La compréhension de la couleur de polymères chargés, utilisés en revêtement de sol pour un environnement lumineux, peut être abordée soit par une approche perceptive, soit par une approche optique et spectrale de la couleur. Sur la base d'un travail principalement expérimental, les travaux de thèse explorent cette seconde voie. A partir de films composites calandrés, nous avons d'abord montré comment les types de polymères et de pigments, leur concentration, et la mise en forme de la surface, influencent l'aspect. D'une part, une formulation PVC existante ne peut être contretypée par une nouvelle matrice PE, en raison d'un fort couplage entre luminance et chrominance. Ce sont les écarts d'indices de réfraction aux interfaces entre particules et matrice, couplés aux pertes intrinsèques des pigments, qui interviennent au premier ordre pour expliquer la couleur. D'autre part, trois types de rugosité contrôlée induits par grainage ont permis de montrer que toutes les échelles, caractérisées par rugosimétrie confocale et AFM, influencent la luminance L* des matériaux, mesurée par gonio-spectro-colorimétrie. Le modèle géométrique proposé a permis de quantifier les variations de L* en fonction de la topographie des matériaux et de leur orientation. Le rôle de l'éclairage sur la couleur a été étudié avec une source halogène et une LED. L'analyse de matériaux PVC colorés a montré que l'approche spectrale permet de déterminer l'origine du métamérisme et de rechercher ses effets maximaux, par l'association de méthodes perceptive et quantitative dans l'espace CIE-L*a*b*. Le couplage des spectres d'émission des illuminants, de réflectance des matériaux, et de réponse de l'observateur est le principal résultat utilisé pour la conception d'un matériau à changement chromatique. Ces changements sont caractérisés et validés dans un espace réel, où intervient la réflexion-diffusion liée à l'environnement. La recherche par le design a finalement permis de faire émerger de nouvelles typologies de sol, à partir d'un revêtement d'aspect changeant en fonction de l'ambiance lumineuse. Si l'innovation s'accomplit au-delà de la seule réalisation des prototypes, ceux-ci révèlent néanmoins des variations d'aspects marquées pouvant induire de nouveaux usages du sol dans l'habitat.

Bordetella pertussis is one of two Gram-negative bacteria responsible for causing whooping cough in humans, a highly contagious disease that infects the human upper respiratory tract. Whole-cell and acellular vaccines have been developed but due to side-effects resulting from whole-cell vaccines, acellular vaccines are currently preferred to prevent this disease. A second bacterium known to cause whooping cough is Bordetella parapertussis, but since it causes less aggressive symptoms, only B. pertussis is utilized in the manufacture of the vaccine. One acellular vaccine is based on four virulence factors: pertussis toxin (PT), filamentous hemagglutinin (FHA), pertactin (PRN), and fimbriae (FIM). The focus of this thesis was to explore the use of spectrofluorometry for monitoring and forecasting the performance of the upstream and downstream operations in the PRN purification process at Sanofi Pasteur. The upstream fermentation process includes a series of reactors of increasing volume where the microorganism is grown under controlled conditions. The PRN purification process involves a series of sequential steps for separating this protein from other proteins for later use in the vaccine. The PRN is precipitated in three steps with ammonium sulphate at three different concentrations. The pellet is collected by centrifugation and dissolved in a buffer solution followed by chromatographic separation. The run-through is then ultra-filtered and diafiltered in two separate steps. The resulting concentrate is dissolved in water and subjected to another chromatographic step and diafiltration. The final filtration of PRN involves a pre-filtration and sterile filtration. Finally, the samples are collected for quality control. The objective of this work was to monitor the process at different steps of the upstream and downstream purification process by multi-wavelength fluorescence spectroscopy in combination with multi-variate statistical methods. From the spectra, it was possible to identify fluorescent compounds, such as amino acids and enzyme cofactors, without performing an additional pre-treatment or purification step. Also, the identification of conformational changes in proteins and formation of complexes, such as NAD(P)-enzyme complex, was possible based on the shift in the emission peaks of the compounds identified. These results demonstrated the feasibility of using this tool for qualitative evaluation of the process. Multivariate methods, such as PCA and PLS, were used to extract relevant information and compress the fluorescence data acquired. PCA was effective for correlating variability in the yield of pertactin to a particular fluorescence fingerprint. As a result of the study, it was concluded that a possible source of variability in the productivity that is observed might be a metabolic shift during the fermentation steps that leads to the accumulation of NAD(P)H (or NAD(P)H-enzyme complex) probably due to oxygen transfer limitations. This conclusion was reached after investigating changes in the dissolved oxygen, aeration, agitation, supplementation time and key metabolites (lactate, glucose, glutamine) profiles. The correlation of these parameters with low productivity it was not straightforward; however, some consistencies were observed, for example, high levels of glutamine in batches with low productivity. This fact might be related to the start of the supplementation time, which may be related to the dissolved oxygen, since the