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Cromolyn sodium (CS) is a mast cell stabilizer which has been used to treat systemic mastocytosis, allergic- and exercise-induced asthma, and allergic reactions induced by atopic dermatitis. Presently, CS is administered orally and intranasally, and with a short half-life and poor absorption, 4 to 8 doses are required daily for treatment. Developing a transdermal product for CS would eliminate such drawbacks that lead to inconsistent patient dosing and provide sustained therapeutic effects when administered via skin. Our long-term goal is to determine the feasibility of delivering CS through skin. However, a prerequisite for evaluating the performance of any transdermal system is to have a sensitive analytical method that can selectively detect and quantify the drug without any interference from compounds that may leach from skin during permeation studies. Therefore, our preliminary goal was to develop and validate such a method that can be employed for transdermal studies. The optimized liquid chromatography-mass spectrometry (LC-MS) method utilized a chromatographic separation which involved an isocratic mobile phase (10mM ammonium bicarbonate, pH 8.0, 90% and acetonitrile, 10%) at a flow rate of 0.2500 mL/min. Detection involved direct MS/MS channels with m/z 467.0255 (precursor) and m/z 379.0517 (fragment) with argon as the collision gas. CS calibrants were prepared in phosphate-buffered saline (PBS), pH 7.4, for validation (0.1, 0.25, 0.5, 0.75, 1, and 2.5 μg/mL). To ensure no skin interference, dermatomed porcine ear skin was minced, placed in PBS, and shaken for 15 hours to extract any possible interfering components. The extract was filtered and analyzed with the optimized LC-MS conditions. Calibrants were also analyzed over 3 days with each day examining 6 injections (20 μL) of each sample. Peak areas determined by LC-MS were used to construct calibration curves for CS and to calculate % error and % RSD to elucidate accuracy and precision of the method. Results showed CS retention time to be around 4.4 minutes with no interfering peak from skin extract, and linearity was observed between 0.1-2.5 μg/mL. Inter- and intra-day accuracy and precision of the method were within the acceptable limit of ±20% at the lower limit of quantitation and ±15% at other concentrations. Future studies will involve using the validated method for quantification of CS in skin permeation studies to investigate our long-term goal.

The goal of this study is to establish an accurate, simple and fast method for analysis of organotin in bio-tissues and for routine analysis of organotin in pollution control. This study also conducted the field survey investigating the accumulation status of butyltin (BT) in organisms and environments for validation of analytical method and applicability in different environmental samples. Stations had been set up from the Sih-Cao fishing port to the upstream of Luermen Stream Estuary. General water quality factors were measured in situ, and water samples, suspended particles, Pacific oysters (Crassostrea gigas), green mussels (Perna viridis), and rockshells (Thais clavigera and Thais rufotincta) were collected in summer (July 2003) and winter (February 2004) seasons and the concentrations of butyltins were measured. Surface sediment samples were also collected from each sampling station and the concentrations of butyltins were measured to present pollution status of butyltins in Luermen Stream Estuary. To determine butyl- and phenyl-tins in fish muscle, a method including base digestion pretreatment, followed by an ethylation-extraction procedure together with gas chromatography-flame photometric detection (GC-FPD) analysis is outlined. Parameters that affect analyte recovery were investigated and optimized. A solution of 3 % (w/v) potassium hydroxide and 1 h digestion time at 60 ¢J were chosen in the base digestion step to ensure complete solubilization of fish muscle and the decomposition of organotins was found to be negligivle. We found that the ratio of fish muscle/reaction solution volume should not exceed 0.2 g (dry weight) per 100 mL in order to avoid the matrix effect caused by the binding of hydrolyzed fish tissue with organotin ions. Ethylation of organotins were conducted at pH 6~7 with a 1 % (w/v) sodium tetraethylborate (NaBEt4) solution for 1 h. This simple and timesaving procedure could be applied to the routine analysis of organotins in other bio-tissues. The BT content of environments and organisms reflected that the tributyltin (TBT) pollution levels were higher in Sih-Cao fishing port than in Luermen Stream. The BT content of organisms reflected more detail TBT pollution status between Sih-Cao fishing port and Luermen Stream. However, the MBT pollution status in Luermen Stream was not reflected in MBT accumulation status of organisms. The ability of TBT accumulation in oysters and mussels was higher than in rockshells. Moreover, oysters had higher TBT accumulation ability than mussels at lower TBT pollution level, but following the increase of TBT pollution level, the ability of TBT accumulation in oysters had shifted to be lower than in mussels. The results also showed that in the higher TBT pollution level, the ratios of MBT and DBT over the total butyltins had changed to higher status and the bioaccumulation factors (BAF) had changed to smaller values in oysters and rockshells. In mussels, this phenomenon was not significant. However, the organisms (oyster, mussel and rockshells) revealed smaller BAF of TBT in Luermen Stream than in the Sih-Cao fishing port entrance. For oysters and mussels, the TBT contents and the composition ratios of TBT in total butyltins were both higher in winter season. All organisms (oysters, mussels and rockshells) had higher ability to accumulate TBT according to the larger BAF observed in summer season. The ability of TBT accumulation in rockshells was lower than in oysters or mussels. Moreover, the BT accumulation status was mainly composed of MBT and DBT (the metabolites of TBT ) in rockshells and TBT in oysters and mussels. That was attributed to higher metabolic rate of TBT in rockshells.

