Made available in DSpace on 2016-06-02T19:39:32Z (GMT). No. of bitstreams: 1 5020.pdf: 1446710 bytes, checksum: 36799f21e9a4eac620a708772b82d4f9 (MD5) Previous issue date: 2013-02-25 / The Learning Management System (LMS) has become extremely attractive because of the development of tools that enable synchronous and asynchronous interaction between users connected to the internet. The system has being adopted by many educational institutions, especially in the higher education ones. In this paper we describe the development, use and evaluation of a course built on the LMS Moodle with the main objective of checking its potential to complement the lessons of subject "Experimentação para o ensino de Química 1 e 2", offered to undergraduate students in Chemistry of Universidade Federal de São Carlos (UFSCar). Moodle course area was built to provide students some materials and activities that allow communication about issues related to experiment on teaching with a focus on environmental sustainability and Green Chemistry. Undergraduate chemistry students voluntarily participated in the research during the first and second semesters of 2012. The data was collected through the textual productions in forums with the participation of all undergraduates and where there was a questionnaire and a final evaluation of the course "Experimentação para o ensino de Química 2". Throughout the course the students used the environment as a privileged place to express themselves and to build the collective knowledge, since this tool has provided to licensees recognition and appropriation of another training space that supports debate which is not possible in the classroom very often. We conclude that virtual learning environments focused on teacher education can enhance the work done in the classroom. / Com o desenvolvimento das ferramentas que permitem a interação sincrônica e assincrônica entre usuários conectados à internet, os ambiente virtuais de aprendizagem (AVA) tornaram-se extremamente atrativos, sendo adotados por diversas instituições de ensino, principalmente as de ensino superior. No presente trabalho descrevemos a elaboração, utilização e a avaliação de um curso construído no AVA Moodle com o objetivo principal de averiguarmos seu potencial para complementar as aulas da disciplina Experimentação para o ensino de Química 1 e 2 , ofertadas aos licenciandos em Química da Universidade Federal de São Carlos (UFSCar), do campus de São Carlos. A área do curso no Moodle foi construída para disponibilizar materiais de estudo e atividades que permitissem o diálogo a respeito de questões relativas à experimentação voltada ao ensino com enfoque na sustentabilidade socioambiental e Química Verde. Participaram voluntariamente da pesquisa licenciandos em Química no primeiro e segundo semestres de 2012. Os dados foram coletados por intermédio das produções textuais em fóruns que contaram com a participação de todos os licenciandos, de um questionário e da avaliação final da disciplina Experimentação para o ensino de Química 2 . Ao longo da disciplina os alunos utilizaram o ambiente como um locus privilegiado para expressarem-se e para a construção do saber coletivo, visto que essa ferramenta propiciou aos licenciandos o reconhecimento e apropriação de um espaço formativo que favorece o debate, muitas vezes, não possível de ocorrer em sala de aula. Conclui-se que os ambientes virtuais de aprendizagem voltados à formação docente podem potencializar o trabalho realizado em sala de aula.

Made available in DSpace on 2015-05-14T13:21:06Z (GMT). No. of bitstreams: 1 parte1.pdf: 1561006 bytes, checksum: 92830d9ef59f992edaa0a7616cdb4412 (MD5) Previous issue date: 2011-03-30 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPES / This study was conducted in order to develop the synthesis of new Morita-Baylis-Hillman adducts of (MBHA) water soluble (29-34) with potential parasitic activity, using glycerol (1) as raw material. Two synthetic routes were carried out producing twelve new MBHA (23 - 34), six of which have hydrophilic characteristics 29-34 (main target of the work) and six more hydrophobic 23 28 (as synthesis intermediates), and these intermediaries are also important for comparative studies of structure and biological activity (SAR). Starting from glycerol (1), we synthesize the 2,2-dimethyl-1,3-dioxolan-4-yl)methyl acrylates (21, 94%) and from this, two synthetic routes were investigated to produce the 29- 34 adducts. On Route 1, the adducts 29-34 were produced in one-step (54 - 82%) from the Michael acceptor 2,3-dihydroxypropyl acrylate 22, which was prepared in 100% yield from 21. In route 