addition of the supplement is done manually when an increase of the dissolved oxygen is detected. It is believed that this factor is related to the low production of protein product, such as pertactin. By means of PLS, it was possible to build regression models that allow for predicting the final concentration of pertactin from the fluorescence measurements. The models were built using the new variables obtained from data compression performed with PCA, and the final pertactin concentration measured by a Kjeldahl test. With this method, two regressions were constructed: (i) between NAD(P)H-enzyme complex spectra from the fermenters and pertactin concentration and (ii) between the pertactin fluorescence spectra from the last step of purification and pertactin concentration. A third model was built using the protein content, the NAD(P)H-enzyme complex content in the fermenters and pertactin concentration. Attempts were made to identify the possible enzyme that may bind to NAD(P)H, assumed to be a dehydrogenase. Substrates for different enzymes were employed with the objective of measuring changes in the fluorescence of the characteristic peak for this binding (Ex/Em=280/460 nm). Major changes were detected after addition of the substrates oxaloacetate, ubiquinone and succinate dehydrogenase. Since changes were detected with more than one substrate, it was not possible to unequivocally identify the enzyme; however, the results provide some insight into what may be happening at the metabolic level. The work carried out in this thesis involved both analysis of samples provided or collected by the industrial sponsor as well as analysis of samples prepared at the University of Waterloo for measurement, interpretation and calibration. The proposed fluorescence-based method was found suitable for assessing protein quantity as well as for providing an indication of possible protein aggregation and conformational changes. Future work will be required to identify the exact source of variability in the production of pertactin, by means of monitoring the evolution of fermentation, NAD(P)H and ATP measurements, and oxidation redox potential assays.

Made available in DSpace on 2016-12-23T14:33:46Z (GMT). No. of bitstreams: 1 Dissertacao de Diego Barcelos Rodrigues.pdf: 434389 bytes, checksum: 1deed45ceca5ef4fe6169aeed7e5e4d5 (MD5) Previous issue date: 2011-08-29 / Spectral Graph Theory (SGT) studies graph properties by graph representation matrix and its spectrum. A property from SGT, the eigencentrality, provides an important invariant to Graph Isomorphism Problem: if two graphs are isomorphic, they have proportional eigencentralities. However, this property can not be directly used for solving the Regular Graph Isomorphism Problem (RGIP), as every regular graph has the same eigencentralities. This work presents a strategy for solving the RGIP through the use of eigencentralities to prune the search tree and restricting the possibilities for mapping / A Teoria Espectral de Grafos (TEG) busca analisar propriedades dos grafos através de matrizes representativas de grafos e seus espectros. De uma propriedade proveniente da TEG, a autocentralidade, surge um importante invariante para o Problema de Isomorfismo de Grafos: se dois grafos são isomorfos então eles possuem autocentralidades proporcionais. Porém, esta propriedade não pode ser usada diretamente para resolução do Problema de Isomorfismo de Grafos Regulares (PIGR), pois todo grafo regular possui autocentralidades iguais. Este trabalho apresenta uma estratégia para resolver o PIGR através do uso das autocentralidades para podar a árvore de busca e restringir as possibilidades de mapeamento

L’analyse en ligne et in situ constitue aujourd’hui un axe de développement stratégique pour la chimie analytique. C’est particulièrement vrai dans le domaine nucléaire pour lequel les contraintes de sécurité liées à la radioactivité des échantillons, et la nécessité de limiter au maximum les déchets issus des analyses, plaident en faveur de techniques de mesure à distance, sans prélèvement ni préparation d’échantillon. La spectroscopie d’émission de plasma créé par laser (ou LIBS pour laser-induced breakdown spectroscopy), technique d’analyse élémentaire des matériaux basée sur l’ablation laser et la spectroscopie d’émission optique, possède ces qualités. C’est donc une technique de choix pour l’analyse en ligne. Cependant, la maîtrise de la mesure est délicate pour plusieurs raisons. D’abord, la LIBS est multiparamétrique et l’effet des paramètres expérimentaux sur les performances analytiques n’est pas toujours clairement établi. Ensuite, les phénomènes physiques donnant lieu au signal LIBS sont non linéaires, couplés, et transitoires. Enfin, un système d’analyse en ligne doit être le plus robuste possible face aux variations non contrôlées des conditions de mesure. L’objectif de cette thèse est donc d’améliorer la maîtrise et les performances de l’analyse quantitative par LIBS en utilisant des méthodes multivariées capables de gérer la multidimensionalité, la non linéarité et le couplage des paramètres et des données. Pour cela, le travail se décompose en deux parties. Dans un premier temps, nous avons réalisé un plan d’expériences composite centré visant à relier les paramètres expérimentaux de l’ablation laser (énergie de l’impulsion et paramètres de focalisation du faisceau) et de la détection du signal (délai après le tir laser) aux caractéristiques physiques du plasma (masse ablatée, température) et aux performances analytiques (intensité et répétabilité du signal). L’optimisation des paramètres qui en résulte est alors interprétée comme le meilleur compromis, pour l’analyse quantitative, entre efficacité d’ablation laser et chauffage du plasma. Dans un