A description of several experiments carried out to study the existence of evanescent waves behind totally reflecting dielectric surfaces is given in this thesis. Chapter I describes the experimental apparatus used to generate and measure the electromagnetic radiation. A detailed description of the construction of the radiating horns used and the casting of a plastic prism is also given. Chapters II and III give the results of two experiments in the region behind a totally reflecting face of the plastic prism and similar effects noted behind a lucite semicylinder with its plane face towards the source of radiation. Near field diffraction patterns of this cylinder with its plane face towards the source, away from the source, and parallel to the axis of radiation are also given. The above three cases are compared with results obtained by coating the semicylinder with aluminum foil. / Thesis / Master of Science (MSc)

The aim of this diploma thesis is the application of vibrational spectroscopy in pharmaceutical analysis in studying solid pharmaceutical forms. The surface of tablet samples containing the active substance from the group of statins has been studied especially by the methods infrared microscopy. Spectral maps of samples were collected thanks to the techniques of specular reflection, attenuated total reflection (ATR) and "inverse" ATR after determining optimal conditions for measurements. In order to evaluate these measured maps, one-dimensional analysis and principal component analysis were used. As the same samples of tablets were also measured by Raman microscopy, the comparison has been provided. The measured distribution maps enable both a determination of substances in the sample and conclusion concerned a method of tablets' preparation. The method in this case is a granulation, which has been found out from a comparison of maps of generic and original medicament. The specular reflection method was selected to be the most appropriate technique for obtaining the maps of the surface of a tablet, via confrontation of particular methods consequently with consideration of their advantages and disadvantages in the measurement and data processing.

Disease- and drug-related bone disorders are rapidly increasing in the population. The drugs which are used for the treatment of neurodegenerative diseases and metabolic derangements, may have negative or positive effects on bone tissues. In the first study, the possible side-effects of Carbamazepine and epileptic seizures on bone structure and composition were investigated by FTIR and synchrotron-FTIR microspectroscopy, AFM and micro- and nano-hardness analysis. The effects on the blood parameters, bone turnover and vitamin D metabolism were also investigated by ELISA and western blot analysis. The current study provides the first report on differentiation of the effects of both epileptic seizures and AED therapy on bones. Besides Carbamazepine treatment, seizures also caused a decrease in the strength of bone. The biochemical data showed that both the epileptic and drug-treated groups decreased vitamin D levels by increasing the vitamin D catabolism enzyme / 25-hydroxyvitamin D-24-hydroxylase. In the second study, the possible pleiotropic (positive) effects of cholesterol lowering drug / Simvastatin on bones were investigated by ATR-FTIR spectroscopy. The current study provides the first report on dose-dependent effects of simvastatin on protein structure and lipid conformation of bones. ATR-FTIR studies showed that although both high and low dose simvastatin strengthen bones, low dose simvastatin treatment is much more effective in increasing bone strength. Neural network analysis revealed an increased antiparallel and aggregated beta sheet and random coil in the protein secondary structure of high dose group implying a protein denaturation. Moreover, high dose may induce lipid peroxidation which limit the pleiotropic effects of high dose treatment on bones. This study clearly demonstrated that using low dose simvastatin is safer and more effective for bone health than high dose simvastatin treatment.

