Submitted by Luciana Ferreira (lucgeral@gmail.com) on 2014-08-22T11:23:26Z No. of bitstreams: 2 license_rdf: 23148 bytes, checksum: 9da0b6dfac957114c6a7714714b86306 (MD5) Dissertação_Eloiza da Silva Nunes.pdf: 2557684 bytes, checksum: 485672a5e5df50e25a70cde5803fbfb4 (MD5) / Made available in DSpace on 2014-08-22T11:23:26Z (GMT). No. of bitstreams: 2 license_rdf: 23148 bytes, checksum: 9da0b6dfac957114c6a7714714b86306 (MD5) Dissertação_Eloiza da Silva Nunes.pdf: 2557684 bytes, checksum: 485672a5e5df50e25a70cde5803fbfb4 (MD5) Previous issue date: 2010-03-10 / In this work are described the synthesis and characterization of dinuclear rhodium(II) citrate, adsorption study in maghemite nanoparticles, and preparation of nanoparticles-modified based magnetic fluids. Rhodium(II) citrate has significant antitumor activity being promissory to cancer chemotherapy. Due to the existence of free functional groups in its molecular structure this complex has capacity to functionalize iron oxide nanoparticles to produce drug-particles formulations. The modified nanoparticles show features of biocompatibility suitable to use the system in medical applications. Rhodium(II) citrate was synthesized by an exchange reaction of trifluoroacetate ligands from the precursor rhodium(II) trifluoroacetate by citrate ligands. The products were characterized by C and H elemental and thermogravimetric analysis, mass spectrometry, and infrared, UV/visible and 13C nuclear magnetic resonance spectroscopy. The results are consistent with the formation of dinuclear structure characteristic for rhodium(II) carboxylates. Changing the synthesis conditions were obtained products with stoichiometries [Rh2(H2cit)2(H2O)4] and [Rh2(H2cit)4(H2O)2]. The results and compounds solubility observations suggest that the first one occur as a coordination polymer. The second one showed composition e solubility behavior consistent with the formation of monomeric units. Maghemite nanoparticles with size mean between 5 and 7 nm were obtained through alkaline coprecipitation of Fe2+ and Fe3+ ions with further oxidation with oxygen gas. The solids were characterized by X-ray difratometry and the Scherrer relation was use to calculate the crystallite size mean. Adsorption experimental data were adjusted to Langmuir model and linear coefficients obtained, R2, were greater than 0,99. Functionalized nanoparticles were dispersed into water producing a stable colloid. Dispersion s characterization was performed by absorbance, zeta potential, and hydrodynamic diameter measurements. Surface properties and colloidal behavior of functionalized nanoparticles are much affected by adsorbed species. The colloidal stability of the magnetic fluids is dependent on the adsorbed amounts of rhodium(II) citrate and pH. When the adsorbed amount of rhodium(II) citrate is next to saturation, the magnetic fluids are stable in pH over 3 and show hydrodynamic diameter around 60 nm. Fluids colloidal stability is preserved against physiologic saline solution, PBS buffer, and fetal bovine serum over a period of 30 days. / Neste trabalho estão descritos a síntese e a caracterização do complexo dimérico citrato de ródio(II), estudo de sua adsorção em nanopartículas de maghemita e a preparação de fluidos magnéticos á base de nanopartículas modificadas com o complexo. O citrato de ródio (II) apresenta significante atividade antitumor sendo promissor para aplicação na quimioterapia do câncer. Devido à existência de grupos funcionais livres em sua estrutura molecular esse complexo possui capacidade de funcionalizar nanopartículas de óxidos de ferro para produzir formulações droga-partícula. As nanopartículas modificadas apresentam características de biocompatibilidade adequadas para utilização do sistema em aplicações médicas. O citrato de ródio(II) foi sintetizado via reação de troca de ligantes trifluoroacetato do precursor trifluoroacetato de ródio(II) por citrato. Os produtos foram caracterizados por análise elementar de C e H e termogravimétrica, espectrometria de massas e espectroscopia nas regiões do UV/visível e infravermelho e ressonância magnética nuclear de 13C. Os resultados são consistentes com a formação da estrutura dimérica. Variando-se as condições de síntese pode-se obter produtos com estequiometrias [Rh2(H2cit)2(H2O)4] e [Rh2(H2cit)4(H2O)2]. Os resultados somados às observações sobre a solubilidade dos compostos sugerem que o primeiro ocorre como um polímero de coordenação. O segundo composto apresentou características de composição e solubilidade