O objetivo deste trabalho é o estudo das condições de existência e a determinação da concentração da molécula H2 em diferentes condições típicas de nebulosas planetárias, dentro da região ionizada. Para este cálculo, desenvolvemos sub-rotinas computacionais que se acoplam ao código de fotoionização unidimensional Aangaba que, até agora, somente considerava espécies atômicas (H, He, C, N, O, Mg, Ne, Si, S, Ar, Cl e Fe) e seus íons. Inserimos nesse código os equilíbrios químico e de ionização envolvendo a molécula H2 e os demais compostos de hidrogênio, H-, H2+, H3+, além do H, H+ e dos elétrons que o código de fotoionização Aangaba já considerava em sua forma original. A molécula H3 não é considerada por ser instável. Levamos em conta 41 diferentes mecanismos de formação e destruição desses compostos do hidrogênio. Destacamos particularmente o efeito da reação de formação de H2 na superfície de grãos na produção global dessa molécula em nebulosas planetárias, considerada na literatura como a rota mais importante de formação dessa molécula no meio interestelar. Para isso, estudamos a possibilidade da sobrevivência de grãos dentro da região ionizada da nebulosa planetária. Analisamos também a influência das propriedades da estrela central e da densidade do gás, assim como das propriedades dos grãos astrofísicos, na concentração de H2. Demonstramos que quantidades significativas de H2 podem sobreviver dentro da região ionizada de nebulosas planetárias, principalmente na região de recombinação do hidrogênio. A concentração de H2 relativa à densidade total de H alcança valores de até 1E-4 e a razão entre a massa de H2 e a massa total de H da NP chega a valores de 4E-4. Verificamos que a razão entre a massa de H2 e a massa de H total da nebulosa aumenta significativamente com o aumento da temperatura de estrela central. Essa maior quantidade de H2 em nebulosas planetárias com estrela central mais quente pode explicar porque é mais comum encontrar emissão da molécula H2 em nebulosas planetárias com estrutura bipolar (regra de Gatley), já que nebulosas com esse tipo morfológico têm estrela central tipicamente mais quente. Na literatura, o valor 6,9E-5 é obtido para a razão entre a massa de H2 e a massa de H total da nebulosa planetária NGC 6720, a partir de dados observacionais. Usando os mesmos parâmetros deste artigo, calculamos com o código de fotoionização Aangaba o valor de 3,3E-5, que está razoavelmente próximo do valor da literatura. / The goal of this work is the study of the H2 molecule survival and the determination of its abundance in different typical planetary nebulae conditions inside the ionized region. In order to do these calculations, we developed Fortran subroutines for the Aangaba one-dimensional photoionization code that, until this work, only took into account the atomic species (H, He, C, N, O, Mg, Ne, Si, S, Ar, Cl, and Fe) and their ions. Ionization and chemical equilibria of H, H+, H-, H2, H2+, and H3+ are assumed. The H3 molecule is not included because it is unstable. Fortyone different reactions that could form and destroy these species are taken into account. Reaction on grain surfaces, the most important mechanism for the production of H2 molecules in the interstellar medium, is analyzed in detail in the conditions of planetary nebulae ionized regions. We make a careful analysis of the grain survival in these regions. We also study the influence of the central star properties and gas density, as well as the astrophysical grain properties in the obtained H2 concentration. It is shown that a significant concentration of H2 can exist inside the ionized region of planetary nebulae, mostly in the recombination zone. The H2 concentration relative to the total hydrogen concentration reaches values as high as 1E-4 and the H2 mass to total hydrogen mass ratio inside the ionized region reaches values as high as 4E-4. The ratio increases with increasing temperature. This fact can explain why the H2 emission is more often observed in bipolar planetary nebulae (Gatley?s rule), since this kind of object has typically hotter stars. In the literature a H2 mass to total hydrogen mass ratio equal to 6.9E-5 is estimated from observations for the planetary nebula NGC6720. With the same input parameters for the gas density and the stellar spectrum, we calculated a ratio equal to 3.3E-5, close to the observed value.

