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Síntese e caracterização de complexos de lantanídeos pesados e ítrio(III) como o fármaco ibuprofeno no estado sólido /Holanda, Bruno Barreto da Cunha. January 2015 (has links)
Orientador: Gilbert Bannach / Co-orientador: Alexandre Oliveira Legendre / Banca: Luiz Carlos da Silva Filho / Banca: Egon Schnitzler / O Programa de Pós Graduação em Ciência e Tecnologia de Materiais, PosMat, tem caráter institucional e integra as atividades de pesquisa em materiais de diversos campi / Resumo: Nos anos sessenta o ibuprofeno foi desenvolvido e introduzido no mercado como um fármaco do grupo do AINESs (anti-inflamatórios não-esteróides) para o tratamento de uma ampla variedade de enfermidades. Diversas pesquisas estão sendo realizadas com o intuito de estudar as atividades biológicas de complexos metálicos, com isso, o presente trabalho teve objetivo contribuir para ampliar estudos sobre o desenvolvimento de novos metalofármacos envolvendo metais lantanídeos trivalentes pesados (gosolínio, térbio, disprósio, hôlmio, érbio, túlio, iterbio, lutércio) e Ítrio com ibuprofeno, os quais possuem fórmula geral (Ln(ibu)3].nH2O, no estado sólido. Os componentes foram caracterizados por termogravimetria - análise térmica diferencial (TG-DTA), calorimetria exploratória diferencial (DSC), termogravimetria derivada (DTG), espectroscopia vibracional na região do infravermelho com transformada de Fourier (FTIR), difratometria de raios X pelo método do pó (DRX), termogravimetria acoplada à espectroscopia de absorção na região do infravermelhocom transformada de Fourier (TG- FTIR)e titulação complexométrica com EDTA. Com os resultados obtidos pelas curvas TG-DTA foi possível determinar a estabilidade térmica dos compostos, o número de etapas de decomposição térmica e os intervalos de temperaturas que estas ocorreram, além de estabelecer uma estequiometria para os compostos sintetizados. A técnica DSC permitiu verificar a entalpia de desidratação do composto de térbio e a energia envolvida na primeira perda de massa, a qual foi sugerida perda de molécula de propano em todos os compostos. Os dados de FTIR permitiram estudar os estiramentos do grupo carboxilato e, assim, sugerir uma coordenação metal-ligante para os compostos. A difração de raios X pelo método do pó, mostrou que os compostos apresentaram um perfil de baix cristanilidade sem evidências de formação de uma sério isomórfica. A análise dos... / Abstract: In the sixties ibuprofen was developed and marketed as a drug in the group of NSAIDs (non-steroidal anti-inflammatory drugs) for the treatment of a wide variety of diseases. Several investigations have been performed in order to study the biological activity of metal complexes, with this, the presented workwa to contribute to expand studies on the development of new metallodrugs involvin heavy metals trivalent lanthamides (gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium) and yttrium ibuprofen, which have the general formula [Ln(ibu)3]. nH2O in solid state. The compounds were characterized by thermogravimetry - differential thermal analysis (TG-DTA), differential scanning calorimetry (DSC), derivative thermogravimetry (DIG) vibrational spectroscopy in the infrared Fourier transform spectroscopy (FTIR), X-ray diffraction by the powder method (XRD) coupled to the absorption spectroscopy in the infrared Fourier transform spectroscopy (TG-FTIR) and thermogravimetry complexometric titration with EDTA. Using the TG-DTA technique it was possible to determine the thermal stability of the compounds, the number of stages of thermal decomposition temperatures and that they occurred, and to provide a stoichiometry of these compounds. The DSC technique demonstrated the enthalpy of dehygration in the compound of terbium and the energy loss involved in the first mass, which was suggested loss of propane in each molecule compounds. The infrared study allowed the stretches of the carboxylate group and thus suggest a metal-ligand coordination compounds. The X-ray diffraction by the powder method showed that compounds showed a profile of low cristallinity. The analysis of the spectra in the infrared region of the volatiles showed a great similiraty with the propane spectrum, confirming its potential as the major product release during the first stage of thermal decomposition of the anhydrous compounds A complexometric titration... / Mestre
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Matrizes semicondutoras GaAs e Sn'X IND. 2' dopado com terras-raras Ce ou Eu : investigação do transporte elétrico /Pineiz, Tatiane de Fátima. January 2009 (has links)
