This dissertation focuses on the assessment and development of heterogeneous catalysts for the deperoxidation of cyclohexyl hydroperoxide and oxidation of cyclohexane, which will be based in metal oxides and gold nanoparticles. For this endeavour a multidisciplinary approach will be used combining theoretical chemistry, kinetic studies and synthesis and characterisation of materials. The starting choice for the catalyst to carry out the process is supported gold nanoparticles. The approach of this dissertation is to first model the mecha- nism of cyclohexyl hydroperoxide decomposition and oxidation of cyclohexane on gold nanoparticles by theoretical calculations, and use these findings to synthesise efficient heterogeneous catalysts which will be subsequently tested and optimised experimentally. But as it will be seen, some metal oxides are active rather than acting as mere supports, which will also be studied both theoretical and experimentally. Each chapter has a specific focus and constitutes a strand of the overall goal: Chapter 1 provides an introductory background on the topics that this dissertation lies upon: oxidation of cyclohexane, heterogeneous catalysis and catalysis by gold and metal oxides. Chapter 2 outlines the objectives of the thesis, formulating the relevant hypotheses of this research and the subsequent validation tests. Chapter 3 exposes the methodology with a brief conceptual background that has been used to carry out this work. Chapter 4 is the first chapter dealing with results. It consists in a theoretical study using density functional theory of the reaction mechanism over different models of gold nanoparticles, in order to study the influence of several parameters on their catalytic activity: the particle size, atom coordination, and presence of additional species like oxygen atoms and water. Chapter 5 uses the findings found in chapter 4 to drive the synthesis of supported gold nanoparticles. It consists in a experimental study of gold-based catalysts, which is combined with a theoretical study which takes into account an additional variable: the support. Chapter 6 exploits one of the findings of chapter 5. One of the supports used for anchoring the gold nanoparticles is active by itself, namely cerium oxide. This chapter comprises an experimental work about its activity, studying parameters like particle size, morphology and the effect of doping. Chapter 7 continues with the catalytic activity of cerium oxide-based materials, but now from a theoretical point of view. It first presents a systematic study of the parameters relevant for the proper quantum mechanical description of cerium oxide, which is followed by a mechanistic study on different models. Chapter 8 outlines the conclusions obtained in this dissertation, present- ing them in a summarised way. Even though each chapter presents its corresponding conclusions at its end, this chapter groups them all in a structured way for the reader's convenience, so a global view of the project can be swiftly grasped. The results herein further the knowledge of heterogeneous catalysis for the oxidation of cyclohexane, one of the most important industrial reactions, and which continues to be a challenge. Although the ultimate goal is to develop an industrial catalyst, the dissertation also aims to show how computational chemistry can drive the design of novel materials, and how it can help to understand catalytic reactions at the atomic level. / El presente trabajo se centra en el estudio y desarrollo de catalizadores heterogéneos para la desperoxidación de ciclohexil hidroperóxido y la oxidación de ciclohexano, basados en óxidos metálicos y nanopartículas de Au. Para lograr tal objetivo se ha usado un enfoque multidisciplinar, que combina química teórica y estudios cinéticos, a la vez que síntesis y caracterización de materiales. El candidato inicial para llevar a cabo el proceso consiste en partículas de Au soportadas. El camino a seguir pasa primero por modelizar el mecanismo de descomposición de ciclohexil hidroperóxido y oxidación de ciclohexano mediante cálculos teóricos, y utilizar el conocimiento generado por este estudio para dictar la síntesis de catalizadores heterogéneos, comprobando y optimizando posteriormente su actividad de forma experimental. Sin embargo, como será visto a lo largo de este trabajo, algunos óxidos metálicos dejan de lado su papel como mero soporte físico para las partículas de Au y son activos por sí mismos. Tal hecho será estudiado tanto teórica como experimentalmente. Cada capítulo tiene un objetivo específico, y es a su vez una parte del objetivo global de esta investigación: El capítulo 1 provee al lector de una