deuxième temps, nous avons développé une méthodologie multivariée basée sur les techniques MCR-ALS, ICA et PLS, pour quantifier certains éléments dans différentes matrices métalliques en exploitant, en plus de la dimension spectrale habituelle, la dimension temporelle du signal LIBS. Cette dernière, pourtant essentielle, est généralement négligée dans la littérature. Dans cette partie, nous discutons donc de l’intérêt de cette approche par rapport aux méthodes usuelles de quantification (univariée et multivariée), et de l’apport de cette méthodologie pour diagnostiquer, comprendre et éventuellement compenser les effets de matrice observés en LIBS. / Online and in situ analysis is now a strategic development for analytical chemistry. This is especially true in the nuclear field for which the security constraints related to the radioactivity of samples, and the need to minimize waste from analyzes argue for remote measurement techniques without sampling or sample preparation. Laser-Induced Breakdown Spectroscopy (LIBS) technique for elemental analysis of materials based on laser ablation and the optical emission spectroscopy, has these qualities. It is a technique of choice for online analysis. However, the processes involved in LIBS, namely laser ablation, atomization, plasma formation and emission, are quite complex and difficult to control because the underlying physical phenomena are coupled and nonlinear. In addition, the analytical performance of the LIBS technique depends strongly on the choice of experimental conditions. Finally, an online analysis system should be as robust as possible face to uncontrolled variations in measurement conditions. The processes involved in LIBS, namely laser ablation, atomization, plasma formation and emission, are quite complex and difficult to control because the underlying physical phenomena are coupled and nonlinear. In addition, the analytical performance of the LIBS technique depends strongly on the choice of experimental conditions. The objective of this thesis is to improve control and performance of quantitative analysis by LIBS using multivariate methods capable of handling multi-dimensionality, nonlinearity and the coupling between parameters and data. For this, the work is divided into two parts. First the optimization is carried out using a central composite design to model the relationship between the experimental parameters of laser ablation (pulse energy and beam focusing parameters) and signal detection (delay time) to the physical characteristics of plasma (ablated mass, temperature) and the analytical performance (intensity and repeatability of the signal). The optimization parameters that results is then interpreted as the best compromise for the quantitative analysis between efficiency of laser ablation and plasma heating. Secondly, we developed a multivariate methodology based on MCR-ALS, ICA and PLS techniques to quantify certain elements in different metallic matrices operator, in addition to the usual spectral dimension, the time dimension of LIBS signal. In this part, we discuss the value of this approach over conventional methods of quantification (univariate and multivariate) and the contribution of this methodology to diagnose, understand and possibly compensate matrix effects observed in LIBS.

In order to extend the applications of aluminium, organic coatings may be applied on sheet materials, for instance for corrosion protection or aesthetic surface finish purposes in the automotive and construction industries, or on foil materials in the flexible packaging industry. The most common mechanisms for deterioration and structural failure of organically coated aluminium structures are triggered by exposures to the surrounding environment. Despite the great importance to elucidate the influence of exposure parameters on a buried aluminium/polymer interface, there is still a lack of knowledge regarding the mechanisms that destabilise the structure. It is generally believed that a detailed in situ analysis of the transport of corroding species to the buried interface, or of surface processes occurring therein, is most difficult to perform at relevant climatic and real-time conditions. In this work, Attenuated Total Reflection Fourier Transform Infrared Spectroscopy (ATR-FTIR) in the Kretschmann-ATR configuration was successfully applied to in situ studies of the transport of water and ionic species through polymer films to the aluminium/polymer interface upon exposure to ultra pure deionised water and to a 1 M sodium thiocyanate (NaSCN) model electrolyte. Other main processes distinguished were the formation of corrosion products on the aluminium surface and swelling of the surface-near polymer network. Hence, in situ ATR-FTIR was capable to separate deterioration-related processes from each other. To perform more unambiguous interpretations, a spectro-electrochemical method was also developed for in situ studies of the buried aluminium/polymer interface by integrating the ATR-FTIR technique with a complementary acting technique, Electrical Impedance Spectroscopy (EIS). While transport of water and electrolyte through the polymer film to the aluminium/polymer interface and subsequent oxidation/corrosion of aluminium could be followed by ATR-FTIR, the protective properties of the polymer as well as of processes at the aluminium surface were simultaneously studied by EIS. The integrated set-up provided complementary information of the aluminium/polymer sample investigated, with ATR-FTIR being sensitive to the surface-near region and EIS being sensitive to the whole system. While oxidation/corrosion and delamination are difficult to distinguish by EIS, oxide formation could be confirmed by ATR-FTIR. Additionally, while delamination and polymer swelling may be difficult to separate with ATR-FTIR, EIS distinguished swelling of the polymer network and also identified ultimate failure as a result of delamination. The capability of the integrated ATR-FTIR / EIS in situ technique was explored by studying aluminium/polymer systems of varying characteristics. Differences in water and electrolyte ingress could be monitored, as well as metal corrosion, polymer swelling and delamination. / QC 20101124

