Solvent induced NMR chemical shifts that arise from molecular encounters

Recently Homer and Percival have postulated that intermolecular van der Waals dispersion forces can be characterized by three mechanisms. The first arises via the mean square reaction field < R1; 2> due to the transient dipole of a particular solute molecule that is considered situated in a cavity surrounded by solvent molecules; this was characterized by an extended Onsager approach. The second stems from the extra cavity mean square reaction field < R2; 2> of the near neighbour solvent molecules. The third originates from square field electric fields E2BI due to a newly characterized effect in which solute atoms are `buffeted' by the peripheral atoms of adjacent solvent molecules. The present work concerns more detailed studies of the buffeting screening, which is governed by sterically controlled parameter (2T - T)2, where and are geometric structural parameters. The original approach is used to characterise the buffeting shifts induced by large solvent molecules and the approach is found to be inadequate. Consequently, improved methods of calculating and are reported. Using the improved approach it is shown that buffeting is dependent on the nature of the solvent as well as the nature of the solute molecule. Detailed investigation of the buffeting component of the van der Waals chemical shifts of selected solutes in a range of solvents containing either H or Cl as peripheral atoms have enabled the determination of a theoretical acceptable value for the classical screening coefficient B for protons. 1H and 13C resonance studies of tetraethylmethane and 1H, 13C and 29Si resonance studies of TMS have been used to support the original contention that three (< R1; 2> , < R2; 2> and E2BI) components of intermolecular van der Waals dispersion fields are required to characterise vdW chemical shifts.

Investigation of chromatic function in the normal and abnormal eye

This study examined the use of non-standard parameters to investigate the visual field, with particular reference to the detection of glaucomatous visual field loss. Evaluation of the new perimetric strategy for threshold estimation - FASTPAC, demonstrated a reduction in the examination time of normals compared to the standard strategy. Despite an increased within-test variability the FASTPAC strategy produced a similar mean sensitivity to the standard strategy, reducing the effects of patient fatigue. The new technique of Blue-Yellow perimetry was compared to White-White perimetry for the detection of glaucomatous field loss in OHT and POAG. Using a database of normal subjects, confidence limits for normality were constructed to account for the increased between-subject variability with increase in age and eccentricity and for the greater variability of the Blue-Yellow field compared to the White-White field. Effects of individual ocular media absorption had little effect on Blue-Yellow field variability. Total and pattern probability analysis revealed five of 27 OHTs to exhibit Blue-Yellow focal abnormalities; two of these patients subsequently developed White-White loss. Twelve of the 24 POAGs revealed wider and/or deeper Blue-Yellow loss compared with the White-White field. Blue-Yellow perimetry showed good sensitivity and specificity characteristics, however, lack of perimetric experience and the presence of cataract influenced the Blue-Yellow visual field and may confound the interpretation of Blue-Yellow visual field loss. Visual field indices demonstrated a moderate relationship to the structural parameters of the optic nerve head using scanning laser tomography. No abnormalities in Blue-Yellow or Red-Green colour CS was apparent for the OHT patients. A greater vulnerability of the SWS pathway in glaucoma was demonstrated using Blue-Yellow perimetry however predicting which patients may benefit from B-Y perimetric examination is difficult. Furthermore, cataract and the extent of the field loss may limit the extent to which the integrity of the SWS channels can be selectively examined.

Dispersion engineering of highly nonlinear chalcogenide suspended-core fibers

Chalcogenide optical fibers are currently undergoing intensive investigation with the aim of exploiting the excellent glass transmission and nonlinear characteristics in the near- and mid-infrared for several applications. Further enhancement of these properties can be obtained, for a particular application, with optical fibers specifically designed that are capable of providing low effective area together with a properly tailored dispersion, matching the characteristics of the laser sources used to excite nonlinear effects. Suspended-core photonic crystal fibers are ideal candidates for nonlinear applications, providing small-core waveguides with large index contrast and tunable dispersion. In this paper, the dispersion properties of As2S3 suspended-core fibers are numerically analyzed, taking into account, for the first time, all the structural parameters, including the size and the number of the glass bridges. The results show that a proper design of the cladding struts can be exploited to significantly change the fiber properties, altering the maximum value of the dispersion parameter and shifting the zero-dispersion wavelengths over a range of 400 nm.

