Orientador: Isabel Cristina Sales Fontes Jardim / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Química / Made available in DSpace on 2018-08-19T02:08:02Z (GMT). No. of bitstreams: 1 Begnini_FernandaRibeiro_M.pdf: 1951363 bytes, checksum: fe0989f49b67e9b16db7e81f2c1544f5 (MD5) Previous issue date: 2011 / Resumo: Novas fases estacionárias (FE) para Cromatografia Líquida de Alta Eficiência em fase reversa (CLAE-FR) foram preparadas a partir da sorção e imobilização por micro-ondas do copolímero poli(2- fenilpropil)metilsiloxano (PFPMS) sobre suporte de sílica Kromasil (tipo B, esférica, 5 mm). A FE preparada com carga do copolímero de 50%, imobilizada a 540 W por 80 minutos e extraída com clorofórmio (3 horas) e metanol (2 horas) após 8 dias de imobilização, apresentou desempenho cromatográfico satisfatório, com eficiências acima de 60000 pratos/m e parâmetros cromatográficos na faixa aceita pela literatura. Através da caracterização físico-química da FE preparada, pelas técnicas de RMN Si e C, e espectroscopia de absorção no infravermelho, entre outras, foi possível sugerir que o PFPMS encontra-se fisicamente sorvido e quimicamente ligado à sílica. A caracterização cromatográfica mostrou que a FE possui seletividade hidrofóbica, seletividade estérica, pouca interação com analitos polares e grupos silanóis residuais, sendo características apropriadas para uma FR. A FE preparada apresenta grande potencial na separação de agrotóxicos, fármacos e hidrocarbonetos policíclicos aromáticos, além de possuir estabilidade em meio ácido / Abstract: A new stationary phase for reversed-phase high-performance liquid chromatography (RP-HPLC) was prepared by sorption and microwave immobilization of the copolymer poly(2- phenylpropyl)methylsiloxane (PPPMS) onto a silica support (Kromasil®, type B, 5 mm). The stationary phase prepared with copolymeric content of 50%, immobilized at 540 W for 80 min and extracted with chloroform (3 hours) and methanol (2 hours) eight days after immobilization, showed satisfactory chromatographic performance, with efficiency above 60000 plates/m and symmetrical peaks. The physical¿chemical characterization of the new microwave immobilized stationary phase using solid-state NMR spectroscopy and infrared spectroscopy suggested that the copolymer is physically sorbed and chemically bonded onto the silica support. The chromatographic characterization showed that the stationary phase has hydrophobic selectivity, steric selectivity, low interaction with polar analytes and residual silanols, suggesting that the stationary phase prepared is promising to be used in RP-HPLC. The microwave immobilized stationary phase presented chemical stability and potential applicability to separation of pesticides, pharmaceutical drugs and polycyclic aromatic hydrocarbons / Mestrado / Quimica Analitica / Mestre em Química

L'objectif principal de cette recherche est d'analyser les effets de l'agrégation sur la prévision de la demande. Cet effet est examiné par l'analyse mathématique et l’étude de simulation. L'analyse est complétée en examinant les résultats sur un ensemble de données réelles. Dans la première partie de cette étude, l'impact de l'agrégation temporelle sur la prévision de la demande a été évalué. En suite, Dans la deuxième partie de cette recherche, l'efficacité des approches BU(Bottom-Up) et TD (Top-Down) est analytiquement évaluée pour prévoir la demande au niveau agrégé et désagrégé. Nous supposons que la série désagrégée suit soit un processus moyenne mobile intégrée d’ordre un, ARIMA (0,1,1), soit un processus autoregressif moyenne mobile d’ordre un, ARIMA (1,0,1) avec leur cas spéciales. / Demand forecasting performance is subject to the uncertainty underlying the time series an organisation is dealing with. There are many approaches that may be used to reduce demand uncertainty and consequently improve the forecasting (and inventory control) performance. An intuitively appealing such approach that is known to be effective is demand aggregation. One approach is to aggregate demand in lower-frequency ‘time buckets’. Such an approach is often referred to, in the academic literature, as temporal aggregation. Another approach discussed in the literature is that associated with cross-sectional aggregation, which involves aggregating different time series to obtain higher level forecasts.This research discusses whether it is appropriate to use the original (not aggregated) data to generate a forecast or one should rather aggregate data first and then generate a forecast. This Ph.D. thesis reveals the conditions under which each approach leads to a superior performance as judged based on forecast accuracy. Throughout this work, it is assumed that the underlying structure of the demand time series follows an AutoRegressive Integrated Moving Average (ARIMA) process.In the first part of our1 research, the effect of temporal aggregation on demand forecasting is analysed. It is assumed that the non-aggregate demand follows an autoregressive moving average process of order one, ARMA(1,1). Additionally, the associated special cases