2, MBHA intermediates 23 - 28 were prepared directly from 21 (90 - 100%) and these adducts were subsequently processed in adducts 29-34 (70 - 90%). In the synthesis of adduct 32 was observed the formation of the Michael addition product 47 and Indolizines unprecedented 48 as co-products of synthesis and characterized only by CGMS during the synthetic route 2. All syntheses in this work were developed in industry standards convenient. The activation reaction by microwave irradiation (MW) was widely used in most steps of this synthetic work, leading to high chemical yields and reduced reaction times. / Este trabalho foi realizado no intuito de desenvolver a síntese de novos adutos de Morita-Baylis-Hillman (AMBH) hidrossolúveis (29-34) com potenciais atividades antiparasitárias, usando o glicerol (1) como matéria-prima. Duas rotas sintéticas foram desenvolvidas conduzindo a doze AMBH inéditos (23 - 34), dos quais seis possuem as características hidrofílicas 29-34 (alvo principal do trabalho) e as outras seis mais hidrofóbicas 23 - 28 (como intermediários de síntese), sendo que estes intermediários são também importantes para estudos comparativos entre estrutura e atividades biológicas (SAR). Partindo do glicerol (1), sintetizamos o acrilato de 2,2-dimetil-1,3-dioxalila (21, 94%) e a partir deste, duas rotas sintéticas foram investigadas para os adutos-alvo 29- 34. Na rota 1, os adutos 29-34 foram produzidos em uma única etapa sintética (54 - 82%) a partir do aceptor de Michael acrilato de 2,3- dihidroxipropila 22, que foi preparado em 100% de rendimento a partir de 21. Na rota 2, os AMBH intermediários 23 28 foram preparados em 90 - 100% diretamente de 21 e estes adutos foram subseqüentemente transformados nos adutos 29-34 (70 - 90%). Na síntese do aduto 32 foi observado a formação do produto de adição de Michael 47 e da indolizina inédita 48 como co-produtos de síntese e caracterizados apenas por CGMS, durante a rota sintética 2. Todas as sínteses neste trabalho foram desenvolvidas em padrões convenientes a indústria. A ativação reacional por irradiação de microondas (MO) foi amplamente utilizada na maioria das etapas sintéticas deste trabalho, conduzindo aos altos rendimentos químicos e aos tempos reacionais reduzidos.

De nos jours, l’industrie chimique est de plus en plus confrontée à la question de son impact environnemental. Dans le même temps, elle doit faire face à la diminution des ressources de matières premières importantes tels que les métaux de transition, tout en respectant des contraintes économiques. Ces travaux de thèse avaient pour but de tenter de répondre à ces exigences, par le développement de méthodologies de synthèse basées sur l’utilisation de catalyseurs hétérogènes recyclables. En combinant les propriétés catalytiques de certains ions métalliques avec les propriétés de catalyseurs solides tels que les polyoxométallates ou les zéolithes, nous avons pu mettre au point de nouveaux outils pour la synthèse organique. Les polyoxométallates dopés à l’argent ont démontré leur efficacité dans le réarrangement d’alcynyloxiranes en furanes. La synthèse de spiroacétals et d’acétals par dihydroalkoxylation d’alcyne diols a été effectuée pour la première fois en catalyse à l’argent, via l’utilisation de zéolithes. En perspective, nous avons mis en évidence les applications potentielles de ces procédés verts dans la synthèse totale de molécules plus complexes. Les premiers résultats suggèrent que de telles synthèses plus respectueuses de l’environnement ont tout intérêt à être davantage utilisées à l’avenir. / Nowadays, the modern chemical industry has to deal with increasing environmental concerns, including the disposal of waste and its economic impact, or the diminution of important worldwide resources such as transition metals. In this Ph.D. thesis, we aimed to bring improvement in this area by the development of green processes, based on the use of recyclable heterogeneous catalysts. By combining the catalytic properties of several metal cations with the properties of solid catalysts such as polyoxometalates or zeolites, we were able to set up new tools for organic synthesis. Silver-doped polyoxometalates proved to be very efficient catalysts in the rearrangement of alkynyloxiranes to furans. Acetals and spiroketals were synthetized by dihydroalkoxylation of alkynediols under catalysis with silver-zeolites. As a perspective, we highlighted the potential applications of such green procedures in the total synthesis of more complex molecules. The first results suggested that these environmental friendly processes should gain increasing interest in the future.