Chalcogenide suspended-core fibers for supercontinuum generation in the mid-infrared

Chalcogenide suspended core fibers are a valuable solution to obtain supercontinuum generation of light in the mid-infrared, thanks to glass high transparency, high index contrast, small core diameter and widely-tunable dispersion. In this work the dispersion and nonlinear properties of several chalcogenide suspended core mi-crostructured fibers are numerically evaluated, and the effects of all the structural parameters are investigated. Optimization of the design is carried out to provide a fiber suitable for wide-band supercontinuum generation in the mid-infrared.

Three essays on asset pricing

In this dissertation, I investigate three related topics on asset pricing: the consumption-based asset pricing under long-run risks and fat tails, the pricing of VIX (CBOE Volatility Index) options and the market price of risk embedded in stock returns and stock options. These three topics are fully explored in Chapter II through IV. Chapter V summarizes the main conclusions. In Chapter II, I explore the effects of fat tails on the equilibrium implications of the long run risks model of asset pricing by introducing innovations with dampened power law to consumption and dividends growth processes. I estimate the structural parameters of the proposed model by maximum likelihood. I find that the stochastic volatility model with fat tails can, without resorting to high risk aversion, generate implied risk premium, expected risk free rate and their volatilities comparable to the magnitudes observed in data. In Chapter III, I examine the pricing performance of VIX option models. The contention that simpler-is-better is supported by the empirical evidence using actual VIX option market data. I find that no model has small pricing errors over the entire range of strike prices and times to expiration. In general, Whaley’s Black-like option model produces the best overall results, supporting the simpler-is-better contention. However, the Whaley model does under/overprice out-of-the-money call/put VIX options, which is contrary to the behavior of stock index option pricing models. In Chapter IV, I explore risk pricing through a model of time-changed Lvy processes based on the joint evidence from individual stock options and underlying stocks. I specify a pricing kernel that prices idiosyncratic and systematic risks. This approach to examining risk premia on stocks deviates from existing studies. The empirical results show that the market pays positive premia for idiosyncratic and market jump-diffusion risk, and idiosyncratic volatility risk. However, there is no consensus on the premium for market volatility risk. It can be positive or negative. The positive premium on idiosyncratic risk runs contrary to the implications of traditional capital asset pricing theory.

Effect of Hydrologic Restoration on the Habitat of The Cape Sable Seaside Sparrow, Annual Report of 2003-2004

Following on our previous year’s work on ‘Effect of hydrologic restoration on the habitat of the Cape Sable seaside sparrow (CSSS)’, we presented first year results at the Cape Sable seaside sparrow – fire planning workshop at Everglades National Park in December 2003. Later, with almost the same set of crews as in the previous year, we started field work in the first week of January and continued till May 26, 2004. Protocols for sampling topography and vegetation in 2004 were identical to the previous year. In the early season, we completed topographic surveys along two remaining transects, B and E (~16.5 km), and vegetation surveys along three transects, D, E and F (~10.8 km), leaving only the vegetation sampling on transects B and C to be completed in 2005. During April and May, vegetation sampling was completed at 230 census sites, making the total of 409 CSSS census sites for which we have complete vegetation data. We updated data sets from both 2003 and 2004, and analyzed them together using cluster analysis, ordination, weighted-averaging regression and analysis of variance, as we had in 2003. Additionally, we used logistic regression to examine the effect of vegetation structural parameters on the recent occurrence of CSSS. We also analyzed vegetation observations recorded by the sparrow census team in 1981 and annually between 1992 and 2004 to assess historical patterns of vegetation change in CSSS habitat.