breve introducción a los temas sobre los que yace este trabajo: oxidación de ciclohexano, catálisis heterogénea y catálisis mediante Au y óxidos metálicos. El capítulo 2 expone de una forma breve y concisa los objetivos de esta investigación, formulando la hipótesis de partida y los correspondientes experimentos para su validación. El capítulo 3 describe la metodología utilizada junto a una explicación de los fundamentos en los que se basa cada técnica. El capítulo 4 es el primer capítulo que discute los resultados obtenidos en esta investigación. Se trata de un estudio usando la teoria del funcional de densidad para investigar el mecanismo de reacción del proceso sobre diferentes modelos teóricos de Au, con el objetivo de comprender la influencia de diversos factores en la actividad catalítica, tales como el tamaño de partícula, la coordinación de los á'tomos de Au y la presencia de especies adicionales como átomos de O y agua. El capítulo 5 hace uso de los resultados obtenidos en el estudio anterior, y los utiliza para dirigir la síntesis de nanopartículas soportadas de Au. Se trata de un estudio experimental en el que se investigan diversos factores que pueden afectar a su actividad catalítica. Este estudio se combina a su vez con uno de tipo teórico en el que se tiene en cuenta la influencia del soporte en la actividad catalítica de las particulas de Au. El capítulo 6 se basa en uno de los resultados obtenidos en el capítulo 5. Uno de los soportes utilizados para anclar las partículas de Au resulta de por sí activo: el CeO2. Su notable actividad para catalizar este proceso exige un estudio en mayor profundidad, el cual se lleva a cabo en este capítulo. Parámetros como el tamaño de particula, la morfología de superficie y el dopaje entre otros se investigan en este punto. El capítulo 7 sigue la estela del trabajo anterior sobre CeO2, pero ahora desde el punto de vista de la química teórica. Presenta primero un estudio sistemático de parámetros relacionados con la mecánica cuá'ntica que afectan al CeO2, con el objetivo de alcanzar una descripción satisfactoria de los modelos teóricos para este óxido. Tras esto, se lleva a cabo un estudio del mecanismo de reacción en dichos modelos de CeO2, a fin de comprender el origen de su actividad catalítica. El capítulo 8 presenta de forma estructurada y concisa todas las conclusiones que se han sacado a raíz de los resultados obtenidos. Aún a pesar de que cada capítulo presenta sus correspondientes conclusiones al final, aquí se presentan de una forma agrupada a comodidad del lector, para que pueda obtener de forma ágil una visión global de los resultados de esta investigación. / Aquest treball es centra en l'estudi i desenvolupament de catalitzadors hetero- genis per a la desperoxidació de ciclohexil hidroperòxid i la oxidació de ciclohexà, basats en òxids metàl·lics i nanopartícules de Au. Per aconseguir aquest objectiu s'ha utilitzat un enfocament multidisciplinari, en el qual es combinen química teòrica i estudis cinètics amb síntesi i caracterització de materials. El candidat inicial per dur a terme el procés consisteix en partícules de Au suportades. El camí a seguir passa primer per modelitzar el mecanisme de descomposició del ciclohexil hidroperòxid i la oxidació de ciclohexà mitjançant càlculs teòrics, i utilitzar el coneixement generat per aquest estudi per dirigir la síntesi de catalitzadors heterogenis, comprovant i optimitzant posteriorment la seua activitat de forma experimental. No obstant això, com es veurà al llarg d'aquest treball, alguns òxids metàl·lics deixen de costat el seu paper com a suport físic de les partícules de Au y són actius per si mateixos. Aquest fet s'ha estudiat tant teòrica com experimentalment. Cada capítol té un objectiu específic i és al mateix temps una part de l'objectiu global d'aquesta recerca: El capítol 1 proporciona al lector una breu introducció als temes tractats en aquest treball: oxidació de ciclohexà, catàlisi heterogènia i catàlisi mitjançant Au i òxids metàl·lics. El capítol 2 exposa d'una forma breu i concisa els objectius d'aquesta investigació, formulant la hipòtesi inicial i els corresponents experiments per a la seua validació. El capítol 3 descriu la metodologia utilitzada conjuntament amb una explicació dels fonaments en els quals es basa cada tècnica. El capítol 4 és el primer capítol que discuteix els resultats obtinguts en aquesta investigació. Es tracta d'un estudi usant la teoria del funcional de densitat per investigar el mecanisme de reacció del procés en diferents models teòrics de Au, amb l'objectiu de comprendre la influència en l'activitat catalítica de diversos factors, com ara la grandària de partícula, la