In this work, a unicycle system with reaction wheel is presented, considering the construction, the modeling, the design and test of the controllers. Firstly, a mechanical model considering a tridimensional computer aided design (3D CAD) is built in order to assist the construction and, after that, the modeling using the Lagrange method. In this work, linear controllers are designed and, therefore, the linearization of the system is done by the Jacobian, that is, assuming small variations around the equilibrium point. In this situation, there is no coupling between the pitch and the roll angles, thus resembling two inverted pendulums. The prototype is constructed by attaching the electronic components, the battery, the wheels and the motors to a body, to make it fully autonomous. The positioning of the parts has to balanced in order to maintain the position of the center of mass along the vertical and horizontal axis of symmetry. Then, a linear control project is done to stabilize the plant using two techniques that are validated considering simulations of the nonlinear coupled system. Then, the techniques were tested in the built prototype. The first one consists of the optimal LQR control that, although it worked, presented some problems due to parametric uncertainties. Therefore, the H2 control is used via LMI in such a way that the project becomes similar to the LQR, but in this way it is possible to insert parametric uncertainties and find a controller with some degree of robustness to them. / Neste trabalho, é apresentado um sistema de um monociclo com roda de reação, mostrando desde a construção, passando pela modelagem até o projeto e teste dos controladores. Primeiramente, é feito o projeto mecânico por meio de um desenho assistido por computador tridimensional (3D CAD), para auxiliar a construção e, em seguida, a modelagem por meio do método de Lagrange. Naturalmente, o sistema é não linear e os ângulos de arfagem e rolamento são acoplados. Neste trabalho, controladores lineares são projetados e, portanto, a linearização do sistema é feita pelo Jacobiano, ou seja, assumindo pequenas variações em torno do ponto de equilíbrio. Nesta situação, o modelo desacopla os ângulos de arfagem e rolamento. O protótipo é construído fixando os componentes eletrônicos, a bateria, as rodas e os motores a um corpo, de forma a ser totalmente autônomo. O posicionamento das peças precisa ser equilibrado, de forma a manter a posição do centro de massa ao longo dos eixos de simetria vertical e horizontal. Em seguida, é feito um projeto de controle linear para estabilização da planta usando duas técnicas que são validadas via simulações do sistema não linear acoplado. Depois, as técnicas são testadas no protótipo construído. A primeira consiste do controle ótimo LQR que, apesar de ter funcionado, apresentou alguns problemas devidos a incertezas paramétricas. Logo, é usado o controle H2 via LMI, de tal forma que o projeto equivalha ao LQR, mas desta forma é possível inserir incertezas paramétricas e achar um controlador com algum grau de robustez a elas.

Artificial photosynthesis utilises solar-light for clean fuel H2 production and is emerging as a potential solution for renewable energy generation. Photocatalytic systems that combine a light harvester and catalysts in one-pot reactor are promising strategies towards this direction. Yet, most of the reported systems function by consuming excess amount of expensive sacrificial reagents, preventing commercial development. In this thesis, carbon nitrides (CNx) have been selected as non-toxic, stable and low-cost photocatalysts. CNx are first introduced as efficient light harvesters, to couple alcohol oxidation with proton reduction, in the presence of a Ni-based molecular catalyst. This system operated in a single compartment while the oxidation and reduction products were collected in the solution and gaseous phases, respectively, demonstrating a closed redox system. In the presence of an organic substrate and absence of a proton reduction catalyst, photoexcited CNx was found to accumulate long-lived "trapped-electrons", which enables decoupling oxidation and reduction reactions temporarily and spatially. This allows solar H2 generation in the dark, following light exposure, replication light and dark cycle of natural photosynthesis in an artificial set-up. The stability of the designed system was found to be limited by the Ni-based molecular catalyst, and the spectroscopic studies revealed electron transfer from CNx to catalyst as the kinetic bottleneck. Graphene based conductive scaffolds were introduced to the CNx-Ni system, to accelerate the rate of electron transfer from CNx to the Ni catalyst. Time-resolved spectroscopic techniques revealed that introducing these conductive binders enabled better electronic communication between CNx and Ni, resulting in significantly enhanced photocatalytic activity. To improve the solar-light utilisation and the photocatalytic performance of bulk CNx, a straightforward ultra-sonication approach was introduced. This pre-treatment was found to break aggregates of bulk CNx, and the resulting activated CNx had significantly improved activity. The activated CNx showed record activities per gram of the material used, for H2 evolution with a molecular Ni catalyst. The use of abundant waste sources instead of organic substrates was investigated in the presence of activated CNx. The system demonstrated to photoreform purified and raw lignocellulose samples into H2 in the presence of various H2 evolution catalysts over a wide range of pH.

