O câncer colorretal (CRC) é um tumor maligno que afeta o intestino grosso e o reto, o tipo de câncer mais comum do trato gastrointestinal, o terceiro mais comumente diagnosticado no mundo e a segunda principal causa de morte relacionada ao câncer nos Estados Unidos. Hoje em dia, os procedimentos terapêuticos disponíveis para este tipo de câncer são limitados e ineficazes. A radioterapia convencional não é uma abordagem comumente utilizada no tratamento de CRC, devido ao fato de que os movimentos peristálticos dificultam o direcionamento da radiação ionizante e, assim, este tipo de tratamento é utilizado como adjuvante e paliativo para controlar sintomas. Portanto, a intervenção cirúrgica é a opção terapêutica primária contra esta doença. As pesquisas com base na combinação de radioisótopos e sistemas carreadores nanoestruturados têm demonstrado resultados significativos na melhoria da seletividade de ação, bem como na redução da dose de radiação nos tecidos saudáveis. As nanopartículas de sílica mesoporosa MCM-41 têm características únicas, tais como elevada área superficial e diâmetros de poros bem definidos, fazendo destas nanopartículas um candidato ideal como carreador de agentes terapêuticos. A funcionalização desses carreadores com moléculas específicas tem sido utilizada como uma forma de direcionar essas partículas para as regiões desejadas, aumentando o acúmulo dessas partículas nos tecidos-alvo e diminuindo o efeito adverso em tecidos sadios. Uma molécula específica de destaque é o aptâmero anti-CEA, que é uma porção de cadeia de DNA que tem a capacidade de se ligar e reconhecer receptores de antígeno carcinoembriogênico superexpressos em células de tumor colorretal. Assim, o objetivo deste trabalho consistiu em sintetizar e caracterizar nanopartículas de sílica mesoporosa MCM-41, funcionalizadas com aptâmero anti-CEA e conjugados com ítrio-90 ou gadolínio-159 e avaliar esses sistemas como potenciais agentes terapêuticos. As nanopartículas foram sintetizadas através do método de sol-gel. As amostras foram caracterizadas através das técnicas de espectroscopia na região do infravermelho com transformada de Fourier (FTIR), espalhamento de raios X a baixos ângulos (SAXS), espectroscopia de correlação de fótons (PCS), análise de potencial zeta, análise termogravimétrica (TGA), análise elementar (CHN), adsorção de nitrogênio (BET) e microscopia eletrônica de transmissão (TEM) e de varredura (SEM). A capacidade de incorporar íons Y+3 e Gd+3 foi determinada in vitro, utilizando diferentes proporções (1:1 e 1:3 v/v) de YCL3 e Gd203 e nanopartículas de sílica dispersas em água MilliQ. Os íons não incorporados foram removidos por ultracentrifugação e a concentração de íons no sobrenadante foi determinada por espectrometria de emissão atômica com plasma indutivamente acoplado (ICP-AES). A viabilidade celular foi avaliada por um ensaio MTT colorimétrico no qual foram usadas células específicas de câncer colorretal T84. Os resultados mostraram que as nanopartículas foram sintetizadas com sucesso, obtendo nanopartículas com morfologia esférica, tamanho de partícula de 400 nm, PDI (índice de Polidispersividade) 0,1, potencial zeta de -25,8 meV , arranjo hexagonal de poros com diâmetros de 3 nm e área superficial de 1.400 m2.g-1. Os resultados do ensaio de viabilidade celular sugerem o uso de nanopartículas incorporadas com radioisótopos como potenciais agentes terapêuticos. / Colorectal cancer (CRC) is a malignancy that affects large intestine and rectum, and it is the most common malignancy of the gastrointestinal tract, the third most commonly diagnosed type of cancer in the world and the second leading cause of cancer-related death in the United States. Nowadays, available therapeutic procedures for this type of cancer are limited and ineffective. Conventional radiotherapy is not an often used approach in the treatment of CRC due to the fact that peristaltic movements hamper the targeting of ionizing radiation and this type of treatment is used as adjuvant and palliative to control symptoms. Therefore, surgical intervention is the primary therapeutic choice against this disease. Researches based on the combination of radioisotopes and nanostructured carriers systems have demonstrated significant results in improving the selectivity action as well as reducing the radiation dose into healthy tissues. MCM-41 mesoporous silica nanoparticles have unique characteristics such as high surface area and well-defined pore diameters making these nanoparticles an ideal candidate of therapeutic agent carrier. Thus, the objective of this work is to synthesize and characterize MCM-41 mesoporous silica nanoparticles conjugated with yttrium-90 and gadolinium-159 and evaluate this system as a potential therapeutic agent. The nanoparticles were synthesized via sol-gel method. The sample was characterized using FTIR, SAXS, PCS, Zeta Potential analysis, Thermal analysis, CHN elemental analysis, nitrogen adsorption, scanning and transmission electron microscopy. The ability to incorporate Y+3 and Gd+3 ion was determined in vitro using different ratios (1:1, 1:3, 1:5 v/v) of YCL3 and Gd2O3 and silica nanoparticles dispersed in saline, pH 7.4. The non-incorporated Y+3 and Gd+3 ions were removed by ultracentrifugation procedure and the concentration of ions in the supernatant was determined by ICP-AES. Cell viability was assessed by colorimetric MTT assay in which specific colorectal cancer cells T84 were used. The results showed that the nanoparticles were successfully synthesized, obtaining nanoparticles with spherical morphology, particle size of 400 nm, PDI 0,1, zeta potential of -25, 8 meV, hexagonal arrangement of pores with 3 nm diameters and superficial area of 1400 m2.g-1. Cell viability assay results suggest the use of incorporated nanoparticles as a potential therapeutic agent.

