Cette thèse traite du domaine de la cryptographie basée sur des dynamiques chaotiques hybrides.Afin de robustifier la transmission sécurisée de données à l'égard de l'attaque à texte-claire connue, ce travail a été particulièrement axée sur deux directions, l'approche statistique, et l'approche automatique.Les principales contributions de ce travail sont organisées dans ces deux directions.Le choix de la variable mesurée et son influence sur l'émetteur d'un message secret et la possibilité de récupérer la dynamique à la réception.Ceci a été étudié dans le contexte des systèmes chaotiques discrets et continus.L'indépendance statistique des variables d'état des systèmes chaotiques est étudié en relation avec la non-corrélation spatiale de ces états.Ainsi une méthode pour cacher le message secret en fonction de l'évolution de l'émetteur chaotique, et ceci avant son inclusion dans cette dynamique, est proposée.La faisabilité d'un système retardée hybride qui est utilisée pour la transmission sécurisée des données est analysée dans une mise en œuvre analogique.Des simulations et les analyses des résultats obtenus sont faits, afin de prouver l'efficacité des études et des méthodes proposées.La thèse est organisée comme suit: le Chapitre I reprend les notions théoriques et les algorithmes utilisés pour atteindre l'objectif de ce travail.Le chapitre II est consacré à l'étude des exposants de Lyapunov.Les systèmes chaotiques utilisés dans le présent document sont ensuite décrits.Le chapitre III présente une étude de certaines propriétés structurales des systèmes du chapitre II.L'étude se concentre sur le calcul des indices d'observabilité et la détermination des hypersurfaces de la singularité d'observabilité.Le chapitre IV analyse l'indépendance statistique dans le contexte des systèmes chaotiques considérés:la taille de la distance d'échantillonnage (combien d'itérations ou de manière équivalente, combien de temps) pour assurer l'indépendance statistique entre les variables extraites des systèmes chaotiques.Un test original pour l'indépendance statistique (le test Badea-Vlad) a été utilisée; la procédure est applicable à tous les types de variables aléatoires continues, même reparties selon une loi de probabilité inconnue au besoin ici.Le chapitre V illustre le point de vue physique. Le temps transitoire correspond au temps passé par le système chaotique dans le bassin d'attraction avant de rejoindre l'attracteur étrange.De même il est important de savoir après combien de temps les points localisés dans une certaine région de l'attracteur étrange devient non-corrélés.Dans le chapitre VI, sachant l'identifiabilité des paramètres des systèmes chaotiques décrits par des équations polynomiales, une amélioration des inclusions du message dans ce type de cryptographie, est proposé.Le message clair est chiffré en utilisant une substitution classique avec boîtes de transposition, avant son inclusion dans l'émetteur chaotique.Les résultats de l'algorithme proposé sont évalués sur le texte et sur l'image.Le chapitre VII pose quelques questions, et essaie de trouver quelques-unes des réponses à ces questions, dans le cadre du schéma hybride.Comme par exemple, est-il possible de récupérer le message secret en utilisant un observateur, lorsque la dynamique qui lui inclut est retardée?La réponse est positive, et cela est montrée dans le cas d'une transmission intégrale de la sortie du système.Il est important de mentionner que ce travail est pluridisciplinaire, allant de la théorie du contrôle aux statistiques en passant par les domaines de l'électronique, de la mathématique et de l'informatique. / This Thesis deals with the domain of cryptography based on hybrid chaotic dynamics.In order to increase the robustness of the security in data transmission with respect to known text attack, this work was particularly focused on two directions: the statistical approach and the automation control.The main contributions of this work are organized in the mentioned two directions.The choice of the measured variable and its influence on the transmitter of plain messages, alongside the possibility to recover the dynamics at the reception.These are studied in the context of discrete and continuous-time chaotic systems.Statistical independence of the state variables of chaotic systems is investigated in relation with the spatial non-correlation of the states.A method of hiding the secret message, depending on the evolution of the chaotic transmitter and prior to its inclusion in this dynamics is proposed.The feasibility of a delayed time hybrid scheme that is used for secure data transmission is shown in an analog implementation.Simulations and analysis of the obtained results are done in order to prove the efficiency of the proposed studies and methods.The Thesis is organized as follows: Chapter I resumes theoretical notions and algorithms used to achieve the goal of this work.Chapter II is dedicated to the study of the Lyapunov exponents. The chaotic systems used in this report are described.Chapter III presents a study of some structural properties of the chaotic systems from Chapter II.The investigation is focused on the calculation of the observability indexes and the determination of the manifolds of observability singularity.Chapter IV analyses the statistical independence in the context of the considered chaotic systems:how large should be the sampling distance (how many iterations or, equivalently, time) to ensure statical independence between variables extracted from the chaotic systems.An original test for statistical independence (the Badea-Vlad test) was used; the procedure is applicable to all kind of continuous random variables, even of unknown probability law as needed here.Chapter V illustrates the physical point of view.The transient time corresponds to the time spent by the chaotic system in the basin of attraction before rejoining the strange attractor.It is also important to know after how long the points localized in a certain region of the strange attractor become uncorrelated.In Chapter VI, knowing the identifiability of the parameters of chaotic systems described by polynomial equations, an improvement of the inclusion of messages in this type of enciphering is proposed.The plain-message is enciphered using classical substitution and transposition boxes, prior to its inclusion in the chaotic transmitter.The results of the proposed algorithm are evaluated on text and image.Chapter VII rises some questions, and tries to find some answers to these questions, in the context of hybrid dynamical schemes.As for example if it is possible to recover the secret message by using an observer, when the dynamics that includes it is time-delayed.The answer is positive and this is shown in the case of a full transmission of the output of the system.It is important to mention that this work is multidisciplinary, starting from control theory and going to the statistical methods through the fields of electronics, mathematics and computing.