The life time of mechanical components can be increased by the presence of compressive residual stresses. Inherent to most production processes, residual stresses play a critical role on the mechanical parts behaviour. The knowledge and mastering of residual stresses and linked processes are thus fundamental. The development of efficient numerical methods to predict these residual stresses will allow to save costly experiments and to study the influence of the main parameters. This PhD presents the development and application of semi analytical methods (SAM) to the modelling of mechanical processes of compressive residual stress generation. The SAMs, initially developed for the simulation of elasto-plastic contacts, have the advantage of significantly low computation time compared to classical numerical methods. This method is first used to simulate the low plasticity burnishing process, with a rolling loading. Then, it is used for the simulation of impacts, first unique and then repeated. The frictionless rolling contact between two elasto-plastic bodies is first studied. The influence of plasticity, of the hardening model (isotropic or kinematic), of the geometry of the bodies in contact (spheres or ellipsoids) and of the loading type (indentation or rolling) on the contact pressure and plastic strains are analysed. Impacts simulation is then addressed. The developed method is first validated numerically then confronted to experimentations. Three materials have been particularly studied: 316L, AA 7010 and Inconel 600. The impacts dimensions and the generated strains, measured by digital image correlation, are used to validate experimentally the method. The ultrasonic shotpeening process has been specifically studied. The description of the kinematics of the shots put in movement by a sonotrode in a closed peening chamber has first been studied. The use of analytical formulae for the estimation of the coefficients of restitution, during the numerous impacts between shots and with the chamber's walls, allowed refining the calculation of the average impact velocity as a function of the process parameters. The SAM is the used to determine the plastic strain field induced by the impacts. At last a projection method is proposed to finally determine the residual stress field in thick or thin structures.

<p>This thesis covers the four topics discussed in each of the following paragraphs. It is unified by the dual ability of ambient ionization mass spectrometry as a useful analytical tool allowing for monitoring of chemical reactions, in addition to its capability to accelerate reaction rates using the same equipment under accelerating or non-accelerating conditions. The ability to manipulate reactions and monitor the subsequent effects to the rate of the reactions can provide vital information for many industrial arenas. Current process analytical technology (PAT) is extremely time-consuming, and typically costly due to dependence on analysis conducted at the end stage of production. Additionally, many chemical reactions found to be useful in pharmaceutical or manufacturing industries are labor intensive and require harsh conditions such as heat or expensive catalysts. Several methods have been developed to overcome these current limitations, while providing vital information on short-lived intermediates, degradation products, and accelerated reaction rates. A sampling device was developed and coupled with nESI allowing for monitoring of heterogeneous chemical reactions by mass spectrometry without the additional requirement of separation (filters, chromatography, etc.) In addition, this technique maintains the high sensitivity, specificity, speed and structural elucidation provided by mass spectrometry analysis. The analysis provided kinetic profiles of all reactants, intermediates, products and coproducts throughout the course of the reaction.</p><p> The ability to effectively control chemical reactions and their rates is a priority across several fields of study. Several factors affecting reaction rates, such as heat and catalysts selected, have been well studied. However, there has been recent interest in exploring the capabilities for reaction acceleration in charged microdroplets. It is known that reaction rates on the surface of a droplet greatly differ from reactions occurring in the droplet. The Katritzky transamination reaction was used as a model to identify the effects of the air-solution interface on reaction acceleration by varying the air-liquid surface to volume ratio. The significant increase in reaction rate constants was further enhanced by solid–solution interfacial effects observed after addition of glass nanoparticles.