Orientador: Luis Vicente de Andrade Scalvi / Banca: Valmor Roberto Mastelaro / Banca: Paulo Noronha Lisboa Filho / O Programa de Pós-Graduação em Ciência e Tecnologia de Materiais, PosMat, tem caráter institucional e integra as atividades de pesquisa em materiais de diversos campi da Unesp / Resumo: Dióxido de estanho (Sn'X IND. 2') é um semicondutor de bandgap largo com condutividade do tipo-n na forma não dopada, sendo aplicado em dispositivos diversos. Neste trabalho, filmes finos e géis secos de Sn'X IND. 2' dopados com os íons terras-raras 'Ce POT. 3+' e "Eu POT 3+' foram sintetizados através do processo sol-gel. Por outro lado, filmes finos de GaAs têm também sido amplamente utilizados, devido a alta mobilidade eletrônica e transição direta. Neste trabalho, também foram produzidos filmes finos de GaAs através da técnica de evaporação resistiva. Serão mostrados e discutidos aqui resultados referentes a filmes finos de Sn'X IND. 2' dopado com íons terras-raras, filmes finos de GaAs e resultados referentes ao crescimento de filmes finos de GaAs sobre filmes finos de SnO2 dopados com terras-raras. Medidas de absorção óptica permitiram avaliar a qualidade óptica dos filmes e estimar a energia do bandgap. Dados de difração de raios-X mostraram estrutura do tipo rutilo e fase cassiterita dos filmes de Sn'X IND. 2' e também as direções principais dos filmes de GaAs. A microscopia eletrônica de varredura permitiu a espessura e a qualidade morfológica da heterojunção, tanto com relação à interface Sn'X IND. 2'/GaAs como da superfície. A investigação das propriedades elétricas em Sn'X IND. 2' mostra a alta resistividade do material devido ao caráter aceitador de íons terras-raras na matriz. Foi investigada também a captura de elétrons fotoexcitados por centros de 'Ce POT 3+' termicamente ativados. Do modelo proposto, foram obtidos parâmetros importantes, como a barreira de captura devido aos defeitos dominantes. Resistividade em função da temperatura na heterojunção Sn'X IND. 2'/GaAs mostrou a diminuição da resistência do conjunto. / Abstract: Tin dioxide (Sn'X IND. 2') is a wide bandgap semiconductor material whith n-type conductivity the undoped form. This compound has been applied for several kinds of devices. In this work, thin films and xeogels of Sn'X IND. 2' doped with the rare-earth ions 'Ce POT. 3+' and "Eu POT 3+' have been produced by the sol-gel process. On the other band, GaAs thin films have also been widely used, due to high electronic mobility and direct bandgap transition. In this work, GaAs thin films have been deposited by the resistive evaporation technique. It is shown and discussed here results concerning rare-earth doped Sn'X IND. 2' thin films. GaAs thin films and the growing of GaAs on the top of rare-earth doped Sn'X IND. 2'. Through the optical absorption spectra it has been possible to evaluate the films optical quality and to estimate the optical bandgap. X-ray diffraction data show the rutile like structure and cassiterie phase of Sn'X IND. 2' thin films and also show the main directions of GaAs films. Scanning electron microscopy allowed evaluating the thickness and morphological quality of the heterojunction, concerning the infarce as well as the surface. Investigation of electrical properties of Sn'X IND. 2' shows high resistivity of this material due to the acceptor-lide character of rare-earth ions in the matrix. It has also been investigated the trapping of photo-induced electrons by the thermally activated Ce centers. From a proposed model, it has been obtained some relevant parameters, such as the capture barrier due to the dominant defects. Data of resistivity as function of temperature for the Sn'X IND. 2'/GaAs heterojunction show the decrease of overall resistance. / Mestre
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Sorção de lantanídeos em meio aquoso visando ao estudo de rejeitos nuclearesBelline, Jean de Brito January 2009 (has links)
O problema de rejeitos radioativos é uma preocupação de âmbito mundial, uma vez que não há, ainda, um local definido para a construção de um repositório para rejeitos radioativos de alto nível. Uma das etapas preliminares para a escolha do local mais apropriado é o estudo geológico associado a estudos experimentais de adsorção das espécies químicas envolvidas nos processo. Neste trabalho foi utilizado uma amostra de rocha basáltica, da região sul da Formação Serra Geral, coletada em Frederico Westphalen (RS), que servirá como candidata à rocha hospedeira para locação de rejeitos radioativos. Foram realizados dois experimentos, a saber: "Batch Test" e percolação, ambos sob pressão atmosférica, à temperatura ambiente de 25°C, com a finalidade de estudar a capacidade de sorção dos elementos terras raras - ETR. Os ETR são utilizados neste trabalho em função de sua analogia com os actinídeos, visando a investigar o comportamento geoquímico e a especiações dos mesmos em águas naturais, buscando a possibilidade de armazenamento geológico de rejeitos radioativos, uma vez que a adsorção dos ETR depende de variáveis do ambiente como pH, força iônica, temperatura e presença de ligantes, como carbonatos e constituintes de superfícies dos minerais. Foi realizado experimento de percolação dos ETR, a 100ppb, no basalto (com granulometria 80 mesh) em soluções com força iônica I= 0,025 M e I=0,5 M de NaCl. O pH foi controlado em uma faixa de 5,6 a 7,6 com adição de HNO3. As