Ces dernières années, les coûts et la demande en énergie n’ont cessé d’augmenter. Par conséquent, l’humanité fait face à de graves menaces environnementales telles que l'augmentation des rejets de CO2. À cet égard, la communauté internationale doit parvenir à réduire de son empreinte carbone et à veiller à ce que les besoins en énergie thermique soient couverts de manière durable. D’importantes quantités de chaleur résiduaire à basse température (60 - 100°C) sont libérées quotidiennement dans l'atmosphère par de nombreuses installations industrielles. Les thermo-transformateurs de chaleur à absorption constituent un outil intéressant car ils peuvent revaloriser des chaleurs résiduaires pour produire de la chaleur utile pour le chauffage et la production d’eau chaude. Actuellement, les mélanges de travail utilisés dans les pompes à absorption sont les systèmes {ammoniac + eau} et {eau + bromure de lithium}. Cependant, ces deux fluides de travail présentent certains inconvénients tels que la toxicité, la cristallisation et la corrosivité. Par conséquent, il est important de rechercher de nouveaux mélanges de travail. Cette étude a pour objectif d’évaluer l’intérêt d’utiliser des mélanges constitués de liquides ioniques et d'eau au sein de thermo-transformateurs à absorption. Tout d'abord, les propriétés thermodynamiques de ces systèmes binaires (pression de vapeur, densité, capacité thermique et enthalpie d’excès) ont été mesurées dans un large domaine de température et de composition. Ces données expérimentales ont été corrélées à l’aide de modèles thermodynamiques adéquats. Ensuite, les performances de ces fluides de travail ont été évaluées. Les résultats montrent que les systèmes binaires {H2O + Ils} sont une alternative prometteuse aux fluides de travail traditionnels tels que {H2O + LiBr} / Recently, the cost and use of energy continually rise. Hence, humans are close to face serious environmental problems such as increasing CO2 discharges. In this regard, global community is to achieve the ambitious objective of reducing carbon footprint and to ensure that the heating demand is covered in a sustainable manner. Since, enormous amounts of low-temperature waste heat are released on daily bases from many industrial plants to the atmosphere at temperatures between 60 - 100°C. Absorption heat transformers (AHT) are interesting because they can recover low temperature waste heat from different industrial activities and renewable energy sources such as solar and geothermal. AHT can be used to upgrade waste heat to produce useful heat for heating and hot water supplies. Nowadays, the standard working pairs used for AHTs are {ammonia + water} and {water + lithium bromide}. However, both of the working pairs show questionable behavior such as toxicity, crystallization and corrosiveness. Therefore, exploring new working pairs which do not exhibit limitations become of great importance. This work includes an investigation to analyze the AHT systems using {water + ionic liquids} binary systems as working fluids. First, basic thermodynamic properties including vapor pressure, density, heat capacity as well as excess enthalpy of these binary systems were measured at various temperatures with different ionic liquid concentrations. The thermodynamic properties data were correlated by different equations, respectively. The correlated values were significantly consistent with the experimental data. Next, simulation of the AHT performance based on the thermodynamic properties of the new working pairs and on the mass and energy balance for each component of the system were performed. Results show that the {H2O + ILs} binary systems are promising alternatives to replace the already used {H2O + LiBr} working pairs

A importância das questões sócio-ambientais vem crescendo rapidamente, sobretudo na elaboração de currículos de ciências, com conseqüências para a formação de professores. No entanto, atuar nessa perspectiva vai além da disponibilidade de materiais didáticos comprometidos com essa proposta, faz-se necessário formar professores capazes de utilizálos, dotados de visão multidisciplinar do corpo teórico específico de sua área de atuação e com condições de adotarem um modelo de ensino diferente do vivenciado por eles durante toda a sua vida escolar. As metas de uma formação comprometida com as questões sócioambientais envolvem não somente a apropriação do conhecimento científico tanto teórico quanto experimental, mas também o reconhecimento dos impactos ambientais envolvidos no ciclo de vida de produtos de consumo duráveis e não duráveis, e até mesmo o planejamento do ensino experimental contemplando formas de minimização dos impactos ambientais. Nossa pesquisa procurou tornar viável a avaliação da formação de professores de Química na perspectiva de um comprometimento com as questões sócio-ambientais. Para tanto acompanhamos a elaboração e aplicação de uma metodologia de ensino apoiada nos princípios da Química Verde e voltada para tais questões pela docente, e também pesquisadora da própria prática, de disciplinas da licenciatura em Química em uma Instituição de Ensino Superior particular no interior de São Paulo no período de 2005-2008. Tal acompanhamento nos permitiu estabelecer indicadores de comprometimento sócio-ambiental durante a evolução da elaboração