Resumo: O papel dos elementos traço em tumores mamários tem sido investigado nas últimas décadas, mas comparações de subclasses de tumores mamários malignos são ainda inéditas em medicina veterinária. Portanto, o objetivo do presente trabalho foi identificar a concentração dos elementos cálcio, ferro, cobre e zinco em neoplasias mamárias de cadelas, comparando-se um grupo controle com três tipos histológicos malignos. Cinquenta e uma biopsias mamárias foram avaliadas e divididas em quatro grupos (G1 - controle, G2 - carcinoma complexo, G3 - carcinoma tubular/tubulopapilífero e G4 - carcinoma sólido). O material foi colhido de mastectomias realizadas na rotina do Hospital Veterinário da UNESP-Araçatuba sendo classificado segundo os critérios diagnósticos propostos pela Organização Mundial de Saúde. As amostras foram analisadas, quanto aos elementos traço, pela técnica de Fluorescência de Raios X por Dispersão de Energia (EDXRF). A análise estatística revelou aumento significativo (p<0,05) dos elementos cálcio, ferro e zinco entre os grupos G1 e G2. Comparações entre o sistema TNM (Tumor/Linfonodo/Metástases) e os elementos traço não foram significativas (p˃0,05) à análise estatística, já que os mesmos demonstraram estar correlacionados ao tipo histológico e não ao sistema TNM de prognóstico de vida. O aparelho de EDXRF mostrou-se eficaz para a análise dos elementos traço, além de ser uma técnica mais acessível, multielementar e não destrutiva, permitindo que outras metodologias possam ser utilizadas para estudos complementares com as mesmas amostras / Abstract: The role of trace elements in breast cancer has been investigated in recent decades, but comparisons of subclasses of malignant mammary tumors are still unpublished in veterinary medicine. So, the aim of this work was to identify the concentration of calcium, iron, cooper and zinc in canine mammary tumors, comparing them with a control group and three malignant neoplasias. 51 mammary fragments of biopsies were analyzed and divided in four groups (G1 - Control, G2 - Complex Carcinomas, G3 - Tubular/Tubulopapillary Carcinoma and G4 - Solid Carcinoma). Samples of the tumors were collected during surgical procedures, mastectomy, performed at Veterinary Hospital of Sao Paulo State University - Araçatuba and were classified according to the diagnostic criteria proposed by the World Health Organization. Samples were analyzed by Energy Dispersive X-Ray Fluorescence Equipment (EDXRF). Statistical analysis revealed a significant difference (p<0.05) only in the groups G1 and G2, concerning to the calcium, iron and zinc elements. The comparison between TNM system and trace elements revealed an absence of statistical evaluation, because trace elements were connected with histopathologycal graduation. The EDXRF was useful for trace element analyses and it is a non-destructive, multielementar technology that permits complementary studies with the same samples / Orientador: Alexandre Lima de Andrade / Coorientador: Maria Cecília Rui Luvizotto / Coorientador: Andrea Antunes Pereira / Banca: Flávia de Rezende Eugênio / Banca: Paula Rahal / Mestre

Na condução por saltos dispersiva, os portadores de carga são caracterizados por tempos de residência não exponenciais. Como uma conseqüência, efeitos hereditários aparecem e o problema deve ser conduzido no espaçõ de Laplace. Distribuições dielétricas conhecidas e algumas outras foram usadas como possíveis funções capazes de descrever o meio desordenado. Um estudo cuidadoso de seus espectros de freqüência foi realizado. O método de inversão de Widder truncado foi desenvolvido para possibilitar a volta do espaço de Laplace para o do tempo real. Dois tipos de problemas práticos foram abordados: condução dispersiva na qual o campo elétrico das cargas móveis pode ser desprezado e o caso de carga espacial para o qual essa aproximação não pode ser feita. Duas configurações de interesse foram escolhidas: decaimento do potencial de superfície de amostras carregadas por descarga corona e a subida do potencial no carregamento por corrente constante. / Dispersive conductive process are characterized by non-exponential residence times of the hopping carrier. As a consequence, hereditary effects appear and the problem must be conducted in the Laplace space. A bunch of known dielectric distributions functions and others were used as possible functions describing the disordered medium. A careful study of their frequency spectrum was carried out. The truncate Widder inversion was developed in order to allow returning from the Lapace to the real time space. Two kind of practical problems were studied: dispersive conduction in which the electric field of the mobile charge may be neglected and the space charge ones when that approximation cannot be made. Two configurations of interest were selected: the corona discharge potential decay and the constant current potentinal build-up.

