Orientador: Cecília Amélia de Carvalho Zavaglia / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Mecânica / Made available in DSpace on 2018-08-20T14:53:53Z (GMT). No. of bitstreams: 1 Silva_LeonardoAntonioJanuarioda_M.pdf: 2783644 bytes, checksum: 54071fa830084c4e19ccf56938bc9ee4 (MD5) Previous issue date: 2012 / Resumo: As cerâmicas porosas à base de hidroxiapatita possuem grande potencial de aplicação na área de implantes ósseos, devido sua similaridade química com a fase mineral dos tecidos ósseos, porém possuem baixa resistência mecânica, o que causa limitações em suas aplicações. Este trabalho tem como objetivo avaliar as características estruturais de cerâmicas porosas obtidas através da adição de Hidroxiapatita (HA, sintetizada no laboratório e comercial), Amido de Milho (AM, comercial), Al2O3 (3000SG ALCOA e 5SG ALCAN) e TiO2 (VETEC), sinterizadas em diferentes temperaturas. Foram preparadas amostras de HA densa (100% HA), HA porosa (50%HA - 50% de AM e 70% HA - 30% de AM), com adição de 2,5%, 5% e 7,5% de Al2O3 e 7,5% de TiO2 na composição porosa com 30% de AM, como alternativa de comparação dos resultados. As amostras foram sinterizadas à 1250ºC, 1300ºC e 1350ºC e caracterizadas por: FRX, DRX e MEV, distribuição granulométrica e densidade pelo princípio de Arquimedes. Concluiu-se que é possível obter amostras porosas utilizando-se o amido como agente porogênico e que as adições da alumina nas porcentagens utilizadas não aumentaram a resistência mecânica das amostras conforme esperado, devido à temperatura de sinterização trabalhada ser bem inferior do que a temperatura de sinterização da alumina ao contrário das amostras com Titânia / Abstract: The porous ceramics based on hydroxyapatite have great potential for application in bone grafts due to its chemical similarity with the mineral phase of bone tissue, but have poor biomechanical properties, which cause limitations in its applications. This work aims to analyze the structural characteristics of porous ceramics obtained by addition of hydroxyapatite (HA, sintered in the laboratory and commercial), Corn Starch (CS, commercial) and Al2O3 (3000SG ALCOA and 5SG ALCAN), sintered at different temperatures. Samples were made of dense HA (100% HA), HA porous (50%HA - 50%CS and 70% HA - 30% CS) and with addition of 2,5%, 5% and 7,5% Al2O3 and 7,5% TiO2 porous composition with 30% AM, as an alternative to compare the results. The samples were sintered at 1250°C, 1300ºC and 1350°C and characterized by: XRF, XRD, SEM, particle size distribution and density by the Archimedes principle. It concluded that it is possible to obtain porous samples using starch as the agent porogênico and that the additions of alumina used in the percentages did not increase the mechanical resistance properties of samples as expected, due to the sintering temperature worked being much lower than the sintering temperature of alumina as opposed samples with titania / Mestrado / Materiais e Processos de Fabricação / Mestre em Engenharia Mecânica

Methotrexate (MTX), as a pharmaceutical, is frequently used in tumor chemotherapy and is also a part of the established treatment of a number of autoimmune inflammatory disorders. Radiolabeled MTX has been studied as a tumor-diagnostic agent in a number of published studies. In the present study, the potential use of technetium-99m-labelled MTX (Tc-99m-MTX) as a radiotracer was investigated for the identification of inflammatory target sites. The labelling of MTX was carried out via a Tc-99m-gluconate precursor. Evaluation studies included in vitro stability, plasma protein binding assessment, partition-coefficient estimation, in vivo scintigraphic imaging and ex vivo animal experiments in an animal inflammation model. MTX was successfully labelled with Tc-99m, with a radiochemical purity of >95%. Stability was assessed in plasma, where it remained intact up to 85% at 4 h post-incubation, while protein binding of the radiotracer was observed to be similar to 50% at 4 h. These preclinical ex vivo and in vivo studies indicated that Tc-99m-MTX accumulates in inflamed tissue, as well as in the spinal cord, joints and bones; all areas with relatively high remodeling activity. The results are promising, and set the stage for further work on the development and application of Tc-99m-MTX as a radiotracer for inflammation associated with rheumatoid arthritis.