dessa metodologia. Esses indicadores foram analisados sobre a perspectiva do amadurecimento do aparelho psíquico proposto por Melanie Klein e generalizados para propiciar a análise dos projetos de ensino, elaborados pelos licenciandos da turma de 2008, com ênfase para as questões sócio-ambientais na perspectiva CTS. Essa análise nos permitiu concluir sobre o nível de comprometimento dos licenciandos com essas questões. Analisamos também os efeitos da pesquisa sobre a própria prática, resultando em uma reflexão que permitiu tanto uma mudança do discurso da docente, como também uma evolução na relação professor/aluno, através da superação parcial tanto das limitações institucionais como pessoais. Essa evolução foi percebida através de análise de projetos de ensino, das participações dos alunos, dos artigos elaborados pela docente, da orientação de projetos de iniciação científica, desde 2005 até 2008. / The importance of socio-environmental issues is growing rapidly, especially in developing science curricula, with consequences for the teacher training. However, work in this perspective goes beyond the availability of materials involved in this proposal, it is necessary to train teachers to use them and having multidisciplinary view of the theoretical specific to your area of expertise and that could adopt a model education other than experienced by them throughout their school life. The goals of training committed to the socio-environmental issues not only involve the appropriation of scientific knowledge, both theoretical and experimental, but also a recognition of the environmental impacts involved in the life cycle of consumer durable and nondurable goods, and even planning of experimental teaching contemplating ways to minimize environmental impacts. Our research sought to make viable the evaluation of chemistry teachers training at the prospect of a commitment to the socio-environmental issues. To this end we follow the development and implementation of a teaching methodology supported the principles of green chemistry and attention to those issues by the teacher, researcher and also of the practice of disciplines in Teachers College in an Institution of higher education particularly in São Paulo in the period 2005-2008. Such monitoring has allowed us to establish indicators of socioenvironmental commitment during the course of developing this methodology. These indicators were analyzed from the perspective of maturation of the psychic apparatus proposed by Melanie Klein and generalized to provide an analysis of the teaching projects, prepared by students teachers of class of 2008, with emphasis on socio-environmental perspective STS. This analysis allowed us to conclude about the level of commitment to these issues by the teacher training student. We also analyzed the effects of own practice research, resulting in a reflection that enabled both a change in the discourse of teaching as well as developments in the teacher / student, in part by overcoming the limitations both institutional and personal. This process has been perceived through analysis of education projects, the participation of the students, the articles written by the teacher, the guidance of basic scientific research projects, from 2005 to 2008.

A mecanização do preparo de amostras minimiza erros sistemáticos, a geração de efluentes e o tempo de análise. Sistemas em fluxo com microbombas solenoide (MPFS) atendem aos requisitos da mecanização de maneira robusta e versátil. Sendo assim, foram desenvolvidos procedimentos analíticos baseados em MPFS e foto-oxidação em linha visando ao fracionamento de fósforo em extratos de alimentos e águas naturais e à determinação de cloreto em águas naturais e urina. Fósforo é um nutriente importante cuja biodisponibilidade depende de sua forma química, tornando importante o fracionamento. O monitoramento de cloreto também é importante porque altas concentrações causam efeitos adversos ao meio ambiente e à saúde. Um MPFS foi proposto para o fracionamento de fósforo solúvel em extratos de alimentos, empregando foto-oxidação em linha do fósforo orgânico a ortofosfato, que foi quantificado pelo método do azul de molibdênio. Foi obtida resposta linear entre 5,0 e 40 mg L-1 para fósforo inorgânico (PI) e orgânico (PO), com limites de detecção de 0,5 e 1,2 mg L-1, respectivamente. Coeficientes de variação foram estimados em 1,2 e 3,6% para PI e PO, respectivamente, com frequência de amostragem de 80 determinações por hora. Por determinação, foram consumidos 380 µg de (NH4)6Mo7O24, 620 µg de ácido ascórbico e 790 µg de K2S2O8, gerando 2,5 mL de efluentes. Os resultados do fracionamento em extratos de alimentos concordaram com os obtidos pelo procedimento de referência (95% de confiança), baseado na digestão nitro-perclórica para a determinação de PO. Um procedimento com MPFS e espectrofotometria de longo caminho óptico foi desenvolvido para o fracionamento de fósforo (inorgânico e orgânico dissolvidos) em águas naturais. A quantificação foi baseada no método do azul de molibdênio, após fotoconversão das espécies a ortofosfato. Resposta linear foi observada entre 10 e 75 µg L-1 P, com limite de detecção de 2,0 µg L-1. Foram obtidos coeficiente de variação de 1,8% e frequência de amostragem de 40 determinações por hora. Por determinação, foram