Dentre os materiais de estrutura perovskita, o titanato de estrôncio, SrTiO3, é um dos mais conhecidos e estudado por apresentar interessantes propriedades como a ferroeletricidade, fotoluminescência, entre outras. Além disso, tem sido reportado na literatura que a adição de diferentes dopantes ao composto SrTiO3 modifica suas propriedades dando origem, por exemplo, a materiais para serem aplicados como sensores de gás ou na fotocatálise. Diferentes trabalhos encontrados na literatura descrevem a síntese do composto SrTiO3 e suas soluções sólidas através do método hidrotermal. Entretanto, poucos trabalhos tiveram como foco o estudo do precursor de Ti e do íon dopante nas propriedades estruturais, morfológicas, ópticas e elétricas destes materiais. Desta forma, este trabalho de tese teve como objetivo o estudo da influência da composição e de alguns parâmetros de síntese sobre as propriedades estruturais, morfológicas e ópticas do composto SrTiO3 preparado através do método hidrotermal assistido por microondas HAM. Inicialmente, foi realizada a síntese do composto SrTiO3 a 140oC por 10 minutos, onde se verificou a possibilidade de controlar a morfologia e a propriedade fotoluminescente das amostras através do tipo de precursor de Ti utilizado. Em uma segunda etapa do trabalho, o composto SrTiO3 foi sintetizado por tempos variando de 10 a 640 minutos. A caracterização destas amostras mostrou a formação da fase cúbica do SrTiO3 exibindo morfologia na forma de cubos, formados pelo processo de auto-organização, que tornam-se mais bem definidos com o aumento do tempo de síntese. Medidas de espectroscopia XANES e EXAFS na borda K do Ti mostraram que as amostras de SrTiO3 sintetizadas pelo método HAM apresentam um alto grau de desordem na estrutura local, caracterizada pela coexistência de unidades do tipo TiO5 e TiO6. Além disso, observou-se que o aumento do tempo de síntese leva a uma redução da intensidade fotoluminescente que foi atribuído à redução na concentração de vacâncias de oxigênio. Medidas de DRX das amostras do sistema SrTi1-xFexO3, ao nosso conhecimento pela primeira vez sintetizadas com sucesso através do método HAM, mostraram a formação da fase cúbica quando x &#8804 0,4. Medidas do espectro XANES e EXAFS revelaram a substituição Ti por íons Fe+2 e Fe+3, levando a formação de vacâncias de oxigênio as quais contribuem para a diminuição da energia do band-gap das amostras de 3,2 para 2,8 eV, bem como na total supressão da intensidade fotoluminescente das amostras. A análise por microscopia eletrônica de varredura FE-MEV mostrou a existência de partículas na forma de cubos cuja cinética de formação é influenciada pela variação da quantidade de ferro. Imagens de microscopia eletrônica de transmissão (MET) confirmaram a natureza mesocristalina destas partículas cujo mecanismo de crescimento ocorre por coalescência orientada, originada pelo processo de auto-organização. As amostras do sistema SrTi1-xFexO3 na forma de filmes finos foram avaliadas como sensores O3, NO2, NH3 e CO. As análises indicaram que os filmes depositados pela técnica de evaporação de feixe de elétrons apresentam um grande potencial para serem aplicados como sensor de gás ozônio, exibindo uma boa sensibilidade e seletividade comparada a outros tipos de materiais sensores. / Strontium titanate, SrTiO3, it is one of the most known and intensively studied perovskite compounds due its interesting properties such as ferroelectricity, photoluminescence, etc. According to the literature, the dopant addition into SrTiO3 network can create materials with desirable functions, for example, gas sensing and photocatalytic activity. Despite some authors reported the synthesis of pure or doped SrTiO3 by hydrothermal method, few studies have been devoted to investigate the effects of the Ti precursor and type of dopant ion on the structural, morphological and electrical properties of SrTiO3 compound. In this work, we investigated the influence of synthesis parameters and concentration iron on the structural, morphological and optical properties of SrTiO3 prepared by microwave-assisted hydrothermal method (MAH). Firstly, it was observed that the appropriate choice of the Ti precursor allowed the control of morphological and photoluminescence properties of SrTiO3 compound synthesized at 140oC for 10 minutes by MAH method. Next, SrTiO3 was synthesized during different treatment times varying from 10 to 640 minutes. X-ray diffraction (XRD) measurements indicate a SrTiO3 cubic perovskite structure and FE-SEM images revealed that the samples exhibit a cube-like shape formed by an assembly process, becoming well defined as a function of MAH treatment time. Ti-K edge XANES and EXAFS measurements indicated a large local structural distortion, revealed by the presence of TiO6 and TiO5 units. Moreover, we observed a reduction of the photoluminescence intensity as a function of treatment time probably due to decreasing of the oxygen vacancy concentration. To the best of our knowledge, this is the first time that the SrTi1-xFexO3 solid solution was synthesized by MAH method. XRD analyses indicated a cubic perovskite structure when x &#8804 0.4. XANES and EXAFS measurements revealed that iron ions present a mixed Fe+2/Fe+3 oxidation state and occupy preferentially the Ti4+-site. A UV-visible spectrum shows that the addition of iron reduces the value of optical gap of the 3.2 eV to 2.8 eV and consequently suppresses the photoluminescence intensity. An analysis of FE-SEM and HRTEM images point out that, independently of iron content, the nanoparticles have a cube-like morphology and are formed by a self-assembly of small primary nanocrystals. In addition, SrTi1-xFexO3 thin films were investigated as gas sensor towards O3, NO2, NH3 and CO gases The results indicate that the films deposited by electron beam deposition method exhibits a good response as ozone sensor compared to others gas sensors materials.