Bone marrow mesenchymal stem cells (BM-MSCs) are pluripotent cells that can differentiate into a variety of non-hematopoietic tissues. They also maintain healthy heamatopoiesis by providing supportive cellular microenvironment into BM. In this thesis, MSCs were characterized in terms of their morphological, immunophenotypical and differentiation properties. Then, they were examined by attenuated total reflection-Fourier transform infrared (ATR-FTIR) spectroscopy together with hierarchical clustering, and FTIR microspectroscopy. In the first part of this study, global structural and compositional changes in BM-MSCs during beta thallasemia major (

Bone marrow mesenchymal stem cells (BM-MSCs) are pluripotent cells that can differentiate into a variety of non-hematopoietic tissues. They also maintain healthy heamatopoiesis by providing supportive cellular microenvironment into BM. In this thesis, MSCs were characterized in terms of their morphological, immunophenotypical and differentiation properties. Then, they were examined by attenuated total reflection-Fourier transform infrared (ATR-FTIR) spectroscopy together with hierarchical clustering, and FTIR microspectroscopy. In the first part of this study, global structural and compositional changes in BM-MSCs during beta thallasemia major (

Tunneling phenomenon has been studied since the time of Sir Isaac Newton. In the case of neutron tunneling phenomenon, it is the quantum mechanics wave-particle duality which manifests itself. In this case, particularly, the neutron wave-packet under total reflection condition suffers the so-called frustrated total reflection as known in standard optics. More accurately, this tunneling phenomenon shows itself via sharp dips in the plateau of total reflection. The prerequisite to observe such quantum mechanics phenomenon lies within a thin film Fabry-Perot resonator configuration. This thin film Fabry-Perot resonator geometry consists of two reflecting mirrors separated by a transparent material from a neutron optics viewpoint. In view of the specific neutron scattering properties related to the spin of the neutron wave-packet. As a direct proof, isotopic nickel based thin films Fabry-Perot resonator have been fabricated by depositing thin film of nickel by ion beam sputtering. The vacuum chamber was pumped down to the pressure of 10-8 mbar and deposition was performed at pressure of 2x10-4 mbar. The deposition rate was kept at 1.5 nm / minute and thickness layers were monitored by a calibrated quartz microbalance. Unpolarized neutron reflectometry measurements were carried out at the ORPHEE reactor using the time-of-flight EROS reflectometer. The incidence neutron wavelength varied between 3 – 25 Å. The grazing angle and angular resolution were of the order of 0.8˚ and 0.05 respectively. The software program, a Matlab routine for the simulation of specular X-ray and neutron reflectivity data with matrix technique, was employed to simulate the phenomenon and thereafter the experimentally obtained data and calculated (theoretical) data were compared. From the analysis of the comparison, a conclusion was drawn about the agreement between experimental data and theoretical data. The tunneling phenomenon has been observed in nanostructured isotopic nickel based thin film Fabry-Perot resonator. It manifested itself by the existence of dips, tunneling resonances, in the total reflection plateau due to quasi-bound states in the isotopic nickel based thin film Fabry-Perot resonator. In total, there were 7 tunneling resonances. The full widths at half maximum of these dips were found to decrease with increasing momentum wave vector transfer (Q) and this correlated to the neutron lifetime in the nanostructured isotopic nickel based thin film Fabry-Perot resonator. / Physics / M. Sc. (Physics)