In recent years, the study of metamaterials has been a subject of much interest, with acoustic metamaterials being applied to a wide range of applications. This utility is in part due to the incorporation of various elements in their design. The addition of local resonators provides greater versatility in controlling vibrations. Nonlinear elements introduce features such as discrete breathers and frequency shift. Electromechanical metamaterials have been established to have great potential for use in simultaneous energy harvesting in addition to vibration control. Furthermore, metamaterials with quasiperiodic patterning have been shown to possess useful properties such as edge-localized modes. However, no works investigate the interaction between all these elements, especially in the nonlinear regime. In this work, we investigate a unique metamaterial with local resonators, nonlinearity, electromechanical elements, and quasiperiodicity. The proposed metamaterial is examined using both analytical and numerical techniques in order to firmly establish the effects of each element. First, a nonlinear metamaterial with electromechanical local resonators is studied using the perturbation method of multiple scales, wavepacket excitation and direct integration, and specto-spatial processing techniques. The effect of the electromechanical local resonators is established for both the linear and nonlinear regimes, notably including the addition of new bandgaps and pass bands. The influence of electrical parameters on the system dynamics is explored through parametric analysis, demonstrating their use in tuning the system response. It is also shown that nonlinear phenomena such as localized solitons and frequency shift are present in the voltage response of the electromechanical metamaterial. Next, a nonlinear metamaterial with local resonators and quasiperiodicity is investigated using the method of multiple scales as well as numerical solution of the method of harmonic balance. Topological features stemming from quasiperiodicity are observed in the linear and nonlinear regimes. The presence of local resonators is shown to result in an additional, topologically trivial bandgap. The influence of quasiperiodic parameters and the source of quasiperiodicity on the system's band structure and mode shapes are established in both the linear and nonlinear regimes. Nonlinearity is also shown to affect topological features such as edge modes, resulting in amplitude dependence that can affect the localization of these modes in the nonlinear regime. Finally, a metamaterial with nonlinearity, electromechanical local resonators, and quasiperiodic patterning is modeled and investigated. Multiple configurations are examined, including different shunt circuits coupled to the electromechanical resonators and different sources of quasiperiodic patterning. It is shown that electromechanical local resonators produce two topologically trivial bandgaps, compared to the single trivial bandgap of the purely mechanical resonator. The influence of mechanical, electrical, and quasiperiodic parameters is explored to establish the effects of these parameters on bandgap formation in the linear regime. The behavior of the metamaterial in the nonlinear regime was found to be consistent with a purely mechanical system, with no adverse effects from the presence of electromechanical elements. The impact of nonlinear and quasiperiodic phenomena on energy harvesting is also investigated. Through exploration of this unique metamaterial, it is shown that beneficial features from all elements can be present at once, resulting in a versatile metamaterial with great potential for numerous applications. / Doctor of Philosophy / In recent years, the study of metamaterials has been a subject of much interest. Despite their name, metamaterials are not homogenous materials, but engineered structures designed to possess properties not found in naturally occurring materials. Many elements can be incorporated into metamaterial design, each with its own benefits. These can range from nonlinear springs, which allow the metamaterial to behave differently as its deformation increases, to electromechanical components, which convert the motion of the metamaterial into electrical voltage. While these elements have been examined individually and in certain combinations, no works examine the combination of elements proposed in this dissertation. In this work, we investigate the impact of nonlinearity, electromechanical components, and two other beneficial elements on the system's vibration response. Combinations of these elements are examined using various analysis techniques, which are used to establish the effects of each element individually as well as their interaction when combined. Multiple variations are examined for each element, such as different types of nonlinearity or different circuits attached to the electromechanical elements. This allows us to confirm the presence of valuable features exclusive to the elements incorporated into the metamaterial. Through exploration of multiple combinations of these metamaterial elements, it is shown that beneficial features from all elements can be present at once, resulting in a versatile metamaterial with great potential for numerous applications.

