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  • About
  • The Global ETD Search service is a free service for researchers to find electronic theses and dissertations. This service is provided by the Networked Digital Library of Theses and Dissertations.
    Our metadata is collected from universities around the world. If you manage a university/consortium/country archive and want to be added, details can be found on the NDLTD website.
251

O colapso da URSS: um estudo das causas / The collapse of the USSR: a study of its motives

Rodrigues, Roberio Paulino 20 March 2006 (has links)
Investiga as causas históricas, políticas, sociais e econômicas que mais contribuíram para o colapso e desaparecimento da União Soviética em 1991. Como um esforço de reinterpretação do fenômeno, desde a gênese até o esgotamento da URSS, apóia-se em análises e dados de alguns dos mais conhecidos especialistas no assunto. Considera que um conjunto de elementos se combinou para tal desfecho. Aponta como causas principais: a) o atraso material e cultural da velha Rússia para iniciar a construção do socialismo; b) o isolamento da Revolução Russa, fruto, entre outros fatores, do reformismo político que paralisou a classe operária no Ocidente; c) as agressões militares que a URSS sofreu, com suas imensas perdas humanas e os custos insuportáveis de defesa, derivados da ameaça permanente que vinha do exterior, que contribuíram para exauri-la economicamente; d) a natureza ditatorial do sistema político, como elemento central, que se pôde acelerar a industrialização e a modernização em uma primeira fase, trouxe imensos prejuízos humanos por outro e funcionou a partir de certo ponto no tempo como uma trava à continuidade do desenvolvimento da economia e da sociedade; e) o esgotamento do modelo extensivo de crescimento na virada para os anos 70, a desaceleração econômica que chega à estagnação no início dos anos 80 e o acentuado atraso tecnológico em relação ao mundo capitalista, verificado já na década de 70; f) As grandes transformações sociais, culturais e comportamentais ocorridas no mundo e na URSS, a Revolução da Informação e as mobilizações democráticas em todo Leste Europeu, que erodiram as fundações do sistema soviético; g) A Perestroika, que como programa de reformas acelerou a democratização do regime político, levando à desagregação do velho mecanismo burocrático de planejamento e gestão estatais da economia, o que por sua vez gerou caos; h) As mobilizações nacionalistas e a ofensiva restauracionista selaram a desagregação do sistema soviético. O processo final que levou ao colapso da URSS parece mais uma combinação de progressivas revoluções ou mobilizações democráticas - que em muito se assemelham às revoluções burguesas, já que suas bandeiras e demandas não diferem muito daquelas levantadas nas revoluções de 1789 e 1848 - com a implosão de um sistema político debilitado e ultrapassado, onde já não cabiam as forças produtivas e sociais que dentro dele se desenvolviam / The major historical, political, social and economic reasons contributing to the collapse as well as the disintegration of the USSR in 1991 are the core aspects scrutinized in this study. In an effort to make sense of the phenomenon from a different perspective, departing from the genesis to the collapse of the USSR, data analyzed by some of the most renowned researchers has been used as a theoretical basis. In this sense, such an outcome is attributed to a series of combined factors. Not only the material and cultural backwardness of slow-tochange Russia in order to set up socialism, but also the consequent isolation of the Russian Revolution, a result - amongst other factors - of the political conventionalism that paralyzed the Western working class, are two of the main explanations pointed out. A third aspect equally relevant refers to the military attacks that Russia had to cope with, not to mention its huge human losses and the unbearable defense costs - a consequence of permanent external threats -, thus impoverishing the country. On top of that, there is - as a crucial component - the double-edged essence of the dictatorial political system for, if on one hand, it speeds up both industrialization and modernization, on the other hand, it also accounts for huge human losses, thus representing - from a given moment - an obstacle to the continuing economic and social development. A fifth chain of events worth highlighting is the failure of the extensive economic development pattern at the turn of the seventies, followed by the economic deceleration, almost on the verge of stagnation in the eighties, not to mention the conspicuous technological delay when compared to the capitalist world, where it had been in evidence since the seventies. In addition to this, the huge social, cultural and behavioral changes - which took place in the world as well as in the USSR, followed by both the Information Revolution and democratic mobilizations throughout Eastern Europe - undermined the foundations of the Soviet system. Furthermore, while the Perestroika - as a restructuring program - became the catalyst for dismantling the conservative bureaucratic structures of government led planning and management, on the other hand, it also accelerated the democratization of the political government, which produced chaos. Last but by no means least, the nationalist mobilizations allied to the restoration offensive determined the downfall of the Soviet system. By and large, the final process responsible for the collapse of the USSR resembles more a combination of consecutive revolutions or a series of democratic mobilization - very similar to the bourgeois revolutions in many aspects given that its causes and demands do not differ substantially from the ones arisen in the 1789 and 1848 revolutions, - with the dismantling of a debilitated and outdated political system, since productive and social forces in full development in its interior could not fit into such a structure anylonger
252