of a first-order autoregressive process, AR(1) and a moving average process of order one, MA(1) are also considered, and a Single Exponential Smoothing (SES) procedure is used to forecast demand. These demand processes are often encountered in practice and SES is one of the standard estimators used in industry. Theoretical Mean Squared Error expressions are derived for the aggregate and the non-aggregate demand in order to contrast the relevant forecasting performances. The theoretical analysis is validated by an extensive numerical investigation and experimentation with an empirical dataset. The results indicate that performance improvements achieved through the aggregation approach are a function of the aggregation level, the smoothing constant value used for SES and the process parameters.In the second part of our research, the effect of cross-sectional aggregation on demand forecasting is evaluated. More specifically, the relative effectiveness of top-down (TD) and bottom-up (BU) approaches are compared for forecasting the aggregate and sub-aggregate demands. It is assumed that that the sub-aggregate demand follows either a ARMA(1,1) or a non-stationary Integrated Moving Average process of order one, IMA(1,1) and a SES procedure is used to extrapolate future requirements. Such demand processes are often encountered in practice and, as discussed above, SES is one of the standard estimators used in industry (in addition to being the optimal estimator for an IMA(1) process). Theoretical Mean Squared Errors are derived for the BU and TD approach in order to contrast the relevant forecasting performances. The theoretical analysis is supported by an extensive numerical investigation at both the aggregate and sub-aggregate levels in addition to empirically validating our findings on a real dataset from a European superstore. The results show that the superiority of each approach is a function of the series autocorrelation, the cross-correlation between series and the comparison level.Finally, for both parts of the research, valuable insights are offered to practitioners and an agenda for further research in this area is provided.

L’introduction de dégradations lors du processus de formation d’images est un phénomène inévitable: les images souffrent de flou et de la présence de bruit. Avec les progrès technologiques et les outils numériques, ces dégradations peuvent être compensées jusqu’à un certain point. Cependant, la qualité des images acquises est insuffisante pour de nombreuses applications. Cette thèse contribue au domaine de la restauration d’images. La thèse est divisée en cinq chapitres, chacun incluant une discussion détaillée sur différents aspects de la restauration d’images. La thèse commence par une présentation générale des systèmes d’imagerie et pointe les dégradations qui peuvent survenir ainsi que leurs origines. Dans certains cas, le flou peut être considéré stationnaire dans tout le champ de vue et est alors simplement modélisé par un produit de convolution. Néanmoins, dans de nombreux cas de figure, le flou est spatialement variable et sa modélisation est plus difficile, un compromis devant être réalisé entre la précision de modélisation et la complexité calculatoire. La première partie de la thèse présente une discussion détaillée sur la modélisation des flous spatialement variables et différentes approximations efficaces permettant de les simuler. Elle décrit ensuite un modèle de formation de l’image générique. Puis, la thèse montre que la restauration d’images peut s’interpréter comme un problème d’inférence bayésienne et ainsi être reformulé en un problème d’optimisation en grande dimension. La deuxième partie de la thèse considère alors la résolution de problèmes d’optimisation génériques, en grande dimension, tels que rencontrés dans de nombreux domaines applicatifs. Une nouvelle classe de méthodes d’optimisation est proposée pour la résolution des problèmes inverses en imagerie. Les algorithmes proposés sont aussi rapides que l’état de l’art (d’après plusieurs comparaisons expérimentales) tout en supprimant la difficulté du réglage de paramètres propres à l’algorithme d’optimisation, ce qui est particulièrement utile pour les utilisateurs. La troisième partie de la thèse traite du problème de la déconvolution aveugle (estimation conjointe d’un flou invariant et d’une image plus nette) et suggère différentes façons de contraindre ce problème d’estimation. Une méthode de déconvolution aveugle adaptée à la restauration d’images astronomiques est développée. Elle se base sur une décomposition de l’image en sources ponctuelles et sources étendues et alterne des étapes de restauration de l’image et d’estimation du flou. Les résultats obtenus en simulation suggèrent que la méthode peut être un bon point de départ pour le développement de traitements dédiés à l’astronomie. La dernière partie de la thèse étend les modèles de flous spatialement variables pour leur mise en oeuvre pratique. Une méthode d’estimation du flou est proposée dans une étape d’étalonnage. Elle est appliquée à un système expérimental, démontrant