Os materiais nanoestruturados vêm sendo extensivamente estudados, não somente pelas novas propriedades e suas possíveis aplicações tecnológicas, mas também pela busca de uma melhor compreensão dos aspectos físicos e químicos causados por suas reduzidas dimensões. A céria (CeO2) tem despertado grande interesse nas últimas décadas, pois tem papel vital em tecnologias emergentes para aplicações em setores que vão desde a área ambiental através do desenvolvimento de novos catalisadores, passando pela área energética com o desenvolvimento de células de combustível em estado sólido e em novas tecnologias como a spintrônica por meio do desenvolvimento de novos materiais, os óxidos magnéticos diluídos. As propriedades físico-químicas da céria são diretamente dependentes do método de síntese e da morfologia das partículas. Nesse contexto, esse trabalho teve como objetivo realizar a síntese através dos métodos dos precursores poliméricos e hidrotérmico assistido por micro-ondas e a caracterização físico-química de nanopartículas do sistema Ce(1-x)MxO2 (M = Cu, Co). Ensaios catalíticos destes pós foram realizados para verificar sua eficácia como catalisadores na reação de oxidação preferencial de monóxido de carbono, e na produção de hidrogênio através da reforma a vapor de etanol. As amostras foram caracterizadas por difração de raios X, espectroscopia UV-Visível, EPR, Raman e fotoluminescência, BET, microscopia eletrônica de varredura e transmissão e TPR. As amostras sintetizadas pelo método dos precursores poliméricos são constituídas por nanopartículas com tamanho da ordem de 30 nm, enquanto que as amostras sintetizadas pelo método hidrotérmico assistido por micro-ondas são constituídas por nanobastões com tamanho da ordem de 10 nm de diâmetro por 70 nm de comprimento. Dentre as amostras sintetizadas pelo método dos precursores poliméricos, o catalisador Ce0,97Cu0,03O2 foi o que apresentou o melhor resultado na conversão do CO (100%)(CO-PROX), e o catalisador Ce0,80Co0,20O2 apresentou 100% de conversão de etanol. Para as amostras sintetizadas pelo método hidrotérmico assistido por micro-ondas o catalisador Ce0,97Cu0,03O2 foi o que apresentou o melhor resultado na conversão do CO (85%)(CO-PROX), e todos os catalisadores com cobalto apresentaram 100% de conversão de etanol. As caracterizações físico-químicas revelaram que diferentes espécies de cobre/cobalto presentes nos catalisadores, o teor de cobre/cobalto presente e as interações entre o cobre/cobalto e o suporte de CeO2 são os fatores que mais contribuem na eficiência dos catalisadores. / Nanostructured materials have been extensively studied, not only by new properties and their possible technological applications, but also by the search for a better understanding of the physical and chemical aspects caused by its small size. Ceria (CeO2) have attracted great interest in recent decades, because it plays a vital role in emerging technologies for applications in sectors ranging from environmental area through the development of new catalysts, passing by the energy area with the development of solid state fuel cells and in new technologies such as spintronics through the development of new materials, the diluted magnetic oxides. The physico-chemical properties of ceria are directly dependent on the synthesis method and the morphology of the particles. In this context, this study aimed the synthesis via polymeric precursors and microwave-assisted hydrothermal methods and the physico-chemical characterization of nanoparticles from the Ce(1-x)MxO2 (M = Cu, Co) system. Catalytic tests of the powders were carried out to verify its efficiency as catalysts on carbon monoxide preferential oxidation reaction, and hydrogen production by steam reforming of ethanol. The samples were characterized by X-ray diffraction, UV-visible, EPR, Raman and photoluminescence spectroscopies, BET, scanning and transmission electron microscopy and TPR. Samples synthesized by polymeric precursors method consist of nanoparticles with sizes of about 30 nm, while the samples synthesized by microwave-assisted hydrothermal method consist of nanorods with 10 nm average diameter and 70 nm length. Among the samples synthesized by the polymeric precursors method, Ce0,97Cu0,03O2 was the one that presented the best result in the CO conversion (100%)(CO-PROX), and the Ce0,80Co0,20O2 catalyst presented 100% of ethanol conversion. For samples synthesized by microwave-assisted hydrothermal method the Ce0,97Cu0,03O2 catalyst was the one that presented the best result in the CO conversion (85%) (CO-PROX), and all catalysts with cobalt presented 100% of ethanol conversion. The physical-chemical characterizations revealed that different species of copper/cobalt present in the catalysts, the copper/cobalt content and interactions between copper/cobalt and the CeO2 support are the main factors that contribute on the efficiency of the catalysts.