consumidos 160 µg de (NH4)6Mo7O24, 10 µg de SnCl2, 640 de µg K2S2O8 e 10 mg de NaOH, gerando 4,0 mL de efluentes. Os coeficientes angulares das curvas obtidas com 4 tipos diferentes de espécies de PO indicaram conversão quantitativa e os resultados obtidos para amostras de águas de rios foram concordantes com os obtidos pelo procedimento descrito pela AOAC (95% de confiança). Um procedimento limpo foi também desenvolvido para a determinação de cloreto em águas naturais e urina, evitando o uso de reagentes tóxicos. O analito foi foto-oxidado a cloro, que foi determinado por espectrofotometria através da descoloração do alaranjado de metila. Resposta linear foi observada entre 2,0 e 20 mg L-1, com limite de detecção de 0,7 mg L-1. O coeficiente de variação foi estimado em 1,6%, com frequência de amostragem de 75 determinações por hora e consumo de 7,5 µg de corante por determinação. Espécies concomitantes usualmente presentes nas amostras não interferiram mesmo em excesso em relação às concentrações normalmente encontradas. Os resultados das análises das amostras concordaram com os obtidos pelo procedimento de referência (95% de confiança). Os procedimentos propostos são alternativas limpas e rápidas para o fracionamento de fósforo e determinação de cloreto. / Mechanization of sample preparation minimizes systematic errors, waste generation and analysis time. Flow-based systems with solenoid micropumps (MPFS) attain the requirements for mechanization in a versatile and robust way. Therefore, analytical procedures based on MPFS and on-line photo-oxidation were developed aiming phosphorus fractionation in foodstuff and river waters and chloride determination in natural waters and urine. Phosphorus is an important nutrient for plants and animals and its bioavailability depends on its chemical form, making fractionation studies important. Chloride monitoring is relevant because the concentration unbalance leads to environmental and health issues. A MPFS was proposed for the fractionation of water soluble phosphorus in foodstuff, incorporating on-line photo-oxidation of organic phosphorus to phosphate, which was quantified by the spectrophotometric molybdenum blue method. Linear response was observed from 5 to 40 mg L-1 for both inorganic (PI) and organic (PO) phosphorus, with detection limits of 0.5 and 1.2 mg L-1, respectively. Coefficients of variation (n = 20) were estimated as 1.2 and 3.6% for PI and PO, respectively, with a sampling rate of 80 determinations per hour. Per determination, 380 µg of (NH4)6Mo7O24, 620 µg of ascorbic acid and 790 µg of K2S2O8 were consumed, generating 2.5 mL of waste. The results for food extracts agreed with those obtained by the reference procedure (95% confidence level) based on nitro-percloric digestion for PO determination. A MPFS procedure with long pathlength spectrophotometry was developed for phosphorus fractionation (dissolved organic and inorganic) in natural waters. Quantification was also based on the formation of molybdenum blue, after on-line photo-convertion of the organic species to orthophosphate. The analytical response was linear within 10 and 75 µg L-1 with a detection limit of 2.0 µg L-1. Coefficient of variation of 1.8% and sampling rate of 40 determinations per hour were achieved. Per determination, 160 µg of (NH4)6Mo7O24, 10 µg of SnCl2, 640 µg of K2S2O8 and 10 mg of NaOH were consumed, generating 4.0 mL of waste. Slopes of analytical curves obtained for four different PO species agreed with those obtained for orthophosphate, indicating quantitative conversion and the results for five freshwater samples agreed with those obtained by the AOAC reference procedure at 95% confidence level. A green procedure for chloride determination in urine and natural waters was also developed, avoiding hazardous chemicals. The analyte was on-line photo-converted to chlorine which was spectrophotometrically detected by methyl orange discoloration. The analytical response was linear from 2.0 to 20 mg L-1 Cl with a detection limit of 0.7 mg L-1. The coefficient of variation was 1.6% with a sampling rate of 75 determinations per hour, consuming 7.5 µg of the dye per determination. Usual concomitant species did not cause significant interference even in excess in relation to their highest concentration expected in the samples. The results for urine and water samples agreed with those obtained by the reference procedures at the 95% confidence level. The proposed procedures are environmentally friendly and fast alternatives for phosphorus fractionation and chloride determination