Biomaterials have been used for more than a century in the human body to improve body functions and replace damaged tissues. Currently approved and commonly used metallic biomaterials such as, stainless steel, titanium, cobalt chromium and other alloys have been found to have adverse effects leading in some cases, to mechanical failure and rejection of the implant. The physical or chemical nature of the degradation products of some implants initiates an adverse foreign body reaction in the tissue. Some metallic implants remain as permanent fixtures, whereas others such as plates, screws and pins used to secure serious fractures are removed by a second surgical procedure after the tissue has healed sufficiently. However, repeat surgical procedures increase the cost of health care and the possibility of patient morbidity. This study focuses on the development of magnesium based biodegradable alloys/metal matrix composites (MMCs) for orthopedic and cardiovascular applications. The Mg alloys/MMCs possessed good mechanical properties and biocompatible properties. Nine different compositions of Mg alloys/MMCs were manufactured and surface treated. Their degradation behavior, ion leaching, wettability, morphology, cytotoxicity and mechanical properties were determined. Alloying with Zn, Ca, HA and Gd and surface treatment resulted in improved mechanical properties, corrosion resistance, reduced cytotoxicity, lower pH and hydrogen evolution. Anodization resulted in the formation of a distinct oxide layer (thickness 5-10 μm) as compared with that produced on mechanically polished samples (~20-50 nm) under ambient conditions. It is envisaged that the findings of this research will introduce a new class of Mg based biodegradable alloys/MMCs and the emergence of innovative cardiovascular and orthopedic implant devices.

Orientador: Celso Aparecido Bertran / Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Química / Made available in DSpace on 2018-08-22T10:56:23Z (GMT). No. of bitstreams: 1 Campos_DaniellaDiasPalombinode_D.pdf: 44951379 bytes, checksum: 1a18d9ffcb14751022a3de58b577f652 (MD5) Previous issue date: 2012 / Resumo: Sistemas auto-organizados, preparados com surfactantes nonilfenil etoxilados com diferentes tamanhos de cadeia etoxilada, foram utilizados para sintetizar nanopartículas de hidroxiapatita (HAP - Ca5(PO4)3OH), que é o fosfato de cálcio majoritariamente presente nos tecidos mineralizados dos vertebrados. O efeito do tamanho do grupo etoxilado do surfactante foi avaliado tanto na formação dos sistemas auto-organizados quanto nas propriedades das partículas de HAP precipitadas in situ nestes sistemas. Cristais líquidos hexagonal reverso, lamelar, hexagonal e cúbicos foram formados, nesta ordem, a medida que surfactantes com maiores grupos etoxilados foram empregados. Os fosfatos de cálcio sintetizados em todos os sistemas auto-organizados apresentaram-se na forma de nanohastes, de modo que as nanohastes formadas nas fases anisotrópicas (cristais líquidos hexagonais e lamelares) apresentaram diâmetros mais uniformes quando comparadas àquelas sintetizadas nos sistemas auto-organizados isotrópicos. O diâmetro das hastes de HAP comparado com as dimensões dos sistemas auto-organizados sugere que estas se formaram pela aglomeração orientada de partículas ainda menores de HAP, o que foi evidenciado por microscopia eletrônica de varredura (SEM-FEG). Estes resultados, em conjunto com medidas de tempo de relaxação transversal (T2) do hidrogênio das moléculas de água presentes nos sistemas auto-organizados, permitem propor que a limitação do tamanho das nanopartículas de HAP seja conseqüência da limitação da difusão iônica in situ e que a morfologia de hastes é resultante da autoorganização das fases. / Abstract: Self-assembled systems from nonylphenol ethoxylate surfactants were prepared using surfactants with different hydrophilic chain lengths. These systems were used to synthesize hydroxyapatite (HAP - Ca5(PO4)3OH) nanoparticles, the main constituent of vertebrates mineralized tissues. The surfactant hydrophilic length influence was evaluated both on the self-assembled systems formation and on the properties of HAP nanoparticles which were obtained by in situ precipitation in these systems. As the surfactant hydrophilic length increased different liquid crystals were formed in this sequence: reverse hexagonal, lamellar, normal hexagonal and cubic mesophases. HAP nanoparticles synthesized in all selfassembled systems had morphology of rods. Particles precipitated in the anisotropic systems (hexagonal and lamellar liquid crystals) had more uniform diameters compared to particles precipitated in the isotropic systems (cubic liquid crystals). The HAP nanorods diameters were bigger than the repetition distances of the self-assembled systems. This occurrence, evidenced by SEM-FEG micrographs of the HAP nanoparticles, suggests that the nanorods were formed by even smaller HAP particles which were previously confined in the hydrophilic domains of the phases, and after the surfactant removal they were neatly clustered as induced by the self-assembled systems. These results along with the transversal relaxation times measurements (T2) for hydrogen in water molecules belonging self-assembled systems, allow us to propose the following: there is a reduced ionic diffusion within the liquid crystals hydrophilic domains and it is the cause for the size particles limitation and the particles morphology is influenced by the self-assembling of the systems. / Doutorado / Físico-Química / Doutora em Ciências