L'évolution des systèmes de télécommunications conduit à la conception de codecs de la parole et du son de plus en plus sophistiqués, accroissant ainsi la concurrence de l'industrie de l'audio et accordant une importance grandissante à la qualité de service. Si l'évaluation de la qualité des codecs peut s'opérer suivant des mesures objectives ou subjectives, les secondes restent les plus fiables dans la mesure où la qualité perçue par les utilisateurs est intrinsèquement subjective. Toutefois, les tests subjectifs requièrent des signaux d'ancrage, i.e. des signaux artificiels visant la reproduction des défauts perceptifs des codecs de sorte que les dégradations provoquées soient aisément contrôlables. Le système de référence actuellement normalisé par l'Union Internationale des Télécommunications est le MNRU (Modulated Noise Reference Unit) qui simule le bruit de quantification introduit par les premiers codecs en forme d'onde. L'évolution de la technologie rend aujourd'hui ce système obsolète, et il s'agit donc de concevoir un nouveau système d'ancrage plus adapté aux codecs actuels. En considérant la qualité audio comme un objet multidimensionnel, nous avons mis en évidence un espace perceptif à quatre dimensions, et ce à partir de deux approches de réduction de dimensionnalité, l'AFM (Analyse Factorielle Multiple) et la MDS 3–voies (MultiDimensional Scaling). A partir des quatre dimensions identifiées – « Réduction de la largeur de bande », « Bruit de fond », « Écho/Réverbération » et « Distorsion de la parole » –, nous avons modélisé puis validé les signaux d'ancrage des trois premières dimensions et proposé deux modèles de signaux d'ancrage pour la quatrième. / The evolution of technology led to the design of very sophisticated speech and audio codecs. Accordingly, the competition in audio devices manufacturing has increased and today the quality of service becomes crucial for telecommunications operators. Quality of codecs is assessed through objective and subjective measures, the second ones being the most reliable since the quality perceived by users is inherently subjective. Nevertheless, subjective tests require anchor signals corresponding to artificial signals, which reproduce the perceptual impairments of codecs in such a manner that the amount of degradation can be easily controlled. The reference system currently standardized by the International Telecommunication Union is the Modulated Noise Reference Unit (MNRU), which simulates the quantization noise of the first generation of waveform codecs. Due to the evolution of codecs, the MNRU system became obsolete and researchers aim at designing a new reference system of anchor signals more suited to current codecs. Assuming that speech and audio quality is multidimensional, we first identified four perceptual dimensions using two dimensionality reduction techniques – the MFA (Multiple Factor Analysis) and the 3–way MDS (MultiDimensional Scaling). From the identified dimensions, namely “Bandwidth limitation”, “Background noise”, “Echo/Reverberation” and “Speech distortion”, we succeeded in modeling and validating anchor signals for three of them and we suggested two models of anchor signals for the last one.