Orientador: Celio Pasquini / Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Química / Made available in DSpace on 2018-08-21T16:25:47Z (GMT). No. of bitstreams: 1 Cortez_Juliana_D.pdf: 25144768 bytes, checksum: bb2f3753af786e01a3f99e0a7e89fe95 (MD5) Previous issue date: 2012 / Resumo: A técnica de ring oven, originalmente desenvolvida por Weisz em 1954 e revisitada com o objetivo de ser utilizada em um procedimento simples e altamente eficiente de pré-concentração de analitos antes da determinação por técnicas analíticas de microanálise. A técnica de pré-concentração proposta e baseada na utilização de um pequeno volume de amostra que e transferida gota-a-gota, com o auxílio de um sistema de análise por injeção em fluxo, para um substrato de papel de filtro. O papel de filtro e mantido em um pequeno forno circular aquecido (ring oven). As gotas da solução da amostra difundem por capilaridade do centro do papel de filtro para a frente do solvente. Depois do término do processo, um anel com um contorno circular bem definido (0,35 mm de largura e cerca de 2,0 cm de diâmetro) e formado no papel de filtro e este contém, pré-concentrados, os elementos presentes no volume processado de amostra. Coeficientes de preconcentração do analito podem alcancar 250 vezes (m/ m) para um volume de amostra de 600 mL. O sistema proposto foi avaliado para pré-concentrar Na, Fe e Cu presentes em amostras de etanol hidratado combustível, em nível de mg mL. O procedimento de pré-concentração não utiliza nenhum solvente adicional, aos já existentes na amostra, nem reagentes adicionais, podendo ser considerado um método limpo, de acordo com os preceitos da química analítica verde. A determinação direta e simultânea dessas espécies, no contorno do anel, foi realizada empregando a técnica microanalítica de espectroscopia de emissão óptica em plasma induzida por laser (LIBS). Os limites de detecção encontrados atendem as exigências da Agencia Nacional de Petroleo (ANP) para controle do etanol combustível. Os limites de detecção são de 0,9; 0,5 e 0,4 mg kg para sódio, ferro e cobre, respectivamente. O potencial da associação da técnica de ring oven e LIBS, uma representante das técnicas analíticas de microanálise, foi demonstrado, ajudando os limites de detecção das medidas LIBS e abrindo um novo caminho para o uso do ring oven em novas propostas analíticas e na associação com outras técnicas de microanálise / Abstract: The ring oven technique, originally developed by Weisz in 1954, is revisited to be used in a simple though highly efficient procedure for analyte preconcentration prior its determination by the micro-analytical techniques presently available. The proposed preconcentration technique is based on the dropwise delivery of a small volume of sample to a filter paper substrate, assisted by a flow-injection system. The filter paper is maintained in a small circular heated oven (the ring oven). Drops of the sample solution diffuse by capillarity from the center of filter paper to the solvent front. After the total sample volume has been delivered, a ring with a sharp (c.a. 0.35 mm) circular contour, of about 2.0 cm diameter is formed on the paper to contain most of the analytes originally present in the sample volume. Preconcentration coefficients of the analyte can reach 250 fold (on a m/m basis) for a sample volume small as 600 mL. The proposed system and procedure have been evaluated to concentrate Na, Fe and Cu in levels of mg mL in fuel ethanol. The preconcentation procedure uses no solvent or reactant, besides the already existing in the sample, in agreement with the principles of green analytical chemistry. The simultaneous determination of these species in the ring contour, was made by employing the micro-analytical technique of laser induced breakdown spectroscopy (LIBS). The detection limits are sufficient to attend to the requirements of the National Agency of Petroleum (ANP) aiming at the quality control of fuel ethanol. The detection limits are 0.9, 0.5 and 0.4 mg kg for sodium, iron and copper, respectively. The potential of association between the ring oven technique and LIBS, representative of the microanalytical techniques, was demonstrated, helping to achieved a better detectivity in LIBS measurements and opening the path for new analytical proposals and for the association with others microanalytical techniques / Doutorado / Quimica Analitica / Doutora em Ciências

L'objectif central de notre thèse de doctorat visait l'utilisation d'halogénures d'aryles en tant qu'électrophiles dans des réactions de substitution nucléophile aromatique (SNAr). D'abord, nous avons cherché à former des liaisons C(aryl) hétéroatome par réaction entre des nucléophiles hétéroatomiques et des halogénures d'aryles substitués par des groupements électro-attracteurs. Les résultats de cette étude ont été comparés à des incohérences relevées dans la littérature et montrent que l'ordre de réactivité d'halogénures d'aryles communément accepté n'est pas toujours respecté. Un effet positif a été observé par l'ajout de 2,2,6,6-tétraméthyl-3,5-heptanedione pour l'arylation de phénols avec des halogénures d'aryles substitués par des groupements électro-donneurs, ce qui en fait la première méthode capable de générer des diaryléthers par cette voie réactionnelle sans ajout de catalyseurs métalliques. Ensuite, nous avons mis au point une réaction générale d'± arylation de cétones aromatiques avec des halogénures d'aryles dans des conditions réactionnelles douces. L'utilisation du t-BuOK, une base inorganique capable de transferts mono-électroniques, et de DMF comme additif permet la synthèse d'±-arylcétones avec d'excellents rendements. Cette méthode a été appliquée à la synthèse d'hétérocycles fusionnés et de (Z)-tamoxifène, des molécules montrant une activité biologique. Une étude mécanistique a montré que l'anion carbamoyle du DMF est impliqué dans une étape clé de transfert mono-électronique avec des halogénures d'aryles. Nous avons également appliqué cette méthode à la substitution nucléophile vinylique de ″-halostyrènes. Bien