coordinació dels àtoms de Au i la presencia d'espècies addicionals, com àtoms de O i aigua. El capítol 5 fa ús dels resultats obtinguts en l'estudi anterior, i els utilitza per dirigir la síntesi de nanopartícules suportades de Au. Es tracta d'un estudi experimental en el qual s'investiguen diversos factors que poden afectar a la seua activitat catalítica. Aquest estudi es combina amb un altre de caràcter teòric en el qual es té en compte la influència del suport en la activitat catalítica de les partícules de Au. El capítol 6 es basa en un dels resultats obtinguts en el capítol 5. Un dels suports utilitzats per fixar les partícules de Au resulta de per si actiu: el CeO2. La seua notable activitat per catalitzar aquest procés demana un estudi de major profunditat, el qual es duu a terme en aquest capítol. Paràmetres com la grandària de partícula, la morfologia de superfície i el dopatge, entre altres, s'investiguen en aquest punt. El capítol 7 continua l'estudi anterior sobre el CeO2, però ara des del punt de vista de la química teòrica. Presenta en primer lloc un es- tudi sistemàtic de paràmetres relacionats amb la mecànica quàntica que afecten al CeO2, amb l'objectiu d'aconseguir una descripció satisfactòria pels models teòrics d'aquest òxid. Després, es duu a terme un estudi del mecanisme de reacció en aquests models de CeO2, a fi de com- prendre l'origen de la seua activitat catalítica. El capítol 8 presenta de forma estructurada i concisa totes les conclusions que s'han extret arran dels resultats obtinguts. Encara que cada capí- tol presenta les seues corresponents conclusions al final, ací es presenten d'una forma agrupada per a la comoditat del lector, per què puga obtindre de forma àgil una visió global dels result d'una forma agrupada per a la comoditat del lector, per què puga obtindre de forma à / López Auséns, JT. (2016). From Quantum Mechanics to Catalysis: Studies on the oxidation of alkanes by gold and metal oxides [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/76806

<p dir="ltr">Aromatic phosphonates and phosphine oxides are highly desirable synthetic targets used in pharmaceuticals, natural products, agrichemicals, catalysis, and materials science. While a variety of aromatic precursors have been used to access these motifs, aryl halides remain one of the most desirable coupling partners owing to their low cost, commercial availability, and regioselective reactivity. Traditional phosphonation often requires the use of harsh reductants in the presence of liquid ammonia, which are caustic and pose incredible environmental concerns. Milder, transition metal-catalyzed approaches have been developed, but can be limited by air sensitivity, cost, low reaction selectivity, and low functional group compatibility. Photoredox catalysis has been significantly advanced in the past decade in the pursuit of greener, more sustainable avenues to facilitate desirable reaction transformations under mild conditions. These methods most commonly use a dual catalytic strategy in which a metal is paired with an organocatalyst. While these approaches enable facile phosphonation of a variety of aromatic precursors, the metals and organocatalysts used are often expensive and toxic. Indeed, there remains unexplored chemical space for transition metal-free photoredox-catalyzed aryl C-P bond formations. Herein, we present a series of transition metal-free, photoredox-catalyzed approaches to the phosphonation of aryl halides. The approaches and mechanistic works will be discussed in the following order: </p><p dir="ltr">First, the discovery that 10<i>H</i>-phenothiazine (PTZ) enables the transition metal-free phosphonation of aryl halides using trialkyl phosphites will be presented. PTZ serves as a photocatalyst capable of reducing the aryl halide to access aryl radicals, which readily couple with phosphite esters. This transformation exhibits broad functional group tolerance in good to excellent yields. Then, photoredox catalysis by PTZ enables the formation of unsymmetrical aromatic phosphine oxides using triphenylphosphine (PPh₃) and aryl halides. This is the first work in which PPh₃ has been used as the starting material, and the reaction proceeds via the alkaline hydrolysis of quaternary phosphonium salts. The final work exhibits novel photocatalytic activity of <i>N</i>-heterocyclic carbenes (NHC) to activate aryl halides, form aryl radicals, and enable phosphonation. This method displays broad functional group tolerance under mild conditions and highlights its untapped synthetic utility as a photocatalyst.</p>