A ocupação pré-colonial da região dos Lagos, RJ: sistema de assentamento e relações intersocietais entre grupos sambaquianos e grupos ceramistas Tupinambá e da tradição Una / The precolumbian occupation of "Região dos Lagos, RJ": settlement system and intersocietal relationships between sambaqui groups and Tupinambá and Una tradition

Guimarães, Márcia Barbosa da Costa 10 July 2007 (has links)
A pesquisa teve por objetivo compreender o sistema de assentamento dos grupos sambaquianos que ocuparam o Complexo Lagunar de Saquarema entre 6.600-1.500 anos cal BP. Tendo por base o pressuposto de que o estudo da continuidade e da mudança é fundamental para o desenvolvimento de estudos regionais, foi construído um modelo onde dois fatores, mudança ambiental e contato intersocietal, influenciaram o processo de transformação sociocultural verificado entre os grupos sambaquianos. Assim, embora partilhassem traços comuns, o que lhes permitia manter um caráter identitário - podendo esse ser vislumbrado num sistema de assentamento onde as relações sociais se davam em função da laguna de Saquarema - os grupos sambaquianos apresentavam diferenças entre si, resultado de um longo processo adaptativo. A gradual mudança na disponibilidade de recursos malacológicos acabou por resultar no fortalecimento de um grupo sobre outro. Os melhores adaptados, representados pelos ocupantes dos sambaquis de Saquarema e da Pontinha, tiveram contato com grupos ceramistas relacionados à tradição Una, ocupantes do sítio Ilha dos Macacos. Tal contato pôde ser verificado através do aparato tecnológico (predomínio absoluto dos artefatos de lascamento), pela adoção de novas práticas funerárias (cremação, manipulação de ossos humanos) e pela concomitância das ocupações. Assim, por volta de 2.000 anos cal AP, esse contato, somado a um processo que já vinha se desenvolvendo no interior do sistema, marcou o início do colapso da sociedade sambaquiana no Complexo Lagunar de Saquarema. / This research aimed contributing to the understanding of the settlement pattern of sambaqui dwellers who occupied the Saquarema lagoonar system (Rio de Janeiro State, Brazil) between 6600 and 1500 cal years BP. It considers the premise that studies of continuity and change are the base to the development of regional synthesis. The model developed presumes that two factors, environmental change and intersocietary contact, have influenced the processes of sociocultural change in the sambaqui society. From this point of view, it is suggested that, although sambaqui people shared common characteristics that allowed them to keep an identity, sambaqui groups presented differences between each other, which resulted from a long adaptative process. This identitary character may be recognized in their settlement pattern, in which social relationships were established in relation with the Saquarema Lagoon. However, gradual changes in the availability of malacological resources induced the reinforcement of some groups over the others. Better-adapted groups, represented by the occupants of sambaquis Saquarema and Pontinha, have established contacts with ceramists related to Una tradition, who occupied Ilha dos Macacos. This contact is attested by the characteristics of the technological apparatus (absolute predominance of flaked artifacts), by the adoption of new funerary practices (cremation, manipulation of human bones) and by the concomitance of occupations. Around 2000 cal years BP, this contact, associated to a process that had already been developing inside the sambaqui system, marked the beginning of the collapse of the sambaqui society in the Saquarema lagoonar system.
253