Cette thèse s'inscrit dans la thématique de l'étude de la formation et de l'évolution des systèmes planétaire grâce à la méthode de l'imagerie à haut contraste, aussi appelée imagerie directe, par comparaison aux méthodes de détection dites "indirectes". Le travail que je présente dans ce manuscrit s'articule en deux parties bien distinctes. La première partie concerne la composante observationnel de ma thèse, à l'aide de l'instrument SPHERE installé au Very Large Telescope, au sein du consortium du même nom. L'instrument SPHERE a pour objectif la détection et la caractérisation de jeunes et massives exoplanètes mais également de disques circumstellaires allant des très jeune disques protoplanétaires aux disques de débris, plus âgés. Ainsi, je présente dans ce manuscrit ma contribution au programme SHINE, un grand relevé de 200 nuits dont le but est la détection de nouvelles exoplanètes ainsi que la caractérisation spectrale et orbitale des quelques compagnons déjà connus. J'y présente également les deux études de disques circumstellaires que j'ai réalisées, autour des étoiles HD 141569 et HIP 86598. La première étude ayant permis la découverte d'anneaux concentriques à quelques dizaine d'UA de l'étoile ainsi que de asymétrie dans le flux du disque inhabituelle. La seconde étude porte sur la découverte d'un disque de débris présentant également une asymétrie en flux inhabituelle. La deuxième partie concerne la composante instrumentale de mon travail de thèse, au sein du consortium MICADO, en charge de la conception de la caméra du même nom qui sera l'un des instruments de première lumière de l'Extremely Large Telescope Européen (ELT). Dans ce manuscrit, je présente l'étude que j'ai menée afin de définir le design de certain composant du mode coronographique de MICADO tout en tenant compte des contraintes de l'instrument qui n'est pas dédié à l'imagerie haut contraste, contrairement à SPHERE. / This thesis is performed in the context of the study of the formation and evolution of planetary systems using high contrast imaging, also known as direct imaging in contrast to so-called "indirect" detection methods. The work I present in this manuscript is divided into two distinct parts.The first part concerns the observational component of my thesis, using the SPHERE instrument installed at Very LargeTelescope. This work was done as part of the consortium of the same name. The purpose of the SPHERE instrument is to detect and characterize young and massive exoplanets, but also circumstellar disks ranging from very young protoplanetary disks to older debris disks. In this manuscript, I present my contribution to the program SHINE, a large survey with an integration time of 200 nights' worth of observation, the goal of which is the detection of new exoplanets and the spectral and orbital characterization of some previously-known companions. I also present the two studies of circumstellar disks that I made, around the stars HD 141569 and HIP 86598. The first study allowed the discovery of concentric rings at about ten AU of the star along with an unusual flux asymmetry in the disk. The second study is about the discovery of a debris disk that also has an unusual flux asymmetry. The second part concerns the instrumental component of my thesis work done within the MICADO consortium, in charge of the design of the camera of the same name which will be one of the first light instruments of the European Extremely Large Telescope (ELT). In this manuscript, I present the study in which I define the design of some components of the coronagraphic mode of MICADO while taking into account the constraints of the instrument - which is not dedicated to high contrast imaging, unlike SPHERE.

Il y a près d’une décennie, l'utilisation des supernovae de type Ia comme indicateurs de distances a permis de découvrir l'expansion accélérée de l'univers. Les expériences de seconde génération ont augmenté de manière significative la taille et la qualité des échantillons à grand décalage vers le rouge. Cependant, l'échantillon de référence des supernovae à faible décalage vers le rouge, nécessaire à la cosmologie restait très restreint. The Nearby Supernova Factory a mesuré, à l'aide d'un instrument spectro-photométrique dédié (the Supernova Integral Field Sepctrograph), près de 200 nouvelles supernovae de type Ia. Ma thèse de doctorat a été effectuée à l'Institut de Physique Nucléaire de Lyon et au Lawrence Berkeley National Laboratory dans le cadre du projet international the Nearby Supernova Factory et a pour but l'étalonnage spectro-photométrique du spectrographe à champ intégral. Afin d'atteindre la précision souhaitée, une attention particulière a été apportée à plusieurs aspects majeurs de la procédure d'étalonnage, incluant: la détermination de la réponse impulsionnelle de l'instrument en vue de l'extraction 3D de sources ponctuelles, l'estimation de la qualité photométrique d'une nuit, l'obtention de l'extinction atmosphérique par nuit sur un domaine de longueur d'onde étendu, sa modélisation en terme de composantes physiques et sa variabilité au cours d'une nuit donnée. Une chaîne d'étalonnage multi-standard a été mis en \oe{}uvre utilisant approximativement 4000 observations spectro-photométriques d'étoiles standards. J'exposerai également à la fin de ce manuscrit les résultats scientifiques préliminaires de la collaboration SNfactory. / Ten years ago, type Ia supernovae used as distances indicators led to the discovery of the accelerating expansion of the universe. Today, a second generation of surveys has significantly increased the high-redshift type Ia supernovae sample. The low-redshift sample was however still limiting the cosmological analysis using SNe. In this framework, the Nearby Supernova Factory has followed 200 nearby type Ia supernovae using the dedicated Supernovae Integral Field Spectrograph with spectro-photometric capacities. My PhD thesis has been carried out at the Institut de Physique Nucléaire de Lyon and at the Lawrence Berkeley National Laboratoryin the framework of the international cosmological project SNfactory. In order to reach the design spectrophotometric accuracy, attention has been focused on several key aspects of the calibration procedure, including: determination of a dedicated point spread function for 3D point source extraction, estimating the nightly photometric quality, derivation of the nightly sky extinction over the extended optical domain, its modeling in terms of physical components and its variability within a given night. A full multi-standards calibration pipeline has been implemented using approximately 4000 observations of spectrophotometric standard stars taken throughout the night over nearly 500 individual nights. Preliminary scientific results of the whole SNfactory collaboration will be presented at the end of this thesis.