La topographie d'une surface se compose généralement de plusieurs échelles, depuis l'échelle macroscopique (sa géométrie physique), jusqu'aux échelles microscopiques ou atomiques appelées rugosité. L'évolution spatiale et géométrique de la rugosité fournit une description plus complète de la surface, et une interprétation physique de certains problèmes importants tels que le frottement et les mécanismes d'usure pendant le contact mécanique entre deux surfaces. La topographie d'une surface rugueuse est de nature aléatoire, ce qui traduit par des altitudes spatialement corrélées, appelées pics et vallées. La relation entre leurs densités de probabilité et leurs propriétés géométriques sont les aspects fondamentaux qui ont été développés dans cette thèse, en utilisant la théorie des champs aléatoires et la géométrie intégrale. Un modèle aléatoire approprié pour représenter une surface rugueuse a été mis en place et étudié au moyen des paramètres les plus significatifs, dont les changements influencent la géométrie des ensembles de niveaux (excursion sets) de cette surface. Les ensembles de niveaux ont été quantifiés par des fonctionnelles connues sous le nom de fonctionnelles de Minkowski, ou d'une manière équivalente sous le nom de volumes intrinsèques. Dans un premier temps, les volumes intrinsèques des ensembles de niveaux sont calculés analytiquement sur une classe de modèles mixtes, qui sont définis par la combinaison linéaire d'un champ aléatoire Gaussien et d'un champ de t-student (t-field), et ceux d'une classe de champs aléatoires asymétriques appelés skew-t. Ces volumes sont comparés et testés sur des surfaces produites par des simulations numériques. Dans un second temps, les modèles aléatoires proposés ont été appliqués sur des surfaces réelles acquises à partir d'une cupule d'UHMWPE (provenant d’une prothèse totale de hanche) avant et après les processus d'usure. Les résultats ont montré que le champ aléatoire skew-t est un modèle mieux approprié pour décrire la rugosité de surfaces usées, contrairement aux modèles adoptés dans la littérature. Une analyse statistique, basée sur le champ aléatoire skew-t, est ensuite proposée pour détecter les niveaux des pics/vallées de la surface usée et pour décrire le comportement et la fonctionnalité de la surface usée. / Surface topography is, generally, composed of many length scales starting from its physical geometry, to its microscopic or atomic scales known by roughness. The spatial and geometrical evolution of the roughness topography of engineering surfaces avail comprehensive understanding, and interpretation of many physical and engineering problems such as friction, and wear mechanisms during the mechanical contact between adjoined surfaces. Obviously, the topography of rough surfaces is of random nature. It is composed of irregular hills/valleys being spatially correlated. The relation between their densities and their geometric properties are the fundamental topics that have been developed, in this research study, using the theory of random fields and the integral geometry.An appropriate random field model of a rough surface has been defined by the most significant parameters, whose changes influence the geometry of its excursion. The excursion sets were quantified by functions known as intrinsic volumes. These functions have many physical interpretations, in practice. It is possible by deriving their analytical formula to estimate the parameters of the random field model being applied on the surface, and for statistical analysis investigation of its excursion sets. These subjects have been essentially considered in this thesis. Firstly, the intrinsic volumes of the excursion sets of a class of mixture models defined by the linear combination of Gaussian and t random fields, then for the skew-t random fields are derived analytically. They have been compared and tested on surfaces generated by simulations. In the second stage, these random fields have been applied to real surfaces measured from the UHMWPE component, involved in application of total hip implant, before and after wear simulation process. The primary results showed that the skew-t random field is more adequate, and flexible for modelling the topographic roughness. Following these arguments, a statistical analysis approach, based on the skew-t random field, is then proposed. It aims at estimating, hierarchically, the significant levels including the real hills/valleys among the uncertain measurements. The evolution of the mean area of the hills/valleys and their levels enabled describing the functional behaviour of the UHMWPE surface over wear time, and indicating the predominant wear mechanisms.

Since the field of computer networks has rapidly grown in the last two decades, congestion control of traffic loads within networks has become a high priority. Congestion occurs in network routers when the number of incoming packets exceeds the available network resources, such as buffer space and bandwidth allocation. This may result in a poor network performance with reference to average packet queueing delay, packet loss rate and throughput. To enhance the performance when the network becomes congested, several different active queue management (AQM) methods have been proposed and some of these are discussed in this thesis. Specifically, these AQM methods are surveyed in detail and their strengths and limitations are highlighted. A comparison is conducted between five known AQM methods, Random Early Detection (RED), Gentle Random Early Detection (GRED), Adaptive Random Early Detection (ARED), Dynamic Random Early Drop (DRED) and BLUE, based on several performance measures, including mean queue length, throughput, average queueing delay, overflow packet loss probability, packet dropping probability and the total of overflow loss and dropping probabilities for packets, with the aim of identifying which AQM method gives the most satisfactory results of the performance measures. This thesis presents a new AQM approach based on the RED algorithm that determines and controls the congested router buffers in an early stage. This approach is called Dynamic RED (REDD), which stabilises the average queue length between minimum and maximum threshold positions at a certain level called the target level to prevent building up the queues in the router buffers. A comparison is made between the proposed REDD, RED and ARED approaches regarding the above performance measures. Moreover, three methods based on RED and fuzzy logic are proposed to control the congested router buffers incipiently. These methods are named REDD1, REDD2, and REDD3 and their performances are also compared with RED using the above performance measures to identify which method achieves the most satisfactory results. Furthermore, a set of discrete-time queue analytical models are developed based on the following approaches: RED, GRED, DRED and BLUE, to detect the congestion at router buffers in an early stage. The proposed analytical models use the instantaneous queue length as a congestion measure to capture short term changes in the input and prevent packet loss due to overflow. The proposed analytical models are experimentally compared with their corresponding AQM simulations with reference to the above performance measures to identify which approach gives the most satisfactory results. The simulations for RED, GRED, ARED, DRED, BLUE, REDD, REDD1, REDD2 and REDD3 are run ten times, each time with a change of seed and the results of each run are used to obtain mean values, variance, standard deviation and 95% confidence intervals. The performance measures are calculated based on data collected only after the system has reached a steady state. After extensive experimentation, the results show that the proposed REDD, REDD1, REDD2 and REDD3 algorithms and some of the proposed analytical models such as DRED-Alpha, RED and GRED models offer somewhat better results of mean queue length and average queueing delay than these achieved by RED and its variants when the values of packet arrival probability are greater than the value of packet departure probability, i.e. in a congestion situation. This suggests that when traffic is largely of a non bursty nature, instantaneous queue length might be a better congestion measure to use rather than the average queue length as in the more traditional models.