concentrações foram analisadas por ICP-MS. O "Batch Test" é uma eficiente forma de se obter isotermas de sorção/dessorção, além de valores da razão entre as distribuições sólido/solução e estimar a solubilidade. O experimento de percolação, foi realizado sob pH controlado em torno de 6, e permitiu verificar a "preferência" dos ETR pesados em relação aos ETR leves. / The problem of radioactive wastes is a concern of world-wide scope, a time that does not still have a defined local for the construction of a repository for radioactive wastes of high level. One of the preliminary stages for the choice of the place more appropriate is the geologic study associated to the experimental studies of adsorprtion of the involved chemical species in the process. In this work, a sample of basaltic rock was used, of the South Region of the Formation Serra Geral, collected in Frederico Westphalen Town (RS), that it will be probably a candidate to the rock hostess for location of radioactive wastes. Two experiments have been carried out through, namely: "Test Batch" and Percolating, both under atmospheric pressure, at the ambient temperature of 25°C, with the purpose to study the capacity of sorption of the rare earth elements - REE. The REE are used in this work in function of its analogy with the actinídes, aiming at to investigate the chemistry behavior and the speciations of the same in natural waters, searching the possibility of geologic storage of radioactive wastes, a time that the adsorption of the REE depends on variables of the environment as pH, ionic strengh, temperature and presence of ligants, as carbonates and constituent of surfaces of minerals. Experiment of percolating of the REE was carried through, 100ppb, in the basalt (with 80 mesh) in solutions with ionic strengh I= 0,025 M and I=0,5 M of NaCl. pH was controlled in a range of 5,6 the 7,6 with HNO3 addition. The concentrations were analyzed by ICP-MS. The "Batch Test" is an efficient form of studing sorption/dessorption isotherms, beyond values of the reason between the distributions solid/solution and estimation of the solubility. The percolating experiment, was carried through under pH controlled around 6, and allowed to verify the behaviour of heavy REE in comparison with the light REE.
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IGNEOUS INTRUSIONS AT HICKS DOME, SOUTHERN ILLINOIS, AND THEIR RELATIONSHIP TO FLUORINE-BASE METAL-RARE EARTH ELEMENT MINERALIZATIONMoorehead, Anthony J. 01 August 2013 (has links)
Hicks Dome is a mineralized intrusive center of alkaline ultramafic dikes, plugs and diatreme breccias that produced ~1200 m of structural doming of Paleozoic sedimentary rocks in southeastern Illinois. It is part of an igneous province referred to as the "Wauboukigou Alnöite Province" or "Middle Mississippi Alkaline Province". The 40Ar/39Ar dating of biotite and hornblende from igneous rocks throughout the region has consistently produced crystallization ages of 270 +/- 2 Ma (Early-Middle Permian). Hicks Dome lies near the intersection of two aulacogens, the Reelfoot Rift and the Rough Creek Graben. The igneous rocks in the Hicks Dome area range from dark-green, porphyritic dikes, through dikes with pelletal lapilli, to carbonate cemented breccias with country rock fragments and, locally, phenocrysts or xenocrysts and pelletal lapilli. Magmatic minerals include diopside, pargasite, phlogopite-biotite, titanomagnetite, ilmenite, and apatite, as well as carbonate (ferroan-dolomite - ankerite and calcite) of possible magmatic origin. This mineral assemblage only partly corresponds with other occurrences in the middle Mississippi Valley region igneous province as melilite, garnet, olivine, and perovskite were not identified in the Hicks Dome samples. The Hicks Dome igneous lithotype is defined here as a minette, a type of calc-alkaline lamprophyre. Evidence for this classification includes abundant Al-rich phlogopite-biotite, diopside, and pargasite, and the absence of melilite, garnet, and perovskite. Additionally, plotted Al2O3 vs. TiO2 compositions of biotite-phlogopite form a trend subparallel to that of minettes and alnöites, and Al vs. Ti values for most clinopyroxenes fall in the minette field. Some other igneous occurrences in the region are classified as types of ultramafic lamprophyres. For example, the North Hutson mine (Kentucky) and the Cottage Grove (Illinois) dikes are identified as alnöites and the Wildcat Hills dike (Illinois) is regarded as an aillikite. The Hicks Dome igneous suite contains 23 - 25 wt. % SiO2 and 13 - 21 wt. % CO2, whereas regional igneous rocks contain 33 - 36 wt. % SiO2 and 1 - 2 wt. % CO2. Such high CO2 values and inferred carbonate abundance is likely related to the elevated REE values at Hicks Dome. Finally, Hicks Dome samples show relative depletions in Ti, Nb, Ta, Zr, and Hf on a spider diagram compared to other regional igneous occurrences. These data indicate more variability among provincial igneous rocks than previously realized and perhaps