coerente com a formação de unidades dimetálicas monoméricas. Foram obtidas nanopartículas de maghemita com diâmetros entre 5 e 7 nm através do método de coprecipitação de íons Fe2+ e Fe3+ em meio alcalino com posterior oxidação com oxigênio gasoso. Os sólidos foram caracterizados por difratometria de raios-X e o diâmetro de cristalito calculado pela equação de Scherrer. Os dados experimentais de adsorção de citrato de ródio(II) em maghemita foram ajustados ao modelo de Langmuir sendo obtido coeficiente de regressão linear, R2, maior que 0,99. As nanopartículas funcionalizadas foram dispersas em água obtendo-se um colóide estável. As dispersões foram caracterizadas por medidas de absorvância, potencial zeta e de diâmetro hidrodinâmico. As propriedades de superfície bem como o comportamento coloidal das nanopartículas funcionalizadas são influenciadas pelas espécies adsorvidas. A estabilidade coloidal dos sóis obtidos é dependente das quantidades de citrato de ródio(II) adsorvida e do pH. Quando a quantidade de citrato de ródio adsorvida é próxima da capacidade de adsorção, os fluidos magnéticos obtidos apresentam estáveis em pH acima de 3 com diâmetros hidrodinâmicos próximos de 60 nm. A estabilidade coloidal dos fluidos obtidos é preservada frente a soluções de soro fisiológico, tampão PBS e soro fetal bovino por períodos superiores a 30 dias.

Apesar da quantidade de variáveis envolvidas, ainda persiste uma dúvida na comunidade acadêmica sobre o comportamento do concreto de alta resistência em situação de incêndio, considerando-o como mais ou menos suscetível à ocorrência do fenômeno de desplacamento (spalling) tipo explosivo. Em parte, essa dúvida decorre do fato de que, muitas vezes, os programas experimentais são conduzidos em amostras envolvendo corpos-de-prova padronizados, cilíndricos ou cúbicos, que não levam em consideração a influência de parâmetros relacionados com as dimensões dos elementos estruturais nem com a taxa e configuração das armaduras. Outros aspectos relevantes, como o tipo de agregado utilizado na mistura de concreto, bem como a idade e umidade interna do elemento ensaiado, dificilmente são abordados nas pesquisas e, muitas vezes, simplesmente são omitidos, o que dificulta a visão ampla e real do comportamento térmico do concreto de alta resistência. Esta pesquisa apresenta um programa experimental pioneiro realizado no Brasil em um pilar de concreto de alta resistência, armado, colorido, com idade de oito anos, fc,8anos de 140MPa, agregado graúdo basáltico, agregado miúdo quartzoso, seção transversal de 70cm x 70cm, 200cm de altura, ensaiado sem carregamento e com exposição de três faces pelo período de 180 minutos (3h), sob as temperaturas da curva-padrão de incêndio ISO 834. O pilar protótipo ensaiado é réplica dos pilares reais do edifício e-Tower, construído em 2002, na cidade de São Paulo, Brasil. Os resultados obtidos demonstraram que, neste caso, o concreto colorido de alta resistência comportou-se de forma íntegra frente ao fogo e que a utilização de pigmento à base de óxido de ferro, pode atuar também como um excelente termômetro natural, auxiliando na avaliação da condição da estrutura pósincêndio. / In spite of the several factors that influence the behavior of concrete columns under fire conditions, there is a belief among the research community, that the high-strength concrete is more susceptible to explosive spalling than normal-strength concrete. This doubt, in part, is attributed to the small unreinforced concrete samples (specimens) used in experimental programs, to evaluate the fire resistance of structural concrete. On the other hand, relevant aspects as the coarse aggregate type used in the concrete mixture, as well as the age and content moisture (relative humidity) are not considered in the researches and sometimes simply omitted. This research presents a pioneer experimental program, carried out in Brazil on a high strength colored reinforced concrete column (HSCC) with 200cm high, eight yearsold, fc,8years of 140MPa, basalt coarse aggregate, cross section of 700mm x 700mm, tested under no load and with three faces exposed to a standard fire curve ISO 834 for a period of 180min (3h). The column prototype is a replica of the actual columns of the e-Tower Building, constructed in 2002 in São Paulo city, Brazil. The results demonstrated concrete column integrity under experimental fire and that the iron oxide pigments can work as an excellent natural thermometer, contributing in the evaluation of the structure post-fire.