Fez-se a separação, enriquecimento e purificação de iantânio e ítrio partindo-se de um concentrado de terras raras empobrecido em cério, conhecido como LCC, \"low cerium carbonate\", um concentrado de ítrio designado como \"carbonato de ítrio\" e um terceiro concentrado designado como \"oxido de terras ítricas\". Os dois primeiros concentrados foram produzidos industrialmente pela NUCLEMON - Nuclebrás de Monazita e Associados Ltda, usando monazita brasileira. O \"oxido de terras ítricas\" é proveniente do processo de obtenção de Iantânio durante a execução do trabalho experimental desta tese. Fez-se uso das seguintes tecnologias: 1) precipitação fracionada com uréia; 2) lixiviação fracionada do LCC com carbonato de amônio e 3) precipitação dos peroxicarbonatos de terras raras usando-se seus carbonatos complexos. Obtidas frações enriquecidas em terras raras estas foram refinadas por meio de tecnologia de troca iônica em leito de resina catiônica sem uso de ion retentor e eluição com sais de amônio do ácido etilenodiaminotetraacético. Com a associação das técnicas acima mencionadas foram obtidos óxidos puros de ítrio (>97,7%), oxido de Iantânio (99,9%), óxido de gadolínio (96,6 %) e oxido de samário (99,9%). O processo aqui desenvolvido tem viabilidade técnica econômica para a instalação de uma unidade de maior porte visando a industrialização. / In this work, separation, enrichment and purification of lanthanum and yttrium were performed using as raw material a commercial low cerium rare earth concentrate named LCC (low cerium carbonate), an yttrium concentrate named \'yttrium carbonate\', and a third concentrated known as \'yttrium earths oxide. The first two were industrially produced by the late NUCLEMON - NUCLEBRAS de Monazita e Associados Ltda, using Brazilian monazite. The \'yttrium earths oxide\' come from a process for preparation of lanthanum during the course of the experimental work for the present thesis. The following techniques were used: fractional precipitation with urea; fractional leaching of the LCC using ammonium carbonate; precipitation of rare earth peroxycarbonates starting from the rare earth complex carbonates. Once prepared the enriched rare earth fractions the same were refined using the ion exchange chromatography with strong cationic resin without the use of retention ion and elution using the ammonium salt of ethylenediaminetetraacetic acid. With the association of the above mentioned techniques were obtained pure oxides of yttrium (>97,7%), lanthanum (99,9%), gadolinium (96,6%) and samarium (99,9%). The process here developed has technical and economic viability for the installation of a large scale unity.