two types of lamprophyres, one a calc-alkaline such as at Hicks Dome, and the other an alkaline ultramafic type. Rock samples from Hicks Dome and the surrounding region that were analyzed far exceed the silica cut-off to be considered a carbonatite (sensu stricto), yet a strong, consistent spatial association of abundant carbonate with igneous rocks throughout the region and similar patterns in LIL (large ion lithophyle), HFS (high field strength) and RE (rare earth) elements with carbonatites worldwide supports that magmatic carbon was part of the lamprophyre system at Hicks Dome. Carbon and oxygen isotope values for carbonate from Hicks Dome and other regional igneous samples do not plot within the field for primary carbonatite or the field for unaltered Mississippian limestone and instead form a broad linear trend between these two reference fields. The observed isotopic trend was possibly due to alteration of primary carbonatite by magmatic-hydrothermal and later low-temperature connate fluids. Parisite and/or synchysite, two REE fluorocarbonates of the bastnäsite group, and xenotime, a Y-(REE) phosphate, were identified in the Hicks Dome samples and occur as fibroradial aggregates in dissolution cavities in fluorite and carbonate and as anhedral crystals infilling microfractures and cleavage planes of phlogopite-biotite and paragasite. These textures clearly indicate the REE minerals are secondary phases most likely resulting from hydrothermal alteration-replacement by magmatic-hydrothermal fluids. A fertile (LREE enriched) lithospheric metasomatized mantle likely sourced the Hicks Dome carbonated alkaline silicate magma that, during emplacement, domed and brecciated the Paleozoic strata, expelled magmatic-hydrothermal fluids, and generated a F-REE mineralizing fluid with abundant carbonate. Igneous activity at Hicks Dome is genetically related to F-REE-base metal mineralization hosted by diatreme breccias, and likely contributed fluorine to the connate brines responsible for the F-base metal mineralization of the surrounding Illinois-Kentucky Fluorspar District (IKFD). Although resource estimates for the Hicks Dome area are beyond the scope of this work, an economic deposit of F, REEs, and/or base metals may be present at Hicks Dome and other igneous occurrences. The igneous lithotype, mineralogy, whole rock geochemistry, and regional geologic context support such a conclusion.
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Mineralogia e geoquímica dos nyf-pegmatitos da mina de Pitinga (Amazonas-Brasil)Paludo, Carina Machado January 2017 (has links)
Os pegmatitos estudados estão associados à fácies albita granito do granito Madeira, a qual corresponde ao depósito de Sn-Nb-Ta (F, ETR, U, Th) Madeira, na mina Pitinga (AM) e estão associados a falhas de orientação N320/60SW. Estas rochas contêm minerais poucos comuns como gagarinita (NaCaYF6), genthelvita (Zn4Be3(SiO4)3S) e polilitionita (KLi2AlSi4O10(F, OH)2), além de grandes quantidades de criolita (Na3AlF6). Com base na composição química e mineralógica, estes pegmatitos foram classificados em três tipos: PEG ANF (teores médios de K e Na, com alta concentração de anfibólios), PEG POL (rico em K e com alta concentração de polilitionita) e PEG CRIO (rico em Na e com alta concentração de criolita). Estes pegmatitos contêm altos teores de ETR (especialmente ETRP) e Y, que estão concentrados principalmente na xenotima e na gagarinita. Estes elementos também ocorrem em elevados teores na grande parte dos demais minerais analisados. Também se destacam as concentrações anômalas de F, muito superiores às detectadas nos pegmatitos de outras localidades, e que promoveram o enriquecimento em Li, Na, K, Rb e Cs. A similaridade na composição química do AGN com os pegmatitos indica que eles possuem a mesma fonte. / The pegmatites studied are associated with the albite granite facies of the Madeira granite, which corresponds to the Sn-Nb-Ta (F, ETR, U, Th) Madeira deposit at the Pitinga mine (AM). They are associated with N320/60SW orientation faults. These rocks contain few common minerals such as gagarinite (NaCaYF6), genthelvite (Zn4Be3(SiO4)3S) and polylithionite (KLi2AlSi4O10(F,OH)2), as well as large amounts of cryolite (Na3AlF6). Based on the chemical and mineralogical composition, these pegmatites were classified into three groups: PEG ANF (medium K and Na, with high concentration of amphiboles), PEG POL (K rich and with high polylithionite concentration) and PEG CRIO (rich in Na and with high concentration of cryolite). These pegmatites contain high levels of REE (especially HREE) and Y, which are mainly concentrated in xenotime and gagarinite. These elements also occur at high levels in most of the other minerals analyzed. Anomalous concentrations of F, much higher than those detected in pegmatites from other localities, were also highlighted, and promoted enrichment in Li, Na, K, Rb and Cs. The similarity in the chemical composition of AGN with pegmatites indicates that they have the same source.