La réaction de CO sur métaux est d'un grand intérêt, car il sert de système modèle pour comprendre la chimisorption et les réactions catalytiques sur les métaux. Cette thèse se place dans la démarche générale de la science des surfaces de franchir les « fossés » de pression et de materiaux pour l’étude de la catalyse. La Génération de Somme de Fréquences (SFG) est au cœur de ce travail. Elle implique un processus optique non linéaire créé par une impulsion IR qui induit une polarisation cohérente du premier ordre, convertie par une impulsion visible en une polarisation du second ordre à la fréquence somme. La SFG est utilisée pour mesurer les spectres vibrationnels de CO sur Pd nanoparticule (NP)/MgO/Ag(100) grâce à des avantages spécifiques en science de la surface de SFG : sensibilité, sélectivité de surface. Les questions posées sont les rôles possibles des sites d'adsorption qui n'existent que sur les NP, l'effet de taille des NP, l'adsorption de l'oxygène (de « normal » - chimisorption dissociative - à « sub-surface »), sur l'adsorption de CO et la réactivité catalytique, la variation de la réactivité de CO dans les différents sites lors de l'augmentation de la pression et de la température. (1) Nous avons étudié l’adsorption de CO sur Pd (100) comme une référence. En dessous d’une couverture de 0.5 ML de CO, les résultats de SFG confirment les études IRAS antérieures. Au-dessus de 0.5 ML, nous avons observé deux bandes vibrationnelles attribuées à CO dans des sites pontés « comprimés » et « non comprimés », dont nous avons mesuré la fréquence et l’intensité en fonction de la couverture, ainsi que le temps de décohérence T₂. (2) L’effet de taille des NP de Pd sur l'adsorption de CO a été observé (depuis Pd(100) à NP d’environ 300 atomes). Aux pressions ≤ 10⁻³ mbar, les spectres de CO sur une couche coalescées et sur des NP larges sont dominés par la même bande de sites pontés que sur Pd (100). La fréquence « singleton » de CO diminue avec la taille des NP, ce qui révèle l'évolution de la chimisorption avec la taille des NP. Des calculs DFT faits à l'ENS Lyon révèlent que le mécanisme principal est la contrainte induite par le substrat qui augmente la longueur de liaison Pd-Pd, favorise la rétrodonation d’électrons vers CO, affaiblit la liaison interne de CO et probablement renforce la liaison CO-métal. (3) Pour CO oxidation catalytic, les résultats suggèrent fortement que les sites pontés sont les sites clé dans la catalyse dans nos conditions expérimentales. Cependant, tandis qu'une fraction des sites pontés sont plus réactifs sur les NP, une grande fraction sont moins réactifs par rapport à Pd(100). La réactivité de CO sur les facettes (100) diminue à plus petite taille des NP. Il se dégage l’idée que la réaction procède par les sites les plus réactifs, et que les autres sites servent seulement de réservoirs en réactifs, à condition que la diffusion entre sites soit suffisamment élevée. L’oxygène modifie l'adsorption de co-réactifs. Dans le cas de CO+O/NP de Pd/MgO, au-dessus de 1 mbar, une nouvelle classe de sites linéaires apparaît, qui est probablement due à "sub-surface" oxygen. Une expérience pompe-sonde a été faite pour comparer l’effet de pompe sur les différents sites d’adsorption. Tous ces résultats confirment l'intérêt de spectroscopie vibrationnelle de SFG pour l’étude de la catalyse. Une contribution supplémentaire de cette thèse est l'étude des aspects spectro-temporels de l’émission SFG. Des spectres SFG qui contiennent plusieurs bandes sont modélisés en détail dans le cas du système modèle ODT/Au, et comparés à des spectres expérimentaux. Les spectres SFG sont affectées par la forme spectro-temporel du laser visible. La comparaison montre que l’interprétation quantitative des intensités relatives des spectres SFG obtenus avec des impulsions femtosecondes nécessite une analyse spectro-temporelle et pas seulement spectrale. La méthode de déconvolution standard utilisée dans la