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Neste trabalho estudou-se o pós-tratamento de efluente de lagoa anaeróbia e lagoa facultativa por processo físico-químico à base de coagulação, floculação e separação sólido-líquido. A motivação principal para o desenvolvimento da pesquisa foi a dificuldade que os sistemas de lagoas de estabilização apresentam para atender aos limites de qualidade da água impostos pela Resolução Nº 357/2005 do CONAMA para os corpos receptores. Os efluentes de lagoa anaeróbia e lagoa facultativa utilizado nesta pesquisa são provenientes da Estação de Tratamento de Esgoto de Lins-SP. Para o pós-tratamento utilizou-se um sistema de fluxo contínuo, em escala piloto, de coagulação, floculação e decantação lamelar ou flotação com ar dissolvido para a separação de sólidos, determinando-se dosagens prévias de sulfato de alumínio ou cloreto férrico em ensaios em escala de laboratório. Após a escolha da dosagem a ser trabalhada em escala piloto, foram feitas seis repetições para cada dosagem, variando o tipo de efluente, o tipo de coagulante, o processo de separação sólido-líquido. Através dos processos testados foi possível remover fósforo de forma a obter-se concentração da ordem de 1,0 mg P/L. Utilizando a dosagem de 24 mg Al/L no tratamento do efluente da lagoa facultativa, este processo obteve os melhores resultados de remoção de DQO, SST, Clorofila a e coliformes, além de ter apresentado bons resultados de remoção de fósforo. O pós-tratamento físico-químico aplicado ao efluente da lagoa anaeróbia também apresentou boa eficiência na remoção de fósforo, na utilização do sulfato de alumínio tanto na flotação quanto na sedimentação atingiu valores em torno de 0,2 mg P/L. Este estudo permite ainda concluir que o tratamento do efluente da lagoa anaeróbia por processo físico-químico é mais eficiente com relação a remoção de fósforo e menos oneroso que se aplicado ao efluente da lagoa facultativa. Porém a maior eficiência na remoção de DQO e patogênicos ocorreram no pós-tratamento do efluente da facultativa. / It was studied in this paper the anaerobic and facultative pond effluent post-treatment through physico-chemical process based on coagulation, flocculation and solid-liquid separation. The main motivation to develop such research was the difficulty that the stabilization pond systems present to be in accordance with the limits of water quality imposed by Resolution number 357/2005 of Brazilian Federal Environmental Council Legislation to receiving bodies. The anaerobic and facultative pond effluents used in this survey come from Sanitary Wastewater System from Lins-SP. For post-treatment was used a continuous flow system, in a pilot scale of coagulation, flocculation and multiple-tray clarification or dissolved air flotation to separate solids, by determining previous dosages of alum or ferric chloride in experiences in laboratory scale. After the dosage choice to be worked in a pilot scale were made six repetitions for each dosage, varying the effluent type, the kind of coagulant and solid-liquid separation process. Through tested processes it was possible a phosphorus removal in order to get a concentration around 1,0 mg P/L. By making the use of 24 mg Al/L dosage on the facultative pond effluent treatment this process got the best removal results of COD, TSS, chlorophyl A and coliforms, yet having presented good results on phosphorus removal. The physico-chemical post-treatment given to anaerobic pond effluent also presented a good efficiency regarding to phosphorus removal, by using alum both in the flotation and sedimentation reached values around 0,2 mg P/L. This search also allows us to conclude that the anaerobic pond effluent treatment through physicochemical process is more efficient relating to phosphorus removal and less harmful than that applied to facultative pod effluent. But, the greatest efficiency on COD and pathogenic removal occurred in the facultative effluent post-treatment.