Orientador: Silvana Moreira / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Civil, Arquitetura e Urbanismo / Made available in DSpace on 2018-08-11T03:52:29Z (GMT). No. of bitstreams: 1 Fazza_ElizeteVieira_M.pdf: 2172063 bytes, checksum: 9efe3c01da1dbb554288a537bfa44ea7 (MD5) Previous issue date: 2007 / Resumo: A cidade de Limeira está localizada no Estado de São Paulo e possui economia expressiva, com indústrias em vários setores produtivos, entre elas, galvanoplastias voltadas para a produção de jóias, semijóias e bijuterias. Visando elucidar se há influência antropogênica nos mananciais da cidade, avaliou-se a qualidade das águas e as concentrações de metais presentes na água e nos sedimentos dos ribeirões Graminha e Águas da Serra, cujas nascentes estão na zona urbana de Limeira. As determinações de metais foram realizadas pela técnica de Fluorescência de Raios X por Reflexão Total com Radiação Síncrotron (SR-TXRF). Os limites de detecção para amostras de água estão na faixa de 0,50 a 0,05 µg.L-1 para Ca e Zn, respectivamente, enquanto que para as amostras de sedimento os limites de detecção obtidos foram iguais a 0,22 e 0,02 µg.g-1 para os mesmos elementos. Nas amostras de água dos dois mananciais e para ambos os períodos amostrados (seco e húmido) as concetrações de Al e Fe foram superiores aos limites máximos permissíveis estabelecidos pela legislação vigente. Os elementos Zn e Cu apresentaram o mesmo comportamento. Para o Cr e Ni apenas alguns pontos de amostragem apresentaram valores acima dos limites permitidos. No ribeirão Águas da Serra os valores foram superiores ao permitido para todos os pontos exceto pra dois pontos no período seco, enquanto que para o ribeirão Graminha os resultados foram superiores para quatro pontos no período úmido. Nas amostras de sedimento o elemento Cu ultrapassou o valor estabelecido pela legislação em ambos os mananciais. Os valores para Pb nas amostras de sedimento também foram ultrapassados para todas as amostras do ribeirão Águas da Serra e em alguns pontos do Graminha. Os resultados obtidos para Cr foram excedidos em três pontos no período húmido e em dois pontos no período seco para o ribeirão Águas da Serra, e no Graminha apenas no período seco os valores para dois pontos foram excedidos. Para Ni e Zn em apenas alguns pontos foram observados valores acima do permitido. A metodologia aplicada foi eficiente porque permitiu a determinação dos metais a níveis exigidos pela legislação brasileira. As concentrações dos metais foram superiores aos valores máximos permissíveis estabelecidos pela legislação vigente para vários elementos tanto nas amostras de água quanto nas amostras de sedimento. Os resultados apontam para a necessidade de ações para recuperar a qualidade dos mananciais bem como protegê-los de novas alterações antrópicas negativas. Palavras Chave: Metais pesado, Água ¿ Qualidade, Sedimentos, Poluição -- Aspectos Ambientais, Meio ambiente, Fluorescência de raio X, Síncrotron / Abstract: The city of Limeira is located in the State of São Paulo and has expressive economy, with industries in several productive sectors, as galvanization industries for the jewels, semi-jewels and bijoux production. Aiming to explain the anthropogenic influence in the sources, the water and sediment qualities of the Graminha and Águas da Serra brooks were evaluated whose springs are in the urban zone of Limeira. The metal determination was performed using Synchrotron Radiation Total Reflection X-Ray Fluorescence (SRTXRF). The detection limits for water samples were in the range of 0.50 to 0.05 µg.L-1 for Ca and Zn, respectively while for sediment samples the detection limits were 0.22 to 0.02 µg.g-1 for the same elements. For water samples in both brooks and for all periods (dry and humid) the concentrations of Al and Fe were higher than the maximum permissive values (MPV) established by the legislation. For Zn and Cu the same behaviour was observed. For Cr and Ni just some locations presented values higher than MPV for water samples. Moreover in Águas da Serra brook values higher than MPV were observed for all points except for two points in the dry period, for Graminha 12 stream the results were higher for four sample locations in the humid period. For sediment samples Cu surpass the value established by the legislation for both springs. For Pb the values surpass the limit for all samples in Águas da Serra and some points for Graminha stream. The results for Cr in sediment samples were surpassed for three points in the humid period and two points in the dry period for Águas da Serra brook, and in Graminha just in the dry period for two points the values were exceeded. For Ni and Zn only a few points surpassed the limits for both springs.The applied methodology was efficient because the detection limits turned possible the determination of the metals in levels in according to legislation. The metal concentrations were higher than the maximum permisse values established by the Brazilian Legislation for several elements in water and sediment samples. The results point to the action necessity to recover the quality of the sources as well as to protect the brooks of new negative anthropogenic alterations. Keywords: Heavy metals, Water quality, Sediment, Pollution, Environment, Synchrotron Radiation Total Reflection X-Ray Fluorescence (SR-TXRF) / Mestrado / Saneamento e Ambiente / Mestre em Engenharia Civil

