The unsteady forces on slender delta wing hydrofoils oscillating in heave

The investigations described herein are both experimental and theoretical. An experimental technique is described by which the models tested could be oscillated sinusoidally in heave. The apparatus used to gather the unsteady lift, drag and pitching moment data is also described.

The models tested were two flat delta wings with apex angles of 15° and 30° and they had sharp leading edges to insure flow separation. The models were fabricated from 0.25 inch aluminum plate and were approximately one foot in length.

Three distinct types of flow were investigated: 1) fully wetted, 2) ventilated and 3) planing. The experimental data are compared with existing theories for steady motions in the case of fully wetted delta wings. Ventilation measurements, made only for the 30° model at 20° angle of attack, of lift and drag are presented.

A correction of the theory proposed by M.P. Tulin for high speed planing of slender bodies is presented and it is extended to unsteady motions. This is compared to the experimental measurements made at 6° and 12° angle of attack for the two models previously described.

This is the first extensive measurement of unsteady drag for any shape wing, the first measurement of unsteady planing forces, the first quantitative documentation of unstable oscillations near a free surface, and the first measurements of the unsteady forces on ventilated delta wings. The results of these investigations, both theoretical and experimental, are discussed and further investigations suggested.

Nature of the radical intermediates in a substituted cyclopropylcarbiny-allylcarbinyl system

We have sought to determine the nature of the free-radical precursors to ring-opened hydrocarbon 5 and ring-closed hydrocarbon 6. Reasonable alternative formulations involve the postulation of hydrogen abstraction (a) by a pair of rapidly equilibrating classical radicals (the ring-opened allylcarbinyl-type radical 3 and the ring-closed cyclopropylcarbinyl-type 4), or (b) by a nonclassical radical such as homoallylic radical 7.

[Figure not reproduced.]

Entry to the radical system is gained via degassed thermal decomposition of peresters having the ring-opened and the ring-closed structures. The ratio of 6:5 is essentially independent of the hydrogen donor concentration for decomposition of the former at 125° in the presence of triethyltin hydrdride. A deuterium labeling study showed that the α and β methylene groups in 3 (or the equivalent) are rapidly interchanged under these conditions.

Existence of two (or more) product-forming intermediates is indicated (a) by dependence of the ratio 6:5 on the tin hydride concentration for decomposition of the ring-closed perester at 10 and 35°, and (b) by formation of cage products having largely or wholly the structure (ring-opened or ring-closed) of the starting perester.

Relative rates of hydrogen abstraction by 3 could be inferred by comparison of ratios of rate constants for hydrogen abstraction and ortho-ring cyclization:

[Figure not reproduced.]

At 100° values of k_a/k_r are 0.14 for hydrogen abstraction from 1,4-cyclohexadiene and 7 for abstraction from triethyltin hydride. The ratio 6:5 at the same temperature is ~0.0035 for hydrogen abstraction from 1,4-cyclohexadiene, ~0.078 for abstraction from the tin hydride, and ≥ 5 for abstraction from cyclohexadienyl radicals. These data indicate that abstraction of hydrogen from triethyltin hydride is more rapid than from 1,4-cyclohexadiene by a factor of ~1000 for 4, but only ~50 for 3.

Measurements of product ratios at several temperatures allowed the construction of an approximate energy-level scheme. A major inference is that isomerization of 3 to 4 is exothermic by 8 ± 3 kcal/mole, in good agreement with expectations based on bond dissociation energies. Absolute rate-constant estimates are also given.

The results are nicely compatible with a classical-radical mechanism, but attempted interpretation in terms of a nonclassical radical precursor of product ratios formed even from equilibrated radical intermediates leads, it is argued, to serious difficulties.

The roles played by hydrogen abstraction from 1,4,-cyclohexadiene and from the derived cyclohexadienyl radicals were probed by fitting observed ratios of 6:5 and 5:10 in the sense of least-squares to expressions derived for a complex mechanistic scheme. Some 30 to 40 measurements on each product ratio, obtained under a variety of experimental conditions, could be fit with an average deviation of ~6%. Significant systematic deviations were found, but these could largely be redressed by assuming (a) that the rate constant for reaction of 4 with cyclohexadienyl radical is inversely proportional to the viscosity of the medium (i.e., is diffusion-controlled), and (b) that k_a/k_r for hydrogen abstraction from 1,4-cyclohexadiene depends slightly on the composition of the medium. An average deviation of 4.4% was thereby attained.