Simulação numérica de resultados de provas de carga em placa em solo não saturado colapsível / Numerical simulation of results on plate loading tests in collapsible unsaturated soil

Dumont, Rodrigo Botelho [UNESP] 12 December 2016 (has links)
Submitted by Rodrigo Botelho Dumont null (botelhodumont@hotmail.com) on 2017-02-01T18:36:09Z No. of bitstreams: 1 Dissertação Rodrigo Dumont FINAL.pdf: 2885082 bytes, checksum: 1ce7aca2f53fea3c38a490103ddb8948 (MD5) / Approved for entry into archive by LUIZA DE MENEZES ROMANETTO (luizamenezes@reitoria.unesp.br) on 2017-02-06T11:52:21Z (GMT) No. of bitstreams: 1 dumont_rb_me_bauru.pdf: 2885082 bytes, checksum: 1ce7aca2f53fea3c38a490103ddb8948 (MD5) / Made available in DSpace on 2017-02-06T11:52:21Z (GMT). No. of bitstreams: 1 dumont_rb_me_bauru.pdf: 2885082 bytes, checksum: 1ce7aca2f53fea3c38a490103ddb8948 (MD5) Previous issue date: 2016-12-12 / Os solos não saturados são materiais multifásicos e de comportamento complexo que podem ser encontrados em depósitos de grande espessura onde são construídas as obras de engenharia civil. O entendimento do comportamento tensão-deformação/fluxo desses solos tem sido aprimorado com o desenvolvimento de experimentos e modelos constitutivos que são aplicados para a previsão de comportamentos e análises de desempenho das obras geotécnicas. Tais modelos têm sido utilizados para simular diversos resultados de ensaios de laboratório de solos não saturados compactados, porém, simulações de resultados de ensaios de campo em solos não saturados naturais ainda têm sido pouco exploradas. A proposta deste trabalho é simular numericamente o comportamento Hidro-Mecânico de um solo arenoso não saturado via método de elementos finitos em ensaios de prova de carga em placa. Os parâmetros constitutivos do solo são provenientes de resultados de ensaios de laboratório realizados com controle de sucção. O programa de elementos finitos Code_Bright foi utilizado para a simulação dos resultados dos ensaios das provas de carga em placa realizadas em campo. Os resultados obtidos numericamente demonstraram a capacidade do modelo constitutivo mecânico em reproduzir adequadamente os resultados dos ensaios. A partir dos resultados, constatou-se que os recalques são fortemente afetados pela variação da sucção, demonstrando o comportamento colapsível do solo diante de aplicação de tensões e mudanças de umidade e sucção. O parâmetro constitutivo mecânico po*, tensão de pré-adensamento isotrópica do solo saturado, influencia significativamente o comportamento do solo, assim como a magnitude do colapso por inundação. Os resultados demonstraram a importância da condição não saturada na previsão de comportamento e o quanto tal condição pode afetar o dimensionamento de fundações diretas em solo não saturado de comportamento colapsível. O trabalho oferece informações básicas no tocante à estimativa da tensão admissível considerando a variabilidade sazonal decorrente da sucção no solo. / Unsaturated soils are multiphase materials with complex behavior that can be found in large thickness deposits where civil engineering works are built. The understanding of the stress-strain/flow behavior of these soils has been improved with the development of experiments and constitutive models that are applied to behavior predictions and performance analysis of geotechnical works. Such models have been used to simulate several laboratory test results on compacted unsaturated soils, however, simulation of field test results on natural unsaturated soils have been little explored. This work aims to simulate numerically the Hydro-Mechanical behavior of an unsaturated sandy soil by finite element method in plate loading tests. Constitutive parameters of the soil come from the laboratory test results performed with controlled soil suction. The program Code_Bright was used to simulate plate loading test results. The results showed the capacity of the constitutive mechanical model to reproduce the test results. The settlements are strongly affected by the soil suction variation, demonstrating the collapsible behavior for stress, moisture content or soil suction changes. The constitutive mechanical parameter po*, preconsolidation stress for saturated condition, affected significantly the soil behavior, as well as the magnitude of the collapse by wetting. The results presented the great importance of the unsaturated status of the soil in prediction behavior and how this condition can affect the design of foundations in unsaturated soils with collapsible behavior. This study provides basic information concerning the estimation of admissible stress, taking the seasonal variability due to the soil suction.
254