</p><p> The effective degradation of non-polar hydrocarbons is an environmental concern as they are the main composition of waste generated from petroleum processing. Saturated alkanes are relatively stable molecules which present a challenge for analysis by mass spectrometry without the use of extreme experimental conditions. A rapid analysis method by paper spray ionization was developed that allows for the oxidation products of saturated alkanes to be monitored by MS in under two minutes. This method relies on the generation of a hydroxyl radical by reacting iron (III) chloride with aqueous hydrogen peroxide on the principle of Fenton’s chemistry. The presence of this radical in direct contact with an alkane produces several oxidation products which can be easily monitored by MS. The reagents are added to a paper triangle sequentially, creating a thin film which allows reaction acceleration in relatively small volumes analyzed directly from paper at atmospheric pressure.</p><p> The dimerization of 4-ethynylaniline derivatives in acetonitrile was monitored by nano electrospray ionization mass spectrometry. Dimer products formed by electrocyclization and radical processes were observed that are not detected as a corresponding bulk reaction. This gas-phase reaction has been interrogated in a solution phase analog with radical initiators and characterized by ¹H NMR. This work demonstrates that compounds can be synthesized by the electrospray process. Future studies may reveal how this observation affects the interpretation of the MS results involving electrospray.</p>

La gravitation joue un rôle important dans de nombreux domaines de l'astrophysique : elle assure notamment la cohésion et la stabilité des planètes, des étoiles et des disques. Elle est aussi motrice dans le processus d'effondrement de structure et conduit, dès lors qu'un moment cinétique initial est significatif, à la formation d'un disque.Ma thèse est consacrée à l'étude des disques de gaz, et plus particulièrement à la description du potentiel et du champ de gravité qu'ils génèrent dans l'espace et sur eux-mêmes (l'auto-gravitation). Bien que la force de Newton soit connue depuis longtemps, la détermination des interactions auto-gravitantes reste difficile, en particulier lorsque l'on s'écarte significativement de la sphéricité. La principale difficulté tient dans la divergence hyperbolique du Noyau de Green 1/(r'-r) et nécessite un traitement propre. L'approche théorique est intéressante car elle fournit de nouveaux outils (techniques numériques, formules approchées, etc...) qui peuvent aider à produire des solutions de référence et à améliorer les simulations numériques.Dans une première partie, nous introduisons le sujet, les notions et les bases essentielles. Le chapitre $1$ est consacré à une présentation succinte du contexte scientifique et aux motivations de notre travail. Dans le chapitre $2$, nous reproduisons dans ces grandes lignes le cheminement conduisant au développement multipolaire, à partir de l'équation de Poisson et de la formule intégrale de Newton. Il s'agit de l'une des méthodes les plus classiques permettant d'obtenir le potentiel gravitationnel d'un corps. Les deux systèmes de coordonnées les plus utilisées sont mis en avant : sphériques et cylindriques. A travers quelques exemples, nous montrons les limites de cette approche, en particulier dans le cas de l'auto-gravité des disques.Dans une deuxième partie, nous abordons le vif du sujet. Le chapitre $3$ présente l'approche basée sur les intégrales elliptiques que nous retrouverons dans l'ensemble du manuscrit (cas général d'abord, puis cas axi-symétrique). Dans le chapitre $4$, nous établissons un premier résultat concernant le noyau de Green dans des systèmes axi-symétriques et verticalement homogènes : une forme alternative et régulière du noyau, quelque soit le point de l'espace. Nous avons exploité cette nouvelle formule pour déduire une bonne approximation du potentiel des disques géométriquement minces, des anneaux et des systèmes faiblement étendus en rayon. Ceci fait l'objet du chapitre $5$.Dans une troisième partie, nous étudions les effets de bords sur la composante verticale du champ de gravité, $g_z$, causés par un disque mince axi-symétrique. Le chapitre $6$ est dédié à l'approximation de Paczynski \citep{pacz78}, qui permet traditionnellement d'exprimer le champ comme une fonction linéaire de la densité