littérature est approximative. / The CO reaction on metals is of great interest experimentally and theoretically because it serves as a model system to understand molecular chemisorption and catalyzed reactions on metals. This thesis aims at progressing along the general trends of surface science: bridging the pressure and material gaps in the study of catalysts. Sum Frequency Generation (SFG) is at the heart of this work. It involves a nonlinear optical process with an IR pulse induced coherent first-order polarization up-converted by a visible pulse into a second-order polarization at the sum frequency. In this thesis it is used to record CO vibrational spectra on the Pd nanoparticles (NP)/MgO/Ag(100) to understand the adsorption and oxidation thanks to its specific advantages in surface science: sensitivity and surface selectivity. The questions proposed are the possible roles of the adsorption sites which only exist on the NPs, the effect of the size of NPs and the presence of oxygen on the CO adsorption and catalytic reactivity, the effect of adsorption of oxygen (from ‘normal’ – dissociative chemisorption to ‘sub-surface’), the variation of reactivity of CO in the different sites when pressure and temperature increase. (1) We have studied CO adsorption on Pd(100) as a reference. Below a CO coverage of 0.5 ML SFG results confirm previous IRAS studies. Above 0.5 ML, we have observed in much more details than previously two vibrational bands assigned to CO at compressed and uncompressed bridge sites, of which we have measured the frequency and intensity and the decoherence time T₂ as a function of coverage. (2) Pd NP size effect on CO adsorption is studied (from Pd(100) to particles with about 300 atoms). At pressures below 10⁻³ mbar the CO spectra on a coalesced layer and on large NPs are dominated by the same bridge band as on Pd(100). The CO singleton frequency decreases with coverage, revealing the evolution of chemisorption with size. DFT calculations done at ENS Lyon reveal that the main mechanism is the strain induced by the substrate which increases the Pd-Pd bondlength, favors electron back donation to CO, weakens the CO bond and probably reinforce the CO-metal bond. (3) Because of a limit of our maximal temperature, we have to study the CO catalytic oxidation in an excess of oxygen to avoid self-poisoning by CO. The results strongly suggest that bridge sites are the key sites in catalysis in our experimental condition. However, while a fraction of bridge sites are more reactive on NPs, a large fraction of them seem less reactive with respect to Pd(100). The reactivity of CO on (100) facet decreases at smaller NP size. It emerges the ideal that the reaction proceeds by the most reactive sites, and that the other sites are only reservoir in reactivity, if the diffusion between sites are high enough. Oxygen modifies the adsorption of co-reactants. In the case of CO + O / Pd NPs / MgO, below 10⁻⁴ mbar oxygen does not seem to influence significantly CO adsorption; between 10⁻³ and 10⁻¹ mbar the spectroscopic signature of CO compression disappears, and above 1 mbar a new class of a top sites appears, suggesting that some oxygen species (perhaps “subsurface”) favors CO adsorption on linear sites. A pump-probe experiment has been done to compare the effect of pump on different adsorption sites. All this confirms the interest of SFG vibrational spectroscopy for catalysis. An additional contribution of this thesis to SFG is the study of the spectro-temporal aspects of SFG emission. SFG spectra containing several bands are modeled in details based on an ODT/Au system and compared to experimental spectra, showing that in SFG spectra are affected by the spectro-temporal shape of the visible laser. The standard deconvolution method used in the literature is only approximate. Accurate spectro-temporal spectrum modeling is required to evaluate precisely the relative intensities when several bands are present.