qu’il est possible d’imposer des contraintes de régularité et d’invariance lors de l’estimation du flou. L’inversion du flou estimé permet ensuite d’améliorer significativement la qualité des images. Les deux étapes d’estimation du flou et de restauration forment les deux briques indispensables pour mettre en oeuvre, à l’avenir, une méthode de restauration aveugle (c’est à dire, sans étalonnage préalable). La thèse se termine par une conclusion ouvrant des perspectives qui pourront être abordées lors de travaux futurs / Degradations of images during the acquisition process is inevitable; images suffer from blur and noise. With advances in technologies and computational tools, the degradations in the images can be avoided or corrected up to a significant level, however, the quality of acquired images is still not adequate for many applications. This calls for the development of more sophisticated digital image restoration tools. This thesis is a contribution to image restoration. The thesis is divided into five chapters, each including a detailed discussion on different aspects of image restoration. It starts with a generic overview of imaging systems, and points out the possible degradations occurring in images with their fundamental causes. In some cases the blur can be considered stationary throughout the field-of-view, and then it can be simply modeled as convolution. However, in many practical cases, the blur varies throughout the field-of-view, and thus modeling the blur is not simple considering the accuracy and the computational effort. The first part of this thesis presents a detailed discussion on modeling of shift-variant blur and its fast approximations, and then it describes a generic image formation model. Subsequently, the thesis shows how an image restoration problem, can be seen as a Bayesian inference problem, and then how it turns into a large-scale numerical optimization problem. Thus, the second part of the thesis considers a generic optimization problem that is applicable to many domains, and then proposes a class of new optimization algorithms for solving inverse problems in imaging. The proposed algorithms are as fast as the state-of-the-art algorithms (verified by several numerical experiments), but without any hassle of parameter tuning, which is a great relief for users. The third part of the thesis presents an in depth discussion on the shift-invariant blind image deblurring problem suggesting different ways to reduce the ill-posedness of the problem, and then proposes a blind image deblurring method using an image decomposition for restoration of astronomical images. The proposed method is based on an alternating estimation approach. The restoration results on synthetic astronomical scenes are promising, suggesting that the proposed method is a good candidate for astronomical applications after certain modifications and improvements. The last part of the thesis extends the ideas of the shift-variant blur model presented in the first part. This part gives a detailed description of a flexible approximation of shift-variant blur with its implementational aspects and computational cost. This part presents a shift-variant image deblurring method with some illustrations on synthetically blurred images, and then it shows how the characteristics of shift-variant blur due to optical aberrations can be exploited for PSF estimation methods. This part describes a PSF calibration method for a simple experimental camera suffering from optical aberration, and then shows results on shift-variant image deblurring of the images captured by the same experimental camera. The results are promising, and suggest that the two steps can be used to achieve shift-variant blind image deblurring, the long-term goal of this thesis. The thesis ends with the conclusions and suggestions for future works in continuation of the current work

in english The aim of this thesis is to provide a systematic insight into the regulation of air protection from pollution produced by so called "enumerated stationary sources", which means from sources enumerated in annex no. 2 of Act no. 201/2012 Coll., focused on the on air protection. The work is divided into two sub-parts when the first part focuses on the proposed legislation in the field of air protection from pollution, its historical development, and legislation at all levels - expressly international law, law of European union and national legislation. Subsequently, the thesis describes the basic objectives of current legislation with regard to all sources of air pollution. The second part of the thesis concerns only on legislation that adjusts enumerated stationary sources and presents a list of various legal instruments of control in a systematic division of conceptual, administrative and economic tools, which is always given to the appropriate section. These particular tools are discussed with regard to the specifics applied to these enumerated stationary sources. The conclusion is a separate chapter devoted to liability for infringement of operators that run the enumerated stationary sources.