Neste trabalho estudou-se o pós-tratamento de efluente de lagoa anaeróbia e lagoa facultativa por processo físico-químico à base de coagulação, floculação e separação sólido-líquido. A motivação principal para o desenvolvimento da pesquisa foi a dificuldade que os sistemas de lagoas de estabilização apresentam para atender aos limites de qualidade da água impostos pela Resolução Nº 357/2005 do CONAMA para os corpos receptores. Os efluentes de lagoa anaeróbia e lagoa facultativa utilizado nesta pesquisa são provenientes da Estação de Tratamento de Esgoto de Lins-SP. Para o pós-tratamento utilizou-se um sistema de fluxo contínuo, em escala piloto, de coagulação, floculação e decantação lamelar ou flotação com ar dissolvido para a separação de sólidos, determinando-se dosagens prévias de sulfato de alumínio ou cloreto férrico em ensaios em escala de laboratório. Após a escolha da dosagem a ser trabalhada em escala piloto, foram feitas seis repetições para cada dosagem, variando o tipo de efluente, o tipo de coagulante, o processo de separação sólido-líquido. Através dos processos testados foi possível remover fósforo de forma a obter-se concentração da ordem de 1,0 mg P/L. Utilizando a dosagem de 24 mg Al/L no tratamento do efluente da lagoa facultativa, este processo obteve os melhores resultados de remoção de DQO, SST, Clorofila a e coliformes, além de ter apresentado bons resultados de remoção de fósforo. O pós-tratamento físico-químico aplicado ao efluente da lagoa anaeróbia também apresentou boa eficiência na remoção de fósforo, na utilização do sulfato de alumínio tanto na flotação quanto na sedimentação atingiu valores em torno de 0,2 mg P/L. Este estudo permite ainda concluir que o tratamento do efluente da lagoa anaeróbia por processo físico-químico é mais eficiente com relação a remoção de fósforo e menos oneroso que se aplicado ao efluente da lagoa facultativa. Porém a maior eficiência na remoção de DQO e patogênicos ocorreram no pós-tratamento do efluente da facultativa. / It was studied in this paper the anaerobic and facultative pond effluent post-treatment through physico-chemical process based on coagulation, flocculation and solid-liquid separation. The main motivation to develop such research was the difficulty that the stabilization pond systems present to be in accordance with the limits of water quality imposed by Resolution number 357/2005 of Brazilian Federal Environmental Council Legislation to receiving bodies. The anaerobic and facultative pond effluents used in this survey come from Sanitary Wastewater System from Lins-SP. For post-treatment was used a continuous flow system, in a pilot scale of coagulation, flocculation and multiple-tray clarification or dissolved air flotation to separate solids, by determining previous dosages of alum or ferric chloride in experiences in laboratory scale. After the dosage choice to be worked in a pilot scale were made six repetitions for each dosage, varying the effluent type, the kind of coagulant and solid-liquid separation process. Through tested processes it was possible a phosphorus removal in order to get a concentration around 1,0 mg P/L. By making the use of 24 mg Al/L dosage on the facultative pond effluent treatment this process got the best removal results of COD, TSS, chlorophyl A and coliforms, yet having presented good results on phosphorus removal. The physico-chemical post-treatment given to anaerobic pond effluent also presented a good efficiency regarding to phosphorus removal, by using alum both in the flotation and sedimentation reached values around 0,2 mg P/L. This search also allows us to conclude that the anaerobic pond effluent treatment through physicochemical process is more efficient relating to phosphorus removal and less harmful than that applied to facultative pod effluent. But, the greatest efficiency on COD and pathogenic removal occurred in the facultative effluent post-treatment.

La glace de mer couvre jusqu’à 6% de la surface de notre planète. Autour du continent Antarctique, sa superficie varie entre 3.8 et 19 millions de km² (en février et septembre respectivement). Cette superficie présente des variations interannuelles. En parallèle, une évolution de la superficie de la glace de mer a également pour origine le réchauffement climatique global, très médiatisé à l’heure actuelle. Dans ce contexte, et étant donné le rôle que joue la banquise au sein de l’Océan Austral, des études de l’évolution de la glace de mer sont devenues fondamentales. Ce travail a pour objectif d’étudier les relations complexes qui existent entre les processus chimiques, physiques et biologiques qui se déroulent au sein de la glace de mer. La détermination des propriétés physiques et de la composition chimique des glaces de mer correspond en effet à un pré-requis indispensable à l’étude des cycles géochimiques qui existent dans la banquise. Différentes glaces de mer, naturelles ou artificielles, ont été analysées. Pour ce faire, les caractéristiques spécifiques à ce type de glace font que des méthodes d’analyse de la composition en gaz particulières ont été nécessaires. Nous avons ainsi pu montrer que le contenu et la composition en gaz des différentes glaces analysées dépendent de facteurs physico-chimiques et de facteurs biologiques. L’impact des facteurs physico-chimiques se marque lors de l’incorporation initiale des impuretés dans la glace de mer et via une diffusion "post-génétique" tant que la glace est plus chaude que –5°C. En outre, les organismes photosynthétiques sont à l’origine d’une production d’oxygène et d’une consommation de dioxyde de carbone. La composition en gaz résultante peut donc être sensiblement différente de la composition atmosphérique ou de celle des gaz dissous dans l’eau de mer sous-jacente, en été comme en hiver. Il s’agit par conséquent de sérieusement envisager l’impact potentiel de la glace de mer et des microorganismes qu’elle contient, lors du réchauffement et de la débâcle, sur les échanges entre atmosphère et océan comme sur leurs compositions respectives.