A Mina de Santa Rita, situada no complexo máfico-ultramáfico Fazenda Mirabela, é uma intrusão máfica-ultramáfica, mineralizada a sulfetos de níquel e cobre, situada no sudeste do Estado da Bahia, município de Itagibá. Esse depósito é composto por rochas de idade Paleoproterozóica, metamorfizadas em fácies granulito. Os sulfetos de níquel e cobre ocorrem disseminados e, preferencialmente, associados a harzburgitos, olivina ortopiroxenitos e ortopiroxenitos. O minério é composto por uma grande variedade de Mg-silicatos, sendo que o níquel ocorre essencialmente como pentlandita nos peridotitos, além de se apresentar como elemento menor em silicatos e espinélios em rochas mais máficas. Informações de processo demonstram a impossibilidade de se estabelecer uma correlação robusta entre a composição química do minério e seu comportamento na etapa de beneficiamento mineral. Desta forma, o conhecimento da variabilidade mineralógica no depósito é de fundamental importância para o planejamento de lavra e processamento mineral. Mais de 300 amostras do plano de mineração de curto prazo (2013-2017) relativas a intervalos de furos de sondagem considerados no estudo de viabilidade econômica (período de 1985-2004) foram agrupadas em domínios mineralógicos, utilizando a análise estatística multivariada de dados de difração de raios X (DRX-AEM). Dezessete domínios mineralógicos inicialmente definidos são essencialmente diferenciados com base na presença e conteúdos relativos dos principais minerais de ganga: serpentina, olivina e piroxênio. Amostras representativas dos principais domínios mineralógicos, pré-definidos por DRX-AEM, foram submetidas a estudos de caracterização mineralógica de detalhe por análise de imagens (MEV-MLA). Os resultados indicam que os grupos com composições mais peridotíticas e/ou carbonáticas, com maiores conteúdos de serpentina, apresentam menor tempo de moagem para atingir P95 igual a 0,15 mm; maior alteração dos grãos de pentlandita; maior parcela de total de níquel associado a silicatos; menor grau de liberação dos sulfetos; e maior quantidade de sulfetos abaixo de 10 ?m, em relação aos grupos de composição mais piroxenítica. / The Santa Rita mine, located in the mafic-ultramafic complex Fazenda Mirabela, is a mafic-ultramafic intrusion mineralized to nickel and copper sulphides located in the southeast of Bahia state, Itagibá municipality. The nickel sulphide deposit comprises a portion of a mafic-ultramafic layered complex under granulite metamorphism facies. Disseminated Ni and Cu sulphides form a stratiform body parallel to the lithostratigraphic contacts extending upwards essentially from the harzburgite unit and through the olivine orthopyroxenite unit. The nickel content is mainly associated to pentlandite in peridotitic rocks but also enriched in silicates and spinels in mafic rocks (dunites). Industrial plant benchmark data have shown the unfeasibility of establishing a strong relation between the ore chemical composition and its behavior in the mineral beneficiation process. Therefore, the knowledge of the mineralogical variability in the deposit is crucial for mine planning and mineral/metallurgical processing. More than 300 samples from drill core samples from the feasibility studies (period of 1985-2004) included in the short-term mining plan (2013-2017) were clustered into geological domains applying multivariate statistical analysis (MSA) of X-ray diffraction data (XRD). Results discriminated seventeen initial mineralogical domains considering the content of major gangue minerals: serpentine, olivine and pyroxene. Representative samples of the main mineralogical domains pre-defined by XRD-MSA ore-types were later subject to sieve size analysis followed by detailed mineralogical studies by automated SEM image analysis (MLA). The results indicate that groups with more peridotite and / or carbonatic compositions, with higher content of serpentine, have less time of grinding to reach P95 equal to 0,15 mm; high level of pentlandite alteration; greater portion of nickel associated into silicates; lower sulphides liberation degree; and a higher amount of sulphides below 10 ?m; in relation to the most pyroxenic composition groups.