The radar transmitter identification problem involves the identification of a specific radar transmitter based on a received pulse. The radar transmitters are of identical make and model. This makes the problem challenging since the differences between radars of identical make and model will be solely due to component tolerances and variation. Radar pulses also vary in time and frequency which means that the problem is non-stationary. Because of this fact, time-frequency representations such as shift-invariant quadratic time-frequency representations (Cohen’s class) and wavelets were used. A model for a radar transmitter was developed. This consisted of an analytical solution to a pulse-forming network and a linear model of an oscillator. Three signal classification algorithms were developed. A signal classifier was developed that used a radially Gaussian Cohen’s class transform. This time-frequency representation was refined to increase the classification accuracy. The classification was performed with a support vector machine classifier. The second signal classifier used a wavelet packet transform to calculate the feature values. The classification was performed using a support vector machine. The third signal classifier also used the wavelet packet transform to calculate the feature values but used a Universum type classifier for classification. This classifier uses signals from the same domain to increase the classification accuracy. The classifiers were compared against each other on a cubic and exponential chirp test problem and the radar transmitter model. The classifier based on the Cohen’s class transform achieved the best classification accuracy. The classifier based on the wavelet packet transform achieved excellent results on an Electroencephalography (EEG) test dataset. The complexity of the wavelet packet classifier is significantly lower than the Cohen’s class classifier. Copyright / Dissertation (MEng)--University of Pretoria, 2010. / Electrical, Electronic and Computer Engineering / unrestricted

Studies on stationary phase cultures of microorganisms in the laboratory have helped us understand the genetic and physiological basis of adaptation in their natural habitats. Stasis or decline in bacterial populations due to nutrient depletion during stationary phase has been shown to lead to the selection of mutants that are able to survive better than their parent. This phenomenon, where a mutant exhibits relatively better growth than its immediate parent, under the conditions that prevailed during its appearance, is termed as Growth Advantage in Stationary Phase (GASP) and constitutes a general strategy to survive prolonged stationary phase. A mutation conferring growth advantage in one environment, however, can result in the loss of fitness in another environment, typifying the environment-specificity of the adaptation. Several GASP loci have been isolated over the last two decades and they have enhanced our understanding of the rapid evolution of microorganisms under nutrient starvation and the forces driving it. The results presented in this thesis detail the isolation and characterization of one such survivor from the culture of an E. coli strain ZK819 that was grown for 28 days without any additional nutrients. The strain ZK819 carries the rpoS819 allele that was isolated as the first GASP mutation resulting in attenuated activity of the stationary phase - specific sigma factor RpoS. Among the several possible mutations accumulating in the survivors over this long incubation period, one was identified to be within the hns gene encoding the global regulator H-NS. Expression of a majority of genes regulated by H-NS is environmentally modulated and their products are required under various stress conditions. The presence of the hns66 mutation was identified by the derepression of the bgl operon, one of the well-studied targets of H-NS mediated repression. The primary question being addressed in this study is whether this naturally isolated hns66 mutation has any role in the survival of its bearer during prolonged stationary phase. The hns66 mutation results in a partially active longer polypeptide due to a single nucleotide alteration within the stop codon of the H-NS ORF. Strains carrying the hns66 allele showed differential fitness under two different environments relative to the parent. In early stationary phase there is a strong disadvantage associated with the hns66 allele in the rpoS819 background, when competed against the parent, highlighted by the observation that there is a sharp fall in the number of mutants and a concomitant appearance of revertants that lead to the rapid displacement of the original mutant. The reversion is predominantly due to suppressor mutations within the ssrA locus encoding a tmRNA involved in the release of stalled ribosomes and degradation of aberrant proteins. Analysis of the suppression phenomenon revealed that the altered H-NS66 protein is a substrate for SsrA-mediated tagging for proteolysis. The H-NS66 protein is sub-optimally functional and can repress the bgl operon when its level is increased either by over-expression from a plasmid or a mutation in ssrA. Mutation in ssrA suppressed the strong growth disadvantage displayed by the original survivor in early stationary phase. The growth disadvantage of the hns66 survivor was also lost upon introduction of the wild type rpoS allele, indicating that the combined presence of the hns66 and rpoS819 alleles is detrimental in early stationary phase. In