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Biologie de syndecan-1 au cours du myélome multiple : synthèse, modifications et inhibition / Syndecan-1 and multiple myeloma : synthesis, modifications and inhibitionBret, Caroline 15 December 2010 (has links)
Ce travail de thèse a eu pour thème principal le protéoglycane syndecan-1 au cours du myélome multiple, une hémopathie maligne caractérisée par la présence d'un clone de plasmocytes tumoraux au sein de la moelle osseuse. Syndecan-1 est un élément majeur de la physiopathologie du myélome multiple, ce protéoglycane étant au coeur d'un réseau complexe d'interactions moléculaires conditionnant le devenir des cellules plasmocytaires tumorales.Les chaînes de glycosaminoglycanes présentes sur le core protéique de syndecan-1sont responsables d'une grande partie de son activité. Nous avons ainsi caractérisé, par une approche transcriptomique, 100 gènes codant les protéines impliquées dans la synthèse et la modification de ces chaînes. Nous avons de cette manière identifié des cibles moléculairesen vue de moduler, voire d'inhiber leur activité.Dans le but d'identifier les métalloprotéinases des familles ADAM et ADAMTS susceptibles d'interagir avec syndecan-1, nous avons réalisé l'étude du profil d'expression des gènes codant ces reprolysines et leurs inhibiteurs dans les cellules de la différentiation lymphocytaire B, les cellules plasmocytaires normales et tumorales ainsi que dans l'environnement médullaire.Dans une dernière partie, nous avons évalué l'efficacité d'une approche d'inhibitiondes chaînes héparanes sulfates via l'utilisation de l'héparine. Nous observons que certaines lignées myélomateuses sont inhibées par l'héparine et ses dérivés et que ces mêmes lignées sont stimulées par l'antidote de l'héparine, le sulfate de protamine. Les mécanismes mis enjeu sont en relation avec la modulation de la biodisponibilité des facteurs permettant la croissance des cellules. / Multiple myeloma is a hematological malignancy characterized by the expansion of aclone of malignant plasma cells in the bone marrow compartment. Syndecan-1 is a majorproteoglycan involved in a complex network of molecular interactions in multiple myelomaphysiopathology. As heparan sulfate and chondroitin sulfate chains are the bioactive components ofsyndecan-1, we first analysed the signature of genes encoding 100 proteins involved in thesynthesis of these chains, from precursor uptake to post-translational modifications, usingAffymetrix microarrays.In order to identify the metalloproteinases belonging to ADAM and ADAMTS familiespotentially implicated in the interactions with syndecan-1, we performed a gene expressionprofile focused on the genes encoding these reprolysines and their inhibitors.In a last part, we evaluated the efficacy of an inhibitory approach based on theutilization of heparin in human myeloma cell lines in vitro, inhibitory effects being in relationwith a modulation of the biodisponibility of heparin-binding factors.This work led us to identify targets of interest in relation with syndecan-1 biology inmultiple myeloma. They could be used to design new therapeutic strategies.
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Investigations Of Open-Framework Metal Carboxylates, Sulfates And Related MaterialsDan, Meenakshi 07 1900 (has links)
Open-framework materials constitute an important area of study in materials chemistry, because of their potential applications in areas such as sorption and catalysis. Furthermore, these materials exhibit fascinating architectures with unusual bonding and coordination patterns. Besides aluminosilicate zeolites and metal phosphates, metal carboxylates constitute an important family of open-framework structures. In this thesis, results of investigations of a variety of open-framework metal carboxylates, as well as a new family of rare-earth sulfates are presented. More importantly, studies directed towards an understanding of the mechanism of formation of open-framework phosphates and carboxylates and the importance of synthesis parameters like temperature in determining the dimensionality of the products are discussed at length.
After providing an introduction to open-framework compounds (Part 1), the thesis (Part 2) presents the results of the investigations of metal carboxylates employing both transition metal and rare-earth metal ions with various organic linkers, ranging from aromatic squarate dianion, aliphatic dicarboxylates like oxalate, adipate, succinate, aminocarboxylates (which contain both the amine and the carboxylate group in the same moiety) and dihydroxybenzoates. Some of these compounds have large channels, for example, both the lanthanum mixed aliphatic dicarboxylates, strontium dihydroxybenzoate etc. Some even show unusual properties, example, a mixed valent iron (II, III) glycinate has a perfect kagome structure and shows unusual magnetic properties, entirely different from those of ordinary Fe(III) kagome structures, copper derivative of 6-amincaproic acid has large channels and remains crystalline porous even after dehydration, a cobalt oxalato-squarate has both oxalate and squarate moiety in the same structure, where the oxalate is produced in situ by the oxidation of squarate under hydrothermal conditions in the basic medium.