de surface locale. Cette approximation n'est en fait strictement valide que dans le cas du modèle du "plan infini", loin d'un disque réaliste. Près du bord externe des disques où la gravité décroit, l'approximation de Paczynski s'avère assez imprécise (facteur $2$ typiquement), et ne donne pas de bons résultats et doit être corrigée. Toujours dans l'hypothèse d'une homogénéité verticale de la densité, nous avons construit une expression pour $g_z$ qui tient compte de ces effets de bords. Le chapitre $7$ est consacré à ce résultat.Dans une dernière partie, nous relâchons l'hypothèse de symétrie axiale (le disque est discrétisé en cellules cylindriques homogènes). Nous nous sommes inspirés du travail d'\cite{ansorg03} afin d'exprimer, via le théorème de Green, le potentiel d'une cellule cylindrique homogène par une intégrale de contour. Ce résultat s'applique directement aux simulations de disques, où ceux-ci sont découpés en cellules cylindriques, chacune ayant sa propre densité.Une conclusion et quelques perspectives sont données en fin de manuscrit. / Gravitation plays an important role in many fields in astrophysics: it appears in the cohesion and stability of bodies such as planets, stars, disks and galaxies. In the Universe, the formation of most astrophysical objects involves disk-like configurations by a main process: the gravitational collapse. The structure and the evolution of these disks (protoplanetary disks, circumplanetary disks...), are an important stage in the process of the formation of stars, planets or satellites. It is therefore fundamental to understand their physics and develop appropriate tools. I devoted my Ph.D. to the computation of the gravitational potential and field of astrophysical disks. Although Newton's force is known for long, the determination of self-gravitating interactions inside bodies remains a difficult task. Strong deviations to sphericity require more efforts. The main difficulty is to manage properly the hyperbolic divergence of the Green kernel $\frac{1}{|r-r'|}$. In this purpose, the theoretical approach is interesting as it can provide powerful formulae and new tools, which can also help to produce reference solutions. So, I have investigated new methods able to treat this question as rigorously as possible.In a first part, chapter $1$ is devoted to the scientifc context and motivations. In the chapter $2$ we derive the well known multipole expansion in spherical and cylindrical coordinates from the Poisson equation and Newton's equation. We show the limits of these two developments in the context of astrophysical disks. In chapter $3$, we discuss the formalism based on elliptic integrals, its advantages and drawbacks, and we describe two methods which use this approach in the special case of axisymmetrical disks.In the second part, chapter $4$ is about the discovery of an alternate formula for the Green kernel, which involves regilar function. To obtain this result, we assume that the disk is vertically homogeneous (i.e., the density varies only with the radius), and that it is axially symetric. In chapter $5$, by using this new expression, we build an approximation for the potential in the special case of geometrically thin disks and rings, and another one for systems which are radially confined.In the third part, chapter $6$ is devoted to the study of edge effects on the vertical component of the gravitational field caused by a thin disk. According to Paczynski's approximation, the field is a linear function of the surface density \cite{pacz78}. This approximation is strictly valid only in the infinite slab model, while we are interested in a realistic disk. Close to the outer edges, where gravity decreases, Paczynski's approximation fails and must be corrected. By assuming again a density varying with the radius only, we have derived a new expression for the vertical component of gravitational field, which properly accounts of the presence of the edge of the disk. This is the main subject of the chapter $7$. In the last part (chapter $8$), we generalize the work by \cite{ansorg03}, valid under axial symmetry only. Using a similar approach, we built an expression for the self-gravitating potential of cylindrical cells, which is not known in closed form yet. This expression is made of a single integral over the boundary of the cell. This result can be applied in hydrodynamical simulations, where disks are usually discretised into homogeneous cylindrical cells, each cell having its own density.A conclusion and a few perspectives end the thesis.