The effects of climate change have made the need to develop sustainable production practices for biofuels and other chemicals imminent. The development of the green economy has also led to many industries voluntarily improving the sustainability of the products they produce. The microbial production of fatty acid-derived chemicals allows for the opportunity to reduce petroleum-based chemicals in the marketplace. However, for microbial produced chemicals to be industrially competitive, significant work is needed to improve the production capacity of industrial strains. There are a number of bottlenecks and challenges related to the production of various fatty acid derivatives that need to be addressed. One of these key challenges relates to the source of the fermentation feedstock. While sources such as corn or sugar cane are currently common, these feedstocks compete with food supply and require nutrient-rich soils. The use of lignocellulosic feedstocks is preferred to combat this issue, however these feedstocks present their own unique challenges. Pretreatment is required to release fermentable sugars, and this process also results in various fermentation inhibitors released into the solution. A better understanding of how engineered strains utilize these fermentable sugars as well as improving resistance to the inhibitors will help to improve the chemical production capacity of these chemical products. This work will focus on describing key bottlenecks related to fatty acid-derived products, while also evaluating proposed solutions to these bottlenecks. / Master of Science / Currently, many common household products and plastics are developed using petroleum-based components. From plastic bottles to common cosmetics, these contain ingredients that are derived from petroleum. In order to combat our reliance on petroleum for these every day products, it is essential to develop alternate sources for these materials. A potential source involve using plant material and by-products to produce these same compounds that we are able to produce from petroleum. While there has been significant research to produce useful products such as bioethanol from corn, this is not an ideal crop. Corn requires more water and space than other crops such as grasses. In addition, these grasses can grow in soil that food crops are unable to grow in, so we don’t utilize valuable land to develop common household products. However, these grasses are much more difficult to treat and process in order to form these basic chemical ingredients. In order to use grass-based crops, it is possible to engineer organisms such as yeast to process the raw material into valuable chemical precursor. This work aims to genetically engineer yeast in order to produce some of these chemical precursors from a grass-like feedstock. In addition, this work also analyzes how physical characteristics of yeast affect the final product formation. Finally, a model was developed to show how yeast ferments corn-like and grass-like feedstocks differently.

Un nouveau procédé d'extraction des huiles essentielles a été développé, mis au point et optimisé nommé «Vapo-diffusion Assistée par Micro-ondes (MSDf)». Le procédé MSDf à été appliqué à l'extraction des huiles essentielles des peaux d'oranges et de fleurs de lavande. Ce procédé est basé sur la combinaison d'une technique d'extraction classique : l'hydro-diffusion et le chauffage micro-ondes comme technologie d'intensification. Une deuxième nouvelle approche pour l'extraction des huiles essentielles à partir de matrices aromatiques sèches et sans ajout de vapeur ni d'eau nommé «Diffusion à sec générée par micro-ondes (MDG)». Le procédé MDG à été appliqué à l'extraction des huiles essentielles des graines de carvi. Le MSDf et le MDG apparaissent comme des procédures «douces» permettant un gain de temps et d'énergie considérable et la diminution des rejets de CO2 dans l'atmosphère / Microwave steam diffusion (MSDf) was developed as a cleaner and new process design and operation for isolation of essentials oils and was compared to conventional steam diffusion (SDf). This green process has been applied and tested using two aromatic matrixes: fresh orange peels and dry lavender flowers. This process is based on the combination of a traditional technique of extraction: hydro-diffusion and the microwave irradiation energy. Without adding any steam or water, we proposed also a novel and green approach for extraction of secondary metabolites from dried plant materials. This “steam and water free” approach based on a simple principle involves the application of microwave irradiation and earth gravity to extract the essential oil from dried caraway seeds. MSDf and MDG were better than SDf in terms of energy saving, cleanliness and reduced waste water