A luminescência persistente é um fenômeno em que o material emite radiação de segundos a várias horas após cessada a irradiação (luz, radiação UV, feixe de elétrons, etc.). No entanto, os mecanismos que geram o fenômeno da luminescência persistente ainda não são totalmente estabelecidos. Neste trabalho os materiais Lu2O3:TR3+,M (TR,M: Pr,HfIV; Eu, Ca2+ ou Tb,Ca2+) foram preparados pelo método de estado-sólido assistido por micro-ondas (MASS) e comparados com aqueles sintetizados pelo método cerâmico. As vantagens do método MASS incluem curto tempo de processamento, aquecimento dielétrico seletivo, baixo consumo de energia e uso de equipamentos de baixo custo (forno micro-ondas doméstico), muitas vezes produzindo produtos de alta pureza e alto rendimento. Os materiais foram caracterizados pelas técnicas de espectroscopia de absorção na região do infravermelho (IR), espectroscopia Raman, difração de raios X método do pó (DRX), microscopia eletrônica de varredura (MEV), X-ray absorption near edge structure (XANES), Extended X-ray absorption fine structure (EXAFS), X-ray Excited Optical Luminescence (XEOL), espectroscopia de fotoluminescência na região do UV-Visível, espectroscopia de fotoluminescência na região do UV-UV vácuo e termoluminescência (TL). Os fósforos Lu2O3:TR3+,M (TR,M: Pr,HfIV; Eu, Ca2+ ou Tb,Ca2+) foram preparados em um curto período de tempo (22-26 min) pelo método MASS utilizando forno micro-ondas doméstico, carvão ativado como susceptor, fluxos (H3BO3 ou Na2CO3) e sem a aplicação de gases. Todos materiais preparados com fluxo de H3BO3 exibem impurezas de LuBO3 que foram quantificadas por refinamento Rietveld. Os fluxos e os dopantes não alteraram consideravelmente a estrutura cristalina da matriz C-Lu2O3. As micrografias MEV sugerem que o fluxo de Na2CO3 e os precursores nitratos geram partículas de Lu2O3 com tamanho menor devido a evolução de gases provenientes da decomposição destes compostos. Por outro lado, quando é usado óxidos como precursores os materiais apresentam maiores tamanhos de partícula e na presença de H3BO3 leva a maior agregação. Os dados de XANES indicam que houve completa redução do íon TbIV &#8594 Tb3+ e parcial do PrIV &#8594 Pr3+, devido ao uso de carvão ativado que gera CO(g) durante o tratamento térmico. Os espectros da luminescência persistente indicam emissões nas regiões do vermelho/NIR, vermelho alaranjado e verde atribuídas as transições 4fN &#8594 4fN características dos íons Pr3+, Eu3+ e Tb3+, respectivamente. As diferenças entre os espectros registrados sob excitação UV e após cessada a irradiação podem ser explicadas pela emissão da luminescência persistente predominante dos íons TR3+ no sítio S6 do que no C2. Além disso, a co-dopagem aliovalente com os íons HfIV e Ca2+ aumentam a intensidade e duração da luminescência persistente. Isto ocorre através da geração de armadilhas provenientes dos dois co-dopantes nos sítios de Lu3+ e por defeitos produzidos na compensação de carga. Os materiais fotônicos preparados pelo método MASS com fluxo de H3BO3 apresentam maior intensidade e duração da luminescência persistente comparados aos preparados pelo método cerâmico ou sem a presença de H3BO3. Os mecanismos da luminescência persistente foram desenvolvidos através de princípios similares baseados nos dados experimentais da energia do band gap, posição dos níveis de energia dos íons TR3+/2+ na matriz e energia das armadilhas. Isto confirma a solidez da interpretação dos dados experimentais dos materiais Lu2O3:TR3+,M exibindo luminescência persistentes e encoraja a expansão de modelos similares para outros materiais apresentando esse fenômeno. Os fósforos Lu2O3:Pr3+,HfIV,Lu2O3:Eu3+(,Ca2+) e Lu2O3:Tb3+,Ca2+) apresentaram sintonização de cores de emissão tanto para o fenômeno da fotoluminescência como da luminescência persistente, podendo atuar como bons candidatos nas aplicações de bioimageamento ou sensibilizadores de células solares. / Persistent luminescence is a phenomenon where the material emits radiation from seconds to several hours after cessation of irradiation (light, UV radiation, electron beam, etc.). The persistent luminescence mechanisms are not entirely established, however. In this work, the materials Lu2O3:TR3+,M (TR,M: PrHfIV; Eu, Ca2+ or Tb,Ca2+) were prepared by MASS method as well as compared to these materials synthetized by ceramic method. The advantages of MASS method include short processing time, selective dielectric heating, low energy consumption and use of inexpensive equipment (domestic microwave oven), often affording high-purity and high-yield products. The materials were characterized by Infrared absorption spectroscopy (IR), Raman spectroscopy, X-ray powder diffraction (XPD), Scanning electron microscopy (SEM), X-ray absorption near edge structure (XANES), Extended X-ray absorption fine structure (EXAFS), X-ray excited optical luminescence (XEOL), photoluminescence spectroscopy in the UV-Visible range, photoluminescence spectroscopy in the UV-UV vacuum region and thermoluminescence (TL). The phosphorsLu2O3:TR3+,M (TR,M: Pr,HfIV; Eu, Ca2+ or Tb,Ca2+) were rapidly (22-26 min) and successfully prepared by MASS method using a domestic microwave oven, carbon as susceptor, fluxes (H3BO3 or Na2CO3) and without special gases application. All materials prepared with H3BO3 flux exhibit