Os problemas ambientais originados pela produção e consumo das tradicionais fontes de energia pressionam a sociedade pelo desenvolvimento e utilização de fontes de energia limpas e renováveis. Dentre as novas tecnologias, células a combustível de membrana de troca protônica (PEMFC) apresentam-se como uma alternativa viável, aliando elevadas taxas de conversão energética a níveis mínimos de poluentes gerados. No entanto, a utilização plena desses dispositivos depende de fatores como desempenho, estabilidade e custo dos mesmos. Um dos principais elementos que afeta o desempenho de uma PEMFC é a eficiência com o qual o oxigênio é reduzido no cátodo. Assim, diversos estudos visando a obtenção de eletrocatalisadores à base de Pt que apresentem bom desempenho frente à reação de redução de oxigênio (RRO) e elevada estabilidade têm sido desenvolvidos, recebendo destaque os catalisadores Pt-Y. Neste trabalho catalisadores Pt-Y, com diferentes proporções entre os metais, suportados em carbono de alta área superficial foram sintetizados através de uma modificação no método do ácido fórmico. Os materiais foram caracterizados através das técnicas de EDX, XRD, TEM e XPS, e avaliados frente à RRO através de medidas em meia célula, empregando-se a técnica de eletrodo de disco rotatório, e em célula unitária, como cátodo de PEMFC. O catalisador Pt-Y/C 7:3 foi o que apresentou melhor desempenho dentre os materiais bimetálicos. Através dos testes de envelhecimento acelerado (TEA) constatou-se que, além da degradação das nanopartículas de platina, o ítrio passa por dissolução. / The environmental impacts generated by the production and consumption of traditional energy sources leads society to develop clean and renewable energy sources. Among the new technology, proton exchange membrane fuel cells (PEMFC) appear as viable alternative, allying high energy conversion rates to minimum levels of pollutants generated. However, the full utilization of these devices depends on factors such as its performance, stability and cost. One of the major elements that affect the PEMFC performance is the cathode performance. Thus, several studies aiming at obtaining Pt based electrocatalysts with good performance for oxygen reduction reaction (ORR) and high stability have been developed, receiving attention the Pt-Y catalysts. In this work Pt-Y catalysts, supported on high surface area carbon, were synthesized through a modification on formic acid method. The materials were characterized using EDX, XDR, TEM and XPS, and evaluated towards ORR through measurements in half cell, using rotating disk electrode technique, and in unit cell, as cathode of PEMFC. The catalyst Pt-Y/C 7:3 had the best performance among the bimetallic materials. Through accelerated aging tests (AGT), in addition to platinum nanoparticles degradation, yttrium dissolution was also observed.

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.

Thesis (Elec.E)--Massachusetts Institute of Technology, Dept. of Electrical Engineering and Computer Science, 1982. / MICROFICHE COPY AVAILABLE IN ARCHIVES AND ENGINEERING. / Bibliography: leaves 172-176. / by Chon Meng Wong. / Elec.E

Transparent ceramics are used in a variety of applications such as protective visors, thermo-graphic lens, night vision devices and windowpane of an armed vehicle, missile domes and in aircrafts. Yttrium Aluminium Garnet (YAG, Y3Al5O12) exhibits uniform index of refraction without birefringence owing to its cubic crystal structure and offers a range of optical and mechanical properties that makes it suitable for transparent applications.