Cette thèse porte sur la mise en œuvre de procédés innovants d'extraction de composés naturels bioactifs de plantes. Nous avons considéré ici l'extraction d'un composé anti-oxydant, l'acide rosmarinique, à partir du végétal mélisse (Melissa officinalis L.), qui contient également d'autres composés d'intérêt (citral et caryophyllène). Différentes techniques d'extraction-purification, soit à haute pression (extraction au CO2 supercritique) ou à pression atmosphérique (extraction Soxhlet, extraction batch, nanofiltration etc.) ont été envisagées. L'objectif de ce travail a été d'étudier expérimentalement l'influence des paramètres opératoires (débit, composition et concentration du solvant, taille des particules, pression et température) sur la cinétique des processus afin de sélectionner les meilleures conditions pour chaque opération. Les résultats expérimentaux ont été ensuite comparés avec plusieurs modèles mathématiques décrivant les phénomènes de transfert de masse et l'écoulement au travers du milieu poreux constitué par la matière végétale broyée. Cette démarche, à partir de la détermination des paramètres physiques du modèle, a fourni les éléments pour une extrapolation potentielle à l'échelle industrielle. Du point de vue du procédé complet d'extraction-purification, l'originalité du travail a été de proposer plusieurs scénarii d'enchainement d'opérations, couplant en synergie des opérations conventionnelles à pression atmosphériques (macération, nano-filtration etc.) et des opérations de traitement au CO2 supercritique avec co-solvant. / This thesis deals with the extraction of natural bioactive compounds from plants (case study with Lemon Balm (Melissa officinalis L.)) by using different separation techniques at high (supercritical extraction) and atmospheric pressure (Soxhlet extraction, batch extraction, nanofiltration etc.). The influence of main operational parameters (solvent composition and flow rate, particle size of the raw material, pressure, temperature) on the process kinetics is studied experimentally with the aim to determine appropriate operational conditions for better extraction. The experimental results are confronted to a number of mathematical models in order to estimate the applicability of different theoretical concepts to the particular process and to select and apply appropriate models for determination of important parameters, characterizing the mass transfer process and necessary for scale-up and design purposes. Coupling between different separation methods is also considered and a number of integrated process schemes are proposed resulting in better yield of the targeted compounds.

Ce mémoire porte sur la synthèse de matériaux composites nanostructurés à base de polyoxométallates pour la conversion de l’énergie et des applications à des problèmes environnementaux. Pour atteindre ces objectifs, de nombreux composés nouveaux de cette famille d’oxydes moléculaires ont été synthétisés puis ont été associés à différentes matrices éco-compatibles dans le respect des principaux critères de la Chimie Verte. Les principales techniques d’étude sont l’électrochimie, la photochimie et la spectroscopie UV-visible. Dans le domaine de l’énergie, les catalyseurs obtenus se sont révélés très efficaces dans des réactions très importantes mais difficiles à réaliser, comme la production de l’hydrogène, la réduction de l’oxygène et l’oxydation de l’eau. De même, parmi les applications aux problèmes de dépollution, ces nanomatériaux ont montré une forte activité électrocatalytique et photocatalytique pour la réduction des oxydes d’azote, des bromates et la photodégradation d’un colorant textile toxique, l’Acide Orange 7. Les performances de ces nouveaux catalyseurs sont comparables à celles des meilleurs systèmes connus. / This thesis focuses on the synthesis of nanostructured composite materials based on polyoxometalates for energy conversion and applications to environmental problems. To achieve these goals, many new compounds of this family of molecular oxides were synthesized and were associated with different nature friendly matrices, in agreement with the main criteria of Green Chemistry. In the field of energy, the new catalysts have proved very effective in important but difficult to achieve reactions, such as producing hydrogen, oxygen reduction or water oxidation. Similarly, among applications to pollution problems, these nanomaterials have shown a strong electrocatalytic and photocatalytic activity for the reduction of nitrogen oxides, bromate and for the photodegradation of a toxic textile dye, Acid Orange 7. The performances of these new catalysts are comparable to those of the best known systems.