While the phosphate and the silicate anions are the most common basic building units in open-framework inorganic structures, the possibility of building open architectures with the sulfate anion as the basic building unit has been explored in Part 3. The results have been rewarding and both layered and three-dimensional rare-earth sulfates with large channels and possessing a α-Po structure or (6, 3) nets with continuous M-O-M connectivity in two dimensions have been obtained.
The most intriguing question in the area of open-framework structures relates to the mode of formation. In Part 4, the mechanism of formation of both metal phosphates and metal carboxylates have been discussed. This part includes a study of the transformations of four-membered ring phosphates to higher dimensional structures (like 3D sodalite-related structure), through lower-dimensional structures, involving a progressive building-up mechanism. Similar progressive building-up mechanism has also been studied for metal carboxylates. The importance of synthesis parameters like temperature in governing the dimensionality of the products has been studied.
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Desenvolvimento dos dosímetros termoluminescentes de CaSOsub(4):Ce, Eu para a monitoração individual externa e a dosimetria clínica de fótons e elétrons / Development of CaSOsub(4):Ce, Eu thermoluminescent dosimeters for individual monitoring for external exposures and clinical dosimetryNUNES, MAIRA G. 09 October 2014 (has links)
Made available in DSpace on 2014-10-09T12:42:03Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T14:04:42Z (GMT). No. of bitstreams: 0 / Tese (Doutoramento) / IPEN/T / Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP
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Desenvolvimento dos dosímetros termoluminescentes de CaSOsub(4):Ce, Eu para a monitoração individual externa e a dosimetria clínica de fótons e elétrons / Development of CaSOsub(4):Ce, Eu thermoluminescent dosimeters for individual monitoring for external exposures and clinical dosimetryNUNES, MAIRA G. 09 October 2014 (has links)
Made available in DSpace on 2014-10-09T12:42:03Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T14:04:42Z (GMT). No. of bitstreams: 0 / Detectores de sulfato de cálcio ativado com cério IV e európio III utilizando o politetrafluoretileno (PTFE, Teflon®) free-flow como aglutinante (CaSO4:Ce,Eu + Teflon®) foram produzidos pelo método da estampagem, desenvolvido em colaboração com a empresa Tecnoflon, a partir de cristais crescidos de acordo com uma nova variação da rota da evaporação lenta, também apresentada nesse trabalho, com as concentrações de 0,16 mol% de Eu3+ e de 0,15 mol% de Ce4+ na solução ácida precursora. O modelo de dosímetro pessoal desenvolvido consiste em cinco detectores aderidos a um cartão de 30 x 48 mm de cloreto de polivinila (PVC) 95% opaco à luz na faixa do espectro eletromagnético que vai do infravermelho ao ultravioleta, idêntico aos cartões de identificação utilizados no IPEN, por uma tira de 10 x 35 mm de filme adesivo do mesmo material e foi submetido aos testes de aceitação descritos no regulamento técnico IRD-RT Nº 002.01/95, Desempenho de Sistemas de Monitoração Individual Critérios e Condições, sendo aprovado em todos os testes. Para a dosimetria clínica, os próprios detectores foram considerados dosímetros termoluminescentes e submetidos aos testes de aceitação descritos no código de práticas da Agência Internacional de Energia Atômica Technical Report Series Nº 398, Absorbed Dose Determination in External Beam Radiotherapy: An International Code of Practice for Dosimetry based on Standards of Absorbed Dose to Water, [TRS-398, IAEA, 2000] adotado como protocolo de dosimetria pela maioria dos hospitais, sendo igualmente aprovados nesses testes. Os dosímetros desenvolvidos podem ser utilizados para a monitoração individual externa e para dosimetria clínica, apresentando a diferenciação do tipo e da energia da radiação com que foram irradiados e a redução de custos como as principais vantagens em relação aos dosímetros termoluminescentes atualmente utilizados nessas aplicações. / Tese (Doutoramento) / IPEN/T / Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP
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Pathogenèse de l’infection par le virus Nipah / Pathogenesis of Nipah virus infectionMathieu, Cyrille 15 December 2011 (has links)