A crise econômica no Japão após os anos 90 /

Fraga, Jefferson Souza. January 2011 (has links)
Orientador: Eduardo Strachamn / Banca: Enéas Gonçalves de Carvalho / Banca: Ernani Torres Teixeira Filho / Resumo: O presente trabalho tem como objetivo analisar a experiência do Japão após os colapsos das bolhas especulativas dos ativos na década de 1990. Aceitando que o pior já passou, ou seja, que a crise financeira japonesa foi finalmente resolvida, uma coisa é certa; não antes de uma "década perdida" caracterizada por um longo período, de baixo crescimento, aumento das taxas de desemprego, deflação nos preços dos ativos, falências bancárias e persistência dos no-performing loans. Nesse contexto, as principais respostas obtidas por este trabalho foram: a crença que a recuperação econômica viria com o passar do tempo e a falta de entendimento sobre o tamanho do problema que a morosidade de atuação levaria ao sistema, explica em certo ponto a tolerância inicial do governo japonês frente à crise econômica. A política fiscal expansionista foi eficaz, mas, não utilizada de forma consistente, a natureza "stop-start" dos estímulos realizados, e em particular as prematuras reversões fiscais diminuíram a sua eficácia, outros fatores prováveis para a baixa eficácia durante os anos 90 foram: os estímulos fiscais podem ter sido prejudicados pela queda dos multiplicadores fiscais; os efetivos investimentos públicos foram menores que os anunciados e ao invés de se dar ênfase a obras públicas, priorizou-se cortes em impostos. De outra forma, um caminho fundamental de maximizar os estímulos fiscais é através da restauração do crédito do setor bancário, caso a recapitalização e as restaurações do setor fossem realizas em uma fase inicial, os efeitos dos estímulos poderiam ser de curta duração, se o sistema financeiro estivesse em boa saúde. No Japão, as injeções nos bancos "em grande escala" ocorreram apenas em 1999. Por outro lado, a política monetária, com base em uma versão alternativa da armadilha da liquidez levou o BOJ a tomar algumas medidas... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: This dissertation intend to analyze the experience of Japan after the collapse of speculative bubbles in assets in the 1990s. Accepting that the worst is over, that is to say, that the Japanese financial crisis was finally resolved, one thing is certain; not before a "lost decade" characterized by a long period of low growth, increasing rates of unemployment, deflation in asset prices, bank failures and persistence of no-performing loans. In this context, the main responses received for this work were: the belief that economic recovery would come with the passage of time and lack of understanding about the size of the problem that the slowness of action would lead to the system; this explains in some degree the initial tolerance of the Japanese government by the economic crisis. The expansionary fiscal was effective, but not consistently used, the nature of "stop-start" of the stimuli made, and in particular the early tax reversals decreased its effectiveness, other likely factors for the low efficiency during the year 1990 were: the fiscal stimuli may have been harmed by falling tax multipliers; the effective public investments were lower than those advertised instead of giving emphasis to public works, the priority was tax cuts. On the other hand, a fundamental way to maximize the tax incentives is through the restoration of credit from the banking sector, if the recapitalization and the restorations of the sector were held in an early stage, the effects of stimuli could be short term, if the financial system was in good health. In Japan, the injections in banks "large scale" occurred only in 1999. Moreover, monetary policy, based on an alternative version of the liquidity trap led the BOJ to take some innovative measures since 2001. Centered on a strategy to ensure liquidity and extend the warranties on direct purchases of assets, quantitative easing was implanted... (Complete abstract click electronic access below) / Mestre
255