A utilização da enzima fitase nas dietas de não ruminantes permite a quebra da molécula de ácido fítico presente em ingredientes de origem vegetal e disponibilização do fósforo. O objetivo deste trabalho foi avaliar a eficiência de uma fitase bacteriana na liberação de fósforo fítico utilizando curvas de calibração para características ósseas e de desempenho em frangos de corte, e comparar os critérios de resposta quanto a adequação para estimativa da liberação de fósforo, assim como a viabilidade econômica da inclusão da fitase em dietas de frangos de corte. O delineamento experimental adotado foi inteiramente casualisado com 6 tratamentos e 6 repetições no período de 1 a 28 dias de idade. O tratamento controle consistiu de dieta à base de milho e farelo de soja deficiente em fósforo disponível (0,20% e 0,15% de P disponível para as fases de 1 a 21 e 22 a 28 dias, respectivamente). Dois tratamentos corresponderam às dietas basais acrescidas de fósforo inorgânico nos níveis de 0,05% e 0,10%, e os outros três a dieta basal com a inclusão de 66, 99 e 131 FTU/kg de ração. A curva padrão foi construída através do efeito de três níveis de P suplementar consumido sobre variáveis de desempenho e características ósseas. Em seguida, os resultados obtidos com inclusão de fitase foram confrontados com a curva padrão para o cálculo de P liberado pela fitase. O desempenho dos frangos de corte foi prejudicado em função da deficência em P na dieta. Os níveis crescentes de P suplementar influenciaram as variáveis ganho de peso, peso vivo e consumo de ração de forma quadrática, e de forma linear a variável miligramas de cinzas ósseas. A resposta linear é a que melhor descreve a curva padrão, dessa forma, a equação da variável mg de cinzas ósseas foi utilizada para construção da curva. As inclusões de 66, 99 e 131 FTU/kg liberaram, respectivamente, 0,048%, 0,049% e 0,062% de P em dieta à base de milho e farelo de soja. Este estudo demonstra a eficiência da fitase bacteriana em liberar fósforo fítico em dietas com baixos níveis de P, e o benefício econômico da utilização da enzima em dietas de frangos de corte. / Use of the enzyme phytase in the diets of nonruminants allows the hydrolysis of the molecule of phytic acid present in ingredients of plant origin, increasing phosphorus avalilability. The objective of this study was to determine the efficiency of a bacterial phytase to release phytate phosphorus using calibration curves for performance and bone characteristics in broiler chickens, and compare the response criteria for adequacy for estimating the release of phosphorus, as well the economic viability of inclusion of phytase in broiler chickens diets. A completely randomized design with 6 treatments and 6 replicates was used in an experiment with chickens from 1 to 28 days of age. The control treatment was a diet based on corn and soybean meal deficient in availability phosphorus (0,20% and 0,15% available P in the 1 21 and 21 28 days periods, respectively). Two treatmens consisted of the basal diet supplemented with inorganic phosphorus, and the other three treatments received 66, 99 and 131 FTU/kg of feed. The standard curves represented the effect of three levels of additional P intake on performance and bone variables. Then, the responses of the phytase treatments were compared to the standard curves to calculate the P released by phytase. Performance was negatively affected by the P-deficient diets. The increasing levels of supplemental P had quadratic effect on weight gain, live weight and feed intake, and linear effect on mg of bone ash. The linar response is the on that better represents the standard curve, thus the equation of bone ash was elected to estimative the P released. Inclusion of 66, 99 and 131 FTU/kg released 0.048%, 0.049% and 0.062% P from the corn-soy diet. This study demonstrates the efficiency the efficiency of the bacterial phytase to release phosphorus at low levels of inclusion, which may be of economical significance in diets broiler chickens.