Les nanotechnologies sont en pleine expansion et leurs propriétés remarquables ouvrent la voie à des applications très variées intéressant la science des matériaux comme la nanomédecine. Cependant cet essor fulgurant doit s’accompagner d’interrogations justifiées sur les risques sanitaires pour l’homme et l’environnement compte tenu de leur potentielle toxicité biologique. Dans ce contexte le travail de cette thèse porte sur l’amélioration de la compréhension des mécanismes d’internalisation de particules au niveau cellulaire. Pour cela plusieurs types de micro- et nanoparticules fluorescentes de physico-chimie contrôlée (taille et groupements de surface) ont été synthétisés. Des contacts ont ensuite été établis avec une lignée cellulaire in vitro de macrophages (RAW 264.7) qui représente une cible préférentielle de l’organisme au niveau des moyens de défense. Différentes méthodologies de quantification en cytométrie en flux et fluorimétrie ont été développées dans le but de distinguer précisément les nanoparticules internalisées de celles adhérées au niveau des membranes. Des techniques complémentaires de microscopie confocale et MEB/MET ont été mises au point afin de mieux visualiser leur localisation intracellulaire. Enfin, pour nos diverses conditions expérimentales, une étude de l’activité biologique des particules a été évaluée sur la base des paramètres de réaction inflammatoire, d’altération membranaire et de stress oxydant. Ainsi, la première partie de ces travaux a concerné la mise au point d’une méthodologie de quantification de l’internalisation de particules fluorescentes microscopiques. Ensuite nous avons développé un modèle de nanoparticules doublement fluorescentes sensibles aux variations de pH permettant une quantification plus ciblée du processus de phagocytose. Enfin la dernière partie s’est attachée à étudier spécifiquement l’impact de la taille des nanoparticules sur leur internalisation. / Nanotechnologies are in full extension and the remarkable properties showed by nanomaterials pave the way for a variety of applications such as materials science or nanomedicine. However, this rapid expansion must be accompanied by justified interrogations about human’s health risks or impact on the environment because of their potential biological toxicity. In this context, this thesis aimed at improving the understanding of the cellular internalization mechanisms of particles. Different types of fluorescent micro- and nanoparticles with well-controlled physico-chemistry (size and surface groups) were synthesized. The contacts were established with an in vitro macrophage cell line (RAW 264.7), which represents the first line target cells in the human defense mechanisms. Different methodologies to accurately quantify and distinguish internalized nanoparticles from those just adhering to cell membranes were developed using flow cytometry and fluorimetry. Complementary confocal microscopy and SEM/TEM techniques were carried out to better visualize nanoparticles intracellular localization. Finally, for each experimental condition tested, the biological activity of the particles was evaluated in terms of inflammatory response, membrane alteration and oxidative stress. Thus, the first part of this work allowed the development of a methodology to quantify fluorescent microscopic particles internalization. Then a model of double fluorescent nanoparticles sensitive to pH variations was developed in order to quantify more precisely the phagocytic process. Finally the last part aimed at evaluating the impact of the size of the nanoparticles on their internalization.