Degassed thermal decomposition of the ring-opened perester in the presence of the triethyltin hydride occurs primarily by attack on perester of triethyltin radicals, presumably at the –O-O- bond, even at 0.01 M tin hydride at 100 and 125°. Tin ester and tin ether are apparently formed in closely similar amounts under these conditions, but the tin ester predominates at room temperature in the companion air-induced decomposition, indicating that attack on perester to give the tin ether requires an activation energy approximately 5 kcal/mole in excess of that for the formation of tin ester.

Imaging the earth with ambient noise and earthquakes

In this thesis, I develop the velocity and structure models for the Los Angeles Basin and Southern Peru. The ultimate goal is to better understand the geological processes involved in the basin and subduction zone dynamics. The results are obtained from seismic interferometry using ambient noise and receiver functions using earthquake- generated waves. Some unusual signals specific to the local structures are also studied. The main findings are summarized as follows:

(1) Los Angeles Basin

The shear wave velocities range from 0.5 to 3.0 km/s in the sediments, with lateral gradients at the Newport-Inglewood, Compton-Los Alamitos, and Whittier Faults. The basin is a maximum of 8 km deep along the profile, and the Moho rises to a depth of 17 km under the basin. The basin has a stretch factor of 2.6 in the center decreasing to 1.3 at the edges, and is in approximate isostatic equilibrium. This "high-density" (~1 km spacing) "short-duration" (~1.5 month) experiment may serve as a prototype experiment that will allow basins to be covered by this type of low-cost survey.

(2) Peruvian subduction zone

Two prominent mid-crust structures are revealed in the 70 km thick crust under the Central Andes: a low-velocity zone interpreted as partially molten rocks beneath the Western Cordillera – Altiplano Plateau, and the underthrusting Brazilian Shield beneath the Eastern Cordillera. The low-velocity zone is oblique to the present trench, and possibly indicates the location of the volcanic arcs formed during the steepening of the Oligocene flat slab beneath the Altiplano Plateau.

The Nazca slab changes from normal dipping (~25 degrees) subduction in the southeast to flat subduction in the northwest of the study area. In the flat subduction regime, the slab subducts to ~100 km depth and then remains flat for ~300 km distance before it resumes a normal dipping geometry. The flat part closely follows the topography of the continental Moho above, indicating a strong suction force between the slab and the overriding plate. A high-velocity mantle wedge exists above the western half of the flat slab, which indicates the lack of melting and thus explains the cessation of the volcanism above. The velocity turns to normal values before the slab steepens again, indicating possible resumption of dehydration and ecologitization.

(3) Some unusual signals

Strong higher-mode Rayleigh waves due to the basin structure are observed in the periods less than 5 s. The particle motions provide a good test for distinguishing between the fundamental and higher mode. The precursor and coda waves relative to the interstation Rayleigh waves are observed, and modeled with a strong scatterer located in the active volcanic area in Southern Peru. In contrast with the usual receiver function analysis, multiples are extensively involved in this thesis. In the LA Basin, a good image is only from PpPs multiples, while in Peru, PpPp multiples contribute significantly to the final results.

The Design and Synthesis of Transition Metal Complexes Supported by Non-innocent Ligand Scaffolds for Small Molecule Activation

This dissertation focuses on the incorporation of non-innocent or multifunctional moieties into different ligand scaffolds to support one or multiple metal centers in close proximity. Chapter 2 focuses on the initial efforts to synthesize hetero- or homometallic tri- or dinuclear metal carbonyl complexes supported by para-terphenyl diphosphine ligands. A series of [M₂M’(CO)₄]-type clusters (M = Ni, Pd; M’ = Fe, Co) could be accessed and used to relate the metal composition to the properties of the complexes. During these studies it was also found that non-innocent behavior was observed in dinuclear Fe complexes that result from changes in oxidation state of the cluster. These studies led to efforts to rationally incorporate central arene moieties capable managing both protons and electrons during small molecule activation.