Orientador: Miguel Angel Ramirez Gil / Resumo: O titânio e as suas ligas são utilizados em aplicações biomédicas devido às suas excelentes propriedades, tais como resistência mecânica e biocompatibilidade. As técnicas de modificação de superfície são utilizadas nestas ligas para alterar as propriedades de superfície, aumentar a osseointegração e evitar falhas em implantes. Além destas técnicas, a incorporação de nanopartículas na superfície do implante têm sido grande aliada dos biomateriais, em especial às do óxido de ferro, devido às suas propriedades físico-químicas, sua biocompatibilidade e biodegradabilidade. O objetivo dessa dissertação foi propor método de incorporação de óxido de ferro na superfície nanoporosa da liga experimental Ti10Mo8Nb modificada por oxidação anódica, visando aplicações biomédicas. Os lingotes da liga experimental Ti10Mo8Nb foram obtidos a partir da fusão dos metais puros em forno a arco voltaico. A anodização foi realizada para obtenção das nanoestruturas de TiO2 (tensão de 20 V por 3 h), resultando em diâmetro interno dos nanoporos igual a aproximadamente 24 nm. A síntese do óxido de ferro foi realizada usando o método dos precursores poliméricos, sendo avaliado o comportamento reológico (viscosidade de 22,65 mPa.s) e a temperatura de cristalização para formação de nanopartículas de óxido de ferro. A partir da difratometria de raios X e da microscopia eletrônica de varredura, a temperatura de calcinação mais adequada para a formação da fase pura de hematita foi 600°C. A incorporação do óxid... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: Titanium and its alloys are used in biomedical applications because of their excellent properties, such as mechanical resistance and biocompatibility. Surface modification techniques are used to alter the surface properties, increase osseointegration and avoid implant failure. Beside these techniques, nanoparticles incorporation on implant surface are great biomaterials allies, specially iron oxides, due to their physicochemical properties, biocompatibility and biodegradability. The objective of this dissertation was to propose a method of iron oxide incorporation on the surface of experimental alloy Ti10Mo8Nb modified by anodization. The ingots of experimental alloy Ti10Mo8Nb were obtained from melting pure metals in an arc furnace. Anodization process was performed to obtain the TiO2 nanostructures, with internal diameter 24 nm. Iron oxide synthesis was carried out using the method of the polymeric precursors, assessing rheological behavior (22,65 mPa.s viscosity) and crystallization temperature ideal to produce iron oxide nanoparticles. Results from X Ray Diffratogram and Scanning Electron Microscopy presented that the most adequated annealing temperature to pure phase hematite was 600°C. Iron oxide incorporation on alloy surface was performed by immersion and spin coating, and in the second method the deposition was uniform and widespread. Spin coating was performed with 3 and 5 layers of iron oxide deposition, implying that with 5 layers is most appropriate because it do... (Complete abstract click electronic access below) / Mestre

<p>This work reports the chemical synthesis, characterisation and electrochemical application of titanium dioxide (TiO2) and iron oxide (Fe2O3) nanoparticles in the determination of phthalates. The other part of this work involved electrochemical polymerization of aniline doped with titanium and iron oxide nanoparticles for the sensor platform in the electrolytic determination of phthalates. The TiO2 and Fe2O3 nanoparticles were prepared by sol gel and hydrothermal methods respectively. Particle sizes of 20 nm (TiO2) and 50 nm (Fe2O3) were estimated from transmission electron microscopy (TEM) The other technical methods used in this study for the characterization of the TiO2 and iron oxide Fe2O3 NPs were SEM, XRD and UV- visible spectroscopy. Cyclic voltammetry, square wave voltammetry and electrochemical impedance spectroscopy (EIS) were used to study the electrochemical properties of the nanoparticles. These electrochemical studies of the nanoparticles were performed with a Fe2O3 or TiO2/nafion/glassy carbon membrane electrode in 0.1 M phosphate buffer (pH 7.0) and 0.1 M lithium perchlorate (pH 6.8) under an aerobic condition.</p>