Orientador: Mônica Alonso Cotta / Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Física Gleb Wataghin / Made available in DSpace on 2018-08-18T17:58:13Z (GMT). No. of bitstreams: 1 Lorite_GabrielaSimone_D.pdf: 14464970 bytes, checksum: f2238701a88fbbba91e337eda7db2965 (MD5) Previous issue date: 2011 / Resumo: Apresentamos nesta tese uma investigação dos processos físico-químicos da adesão e desenvolvimento de biofilmes da bactéria fitopatogênica Xylella fastidiosa (Xf) em diferentes superfícies. Este estudo visa corroborar ou complementar diferentes aspectos dos modelos atualmente em discussão para biofilmes bacterianos, além de, num caráter tecnológico, fornecer subsídios para um eventual controle da formação dos biofilmes de Xf. Para isso utilizamos uma abordagem diferenciada à comumente empregada em biologia - e mais próxima à ciência dos materiais - visando isolar e quantificar a relevância dos parâmetros que contribuem na formação de um biofilme em diferentes superfícies, tentando aproximá-las do xilema da planta. Nossos resultados mostram uma semelhança de desenvolvimento (forma, tamanho e quantidade) nos biofilmes de Xf cultivados em superfícies de vidro e Si, e um melhor desenvolvimento dos biofilmes em Si do que nas superfícies de etil celulose, EC, e acetato de celulose, AC. De um ponto de vista fenomenológico, os biofilmes apresentam diferentes estruturas, taxa de desenvolvimento e tendências na expressão gênica entre superfícies com e sem presença de celulose derivatizada. Na caracterização das superfícies utilizadas consideramos o efeito do meio de cultura em suas propriedades. Nas superfícies de vidro e Si, constatamos a formação de um filme condicionante devido à adsorção dos constituintes deste meio. O grau de hidrofobicidade das superfícies de vidro e Si diminui significativamente após contato com o meio de cultura enquanto as superfícies de celulose derivatizada apresentam pouca (EC) ou nenhuma alteração (AC); observamos também um aumento do potencial de superfície (PS) para Si e EC e, ainda, uma diminuição de PS em AC. Estas evidências sugerem uma correlação entre PS mais altos e grau de hidrofobicidade baixos com a presença de biofilmes de Xf em maior número e tamanho. Além disso, medidas de espectroscopia de força utilizando ponta funcionalizada com a proteína de adesão XadA1 evidenciam também um comportamento distinto na superfície de AC. Estes resultados apontam para a importância da interação eletrostática no processo inicial de adesão da bactérias às superfícies estudadas. Por fim, a presença de material extracelular ao redor dos biofilmes e células de Xf em superfícies de vidro e Si foi observada indicando a presença de uma matriz exopolimérica protetora. Espectroscopia de infravermelho mostra a presença de polissacarídeos ¿ constituinte da matriz polimérica ¿ desde o estágio inicial de formação do biofilme, indicando uma possível contribuição dessa matriz para o processo de adesão que precede o desenvolvimento do biofilme / Abstract: In this work, we report an investigation on relevant physicochemical processes of bacterial surface adhesion and biofilm development for the phytopathogen Xylella fastidiosa (Xf) on different surfaces. This study aims to corroborate or supplement different aspects of the bacterial biofilms models currently under discussion and, in a technological point of view, provides experimental input for an eventual control of Xf biofilm formation. For this purpose, we have used an approach not commonly found in biology ¿ and more similar to materials science ¿ in order to isolate and quantify the relevance of the parameters that contribute to the formation of a biofilm on different surfaces, as well as trying to make these surfaces closer to the plant xylem. Our results show a similar development (shape, size and quantity) for Xf biofilms grown on Si and glass surfaces, and an improved development of biofilms grown on Si than on ethyl cellulose, EC, and cellulose acetate, AC. Under a phenomenological point of view, biofilms present different structures, rate of development and trends in gene expression between surfaces with and without the presence