Le virus Nipah (NiV) est un Paramyxovirus zoonotique hautement pathogène, porté par les chauves-souris frugivores, qui a émergé en 1998 en Malaisie. Les épidémies liées à ce virus encéphalitogène continuent de se succéder en Inde et au Bangladesh avec une mortalité pouvant dépasser les 90%. Devant l’absence de traitement et de vaccin, le NiV a été placé parmi les pathogènes de classe 4 requérant le plus haut niveau de biosécurité pour sa manipulation. L’étude des interactions entre le virus et les cellules du sang nous a permis de montrer que le NiV utilise les héparanes sulfates présents sur les leucocytes pour s’accrocher et se disséminer dans l’organisme et atteindre les cellules endothéliales. L’héparine inhibe ce processus ainsi que l’infection in vitro et in vivo mettant en avant une perspective de traitement applicable dans les pays émergents. Par ailleurs, l’analyse transcriptomique des cellules endothéliales infectées par le NiV a révélé l’implication de chimiokines dans la pathogenèse. CXCL10 apparaît en effet comme un marqueur voir une cible dans le cadre du développement de l’encéphalite virale, et l’interféron type 1 comme l’un des facteurs essentiels de la résistance des souris au NiV. Enfin, j’ai montré que la protéine non structurale C du NiV joue un rôle essentiel dans sa virulence, en atténuant la réponse interféron, en perturbant la réponse chimiokine lors de l’infection et en intervenant dans le maintien de la balance génome / antigénome lors du cycle réplicatif viral. Ces résultats permettent une meilleure compréhension de la pathogenèse du NiV et ouvrent de nouvelles perspectives de traitement contre ce virus zoonotique très dangereux pour l’homme / Nipah virus (NiV) is a highly pathogenic zoonotic Paramyxovirus that emerged in 1998 in Malaysia from frugivorous bats. The outbreaks of this encephalitic virus still occur annually in India and Bangladesh with the mortality rate reaching up to 90%. The lack of an effective vaccine or treatment limits experimentation with live virus to specially equipped BioSafety Level 4 laboratories. Studies of the interaction between the virus and blood cells revealed that NiV uses Heparan sulfates to stick on the surface of leukocytes for its dissemination within the host and reach endothelial cells. Heparin provided de possibility to inhibit this mechanism of transinfection, such as the infection in vitro and in vivo, opening new perspectives of low cost treatment for emerging countries. Then, transcriptomic analysis of NiV infected endothelial cells revealed the importance of cytokine in the pathogenesis. While CXCL10 appears as a good marker of encephalitis, interferon type 1 explains why mice are resistant to the infection with NiV. Finally, we show the essential role of the non structural C protein of NiV in its virulence, by limiting the interferon response, unbalancing the chemokine response during the infection and through the regulation of the genomic/antigenomic balance during the viral replication cycle. These results shed new light on NiV related pathogenesis and open new perspectives of treatment against this highly lethal zoonotic virus
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Evaluation of hydrogen as energy source for biological sulphate removal in industrial wastewatersEloff, Estie 03 1900 (has links)
Thesis (MSc)--University of Stellenbosch, 2005. / ENGLISH ABSTRACT: Biological removal of sulphate from wastewater can be achieved by using a gas mixture
consisting of 80% hydrogen and 20% carbon dioxide as energy and carbon sources. A novel
reactor, including a venturi device for optimal hydrogen gas-liquid contact, and geotextile for
immobilisation of the sulphate reducing bacterial community, was introduced. Efficient,
relatively stable sulphate removal was obtained when the reactor was operated in continuous
mode. The maximum sulphate removal rate obtained when the reactor was 8% packed with
geotextile, was 1 g S04/(L.d) and 4 g S04/(L.d) when the reactor was 80% packed with
geotextile. Kinetic batch studies showed that the highest sulphate removal rates were
obtained at 29.5 °C; a pH of 7.5; initial sulphate concentration of 4000 mg/L; initial alkalinity
of 1600 mg/L; cobalt concentration of 3 mg/L and when excess hydrogen gas was fed
compared to what is stoichiometrically required (900 ml/min). Nickel addition showed
inhibition at increased concentrations (>3 mg/L).