que des précédents de la littérature font état de mécanismes ioniques pour les réactions de ces substrats, nos résultats expérimentaux supportent un mécanisme radicalaire. Enfin, nous avons tenté de mettre au point le premier protocole permettant la synthèse de biaryles dissymétriques au départ d'halogénures d'aryles et de triarylbismuths(III) via une catalyse par des sels de cuivre. Malgré le fait que de nombreux ligands bidentates et tétradentates ont été testés, les faibles rendements obtenus font que les conditions réactionnelles demeurent à optimiser. Globalement, nous avons donc apporté une contribution en ce qui concerne la détermination de la frontière expérimentale entre la SNAr et la catalyse métallique, la fonctionnalisation en ± de cétones aromatiques et la synthèse de biaryles dissymétriques par réactions de couplages croisés de triarylbismuths catalysées au cuivre. / The primary objective of our doctoral research was centered on the use of aryl halides as electrophiles for nucleophilic aromatic substitution (SNAr). First, we tried to create C(aryl)−heteroatom bonds by reacting heteroatom nucleophiles with aryl halides substituted by electron-withdrawing groups. The results of this study were compared with inconsistencies found in the literature and show that the expected order of reactivity of aryl halides is not always observed. A beneficial effect was observed by adding 2,2,6,6-tetramethylheptane-3,5-dione to the reaction of phenols and aryl halides substituted by electron-donating groups in what is the first method allowing the synthesis of diarylethers without added metal catalysts by this pathway. Second, we developed a general α-arylation reaction of aryl ketones with aryl halides under mild reaction conditions. Use of KOt-Bu, an inorganic base capable of single-electron transfer, and DMF as additive enables the synthesis of α-arylketones in excellent yields. This method was applied to the synthesis of fused heterocycles and (Z) tamoxifen, molecules possessing biological activity. A mechanistic study showed that the carbamoyl anion of DMF is involved in a single-electron transfer reaction with aryl halides as the key step of the mechanism. We next applied this method to the nucleophilic vinylic substitution of β-halogenostyrenes. While literature precedents suggest ionic mechanisms for reactions involving these substrates, we obtained experimental evidence suggesting a radical mechanism. Third, we tried to develop the first protocol enabling the copper-catalyzed synthesis of unsymmetrical biaryls starting from aryl halides and triarylbismuthanes(III). Although many bidentate and tetradentated ligands were tested, further optimization is required in order to develop a general method, as only low yields are obtained. Globally, we have contributed to the determination of the experimental frontier between SNAr and metallic catalysis, to the α-functionnalization of aryl ketones and to the synthesis of biaryls through copper-catalyzed cross-coupling reactions of triarylbismuths.

Les triarylbismuths sont des réactifs organométalliques d’un intérêt croissant en synthèse organique, pour leur aptitude à transférer leurs trois groupements aryles dans les réactions de couplage croisé C-C pallado-catalysées. Ces réactifs essentiellement non toxiques et « économiques en atomes » sont attrayants dans le cadre d’une chimie plus respectueuse de l’environnement, et présentent des applications en chimie pharmaceutique et en science des matériaux. Cependant, leur développement est ralenti par le manque de connaissances théoriques à leur sujet. Cette thèse vise alors à comprendre la réactivité de ces espèces en confrontant les données expérimentales avec celles obtenues à travers une étude théorique fondamentale (propriétés structurelles, spectroscopiques, thermodynamiques et cinétiques) résultant de calculs DFT. Le but ultime est de prévoir de nouvelles réactivités et sélectivités. Un premier volet se rapporte à une étude comparative de relation structure-propriétés sur des composés incluant un pnictogène comme atome central, tel que le bismuth, et sur différents organobismuths. Les données expérimentales existantes (cristallographiques, RMN, IR) ont été comparées aux résultats théoriques (structures, énergies, modes de vibration, indices de réactivité, etc.). Une fois les propriétés intrinsèques de ces composés mises en évidence et la méthode DFT validée, une nouvelle étude de relation structure-réactivité a été entreprise. Dans ce deuxième volet, nous avons validé le mécanisme des réactions de couplage croisé impliquant des triarylbismuths catalysées par le palladium. Les trois étapes principales du cycle catalytique ont été examinées, à savoir l'addition oxydante, la transmetallation et l'élimination réductrice, et validées en caractérisant les différents intermédiaires et états de transition. La deuxième étape de transmetallation impliquant les triarylbismuths a également fait l'objet d'une étude approfondie. En particulier, la transférabilité des trois groupements aryles et l'influence des substituants (effets électroniques et stériques) sur les barrières de transfert ont été évaluées. Enfin, la réactivité des triarylbismuths a été comparée avec celle d’autres organométalliques afin de développer de nouvelles voies de synthèse / Triarylbismuths