O sistema histaminérgico no sistema nervoso central (SNC) apresenta funções que modulam o aprendizado e consolidam a memória. O objetivo foi estudar o efeito da histamina através dos receptores histaminérgico (H1 e H2) na reconsolidação da memória discriminativa na região CA1 do hipocampo de ratos. Foram utilizados 153 ratos Wistar submetidos à cirurgia exterotáxica para implantação de cânulas guia na região CA1 do hipocampo. Os animais foram habituados por quatro dias consecutivos no campo aberto durante 20 minutos. Na sessão de treino os ratos foram expostos a dois diferentes objetos (A e B) por 5 min. Após 24h (reativação), um dos objetos foi trocado para um novo (objeto C), e os ratos foram reexpostos no campo aberto por 5 min. Imediatamente após, os animais receberam infusões bilaterais intra-CA1 dos agonistas/antagonistas histaminérgicos. O teste da reconsolidação da memória discriminativa foi realizado na tarefa de reconhecimento de objetos (RO). Os dados foram expressos pela média ± erro padrão da média para o teste de t-student para p<0,05 de significância. Foi realizado 3 dias, 7 dias ou 10 dias após a sessão de reativação. Resultados:Nossos dados mostraram que 3 dias após a infusão tanto os grupos salina (56.69 ± 4,651) quanto o grupo histamina (61.10 ± 4,712) exploraram mais o objeto novo (D) em relação ao objeto familiar. Em 7 dias após a reativação os animais tratados com histamina (55.96 ±7,022) exploraram mais o objeto (D) em relação ao objeto familiar, comparados aos salina (39.40 ± 4,845) p< 0,01. No teste do dia 10 não houve mais diferença estatística entre os grupos p>0.05. O SKF 91488 mostrou que o aumento da histamina endógena induz a melhora a memória discriminativa quando testados 7 dias (57.60 ± 5.210) comparado ao salina (48.09 ± 7.582) para p<0,001. O agonista H2 Dimaprit (56.14 ± 7.425) também melhorou a memória discriminativa comparado à salina (49.04 ± 9, 309) p < 0,05. O mesmo não ocorreu com o agonista H1 Piridiletiletanolamina (52.93 ± 8.946) e o grupo salina (49.04 ± 9,309). Nas coinfusões os antagonistas e histamina, os animais que receberam Pirilamina + histamina (56.41 ± 6.694) e histamina (60.04 ± 10.16) obtiveram uma taxa exploratória maior do objeto novo comparado a os animais que receberam Ranitidina + histamina (51.06 ±7.238) e o salina (47.04 ± 4.718) que tiveram a memória bloqueada com significância de p<0.05. As doses utilizadas nas infusões intra- CA1 bilaterais foram de (1μl) de salina, Histamina 10mM/μl, SKF 91488 50mM/μl, os agonistas Piridiletiletanolamina (PEA) e Dimaprit nas doses de 10mM/μl e os antagonistas Pirilamina e Ranitidina nas doses de 50mM/μl. De acordo com os dados obtidos neste estudo pode-se concluir que a histamina infundida na região CA1 do hipocampo dorsal de ratos imediatamente após a reativação melhora a memória discriminativa na tarefa de RO via receptor do tipo H2. / The histaminergic system in the central nervous system is involved in the regulation of learning and memory. Therefore, the aim of this study was to investigate the effects of histamine through histaminergic receptors activation (H1,H2) in discriminative memory reconsolidation in rat hippocampal region CA1. Wistar male rats (n= 154) were used to investigate whether histamine itself or receptor-selective histamine agonist and antagonist given into the CA1 region of this hippocampus immediately post-reactivation can affect the object recognition test (RO) performance. Our results showed an improve in RO test performance seven days after memory reactivation caused by histamine and SKF-98144 infusion. The same test ten days after memory reactivation not show difference between saline and histamine group. H1 agonist did not improve discriminative memory in RO. The enhancing effect of histamine was blocked by the H2 receptor antagonist, ranitidine, but not by the H1 receptor antagonist, pyrilamine. The present results suggest that histamine infusion in rat hippocampal region CA1 post-activation improves discriminative memory in RO trough H2 receptor.