A microextração líquido-líquido dispersiva (DLLME) é uma técnica de preparo de amostra baseada no equilíbrio de distribuição do analito entre a fase doadora (amostra) e a fase aceptora (solvente orgânico) em um sistema ternário de solventes. Foi desenvolvida em 2006 por Rezaee e colaboradores para a determinação de hidrocarbonetos policíclicos aromáticos em amostras de água e por ser uma técnica muito recente,ainda é pouca explorada para o preparo de amostras biológicas. Portanto, o objetivo deste trabalho foi avaliar a DLLME como técnica para a extração da oxibutinina (OXY), fármaco usado para o tratamento da incontinência urinária, e da N-desetiloxibutinina (DEO), seu principal metabólito ativo, em amostras de urina. A análise da OXY e DEO foi realizada por eletroforese capilar (CE), utilizando um capilar de sílica fundida de 50 ?m de diâmetro interno, com comprimento efetivo de 36,5 cm, trietilamina 50 mmol/L, pH 3 como solução de eletrólito, tensão de30 kV, temperatura de 30°C e detecção em 204 nm. Nestas condições o tempo de migração da DEO foi de 7,12 min e da OXY foi de 7,42 min, com resolução de 3,1. O procedimento utilizado para preparo da amostra foi baseado na DLLME, utilizando 5 mL de urina,na qual foi adicionado 2,5% de NaCle cujo pH foi ajustado para 11. O solvente para a extração consistiu de uma mistura de 140 ?L de tetracloreto de carbono (solvente extrator) e 260 ?L de acetonitrila (solvente dispersor), que permaneceram em contato com a amostra pordois minutos. A avaliação das características de desempenho analítico apresentou faixa linear de 90-300 ng/mL para a OXY e 187,5-750ng/mL para a DEO. A recuperação absoluta foi de 71,4 e 60,9% e o limite de quantificação foi de 90 e 187,5 ng/mL para a OXY e DEO, respectivamente. Os estudos de precisão e exatidão apresentaram coeficientes de variação e erros relativos inferiores a 15% e as amostras foram estáveis nos estudos de estabilidade. Portanto, foi possível desenvolver um método rápido, fácil e confiável para analisar e quantificar a OXY e a DEO em amostras de urina por CE, usando a DLLME como técnica de preparo de amostra. / The dispersive liquid-liquid microextraction (DLLME) is a sample preparation technique based on the equilibrium distribution between an extraction solvent and a sample solution in a ternary solvent system. It was developed by Rezaee and co-workers in 2006 for the determination of polycyclic aromatic hydrocarbons in water samples. Until now, for being a very recent technique it was little explored for the analysis of drugs in biological fluids. Therefore, the aim of this work was to evaluate the DLLME as an extraction technique for oxybutynin (OXY), a drug used to treat urinary incontinence, and N-desethyloxybutynin (DEO), its main active metabolite in urine samples. The OXY and DEO\'s analysis was performed by capillary electrophoresis (CE) using a 50 ?m ID fused-silica capillary with an effective length of 36.5 cm with a photodiode array detector set at 204 nm. It made use of triethylamine 50 mmol/L pH 3 as background electrolyte, voltage of +30 kV and temperature of 30°C. Under these conditions the migration time were 7.12 minutes for DEO and 7.42 minutes for OXY, with a resolution of 3.1. The sample preparation procedure was based on DLLME and used 5 mL of urine samples whichionic strength was increased by the addition of 2.5% NaCland pH were adjusted to 11. The extraction mixture consisted of 140 ?L of carbon tetrachloride (extraction solvent) and 260 ?L of acetonitrile (disperser solvent), which remained in contact with the sample for two minutes. The analytical performance\'s evaluation presented linear range of 90-300 ng/mL for OXY and 187.5-750ng/mL for DEO. The absolute recovery were 71.4 and 60.9% and the limit of quantification were 90.0 and 187.5 ng/mL for OXY and DEO, respectively. The accuracy and precision studies showed coefficients of variation and errors below 15% and the samples were stable at stability studies. Therefore, it was possible to develop a fast, reliable and easy method to analyze and quantify OXY and DEO in urine samples by CE, using DLLME as a sample preparation technique.