Dióxido de carbono supercrítico (scCO2) é um solvente pouco eficiente para substâncias polares em geral. Uma maneira interessante de superar esta limitação e explorar todo o seu potencial como solvente verde, possível substituto para os solventes orgânicos voláteis comuns, é a introdução de tensoativos específicos para scCO2 no sistema. No presente trabalho, foram sintetizadas três novas séries de tensoativos oxigenados para scCO2. As moléculas possuem cabeças CO2-fóbicas mono e poli-hidroxiladas, em sua maioria à base de açúcares, e três tipos de cadeias CO2-fílicas, duas delas perfluoradas (-C7F15 e -C9F19) e uma peracetilada (derivada do ácido D-glucônico). Foram investigadas as suas solubilidades e comportamentos de fase em CO2 e em sistemas ternários (água-CO2-tensoativo), bem como a atividade na interface CO2-água. Todos eles dispersaram água em scCO2 com [água] / [tensoativo] (W) igual a 10, exibindo pressões de névoa comparáveis àquelas do sistema \"a seco\". Adicionalmente, os tensoativos reduziram a tensão interfacial CO2-água. O efeito das cabeças CO2-fóbicas e cadeias CO2-fílicas nessa redução pôde ser analisado separadamente. Os resultados dos experimentos de tensão interfacial dinâmica sugerem que tanto a difusão das moléculas da fase contínua para a subinterface, quanto a sua inserção e migração na interface contribuem para o decaimento das tensões interfaciais. / Supercritical carbon dioxide (scCO2) is a poor solvent for polar substances in general. An interesting way to overcome this limitation and fulfill its potential as a green solvent, a possible substitute for common volatile organic solvents, is the introduction of scCO2-suitable surfactants in the system. In the present work, three series of novel oxygenated surfactants for scCO2 were synthesized. The amphiphiles contain mono and poly-hydroxylated CO2-phobic heads, most of them sugar-based, as well as three types of CO2-philic tails, two of them perfluorinated (-C7F15 and -C9F19) and one peracetylated (D-gluconic acid derivative). Their solubilities and phase behaviors in CO2 and in ternary systems (water-CO2-surfactant), as well as their activities at the CO2-water interface, were investigated. All of them dispersed water in scCO2- with water-to-surfactant ratio (W) of 10, exhibiting cloud pressures comparable to those of \"dry\" systems. Also, the surfactants reduced the CO2-water interfacial tension. The effect of both the CO2-phobic heads and the CO2-philic tails could be analyzed separately. Dynamic interfacial tension results suggest that both diffusion from bulk CO2 to subinterface and insertion and migration of molecules within the interface contribute to the time-dependent decay of the interfacial tensions.

Através do uso de reagentes ambientalmente corretos, foram desenvolvidos métodos mais simples que os tradicionais para obtenção de diversos tipos de nanopartículas de magnetita (MagNP) funcionalizadas. Em todos os casos foi confirmado um comportamento superparamagnético consistente com a presença de monodomínios magnéticos de Fe3O4, com diâmetros médios de partícula inferiores a 100 nm, além de histerese nula acima de 280 K, Tb=90K em H=500 Oe e magnetização de saturação em torno de 90 emu g-1. Os métodos de síntese das MagNP foram conduzidos em solventes derivados do biodiesel de soja/mamona, em substituição ao insumos importados, permitindo uma redução significativa nos custos de produção desse tipo de nanomaterial, e viabilizando sua produção em larga escala. Os nanomateriais foram voltados inicialmente para captura, separação e reciclagem de insumos e produtos químicos, incluindo poluentes, catalisadores e enzimas, utilizando ímãs externos. Os procedimentos desenvolvidos proporcionaram uma alternativa verde para os processos convencionais que fazem uso extensivo de solventes, geram muito descarte, e utilizam processos com alta demanda de energia, como centrifugação, extração por solventes e filtração sob altas pressões. As MagNP foram especialmente projetadas para serem dispersas em diversos meios polares e apolares, de acordo com o tipo de funcionalização química na superfície, utilizando principalmente moléculas orgânicas anfifílicas capazes de se ligar na superfície do Fe3O4 por meio de grupos polares, e com matrizes carbonáceas por meio de interações hidrofóbicas. Dessa forma foram gerados novos nanomateriais superparamagnéticos incorporando diversos tipos de matrizes que foram testadas para a remoção de óleo e de compostos orgânicos responsáveis por odores e cores indesejadas em efluentes industriais, bem como para a captura, transporte, recuperação, análise de espécies metálicas ou orgânicas. Foram testadas janelas ópticas e displays nos quais a intensidade de luz transmitida ou refletida pode ser modulada com ímãs externos. O projeto, financiado pela PETROBRÁS contemplou ainda outras aplicações