Three Essays on Asset Pricing

In this dissertation, I investigate three related topics on asset pricing: the consumption-based asset pricing under long-run risks and fat tails, the pricing of VIX (CBOE Volatility Index) options and the market price of risk embedded in stock returns and stock options. These three topics are fully explored in Chapter II through IV. Chapter V summarizes the main conclusions. In Chapter II, I explore the effects of fat tails on the equilibrium implications of the long run risks model of asset pricing by introducing innovations with dampened power law to consumption and dividends growth processes. I estimate the structural parameters of the proposed model by maximum likelihood. I find that the stochastic volatility model with fat tails can, without resorting to high risk aversion, generate implied risk premium, expected risk free rate and their volatilities comparable to the magnitudes observed in data. In Chapter III, I examine the pricing performance of VIX option models. The contention that simpler-is-better is supported by the empirical evidence using actual VIX option market data. I find that no model has small pricing errors over the entire range of strike prices and times to expiration. In general, Whaley’s Black-like option model produces the best overall results, supporting the simpler-is-better contention. However, the Whaley model does under/overprice out-of-the-money call/put VIX options, which is contrary to the behavior of stock index option pricing models. In Chapter IV, I explore risk pricing through a model of time-changed Lévy processes based on the joint evidence from individual stock options and underlying stocks. I specify a pricing kernel that prices idiosyncratic and systematic risks. This approach to examining risk premia on stocks deviates from existing studies. The empirical results show that the market pays positive premia for idiosyncratic and market jump-diffusion risk, and idiosyncratic volatility risk. However, there is no consensus on the premium for market volatility risk. It can be positive or negative. The positive premium on idiosyncratic risk runs contrary to the implications of traditional capital asset pricing theory.

Exploitation du potentiel sismique des étoiles naines blanches

Le but de cette thèse est d’explorer le potentiel sismique des étoiles naines blanches pulsantes, et en particulier celles à atmosphères riches en hydrogène, les étoiles ZZ Ceti. La technique d’astérosismologie exploite l’information contenue dans les modes normaux de vibration qui peuvent être excités lors de phases particulières de l’évolution d’une étoile. Ces modes modulent le flux émergent de l’étoile pulsante et se manifestent principalement en termes de variations lumineuses multi-périodiques. L’astérosismologie consiste donc à examiner la luminosité d’étoiles pulsantes en fonction du temps, afin d’en extraire les périodes, les amplitudes apparentes, ainsi que les phases relatives des modes de pulsation détectés, en utilisant des méthodes standards de traitement de signal, telles que des techniques de Fourier. L’étape suivante consiste à comparer les périodes de pulsation observées avec des périodes générées par un modèle stellaire en cherchant l’accord optimal avec un modèle physique reconstituant le plus fidèlement possible l’étoile pulsante. Afin d’assurer une recherche optimale dans l’espace des paramètres, il est nécessaire d’avoir de bons modèles physiques, un algorithme d’optimisation de comparaison de périodes efficace, et une puissance de calcul considérable. Les périodes des modes de pulsation de modèles stellaires de naines blanches peuvent être généralement calculées de manière précise et fiable sur la base de la théorie linéaire des pulsations stellaires dans sa version adiabatique. Afin de définir dans son ensemble un modèle statique de naine blanche propre à l’analyse astérosismologique, il est nécessaire de spécifier la gravité de surface, la température effective, ainsi que différents paramètres décrivant la disposition en couche de l’enveloppe. En utilisant parallèlement les informations obtenues de manière indépendante (température effective et gravité de surface) par la méthode spectroscopique, il devient possible de vérifier la validité de la solution obtenue et de restreindre de manière remarquable l’espace des paramètres. L’exercice astérosismologique, s’il est réussi, mène donc à la détermination précise des paramètres de la structure globale de l’étoile pulsante et fournit de l’information unique sur sa structure interne et l’état de sa phase évolutive. On présente dans cette thèse l’analyse complète réussie, de l’extraction des fréquences à la solution sismique, de quatre étoiles naines blanches pulsantes. Il a été possible de déterminer les paramètres structuraux de ces étoiles et de les comparer remarquablement à toutes les contraintes indépendantes disponibles dans la littérature, mais aussi d’inférer sur la dynamique interne et de reconstruire le profil de rotation interne. Dans un premier temps, on analyse le duo d’étoiles ZZ Ceti, GD 165 et Ross 548, afin de comprendre les différences entre leurs propriétés de pulsation, malgré le fait qu’elles soient des étoiles similaires en tout point, spectroscopiquement parlant. L’analyse sismique révèle des structures internes différentes, et dévoile la sensibilité de certains modes de pulsation à la composition interne du noyau de l’étoile. Afin de palier à cette sensibilité, nouvellement découverte, et de rivaliser avec les données de qualité exceptionnelle que nous fournissent les missions spatiales Kepler et Kepler2, on développe une nouvelle paramétrisation des profils chimiques dans le coeur, et on valide la robustesse de notre technique et de nos modèles par de nombreux tests. Avec en main la nouvelle paramétrisation du noyau, on décroche enfin le ”Saint Graal” de l’astérosismologie, en étant capable de reproduire pour la première fois les périodes observées à la précision des observations, dans le cas de l’étude sismique des étoiles KIC 08626021 et de GD 1212.