LuBO3 impurities that were quantified by Rietveld refinement. The flux and dopants does not considerably affect the crystalline structure of the C-Lu2O3 host matrix. Scanning electron micrographs suggest that Na2CO3 flux and nitrates precursors produce Lu2O3 particles of small size due to the gases evolution from the decomposition of these compounds. On the other hand, the materials prepared from oxides precursors have particles of large size and H3BO3 flux induces particle xi aggregation. The carbon used as the susceptor generates CO gas, leading to complete reduction of TbIV to Tb3+ and partial conversion of PrIV to Pr3+ present in the Tb4O7 and Pr6O11 precursors, as indicated by XANES. Persistent luminescence spectra of the materials show emission in the red/NIR, reddish orange and green ranges assigned to the 4fN &#8594 4fN transitions characteristics of Pr3+, Eu3+ and Tb3+ ions, respectively. Differences between the spectra recorded under UV excitation and after ceased the irradiation can be explained by the predominant persistent luminescence emission of TR3+ ion in the S6 site rather than TR3+ in the C2 site. In addition, inclusion of HfIV and Ca2+ codopants in the Lu2O3 host increases the emission intensity and duration of persistent luminescence due to generation of traps caused by charge compensation in the lattice as well as these metal ions in the Lu3+ sites. The photonic materials prepared by MASS method with H3BO3 flux show higher persistent luminescence performance than those prepared by the ceramic method or MASS without flux. The persistent luminescence mechanisms were developed through similar principles based on experimental data of band gap energy, energy level positions of TR3+/2+ ions in the host and traps energy. This similarity confirms the consistency of the interpretation of experimental data for the Lu2O3:TR3+,M materials and encourages the expansion of similar models for other persistent luminescence materials. Color tuning of persistent luminescence in Lu2O3:TR3+,M (TR,M: Pr,HfIV; Eu,Ca2+ or Tb,Ca2+) provides potential applications in bioimaging as well as in solar cell sensitizers.

Les lichens sont des organismes symbiotiques constitués d'un champignon (mycobionte) associé à une algue et/ou une cyanobactérie (photobionte). Leurs métabolites secondaires sont des molécules originales appartenant au groupe des depsides, depsidones, dibenzofuranes et présentent un intérêt pour la cosmétique et/ou la pharmaceutique en raison de leur propriété antibiotique, anti-inflammatoire, antioxydant, filtre UV. Nous avons choisi d'étudier le lichen Pseudevenia furfuracea qui est l'un des lichens utilisés en tant que matière première pour la parfumerie et la cosmétique (1900 tonnes / an), car il est d'une part abondant dans la nature et d'autre part, il possède des métabolites secondaires très variés. Classiquement, les extraits utilisés sont obtenus par extraction au reflux de solvants organiques; cette méthode à l'inconvénient d'induire des durées d'extractions relativement longues et est consommatrice en solvants. L'objectif de notre travail est d'extraire les métabolites secondaires d'une manière sélective et innovante tout en diminuant la durée d'extraction. Pour cela, nos travaux reposent sur l'extraction assistée sous micro-onde (EAM) combinée ou non aux liquides ioniques. Dans ce dessein, deux familles de liquides ioniques (LIs) "hydrophiles" et "hydrophobes" ayant un cation imidazolium et pyridinium ont été synthétisés. Trois différentes préparations de lichen (mixé, broyé au mortier et broyé planétaire) ont été effectuées en faisant varier la granulométrie et chaque préparation a été étudiée par microscopie électronique à balayage. L'optimisation de l'EAM a été effectuée à une température d'extraction optimale de 75 °C et a permis de générer un énorme gain de temps (24 h sous conditions classiques contre 15 min sous irradiation micro-onde). Une étude comparative des taux d'extraction entre l'EAM et l'extraction en condition classique a été éffectuée par analyse au spectrodensitomètre CAMAG®, celle-ci a montré que la première est plus performante dans la plupart des cas. L'utilisation des liquides ioniques a mis en évidence l'existence d'une sélectivité d'extraction en fonction de la structure des LIs qui résulte d'interactions intermoléculaires entre les LIs et les substances extraites. L'effet de chaque liquide ionique sur la dégradation d'un des métabolites, en particulier l'atranorine, a également été étudié. Également, les interactions entre un liquide ionique et la surface du lichen ont été étudiées par mesure d'angle de contact et par les mesures de Brunauer Emett et Teller. Une extraction à plus grande échelle a été réalisée pour étudier la reproductibilité de la méthode et la possibilité de recycler le liquide ionique. / Lichens are symbiotic organisms constituted of fungus (mycobiont) associated to algae and/or cyanobacteria (photobiont). Their secondary metabolites are original molecules belonging to the group of depsides, depsidones, dibenzofurans. Lichens presented special interest for cosmetic and pharmaceutical industry due to their antibiotic, anti-inflammatory, antioxidant and UV filter properties. In this work we focused our study on Pseudevenia furfuracea lichen, which is intensively used as a raw material