Chapter 3 discusses the synthesis of metal complexes supported by a novel para-terphenyl diphosphine ligand containing a non-innocent 1,4-hydroquinone moiety as the central arene. A Pd⁰-hydroquinone complex was found to mediate the activation of a variety of small molecules to form the corresponding Pd⁰-quinone complexes in a formal two proton ⁄ two electron transformation. Mechanistic investigations of dioxygen activation revealed a metal-first activation process followed by subsequent proton and electron transfer from the ligand. These studies revealed the capacity of the central arene substituent to serve as a reservoir for a formal equivalent of dihydrogen, although the stability of the M-quinone compounds prevented access to the PdII-quinone oxidation state, thus hindering of small molecule transformations requiring more than two electrons per equivalent of metal complex.

Chapter 4 discusses the synthesis of metal complexes supported by a ligand containing a 3,5-substituted pyridine moiety as the linker separating the phenylene phosphine donors. Nickel and palladium complexes supported by this ligand were found to tolerate a wide variety of pyridine nitrogen-coordinated electrophiles which were found to alter central pyridine electronics, and therefore metal-pyridine π-system interactions, substantially. Furthermore, nickel complexes supported by this ligand were found to activate H-B and H-Si bonds and formally hydroborate and hydrosilylate the central pyridine ring. These systems highlight the potential use of pyridine π-system-coordinated metal complexes to reversibly store reducing equivalents within the ligand framework in a manner akin to the previously discussed 1,4-hydroquinone diphosphine ligand scaffold.

Chapter 5 departs from the phosphine-based chemistry and instead focuses on the incorporation of hydrogen bonding networks into the secondary coordination sphere of [Fe₄(μ₄-O)]-type clusters supported by various pyrazolate ligands. The aim of this project is to stabilize reactive oxygenic species, such as oxos, to study their spectroscopy and reactivity in the context of complicated multimetallic clusters. Herein is reported this synthesis and electrochemical and Mössbauer characterization of a series of chloride clusters have been synthesized using parent pyrazolate and a 3-aminophenyl substituted pyrazolate ligand. Efforts to rationally access hydroxo and oxo clusters from these chloride precursors represents ongoing work that will continue in the group.

Appendix A discusses attempts to access [Fe₃Ni]-type clusters as models of the enzymatic active site of [NiFe] carbon monoxide dehydrogenase. Efforts to construct tetranuclear clusters with an interstitial sulfide proved unsuccessful, although a (μ₃-S) ligand could be installed through non-oxidative routes into triiron clusters. While [Fe₃Ni(μ₄-O)]-type clusters could be assembled, accessing an open heterobimetallic edge site proved challenging, thus prohibiting efforts to study chemical transformations, such as hydroxide attack onto carbon monoxide or carbon dioxide coordination, relevant to the native enzyme. Appendix B discusses the attempts to synthesize models of the full H-cluster of [FeFe]-hydrogenase using a bioinorganic approach. A synthetic peptide containing three cysteine donors was successfully synthesized and found to chelate a preformed synthetic [Fe₄S₄] cluster. However, efforts to incorporate the diiron subsite model complex proved challenging as the planned thioester exchange reaction was found to non-selectively acetylate the peptide backbone, thus preventing the construction of the full six-iron cluster.