Estimating Dynamic Treatment Effects from Project STAR (Working Paper 36)

This paper considers the analysis of data from randomized trials which offer a sequence of interventions and suffer from a variety of problems in implementation. In experiments that provide treatment in multiple periods (T>1), subjects have up to 2^{T}-1 counterfactual outcomes to be estimated to determine the full sequence of causal effects from the study. Traditional program evaluation and non-experimental estimators are unable to recover parameters of interest to policy makers in this setting, particularly if there is non-ignorable attrition. We examine these issues in the context of Tennessee's highly influential randomized class size study, Project STAR. We demonstrate how a researcher can estimate the full sequence of dynamic treatment effects using a sequential difference in difference strategy that accounts for attrition due to observables using inverse probability weighting M-estimators. These estimates allow us to recover the structural parameters of the small class effects in the underlying education production function and construct dynamic average treatment effects. We present a complete and different picture of the effectiveness of reduced class size and find that accounting for both attrition due to observables and selection due to unobservable is crucial and necessary with data from Project STAR

Optical properties of chiral thin films and microparticles

In this work I study the optical properties of helical particles and chiral sculptured thin films, using computational modeling (discrete dipole approximation, Berreman calculus), and experimental techniques (glancing angle deposition, ellipsometry, scatterometry, and non-linear optical measurements). The first part of this work focuses on linear optics, namely light scattering from helical microparticles. I study the influence of structural parameters and orientation on the optical properties of particles: circular dichroism (CD) and optical rotation (OR), and show that as a consequence of random orientation, CD and OR can have the opposite sign, compared to that of the oriented particle, potentially resulting in ambiguity of measurement interpretation. Additionally, particles in random orientation scatter light with circular and elliptical polarization states, which implies that in order to study multiple scattering from randomly oriented chiral particles, the polarization state of light cannot be disregarded. To perform experiments and attempt to produce particles, a newly constructed multi stage thin film coating chamber is calibrated. It enables the simultaneous fabrication of multiple sculptured thin film coatings, each with different structure. With it I successfully produce helical thin film coatings with Ti and TiO_{2}. The second part of this work focuses on non-linear optics, with special emphasis on second-harmonic generation. The scientific literature shows extensive experimental and theoretical work on second harmonic generation from chiral thin films. Such films are expected to always show this non-linear effect, due to their lack of inversion symmetry. However no experimental studies report non-linear response of chiral sculptured thin films. In this work I grow films suitable for a second harmonic generation experiment, and report the first measurements of non-linear response.

Updating of Finite Element Models using static and dynamic optical strains with application to damage assessment

In the recent years, vibration-based structural damage identification has been subject of significant research in structural engineering. The basic idea of vibration-based methods is that damage induces mechanical properties changes that cause anomalies in the dynamic response of the structure, which measures allow to localize damage and its extension. Vibration measured data, such as frequencies and mode shapes, can be used in the Finite Element Model Updating in order to adjust structural parameters sensible at damage (e.g. Young’s Modulus). The novel aspect of this thesis is the introduction into the objective function of accurate measures of strains mode shapes, evaluated through FBG sensors. After a review of the relevant literature, the case of study, i.e. an irregular prestressed concrete beam destined for roofing of industrial structures, will be presented. The mathematical model was built through FE models, studying static and dynamic behaviour of the element. Another analytical model was developed, based on the ‘Ritz method’, in order to investigate the possible interaction between the RC beam and the steel supporting table used for testing. Experimental data, recorded through the contemporary use of different measurement techniques (optical fibers, accelerometers, LVDTs) were compared whit theoretical data, allowing to detect the best model, for which have been outlined the settings for the updating procedure.