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Les granites pegmatitiques enrichis en éléments de terres rares légères marqueurs des processus de croissance et de différenciation crustale : exemple de la Province Protérozoïque de Grenville, Québec / Light rare-earth elements enriched pegmatitic granite as tracers of crustal growth and differentiation processes : example of the Proterozoic Grenville Province, QuebecTurlin, François 15 December 2017 (has links)
Les éléments de terres rares (ÉTR) sont des métaux de grand intérêt économique et des traceurs géologiques de premier ordre mais leur cycle métallogénique reste encore méconnu. La Province de Grenville expose sa racine orogénique et présente une grande concentration d’occurrences d’ÉTR, notamment associées à des granites pegmatitiques (« PGD ») dans le Grenville central. Deux mécanismes peuvent être à l’origine de ces PGD, (i) la fusion partielle d’une croûte continentale archéenne et/ou paléoprotérozoïque de la racine orogénique, ou (ii) l’extrême différenciation de magmas mantelliques produits en contexte d’extension post-orogénique. Une approche multi-méthodes (terrain, pétrogéochimie, géochronologie et isotopie) permet de caractériser ces PGD à ÉTR et de discuter leur pétrogénèse dans le cadre de l’évolution géodynamique de la province. Ils ont intrudé à ~1005-1000 Ma (U-Pb monazite et zircon) des métaplutons (minéralisation en allanite) ou des séries métasédimentaires (minéralisation en monazite) du segment de moyenne pression de la ceinture Allochtone. La datation U-Pb sur monazite et apatite d’un leucosome de ces paragneiss migmatitiques met en évidence un pic de métamorphisme au faciès granulite à 1080-1050 Ma suivi d’un refroidissement lent à un taux de 2 à 6°C/Ma, d’abord dans les conditions suprasolidus jusqu’à l’intrusion des PGD dans des conditions proches du solidus hydraté, puis dans des conditions subsolidus jusqu’à l’isotherme 450-500°C enregistré à 970-950 Ma. L’intrusion des PGD est synchrone de l’initiation dès ~1005 Ma de la fusion partielle prolongée (> 20 Ma) des métasédiments parautochtones sous-jacents. Le caractère peralumineux des PGD, l’étude de zircons néoformés des PGD (isotopes U-Pb-Hf-O et éléments traces), et l’étude pétrogéochimique des PGD et des métapélites paléoprotérozoïques à archéennes de la ceinture Parautochtone, issues de l’érosion de la marge de Laurentia, traduisent la formation des PGD par leur fusion partielle. Au contraire, un PGD issu de la remobilisation de plutons allochtones est peu minéralisé en ÉTR, confirmant que l’extraction des ÉTR de ces occurrences du Grenville central est associée à des roches d’affinité crustale du Craton du Supérieur / The Rare Earth Elements (REE) are of great economic interest and first order geological tracers. However, their metallogenic cycle remains poorly defined. The Grenville Province exposes its orogenic root and shows numerous REE occurrences that are especially associated with pegmatitic granite dykes (“PGD”) in the central Grenville. Two hypotheses can account for the genesis of these PGD, whether (i) the partial melting of the orogenic root composed of reworked Archean and/or Proterozoic pre-existing continental crust, or (ii) the extreme differentiation of mantle melts produced during post-orogenic extension. A multi-method approach (field geology, petrogeochemistry, geochronology and isotopy) allow to characterize the PGD and discuss their petrogenesis during the geodynamic evolution of the province. They intruded at ca. 1005-1000 Ma (U-Pb on monazite and zircon) metaplutons (mineralization hosted in allanite) or metasedimentary sequences (mineralization hosted in monazite) from the mid-pressure allochthonous crustal segment. U-Pb dating on monazite and apatite from a single leucosome of these migmatitic paragneisses evidence for a peak of metamorphism at ca. 1080-1050 Ma that was followed by a slow cooling at a rate of 2 to 6°C/Ma, first under suprasolidus conditions until the close to wet-solidus intrusion of PGD, and then under subsolidus conditions down to the 450-500°C isotherm dated at ca. 970-950 Ma. The intrusion of the PGD is coeval with the initiation as early as ca. 1005 Ma of the protracted (> 20 Ma) partial melting of underlying parautochthonous paragneisses. The peraluminous character of the PGD, the investigation of pristine magmatic zircon of the PGD (U-Pb-Hf-O isotopes and trace elements), and the petrogeochemical investigations of parautochthonous Paleoproterozoic-Archean metapelites that derive from the Laurentian margin’s erosion, points to the derivation of the PGD from their partial melting. To the contrary, one PGD derived from the reworking of allochthonous plutonic units is poorly mineralized in REE, and confirms that REE from the central Grenville occurrences are issued from crustal rocks of the Superior Craton
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Synthèse de nanoparticules multifonctionnelles pour le diagnostic et l’imagerie médicale avec de futures applications en radiothérapie / Multifunctional nanoparticles for imaging and tracking with potential applications in radiotherapyLavenas, Magali 06 December 2017 (has links)