sigilosas, que foram omitidas desta tese. Seu andamento abriu uma importante janela em prol da sustentabilidade, levando ao início do desenvolvimento no Laboratório, da nanomagneto-hidrometalurgia verde para obtenção e reciclagem de metais estratégicos, e de trabalhos de despoluição magnética de ambientes contaminados. / New routes for low cost production of functionalized magnetic nanoparticles (MagNP) have been pursued in this Thesis, by employing environmentally compatible chemicals and resources. The nanomaterials exhibited typical superparamagnetic behavior consistent with the presence of magnetic monodomains, revealing no hysteresis above 280 K, Tb = 90 K at H = 500 Oe, and saturation magnetization as high as 90 emu g-1. The synthetic procedures were carried out using biocompatible solvents derived from biodiesel of soybean and Brazilian mamona seeds, leading to substantial reduction of cost for large-scale production. The superparamagnetic nanoparticles were initially designed for capturing, transporting and recycling chemicals or drugs, including pollutants, catalysts and enzymes, using external magnets. They provide a green alternative strategy for conventional processes that make extensive use of solvents, generate too much waste, and proceeds through highly energetic demanding steps such as centrifugation, solvent extraction and high-pressure filtration. In our work, the MagNPs were appropriately modified for working in polar and non-polar media, employing for instance, amphiphilic species for interacting with Fe3O4 using the available polar groups, and also with carbon surfaces by means of hydrophobic interactions. Accordingly, new superparamagnetic nanomaterials incorporating several types of materials carbon based. It was observed that the carbon materials containing 15 to 20% of magnetic nanoparticles could be completely removed from the media with the use of a magnet. In this way, the functionalized superparamagnetic nanoparticles proved useful for the removal of oil spills and of organic pollutants from industrial processing water, as well as for the capture, removal and recovery of metallic elements and organic species from the effluents. In addition, as a proof of concept, smart windows and displays were elaborated based on the modulation of the transmitted or reflected light by the external magnet. This work was sponsored by PETROBRÁS, and also covered missing, non-authorized aspects involved in two patent applications. Finally, an important consequence to be mentioned is the contribution of this project for launching new chemical routes towards sustainability, such as the development in this Laboratory, of green, magnetic nano-hydrometalurgy for processing and recycling strategic metals, and of the magnetic remediation of polluted environments using the functionalized nanomaterials.

O objetivo do trabalho foi investigar como a dimensão ambiental se insere na formação de estudantes de um curso de licenciatura em Química de uma Instituição de Ensino Superior pública, localizada no estado de São Paulo, Brasil. Por meio desse estudo de caso buscou-se analisar a relação desta dimensão com os aspectos científico, tecnológico e social do processo formativo; entre outros aportes, utilizou-se a teoria crítica da sociedade para compreender a realidade observada. A compreensão do currículo como um local onde ocorrem os conflitos pelo poder simbólico em um campo científico, bem como a perspectiva da teoria crítica para as análises documental e das falas dos indivíduos implicados num curso voltado à formação docente, mostrou-se de grande pertinência para os estudos voltados à ambientalização curricular. Foram considerados documentos oficiais (Diretrizes Curriculares Nacionais para a Formação de Professores da Educação Básica, em nível superior, curso de licenciatura, de graduação plena; Diretrizes Curriculares para os cursos de Química, bacharelado e licenciatura plena; Plano de desenvolvimento institucional; Perfil do profissional a ser formado; Perfil do profissional e habilidades a serem desenvolvidas na licenciatura em Química; Projeto pedagógico e estrutura curricular do curso de licenciatura em Química da IES de interesse) bem como entrevistas semi-estruturadas com licenciandas/os, apoiadas na metodologia de grupo focal, e com docentes vinculadas ao curso. Todos os textos foram analisados por meio da metodologia conhecida como análise textual discursiva, a qual assume pressupostos que a localizam entre os extremos da análise de conteúdo e a análise de discurso. Após a análise dos dados coletados, observou-se uma tendência crescente à ambientalização curricular do curso investigado, embora haja várias dificuldades de ordem institucional e prática. As iniciativas individuais em espaços formais e não formais de práticas voltadas à sustentabilidade socioambiental também auxiliam a compor o