Efficiency vs. Stability in a Mixed Network Formation Model

Documentos de Trabajo

Immunodetection of planktonic algae

Interest in the identification and characterisation of cyanobacteria and dinoflagellates in aquatic environments is increasing rapidly due to the perceived roles of these organisms in primary production and nuisance aspects in terms of water treatment and public health. Techniques for the identification and quantification of these organisms currently are limited, and the application of molecular approaches provides fundamental taxonomic information and techniques of practical value. Antigenic properties of algal cells may be useful taxonomic markers. Immunodetection techniques utilise the specificity of the antibody/antigen association as a probe for recognising and distinguishing between microorganisms according to their cell- surface chemistry. Immunofluorescent detection of unicellular cyanobacteria and dinoflagellates has been studied with success in marine and freshwater ecosystems and a range of techniques and results are presented and discussed. The most recent advances in the study of planktonic algae have come with the application of continuous flow cytometric methods (CFC). Flow cytometry makes use of the autofluorescence properties of the algal cells, which alone can be used to demonstrate their presence and permit their quantification in natural water samples. When used in conjunction with immunolabelling techniques, the potential of CFC analysis is broadened to study the serological/strain composition of plankters in natural populations. Changes in algal strains represented within and between waters over periods of time are reported and discussed, along with the ecological issues thus raised.

Resveratrol: Anti-Obesity Mechanisms of Action

Resveratrol is a non-flavonoid polyphenol which belongs to the stilbenes group and is produced naturally in several plants in response to injury or fungal attack. Resveratrol has been recently reported as preventing obesity. The present review aims to compile the evidence concerning the potential mechanisms of action which underlie the anti-obesity effects of resveratrol, obtained either in cultured cells lines and animal models. Published studies demonstrate that resveratrol has an anti-adipogenic effect. A good consensus concerning the involvement of a down-regulation of C/EBPa and PPAR. in this effect has been reached. Also, in vitro studies have demonstrated that resveratrol can increase apoptosis in mature adipocytes. Furthermore, different metabolic pathways involved in triacylglycerol metabolism in white adipose tissue have been shown to be targets for resveratrol. Both the inhibition of de novo lipogenesis and adipose tissue fatty acid uptake mediated by lipoprotein lipase play a role in explaining the reduction in body fat which resveratrol induces. As far as lipolysis is concerned, although this compound per se seems to be unable to induce lipolysis, it increases lipid mobilization stimulated by beta-adrenergic agents. The increase in brown adipose tissue thermogenesis, and consequently the associated energy dissipation, can contribute to explaining the body-fat lowering effect of resveratrol. In addition to its effects on adipose tissue, resveratrol can also acts on other organs and tissues. Thus, it increases mitochondriogenesis and consequently fatty acid oxidation in skeletal muscle and liver. This effect can also contribute to the body-fat lowering effect of this molecule.

Bloqueo de publicidad en la Web: enfoque técnico en la búsqueda de un compromiso entre anunciantes y lectores

[ES]Este proyecto trata el problema del bloqueo de anuncios que existe actualmente en la web. Teniendo en cuenta la opinión de diversos autores sobre el tema, se analiza la problemática del uso de bloqueadores de anuncios. Además, se estudia cómo funcionan estos bloqueadores. En concreto, se analiza cómo está construido y cómo funciona, mediante ingeniería inversa, la extensión más popular en este campo, es decir, AdBlock Plus. Aparte de esto, se proponen una serie de soluciones para atacar al problema. Por último, se desarrolla e implementa una de las propuestas. Como resultado, se mejora el funcionamiento de AdBlock Plus, en el sentido de que da más libertad al usuario para elegir lo que bloquea dando la oportunidad a anunciantes y proveedores de contenido de mantener su modelo de negocio basado en la publicidad.

O herói e o inimigo no imaginário do jacobinismo brasileiro 1894/1897

Esta dissertação tem como objetivo compreender e analisar o jacobinismo brasileiro tendo como foco os anos de 1894 até 1897. Pretende-se perceber como esse grupo conseguiu construir um projeto de personalização do poder em torno do Marechal Floriano Peixoto em momentos críticos da história República brasileira: durante a Revolta da Armada de 1894; no momento de transição do governo militar para o governo civil de Prudente de Moraes em 1894/95; e na ocasião da morte do Marechal Floriano Peixoto em 1895. Para tanto, o estudo propõe uma reflexão sobre a utilização do discurso jornalístico como instrumento na fabricação da imagem dos revoltosos da Marinha como restauradores monarquistas e de Floriano como herói da República, buscando assim, perceber igualmente a dinâmica de sua elaboração e as suas repercussões na sociedade brasileira. Chegaremos a conclusão que as forças jacobinas enfraqueceram no momento do atentado a Prudente de Morais em 1897, mas seus discursos ainda tiveram eco na primeira metade do século XX na República brasileira.