the presence of the rpoS+ allele, the hns66 mutant showed a modet GASP phenotype relative to the parent in early stationary phase. In contrast to the crash observed during early stationary phase, strains carryingthe hns66 allele fared better in late stationary phase conditions compared to the parent. When present in its original genetic context, the hns66 allele conferred growth advantage to the original survivor in late stationary phase conditions when competed against the parent grown for 21 days. The hns66 allele, when introduced in the parent strain ZK819 by transduction could still confer a strong GASP phenotype when competed against one-day old parent cells in medium derived from a 21 day old culture. These observations suggest that the hns66 allele enables the cells to scavenge for limited quantities of specific nutrients available in the aged medium. This is consistent with the observation that the advantage is seen when the mutant is in minority and is lost when the mutant is in majority. These studies highlight the fact that the conditions under stationary phase are constantly changing and to adapt under these rapidly changing conditions, modulation of an already existing function would be a preferred strategy than selection for a new function or the complete loss of a function. In this context, genetic modulation of a global regulator offers a better option due to the pleiotropic effects it may generate. This study adds hns to the list of genes, which upon mutation confer a GASP phenotype to cells. It also highlights that the age of the cells as well as the medium has an impact on the GASP phenotype. Elucidation of the mechanism of the H-NS mediated growth advantage and its relation to the status of the rpoS locus can contribute to our understanding of the dynamics of the stationary phase.

Les processus auto-stabilisants sont définis comme des solutions d'équations différentielles stochastiques dont le terme de dérive contient à la fois le gradient d'un potentiel ainsi qu'un terme non-linéaire au sens de McKean qui attire le processus vers sa propre loi de distribution. On dispose de nombreux résultats lorsque l'environnement est convexe. L'objet de ce travail est de les étendre autant que possible au cas général notamment lorsque le paysage contient plusieurs puits. Des différences fondamentales sont constatées.Le premier chapitre prouve l'existence d'une solution forte. Le second s'intéresse aux lois de probabilités d'une telle solution. En particulier, l'existence et la non-unicité des mesures stationnaires sont mises en évidence sous des hypothèses faibles. Les chapitres trois et quatre sont affectés au comportement de ces mesures lorsque le coefficient de diffusion tend vers 0.Le chapitre cinq met en relation le processus auto-stabilisant avec des systèmes particulaires via une « propagation du chaos ». Il est ainsi possible de transposer certains résultats du système de particules sur le processus non-markovien et réciproquement. Le chapitre six est dédié au dénombrement exact des mesures stationnaires.Le chapitre sept est employé pour l'étude du comportement en temps long. D'une part, un résultat de convergence dans un cas simple est fourni. D'autre part, un principe de grandes déviations est mis en évidence par l'utilisation des résultats de Freidlin et Wentzell / Self-stabilizing processes are defined as the solutions of stochastic differential equations which drift term contains the gradient of a potential and a term nonlinear in the sense of McKean which attracts the process to its own law distribution. There are many results if the landscape is convex. The purpose of this work is to extend these in the general case especially when the landscape contains contains several wells. Essential differences are found.The first chapter proves the strong existence of a solution. The second one deals with the probability measure of the solution. Particularly, the existence and the non-uniqueness of the stationary measures are highlighted under weak assumptions. Chapter three and four are assigned to the asymptotic analysis in the small noise limit of these measures.Chapter five connects the self-stabilizing process and some particle systems via a « propagation of chaos ». It is thus possible to translate some results from the particle systems to the non-markovian process and reciprocally.Chapter seven is used to study the long time behavior. In one hand, a convergence's result is provided in a simple case. In the other hand, a large deviations principle is highlighted by using the results of Freidlin and Wentzell

Todays digitized society have open up for new types of office arrangements and possibilities of working from home in a higher extend. This thesis is based on the flexible working culture that is increasing, which means more personal responsibility regarding ergonomic and environment conditions as well as artifacts needed for a well equipped workplace outside the traditional office. Furniture dealers are having a new approach as open office hubs and home office environment are increasing with new needs. This project contains of a small investigation of which artifacts are needed and wanted from a customer perspective in the home environment due to these new behaviors.  This thesis will as well show the outcome and process of one product in a collection of 5 stationary objects. The name of the project is as well the name of the collection. This project consists of two main objectives, customer orientation and product development.