Une des plus grande cause de mortalité aujourd'hui est le cancer. Acutellement, les nanotechnologies ont permis le développement de nouvelles approches dans le traitement du cancer. Ainsi, il est devenu nécessaire de concevoir et modeler des nanoparticules (NPs) multimodales et d'évaluer leur application thérapeutique potentielle. Les nanoparticules inorganiques étudiées dans le cadre de ce travail sont basées sur des oxydes métalliques (e.g. TiO2 et HfO2) et présentent plusieurs fonctionnalités permettant leur localisation et leur quantification en utilisant différentes techniques telles que l'IRM et l'imagerie optique. Notamment grâce à l'insertion de terres rares dans la matrice NPs. D'autre part, comme la température des cellules saines et cancéreuse diffère, la détermination locale de la température peut être intéressante et obtenue par l'étude de la luminescence d'une paire de terres rares judicieusement choisie.Ainsi des NPs de TiO2 et de HfO2 ont été synthétisées par voie hydrothermale, permettant un contrôle de leur taille et de leur morphologie. De plus, des terres rares, comme l'europium, le terbium et le gadolinium ont été insérées au sein des matrices d'oxyde d'hafnium permettant d'obtenir des nanoparticules multifonctionnelles, basées sur la détection par imagerie optique et magnétique et la détection de la température (nanothermomètre). Les NPs ont été caractérisées et des mesures de relaxivité ont été effectuées. La luminescence de ces NPs a été étudiée et a permis la mise au point d'un nanothermomètre avec une sensibilité de 0.1%.K-1. / Cancer is one of the main cause of mortality in the world. Recently, nanotechnologies have led tonew approaches in cancer therapy. In this context, it is important to design multimodal nanoparticles (NPs) andassess their therapeutic potential. The inorganic NPs studied here are based on metal oxides (e.g., TiO2 and HfO2)exhibiting functionalities that allow their localization and tracking using various techniques (MRI, luminescence),as well as their quantification. For this purpose, rare-earth elements are inserted in the metal oxide matrices. Asthe lethal temperatures for healthy and tumor cells are different, it is also important to ascertain thetemperature of the cells during ionizing radiation treatment. This may be achieved based on the light emissionof suitable pairs of rare-earth elements.Thus, titania and hafnia nanoparticles were synthesized by the hydrothermal method enabling the control ofmorphology and size. Furthermore, the hafnia matrices were doped with rare-earth elements, such as europium,terbium and gadolinium, endowing NPs with functionalities such as luminescence tracking, magnetic resonanceimaging and nanothermometry. The chemical characterizations were performed and the relaxivity constantswere assessed. The luminescence response was also studied, and one nanothermometer with a sensitivity atroom temperature ca. 0.1 %.K-1 was obtained.
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Síntese e caracterização de complexos de lantanídeos pesados e ítrio(III) como o fármaco ibuprofeno no estado sólidoHolanda, Bruno Barreto da Cunha [UNESP] 24 April 2015 (has links) (PDF)
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000853273.pdf: 2757742 bytes, checksum: a26cf1d67c57916f1e91d2dcc231f26b (MD5) / Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) / Nos anos sessenta o ibuprofeno foi desenvolvido e introduzido no mercado como um fármaco do grupo do AINESs (anti-inflamatórios não-esteróides) para o tratamento de uma ampla variedade de enfermidades. Diversas pesquisas estão sendo realizadas com o intuito de estudar as atividades biológicas de complexos metálicos, com isso, o presente trabalho teve objetivo contribuir para ampliar estudos sobre o desenvolvimento de novos metalofármacos envolvendo metais lantanídeos trivalentes pesados (gosolínio, térbio, disprósio, hôlmio, érbio, túlio, iterbio, lutércio) e Ítrio com ibuprofeno, os quais possuem fórmula geral (Ln(ibu)3].nH2O, no estado sólido. Os componentes foram caracterizados por termogravimetria - análise térmica diferencial (TG-DTA), calorimetria exploratória diferencial (DSC), termogravimetria derivada (DTG), espectroscopia vibracional na região do infravermelho com transformada de Fourier (FTIR), difratometria de raios X pelo método do pó (DRX), termogravimetria acoplada à espectroscopia de absorção na região do infravermelhocom transformada de Fourier (TG- FTIR)e titulação complexométrica com EDTA. Com os resultados obtidos pelas curvas TG-DTA foi possível determinar a estabilidade térmica dos compostos, o número de etapas de decomposição térmica e os intervalos de temperaturas que estas ocorreram, além de estabelecer uma estequiometria para os compostos sintetizados. A técnica DSC permitiu verificar a entalpia de desidratação do composto de térbio e a energia envolvida na