O hidrogênio (H2) tem sido considerado uma fonte de energia limpa bastante promissora, pois sua combustão origina apenas moléculas de água, sendo uma alternativa ao uso de combustíveis fósseis. Entretanto, os métodos atuais de produção de H2 demandam matérias-primas finitas e uma grande quantidade de energia, tornando a sua obtenção não sustentável. Mais recentemente, a via fermentativa tem sido considerada para a produção de H2, utilizando como matérias-primas efluentes industriais, materiais lignocelulósicos e biomassa de algas, denominado de bio-hidrogênio de primeira, segunda e terceira geração, respectivamente. Neste trabalho foi isolada uma bactéria anaeróbia a partir de uma cultura mista (lodo) de um sistema de tratamento de vinhaça, após pré-tratamento do lodo a pH 3 por 12 horas. Este microrganismo foi identificado com 99% de similaridade como Clostridium beijerinckii com base na sequência do gene RNAr 16S denominado de C. beijerinckii Br21. A temperatura e o pH mais adequados para o crescimento e produção de H2 por esta cultura foi 35 °C e pH inicial 7,0. A bactéria possui a capacidade de utilizar ampla variedade de fontes de carbono para a produção de H2 por fermentação, especialmente, monossacarídeos resultantes da hidrólise de biomassa de algas, tais como glicose, galactose e manose. Foram realizados ensaios em batelada para a produção de H2 com a bactéria isolada empregando diferentes concentrações de glicose e galactose, visando a sua futura utilização em hidrolisados de alga. Os parâmetros cinéticos dos ensaios de fermentação estimados pelo modelo de Gompertz modificado, como a velocidade máxima de produção (Rm), a quantidade máxima de hidrogênio produzido (Hmáx) e o tempo necessário para o início da produção de hidrogênio (fase lag) para a glicose (15 g/L) foram de: 58,27 mL de H2/h, 57,68 mmol de H2 e 8,29 h, respectivamente. Para a galactose (15 g/L), a Rm, Hmáx e foram de 67,64 mL de H2/h, 47,61 mmol de H2 e 17,22 horas, respectivamente. O principal metabólito detectado ao final dos ensaios de fermentação, foi o ácido butírico, seguido pelo ácido acético e o etanol, tanto para os ensaios com glicose, como com galactose. C. beijerinckii é um candidato bastante promissor para a produção de H2 por fermentação a partir de glicose e galactose e, consequentemente, a partir de biomassa de algas como substratos. / Hydrogen (H2), considered an alternative to fossil fuels, is a promising source of clean energy because its combustion originates water molecules only. However, the current H2 production methods require finite raw materials and a large amount of energy, which makes them unsustainable. The fermentative pathway has been considered for H2 production from renewable raw materials such as industrial wastewater, lignocellulosic materials, and algal biomass, the so-called first, second, and third bio-hydrogen generation, respectively. In this work, after pre-treatment at pH 3 for 12 h, a H2-producing bacterium was isolated from a mixed culture (sludge) collected from an anaerobic bioreactor used to treat sugarcane vinasse. The microorganism was identified as Clostridium beijerinckii based on the sequence of the 16S rRNA gene; it was named C. beijerinckii Br21. The most appropriate temperature and initial pH to achieve H2 production by this strain was 35 °C and 7, respectively. The bacterium was able to use a wide variety of carbon sources, especially the monosaccharides glucose, galactose, and mannose resulting from hydrolysis of algal biomass. Batch assays using different concentrations of glucose and galactose were performed to produce H2. The kinetic parameters of the tests were estimated by the Gompertz modified model. The maximum production rate (Rm), the maximum amount of produced H2 (Hmáx), and the phase lag () for glucose and galactose, both at 15 g/L, were 58.27 and 67.64 mL of H2/h, 57.68 and 47.61 mmol of H2, and 8.29 and 17.22 h, respectively. The main metabolite detected at the end of fermentation tests was butyric acid, followed by acetic acid and ethanol. The results indicated that the new C. beijerinckii isolate is a promising candidate for fermentative H2 production from algal biomass.