in perfumery and cosmetics (1900 tons/year), due to its large availability in nature as well as possessing various secondary metabolites. In this work we presented extraction of the secondary metabolites using a selective and innovative solventfree method in shorter extraction time in comparison to the conventional extraction methods requiring under reflux of large quantities of solvents with longer times for extraction. The proposed method is based on the use of microwave irradiation for extraction (MIE) associated to (or not) appropriate ionic liquids. Two kinds of hydrophilic or hydrophobic imidazolium- and pyridinium-based ionic liquids (ILs) were synthesized. Three different methods of grinding for lichen were used, leading to different particle size and the crushed products were observed by scanning electron microscopy (SEM). Heating optimization of MIE was performed during 15 min at optimal temperature (75 °C) (instead of 24 h under conventional heating). A comparative study of extraction rates between MIE and extraction with conventional heating was realized with a CAMAG® spectrodensitometer and results of analysis showed that MIE is efficient in most of the studied cases. The use of ionic liquids showed selectivity for extraction and it depended on the structure of ILs and also intermolecular interactions between ILs and extracted substances.Effect of each ionic liquid on the degradation of one of the secondary metabolites, atranorin, was also been studied. In addition, interactions between IL and the surface of the lichen surface were studied by measurements of the angle of contact and by Brunauer Emett and Teller measurements. Scale-up for extraction was carried out to investigate the reproducibility of the method and the possibility of reuse of the ionic liquid.

<p>Predviđena istraživanja u ovoj doktorskoj disertaciji su usmerena u<br />pravcu iznalaženja novih, efikasnijih i bržih mikrotalasno-stimulisanih<br />metoda hemijskih transformacija koje ne uključuju prisustvo<br />katalizatora i/ili organskih rastvarača. Primenom specijalnih silicijum-karbidnih reakcionih sudova, brzina i preciznost izvođenja<br />mikrotalasno-stimulisanih transformacija prikazana&nbsp; je kroz stresne<br />studije aktivnih farmaceutskih ingredijenata u SiC&nbsp; ploči, odnosno<br />HPLC/GC vialima kao reakcionim sudovima. Ispitano je postojanje<br />netermičkih mikrotalasnih efekata i njihov značaj za precizno tumačenje<br />rezultata mikrotalasne sinteze.<br />U drugom delu ove doktorske disertacije izvr&scaron;ena jemikrotalasno-stimulisana sinteza potencijalno biolo&scaron;ki aktivnih&nbsp; supstanci iz prirodnih<br />lako dostupnih materijala kao &scaron;to su naftenske kiseline. Sintetizovani su<br />amidi i estri individualnih i prirodnih naftenskih kiselina Velebit.<br />U radu je takođe ispitana biolo&scaron;ka aktivnost sintetizovanih derivata.<br />Proučavan je uticaj prirodnih naftnih kiselina Velebit injenih derivata<br />na rast pet sojeva&nbsp; Pseudomonassp., kao i uticaj odabranih sintetisanih<br />jedinjenja na proliferaciju pet&nbsp; ćelijskih linija humanih tumora pri&nbsp; čemu<br />je kao kontrola služila jedna zdrava humana ćelijska linija.</p> / <p>Scientific research predicted in this PhD thesis isdirected to ascertainment new, efficient and faster microwave-assisted methods of chemical transformations in the absence of catalysts and/or organic solvents. Applaying special silicon-carbide&nbsp; reaction vessels, speed and accuracy of microwave-assisted transformations are ilustrated within stress testing of active pharmaceutical ingredients in HPLC/GC vials placed in SiC plate. Existence of nonthermal microwave effects and their influence on &nbsp;accurate interpretation of microwave synthesis results are also investigated.&nbsp;<br />In the second part of this thesis microwave-assisted synthesis of potentionally biologically active compounds from readily available natural materials, such as &nbsp;naphthenic acid is accomplished. Amides and esters of individual and natural naphthenic acids Velebitare synthetised. The thesis also examined the biological activity ofthe synthesized products. The effect of natural petroleum acids&nbsp; Velebitand its derivatives are examined on the growth of five strains of Pseudomonas&nbsp;sp., and the impact of selected synthesized compounds on the proliferation of five human tumor cell lines in which a healthy human cell line is tused as the control.</p>

<p>Predviđena istraživanja u ovoj doktorskoj disertaciji su usmerena u pravcu&nbsp;<br />modifikacije klasičnih metoda i postupaka za transformaciju karboksilne grupe&nbsp;<br />prirodnih i sintetičkih karboksilnih kiselina. Modifikacije su rađene novim,&nbsp;<br />savremenim, ekonomski i ekolo&scaron;ki opravdanim metodama rada u&nbsp;<br />mikrotalasnom reaktoru. Modifikovanim sintetskim postupcima u&nbsp;<br />mikrotalasnom reaktoru urađena je sinteza amida, hidroksamskih&nbsp; derivata,&nbsp;<br />kao i redukcija individualnih naftnih kiselina i&nbsp; sme&scaron;e&nbsp; prirodnih naftnih kiselina&nbsp;<br />&bdquo;Velebit&ldquo; do alkohola. Prirodne naftne kiseline kori&scaron;ćene u ovom radu su prvo&nbsp;<br />izolovane iz gasne frakcije (interval destilacije 168-290 &deg;C) vojvođanske nafte&nbsp;<br />&bdquo;Velebit&ldquo; a potom preči&scaron;ćene i razdvojene na uže frakcije na osnovu različite&nbsp;<br />kiselosti. Nakon toga, izvr&scaron;ena je njihova karakterizacija GC-MS-EI analizom&nbsp;<br />(čime je potvrđeno da dolazi do strukturne diferencijacije kiselina). U radu je&nbsp;<br />takođe ispitana biolo&scaron;ka aktivnost sintetizovanih derivata. Proučavan je uticaj&nbsp;<br />prirodnih naftnih kiselina &bdquo;Velebit&ldquo; i njenih derivata na rast&nbsp; pet sojeva&nbsp;<br />Pseudomonas sp., kao i uticaj odabranih sintetisanih jedinjenja na proliferaciju&nbsp;<br />četiri ćelijske linije humanih tumora pri čemu je kao kontrola služila jedna&nbsp;<br />zdrava humana ćelijska linija.