are organometallic reagents of growing interest for organic synthesis, for their ability to transfer the three aryl moieties in C-C Pd-catalysed cross-coupling reactions. These essentially non-toxic, atom efficient reactants are attractive in the context of environment-friendly chemistry and have applications in pharmaceutical chemistry and in material science. However, their development is hampered by lack of theoretical understanding. This thesis aims to explore the reactivity of these species by comparing the experimental data to fundamental theoretical studies (structural, spectroscopic, thermodynamic and kinetic properties) resulting from DFT calculations. The ultimate goal is to predict new reactivities and selectivities. A first approach consists in a comparative study on the relation between structure and properties in compounds having a pnictogen central atom like bismuth, and in different organobismuths. The existing experimental data (crystallographic, NMR, IR) were compared to the results of theoretical calculations (structures, energies, vibrational modes, reactivity parameters, etc.). After highlighting the intrinsic properties of these compounds and validating the DFT method, a new study was undertaken to elucidate the relations between structure and reactivity. This second investigation enabled us to validate the mechanism of the cross-coupling reaction involving triarylbismuths under palladium catalysis. The three major steps of the catalytic cycle have been examined, i.e. the oxidative addition, transmetallation and reductive elimination, and validated by characterizing the different intermediates and transition states. The second transmetalation step involving the triarylbismuths has also been deeply investigated. The transferability of the three aryl groups and the influence of the electronic and steric effects of the substituents on the energy barrier have been evaluated. Finally, the reactivity of triarylbismuths has been compared with that of other organometallics, to develop new synthetic approaches

L'utilisation de matières premières renouvelables issues de la biomasse a récemment trouvé un regain d'intérêt pour des raisons économiques et écologiques. Les triglycérides issus d'oléagineux, les terpènes extraits de plantes, et les dérivés phénoliques contenus dans la lignine représentent de grandes familles de molécules naturelles qui offrent un potentiel important pour l'accès à des produits à haute valeur ajoutée. Dans ce contexte, des transformations par catalyse homogène offrent des perspectives intéressantes dans le cadre d'une chimie verte et durable. La métathèse des oléfines en présence de catalyseurs commerciaux du ruthénium a permis d'accéder à de nouveaux terpènes fonctionnalisés par métathèse croisée avec des oléfines fonctionnelles pauvres en électron. L'application de la même réaction de métathèse à des dérivés de l'eugénol en contrôlant en même temps la position de la double liaison terminale dans ces substrats a permis l'accès à de nouveaux dérivés allyliques du phénol par métathèse croisée avec des acrylates, l'acrylonitrile et les acrylamides. Enfin une cascade réactionnelle mettant en jeu la métathèse croisée de dérivés d'esters gras, de terpènes et de l'eugénol insaturés avec des chlorures allyliques suivie d'une réaction d'élimination a conduit à une méthode générale de formation de diènes conjugués terminaux. Ces réactions séquentielles en un seul pot permettent de diminuer les quantités de déchets générés pendant les traitements intermédiaires. Ces transformations catalytiques de ressources renouvelables ont été réalisées dans des solvants ''verts'' tels que des dialkyl carbonates ou en absence de solvant, leur permettant ainsi de répondre à plusieurs critères de la chimie verte. / The utilization of renewable feedstocks arising from biomass has recently found a renewed interest for economic and ecological reasons. Triglycerides arising from oil seeds, terpenes extracted from plants, and phenolic derivatives found in lignin represent important families of natural molecules with important potential for the access to high added value products. In this context, homogeneous catalytic transformations offer interesting perspectives towards green and sustainable chemistry. Olefin metathesis in the presence of commercially available ruthenium catalysts has given access to new functionalized terpenes using cross metathesis with electron deficient alkenes. The same type of reaction applied to eugenol derivatives controlling at the same time the position of their terminal double bond has provided access to new allylic derivatives of phenol by using acrylates, acrylonitrile and acrylamides as cross metathesis partners. Finally a cascade reaction involving cross metathesis of fatty ester, terpene and eugenol derivatives with allylic chlorides followed by an elimination reaction has led to a general method for the synthesis of terminal conjugated dienes. These sequential reactions in one pot allow decreasing the amount of wastes, which are usually generated during intermediate treatments. The reported catalytic transformations of renewable resources have been carried out in green solvents such as dialkyl carbonates or without solvent under neat conditions, and thus fulfill several criteria of green chemistry.