Dynamic Stall on Vertical Axis Wind Turbines

In this study the dynamics of flow over the blades of vertical axis wind turbines was investigated using a simplified periodic motion to uncover the fundamental flow physics and provide insight into the design of more efficient turbines. Time-resolved, two-dimensional velocity measurements were made with particle image velocimetry on a wing undergoing pitching and surging motion to mimic the flow on a turbine blade in a non-rotating frame. Dynamic stall prior to maximum angle of attack and a leading edge vortex development were identified in the phase-averaged flow field and captured by a simple model with five modes, including the first two harmonics of the pitch/surge frequency identified using the dynamic mode decomposition. Analysis of these modes identified vortical structures corresponding to both frequencies that led the separation and reattachment processes, while their phase relationship determined the evolution of the flow.

Detailed analysis of the leading edge vortex found multiple regimes of vortex development coupled to the time-varying flow field on the airfoil. The vortex was shown to grow on the airfoil for four convection times, before shedding and causing dynamic stall in agreement with 'optimal' vortex formation theory. Vortex shedding from the trailing edge was identified from instantaneous velocity fields prior to separation. This shedding was found to be in agreement with classical Strouhal frequency scaling and was removed by phase averaging, which indicates that it is not exactly coupled to the phase of the airfoil motion.

The flow field over an airfoil undergoing solely pitch motion was shown to develop similarly to the pitch/surge motion; however, flow separation took place earlier, corresponding to the earlier formation of the leading edge vortex. A similar reduced-order model to the pitch/surge case was developed, with similar vortical structures leading separation and reattachment; however, the relative phase lead of the separation mode, corresponding to earlier separation, necessitated that a third frequency to be incorporated into the reattachment mode to provide a relative lag in reattachment.

Finally, the results are returned to the rotating frame and the effects of each flow phenomena on the turbine are estimated, suggesting kinematic criteria for the design of improved turbines.

Photosensitized CIS-TRANS isomerization of 2,3-diphenylbutene-2 investigation of anomalous sensitizers for substituted Stilbene isometrization

The behavior of the photosensitized cis-trans isomerization of 2,3-diphenylbutene-2 was studied as a function of sensitizer energy by previously established methods. In addition, certain sensitizers for which parameters other than energy transfer are operative in inducting isomerizations, were studied in more detail. Sensitization of various stilbenes and substituted stilbenes by triphenylene is discussed in terms of excited state complex formation with stilbene. Sensitization by quinones, halogen-containing aromatics and 1,2-diketones is discussed in terms of attack by photolytically produced free radicals, either by addition to and elimination from the double bond, or in the cases of 1,2-diphenylpropene and 2,3-diphenylbutene-2, by hydrogen abstraction from one of the methyl groups and reversible abstraction by the allylic radical to produce cis-trans isomerized substrate and the structurally isomerized products, 2,3-diphenylpropene and 2,3-diphenylbutene-1.

An investigation of wind tunnel wall effects at high Mach numbers

This paper presents the results of an investigation of wind tunnel wall interference in a two-dimensional wind tunnel at high Mach numbers. The results are presented in the form of curves of lift coefficient versus the ratio of model chord to tunnel height, as functions of Mach number and angle of attack. The investigation was carried out by the authors at the Guggenheim Aeronautical Laboratory of the California Institute of Technology during the school year 1944-45.

Tests were carried out on the NACA low drag airfoil section 65,1-012 at Mach numbers from .60 to .80, and angles of attack of from 1 to 3 degrees. Models were 1", 2", 4" and 6" chord, giving values of the chord to tunnel height ration of .1 to .6. Schlieren photographs were made of shock waves where they occurred.

I. Nuclear magnetic resonance analysis of ferrocenylcarbonium ion. II. Ferrocene catalyzed photochemistry

I. Nuclear magnetic resonance spectra of appropriately substituted ferrocenylcarbonium ions reveal the α-protons of the substituted ring to be more shielded than β-protons. The observation is discussed in terms of various models proposed for the ferrocenylcarbonium ion and is found to support a model in which the iron is bonded to all six carbona of the substituted ring.

II. Ferrocene catalyzes the photoisomerization of the piperylenes and the photodimerization of isoprene. Our results suggest a mechanism in which a complex of ferrocene and diene is excited to its second singlet state which dissociates to a triplet-state ferrocene molecule and a triplet-state diene molecule. The triplet-state diene, then, proceeds to isomerize or attack ground-state diene to form dimers.

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.

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.

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.

Modificação química do poli(cloreto de vinila) com nucleófilos nitrogenados assistida por micro-ondas

Nesse trabalho foram realizadas reações de substituição nucleofílica (SN2), utilizando aquecimento térmico convencional e por irradiação de micro-ondas (MO), de alguns átomos cloro em amostras comerciais de poli(cloreto de vinila) (PVC), por grupos nitrila e também por grupos azida. Os grupos nitrila e azida foram substituidos na matriz em diferentes teores (10% e 20%). As reações do PVC com azida foram eficazes, apresentado percentuais de derivatização muito próximos dos valores desejados. Já no estudo com a nitrila não foi obtido o resultado esperado. Os copolímeros PVC azido substituídos foram modificados com propargilato de etila, sob catálise de iodeto de cuproso (CuI), para a obtenção de heterocíclicos do tipo triazólicos. Todos os copolímeros obtidos foram caracterizados por espectroscopia na região do infravermelho (FTIR) e os teores de nitrogênio incorporado foram determinados por análise elementar (AE). Através da análise dos dados obtidos, foi comprovado que a utilização da irradiação micro-ondas, quando comparada ao aquecimento convencional, é um processo mais seletivo e diminui, significativamente, os tempos de reação

Exploring new labelling strategies for boronated compounds: towards fast development and efficient assessment of BNCT drug candidates

208 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