Iron is the most important metal for modern industry and Sweden is the number one iron producer in Europe. The main sources for iron ore in Sweden are the apatite-iron oxide deposits of the "Kiruna-type", named after the iconic Kiruna ore deposit in Northern Sweden. The genesis of this ore type is, however, not fully understood and various schools of thought exist, being broadly divided into "ortho-magmatic" versus the "hydrothermal replacement" approaches. This study focuses on the origin of apatite-iron oxide ore of the Grängesberg Mining District (GMD) in Central Sweden, one of the largest iron reserves in Sweden, employing oxygen and iron isotope analyses on massive, vein and disseminated GMD magnetite, quartz and meta-volcanic host rocks. As a reference, oxygen and iron isotopes of magnetites from other Swedish and international iron ores as well as from various international volcanic materials were also analysed. These additional samples included both "ortho-magmatic" and "hydrothermal" magnetites and thus represent a basis for a comparative analysis with the GMD ore. The combined data and the derived temperatures support a scenario that is consistent with the GMD apatite-iron oxides having originated dominantly (ca. 87 %) through ortho-magmatic processes with magnetite crystallisation from oxide-rich intermediate magmas and magmatic fluids at temperatures of 600 °C to 900 °C. A minor portion of the GMD magnetites (ca. 13 %), exclusively made up of vein and disseminated ore types, is in equilibrium with a high-δ18O and low-δ56Fe hydrothermal fluid at temperatures below 400 °C, indicating the existence of a hydrothermal system associated with the GMD volcano.

Nanostructured materials are the next generation of high-performance materials, harnessing the novel properties of their nanosized constituents. The controlled assembly of nanosized particles and the design of the optimal nanostructure require a detailed understanding of particle interactions and robust methods to tune them. This thesis describes innovative approaches to these challenges, relating to the determination of Hamaker constants for iron oxide nanoparticles, the packaging of nanopowders into redispersible granules, the tuning of the wetting behavior of nanocrystals and the simulation of collective magnetic properties in arrays of superparamagnetic nanoparticles. The non-retarded Hamaker constants for iron oxides have been calculated from their optical properties based on Lifshitz theory. The results show that the magnitude of vdW interactions in non-polar solvents has previously been overestimated up to 10 times. Our calculations support the experimental observations that oleate-capped nanoparticles smaller than 15 nm in diameter can indeed form colloidally-stable dispersions in hydrocarbons. In addition, a simple procedure has been devised to remove the oleate-capping on the iron oxide nanoparticles, enabling their use in fluorometric assays for water remediation, with a sensitivity more than 100 times below the critical micelle concentration for non-ionic surfactants. Nanosized particles are inherently more difficult to handle in the dry state than larger micron-sized powders, e.g. because of poor flowability, agglomeration and potential toxicity. The rheology of concentrated slurries of TiO2 powder was optimized by the addition of sodium polyacrylate, and spray-dried into fully redispersible micron-sized granules. The polymer was embedded into the granules, where it could serve as a re-dispersing aid. Monte Carlo (MC) simulations have been applied to the collective magnetic behavior of nanoparticle arrays of various thicknesses. The decrease in magnetic susceptibility with the thickness observed experimentally was reproduced by the simulations. Ferromagnetic couplings in the arrays are enhanced by the finite thickness, and decrease in strength with increasing thickness. The simulations indicate the formation of vortex states with increasing thickness, along with a change in their orientation, which becomes more and more isotropic as the thickness increases. / <p>At the time of the doctoral defense, the following paper was unpublished and had a status as follows: Paper 2: Manuscript.</p>