</p> / <p>The investigation of this doctoral dissertation is directed toward the modification of the &nbsp;transformation of the carboxylic group of natural and synthetic carboxylic acids. The dissertation takes into consideration the classical methods and procedures of the reaction and modifies them using microwave reactor. The synthesis of amides, hydroxamic derivatives, as well as the reduction&nbsp; of individual petroleum acids and acid mixtures of natural oil &quot;Velebit&quot; to alcohol were achieved&nbsp; by the modifications made to the synthetic methods in the microwave reactor. The natural oil acids used within this study were first isolated from the gas fraction (distillation interval 168-290 &deg;C) of the Vojvodina&#39;s crude oil &quot;Velebit&quot;, and then purified and separated by the narrow fractions under the different acidity. After that, their characterisation was made by the GC-MS-EI analysis which confirmed that the structural differentiation of&nbsp;&nbsp; acids had been achieved. Also, the biological activity of the synthesized derivatives are analysed. The impact of natural petroleum acids &quot;Velebit&quot; and its derivatives on the growth of five strains of&nbsp; Pseudomonas&nbsp; sp. was studied, as well as the impact of selected synthesized compounds on the proliferation of four human tumor cell lines wherein one healthy human cell lines used as the control.</p>

Made available in DSpace on 2014-12-17T15:42:28Z (GMT). No. of bitstreams: 1 MariaJFC_TESE.pdf: 4007652 bytes, checksum: 7bb363c54641679d79bbff5c76de539f (MD5) Previous issue date: 2013-06-03 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior / The processing of heavy oil produced in Brazil is an emergency action and a strategic plan to obtain self-sufficiency and economic surpluses. Seen in these terms, it is indispensable to invest in research to obtain new catalysts for obtaining light fraction of hydrocarbons from heavy fractions of petroleum. This dissertation for the degree of Doctor of Philosophy reports the materials preparation that combine the high catalytic activity of zeolites with the greater accessibility of the mesoporosity, more particularly the HZSM-5/MCM-41 hybrid, done by synthesis processes with less environmental impact than conventional ones. Innovative methodologies were developed for the synthesis of micro-mesoporous hybrid material by dual templating mechanism and from crystalline zeolitic aluminosilicate in the absence of organic template. The synthesis of hybrid with pore bimodal distribution took place from one-single organic directing agent aimed to eliminate the use of organic templates, acids of any kind or organic solvents like templating agent of crystalline zeolitic aluminosilicate together with temperature-programmed microwave-assisted, making the experimental procedures of preparation most practical and easy, with good reproducibility and low cost. The study about crystalline zeolitic aluminosilicate in the absence of organic template, especially MFI type, is based on use of H2O and Na+ cation playing a structural directing role in place of an organic template. Advanced characterization techniques such as X-Ray Diffraction (XRD), Fourier Transform Infrared Spectroscopy (FTIR), Scanning Electron Microscopy (SEM), Highresolution Transmission Electron Microscopy (HRTEM), Adsorption of N2 and CO2, kinetic studies by Thermogravimetric Analysis (TGA) and Pyrolysis coupled to Gas Chromatography/Mass Spectrometry (Pyrolysis-GC/MS) were employed in order to evaluate the synthesized materials. Achieve the proposed objectives, has made available a set of new methodologies for the synthesis of zeolite and hybrid micro-mesoporous material, these suitable for catalytic pyrolysis of heavy oils aimed at producing light fraction / O processamento do petr?leo pesado produzido no Pa?s ? uma a??o emergencial e estrat?gica para obter a auto-sufici?ncia e super?vits econ?micos. Neste sentido, ? indispens?vel o investimento em pesquisas de novos catalisadores para obten??o de derivados leves a partir de fra??es pesadas do petr?leo. O trabalho de doutorado aqui reportado dedicouse ? prepara??o de materiais que combinem, numa ?nica estrutura, a elevada atividade catal?tica de ze?litas, com melhor acessibilidade de materiais mesoporosos, como a estrutura h?brida HZSM-5/MCM-41, utilizando processos de s?ntese com menor impacto ambiental que os convencionais. Metodologias inovadoras foram desenvolvidas para a s?ntese do catalisador h?brido micro-mesoporoso ou ze?lito-mesoporoso por mecanismo de direcionamento estrutural via duplo agente diretor org?nico e tamb?m a partir de estrutura