Metal-organic materials (MOMs) represent a unique class of porous materials that captured a great scientific interest in various fields such as chemical engineering, physics and materials science. They are typically assembled from metal ions or metal clusters connected by multifunctional organic ligands. They represent a wide range of families of materials that varied from 0D to 3D networks: the discrete (0D) structures exemplified by metal-organic polyhedra (MOPs), cubes and nanoballs while the polymeric 1D, 2D and 3D structures exemplified by coordination polymers (CPs). Indeed, the porous 3D structures include metal-organic frameworks (MOFs), porous coordination polymers (PCPs) and porous coordination networks (PCNs). Nevertheless, MOMs are long and well-known from more than 50 years ago as exemplified by CPs that were firstly introduced in early 1960s and reviewed in 1964. However, the scientific interest toward MOMs has been enormously grown only since late 1990s, with the discovery of MOMs with novel properties, especially the high permanent porosity as exemplified by MOF-5 and HKUST-1. The inherent tunability of MOMs from the de novo design to the post-synthetic modification along with their robustness, afford numerous important families of nets "platforms" such as pcu, dia, tbo, mtn and rht topology networks. There are more than 20,000 crystal structures of MOMs in the Cambridge Structure Database (CSD). However, only a few of the networks can be regarded as families or platforms where the structure is robust, fine-tunable and inherently modular. Such robustness and inherent modularity of the platforms allow the bottom-up control over the structure "form comes before function" which subsequently facilitates the systematic study of structure/function in hitherto unprecedented way compared with the traditional screening approaches that are commonly used in materials science. In this context, we present the crystal engineering of two MOM platforms; dia and novel fsc platforms as well we introduce the novel two-step synthetic approach using trigonal prismatic clusters to build multinodal 2D and 3D MOM platforms. For the dia platform, we introduce a novel strategy to control over the level of the interpenetration of dia topology nets via solvent-template control and study the impact of the resulting different pore sizes on the squeezing of CH4, CO2 and H2 gases. New benchmark material for methane isosteric heat of adsorption was produced from this novel work. Indeed we introduce the crystal engineering of a novel versatile 4,6-c fsc platform that is formed from linking two of the longest known and most widely studied MBBs: the square planar MBB [Cu(AN)4]2+( AN = aromatic nitrogen donor) and square paddlewheel MBB [Cu2(CO2R)4] that are connected by five different linkers with different length, L1-L5. The resulting square grid nets formed from alternating [Cu(AN)4]2+ and [Cu2(CO2R)4] moieties are pillared at the axial sites of the [Cu(AN)4]2+ MBBs with dianionic pillars to form neutral 3D 4,6-connected fsc (four, six type c) nets. Pore size control in this family of fsc nets was exerted by varying the length of the linker ligand whereas pore chemistry was implemented by unsaturated metal centers (UMCs) and the use of either inorganic or organic pillars. 1,5-naphthalenedisulfonate (NDS) anions pillar in an angular fashion to afford fsc-1-NDS, fsc-2-NDS, fsc-3-NDS, fsc-4-NDS and fsc-5-NDS from L1-L5, respectively. Experimental CO2 sorption studies revealed higher isosteric heat of adsorption (Qst) for the compound with the smaller pore size (fsc-1-NDS). Computational studies revealed that there is higher CO2 occupancy about the UMCs in fsc-1-NDS compared to other extended variants that were synthesized with NDS. SiF62- (SIFSIX) anions in fsc-2-SIFSIX form linear pillars that result in eclipse [Cu2(CO2R)4] moieties at a distance of just 5.86 Å. The space between the [Cu2(CO2R)4] moieties is a strong CO2 binding site that can be regarded as being an example of a single-molecule trap; this finding has been supported by modeling studies. Furthermore, we present herein the implementation of the two-step synthetic approach for the construction of novel multinodal