Orientador: Carol Hollingworth Collins / Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Quimica / Made available in DSpace on 2018-08-07T20:37:42Z (GMT). No. of bitstreams: 1 Faria_AnizioMarciode_D.pdf: 2871302 bytes, checksum: 58d9a466b2a4724df83a92414de3d9a9 (MD5) Previous issue date: 2006 / Doutorado / Quimica Analitica / Doutor em Quimica

Orientador: Euclides de Mesquita Neto / Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Engenharia Mecanica / Made available in DSpace on 2018-08-04T01:41:44Z (GMT). No. of bitstreams: 1 Menoni_JoseAntonio_D.pdf: 11918799 bytes, checksum: c09bbd80eae74f22092698eb851e1578 (MD5) Previous issue date: 2004 / Resumo: Este trabalho trata da formulação e da implementação da versão direta do Método dos Elementos de Contorno (MEC) para tratamento de problemas acústicos bidimensionais estacionários regidos pelo operador diferencial de Helrnholtz. São abordados tanto problemas internos, associados a domínios limitados, quanto problemas externos, associados a domínios ilimitados. A tese ainda aborda a solução de problemas diretos e inversos. A transformação da equação de Helrnholtz em Equação Integral de Contorno, bem como a síntese de sua Solução Fundamental é recuperada de forma detalhada no texto. Para o caso de problemas internos duas técnicas são estudadas para recuperação de grandezas modais de cavidades acústicas. A primeira é baseada na pesquisa direta das raÍzes do polinômio característico e a segunda é baseada na informação obtida a partir de Funções de Resposta em Freqüência sintetizadas pelo MEC. Os problemas da radiação e espalhamento acústico são formulados, implementados e validados. O trabalho apresenta ainda a solução de problemas inversos, no qual as variáveis acústicas em um contorno geométrico conhecido são determinadas a partir de medições em uma superficie fechada e que envolve o corpo radiante. Duas técnicas são utilizadas no processo inverso, a Decomposição em Valores Singulares e a técnica de regularização de Tikhonov. Discute-se a precisão e eficiência destas técnicas em função dos parâmetros que são variáveis presentes nestas técnicas / Abstract: The present Thesis reports a formulation and an implementation of the direct version of the Boundary Element Method (BEM) to model direct and indirect bidimensional stationary acoustic problems governed by the Helrnholz differential operator. Both internal and external problems, associated, respectively to bounded and unbounded domains, are treated in the analysis. The transformation of the Helmholtz differential equation into an equivalent Boundary Integral Equation (BIE) and the synthesis of its Fundamental Solution is recovered in detail. For internal problem two techniques are employed to obtain modal quantities of acoustic cavities. The fIrs is the direct search method of the characteristic polynomial roots. The second strategy is based on numerical Frequency Response Functions, synthesized by the BEM. Radiation and scatter problems are formulated, implemented and validated within the realm of the Boundary Element Method. The present work still addresses the solution of an inverse problem. The inverse problem consists of determining the acoustic variables on the boundary of a radiating or scattering body of known geometry, based on the acoustic fIelds measured over a c10sed surface which embodies the analized body. Two technique to solve the inversion problem are discussed. The fIrst is the Single Value Decomposition strategy and the other is the Tikhonov regularization strategy. The accuracy of this techniques are discussed as functions of the internal parameters which are intrinsic to those strategies / Doutorado / Mecanica dos Sólidos e Projeto Mecanico / Mestre em Engenharia Mecânica