Aux Antilles Françaises, les animaux d’élevage sont susceptibles d’être exposés à la chlordécone (CLD), Polluant Organique Persistant (POP) présent dans leur environnement. Afin de sécuriser les Denrées Alimentaires d’Origine Animale (DAOA) destinées à la consommation humaine, nos travaux ont porté sur l’étude du devenir de la CLD chez la brebis. Les objectifs de ces travaux étaient de comprendre comment s’effectue l’élimination de la molécule depuis l’organisme animal c’est-à-dire de déterminer par quelle(s) voie(s), sous quelle(s) forme (s), en combien de temps, en quelle quantité et par quels mécanismes s’élimine la CLD. Pour cette étude, deux volets ont été considérés : un volet analytique et un volet toxicocinétique. En effet, les méthodes de dosage connues des métabolites de la CLD ne permettaient pas d’obtenir la sensibilité et la fiabilité attendues pour nos travaux. Ainsi, un développement analytique de méthodes de dosage de la CLD et de ses métabolites dans les matrices d’intérêt a été mené. Ces travaux analytiques se sont appuyés sur une méthodologie d’extraction de type Quick, Easy, Cheap, Effective, Rugged and Safe (QuEChERS), une analyse par chromatographie en phase liquide couplée à la spectrométrie de masse en tandem (LC-MS/MS) et l’utilisation d’étalons internes isotopiques. Ce développement permet de disposer de méthodes de dosage sensibles, rapides et fiables de la CLD et de ses métabolites dans différentes matrices animales. A l’issue de l’étape de développement analytique, les méthodes dans le foie, les fèces et les urines ont été validées à l’aide de profils d’exactitude établis selon la norme V03-110 et le guide SANTE de référence pour les pesticides. Pour exemple, dans la matrice foie, des limites de quantification de 1,36 µg kg-1 PF et de 2,50 µg kg-1 PF respectivement de chlordécone et de chlordécol (métabolite de la CLD) ont été retrouvées. Le deuxième volet de cette thèse s’est appuyé sur deux protocoles toxicocinétiques réalisés chez la brebis. A l’aide de ces expérimentations, il a été possible de combler une partie des lacunes sur la toxicocinétique de la CLD chez la brebis. Nos travaux ont démontré que la CLD est partiellement métabolisée en chlordécol (CLDOH) par la chlordécone réductase dans le foie des brebis. Par la suite, la CLD et le CLDOH peuvent être métabolisés à l’aide d’UDP-glucuronosyl-transferases et de sulfo-transferases en métabolites conjugués de la CLD et du CLDOH (CLD-C et CLDOH-C). Le CLDOH est un métabolite intermédiaire qui n’est quasiment jamais quantifié dans l’organisme animal hormis dans le tissu gras. L’élimination de la CLD se fait majoritairement via les fèces : 1/3 de la molécule parent CLD est éliminé sous forme de CLD et 1/6 est éliminé sous forme de CLDOH. La voie urinaire est une voie mineure d’élimination de la CLD. A l’aide de ces travaux, un modèle compartimental a été proposé. Sur la base de ce modèle, des travaux de modélisation seront possibles et permettront la proposition et la mise en place de stratégies de décontamination des ovins aux Antilles Françaises / In the French West Indies (FWI), farming animals can be exposed to CLD, a persistent organic pollutant (POP) bound to soil in contaminated areas. In order to produce safe animal products, this thesis was focused on the CLD’s fate in ewes. The aims were to determine by which way(s), in which form(s), in how much time, in which quantities and by which mechanisms, CLD would be eliminated from the animal body. In this thesis, two complementary approaches were followed. First it was necessary to improve the analytical methods especially for the metabolites in order to obtain more sensitive and reliable methods than the actual ones. In the analytical approach, methods for CLD and its metabolites were developed in various animal matrices suitable for the toxicokinetic studies. The extraction method was based on the Quick, Easy, Cheap, Effective, Rugged and Safe (QuEChERS) methodology and the analysis was performed with a liquid chromatography with tandem mass spectrometry (LC-MS/MS). Isotopic Standards were also used. Thanks to this work, sensitive, quick and reliable methods were obtained in animal matrices. The set-up methods in liver, feces and urine were validated with accuracy profiles according to the French Standard NF V03-110 and European Union guidelines. Limits of quantifications of 1.36 