Highly polluted urban storm water from e.g. highways can contain large amounts of heavy metals that may cause harm if they are discharged into recipients. To remove the heavy metals a possible low-cost method that does not require much maintenance, could be the use of reactive filters with filter materials consisting of industrial residues or other cheap mineral based materials. Dissolved metal ions are removed by reactive filters through the processes of ions binding to active sites on the surface of the filter materials, or by formation of insoluble precipitates. The ability of CaO-treated granulated blast-furnace slag, iron oxide coated sand, olivine and nepheline to remove seven heavy metals (Cr, Cd, Cu, Ni, Zn, Pb and Hg) from urban storm water was studied. Initially batch experiments were performed where the effect of pH, dissolved organic carbon (DOC) and dissolved ions on the adsorption efficiency was studied. The experiments were conducted with urban storm water and with a reference solution (10 mM NaNO3), both containing the same concentration of heavy metals (approx. 1 μM). The two materials with the best results were further investigated in a column study, where the capacity of the filter was tested. Chemical equilibrium calculations using the program Visual MINTEQ were performed in order to assess the role of precipitation as a mechanism for removal. The results show that the blast-furnace slag was the most effective filter material and that it has great potential to be used as a heavy metal remover. Also the iron oxide coated sand worked satisfactory. The highest degree of removal was obtained for lead, cadmium and nickel, for which the removal efficiency exceeded 90% after a load of 300 times the water volume in the columns. For some metals, mainly copper, chromium and mercury the dissolved organic matter affected the removal negatively. The chemical mechanisms causing the removal are specific adsorption to the surfaces of the materials, and for the blast-furnace slag probably precipitation of insoluble metal sulfides. / Starkt förorenat dagvatten som rinner av från exempelvis motorvägar, kan innehålla betydliga mängder tungmetaller som kan orsaka skada om de kommer ut i omgivande vattendrag. En billig metod för tungmetallavskiljning, som inte kräver så mycket underhåll, skulle kunna vara att använda reaktiva filtermaterial bestående av restprodukter eller andra mineraliska lågkostnadsmaterial. Reaktiva filter fungerar som metallavskiljare genom att de lösta metalljonerna binder till ytgrupper på filtermaterialen eller att svårlösliga utfällningar bildas. Förmågan att avskilja sju tungmetaller (Cr, Cd, Cu, Ni, Zn, Pb och Hg) ur dagvatten har undersökts för fyra mineraliska filtermaterial, kalciumoxiddopad masugnsslagg, järnoxidsand, olivin och nefelin. Studien inleddes med skakförsök där adsorptionens pH-beroende undersöktes. Försöken gjordes dels med dagvatten, dels med en referenslösning (10 mM NaNO3) med samma tungmetallkoncentration (ca 1μM). Detta gjordes för att studera effekter av löst organiskt material och andra ligander på adsorptionen. Därefter testades de material som uppvisat bäst resultat i skakförsöket i kolonnförsök, ett försök som mer efterliknar en praktisk tillämpning och där filtrets kapacitet kan studeras. Genom kemiska jämviktsberäkningar med programmet Visual MINTEQ var det möjligt att undersöka om bildningen av svårlösliga metallutfällningar bidrog till metallavskiljningen. Resultaten visar att slaggen var det effektivaste filtermaterialet och att detta har stor potential att användas för avskiljning av tungmetaller. Även järnoxidsanden fungerade tillfredsställande. De metaller som avskiljdes bäst var bly, kadmium och nickel, för vilka avskiljningen var &gt; 90 % i kolonnförsöket efter en belastning motsvarande 300 gånger vattenmängden i kolonnerna. För vissa metaller, främst koppar, krom och kvicksilver, försämrades avskiljningen betydligt när löst organiskt material fanns närvarande. Mekanismerna som står för avskiljningen är till störst del adsorption till grupper på filtermaterialens ytor, men bildning av svårlösliga metallsulfider är också tänkbar för slaggen.