A leishmaniose é uma doença negligenciada provocada por parasitas do gênero Leishmania, que ocorre em mais de 90 países no mundo, afetando milhões de pessoas. A doença é tratável, mas ainda não tem cura, e o arsenal terapêutico comumente utilizado é limitado, e consiste do uso de fármacos de alta toxicidade. Sendo assim, a busca por novas terapias tem sido encorajada e o uso de compostos ativos isolados de produtos naturais, como plantas, tem se mostrado eficaz. Para uso futuro destes princípios ativos no tratamento, faz-se necessário o entendimento do seu mecanismo de ação. As ciências \"ômicas\", mais especificamente a metabolômica, que é a análise comparativa dos metabólitos alterados em um sistema biológico após intervenção externa, tem sido bastante aplicada com este objetivo. A abordagem metabolômica é multidisciplinar e as análises são realizadas com auxílio de plataformas analíticas modernas, como as técnicas de separação acopladas a espectrometria de massas (MS). Para tratamento dos dados são utilizadas ferramentas estatísticas avançadas, e as substâncias alteradas são correlacionadas com rotas metabólicas. Neste trabalho, o mecanismo de ação em Leishmania infantum da substância ativa (metildihidrodieugenol B) isolada da planta Nectandra leucantha, foi avaliado por abordagem metabolômica global, com multiplataforma de análise (cromatografia gasosa e líquida em fase reversa hifenadas, GC-MS e RPLC-MS, respectivamente). Otimizações de preparo de amostra, extração, e derivatização para GC-MS, para obter o maior número possível de metabólitos foram realizadas nas amostras em estudo. Promastigotas de L. infantum foram crescidos em meio de cultura e após 72 h foram tratados com metildihidrodieugenol B (na concentração de 58.18 &#181g x mL-1); passadas 48 h de tratamento, a ação enzimática foi interrompida, as células lavadas e congeladas para análise posterior. Metanol:água (1:1) e metanol 100% foram utilizados como solventes extratores para acessar os metabólitos intracelulares nas análises por GC-MS e RPLC-MS, respectivamente. Derivatização com O-metoxiamina em piridina (15 mg x mL-1) à temperatura ambiente por 90 min, seguida de sililação com BSTFA + 1% TMCS por 30 min à 40 ºC foi realizada para tornar voláteis e estáveis os metabólitos para análise por GC-MS. Os resultados de ambas plataformas de análise apontou grandes diferenças entre os grupos de amostras tratadas e não tratadas com a substância ativa, e os metabólitos alterados com significância estatística foram correlacionados com o metabolismo de Leishmania. Diferentes aminoácidos, ácidos graxos, carboidratos, glicerolipídeos e fosfoslipídeos foram encontrados, em sua maioria, diminuídos com o tratamento. Devido a complexidade do metabolismo do parasita e a grande diversidade dos metabólitos alterados, um mecanismo de ação multi-target pode ser atribuído ao dímero de fenilpropanoide. Mudanças no metabolismo da glicólise e gluconeogênese são destacadas, indicando alterações nas fontes de energia da célula. Modificações na composição lipídica da membrana plasmática do parasita também foram observadas, sugerindo variações em sua flexibilidade e fluidez. Os resultados obtidos são preliminares, mas muito importantes para dar o primeiro passo na elucidação da ação desta substância no tratamento da leishmaniose, pleiteando a busca por novas terapias. / Leishmaniasis is a neglected disease caused by Leishmania parasites, which occurs in more than 90 countries worldwide, affecting millions of people. The disease is treatable but not curable, and the commonly used therapeutic arsenal is limited and consists in the use of highly toxic drugs. The search for new therapies has been encouraged and the use of active compounds, isolated from natural products, such as plants, has been proven effective. For future use of these active compounds in the treatment, it is necessary to understand its mechanism of action. \"Omics\" sciences, specifically metabolomics, which is the comparative analysis of altered metabolites in a biological system after external intervention, has been widely applied for this purpose. The metabolomic approach is multidisciplinary and the analyzes are performed using modern analytical platforms, such as separation techniques coupled to mass spectrometry (MS). Data treatment are performed with advanced statistical tools and altered metabolites are correlated with metabolic pathways. In this work, the mechanism of action, in Leishmania infantum, of an active compound (methyldehydrodieugenol B), isolated from Nectandra leucantha plant, was evaluated by global metabolomics approach with multiplatform analysis (gas and reversed phase liquid chromatography, GC-MS and RPLC-MS, respectively). Optimizations of sample preparation, extraction and derivatization for GC-MS to obtain the maximum number of metabolites in the samples under consideration were performed. L. infantum promastigotes were grown in culture medium and after 72 h they were treated with metildihidrodieugenol B (at a concentration of 58.18 µg x mL-1); after 48 h of treatment, enzyme activity was quenched, cells washed and frozen for further analysis. Methanol:water (1:1) and 100% methanol are used as solvent extractor to assess intracellular metabolites for analysis by GC-MS and RPLC-MS, respectively. Derivatization with O-methoxyamine in pyridine (15 mg x mL-1) at room temperature for 90 min, followed by silylation with BSTFA + 1% TMCS for 30 min at 40°C was performed to make volatile and stable metabolites for analysis by GC- MS. The results of both analytical platforms showed significant differences between treated and non-treated samples with the active substance, and altered metabolites with statistical significance were correlated with Leishmania metabolism. Different amino acids, fatty acids, carbohydrates, and glycerolipids phospholipids were found, mostly decreased with treatment. Due to the complexity of the parasite metabolism and the great diversity of altered metabolites, a multi-target mechanism can be assigned to the methyldehydrodieugenol B. Changes in the metabolism of glycolysis and gluconeogenesis are highlighted, indicating changes in the cell energy sources. Changes in the lipid composition of the parasite plasma membrane were also observed, suggesting variations in its flexibility and fluidity. The results are preliminary, but very important to take the first step into elucidation of the action of this substance in the treatment of leishmaniasis, aiming the search for new pharmaceutical therapies.