Recomendações para projeto de lajes formadas por vigotas com armação treliçada / Recommendations for design of slabs with lattice reinforcement

Mateus Ortigosa Cunha 09 August 2012 (has links)
As lajes formadas por vigotas pré-moldadas são utilizadas em larga escala no Brasil, em especial as formadas por vigotas treliçadas. As facilidades no manuseio e economia de fôrmas são algumas das vantagens do sistema. Apesar de serem muito utilizadas, ainda existe necessidade de estudo das recomendações no sentido de basear o projeto destas lajes. Os objetivos deste trabalho são: (a) contribuir no projeto de lajes formadas por vigotas com armação treliçadas através de uma análise crítica da bibliografia pesquisada; (b) tratar de temas pouco disseminados no que se refere ao cálculo de lajes pré-moldadas; (c) fornecer recomendações de projeto através de exemplo resolvido que aborda as principais dúvidas de projetistas da área. Neste exemplo avaliam-se as lajes, entre outros aspectos, quanto às flechas iniciais e ao longo do tempo, vibrações e momento negativo nos apoios. Os resultados são analisados e confrontados com as indicações da bibliografia. Comprova-se o fato destas lajes serem mais susceptíveis quanto às vibrações causadas por caminhada e mostra a dificuldade em atender à ABNT NBR 6118:2003. O vão máximo admissível para uma laje do exemplo de aplicação é 28% inferior quando comparado à laje maciça de mesma espessura na análise da vibração excessiva. Enfatiza a importância em prever armadura contra o colapso progressivo e demonstra que o aumento de consumo de aço em 5% é pequeno quando comparado ao total, para uma laje do exemplo de aplicação. / Precast slabs are used in large scale in Brazil, special those formed by lattice reinforcement. Facilities handling and economy mold are some of the advantages of the system. The objectives of this work are: (a) improve study of the design of slabs formed by precast lattice reinforcement through a review of literature; (b) address topics a little spread regards to the calculation of precast slabs; (c) providing design recommendations through examples solved by addressing the main concerns of designers in the area. This example evaluate the slabs to initials and long-term deflections, vibrations and bending moment at the supports. The results are analyzed and compared with indications in the literature. It demonstrates the suscetibility of the slabs for vibrations caused by walking and shows the difficulty in following ABNT NBR 6118:2003. The maximum span for one slab of the aplication example is 28% slower than solid slabs with the same thickness in excessive vibration analysis. This dissertation emphasizes the importance of predicting reinforcement against progressive collapse and shows the increase in steel consumption is small compared to the total, for one slab of the example.
256

Proposição de uma técnica de parametrização geométrica para o fluxo de carga continuado baseado nas variáveis tensão e fator de carregamento /