Au cours d’un incendie dans une installation nucléaire de base (INB), les filtres à très haute efficacité (THE) sont colmatés par un dépôt (ou « gâteau ») de suies (des agrégats de nanoparticules carbonées). L’effet de l’humidité, observée au niveau du gâteau de suies par la présence d’un condensat, n’est pas encore pris en compte dans les modèles de colmatage développés dans la communauté scientifique. Dans ce contexte, la présente étude vise à mieux comprendre le phénomène de sorption de l’eau sur les suies. Pour ce faire, des suies dites « analytiques » ont été produites avec différents combustibles isolés, ceci à différentes teneurs en dioxygène, et des suies « d’incendie » ont été produites à partir d’essais de feux à grande échelle, ceci à différentes ventilations et avec des combustibles réalistes (boîte à gants, câbles électriques, huile hydraulique). Les propriétés physico-chimiques de ces suies (morphologie, porosité, surface spécifique, composition chimique et élémentaire) ont été déterminées parallèlement à l’obtention des isothermes de sorption d’eau, pour des suies sous forme de pastilles et de poudres non tassées. Les paramètres obtenus avec le modèle Dubinin-Serpinski pour une première catégorie de suies hydrophobes ont permis de proposer une modélisation pertinente des isothermes caractéristiques des suies analytiques. Par ailleurs, les isothermes de sorption de l’eau sur des gâteaux de suies dites hydrophiles et essentiellement issues de combustibles et situations réelles d’incendie, ont été modélisées à l’aide de l’équation de D’Arcy et Watt (DW). Pour cette seconde catégorie de suies, les paramètres du modèle DW apparaissent relativement dispersés, comparés à ceux obtenus pour les suies analytiques. Cette relative dispersion s’explique par des propriétés très variables des suies d’incendie et notamment par la présence importante d’oxygène et d’halogènes (chlore, phosphore). Cette étude a donc permis de mettre en évidence une adsorption plus importante pour les suies d’incendie, conduisant à la condensation capillaire, cette dernière étant favorisée pour les suies sous forme de pastilles. In-fine, la composition chimique et élémentaire des suies apparaît ainsi comme le paramètre prépondérant du phénomène de sorption de l’eau sur les suies / During a fire in a nuclear plan, the high efficiency particle air (HEPA) filters are clogged by a deposit (or “cake”) of soot, the latter corresponding to carbonaceous nanoparticles aggregates. The effect of humidity, observed on the filters by the presence of condensed water, is still not considered in the clogging models developed in scientific community. In this context, the aim of this study consists on a better understanding of the water sorption on the soot. The experimental approach was first the production of “analytical” soot with different isolated fuels and at different dioxygen concentrations, and of “fire” soot at large scale with different ventilations and complex elements (glove boxes, electrical cables, hydraulic oil). The physicochemical properties (morphology, porosity, specific surface area, elemental and chemical composition) and the water sorption isotherms, for samples at compacted pellet and powder state, have been determined. The parameters from the model of Dubinin-Serpinski, obtained for a first class of hydrophobic soot, enabled to propose a relevant model, characteristic of the analytical soot. Furthermore, water sorption isotherms on soot cake, coming from realistic fires and fuels, have been modeled with the D’Arcy and Watt (DW) equation. For this second class of hydrophilic soot, the DW parameters appear relatively more dispersed. This relative dispersion is due to the different properties of the fire soot and especially to the presence of high amounts of oxygen and halogens (chlorine, phosphor). This study enabled to highlight a more significant water adsorption on fire soot, leading to the capillary condensation, which is favored for soot compacted into pellet. Soot chemical a and elemental composition appeared to be the most influencing parameter on water sorption phenomenon

No presente trabalho, realizado conjuntamente na Universidade e na Indústria, foi feita a investigação dos catalisadores isopropóxido de alumínio e Aliso B na reação de etoxilação de álcool laurílico, com o objetivo de obter produtos com distribuição estreita de oligômeros. Os experimentos foram realizados em escala piloto e foram investigadas a influência da temperatura, da concentração de catalisador e da relação molar entre ácido (promotor) e catalisador no processo. Todos os estudos tiveram caráter comparativo, tomando como base a reação e os produtos gerados a partir do uso de hidróxido de potássio que é o catalisador mais amplamente empregado para esse tipo de preparação industrial. Primeiramente foi estudada a forma de carregamento do reator, determinando e otimizando seu modo de operação. A partir desses dados, avaliou-se a influência da temperatura na taxa de consumo de óxido de etileno, na distribuição de oligômeros do produto e na formação de glicol como subproduto. Também foi avaliada a influência da concentração de catalisador e relação molar promotor:catalisador na taxa de consumo de óxido de etileno e formação de glicoI. As avaliaçãoes foram feitas para as reações de etoxilação gerando produtos com grau de etoxilação 2, 3, 4 e 6 mols de óxido de etileno. Através dos resultados foram estabelecidas as melhores condições de processo, considerando as limitações de processo dos reatores industriais para gerar o produto desejado. / In the present work, developed in an association between University and Industry, different catalysts were evaluated, such as aluminum isopropoxide and Aliso B, for ethoxylation of laurilic alcohol, aiming to obtain narrowly distributed oligomers. The experiments were carried out in a pilot plant and the influence of temperature, catalyst concentration and molar relationship between acid (promoter of the reaction) and catalyst were evaluated. All the evaluations made were comparative, using for comparison the reaction and the products generated when potassium hydroxide is used as catalyst, which is commonly the case in industry. Initially we studied the charging of the reactional vessel in order to determine and optimize operational procedures. Then, we evaluated the influence of temperature on the ethylene oxide consumption rate, the oligomer distribution and the generation of glycol as a byproduct. We also evaluated the influence of catalyst concentration and molar relation of promoter : catalyst on the ethylene oxide consumption rate and on the generation of glycol. The evaluations were made for the ethoxylation reactions generating products with ethoxylation grades of 2, 3, 4 and 6 moles of ethylene oxide. Through the results, we have optimized processing conditions, considering the process limitations of industrial vessels for the generation of the desired product.