primeira perda de massa, a qual foi sugerida perda de molécula de propano em todos os compostos. Os dados de FTIR permitiram estudar os estiramentos do grupo carboxilato e, assim, sugerir uma coordenação metal-ligante para os compostos. A difração de raios X pelo método do pó, mostrou que os compostos apresentaram um perfil de baix cristanilidade sem evidências de formação de uma sério isomórfica. A análise dos... / In the sixties ibuprofen was developed and marketed as a drug in the group of NSAIDs (non-steroidal anti-inflammatory drugs) for the treatment of a wide variety of diseases. Several investigations have been performed in order to study the biological activity of metal complexes, with this, the presented workwa to contribute to expand studies on the development of new metallodrugs involvin heavy metals trivalent lanthamides (gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium) and yttrium ibuprofen, which have the general formula [Ln(ibu)3]. nH2O in solid state. The compounds were characterized by thermogravimetry - differential thermal analysis (TG-DTA), differential scanning calorimetry (DSC), derivative thermogravimetry (DIG) vibrational spectroscopy in the infrared Fourier transform spectroscopy (FTIR), X-ray diffraction by the powder method (XRD) coupled to the absorption spectroscopy in the infrared Fourier transform spectroscopy (TG-FTIR) and thermogravimetry complexometric titration with EDTA. Using the TG-DTA technique it was possible to determine the thermal stability of the compounds, the number of stages of thermal decomposition temperatures and that they occurred, and to provide a stoichiometry of these compounds. The DSC technique demonstrated the enthalpy of dehygration in the compound of terbium and the energy loss involved in the first mass, which was suggested loss of propane in each molecule compounds. The infrared study allowed the stretches of the carboxylate group and thus suggest a metal-ligand coordination compounds. The X-ray diffraction by the powder method showed that compounds showed a profile of low cristallinity. The analysis of the spectra in the infrared region of the volatiles showed a great similiraty with the propane spectrum, confirming its potential as the major product release during the first stage of thermal decomposition of the anhydrous compounds A complexometric titration...
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Investigação das propriedades ópticas, morfológicas e elétricas da heterojunção SnO2: Ce3+/ GaAs / Investigation of optical, morphological and electrical properties of heterojunction SnO2: Ce3+/ GaAsMachado, Diego Henrique de Oliveira [UNESP] 03 March 2016 (has links)
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Previous issue date: 2016-03-03 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / Este trabalho apresenta o desenvolvimento e algumas conclusões do estudo da heterojunção de filmes finos de SnO2 e GaAs. Os filmes de SnO2, dopados com Ce3+, foram depositados a partir do método sol-gel usando as técnicas de dip e spin coating; os filmes de GaAs foram depositados por evaporação resistiva e por sputtering. As heterojunçõesforam constituídas de filmes de SnO2 sobre filmes de GaAs, e filmes de GaAs sobre filmes de SnO2. Foram investigadas as propriedades ópticas, estruturais, morfológicas e elétricas de filmes finos constituintes das heterojunções e também a influência do dopante Ce3+. Entre os experimentos realizados estão: transmitância óptica, difração de raios X, microscopia eletrônica de varredura (MEV), microscopia óptica, microscopia de força atômica (AFM), fotoluminescência e medidas elétricas na presença de excitações com diferentes fontes de luz monocromáticas (quarto harmônico do laser Nd:YAG (266nm), laser He-Ne (628nm), LED InGaN (450nm)). Entre as principais conclusões, verificou-se: 1) em algumas situações, condutividade independente da temperatura, sugerindo a participação de um gás de elétrons bidimensional (2DEG) na interface SnO2/GaAs; 2) o tamanho dos cristalitos, calculado a partir das análises de difração de raios X, fornece valores da ordem de 10nm tanto para filmes de SnO2 como para filmes de GaAs; 3) a energia de bandgap, avaliada com base em dados de medidas de absorbância, fornece um valor máximo de 3,6 eV para filmes de dióxido de estanho e 1,6eV para filmes de GaAs; 4) MEV e microscopia óptica de para filmes de GaAs (depositado por evaporação resistiva e sputtering) apresentam sua superfície heterogênea, com partículas de variados tamanhos. Além disso, a aderência de filmes de SnO2 sobre filmes de GaAs está relacionada com a técnica utilizada para depositar os filmes da camada de base, o melhor resultado foi obtido quando a camada é a de GaAs depositado por evaporação resistiva. Isto foi verificado utilizando microscopia de força atômica, onde ficou evidente que filmes de GaAs depositado por evaporação resistiva possuem grandes aglomerados enquanto filmes depositados por sputtering possuem uma superfície com material distribuído de maneira