μg kg−1 and 2.50 μg kg−1 of fresh liver were respectively found for chlordecone and chlordecol (the CLD’s metabolite). Secondly, and thanks to the analytical development, in vivo toxicokinetic studies were performed to determine the fate of CLD in ewes. The second approach of this thesis was based on two toxicokinetic protocols realized in ewes. The results revealed that CLD is partially metabolized in chlordecol (CLDOH) by the chlordecone reductase in ewe’s liver. Then, CLD and CLDOH can be conjugated by UDP-glucuronosyl-transferases and sulfo-transferases in conjugated metabolites (CLD-C and CLDOH-C). It appeared that CLDOH is only an intermediate metabolite which is almost never quantified in the organism except in fat tissue. The major route of CLD elimination is in feces: 1/3 of the molecule is eliminated in its CLD’s form and 1/6 in its CLDOH’s form. The urinary way of CLD elimination is minor. Based on the obtained results, a compartmental model was proposed. It will allow to propose and to establish ovine decontamination strategies in the FWI

Orientador: Maria do Rosário Longo Mortatti / Banca: Circe Maria Fernandes Bittencourt / Banca: Lázara Nanci de Barros Amâncio / Resumo: Nesta dissertação, apresentam-se resultados de pesquisa de mestrado em educação (Bolsa Capes - março a agosto de 2008; bolsa Fapesp - setembro de 2008 a fevereiro de 2010), vinculada às linhas "Alfabetização" e "Ensino de Língua Portuguesa" do Grupo de Pesquisa e do Projeto Integrado de Pesquisa "História do Ensino de Língua e Literatura no Brasil", ambos coordenados por Maria do Rosário L. Mortatti. Com o objetivo de contribuir para a compreensão de um importante momento da história do ensino da leitura no Brasil, focalizase a proposta para esse ensino apresentada pelo professor paulista Antonio Firmino de Proença (1880-1946), nos livros didáticos que integram a "Série de leitura Proença", a saber: Cartilha Proença (1926), Leitura do principiante (1926), 1º. livro de leitura (1926), 2º. livro de leitura (1927), 3º. livro de leitura (1928) e 4º. livro de leitura (1948). Os livros que integram essa série foram publicados pela Editora Melhoramentos (SP) e circularam em diferentes estados brasileiros, dentre os quais, Ceará, Minas Gerais, Pernambuco e Santa Catarina, além de São Paulo, tendo contribuído para a formação de muitas gerações de brasileiros. Mediante abordagem histórica centrada em pesquisa documental e bibliográfica, desenvolvida por meio dos procedimentos de localização, recuperação, reunião, seleção e ordenação de fontes documentais, analisou-se a configuração textual dos livros dessa série, que consiste em enfocar os diferentes aspectos constitutivos de seu sentido. Concluiu-se que, nesses livros, apresentada-se uma proposta de concretização do método analítico para o ensino da leitura diretamente relacionada com outros livros de leitura publicados nas décadas iniciais do século XX, como decorrência da institucionalização desse método, no estado de São Paulo. / Abstract: This work deals with the results of a Master degree dissertation research related to "Literacy" and "Portuguese Language" of Research Group and Research Integrated Project "History of Language and Literature Teaching in Brazil" both under the leadership of Maria do Rosário Longo Mortatti. Aiming contributing to understand an important of the history of reading teaching in Brazil, it focus on the proposal concerning reading teaching presented by Professor Antonio Firmino Proença (1880-1946), in the didactic books called "Série de leitura Proença", that is: Cartilha Proença (1926), Leitura do principiante (1926), 1º. livro de leitura (1926), 2º. livro de leitura (1927), 3º. livro de leitura (1928) e 4°. livro de leitura (1948). All those books were published by Editora Melhoramentos (SP) and had circulation in different Brazilian states such as Ceará, Minas Gerais, Pernambuco e Santa Catarina, besides São Paulo, and in this way, they contributed to form many Brazilian generations. Through historical approach centred on documentary and bibliographical investigation, and by means of localizing, retrieving, assembling, selecting and ordering proceedings, those books textual configuration was analysed, that is to say, to focus on different constitutive aspects of their meanings. The conclusion is that in those books, a proposal to make concrete the analytical method for reading teaching is presented, which is directly related to other reading books published at the beginning decades of 20 th century, as a result of the institutionalization of that method in the state of São Paulo. / Mestre