Ce travail concerne la préparation et la caractérisation des systèmes moléculaires photocommutables multifonctionnels incorporant l'unité photochrome diméthyldihydropyrène/cyclophanediène (DHP/CPD) et leur mise en œuvre dans des matériaux et dispositifs.Un dérivé DHP tétrasubstitué par des unités pyridinium, étudié en solution, possède des propriétés exploitables de photocommutation d'absorption, de fluorescence et de communication électronique intramoléculaire. La coordination axiale de certains dérivés de type DHP-pyridyle à une entité métallique porphyrinique améliore les propriétés de photoisomérisation du système photochrome par rapport à celles des ligands libres correspondants. D'autre part, l'association du motif DHP à des complexes métalliques contenant la terpyridine confère au système résultant des propriétés rédox supplémentaires. Parmi les deux familles de complexes élaborés, les systèmes à pont pyridinium reliant le noyau DHP au complexe métallique présentent des propriétés de commutation exploitables pour la conception d'un système quadristable rédox- et photocommutable. Ces systèmes modèles ont été insérés dans une architecture macromoléculaire de type polymère de coordination photocommutable élaboré en solution ou immobilisé sur une surface. Les films assemblés autour du complexe de Zn2+ présentent des propriétés de conductance commutables suivant l'état de l'unité photochrome. Des nanotubes de carbone fonctionnalisés par des dérivés DHP substitués par un groupement pyridinium-CH2-pyrène constituent des nouveaux nanomatériaux photo- et thermocommutables. Enfin, un film mince comportant une unité DHP greffée sur ITO, constitue un générateur de 1O2 à la demande. En présence d'oxygène moléculaire, le dérivé DHP joue le rôle de sensibilisateur de 3O2 et subit une réaction de photooxygénation. L'espèce photogénérée sous forme de CPDO2 libère thermiquement 1O2. / This work deals with the design of molecular multifunctional photoswitchable systems incorporating dimethyldihydropyrene (DHP) photochromic unit and with their implantation and characterization in switchable devices.We show that a tetra pyridinium-appended DHP derivative displays interesting photoswitchable optical properties, emission and excitation fluorescence and electronic communication. Combining DHP pyridine-substituted ligand with porphyrin complex via axial coordination enhances the photoinduced DHP ring-opening reaction. Additionally, associating photoresponsive DHP unit with electron-responsive transition metal complexes confers additional redox properties to the resulting hybrid system. The DHP core photo-isomerization proceeds much more efficiently when the metal complexes and the DHP moiety are connected through pyridinium-bridge vs phenyl bridge. The resulting systems are used for the conception of new multi-addressable photo- and redox- switches. These assemblies are applied for the design of photoswitchable coordination polymers developed in solution or immobilized onto ITO. Photochromic films based on Zn2+ exhibit conductance properties that can be tuned optically and thermally according to the photostate of the photochromic unit. The DHP core associated with a pyrene entity and immobilized onto carbon nanotube electrode via -stacking acts as a switchable material. Finally, we report the possibility of controlling 1O2 production by light irradiation or by heating, of an ITO surface functionalized by pyridinium-substituted DHP derivatives. In the presence of dioxygen, this DHP derivative plays the role of an O2 sensitizer. The photogenerated 1O2 reacts with the open-ring isomer to afford the corresponding endoperoxyde species which then releases 1O2 thermally.