The biofilm structure was observed on the geotextile with electron microscopy, while the
viability of the biofilm was indicated with fluorescence microscopy. These observations
indicated the suitability of the geotextile as a support material for biofilm formation in the
sulphate reducing system. The stability of the sulphate reducing community was analysed,
using the T-RFLP protocol. It was shown that the composition of the community changed
after a period of 3 months, when the reactor was subjected to environmental changes. The
reactor was also observed to be more efficient in terms of sulphate removal after the
environmental changes, of which the temperature change from an average of 39 to 29.5 °C
was the most prominent. Subsequently, it was speculated that the population shift was in
favour of a more efficient system for sulphate removal. A dynamic, viable, mesophilic
sulphate reducing community was therefore observed on the geotextile support, responsible
for successful sulphate removal in a novel venturi-reactor.
Defining optimal operating conditions, and a knowledge of biofilm structure and composition
may contribute to the successful implementation of the biological sulphate removal
component of the integrated chemical-biological process for the treatment of industrial
wastewater, when hydrogen and carbon dioxide are supplied as the energy and carbon
sources, respectively. / AFRIKAANSE OPSOMMING: Ongewenste industriële afval-water kan biologies behandel word deur 'n gasmengsel van 80%
waterstof en 20% koolstofdioksied te gebruik vir sulfaat verwydering. 'n Reaktor wat 'n
venturi apparaat bevat vir optimale waterstofgas-vloeistof kontak, asook geotekstiel vir die
immobilisasie van die bakteriële sulfaatverwyderende gemeenskap, is bekend gestel.
Effektiewe, relatief stabiele sulfaatverwydering is waargeneem sodra die reaktor op 'n
kontinue basis gevoer is. Die optimale sulfaat verwyderingstempo wat bereik is as die reaktor
8% met geotekstiel gevul was, was 1 g S04/(L.d) en 4 g S04/(L.d) wanneer die reaktor 80%
met geotekstiel gevul was. Kinetiese groepstudies het getoon dat die beste
sulfaatverwydering bereik is by 'n gemiddelde temperatuur van 29.5 °C; pH van 7.5;
aanvanklike sulfaatkonsentrasie van 4000 mg/L; aanvanklike sulfied konsentrasie van 268
mg/L; aanvanklike alkaliniteit van 1600 mg/L; kobalt konsentrasie van 3 mg/L, asook
wanneer 'n oormaat waterstofgas gevoer is (900 ml/min), in vergelyking met wat
stoichiometries benodig word. 'n Verhoogde byvoeging van nikkel by die voerwater (3
mg/L), het tekens van inhibisie getoon.
Die biofilm struktuur is waargeneem op die geotekstiel met behulp van 'n
elektronrnikroskoop, terwyl die lewensvatbaarheid van die biofilm aangedui is met behulp
van fluoressensie mikroskopie. Hiermee is die bruikbaarheid van geotekstiel as 'n
ondersteunings-matriks bevestig. Die stabiliteit van die sulfaatverwyderende gemeenskap is
ondersoek deur die T-RFLP protokol te gebruik. Hiermee is aangedui dat die samestelling
van die gemeenskap verander het na die 3 maande toets periode, toe die reaktor onderhewig
was aan omgewings veranderinge. Die reaktor het ook 'n verbetering in sy
sulfaatverwyderings vermoë getoon na hierdie tydperk van omgewingsveranderinge, waarvan
'n temperatuur verandering vanaf 'n gemiddeld van 39 na 29.5 °C die prominentste was. Dit
is dus gespekuleer dat die populasie verskuiwing ten gunste was van 'n beter sisteem vir
sulfaatverwydering. 'n Dinamiese, lewensvatbare, mesofiliese sulfaatreduserende
gemeenskap, verantwoordelik vir die sulfaatverwydering in die venturi-reaktor, is dus
waargeneem op die geotekstiel as 'n ondersteuningsmatriks.
Met hierdie evaluasie kan die insig wat verkry is in die reaktor samestelling en die optimale
kondisies vir die reaktor werking, bydra tot die suksesvolle implementasie van die biologiese
komponent, in die geïntegreerde chemies-biologiese proses vir die behandeling van industriële afval water, wanneer 80% waterstof en 20% koolstofdioksied gas as energie en
koolstofbron respektiewelik, gebruik word.