The cell infiltration into the myocardial infarction (MI) site was studied using magnetic resonance imaging (MRI) with micrometer-sized iron oxide particles (MPIO) as cell labeling probes. MI is a leading cause of global death and disability. However, the roles of inflammatory cells and stem cells during the post-MI remodeling and repair processes are yet to be discovered. This study was to develop noninvasive MRI techniques to monitor and quantify the cellular infiltration into the MI site. MPIO can produce pronounced signal attenuation at regions of interest in MRI. Therefore, cells labeled with these particles can be detected after they are activated and home to the MI site. In the first project, MPIO of various doses were injected into the mouse blood stream 7 days before the MI surgery. Serial MRI was performed at various time points post-MI to monitor the inflammatory cell infiltration into the MI site. Significant signal attenuation caused by labeled cells, in particular macrophages, was observed at the MI site. The study suggests an optimal imaging window should be from 7 to 14 days post-MI, during which the MR signal was inversely proportional to the MPIO dose. The study also suggests an optimal MPIO dose should be between 9.1 and 14.5 µg Fe/g body weight. In the second project, mesenchymal stem cells labeled with MPIO were transplanted into the mouse bone marrow 14 days before the MI surgery. Serial MRI was performed at various time points post-MI to monitor the labeled cells, which mobilized from the bone marrow and homed to the MI site. All the MRI findings were further confirmed by histology. In addition to revealing the characteristics of cell infiltration during MI, this study also provides noninvasive MRI techniques to monitor and potentially quantify labeled cells at the pathological site. The technique can also be used to investigate the function of cells engaged in MI and to test the effect on cell infiltration caused by any treatment strategies.

Im Rahmen der vorliegenden Arbeit wurde eine neuartige Methode und die entsprechenden Katalysatoren für die heterogen katalysierte Gasphasen-Epoxidation von Propen entwickelt und optimiert. Das Propen wurde an FeOx/SiO2-Katalysatoren mit N2O als Oxidationsmittel epoxidiert. Die Katalysatoren wurden mittels XRD, TEM, XPS, Physi- und Chemisorption, TPR/TPO, TPD und IR untersucht und charakterisiert. Der Einfluß der Reaktionsbedingungen auf die Oxidationsergebnisse wurde bestimmt und Untersuchungen zum Reaktionsablauf durchgeführt. Es wurden Selektivitäten zu Propenoxid von 40-70%, bei Propenumsätzen von 3-12%, erreicht. Die maximalen erzielten PO-Ausbeuten betrugen über 5%, und sind damit den berichteten Ergebnisse aus der Literatur überlegen.

<p>This work reports the chemical synthesis, characterisation and electrochemical application of titanium dioxide (TiO2) and iron oxide (Fe2O3) nanoparticles in the determination of phthalates. The other part of this work involved electrochemical polymerization of aniline doped with titanium and iron oxide nanoparticles for the sensor platform in the electrolytic determination of phthalates. The TiO2 and Fe2O3 nanoparticles were prepared by sol gel and hydrothermal methods respectively. Particle sizes of 20 nm (TiO2) and 50 nm (Fe2O3) were estimated from transmission electron microscopy (TEM) The other technical methods used in this study for the characterization of the TiO2 and iron oxide Fe2O3 NPs were SEM, XRD and UV- visible spectroscopy. Cyclic voltammetry, square wave voltammetry and electrochemical impedance spectroscopy (EIS) were used to study the electrochemical properties of the nanoparticles. These electrochemical studies of the nanoparticles were performed with a Fe2O3 or TiO2/nafion/glassy carbon membrane electrode in 0.1 M phosphate buffer (pH 7.0) and 0.1 M lithium perchlorate (pH 6.8) under an aerobic condition.</p>