uniforme. Também foram realizadas medidas de fotoluminescência com excitação de um laser de Kr+ sintonizado na linha de 350nm e também utilizando um laser de He-Cd na linha de 325nm, tanto em filmes como em pastilhas de SnO2 dopado com 1at% Ce3+e também em filmes da heterojunção SnO2:Ce3+/GaAs, sendo observadas pequenas bandas características do Ce3+. / The aim of this work is to present the development and the main conclusions, related the investigation of thin film SnO2/GaAs heterojunction. Ce3+- doped SnO2 thin films were deposited by the sol-gel-dip and -spin coating techniques, whereas GaAs films were deposited by resistive evaporation and sputtering. Heterojunctions were deposited by SnO2 layer growth on top of GaAs film, and in the opposite order: GaAs on top of SnO2. Optical, structural, morphologic and electrical properties of heterojunction films were investigated, as well as the influence of Ce-doping in these measurements. Experiments carried out include: optical transmission, X-ray diffraction, scanning electron microscopy (SEM), optical microscopy, atomic force microscopy (AFM), photoluminescence and electrical measurements under optical excitation. In this last case the excitation sources are monochromatic light from the fourth harmonic of a Nd:YAG laser (266nm), a He-Ne laser (628nm) and a InGaN LED (450nm). Among the main conclusions, it was verified that: 1) in some situations, a temperature independent electrical resistivity was observed and attributed to the possible formation of a two-dimensional electron gas (2DEG) at SnO2/GaAs interface; 2) crystallite size was calculated from X-ray diffraction data, being about 10 nm either for SnO2 films as GaAs films; 3) bandgap energy, evaluated from absorbance data yield a maximum value of about 3.6eV for tin dioxide and 1.6eV for GaAs films; 4) SEM images, obtained for GaAs thin films deposited by resistive evaporation and for the heterojunction SnO2/GaAs, and optical microscopy, for sputtering deposited GaAs films and heterojunction samples, show that GaAs films present an heterogeneous surface, with particles of several distinct sizes. Besides, the adherence of SnO2 films on the GaAs layer is related to the used technique for depositing the base layer, being better in the case of resistive evaporation deposited GaAs. This was verified by atomic force microscopy, where it was evidenced that resistive evaporation deposited GaAs films present large agglomerates whereas sputtering deposited films present a surface with more uniformly distributed material. Photoluminescence data was also obtained with excitation by a Kr+ laser tuned at 350nm as well as a He-Cd laser at 325nm, either in Ce 1at% doped SnO2 pellets as SnO2:Ce3+/GaAs heterojunction, being observed small bands, characteristic of Ce3+.
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Síntese, caracterização e estudo térmico dos succinatos de lantanídeos (III) e ítrio (III), no estado sólidoLima, Liliane Spazzapam [UNESP] 22 February 2013 (has links) (PDF)
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lima_ls_dr_araiq.pdf: 1748247 bytes, checksum: 80701efb22420181e8d4d0411c29aa85 (MD5) / Foram sintetizados, no estado sólido, os compostos Ln2L3∙nH2O, sendo que Ln representa os lantanídeos trivalentes (La ao Lu) e o ítrio(III) e o L representa o succinato (C4H4O4). Os compostos foram sintetizados por adição estequiométrica, sob agitação, do ligante nas respectivas soluções de cloretos ou nitratos de lantanídeos. A caracterização dos compostos foi realizada utilizando métodos como difratometria de raios X pelo método do pó, análise elementar, complexometria e as técnicas termoanalíticas como termogravimetria e análise térmica diferencial simultânea (TG-DTA), caloria exploratória diferencial (DSC) e termogravimetria acoplada à espectroscopia de absorção na região do infravermelho com transformada de Fourier (TG-FTIR). Os resultados forneceram informações sobre o comportamento térmico, cristalinidade, estequiometria dos compostos estudados. Também foi possível identificar os produtos gasosos liberados durante o aquecimento / Solid-state Ln2L3∙nH2O compounds, where Ln stands for trivalent lanthanides (La to Lu) or yttrium(III) and L is succinate(C4H4O4), have been synthesized. The solid-state compounds were prepared by stoichiometric relation adding slowly, with continuous stirring the ligand solution to the respective metal chloride or nitrate solution. The characterization of the compounds was performed using X-ray powder diffratometry, elemental analysis,complexometry, simultaneous thermogravimetry and differential thermal analysis (TG-DTA), differential scanning calorimetry (DSC) and thermogravimetry coupled to absorption spectroscopy in the region of infrared with Fourier transform (TG-FTIR). The results provided information about thermal behaviour, crystallinity, stoichiometry of the compounds studied. It was also possible to identify the gaseous products released during heating
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