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Využití přenosných Ramanovských spektrometrů pro detekci sulfátů: potenciální aplikace v exobiologii / Use of portable Raman spectrometers for detection of sulfates: potential application in exobiologyKošek, Filip January 2014 (has links)
The detection of mineral phases under in situ conditions has become a primary but sometimes also challenging task in many fields of geoscience. Raman spectroscopy has been used as a powerful tool for the identification of various minerals and organic compounds. The advantages and the relative simplicity made this method a promising choice in the future planetary exploration missions to Mars. The deposits of aqueous minerals including sulfates have been found on the Martian surface. With the development of miniaturized handheld spectrometers there is a need for evaluation of Raman spectroscopy as a method of identification of sulfate phases in their natural conditions. In the first part of this work a handheld spectrometer equipped with 532 nm excitation laser was tested under laboratory conditions during which the ability to distinguish mineral samples representing sulfates of different chemical composition and different degree of hydration was investigated. In the second part, two handheld Raman spectrometers equipped with 532 and 785 nm excitation lasers were used for the characterization of sulfate phases on sites of their natural occurrence located in the Czech Republic. The quality of the Raman spectra acquired under outdoor conditions by both spectrometers was rather average but sufficient to...
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Aluminium geochemistry in coastal lowland acid sulfate soils (CLASS) : speciation, reactivity and mobility / Processus géochimiques liés à la spéciation, mobilité et réactivité de l'aluminium dans les sols acides sulfatés australiens côtiersYvanes-Giuliani, Yliane 12 December 2014 (has links)
Ce projet de thèse vise à étudier les processus géochimiques de l'aluminium dans les sols acides à sulfates. Les résultats obtenus avec le dispositif de dialyse de Donnan montrent que l'aluminium dans la solution du sol est presque exclusivement (> 98%) présent sous forme de complexes de charge négative, vraisemblablement des organo-complexes d'aluminium. Les concentrations d'aluminium isotopiquement échangeables (valeurs-E) et les concentrations obtenues par extractions chimiques révèlent qu'une solution de 1 M KCl sous-estime systématiquement les valeurs E. Une méthode d'extraction séquentielle a révélé qu'une quantité importante de minéraux primaires (initialement présents dans les sols) a déjà été dissoute, comme en témoignent les concentrations élevées d'aluminium présentes en tant que minéraux secondaires d'aluminium. Ces études permettent de mieux comprendre la géochimie de l'aluminium dans les sols CLASS et de pouvoir intégrer ces connaissances dans la gestion des sols. / The aim of this thesis was to further understanding on Al geochemistry in coastal lowland acid sulfate soils (CLASS). It was observed that Al was present almost solely (> 98%) as negatively charged complexes in CLASS pore-waters, presumably with natural organic matter. Isotopically exchangeable concentrations (E-values) of Al and extraction solutions used to estimate the exchangeable pool showed that 1 M KCl always underestimated isotopically exchangeable Al concentrations in these soils and that 0.2 M CuCl2 improved agreement between both methodologies but sometimes overestimated corresponding E values. A sequential extraction procedure showed that substantial amounts of Al have already been dissolved from primary aluminosilicates initially present in the soils and remain in the soils mostly as reactive secondary Al minerals. The outcomes of this thesis significantly further our understanding of Al geochemistry in CLASS environments and how this knowledge can be incorporated into land management practices.