京都大学 / 0048 / 新制・課程博士 / 博士(エネルギー科学) / 甲第22796号 / エネ博第410号 / 新制||エネ||78(附属図書館) / 京都大学大学院エネルギー科学研究科エネルギー基礎科学専攻 / (主査)教授 坂口 浩司, 教授 佐川 尚, 准教授 高井 茂臣 / 学位規則第4条第1項該当 / Doctor of Energy Science / Kyoto University / DFAM

This work deals with bioceramic materials based of hydroxyapatite, bioglass and their composites. These materials are commonly used in medicine, especially as hard tissue substituents. They can be prepared by different types of syntheses, from which the most common were picked for this work – precipitation of hydroxyapatite and sol-gel method for bioglass. Thermal analysis and X-ray diffraction were used for characterization of prepared powders. This thesis studies mostly their features within the composite materials, which were foamed for better bone stimulation. Properties and possibility in bio application of materials is firstly studied through their interaction in simulated body fluids, which mimics ionic concentration of human plasma. Experimental part covers synthesis of ceramic powders, their characterization, preparation of mixtures and scaffolds foamed through in situ foaming, their sintering at ideal temperatures, characterization of porosity and phase changes due to sintering. Basic tests of apatite formation ability were provided by incubation of prepared scaffolds in simulated body fluid for 3, 7, 14 and 21 days and their assay in scanning electron microscopy. Changes in concentration of Ca2+ a PO4 3- ions as well as in weight of the specimen were tracked within the incubation period.

Biodegradable metallic materials for medical applications have received considerable attention in recent years. The main reason is that they provide high potential for fabrication of temporal orthopedic implants such as bone fixation devices. Magnesium is an excellent candidate for fabrication of biodegradable implants due to its biocompatibility, mechanical properties similar to human bone and relevance for biological body functions. The fast degradation rate of magnesium and its biodegradable alloys in physiological environment limits its clinical application. Another attractive material in the field of biodegradable materials is zinc, which is among the essential elements in human body. Zinc exhibits an excellent corrosion resistance, and inferior biocompatibility compared to with magnesium. Hence, surface modification to form a hard, dense/porous, biocompatible and corrosion resistant modified layer has become an interesting topic in magnesium base biomaterials. Since hydroxyapatite is well tolerated by living organisms and in addition, improves the bone growth, it appears to be excellent candidate for such coatings on surface of biodegradable materials (e.g. Mg, Zn). This thesis is focused on comparison of corrosion behavior of pure non ferrous metals (Mg, Zn) and metals coated with hydroxyapatite, in simulated body fluids. The present approach is the use of modified atmospheric plasma spray technology to produce the hydroxyapatite coatings – suspension spraying. Composition and structure of the coatings and corrosion products were studied by light microscopy, scanning electron microscopy equipped with energy dispersive microanalyzer and X-ray diffraction. Corrosion of Mg and Zn samples was monitored by weight loss and determined by X ray and micro-tomography. The application of the HA coating resulted in decrease of corrosion rate of pure Mg. The corrosion rate of coated Mg samples was lower by 27,3 % in comparison with the corrosion rate of pure non coated Mg. Corrosion degradation of uncoated and coated Zn samples was minimal. The aplication of HA on the non ferrous surface appears to be a very promising method to improve corrosion and biological properties of these biodegradable materials.