Entre o mar e estrela, um lugar para se bem viver : a problemática da expansão urbana da Cidade de Baía Formosa/RN

The urban expansion problem of Baía Formosa, a southern edge city of de Rio Grande do Norte eastern coast, which has been presented in other coast Brazilian towns, specially on those with tourist activities increase. Therefore, this situation brings huge concerns to their inhabitants, to their technical /scientific community and to the governments, because of the conflicts of interest and of the growth of urban problems that this has been created. At Baía Formosa, the situation is aggravated because the city is confined, once around it, there are large private proprieties, environmental preservation area and the sea, at the eastern edge. The objectives of this study are the analyses of this city expansion process in order to obtain adequate alternatives and defining methodology to apply in other urban nucleus that are subjected to similar situations. Of course, presents social relations, environmental conditions and promoting local population insertion should be considered in order that enjoin this process and contributing to a better social balance. This case study has used bibliography research, field data, maps and soil occupation recorders and photographs of the area, besides the primary data gathering by surveys carried out with many social actors. The present analysis shows that the urban expansion observed today is featured by a recent unsustainable model, which attacks the environment and brings either farm conflicts. On the other hand, the ecological tourism can represent an alternative in order to achieve an adequate expansion form, without forgetting the several structural parameters necessary to support the sustainable activities

ESTRUTURA DO COMPONENTE DE REGENERAÇÃO NATURAL E ARBÓREO DE DOIS MANGUEZAIS NO ESTADO DO PARANÁ

Esse estudo avaliou comparativamente os parâmetros fitossociológicos da regeneração natural e da vegetação arbórea em dois manguezais distintos no Estado do Paraná, um pertencente à Baía de Paranaguá (manguezal de Antonina) e outro à Baía de Guaratuba (manguezal de Guaratuba). Em cada área, três subáreas foram marcadas e amostradas cinco parcelas de 10 x 10 m para avaliação do componente arbóreo e quinze subparcelas de 1 x 1 m para avaliação da regeneração natural. Avicennia schaueriana , Rhizophora mangle e Laguncularia racemosa exibiram domínio e densidade relativa distintos entre as áreas. Manguezais de Antonina e Guaratuba diferiram tanto na estrutura da regeneração natural como no componente arbóreo. A Análise de Coordenadas Principais (PCoA) mostrou que as diferenças entre as áreas em relação às variáveis abióticas do solo estão fortemente relacionadas com os parâmetros estruturais do componente arbóreo dos manguezais. Os fatores edáficos dos manguezais têm grande importância na separação entre as áreas, já que reflete na capacidade de adaptação das plantas.