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Síntese, caracterização termoanalítica e estudo da fotoluminescência dos oxissulfetos e oxissulfatos de terras raras obtidos a partir de sulfatos e sulfonatos / Synthesis, thermoanalitical characterization and photoluminescence study of rare earth oxysulfides and oxysulfates obtained from sulfates and sulfonatesRodrigues, Rodrigo Vieira 13 September 2016 (has links)
Oxissulfetos e oxissulfatos de terras raras vêm sendo explorado por vários pesquisadores há algum tempo, e são aplicados como materiais marcadores, LEDs, OLEDs, absorvedores de gases, materiais de persistência em luminescência, ou como marcadores para materiais biológicos, magnéticos entre outros. A proposta deste trabalho foi apresentar um processo diferenciado de obtenção de oxissulfetos e oxissulfatos de terras raras (RE3+) por meio da decomposição térmica de sulfatos e sulfonatos de terras raras [RE = Eu3+, Tb3+, Dy3+, Gd3+ e Sm3+], utilizando o método de precursores para a obtenção dos materiais. Os produtos foram isolados sob atmosferas dinâmicas de ar sintético e de CO, com as temperaturas variando de acordo com os patamares de estabilização dos respectivos compostos. A pureza das fases foi investigada a partir dos difratogramas de raios X (DRX) de cada composto, indicada pelas características cristalinas de cada produto. Os DRX dos precursores Tb(DAS)3·2H2O e Eu(DAS)3·7H2O indicaram que os materiais são amorfos. A pureza, também, foi investigada por espectroscopia de absorção no infravermelho (FTIR), para a identificação dos oxissulfetos e oxissulfatos e, ainda, a partir da interação entre os sulfonatos com os íons Eu3+ e Tb3+. As imagens de microscopia eletrônica de varredura (MEV) mostraram diferenças morfológicas entre os materiais cristalinos de oxissulfeto e/ou oxissulfato e de seus precursores sulfonatos. A partir dessas imagens foi possível perceber algumas características hexagonais e quase esféricas para os Eu2O2S derivados de sulfato e sulfonato, respectivamente, e ainda o grande aumento no tamanho das partículas dos Tb2O2S, derivado de sulfatos e sulfonatos. Também foram observadas diferenças nas formas entre os respectivos oxissulfatos. Os espectros de fotoluminescência dos compostos apresentaram as bandas de emissão das transições intraconfiguracionais oriundas dos íons Eu3+ (5D0→7FJ, J=0-6) e Tb3+ (5D4→7FJ, J=6-0), exibindo as cores vermelha e verde, características dos respectivos íons. Além disso, foram observadas as bandas características dos íons Dy3+ que apareceram no composto Dy2O2S, com a banda mais intensa monitorada a partir da transição 4F9/2→6H13/2 correspondente a cor amarela do íon Dy3+. Também, foi possível observar bandas largas e acentuadas de transferência de carga metal-ligante (LMCT) O2-(2p)→Eu3+ nos compostos Eu2O2S e Eu2O2SO4, tanto derivado de sulfato como de sulfonato. Os resultados mostraram que os oxissulfetos e oxissulfatos apresentam patamares de estabilização térmica sob atmosferas oxidantes e redutoras, que possibilitaram isolar os respectivos produtos. Esses materiais podem ser utilizados como fósforos para diversas aplicações como sondas, lasers entre outros. O Dy2O2S mostrou-se um fósforo estável podendo ser mais explorado em pesquisas futuras em emissões de cor amarela e azul. A troca do ânion sulfato pelo sulfonato proporcionou a obtenção de partículas de maior tamanho, indicando que é possível a aplicação destes fósforos em diferentes áreas tecnológicas. / Rare earth Oxysulfides and oxysulfates have been explored by several researchers for some time, and are applied as labels materials, LEDs, OLEDs, gas absorbers, persistence of luminescence materials, or as markers of biological material, magnetic, among others. The purpose of this study was to present a differentiated process of obtaining oxissulfetos and oxissulfatos rare earth (RE3+) by thermal decomposition of sulfates and sulfonates of rare earths [RE = Eu3+, Tb3+, Dy3+, Gd3+ and Sm3+] using the method precursor to obtain the material. The products were isolated under dynamic atmospheres synthetic air and CO, with temperatures varying according to stabilization levels of the respective compounds.The purity of the phases was investigated from of diffraction of X-rays (XRD) of each compound, indicated by the crystalline characteristics of each product. The XRD of precursors Tb(DAS)3·2H2O and Eu(DAS)3·7H2O indicate that the materials are amorphous. Besides, the purity also was investigated by infrared absorption spectroscopy (FTIR), for identifying and oxissulfetos oxissulfatos and also from the interaction between sulfonates with Eu3+ and Tb3+ ions. The scanning electron microscopy images (SEM) showed morphological differences between crystalline materials oxysulfide and/or oxysulfate and their sulfonate precursors. From these images it was possible to realize almost some hexagonal and quasi-spherical characteristics for Eu2O2S derivatives from sulfate and sulfonate, respectively, and also the large increase in particle size of the Tb2O2S derived from sulfates and sulfonates. Also differences were observed in the shapes between the respective oxysulfates. The photoluminescence spectra of the compounds showed the band emission of intraconfigurational transitions from the Eu3+ (5D0→7FJ, J=0-6) and Tb3+ (5D4→7FJ, J=6-0) ions, displaying the red and green colors, characteristics of the respective ions. In addition, they observed the ions of the characteristic bands Dy3+ that appeared in Dy2O2S compound, with the most intense band monitored from the 4F9/2→6H13/2 transition corresponding to yellow ion Dy3+. Also, it was possible to observe large and sharp bands of metal-ligand charge transfer (LMCT) O2-(2p)→Eu3+ the Eu2O2S and Eu2O2SO4 compounds, both derived sulfate and sulfonate. The results showed that the present oxysulfates and oxysulfides and the levels of thermal stabilization under oxidizing and reducing atmospheres, which made it possible to isolate the respective products. These materials can be used as phosphors for various applications as probes, lasers, among others. The Dy2O2S proved to be stable phosphorus can be further explored in future research in yellow and blue color emissions. The anion exchange of sulfate, sulfonate afforded by obtaining larger particles, indicating that the application of these phosphors in different technological areas is possible.