When the big joints like a knee or hip joint are damaged, the solution of this problem is an artificial substitute. The replacement of damaged joints with endoprotesis helps to reduce the pain and to move normally. In the design of the implant is necessary to fulfil all requirements on the properties of the material. The surface of implant is important, because it is directly connected to bone tissue. After implantation, the negative effect include infection, inflammation or release of the implant due to limited osseointegration, may appear. The osseointegration can be improved by modifying the material surface. This thesis is focused on development and evaluation of advanced materials imitating the bone structure, especially nanoroughness and the presence of biomimetic component, such as hydroxyapatite. In this study is evaluated adhesion, proliferation, viability, differentiation, and synthesis of specific proteins of human osteoblasts like Saos-2 on titanium modified with nanotubes and plasma sprayed hydroxyapatite compared with smooth surfaces. Key words: titanium, nanotubes, osteoblasts, hydroxyapatite, nanoroughness

Biomaterials are defined as non-viable materials whose functions strives to interact with biological systems, this makes biomaterials suitable for medical devices and applications. Biomaterials biological properties must be thoroughly investigated and evaluated in order to be approved for clinical usage. In vitro studies are used to characterize the materials biological properties, if promising results are achieved in vitro, in vivo studies may be performed to ensure that the material can interact with living animal models in the intended way. However, for a biomaterial such as calcium-deficient hydroxyapatite there is a gap between results observed in vitro and in vivo studies. Microfluidic systems have been highlighted as a possible evaluation model to achieve reliable results for in vitro studies. The aim of this thesis was to compare and evaluate a biomaterial- on-a-chip, i.e., a biomaterial integrated in a dynamic microfluidic system, with a traditional static in vitro system in the regards of drug release and protein adsorption. Two chemically identical calcium-deficient hydroxyapatites but with different topographies were integrated in the microfluidic system and manufactured as discs for static evaluation. Results from drug release and protein adsorption studies showed different behaviours for dynamic and static control, which is significant since it indicates that the outcome of the characterization correlates to the evaluation model used.

The thesis deals with the precipitation synthesis of nanoparticle hydroxyapatite with goal to study the influence of reaction conditions on the morphology of the particles. The theoretical part is focused on biomaterials, bioceramics and phosphates characterization. Further the work is focused on hydroxyapatite, its characteristics and possible synthesis in particular. The synthesis of hydroxyapatite precipitation is described in the experimental part. Syntheses were performed at a reaction temperature of 0-80 °C at pH = 8-11, at the aging time of 0-24 h, in the presence of surfactant and the chelating agent and with the post-precipitation hydrothermal or ultrasonic treatment. For characterization of the prepared powders, scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), laser diffraction (LD) and the analysis of the specific surface area (BET) were used. Pure hydroxyapatite powders or a mixture of hydroxyapatite and tricalcium phosphate were prepared by precipitation syntheses. HA particle morphology was strongly affected by the reaction temperature – with increasing temperature the larger particles with a clearer morphology were formed, mostly in the rod shape. Postprecipitation hydrothermal treatment had a significant influence on the morphology of HA particles – it caused the formation of spherical or slightly elongated particles. The reaction medium of water/ethanol significantly affected the particle morphology – it inhibited the particle growth.