La radiothérapie interne sélective (RTIS), en plein développement ces dernières années, constitue une alternative thérapeutique pour les cancers primaires et secondaires inopérables du foie. Le principe repose sur l’administration intra-artérielle de microsphères chargées d’yttrium-90 avec pour objectif la destruction des cellules tumorales par l’irradiation.L’activité d’yttrium-90 à administrer au patient est actuellement généralement prescrite à partir d’approches semi-empiriques ou peu personnalisées, faciles à mettre en place cliniquement. De nouveaux outils sont aujourd'hui disponibles semblables à ceux utilisés en radiothérapie externe. Leur utilisation encore peu répandue nécessite un retour d'expérience clinique pour mettre en avant leurs bénéfices et guider l'application clinique. Par ailleurs, le traitement RTIS est précédé d'une étape de simulation. Des différences inhérentes à cette procédure en deux temps (type de particules utilisées, modalité d’imagerie, modifications de flux vasculaires, etc.) existent et pourraient potentiellement conduire à des écarts dosimétriques entre la planification et le traitement. C’est dans ce contexte que s’inscrit le projet de cette thèse qui porte sur l'optimisation de la dosimétrie pour le traitement du carcinome hépatocellulaire par RTIS.Les doses délivrées au cours de 42 traitements par microsphères de résine réalisés entre 2012 et 2015 au CHU de Montpellier, ont été rétrospectivement calculées à l’échelle du voxel sur un logiciel de dosimétrie dédié (PLANET Dose, DOSIsoft, Cachan). Les doses délivrées ont été calculées pour le volume tumoral et le volume de foie sain définis anatomiquement, à partir de l’imagerie post-traitement TEP aux microsphères d’yttrium-90. Ce travail a mené à deux études complémentaires. La première analyse a consisté à confronter les données dosimétriques recueillies (doses moyennes, histogrammes dose-volume) à la réponse tumorale, la toxicité hépatique et la survie du patient. Les résultats obtenus, en accord avec ceux de la littérature, ont confirmé l’existence d’une relation dose-effet en RTIS. La deuxième étude a mis en évidence les limites du modèle BSA (body surface area pour surface corporelle) qui avait été utilisé pour planifier l’activité à administrer, à prédire la dose délivrée et par conséquent l’efficacité du traitement. L’absence de considérations dosimétriques et de prise en compte de l’hétérogénéité de distribution, de ce modèle ont notamment été discutées. Ces deux études ont ainsi souligné l'intérêt de planifier l'activité d'yttrium-90 à administrer en se basant sur des données dosimétriques individualisées.Une troisième étude a été conduite sur une population de 23 patients atteints de CHC, traités par microsphères de verre traités entre 2015 et 2018 au CHU de Montpellier. L’objectif a été de comparer les dosimétries prédictives et post-traitement calculées à l’échelle du voxel. Les résultats cliniques obtenus ont été appuyés par des expérimentations sur fantômes physiques (simple et anthropomorphique). Une bonne corrélation a été montrée, mettant en avant la valeur prédictive de la dosimétrie de planification. En revanche, un écart significatif a été observé et semble lié en partie à la quantification de l’imagerie TEP à l’yttrium-90. De plus, il a été montré que le geste radiologique peut influencer la distribution de particules et donc de dose, d’où la nécessité d’une reproductibilité aussi parfaite que possible entre les deux étapes. / Selective internal radiation therapy (SIRT) is a growing therapeutic alternative for unresectable primary and secondary liver cancer. The principle is based on the intra-arterial administration of yttrium-90 loaded microspheres for tumor cell destruction through irradiation.Yttrium-90 activity to be administered to the patient is, at the moment, usually prescribed using semi-empirical or barely personalized approaches that can be easily clinically implemented. New tools, similar to the ones used in external beam radiotherapy, are available today. These tools, which are not yet widely spread, require clinical feedback to show their benefits and guide the clinical application. Besides, a simulation stage is always performed before SIRT treatment itself. This two-step procedure implies differences (in terms of particles used, imaging modality, vascular flow modifications, etc.) that could potentially lead to dose deviations between planning and treatment. The thesis project comes within this scope, dealing with dosimetry optimization for hepatocellular carcinoma SIRT.Delivered doses during 42 treatment procedures performed between 2012 and 2015 at Montpellier University Hospital, were retrospectively calculated at the voxel level using a dosimetry dedicated software (PLANET Dose, DOSIsoft, Cachan). Two complementary studies were carried out from this work. The first one analyzed dose data (average dose, dose volume histograms) versus patient follow-up including tumor response, liver toxicity and patient survival. The results obtained are consistent with the other teams, confirming the dose-effect relationship in SIRT. The second study highlighted the limitations of the BSA (body surface area) model that was used for activity planning. In particular, the limitations of this model to predict delivered dose and consequently treatment efficiency were quantitatively demonstrated. The lack of dosimetry and heterogeneity distribution considerations were also discussed. These two studies emphasized the interest for yttrium-90 activity planning based on individualized dose data.A third study was conducted on a population of 23 patients treated between 2015 and 2018 at Montpellier University Hospital. The aim was to compare predictive and post-treatment dosimetry calculated at the voxel level. The clinical results were supported by phantom (simple and anthropomorphic) experimentations. A good correlation was observed highlighting the predictive value of dosimetry planning. However, a significant deviation was noticed and seems to be partly related to yttrium-90 TEP quantification. In addition, it was also noted that the radiological gesture can affect particle distribution and consequently dose distribution, this is why reproducibility as perfect as possible is required between the two stages.