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Estudo de argamassas com agregados reciclados contaminados por gesso de construção. / A study on mortars produced with CDW recycled aggregates containing cypsum plaster as impurity.Aguiar, Gerusa de 05 November 2004 (has links)
Esta dissertação teve por objetivo iniciar investigações sobre os efeitos do uso de agregados reciclados contaminados por baixos teores de gesso de construção, em argamassas de assentamento de alvenarias. Na presença de umidade e por ação de minerais do gesso ou de outros mais complexos, que sejam formados, há riscos de fissuras, eflorescências e de deterioração progressiva dessas paredes. Um programa experimental foi realizado para a avaliação acelerada desses processos, por medidas de propriedades químicas, físicas e mecânicas de vinte argamassas. Materiais regionais usados em alvenarias e concreto na cidade de Socorro-SP foram escolhidos, pois lá existe uma usina de reciclagem, que produz areia reciclada para essas argamassas e com elevado teor de finos. Quatro agregados reciclados de granulometria muito fina e similar entre si foram artificialmente produzidos, por processos controlados de construção e demolição. Assim, estudou-se um agregado reciclado não contaminado (A1 com SO3 igual a 0,2 %) e outros três idênticos, com previsão de contaminação progressiva (A2, A3 e A4 , mas que resultaram com teor de SO3 total da ordem de 0,5 % a 0,6 %). Quatro grupos de argamassas foram produzidos com variação do consumo de cimento (200, 150 e 100 kg/m3), tipo de cimento (CP II e CP III) e ainda com e sem o uso de cal hidratada tipo CH III (teor elevado de carbonatos). O consumo de agregado reciclado anidro nas argamassas variou entre 1300 e 1200 kg/m3. Em cada grupo, foi ainda produzida uma argamassa mista, com areia muito pura e quartzosa, de granulometria e dosagem mais próximas às de argamassas normalizadas para alvenarias. A metodologia do programa baseou-se no envelhecimento acelerado das argamassas, a partir de 63 dias de idade e por ciclos de 7 dias em câmara úmida, alternados por 7 dias em estufa ventilada a 40 oC. Essa ciclagem foi adotada após criterioso levantamento bibliográfico e visando-se um processo holístico de deterioração preconizado por Collepardi (2003), inclusive para agregados reciclados contaminados por sulfatos. A partir de 63 dias de idade, foram então caracterizadas regularmente as seguintes propriedades das argamassas: resistência à tração na flexão, resistência à compressão, módulos de elasticidade estático e dinâmico. Durante a ciclagem, foram realizados ensaios complementares de termogravimetria e análise química quantitativa de sulfatos solúveis e de sais solúveis totais nas argamassas. Um conjunto de corpos-de-prova das argamassas permaneceu em câmara seca e foi também ensaiado a 175 dias, inclusive quanto à suscetibilidade a eflorescência. Entre 63 e 175 dias, foram realizados 8 ciclos de envelhecimento e conclui-se que a principal propriedade mecânica afetada durante a ciclagem foi a resistência à tração na flexão das argamassas e isto ocorreu a partir de 91 dias, nos quatro grupos de argamassas com agregado reciclado, sendo que entre 63 e 91 dias se quantificou uma evolução significativa de carbonatação pela termogravimetria. Os grupos de argamassas mistas com cimento e cal hidratada mostraram melhor desempenho neste estudo do que as argamassas simples de cimento e areia reciclada fina, inclusive quanto à eflorescência. Os resultados obtidos são restritos ao estudo de caso, mas permitem concluir que a contaminação de agregados reciclados para argamassas, por baixos teores de gesso de construção já foi suficiente para produzir alterações significativas no desempenho mecânico das argamassas e nos seus níveis de sulfatos solúveis, que foram alterados de forma coerente com a ciclagem e sendo possível a sua interpretação com base em teorias mais recentes de especialistas no tema. Por fim, o trabalho confirmou ser recomendável um limite máximo de sulfatos solúveis na faixa entre 0,1 % e 0,2 %, sobre a massa de agregados reciclados para argamassas. Estes níveis são preconizados por instituição alemã especializada em durabilidade de alvenarias. Concluiu-se que também pode ser