A pesquisa realizada tratou do estudo de modelos de estimação da relação ar-combustível e de identificação do tipo de combustível usando o sinal da pressão no cilindro em um motor quatro tempos automotivo, alimentado com gasolina brasileira tipo C, etanol e misturas destes combustíveis. Foi montada uma bancada dinamométrica para realização de testes em um motor originalmente projetado para operar com etanol e que possui relação de compressão de 13,44:1. Durante os testes do motor foram coletados dados referentes às variáveis de desempenho e emissões de gases de exaustão. Os dados coletados em plena carga foram analisados utilizando parâmetros estatísticos e confrontados com os resultados esperados segundo a literatura. As variáveis independentes disponibilizadas nos testes do motor foram utilizadas em conjunto com a aplicação do método dos momentos e da razão de pressões no sinal da pressão no cilindro para o desenvolvimento de novos modelos de estimação da relação ar-combustível e de identificação do tipo de combustível. Os modelos obtidos na presente pesquisa mostraram-se capazes de estimar a relação ar-combustível, sendo sensíveis à variação da composição do combustível nesta estimativa, e de identificar o tipo de combustível utilizado no motor. / This research addressed the study of models for estimating the air-fuel ratio and identifying the type of fuel by in-cylinder pressure signal in a four stroke automotive engine fueled with Brazilian gasoline C type, ethanol, and blends of these fuels. A dynamometer was assembled for tests in an engine originally designed to operate with ethanol and with a 13.44:1 compression ratio. During the engine tests, data were collected related to the performance and exhaustion gas emission variables. Data collected at full load were analyzed using statistical parameters and compared with the expected results according to the literature. The independent variables provided by the engine tests were used together with application of the method of moments and the pressure ratio for in-cylinder pressure in order to develop new models for estimating the air-fuel ratio and to identify the fuel type. The models obtained in this research proved to be capable of estimating the air-fuel ratio, being sensitive to the variation in the type of fuel used in such estimations, and of identifying the type of fuel used in the engine.

O rio Corumbataí, principal tributário do rio Piracicaba, e fonte de abastecimento da cidade de Piracicaba, vêm sofrendo degradação desde a sua nascente, na cidade de Analândia até sua foz, no rio Piracicaba. Entre 2005 e 2006, foram determinados os teores dos elementos: Be, Al, Na, Mg, Ca, K, V, Mn, Fe, Cr, Co, Ni, Cu, Zn, As, Se, Ag, Cd, Sb, Ba, Hg, Pb, Th, Tl, U por Espectrofotometria de massas com fonte de plasma induzido (ICP-MS) e as propriedades físicas, químicas e microbiológicas, na água e sedimento do rio Corumbataí. As coletas foram realizadas em setembro e dezembro de 2005 e em março, junho e setembro de 2006. Na água, os elementos foram determinados na fração dissolvida, filtrando-se a amostra em campo e preservando-se com HNO3 e na fração total, utilizando-se o método de extração aberta com o uso de HNO3 e HCl. No sedimento, os elementos foram determinados na fração trocável, agitando-se por 12 horas em HCl 1 mol L-1 e na fração total, com a extração em forno microonda. Nas amostras de água, foi calculado o Índice de qualidade da água (IQA), o que demonstrou uma diminuição na qualidade ao longo dos anos, principalmente nos pontos localizados na região à jusante de Rio Claro (RJ) e Piracicaba (PI). O Fósforo Total, Turbidez, pH, OD, Clorofila-a, Escherichia Coli, DBO e os metais Fe e Al dissolvido, Mn, Cd e Hg total, apresentaram concentrações acima do Conama 357/2005 para rios classe 2 em diversos pontos e épocas de coleta, ao longo do rio. No sedimento, os metais Cr, Ni, Cu, As, Cd, Hg, Pb não apresentaram valores acima dos preconizados pela Companhia de Tecnologia de Saneamento - CETESB como causadores de efeitos tóxicos. Os outros metais não possuem valores máximos de referência na legislação brasileira. Os elementos que apresentaram fração trocável maior que 50% em todos os pontos de coleta foram: Na, Ca, Mn, Tl, Co, Cu, Be, Pb. A análise estatística multivariada de componentes principais e a análise de agrupamento indica os pontos RJ e PI, como os mais comprometidos e demonstra que o IQA é um bom indicador da qualidade ao longo da bacia hidrográfica. / The Corumbataí River, main tributary of the Piracicaba river and source of water supply to the city of Piracicaba has been suffering degradation