zeol?tica sintetizada na aus?ncia total de direcionador org?nico. Esse ?ltimo, tamb?m chamado de s?ntese do h?brido com distribui??o bimodal de poros a partir de um ?nico agente diretor org?nico, visou eliminar o uso dos direcionadores org?nicos, ?cidos de qualquer natureza ou solventes org?nicos como molde estrutural da estrutura zeol?tica em conjunto com o m?todo hidrot?rmico assistido por irradia??o via micro-ondas, tornando o procedimento experimental de prepara??o pr?tico e simples, com boa reprodutibilidade e menor custo. A metodologia de prepara??o da ze?lita MFI do tipo ZSM-5 utiliza H2O e c?tions Na+ no papel de direcionamento estrutural e compensa??o de cargas na estrutura. T?cnicas relevantes de caracteriza??o, como Difra??o de Raios-X (XRD), Espectroscopia no Infravermelho com Transformada de Fourier (FTIR), Microscopia Eletr?nica de Varredura (SEM), Microscopia Eletr?nica de Transmiss?o de Alta Resolu??o (HRTEM), Adsor??o de N2 e CO2, estudos cin?ticos via An?lises Termogravim?tricas (TGA) e Pir?lise acoplada ? Cromatografia Gasosa/Espectrometria de Massas (Pyrolysis-GC/MS), foram empregadas no intuito de avaliar os materiais sintetizados. Alcan?ados os objetivos propostos, disponibilizou-se um conjunto de novas metodologias para s?ntese de catalisadores zeol?ticos e h?bridos micromesoporosos, estes adequados para pir?lise catal?tica de ?leos pesados visando ? produ??o de derivados leves

Chromatography and extraction techniques, and also chemiluminescence have been utilized to develop new rapid and informative tools in the evaluation of long-term properties and environmental effects of polymeric materials. Methods were developed for classification of materials and for early and rapid degradation detection. Degradable polyethylene films were classified on the basis of their incorporated prooxidant systems using chromatographic fingerprinting of carboxylic acids, the dominating type of degradation product. The fingerprints were also shown to be useful for prediction of the degradation states and evaluation of the degradation mechanisms. Classification and prediction models were obtained by Multivariate Data Analysis, where the diacids were grouped according to both their type of prooxidant system and their state of degradation. The use of total luminescence intensity (TLI) measurements was also investigated as a means of classifying films and for the early detection of degradation. Comparisons were carried out with common techniques, e.g. FTIR and DSC, after both thermal and UV oxidation. TLI gave an earlier detection of degradation and was more sensitive than carbonyl index and crystallinity measurements to relative differences in degradation between the materials. It furthermore offered complementary information regarding changes in activation energies during the course of the degradation. The results were compared with the chromatographic fingerprints. A new way to evaluate the low temperature long-term stabilisation efficiency of antioxidants was investigated. A prooxidant was used to obtain catalytic oxidation, instead of using thermal acceleration, to evaluate the stabilisation efficiency of antioxidants at low temperatures but still during reasonably short aging times. Comparisons were made between polypropylene films stabilised with primary antioxidants (Irganox 1076, Irganox 1010 and α-tocopherol) with and without the prooxidant manganese stearate at different temperatures. The relative efficiencies of the antioxidants obtained under prooxidant acceleration test correlated better than thermal acceleration test with the results of a long-term low temperature test. Additives in plastic packaging materials may affect the environment after migration from the packaging to e.g. their contents, especially if they consist of organic aqueous solutions or oils. The use of Solid-Phase Microextraction (SPME) for the specific task of extraction from an organic aqueous solution such as a simulated food or pharmaceutical solution consisting of 10 vol-% ethanol in water was investigated. Methods were developed and evaluated for extraction both with direct sampling and with headspace sampling. If the extraction method and temperature were selected to suit the concentration levels of the analytes, it was possible to quantify several degradation products simultaneously. Comparisons made with Solid Phase Extraction showed the advantage of SPME for this purpose. / QC 20100929

Les oxydes à base de Cérium, ont fait l’objet de nombreuses études ces dernières décennies et se sont révélés des matériaux de choix, dans le domaine de la catalyse hétérogène. L’objectif à l’heure actuelle, est donc d’accroître la réactivité de ces oxydes, tout en élargissant leur gamme de températures optimales d’utilisation. Dans ce contexte particulier, il semble possible de moduler les propriétés des oxydes à base de cérium en contrôlant la morphologie des cristallites. Ce travail de thèse a donc été consacré à la détermination, l’élaboration et à la caractérisation de matériaux oxydes à base de cérium de morphologies contrôlées. Nous avons tout d’abord déterminé cristallographiquement et thermodynamiquement les morphologies accessibles au système étudié puis par traitement hydrothermale assistée par chauffage micro-ondes nous avons synthétisé les dites morphologies. Après