MOM platforms, using the trigonal prism cluster [M3(µ3-O)(RCO2)6] as a precursor to build novel stable multinodal 2D and 3D frameworks. In the first step, the bifunctional carboxylate ligands are reacted with Fe+3 or Cr+3 salts to isolate highly symmetrical decorated trigonal prismatic clusters with diverse decoration such as pyridine, amine and cyano coordinating functional groups using pyridine carboxylate, amino carboxylate, cyano carboxylate type ligands, respectively. Afterward, the isolated highly soluble trigonal prismatic salts were reacted in the second step with another metal that can act as node or linker to connect the discrete trigonal prismatic clusters to build 2D or 3D networks. Indeed, we were able to develop another novel high-symmetry Cu cluster [Cu3(µ3-Cl)(RNH2)6Cl6] by utilizing CuCl2 salt and amine decorated trigonal prismatic cluster. Two novel 3D water stable frameworks with acs and stp topologies have been afforded. Our work on the crystal engineering design and synthesis of new MOM platforms offer an exceptional level of control over the resulting structure including; the resulting topology, pore size, pore chemistry and thereby enable the control over the resulting physicochemical properties in a manner that facilitates the achieving of the desired properties.

Parmi les différentes structures de l'univers existe ce qu'on appelle le milieu interstellaire (MIS). C'est un endroit où gaz et poussière co-existent et interagissent en parfaite harmonie. L'hydrogène moléculaire est l'espèce la plus abondante et de loin la plus importante du gaz interstellaire. Elle est à la base de trois sur quatre des molécules les plus essentielles à l'apparition de la vie : l'eau, le méthane, l'amine et le monoxyde de carbone. La physico-chimie du MIS qui mène à la formation de nouvelles molécules est divisée en deux : les réactions en phase gazeuse et les réactions sur les grains de poussière qui s'est révélée la voie de formation la plus efficace pour l'hydrogène moléculaire. Ce travail de thèse est une contribution expérimentale à l'étude de l'interaction et de la formation de l'hydrogène moléculaire sur les surface de glace d'eau amorphe qui couvrent les grains de poussière dans les nuages sombres du MIS. Dans ce but, en réunissant techniques ultravides, systèmes cryogéniques, jets atomiques et moléculaires, spectrométrie de masse et modélisation, plusieurs expériences ont été faites en utilisant le dispositif FORMOLISM (FORmation of MOLecules in the InterStellar Medium).

La formation de H2 dans le milieu interstellaire, à partir de deux atomes H, est une question essentielle en astrophysique. Cette réaction exothermique qui a lieu à la surface d'un grain de poussière interstellaire est la première étape d'une suite de réactions primordiales pour la physico-chimie. Dans les nuages diffus et les régions de photodissociation, on invoque pour mécanisme de formation une réaction de catalyse hétérogène Eley Rideal, un des atomes étant chimisorbé. Les grains sont principalement carbonés et constitués notamment de graphite. Les travaux théoriques antérieurs effectués en géométrie réduite n'ont pas permis d'expliquer la formation de H2 dans les états rovibrationnels observés (v<5). Pour prendre en compte les degrés de liberté de tous les atomes, nous avons conçu à partir du potentiel de Brenner, un nouveau potentiel pour modéliser le système graphène-H-H avec lequel nous avons réalisé une étude de dynamique moléculaire classique de la formation de H2. Cette étude a été effectuée pour des énergies de collision d'atomes H incidents de 0.015eV à 0.2eV et pour des surfaces à 0, 10 et 30K. Un des résultats principaux est que la section efficace de réaction est directement reliée à l'allure du potentiel que voit l'atome H incident. De plus, il a été mis en évidence que la distribution rovibrationnelle obtenue en autorisant la relaxation de la surface correspond mieux à celle observée par les astrophysiciens (v < 6), la surface absorbant ~25% de l'énergie disponible. Des travaux étudiant l'influence de la présence d'un atome H supplémentaire sur la surface ou d'une possible structure poreuse des grains, sur la formation de H2, sont présentés en annexe.