Orientadores: Angelo Malachias de Souza, Eduardo Granado Monteiro da Silva / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Física Gleb Wataghin / Made available in DSpace on 2018-08-19T18:22:37Z (GMT). No. of bitstreams: 1 Pauli_Murielde_M.pdf: 18020420 bytes, checksum: ea0b8509035e788d8af363ac04130ca2 (MD5) Previous issue date: 2012 / Resumo: Esta dissertação trata do estudo estrutural e termodinâmico de sistemas orgânicos auto-organizados utilizando diferentes técnicas de espalhamento de raios-x. Multicamadas autoorganizadas de dois tipos de moléculas de ácidos fosfônicos foram analisadas: para o OPA [Ácido octadecilfosfônico - CH2(CH3)17PO(OH)2] e para o OcPA [Ácido octilfosfônico - CH2(CH3)7PO(OH)2]. Utilizando a fonte do Laboratório Nacional de Luz Síncrotron (LNLS) realizamos um conjunto de experimentos para investigar a organização lamelar e planar destas moléculas em função da temperatura. Medidas de difração convencional permitiram introduzir modelos de empilhamento capazes de identificar a coexistência de diferentes configurações de ordenamento e modificações nas mesmas em função da temperatura. Uma vez estabelecidos estes modelos fizemos uso da técnica de difração de raios-x dispersiva em energia, ainda pouco utilizada no Brasil, para obter informações detalhadas sobre o volume relativo de material ordenado com cada uma das configurações encontradas, identificando aquelas que são termicamente mais estáveis. O padrão de organização das moléculas no plano foi também investigado realizando-se medidas em geometria de transmissão de raios-x. Reunindo as informações descritas acima construímos um diagrama de fase ilustrando o ordenamento lamelar e planar das moléculas em função da temperatura. Além disso, fizemos um estudo do comportamento crítico das configurações de ordenamento nas vizinhanças da transição ordemdesordem para cada tipo de molécula e acerca da organização de curto e longo alcance das moléculas nas multicamadas. Os resultados preliminares são apresentados no fim deste trabalho / Abstract: This thesis comprises structural and thermodynamic studies on self-assembled organic systems using synchrotron x-ray scattering techniques. Multilayers obtained from selforganization of phosphonic acid molecules were analyzed for two different compounds: the octadecylphosphonic acid [OPA ¿ CH2(CH3)17PO(OH)2] and the octylphosphonic acid [OcPA ¿ CH2(CH3)7PO(OH)2]. Using the source of the Brazilian Synchrotron Light Laboratory (LNLS) we have performed an ensemble of experiments to investigate their lamellar and in-plane order of these molecules and their behavior. Conventional angle-resolved X-ray diffraction measurements were analyzed using kinematical models and allowed to verify the coexistence of distinct lamellar configurations as well as to track changes as the temperature rises. Once structural parameters were determined from the established models, detailed information about the relative volume of each lamellar configuration was retrieved using energy-dispersive X-ray diffraction, a technique still poorly explored in Brazil. This allowed identifying the most stable configurations at high temperatures. The in-plane order of molecules was also studied using x-ray transmission geometry via a wide-angle x-ray scattering setup. Gathering the above mentioned information we have built phase diagrams depicting the lamellar and planar packing of OPA and OcPA molecules as a function of temperature. Finally, we have performed a study of the critical behavior of the ordered configurations in the vicinity of order-disorder transition temperatures for each molecule. The preliminary results explained in the final chapter of this work shed light into the short- and long-range order behavior of the two systems / Mestrado / Física / Mestre em Física

No description available.

Dans ce travail, nous allons établir des estimations de dispersion et des applications aux inégalités de Strichartz pour les solutions de l’équation des ondes dans un domaine cylindrique convexe Ω ⊂ R³ à bord C∞, ∂Ω ≠ ∅. Les estimations de dispersion sont classiquement utilisées pour prouver les estimations de Strichartz. Dans un domaine Ω général, des estimations de Strichartz ont été démontrées par Blair, Smith, Sogge [6,7]. Des estimations optimales ont été prouvées dans [29] lorsque Ω est strictement convexe. Le cas des domaines cylindriques que nous considérons ici généralise les resultats de [29] dans le cas où la courbure positive dépend de l'angle d'incidence et s'annule dans certaines directions. / In this work, we establish local in time dispersive estimates and its application to Strichartz estimates for solutions of the model case Dirichlet wave equation inside cylindrical convex domains Ω ⊂ R³ with smooth boundary ∂Ω ≠ ∅. Let us recall that dispersive estimates are key ingredients to prove Strichartz estimates. Strichartz estimates for waves inside an arbitrary domain Ω have been proved by Blair, Smith, Sogge [6,7]. Optimal estimates in strictly convex domains have been obtained in [29]. Our case of cylindrical domains is an extension of the result of [29] in the case where the nonnegative curvature radius depends on the incident angle and vanishes in some directions.