Acústica del Acordeón

320 p.

Catalogue des ennemis naturels des macrophytes flottants Pistia stratiotes, Salvinia molesta et Eichhornia crassipes

We identified from bibliographical review and field observations fourty two species composed essentially of molluscs and insects. These animals attack floating plants such as E. crassipes, P. stratiotes and S. molesta. They indifferently consume or destroy the aquatic plants except N. bruchi, N. eichhorniae and S. albiguttalis which specifically attack E. crassipes. N. putchellus, L. guinaicus and P. africana graze preferably P. stratiotes; C. salviniae, C. singularis and P. acuminata consume only Salvinia molesta.

Saberes do corpo: capoeira, cultura corporal e educação

A Capoeira é defesa, é ataque, é ginga de corpo, é malandragem, ação e reação, um jogo de xadrez, segundo alguns capoeiristas. Para uns, esporte, para outros dança, luta, briga, filosofia de vida. Mas há ainda os que a veem como um espetáculo acrobático de habilidades corporais propagado nos filmes, shows, jogos de vídeo game, eventos turísticos, acabando por criar determinados estereótipos corporais de beleza e desempenho físico. Nesse sentido, a pesquisa teve como objetivo descrever, analisar e interpretar a cultura corporal, assim como a percepção de capoeiristas em relação ao corpo na capoeira, e dos seus contramestres/mestrando, localizados em diferentes grupos de capoeira situados em diferentes instituições, tais como: Bloco de carnaval; Clube esportivo; Academia de ginástica. Parte-se do entendimento de cultura corporal enquanto expressão de uma cultura historicamente construída, acumulada, ressignificada e expressa pelos movimentos corporais que destaca traços marcantes de um determinado grupo, de uma determinada localidade. Neste caso, dos diferentes grupos de capoeira e de suas respectivas instituições. Qual a percepção dos capoeiristas em relação ao seu próprio corpo, ao corpo de seus colegas e de seu contramestre/mestrando de capoeira? O que esperam os capoeiristas aprenderem na capoeira? E para esses capoeiristas e seus contramestres/mestrando qual o principal objetivo ao se ensinar/aprender capoeira? Seria algo em torno de um aspecto mais tecnicista que visasse prioritariamente o desenvolvimento e aperfeiçoamento das técnicas dos movimentos, floreios, esquivas? Ou também, aliado a estes aspectos, seria mais importante, para os capoeiristas, conhecer a história da capoeira, como esta veio ao longo do tempo se ressignificando e resistindo para ser hoje reconhecida como um esporte verdadeiramente nacional? Será que haveria aqueles que praticassem capoeira simplesmente para manter um padrão corporal estético propagado pela mídia e pela indústria da moda? A partir das observações, reflexões e interpretações das entrevistas chega-se a conclusão que de fato as instituições nas quais os grupos realizam suas práticas podem influenciar na filosofia de ensino/aprendizado destes. E que as percepções e interesses dos capoeiristas em relação ao próprio corpo variam pela busca de um melhor desempenho técnico, padrão de estética e pelo conhecimento histórico da capoeira, dos movimentos, golpes, esquivas e como estes vem ao longo do tempo se ressignificando

Reparación y reconocimiento a víctimas del terrorismo: prácticas restaurativas desde el punto de vista de las víctimas de ETA