adotado o critério da DIN 4226-100 (< 600 mg/L de SO4), compatível com a faixa citada. / This is an abstract of a Master of Science project carried out at EPUSP, Universidade de São Paulo, Brazil, aimed at investigating the effects of the use of recycled aggregates contaminated by small contents of gypsum plaster on masonry mortars. In the presence of moisture and by the action of gypsum minerals or other more complex ones that may occur, there is the risk of the formation of cracks, efflorescence, and progressive deterioration of the masonry walls. An experimental program was thus developed for the rapid assessment of these processes by assessing the chemical, physical and mechanical properties of twenty mortar mixes. Local materials used for masonry and concrete in Socorro-SP, Brazil, were selected, as in that location there exists a recycling unit producing recycled sand for mortars with a high content of fines. Four recycled aggregates of very fine grain size and similar to each other were artificially produced by controlled construction, demolition and recycling processes. Thus a recycled, non-contaminated aggregate (A1, with SO3 content equal to 0,2 %) and three other identical ones were studied, with expected progressive contamination (A2, A3 and A4, that result with a total SO3 content about 0,5 % to 0,6 %). Four groups of mortars were thus produced with varying cement content (200, 150 and 100 kg/m3), cement type (Brazilian CP II and CP III) and also with and without the use of a comercial hydrated lime, Brazilian type CH III (of a high carbonate filler content). The anhydrous recycled aggregate content in the mortars varied between 1300 and 1200 kg/m3. In each group a blended mortar was also produced, containing very pure quartzous sand, of grain size and mix proportions closer to standard masonry mortars. The approach followed in the experimental program was accelerated aging test of mortars, starting at 63 days of age and at 7 day cycles in the wet chamber, alternated by 7 days in the ventilated oven at 40 oC. This cycling was adopted after critical bibliographical research and under a holistic process of deterioration set up by Collepardi (2003), also for gypsum-contaminated aggregates. From 63 days of age, the following properties were regularly characterized for the mortars: flexural modulus (tensile strength in bending), compressive strength, and static and dynamic elasticity modulus. During cycling, complementary tests were done of thermogravimetrical analysis and quantitative chemical analysis of total soluble sulphate in mortars. A number of the mortar test specimens was left in the dry chamber and tested at 175 days, including tendency to efflorescence. In between 63 and 175 days, 8 weathering cycles were done, and it was concluded that the main mechanical property affected during cycling was tensile strength in bending (indirect tensile strength) of mortars, and this occurred from 91 days, in the four groups of mortars containing recycled aggregates, and in between 63 and 91 days a significant evolution was measured of carbonation by thermogravimetry. The groups of mixed mortars with cement and hydrated lime showed better performance in this study than the plain cement and fine sand mortars, also as regards efflorescence. The results here obtained are to be seen as restricted to this case study, yet they allow us to conclude that the use of recycled aggregates containing even low levels of gypsum plaster as impurity in the production of mortars was sufficient to produce significant alterations in the mechanical performance, as well as the degree of soluble sulphate of mortars, that got altered in a way coherent with the cycling process, and it is possible to interpret this based on more recent theories by experts in the subject. Last, this work confirmed that it is advisable to look for a maximum soluble sulphate limit ranging from 0,1 % to 0,2 % by weight of recycled aggregates for mortars. Such levels was set up by a German institution specializing in masonry durability. It was also concluded that the requirements of DIN 4226-100 (< 600 mg/L of SO4) can be used as appropriate in the range mentioned.
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