caractérisation de la réactivité par ATG et thermographie Infrarouge nous avons optimisé ces matériaux par un dopage extrinsèque tout d’abord (dépôt de métaux précieux), puis par un dopage intrinsèque ensuite (Yttrium et Fer). Enfin, l’obtention de morphologies non accessibles cristallographiquement nous a amené à approfondir le(s) processus de germination croissance de ces particules et la forte réactivité des matériaux dopés fer nous a poussé à une caractérisation fine de la microstructure de ces matériaux. Au final nous avons pu corréler l’influence de la morphologie des cristallites sur la réactivité propre de l’ensemble des familles de matériaux étudiés. / Recent decades, numerous studies on cerium-based oxides have been realized and have revealed that cerium-based oxides were materials of choice in the field of heterogeneous catalysis. The aim now is therefore to increase the reactivity of these oxides, while expanding their range of optimal temperatures of Use. In this particular context, it seems possible to modulate the properties of cerium-based oxides by controlling the morphology of the crystallites. This thesis has been devoted to the identification, development and characterization of materials based on cerium oxides of controlled morphology. We first determined possible morphologies for the studied system, by hydrothermal synthesis by micro-wave assisted heating we have synthesized these morphologies and we characterized reactivity of these materials by infrared thermography and TGA. We have optimized these materials first, by extrinsic doping (deposition of precious metals) and then by intrinsic doping (Yttrium and Iron). New morphologies have been synthesized so we have studied the processes of nucleation-growth set in. The high reactivity of iron-doped materials has led us to a detailed characterization of the microstructure of these materials. Finally correlation reactivity/morphologies of crystallites have been achieved.

L’objectif de la thèse est une mise au point des espèces de Stephania répertoriées au Cambodge par l’étude systématique, phytochimique et pharmacologique. Du point de vue systématique, les travaux ont permis de répertorier sept espèces et deux variétés de Stephania au Cambodge : S. cambodica, S. japonica var. discolor et var. timoriensis, S. oblata, S. pierrei, S. rotunda (espèce-type), S. suberosa, et S. venosa. La clef de détermination établie lors de ce travail de thèse permet d’identifier ces espèces. D’après les résultats phylogénétiques, seul S. pierrei est monophylétique, ce qui représente moins de 10% des espèces de Stephania. L’étude chimique de cinq espèces a été réalisée par des méthodes chromatographiques (CLHP, UCLHP) et des méthodes spectroscopiques. Différents alcaloïdes ont été proposés comme marqueurs : la palmatine, la roémérine et la tétrahydropalmatine pour S. cambodica et S. rotunda, la cépharanthine, la tétrahydropalmatine et la xylopinine pour S. suberosa, la cépharanthine pour S. pierrei, la crébanine, et la tétrahydropalmatine pour S. venosa. Neuf alcaloïdes ont été isolés à partir du tubercule de S. cambodica, dont un nouveau composé dénommé «angkorwatine ». Une méthode d’éco-extraction des alcaloïdes assistée par ultrasons a été mise au point et optimisée par un plan d’expérience pour cette espèce. Une méthode analytique par UCLHP a été développée et validée pour le contrôle qualité de S. cambodica. Les résultats montrent que les extraits hydroéthanoliques obtenus par macération à partir du tubercule de S. suberosa, S. venosa et S. rotunda présentent une activité anti-inflammatoire importante (in vitro) avec un ratio anti-inflammatoire élevé. / The thesis aims to provide update on species of the genus Stephania recorded in Cambodia by systematic, phytochemical and pharmacological studies.The systematic study allowed to list seven species and two varieties of Stephania in Cambodia: S. cambodica, S. japonica var. discolor and var. timoriensis, S. oblata, S. pierrei, S. rotunda (type species), S. suberosa and S. venosa. The presence of S. japonica var. timoriensis and S. oblata is reported for the first time in Cambodia. According to the phylogenetic results, only S. pierrei is monophyletic, which represents less than 10% of species in the genus Stephania. Chemical studies on the tubers of five species were carried out using chromatographic methods (HPLC, UHPLC) and spectroscopic methods. Different isolated alkaloids have been proposed as markers: palmatine, roemerine and tetrahydropalmatine for S. cambodica and S. rotunda, cepharanthine, tetrahydropalmatine, and xylopinine for S. suberosa, cepharanthine for S. pierrei, crebanine, and tetrahydropalmatine for S. venosa. Nine alkaloids belonging to five classes were isolated from the tuber of S. cambodica and a new compound namely "angkorwatine" was described. Ultrasound assisted extraction of alkaloids was developed and optimized by Design of Experiment for this species. This innovative extraction is a good alternative to conventional methods. An analytical UHPLC method was developed and validated for the quality control of S. cambodica. Results show that hydroethanolic extracts obtained by maceration of S. suberosa, S. rotunda and S. venosa exhibit significant anti-inflammatory activity with high anti-inflammatory ratio (selectivity index).