[ES]En este trabajo sobre las víctimas del terrorismo de ETA se abordarán temas relacionados con su recuperación emocional y su reconocimiento, particularmente, distinguiendo entre las víctimas que han tenido experiencias de encuentro con un ex miembro de ETA, y las que no lo han tenido. En ocasiones, las instituciones públicas facilitan la oportunidad a las víctimas de participar en programas o prácticas de justicia restaurativas frente a ex victimarios, mientras que otras víctimas prefieren no participar en estas experiencias, o simplemente no tienen acceso a ellas. Partiendo del derecho que tienen las víctimas de ser reconocidas tanto en una circunstancia como en la otra, este trabajo explora si éstas cuentan con los suficientes recursos y mecanismos para hacer frente a su recuperación emocional y reconocimiento. La primera parte del trabajo está dedicada a la contextualización y conceptualización de las víctimas, sus derechos y sistema normativo, y los mecanismos de justicia restaurativa. En la segunda parte, se analizan brevemente algunas experiencias internacionales de justicia restaurativa con víctimas del terrorismo. A continuación, exploraremos el caso vasco estudiando diferentes casos de recuperación y reconocimiento en víctimas de Euskadi. Y finalmente, se muestran los resultados del trabajo de campo sobre las tres entrevistas realizadas donde víctimas y victimarios valoran experiencias de justicia restaurativa y su potencial reparador.

El ciudadano al desnudo y los seres encubiertos en la antigua Grecia

[EN] Considerando el celebérrimo desnudo masculino heleno, el presente trabajo investiga las coordenadas del imaginario griego que dieron lugar a esta rompedora «puesta en escena» del cuerpo humano e investiga la yuxtaposición vestido/desnudo como un principio diferenciador de primera magnitud en el proceso formativo de las categorías de Ciudadano, Mujer y Bárbaro.

Viveiros de homens do mar: Escolas de Aprendizes-Marinheiros e as experiências formativas na Marinha Militar do Rio de Janeiro (1870-1910

O presente estudo aborda historicamente a formação elementar, profissional e militar dos aprendizes-marinheiros e aprendizes-artífices entre 1870 e 1910 na Marinha Militar do Brasil. Para compreender as experiências compartilhadas que os meninos e os jovens desenvolveram com os marinheiros nacionais e estrangeiros, com o oficialato e com os trabalhadores da cidade utilizamos o referencial teórico do historiador E.P. Thompson. A pesquisa sobre as Escolas de Aprendizes-Marinheiros e sua caracterização como uma instituição total e a análise de seus dispositivos disciplinares foi realizada com o aparato conceitual de Michel Foucault. As fontes históricas analisadas foram os Relatórios Ministeriais do Ministério da Marinha do período, os livros de ofícios do Arsenal de Marinha da Corte, o acervo da Revista Marítima Brasileira e documentos do Fundo/Coleção denominado Grupo de Identificação de Fundos Internos GIFI sob a guarda do Arquivo Nacional. Um dos objetivos foi compreender os fenômenos que envolveram essa instituição militar dentro das políticas de Estado no período localizado entre o fim da Guerra do Paraguai e a Revolta dos Marinheiros de 1910, e quais as mudanças qualitativas, contradições e conflitos na organização interna do trabalho concorreram para a produção de um modelo formativo dos futuros homens do mar. Buscamos compreender os mecanismos internos de recrutamento e controle dos sujeitos sociais dessa instituição permanente do Estado. A abordagem sobre o que seriam as experiências formativas dos aprendizes partiu da ideia de que a educação dos indivíduos acontecia em múltiplas dimensões da vida e não somente através de aulas ou programas de estudos oficiais, de compêndios ou de regras disciplinares repercutidas reiteradas vezes. Questões como o uso do tempo, o campo dos direitos como arena de conflitos, o dualismo no sistema educativo, a alimentação, o descanso, o alcoolismo, as deserções, as acomodações e as revoltas, compuseram a análise da formação dos meninos e jovens da Marinha. Verificamos como os embates em torno da temática da profissionalização e carreira, que passavam pelas discussões que envolviam aspectos como o mérito pessoal, a antiguidade e o bom comportamento interferiram na produção de uma consciência de direitos. Tudo isso fez parte das experiências formativas de meninos e rapazes daquela instituição chamada pelos oficiais de principal viveiro de homens do mar. Por fim, para entendermos aqueles chamados pelo referencial thompsoniano como os de baixo percorremos a dureza da hierarquia e disciplina militares e as concepções de mundo desenvolvidas a partir das classificações e apartações dos indivíduos pela raça, pela origem social, pela constituição física e pelo analfabetismo.