Exploitation du potentiel sismique des étoiles naines blanches

Le but de cette thèse est d’explorer le potentiel sismique des étoiles naines blanches pulsantes, et en particulier celles à atmosphères riches en hydrogène, les étoiles ZZ Ceti. La technique d’astérosismologie exploite l’information contenue dans les modes normaux de vibration qui peuvent être excités lors de phases particulières de l’évolution d’une étoile. Ces modes modulent le flux émergent de l’étoile pulsante et se manifestent principalement en termes de variations lumineuses multi-périodiques. L’astérosismologie consiste donc à examiner la luminosité d’étoiles pulsantes en fonction du temps, afin d’en extraire les périodes, les amplitudes apparentes, ainsi que les phases relatives des modes de pulsation détectés, en utilisant des méthodes standards de traitement de signal, telles que des techniques de Fourier. L’étape suivante consiste à comparer les périodes de pulsation observées avec des périodes générées par un modèle stellaire en cherchant l’accord optimal avec un modèle physique reconstituant le plus fidèlement possible l’étoile pulsante. Afin d’assurer une recherche optimale dans l’espace des paramètres, il est nécessaire d’avoir de bons modèles physiques, un algorithme d’optimisation de comparaison de périodes efficace, et une puissance de calcul considérable. Les périodes des modes de pulsation de modèles stellaires de naines blanches peuvent être généralement calculées de manière précise et fiable sur la base de la théorie linéaire des pulsations stellaires dans sa version adiabatique. Afin de définir dans son ensemble un modèle statique de naine blanche propre à l’analyse astérosismologique, il est nécessaire de spécifier la gravité de surface, la température effective, ainsi que différents paramètres décrivant la disposition en couche de l’enveloppe. En utilisant parallèlement les informations obtenues de manière indépendante (température effective et gravité de surface) par la méthode spectroscopique, il devient possible de vérifier la validité de la solution obtenue et de restreindre de manière remarquable l’espace des paramètres. L’exercice astérosismologique, s’il est réussi, mène donc à la détermination précise des paramètres de la structure globale de l’étoile pulsante et fournit de l’information unique sur sa structure interne et l’état de sa phase évolutive. On présente dans cette thèse l’analyse complète réussie, de l’extraction des fréquences à la solution sismique, de quatre étoiles naines blanches pulsantes. Il a été possible de déterminer les paramètres structuraux de ces étoiles et de les comparer remarquablement à toutes les contraintes indépendantes disponibles dans la littérature, mais aussi d’inférer sur la dynamique interne et de reconstruire le profil de rotation interne. Dans un premier temps, on analyse le duo d’étoiles ZZ Ceti, GD 165 et Ross 548, afin de comprendre les différences entre leurs propriétés de pulsation, malgré le fait qu’elles soient des étoiles similaires en tout point, spectroscopiquement parlant. L’analyse sismique révèle des structures internes différentes, et dévoile la sensibilité de certains modes de pulsation à la composition interne du noyau de l’étoile. Afin de palier à cette sensibilité, nouvellement découverte, et de rivaliser avec les données de qualité exceptionnelle que nous fournissent les missions spatiales Kepler et Kepler2, on développe une nouvelle paramétrisation des profils chimiques dans le coeur, et on valide la robustesse de notre technique et de nos modèles par de nombreux tests. Avec en main la nouvelle paramétrisation du noyau, on décroche enfin le ”Saint Graal” de l’astérosismologie, en étant capable de reproduire pour la première fois les périodes observées à la précision des observations, dans le cas de l’étude sismique des étoiles KIC 08626021 et de GD 1212.

Influência do uso de combustíveis alternativos na síntese por combustão via microondas para a produção de materiais cerâmicos com estrutura espinélio

The development and study of detectors sensitive to flammable combustible and toxic gases at low cost is a crucial technology challenge to enable marketable versions to the market in general. Solid state sensors are attractive for commercial purposes by the strength and lifetime, because it isn t consumed in the reaction with the gas. In parallel, the use of synthesis techniques more viable for the applicability on an industrial scale are more attractive to produce commercial products. In this context ceramics with spinel structure were obtained by microwave-assisted combustion for application to flammable fuel gas detectors. Additionally, alternatives organic-reducers were employed to study the influence of those in the synthesis process and the differences in performance and properties of the powders obtained. The organic- reducers were characterized by Thermogravimetry (TG) and Derivative Thermogravimetry (DTG). After synthesis, the samples were heat treated and characterized by Fourier Transform Infrared Spectroscopy (FTIR), X-ray Diffraction (XRD), analysis by specific area by BET Method and Scanning Electron Microscopy (SEM). Quantification of phases and structural parameters were carried through Rietveld method. The methodology was effective to obtain Ni-Mn mixed oxides. The fuels influenced in obtaining spinel phase and morphology of the samples, however samples calcined at 950 °C there is just the spinel phase in the material regardless of the organic-reducer. Therefore, differences in performance are expected in technological applications when sample equal in phase but with different morphologies are tested