Bonini Neto, Alfredo. January 2006 (has links)
Orientador: Dílson Amâncio Alves / Banca: Francisco Villarreal Alvarado / Banca: Eduardo Nobuhiro Asada / Resumo: Este trabalho apresenta um novo esquema de parametrização geométrico para o fluxo de carga continuado que possibilita o traçado completo das curvas P-V, e o cálculo do ponto de máximo carregamento de sistemas de potência, sem os problemas de mau-condicionamento. O objetivo é o de apresentar de uma forma clara e didática, os passos envolvidos no desenvolvimento de uma técnica de parametrização geométrica a partir da observação das trajetórias de solução do fluxo de carga. A técnica associa robustez com facilidade de compreensão. A singularidade da matriz Jacobiana é eliminada pela adição da equação de uma reta que passa por um ponto no plano formado nas variáveis magnitude da tensão nodal e o fator de carregamento, dois parâmetros físicos de fácil compreensão. O uso desta técnica amplia o grupo das variáveis de tensão que podem ser usadas como parâmetro de continuação. Os resultados obtidos com a nova metodologia para os sistemas testes do IEEE (14, 30, 57, 118 e 300 barras), mostram que as características do método convencional são melhoradas e a região de convergência ao redor da singularidade é ampliada. Vários testes são apresentados com intuito de prover um completo entendimento do método proposto e possibilitar comparação e a avaliação do desempenho do esquema de parametrização proposto. / Abstract: This work presents a new geometrical parameterization scheme to the continuation power flow that allows the complete tracing of P-V curves and the computation of the maximum loading point of a power system, without ill-conditioning problems. The objective is to present in a clear and didactic way, the steps involved in the development of a geometrical parameterization technique from the observation of the behavior of power flow solutions path. The technique associates robustness with simplicity and easy interpretation. The Jacobian matrix singularity is overcome by the addition of a line equation which passes through a point in the plane determined by variables bus voltage magnitude and the loading factor, two physical parameter of easy understanding. The use of this technique enlarges the group of voltage variables that can be used as continuation parameter. The results obtained with the new methodology for the IEEE systems (14, 30, 57, 118 and 300 buses), show that the characteristics of the conventional method are improved and the region of convergence around the singular solution is enlarged. Many tests are also presented in intention to provide the complete understanding of the proposed method and to allow the comparison and assessment of the performance of the proposed parameterization scheme. / Mestre
257

An Australian Mirage

Hoyte, Catherine, n/a January 2004 (has links)
This thesis contains a detailed academic analysis of the complete rise and fall of Christopher Skase and his Qintex group mirage. It uses David Harvey's 'Condition of Postmodernity' to locate the collapse within the Australian political economic context of the period (1974-1989). It does so in order to answer questions about why and how the mirage developed, why and how it failed, and why Skase became the scapegoat for the Australian corporate excesses of the 1980s. I take a multi-disciplinary approach and consider corporate collapse, corporate regulation and the role of accounting, and corporate deviance.
258

Many-body Problems in the Theory of Stellar Collapse and Neutron Stars / Mångkropparsproblem inom teorin för neutronstjärnor och supernovaexplosioner

Olsson, Emma January 2004 (has links)
<p>When modelling the collapse of massive stars leading to supernova explosions and the cooling of neutron stars, understanding the microphysical processes, such as the interaction of neutrinos within a dense medium are of vital importance. The interaction of neutrinos with nucleons (neutrons and protons) is altered by the presence of the medium, compared to the same process with free nucleons. Neutrino scattering and production processes may be characterized in terms of the excitations that are created or destroyed in the nuclear medium. One way to analyse the effects of the medium is by using Landau's theory of normal Fermi liquids. This theory gives simple relationships between physical quantities such as the spin susceptibility or the response to a weak interaction probe in terms of Landau parameters, that are measures of the interaction between quasiparticles. One problem when using Landau Fermi liquid theory for nucleon matter is that the interaction has a tensor component. The tensor interaction does not conserve the total spin and, as a consequence, there are generally contributions to long-wavelength response functions from states that have more than one quasiparticle-quasihole pair in the intermediate state. Such contributions cannot be calculated in terms of Landau parameters alone, since in the usual formulation of Landau theory, only singlepair excitations are considered. In this thesis three problems are addressed. First, we obtain bounds on the contributions from more than one quasiparticle-quasihole pair by using sum-rule arguments. Second, we derive expressions for static response functions allowing for the tensor components of the interaction. We analyse which the most important effects are on the static response of nucleon matter, and find that the major contributions comes from renormalization of coupling constants and transitions to states with more than one quasiparticle-quasihole pair. Third, we show how contributions to the dynamical response coming from states containing two quasiparticle-quasihole pairs may be evaluated in terms of Landau theory if one allows for the effect of collisions in the Landau kinetic equation. We consider the case of asymmetric nuclear matter, and our work goes beyond earlier works in that they contain the effects of collisions in addition to those of the mean field.</p>
259