of derivatized cellulose. In order to characterize the surfaces, we considered the effect of culture medium on their properties. In Si and glass surfaces, we observe the formation of a conditioning film due to adsorption of the constituents of the culture medium. The degree of hydrophobicity of glass and Si surfaces decreases significantly after contact with this medium. On the other hand, cellulose derivatized surfaces present lower (EC) or no (AC) modifications of this property. In addition, we observed an increase in the surface potential (SP) for Si and EC and also a SP decrease for AC. These evidences suggest a correlation between higher SP values and lower degree of hydrophobicity with the presence of biofilms of Xf in larger numbers and size. Furthermore, force spectroscopy measurements using a functionalized tip with the adhesion protein XadA1 also show a different behavior on the AC surface. These results reveal the importance of electrostatic interaction in the initial bacterial adhesion for the surfaces studied here. Finally, the presence of extracellular material around the Xf cells and biofilms on glass and Si surfaces was observed indicating the presence of a protective exopolymeric matrix. Infrared spectroscopy shows the presence of polysaccharides - a constituent of the polymeric matrix - from the very initial stages of biofilm formation, indicating a possible contribution of this matrix for the adhesion process which precedes biofilm development / Doutorado / Biofísica / Doutora em Ciências

The work deals with structrural and morphological characterization of polyamide buckles used to fasten webbins. The buckles were produced in five different years, a few of those produced in 2000 and 2004 were broken. The aime is to determine the type of polyamide and the cause of fracture of the buckles during using. The buckles were characterized in terms of structure and composition by Fourier-transform infrared spectroscopy in a mode of attenuated total reflaction, differential scanning calorimetry, thermogravimetry and X-ray diffraction. The buckles were made of polyamide 12. The broken buckles showed higher melting point, lower thermal stability and, in addition to modification it also contains modification, which is more fragile and probably represents the cause of fracture.

Les hydrogels de polysaccharide sont des biomatériaux utilisés comme matrices à libération contrôlée de médicaments et comme structures modèles pour l’étude de nombreux systèmes biologiques dont les biofilms bactériens et les mucus. Dans tous les cas, le transport de médicaments ou de nutriments à l’intérieur d’une matrice d’hydrogel joue un rôle de premier plan. Ainsi, l’étude des propriétés de transport dans les hydrogels s’avère un enjeu très important au niveau de plusieurs applications. Dans cet ouvrage, le curdlan, un polysaccharide neutre d’origine bactérienne et formé d’unités répétitives β-D-(1→3) glucose, est utilisé comme hydrogel modèle. Le curdlan a la propriété de former des thermogels de différentes conformations selon la température à laquelle une suspension aqueuse est incubée. La caractérisation in situ de la formation des hydrogels de curdlan thermoréversibles et thermo-irréversibles a tout d’abord été réalisée par spectroscopie infrarouge à transformée de Fourier (FT-IR) en mode réflexion totale atténuée à température variable. Les résultats ont permis d’optimiser les conditions de gélation, menant ainsi à la formation reproductible des hydrogels. Les caractérisations structurales des hydrogels hydratés, réalisées par imagerie FT-IR, par microscopie électronique à balayage en mode environnemental (eSEM) et par microscopie à force atomique (AFM), ont permis de visualiser les différentes morphologies susceptibles d’influencer la diffusion d’analytes dans les gels. Nos résultats montrent que les deux types d’hydrogels de curdlan ont des architectures distinctes à l’échelle microscopique. La combinaison de la spectroscopie de résonance magnétique nucléaire (RMN) à gradients pulsés et de l’imagerie RMN a permis d’étudier l’autodiffusion et la diffusion mutuelle sur un même système dans des conditions expérimentales similaires. Nous avons observé que la diffusion des molécules dans les gels est ralentie par rapport à celle mesurée en solution aqueuse. Les mesures d’autodiffusion, effectuées sur une série d’analytes de diverses tailles dans les deux types d’hydrogels de curdlan, montrent que le coefficient