regularities identified in the Cournot experimental literature, such as the adoption of different strategies by players (Huck et al. , 1999), the inter temporal rigidity of choices (Bosch-Dom enech & Vriend, 2003) and the dispersion of quantities in the context of di cult decision making (Bosch-Dom enech & Vriend, 2003). Chapter 3 applies a model of bounded rationality in a game-theoretic set- ting to the well-known turnout paradox in large elections, pivotal probabilities vanish very quickly and no one should vote, in sharp contrast with the ob- served high levels of turnout. Inspired by the concept of rhizomatic thinking, introduced by Bravo-Furtado & Côrte-Real (2009a), we assume that each per- son is self-delusional in the sense that, when making a decision, she believes that a fraction of the people who support the same party decides alike, even if no communication is established between them. This kind of belief simplifies the decision of the agent, as it reduces the number of players he believes to be playing against { it is thus a bounded rationality approach. Studying a two-party first-past-the-post election with a continuum of self-delusional agents, we show that the turnout rate is positive in all the possible equilibria, and that it can be as high as 100%. The game displays multiple equilibria, at least one of which entails a victory of the bigger party. The smaller one may also win, provided its relative size is not too small; more self-delusional voters in the minority party decreases this threshold size. Our model is able to explain some empirical facts, such as the possibility that a close election leads to low turnout (Geys, 2006), a lower margin of victory when turnout is higher (Geys, 2006) and high turnout rates favoring the minority (Bernhagen & Marsh, 1997).

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Given the importance of fiscal balance for ensuring a sustainable fiscal policy, we conduct an empirical examination of fiscal dynamics in the United States in response to unsustainable budget deviations. We concentrate on the role of political factors, namely the Republican - Democrat presidential divide, in determining the fiscal response to budget disequilibria. Making use of an asymmetric cointegration framework, we explore politically motivated fiscal asymmetries in the US, from Eisenhower to Obama. We conclude that political factors such as the government’s political quadrant and the timing of elections are important determinants of the fiscal response to unsustainable budget deviations.

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Os séculos XX e XXI corresponderam ao agudizar de processos globalizantes potenciados pelas novas tecnologias, quer no âmbito comunicacional, quer industrial, sublinhando dinâmicas de desruralização e de construção de tecidos urbanos densos onde o anonimato se tornou possível na vivência de experiências, outrora reconduzidas ao silêncio do sujeito socialmente isolado. A diferença, enquanto experiência vivida, tornou-se comunitariamente possível, surgindo grupos que delimitam geograficamente determinadas áreas urbanas a que correspondem afinidades eróticas ou de práticas sexuais, inicialmente de gays e lésbicas. Quebra-se na prática a uni-direccionalidade entre sexo e género, entre sexo e sexualidade, questionando-se esquemas de relações assimétricas e modelos de pensamento enraizados (heterossexualidade, patriarcado, machismo, etc.). Rubin (1975 in Lewin 2006, in Vance, 1984) propõe a existência de dois sistemas diferenciados de sexo e género que tornam plausível, sob o ponto de vista analítico, a não correspondência entre sexo, género e sexualidade. O paradigma máximo desta autonomia sistémica alcança-se na construção de uma identidade travesti. Esta identidade mutante, mutável e instável parece acompanhar um mundo de fluxos intensos e interdependências múltiplas. É na sociedade global que as travestis encontram espaço para a vivência comunitária da sua experiência, constituindo-se como um grupo com práticas transnacionais, marcado pela mobilidade de género e geográfica, primeiramente dentro das fronteiras brasileiras e depois para a Europa. Cidade, prostituição e migração surgem como factores chave da disseminação geográfica e identitária desta comunidade. Este projecto tomado sob uma perspectiva global mantêm ou reinventa relações com a estrutura, que aparentemente as apaga enquanto actores sociais e da qual, aparentemente, se auto-excluem.

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This work presents an improved model to solve the non-emergency patients transport (NEPT) service issues given the new rules recently established in Portugal. The model follows the same principle of the Team Orienteering Problem by selecting the patients to be included in the routes attending the maximum reduction in costs when compared with individual transportation. This model establishes the best sets of patients to be transported together. The model was implemented in AMPL and a compact formulation was solved using NEOS Server. A heuristic procedure based on iteratively solving Orienteering Problems is presented, and this heuristic provides good results in terms of accuracy and computation time. Euclidean instances as well as asymmetric real data gathered from Google maps were used, and the model has a promising performance mainly with asymmetric cost matrices.

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ABSTRACTResource partitioning is important for species coexistence. Species with similar ecomorphology are potential competitors, especially when phylogenetically close, due to niche conservatism. The aim of this study was to investigate the resource partitioning among populations of two species of lebiasinids (Copella nigrofasciata and Pyrrhulina aff. brevis) that co-occur in a first-order Amazonian stream, analyzing the trophic ecology, feeding strategies and ecomorphological attributes related to the use of food and space by these species. Fish were captured in May and September 2010. The stomach contents of 60 individuals were analyzed and quantified volumetrically to characterize the feeding ecology of both species. Eleven morphological attributes were measured in 20 specimens and combined in nine ecomorphological indices. Both species had an omnivorous-invertivorous diet and consumed predominantly allochthonous items. Both showed a tendency to a generalist diet, but intrapopulational variation in resource use was also detected. Overall feeding niche overlap was high, but differed between seasons: low during the rainy season and high in the dry season. In the latter, the food niche overlap was asymmetric because C. nigrofasciata consumed several prey of P. aff. brevis, which reduced its food spectrum. The ecomorphological analysis suggests that C. nigrofasciatahas greater swimming capacity (greater relative length of caudal peduncle) than P. aff. brevis, which has greater maneuverability and tendency to inhabit lentic environments (greater relative depth of the body). Our results demonstrate that these species have similar trophic ecology and suggest a spatial segregation, given by morphological differences related to locomotion and occupation of habitat, favoring their coexistence.

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Tese de Doutoramento em Biologia de Plantas.

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NIPE WP 04/ 2016