Les galaxies centrales d'amas de galaxies constituent un environnement particulier pouvant parfois être entouré, dans le domaine optique, d'un système filamentaire complexe et étendu. L'étude de ces structures permet de mieux comprendre le phénomène de rétroaction impliqué au sein de ces galaxies et lié à la présence d'un trou noir supermassif en leur centre. La formation de jets et de bulles remplis d'émission radio conduit à réchauffer et sculpter le milieu intra-amas environnant. Ce réchauffement empêche ainsi le refroidissement du gaz intra-amas et donc la formation stellaire. Les filaments visibles dans le domaine optique ne constituent qu'une partie de la structure multiphasique qui entoure la galaxie centrale d'amas. En effet, plusieurs observations en rayons X du gaz intra-amas et radio du gaz moléculaire montrent clairement des corrélations spatiales entre toutes ces types d'émissions. Néanmoins, plusieurs points restent encore incertains concernant ces nébuleuses filamentaires. Deux modèles principaux s'opposent ainsi pour tenter d'expliquer l'origine de leur formation et le phénomène d'ionisation du gaz n'est toujours pas déterminé avec certitude. Dès lors, l'étude de la nébuleuse filamentaire entourant la galaxie centrale de l’amas de Persée, NGC 1275, au moyen d'observations à très haute résolution spectrale à l'aide de l'instrument SITELLE (Spectromètre imageur à transformée de Fourier pour l’étude en long et en large de raies d’émission), se révèle fondamentale. Ce spectromètre imageur à transformée de Fourier installé au télescope Canada-France-Hawaï dispose de caractéristiques exceptionnelles nous permettant d'étudier la nébuleuse filamentaire de NGC 1275 dans son entièreté. En effet, le champ de vue extrêmement large de SITELLE ($11' \times 11'$) ainsi que sa capacité d'atteindre de très hautes résolutions spectrales en font un atout de choix pour l'étude de telle structure. Dans ce mémoire, nous avons analysé de nouvelles observations de NGC 1275 obtenues avec SITELLE, à une très haute résolution spectrale de $R = \lambda/\Delta\lambda = 7000$. L'analyse de ces observations a permis de renouveler les cartes de vitesse, flux et dispersion en vitesse au sein de la nébuleuse filamentaire, démontrant ainsi que la région centrale semble plus dynamique qu'anticipée auparavant. De plus, grâce à la très haute résolution spectrale atteinte au sein de ces données, une analyse détaillée des raies d'émission de [SII] a pu être menée, révélant dès lors plus d'informations sur la densité du gaz au sein des filaments. L'étude de ratio de raies permet également de mieux cerner le mécanisme d'ionisation ayant lieu au sein de cette structure. Finalement, cette étude de données à très haute résolution spectrale des filaments permettra à terme d'obtenir les diagrammes BPT offrant ainsi une meilleure compréhension du phénomène d'ionisation. Une étude sera également menée sur les multiples composantes en vitesse visible localement dans la région centrale des filaments et pouvant être résolues. Enfin, ces données serviront de base pour les futures observations en rayon X de l'instrument XRISM (\textit{X-Ray Imaging and Spectroscopy Mission}). / The central cluster galaxies constitute a particular environment that can sometimes be surrounded, in the optical domain, by a complex and extended filamentary system. The study of these structures makes it possible to better understand the feedback phenomenon involved within these galaxies and linked to the presence of a supermassive black hole in their center. The formation of jets, streams and bubbles filled with radio emissions that it entails leads to heating and sculpting the surrounding intra-cluster medium. This heating thus prevents the cooling of the gas by emission and therefore the formation of stars. Thus, the filaments visible in the optical domain are only part of the multiphase structure that surrounds the central cluster galaxy. Indeed, several X-ray and radio observations clearly show spatial correlations between all these types of emissions. Nevertheless, several points still remain uncertain concerning filamentary nebulae. Two main models thus oppose each other in an attempt to explain the origin of their formation, either through precipitation or lifted up in the wake of radio bubbles, and the phenomenon of gas ionization is still not determined with certainty. Therefore, the study of the filamentary nebula surrounding the central cluster galaxy of the Perseus cluster, NGC 1275, by means of very high spectral resolution observations using the SITELLE instrument (Spectromètre imageur à transformée de Fourier pour l’étude en long et en large de raies d’émission), can yield fundamental results that will shed light on the origin and evolution of these filamentary nebulae. SITELLE is a Fourier transform imaging spectrometer installed at the Canada-France-Hawaii telescope that has exceptional characteristics allowing us to study the filamentary nebula of NGC 1275 in its entirety. Indeed, the extremely wide field of view of SITELLE ($11' \times 11'$) as well as its capacity to reach very high spectral resolutions make it an instrument of choice for the study of such structures. Here, we present the analysis of new observations of NGC 1275 taken with SITELLE at very high spectral resolution of $R = \lambda/\Delta\lambda = 7000$. The analysis of these observations has thus made it possible to produce new maps of velocity, flux and velocity dispersion within the filamentary nebula, thus demonstrating that the central region seems more dynamic than previously anticipated. In addition, thanks to the very high spectral resolution achieved within these data, a detailed analysis of the emission lines of [SII] could be carried out, revealing more information on the density of the gas within the filaments. The study of line ratios also makes it possible to better understand the ionization mechanism taking place within this structure. Finally, this study of very high spectral resolution data from the filaments will ultimately make it possible to obtain BPT diagrams, thus offering a better understanding of the ionization phenomenon. The multiple velocity components, locally visible and resolved in the central region of the filaments, will also be studied. Finally, these data will serve as a basis for future X-ray observations from the XRISM (\textit{X-Ray Imaging and Spectroscopy Mission}) instrument.