Les systèmes implicites (dits aussi " descripteurs ") peuvent décrire des processus régis à la fois par des équations dynamiques et statiques et permettent de préserver la structure des systèmes physiques. Ils comportent trois types de modes : dynamiques finis, infinis (réponse temporelle impulsive (en cas continu) ou acausale (en cas discret)) et statiques. Dans le cadre du formalisme descripteur, les contributions de cette thèse sont triples : i) revisiter des résultats existants pour les systèmes d'état, ii) étendre certains résultats classiques au cas des systèmes implicites, iii) résoudre rigoureusement des problèmes de commande non standard. Ainsi, le présent mémoire commence par revisiter les résultats concernant la caractérisation LMI stricte de la dissipativité, les caractérisations de l'admissibilité et des performances H2 ou H∞ par LMI étendues et les équations de Sylvester et de Riccati généralisées. Il aborde dans un deuxième temps, le problème de stabilisation simultanée, avec ou sans critère H∞, à travers l'extension de certains résultats récents au cas des systèmes implicites. La solution proposée s'appuie sur la résolution combinée d'une équation algébrique de Riccati généralisée (GARE) et d'un problème de faisabilité sous contrainte LMI stricte. Il traite enfin des problèmes H2 et H∞ non standards : i) en présence de pondérations instables voire impropres, ii) sous contraintes de régulation; dans le cas des systèmes implicites. Ces dernières contributions permettent désormais de traiter rigoureusement, sans approximations ou transformations, de nombreux problèmes H2 ou H∞ formalisant des problèmes pratiques de commande, dont ceux faisant intervenir une pénalisation haute fréquence de la commande ou un modèle interne instable des signaux exogènes.

En m'appuyant sur des mesures atmosphériques et à l'aide de la modélisation, je propose une nouvelle estimation du bilan du dihydrogène troposphérique (H2). Pendant mon stage de master, j'ai installé un chromatographe en phase gazeuse pour analyser les concentrations de H2 et CO sur les échantillons du réseau RAMCES. L'analyse des mesures in-situ à Gif-sur-Yvette permet d'estimer le dépôt de H2 dans le sol de cette région (0.027 cm s−1) et le ratio H2/CO (0.5) provenant des émissions dues au transport automobile. La haute tour de Trainou située près de la forêt d'Orléans (100 km au sud-ouest de Paris) a été instrumentée en octobre 2008 pour H2 et CO à trois hauteurs de prélèvement (50, 100 et 180 m), en mai 2009 pour 222Rn à 180 m et en avril 2010 pour 222Rn à 50 m. Avec trois hauteurs de prélèvement, les masses d'air locales à régionales sont échantillonnées. L'infl uence du traffi c n'est pas visible mais pendant l'hiver on observe des évènements pendant lesquels les concentrations de H2 et CO sont fortement corrélées. La vitesse moyenne de dépôt estimée avec la même méthode qu'à Gif-sur-Yvette atteint 0.026 cm s−1. Dans la partie modélisation, les mesures de la concentration de H2 au sein des réseaux RAMCES et EUROHYDROS ont été utilisées dans le système LMDz-SACS-PYVAR. Ce système permet d'optimiser l'estimation quantitative du bilan de H2 : le modèle de transport atmosphérique LMDz est couplé avec le système de chimie simpli fiée SACS et intégré dans le système d'inversion PYVAR. Plusieurs scénarios, impliquant la séparation progressive des sources et puits de H2 ont été testés pour optimiser les flux de H2 à l'échelle globale et européenne. La meilleure estimation du dépôt global de H2 atteint 59 ± 5 Tg an−1.