Many-body Problems in the Theory of Stellar Collapse and Neutron Stars / Mångkropparsproblem inom teorin för neutronstjärnor och supernovaexplosioner

Olsson, Emma January 2004 (has links)
When modelling the collapse of massive stars leading to supernova explosions and the cooling of neutron stars, understanding the microphysical processes, such as the interaction of neutrinos within a dense medium are of vital importance. The interaction of neutrinos with nucleons (neutrons and protons) is altered by the presence of the medium, compared to the same process with free nucleons. Neutrino scattering and production processes may be characterized in terms of the excitations that are created or destroyed in the nuclear medium. One way to analyse the effects of the medium is by using Landau's theory of normal Fermi liquids. This theory gives simple relationships between physical quantities such as the spin susceptibility or the response to a weak interaction probe in terms of Landau parameters, that are measures of the interaction between quasiparticles. One problem when using Landau Fermi liquid theory for nucleon matter is that the interaction has a tensor component. The tensor interaction does not conserve the total spin and, as a consequence, there are generally contributions to long-wavelength response functions from states that have more than one quasiparticle-quasihole pair in the intermediate state. Such contributions cannot be calculated in terms of Landau parameters alone, since in the usual formulation of Landau theory, only singlepair excitations are considered. In this thesis three problems are addressed. First, we obtain bounds on the contributions from more than one quasiparticle-quasihole pair by using sum-rule arguments. Second, we derive expressions for static response functions allowing for the tensor components of the interaction. We analyse which the most important effects are on the static response of nucleon matter, and find that the major contributions comes from renormalization of coupling constants and transitions to states with more than one quasiparticle-quasihole pair. Third, we show how contributions to the dynamical response coming from states containing two quasiparticle-quasihole pairs may be evaluated in terms of Landau theory if one allows for the effect of collisions in the Landau kinetic equation. We consider the case of asymmetric nuclear matter, and our work goes beyond earlier works in that they contain the effects of collisions in addition to those of the mean field.
260

Hydrophobic Hydration of a Single Polymer

Li, Isaac Tian Shi 17 December 2012 (has links)
Hydrophobic interactions guide important molecular self-assembly processes such as protein folding. On the macroscale, hydrophobic interactions consist of the aggregation of "oil-like" objects in water by minimizing the interfacial energy. However, the hydration mechanism of small hydrophobic molecules on the nanoscale (~1 nm) differs fundamentally from its macroscopic counterpart. Theoretical studies over the last two decades have pointed to an intricate dependence of molecular hydration mechanisms on the length scale. The microscopic-to-macroscopic cross-over length scale is critically important to hydrophobic interactions in polymers, proteins and other macromolecules. Accurate experimental determination of hydration mechanisms and their interaction strengths are needed to understand protein folding. This thesis reports the development of experimental and analytical techniques that allow for direct measurements of hydrophobic interactions in a single molecule. Using single molecule force spectroscopy, the mechanical unfolding of a single hydrophobic homopolymer was identified and modeled. Two experiments examined how hydrophobicity at the molecular scale differ from the macroscopic scale. The first experiment identifies macroscopic interfacial tension as a critical parameter governing the molecular hydrophobic hydration strength. This experiment shows that the solvent conditions affect the microscopic and macroscopic hydrophobic strengths in similar ways, consistent with theoretical predictions. The second experiment probes the hydrophobic size effect by studying how the size of a non-polar side-chain affects the thermal signatures of hydration. Our experimental results reveal a cross-over length scale of approximately 1 nm that bridges the transition from entropically driven microscopic hydration mechanism to enthalpically driven macroscopic hydration mechanism. These results indicate that hydrophobic interactions at the molecular scale differ from macroscopic scale, pointing to potential ways to improve our understanding and predictions of molecular interactions. The system established in this thesis forms the foundation for further investigation of polymer hydrophobicity.

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