d’autodiffusion relatif décroit en fonction de la taille de l’analyte. De plus, nos résultats suggèrent que l’équivalence entre les coefficients d’autodiffusion et de diffusion mutuelle dans les hydrogels de curdlan thermo-irréversibles est principalement due au fait que l’environnement sondé par les analytes durant une expérience d’autodiffusion est représentatif de celui exploré durant une expérience de diffusion mutuelle. Dans de telles conditions, nos résultats montrent que la RMN à gradients pulsés peut s’avérer une approche très avantageuse afin de caractériser des systèmes à libération contrôlée de médicaments. D’autres expériences de diffusion mutuelle, menées sur une macromolécule de dextran, montrent un coefficient de diffusion mutuelle inférieur au coefficient d’autodiffusion sur un même gel de curdlan. L’écart mesuré entre les deux modes de transport est attribué au volume différent de l’environnement sondé durant les deux mesures. Les coefficients d’autodiffusion et de diffusion mutuelle similaires, mesurés dans les deux types de gels de curdlan pour les différents analytes étudiés, suggèrent une influence limitée de l’architecture microscopique de ces gels sur leurs propriétés de transport. Il est conclu que les interactions affectant la diffusion des analytes étudiés dans les hydrogels de curdlan se situent à l’échelle moléculaire. / Polysaccharide hydrogels are biomaterials used as controlled drug delivery matrices and serve as model scaffolds for the study of many biological systems like bacterial biofilms and mucus. In every case, the transport of drugs or nutriments across a hydrogel matrix is of prime importance. Therefore, the study of transport properties in hydrogels is an important issue for many fields of application. In this work, curdlan, a neutral bacterial polysaccharide made of β-D-(1→3) glucose repeating units, is used as a model hydrogel. Aqueous suspensions of curdlan can form thermogels of different conformations depending on the incubation temperature. In situ characterization of the preparation of thermo-reversible (low-set) and thermo-irreversible (high-set) curdlan hydrogels was first carried out using variable temperature attenuated total reflection (ATR) Fourier transform infrared spectroscopy (FT-IR). The results allowed optimization of the gelling conditions leading to reproducible gel samples. Structural characterization of fully hydrated hydrogels, carried out by FT-IR imaging, environmental scanning electron microscopy (eSEM) and atomic force microscopy (AFM), allowed visualization of the different gel morphologies susceptible of influencing the diffusion of analytes in hydrogels. Our results show that both types of curdlan hydrogels have distinct microscopic architectures. The combination of pulsed field gradient (PFG) nuclear magnetic resonance (NMR) spectroscopy and NMR profiling allowed the study of self-diffusion and mutual diffusion on the same hydrogel system in similar experimental conditions. We showed that the diffusion of analytes in the gels is slower than in the aqueous solution. The diffusion experiments, carried out on a series of analytes of various sizes in both types of curdlan gels, show a decrease of the relative self-diffusion coefficient as a function of the analyte size. In addition, our results suggest that the equivalence between the self-diffusion and mutual-diffusion coefficients measured in the high-set curdlan gels is mainly due to the fact that the environment probed by the analytes during a self-diffusion experiment is representative of the one probed during a mutual-diffusion experiment. In such conditions, our results show that PFG NMR may present a valuable approach for the characterization of controlled drug release systems. Additional experiments show that the mutual-diffusion coefficient of dextran macromolecules is smaller than its self-diffusion coefficient in the same curdlan hydrogel. The difference between both transport rates is attributed to the different environment volumes probed by the analytes during the measurements. The similarities observed between the self-diffusion and mutual-diffusion coefficients, measured in both types of curdlan gels for all investigated analytes, suggest a limited influence of the microscopic gel architecture on its transport properties. It is therefore concluded that the interactions affecting the diffusion of the investigated analytes in the curdlan hydrogels lie at the molecular scale.