No presente trabalho, realizado conjuntamente na Universidade e na Indústria, foi feita a investigação dos catalisadores isopropóxido de alumínio e Aliso B na reação de etoxilação de álcool laurílico, com o objetivo de obter produtos com distribuição estreita de oligômeros. Os experimentos foram realizados em escala piloto e foram investigadas a influência da temperatura, da concentração de catalisador e da relação molar entre ácido (promotor) e catalisador no processo. Todos os estudos tiveram caráter comparativo, tomando como base a reação e os produtos gerados a partir do uso de hidróxido de potássio que é o catalisador mais amplamente empregado para esse tipo de preparação industrial. Primeiramente foi estudada a forma de carregamento do reator, determinando e otimizando seu modo de operação. A partir desses dados, avaliou-se a influência da temperatura na taxa de consumo de óxido de etileno, na distribuição de oligômeros do produto e na formação de glicol como subproduto. Também foi avaliada a influência da concentração de catalisador e relação molar promotor:catalisador na taxa de consumo de óxido de etileno e formação de glicoI. As avaliaçãoes foram feitas para as reações de etoxilação gerando produtos com grau de etoxilação 2, 3, 4 e 6 mols de óxido de etileno. Através dos resultados foram estabelecidas as melhores condições de processo, considerando as limitações de processo dos reatores industriais para gerar o produto desejado. / In the present work, developed in an association between University and Industry, different catalysts were evaluated, such as aluminum isopropoxide and Aliso B, for ethoxylation of laurilic alcohol, aiming to obtain narrowly distributed oligomers. The experiments were carried out in a pilot plant and the influence of temperature, catalyst concentration and molar relationship between acid (promoter of the reaction) and catalyst were evaluated. All the evaluations made were comparative, using for comparison the reaction and the products generated when potassium hydroxide is used as catalyst, which is commonly the case in industry. Initially we studied the charging of the reactional vessel in order to determine and optimize operational procedures. Then, we evaluated the influence of temperature on the ethylene oxide consumption rate, the oligomer distribution and the generation of glycol as a byproduct. We also evaluated the influence of catalyst concentration and molar relation of promoter : catalyst on the ethylene oxide consumption rate and on the generation of glycol. The evaluations were made for the ethoxylation reactions generating products with ethoxylation grades of 2, 3, 4 and 6 moles of ethylene oxide. Through the results, we have optimized processing conditions, considering the process limitations of industrial vessels for the generation of the desired product.

Les plastiques sont devenus les matériaux les plus utilisés pour la préservation de denrées alimentaires. Malgré leurs nombreux avantages (transparence, prix, modularité, propriété barrière aux gaz), leur imperméabilité à l’oxygène doit être sans cesse améliorée afin d’éviter aux denrées de subir diverses réactions d’oxydation et ainsi prolonger leurs durées de conservation. Pour cela, une solution envisageable consiste à combiner à des polymères, des catalyseurs métalliques pour piéger l’oxygène. Cette possibilité a été étudiée dans cette thèse. Après un premier chapitre introductif, le deuxième décrit les propriétés physico-chimiques des différents catalyseurs métalliques sélectionnés (stabilité, constantes de protonation, constante de complexation envers le cobalt(II) et le manganèse (II), capacité d’oxygénation, électrochimie). Le troisième chapitre est consacré à leur utilisation en tant qu’oxydant métallique de substrats organiques. Enfin le quatrième et dernier chapitre présente une étude à l’état solide de l’oxydation de polymères en présence de catalyseurs métalliques. Une large part de ce dernier chapitre a été consacrée à la caractérisation des produits d’oxydation. / Plastics are becoming the most used material for food and drinks preservation. Despite their numerous advantages (transparency, price, modularity, gas barrier property), their oxygen barrier properties have to be improved to avoid hazardous oxidation reactions to foods and drinks and so to increase their shelf-life. One alternative to solve this problem is to combine polymers and metal catalysts to scavenge oxygen. This possible strategy was investigated during this Ph.D. project. After a first introductive chapter, the second depicts the physico-chemical properties of selected metal catalysts (stability, protonation constants, complexation constants towards cobalt(II) and manganese(II), oxygenation capacity, electrochemistry). The third chapter is devoted to their use as powerful oxidant of organic substrate. Finally, the last chapter is dedicated to a solid-state study of polymer oxidation in the presence of metal catalysts. A large part of this last chapter has been devoted to the thorough elucidation of the nature/structure of the oxidized product(s).