La première partie de cette thèse concerne l'étude du problème de Cauchy pour l'équation de KdV quasi-linéaire.On établit un théorème d'existence locale obtenu grâce à des propriétés structurelles et des techniques de jauge qui permettent de compenser les pertes de dérivées apparentes dans les estimations a priori.Dans la seconde partie, les propriétés de stabilité orbitale co-périodique et modulationnelle sont explorées numériquement en exploitant des critères algébriques tous établis à partir d'une même intégrale d'action et de ses dérivées secondes. Notre méthode utilise des quadratures numériques suivies de différences finies afin de calculer la matrice hessienne de l'intégrale d'action. Le comportement asymptotique de cette matrice nous pousse à prêter beaucoup d'attention à l'étude des ondes de grande période ou de faible amplitude. Les résultats numériquesprésentés fournissent de nombreuses informations en lien avec des questions ouvertes.On effectue également des simulations directes sur le système d' ÉDP original pour étudier à la fois le comportement des ondes périodiques sous différents types de perturbations, et les solutions de problèmes de Cauchy avec donnée initiale discontinue. Pour ces derniers, on s'attend à observer des chocs dispersifs, dont la compréhension est basée sur le problème de Gurevich-Pitaevskii, où les équations modulées à la Whitham sont utilisées pour approcher la zone oscillante des chocs. On compare des simulations directes aux solutions idéales du problème de Gurevich-Pitaevskii, en commençant par la célèbre équation de KdV / The first part of this manuscript presents a well-posedness result for a quasilinear version of the KdV equation.The proof takes advantage of structural properties and gauge techniques to deal with apparent loss of derivativesin a priori estimates.In the second part, we investigate the modulational and orbital coperiodic stability of periodic waves by computingalgebraic criteria involving the same abbreviated action integral and its second order derivatives. Our methoduses numerical integrations followed by finite differences to compute the Hessian matrix of the action integral.We pay attention to the asymptotic behavior of this matrix in the large period and small amplitude limits. Thenumerical results about stability give some new insight on several analytical open questions.Finally, direct numerical computations are done on the original system of PDEs to study the behavior of periodictraveling waves under various kinds of perturbations and the solutions of Cauchy problem with discontinuousinitial data. For the latter, we expect dispersive shock waves to arise. The building block for understandingdispersive shocks is known as the Gurevich-Pitaevskii problem, in which modulated equations 'a la Whitham'are used as an approximate model for the oscillatory zone. We compare direct numerical simulations to idealizedsolutions of Gurevich-Pitaevskii problems, starting with the famous KdV equation

No description available.

No description available.

The mixing of additives into a plastic is an extremely important step in the plastics industry, necessary for the manufacture of almost every conceivable product. Therefore the costs in developing new products can prove very expensive as the testing is usually carried out using full scale machines, usually using twin screw extruders because they are able to provide good dispersive and distributive mixing. This is particularly important when compounding difficult to disperse additives and nano-additives. What is required is a machine that can replicate the mixing abilities of a twin-screw extruder but on a laboratory scale. There have been attempts by industry to develop smaller machines, such as the Thermo Scientific HAAKE Minilab II Micro Compounder which processes on the scale of 7 cm3 of material volume. This can be too small for some needs and therefore a machine is required to produce material on the 10g to 100g scale. To this end a laboratory mixer of novel design was devised and its mixing performance was assessed using conductive carbon black and compared against the Thermo Scientific HAAKE Minilab II Micro Compounder, a 19 mm co-rotating twin-screw extruder and a 40 mm co-rotating twin-screw extruder. Carbon black was used because mixing performance can be assessed by measuring the minimum carbon loading necessary to induce electrical conductivity. It was found that the minimixer was able to induce electrical conductivity at loading of 5.75% but the comparison with the other machines proved difficult as the achievement of the threshold at which semi-conductivity occurred appeared independent of shear rate and mixing duration. / EPSRC / The following files are not available online: Americhem raw data; Carbon Black raw data; Videos.