from its waterhead in the city of Analândia to its mouth in the Piracicaba river. In 2005 and 2006 were determined the concentration of the elements, Be, Al, Na, Mg, Ca, K, V, Mn, Fe, Cr, Co, Ni, Cu, Zn, As, Se, Ag, Cd, Sb, Ba, Hg, Pb, Th, Tl, U by Inductively Coupled Plasma-Mass Spectrometry (ICP-MS), as well as physicochemical and microbiological proprieties, in the water and sediments of the Corumbataí River. The collections were carried out in September and December of 2005 and March, June and September of 2006. In the water, the elements in the dissolved fraction were determined by filtering the sample in field and preserving themselves with HNO3, and in the total fraction, by using the method of open extration using HNO3 and HCl. In the sediment, the elements were determined in the exchangeable fraction, by agitating for 12 hours in HCl 1 mol L-1 and in the total fraction, with the extration in microwave. In the samples of water, the water quality Index (WQI) was calculated, and the results showed a reduction in the quality throughout the years, mainly in the points located in the region downstream regions of Rio Claro, (RJ), and Piracicaba, (PI). The Total Phosphorus, Turbidity, pH, Dissolved Oxygen, Chlorophyill-a, Escherichia Coli, BOD and the dissolved metals Al and Fe, and total Hg, Mn, Cd presented concentrations above Conama 357/2005 for rivers class 2 in several points and periods of collection, along the river. In the sediment, the Cr, Ni, Cu, As, Cd, Hg, Pb did not present values above the recommended ones by Companhia de Tecnologia de Saneamento - CETESB as responsible for toxic effect. Reference values for the the other metals are not indicated in the Brazilian legislation. The elements that presented bigger exchangeable fraction than 50% in all the collection points were: Na, Ca, Mn, Tl, Co, Cu, Be, Pb. The multivaried statistical analysis of main components and the Hierarchical Cluster Analysis indicated RJ and PI points, as the most damaged and showed that the WQI is a good indicative of quality along the hydrographic basin.

Cette thèse s’inscrit dans une démarche d’optimisation des performances de la PEMFC, à travers le développement d’outils de diagnostic dédiés à la gestion de l’eau. Celle-ci est un des éléments clé de l’augmentation des performances et de la durée de vie des piles à combustible. La technique du bruit électrochimique a été utilisée pour détecter des phénomènes liés au comportement de l’eau lors du fonctionnement de la pile dans différentes conditions opératoires (humidité relative des gaz, température et courant). Le bruit électrochimique enregistré pendant ces expériences a été associé à des mécanismes source grâce à une démarche expérimentale appropriée et à un traitement de signal basé sur l’analyse fréquentielle et temporelle. Les résultats de l’analyse spectrale et statistique ont permis de décrire l’état de santé de la pile à combustible (assèchement et noyage), par la génération des descripteurs dans le domaine fréquentiel et temporel, signatures de chaque état de fonctionnement de la pile à combustible. Enfin, de manière à compléter l’approche effectuée sur la détection de l’assèchement de la membrane et le noyage de la cellule par l’étude des bruits électrochimiques, des capteurs de mesure de pression en amont de la cellule de PEMFC ont été utilisées et comparer au signaux de tension pour détecter le phénomène de noyage d’une mono-cellule de PEMFC. / This thesis deals to optimize the performance of the PEMFC, through the development of diagnostic tools dedicated to water management. This water management is one of the key elements to increase the performance and life of fuel cells. The electrochemical noise technique was used to detect the phenomena related to the water behavior during the operation of the cell, under different operating conditions (relative humidity of the gases, temperature and current). The electrochemical noise recorded during these experiments was associated with mechanisms through an appropriate experimental approach and signal processing based on frequency and time analysis. The results of spectral and statistical analysis made it possible to describe the state of health of fuel cell (drying and flooding), by the generation of the descriptors in the frequency and time domain, signatures of each operating state of the fuel cell. Finally, in order to complete, the approach carried out on detecting the drying of the membrane and flooding of the cell by electrochemical noise analysis, the pressure measurement was combined with voltage signals, to detect the flooding phenomena of fuel cell.