Solid Oxide Fuel Cells (SOFCs) are devices that directly convert chemical energy into electrical energy, without proceeding through a Carnot combustion cycle. These devices are based on the usage of solid oxide electrolytes operating at relatively elevated temperatures. Two major hurdles must be overcome in order to decrease the operating temperatures of practical SOFCs. The first relates to reducing ohmic losses within solid electrolytes. The second relates to the need for developing high performance electrodes since electrolyte reaction rates at both anode and cathode are affected detrimentally as operating temperatures fall. This PhD project has focussed on addressing the first hurdle in two innovative ways: 1. the implementation of solid electrolytes with higher ionic conductivity than zirconia, 2. the development of very thin film electrolytes as thick as 5ƒÝm. Several thin films with novel electrode-electrolyte structures were fabricated and evaluated in order to demonstrate the viability of low temperature SOFC operations. Development of such thin films was innovative and challenging to achieve. The approach taken in this work involved fabricating a dense and thin gadolinia doped ceria (10GDC - Gd 10wt%, Ce 90wt%) oxide electrolyte. 10GDC is an electrolyte exhibiting higher conductivities than conventional materials during low temperature operations. A research contribution of this PhD was the demonstration of the deposition of 10GDC thin films using RF magnetron sputtering for the first time. 10GDC thin film electrolytes with thickness in a range between 0.1 to 5ƒÝm were fabricated on 10 yttrium stabilised zirconium (10YSZ) substrates by using a RF magnetron sputterer. The primary parameters controlling 10GDC thin film deposition using this method were explored in order to identify optimal conditions. The fabricated films were subsequently analysed for their morphology, composition and stoichiometry using a variety of methods, including Scanning Electron Microscopy (SEM) with Energy Dispersive X-ray Spectrometry (EDS), optical microscopy, X-ray Photoelectron Spectroscopy (XPS), and X-ray Diffraction (XRD). A preliminary test was conducted in order to examine the function of 10GDC thin film electrolytes together with the cathode and anode substrates at intermediate temperatures (700oC). A complete planar single cell was designed and assembled for this purpose. However, when fully assembled and tested, the cell failed to generate any voltage or current. Consequently, the remainder of the PhD work was focused on systematically exploring the factors contributing to the assembled fuel cell failure. As fabrication failure analysis is seldom reported in the scientific literature, this analysis represents a significant scientific contribution. This analysis proceeded in a series of steps that involved several different methods, including SEM, red dye analysis, surface morphology and cross section analysis of the cell. It was found that pinholes and cracks were present during the fuel cell operating test. Cathode delamination was also found to have occurred during the test operation. This was determined to be due to thermal expansion mismatch between the cathode substrate and the 10GDC electrolyte thin film. A series of suggestions for future research are presented in the conclusion of this work.

En vue d'application à l'éclairage ou dans les dispositifs de visualisation à plama, on a étudié la luminescence de l'ion Eu2+ dans les borates BaLnB9O16 (Ln = La, Ce, Gd, Y) et de l'ion Eu3+ dans les diverses phases des systèmes Gd2O3-P2O5 et Y2O3-P2O5. Des informations sur les structures des réseaux-hôtes lorsqu'elles étaient inconnues, ont pu être obtenues par diffraction X et spectroscopie Raman. Pour Ln = Y, Gd, les borates BaLnB9O16:Eu2+ présentent une émission dans le bleu stable...

In this study, it was aimed to investigate the structural, mechanical and biological properties of nano hydroxyapatite (HA) doped with yttrium and fluoride with different compositions. HAs were synthesized by precipitation method. After sintering at 900oC, 1100oC or 1300oC for 1 hour, the structural properties of HAs were investigated by XRD, FTIR spectroscopy and SEM. High relative densities (above 88 % of relative density) were achieved after sintering. No second phases were observed in XRD measurements. Hexagonal lattice parameters and unit cell volumes of doped HAs decreased indicating the substitutions of ions. Characteristics absorbtion bands of HA and additional bands due to fluoride substitutions were observed in FTIR patterns. SEM images showed that grain sizes decreased with increasing doping amounts and decreasing sintering temperatures. Discs prepared by cold pressing were sintered at 900oC, 1100oC and 1300oC for 1 hour to determine mechanical properties. Mechanical properties of HAs were found to be directly related to the sintering temperatures and amount of dopings. Biocompatibility of pure and doped HA discs was assessed with in vitro cytotoxicity studies. Cell attachment, proliferation and differentiation state of cells were studied using MTT, ALP and calcium assays and SEM. Cell attachment and proliferation were enhanced with dopings and increasing sintering temperatures. The highest ALP production and calcium deposition were observed on HAs sintered at 1100oC. In vitro studies revealed that 1100oC was the sintering temperature for best cell responses. Specifically, 2.5YFHA seemed to be promising as an alternative for pure HA among all doped HAs.