terreno desse campo científico na IES de interesse. / The purpose of this work is to examine how the environmental dimension is included in the education of students in a licentiate course in Chemistry at a public Institution of Higher Learning (IHL) located in the state of São Paulo, Brazil. Based on this study, an analysis was made of the relationship of this dimension with the scientific, technological and social aspects of the educational process. Among other resources, the critical theory of society was used to gain an understanding of the observed reality. Seeing the curriculum as a place where conflicts for symbolic power occur in a scientific field, as well as the perspective of the critical theory in the documental analyses and testimony of the individuals involved in a teacher training course, proved highly pertinent for studies focusing on curricular environmentalization. Official documents were considered (National Curricular Guidelines for Teacher Training for basic education, high school, licentiate courses, undergraduate courses; Curricular Guideline for Chemistry courses, baccalaureate and licentiateship; Institutional development plans; Profile of the professional to be trained; Profile of the professional and of the skills to be developed in Chemistry licentiateship; Pedagogical design and curricular structure of the Chemistry licentiate course of the IHL of interest), as well as semi-structured interviews, based on the focus group methodology, with licentiate students and with docents connected to the course. All the texts were analyzed using the methodology of text-based discourse analysis, which assumes premises that place it between the extremes of content analysis and discourse analysis. After analyzing the collected data, a tendency was detected for increasing curricular environmentalization in the course under investigation, despite the existence of several institutional and practical difficulties. In both formal and informal spaces, individual initiatives of practices focusing on socioenvironmental sustainability also help make up the terrain in this scientific field at the IHL of interest.

Dióxido de carbono supercrítico (scCO2) é um solvente pouco eficiente para substâncias polares em geral. Uma maneira interessante de superar esta limitação e explorar todo o seu potencial como solvente verde, possível substituto para os solventes orgânicos voláteis comuns, é a introdução de tensoativos específicos para scCO2 no sistema. No presente trabalho, foram sintetizadas três novas séries de tensoativos oxigenados para scCO2. As moléculas possuem cabeças CO2-fóbicas mono e poli-hidroxiladas, em sua maioria à base de açúcares, e três tipos de cadeias CO2-fílicas, duas delas perfluoradas (-C7F15 e -C9F19) e uma peracetilada (derivada do ácido D-glucônico). Foram investigadas as suas solubilidades e comportamentos de fase em CO2 e em sistemas ternários (água-CO2-tensoativo), bem como a atividade na interface CO2-água. Todos eles dispersaram água em scCO2 com [água] / [tensoativo] (W) igual a 10, exibindo pressões de névoa comparáveis àquelas do sistema \"a seco\". Adicionalmente, os tensoativos reduziram a tensão interfacial CO2-água. O efeito das cabeças CO2-fóbicas e cadeias CO2-fílicas nessa redução pôde ser analisado separadamente. Os resultados dos experimentos de tensão interfacial dinâmica sugerem que tanto a difusão das moléculas da fase contínua para a subinterface, quanto a sua inserção e migração na interface contribuem para o decaimento das tensões interfaciais. / Supercritical carbon dioxide (scCO2) is a poor solvent for polar substances in general. An interesting way to overcome this limitation and fulfill its potential as a green solvent, a possible substitute for common volatile organic solvents, is the introduction of scCO2-suitable surfactants in the system. In the present work, three series of novel oxygenated surfactants for scCO2 were synthesized. The amphiphiles contain mono and poly-hydroxylated CO2-phobic heads, most of them sugar-based, as well as three types of CO2-philic tails, two of them perfluorinated (-C7F15 and -C9F19) and one peracetylated (D-gluconic acid derivative). Their solubilities and phase behaviors in CO2 and in ternary systems (water-CO2-surfactant), as well as their activities at the CO2-water interface, were investigated. All of them dispersed water in scCO2- with water-to-surfactant ratio (W) of 10, exhibiting cloud pressures comparable to those of \"dry\" systems. Also, the surfactants reduced the CO2-water interfacial tension. The effect of both the CO2-phobic heads and the CO2-philic tails could be analyzed separately. Dynamic interfacial tension results suggest that both diffusion from bulk CO2 to subinterface and insertion and migration of molecules within the interface contribute to the time-dependent decay of the interfacial tensions.