A leishmaniose é uma doença negligenciada provocada por parasitas do gênero Leishmania, que ocorre em mais de 90 países no mundo, afetando milhões de pessoas. A doença é tratável, mas ainda não tem cura, e o arsenal terapêutico comumente utilizado é limitado, e consiste do uso de fármacos de alta toxicidade. Sendo assim, a busca por novas terapias tem sido encorajada e o uso de compostos ativos isolados de produtos naturais, como plantas, tem se mostrado eficaz. Para uso futuro destes princípios ativos no tratamento, faz-se necessário o entendimento do seu mecanismo de ação. As ciências \"ômicas\", mais especificamente a metabolômica, que é a análise comparativa dos metabólitos alterados em um sistema biológico após intervenção externa, tem sido bastante aplicada com este objetivo. A abordagem metabolômica é multidisciplinar e as análises são realizadas com auxílio de plataformas analíticas modernas, como as técnicas de separação acopladas a espectrometria de massas (MS). Para tratamento dos dados são utilizadas ferramentas estatísticas avançadas, e as substâncias alteradas são correlacionadas com rotas metabólicas. Neste trabalho, o mecanismo de ação em Leishmania infantum da substância ativa (metildihidrodieugenol B) isolada da planta Nectandra leucantha, foi avaliado por abordagem metabolômica global, com multiplataforma de análise (cromatografia gasosa e líquida em fase reversa hifenadas, GC-MS e RPLC-MS, respectivamente). Otimizações de preparo de amostra, extração, e derivatização para GC-MS, para obter o maior número possível de metabólitos foram realizadas nas amostras em estudo. Promastigotas de L. infantum foram crescidos em meio de cultura e após 72 h foram tratados com metildihidrodieugenol B (na concentração de 58.18 &#181g x mL-1); passadas 48 h de tratamento, a ação enzimática foi interrompida, as células lavadas e congeladas para análise posterior. Metanol:água (1:1) e metanol 100% foram utilizados como solventes extratores para acessar os metabólitos intracelulares nas análises por GC-MS e RPLC-MS, respectivamente. Derivatização com O-metoxiamina em piridina (15 mg x mL-1) à temperatura ambiente por 90 min, seguida de sililação com BSTFA + 1% TMCS por 30 min à 40 ºC foi realizada para tornar voláteis e estáveis os metabólitos para análise por GC-MS. Os resultados de ambas plataformas de análise apontou grandes diferenças entre os grupos de amostras tratadas e não tratadas com a substância ativa, e os metabólitos alterados com significância estatística foram correlacionados com o metabolismo de Leishmania. Diferentes aminoácidos, ácidos graxos, carboidratos, glicerolipídeos e fosfoslipídeos foram encontrados, em sua maioria, diminuídos com o tratamento. Devido a complexidade do metabolismo do parasita e a grande diversidade dos metabólitos alterados, um mecanismo de ação multi-target pode ser atribuído ao dímero de fenilpropanoide. Mudanças no metabolismo da glicólise e gluconeogênese são destacadas, indicando alterações nas fontes de energia da célula. Modificações na composição lipídica da membrana plasmática do parasita também foram observadas, sugerindo variações em sua flexibilidade e fluidez. Os resultados obtidos são preliminares, mas muito importantes para dar o primeiro passo na elucidação da ação desta substância no tratamento da leishmaniose, pleiteando a busca por novas terapias. / Leishmaniasis is a neglected disease caused by Leishmania parasites, which occurs in more than 90 countries worldwide, affecting millions of people. The disease is treatable but not curable, and the commonly used therapeutic arsenal is limited and consists in the use of highly toxic drugs. The search for new therapies has been encouraged and the use of active compounds, isolated from natural products, such as plants, has been proven effective. For future use of these active compounds in the treatment, it is necessary to understand its mechanism of action. \"Omics\" sciences, specifically metabolomics, which is the comparative analysis of altered metabolites in a biological system after external intervention, has been widely applied for this purpose. The metabolomic approach is multidisciplinary and the analyzes are performed using modern analytical platforms, such as separation techniques coupled to mass spectrometry (MS). Data treatment are performed with advanced statistical tools and altered metabolites are correlated with metabolic pathways. In this work, the mechanism of action, in Leishmania infantum, of an active compound (methyldehydrodieugenol B), isolated from Nectandra leucantha plant, was evaluated by global metabolomics approach with multiplatform analysis (gas and reversed phase liquid chromatography, GC-MS and RPLC-MS, respectively). Optimizations of sample preparation, extraction and derivatization for GC-MS to obtain the maximum number of metabolites in the samples under consideration were performed. L. infantum promastigotes were grown in culture medium and after 72 h they were treated with metildihidrodieugenol B (at a concentration of 58.18 µg x mL-1); after 48 h of treatment, enzyme activity was quenched, cells washed and frozen for further analysis. Methanol:water (1:1) and 100% methanol are used as solvent extractor to assess intracellular metabolites for analysis by GC-MS and RPLC-MS, respectively. Derivatization with O-methoxyamine in pyridine (15 mg x mL-1) at room temperature for 90 min, followed by silylation with BSTFA + 1% TMCS for 30 min at 40°C was performed to make volatile and stable metabolites for analysis by GC- MS. The results of both analytical platforms showed significant differences between treated and non-treated samples with the active substance, and altered metabolites with statistical significance were correlated with Leishmania metabolism. Different amino acids, fatty acids, carbohydrates, and glycerolipids phospholipids were found, mostly decreased with treatment. Due to the complexity of the parasite metabolism and the great diversity of altered metabolites, a multi-target mechanism can be assigned to the methyldehydrodieugenol B. Changes in the metabolism of glycolysis and gluconeogenesis are highlighted, indicating changes in the cell energy sources. Changes in the lipid composition of the parasite plasma membrane were also observed, suggesting variations in its flexibility and fluidity. The results are preliminary, but very important to take the first step into elucidation of the action of this substance in the treatment of leishmaniasis, aiming the search for new pharmaceutical therapies.