CoordenaÃÃo de AperfeiÃoamento de Pessoal de NÃvel Superior / Este trabalho investiga a utilizaÃÃo da radiaÃÃo infravermelha como fonte de aquecimento no preparo de amostras orgÃnicas por via Ãmida visando à determinaÃÃo de elementos traÃos por ICP OES. As estratÃgias foram elaboradas com o objetivo de solubilizar e/ou digerir maiores massas de amostras. Assim, foram estudadas trÃs estratÃgias: 1) sistema IR-MW que combina o uso da radiaÃÃo infravermelha e micro-ondas, por meio de uma digestÃo prÃvia com radiaÃÃo infravermelha e posterior digestÃo no forno de micro-ondas com cavidade; 2) digestÃo parcial utilizando somente radiaÃÃo infravermelha (IR); 3) digestÃo parcial utilizando radiaÃÃo infravermelha e pentÃxido de vanÃdio (IR com V2O5) como reagente oxidante auxiliar. Diferentes procedimentos foram estudados sendo avaliados atravÃs da determinaÃÃo por ICP OES de macro e microelementos (Al, Fe, Cu, Mn, Zn, Se, Cd, Ni, Pb, Ca, K, Mg, Na e P) em diferentes tipos de leite em pÃ. O sistema IR-MW permitiu a digestÃo de massas de amostra de atà 1 g, obtendo-se boas precisÃes para a maioria dos elementos determinados. Para o procedimento IRMW A, a exatidÃo foi confirmada com material certificado Whole Milk Powder NIST 8435. Para os procedimentos IR-MW B e C foram obtidas percentagens de recuperaÃÃo variadas dependendo do elemento e da amostra. As estratÃgias IR e IR com V2O5 possibilitaram a digestÃo parcial de 2 g de amostra. A precisÃo e a exatidÃo desses procedimentos variaram de acordo com o elemento e a amostra. Todavia, a quantificaÃÃo de alguns elementos sà foi possÃvel por meio destas estratÃgias como, por exemplo, a detecÃÃo de Mn (0,30  0,01 Âg g-1 por IR; 0,35  0,01 Âg g-1 por IR com V2O5) na amostra de leite de cabra em pà integral e de Mn (1,63  0,02 Âg g-1 por IR; 1,78  0,06 Âg g-1 por IR com V2O5) na amostra de leite em pà desnatado nÃo enriquecido. O uso do V2O5 foi essencial na quantificaÃÃo de Fe (0,54  0,13 Âg g-1) no leite de cabra em pà integral. De uma maneira geral, dependendo do elemento e de seu teor na amostra, sua determinaÃÃo por ICP OES sà à possÃvel quando se usa maiores quantidades de massa de amostra. O emprego da radiaÃÃo infravermelha no auxilio de digestÃo de maiores massas de amostra à uma alternativa para laboratÃrios que utilizam apenas forno de micro-ondas com cavidade. / In this work it was investigated the use of infrared radiation as heating source in the preparation of organic samples aiming the determination of trace elements by ICP OES. The strategies were developed in order to solubilize and / or digest larger masses of samples. Thus, three strategies were studied: 1) IR-MW system which combines the use of infrared radiation and microwave through a previous digestion with infrared radiation and subsequent digestion in the oven microwave cavity; 2) partial digestion using only infrared radiation (IR); 3) partial digestion using infrared radiation and vanadium pentoxide (IR with V2O5) as auxiliary oxidizing reagent. Various procedures were studied and the efficiencies were evaluated by the determination of macro-and microelements (Al, Fe, Cu, Mn, Zn, Se, Cd, Ni, Pb, Ca, K, Mg, Na, and P) in milk samples by ICP OES. The IR-MW system allowed the digestion of sample masses of up to 1 g, to obtain good precision for most of the elements determined. For the IR-MW A procedure the accuracy was confirmed with certified material of whole milk powder NIST 8435. For the IR-MW B and C procedures were obtained recovery rates varied depending upon the element and the sample. Strategies IR and IR with V2O5 allowed the partial digestion of 2 g of sample. The precision and accuracy of these procedures varied according to the element and the sample. However, the determination of some elements was only possible using these strategies, for instance, the detection of Mn (0.30  0.01 Âg g-1 by IR; 0.35  0.01 Âg g-1 by IR with V2O5) in the goat whole milk powder sample of and Mn (1.63  0.02 Âg g-1 by IR; 1.78  0.06 Âg g-1 by IR with V2O5) in the non-fat milk powder not enriched sample. The use of V2O5 was essential in the quantification of some elements such as Fe (0.54  0.13 Âg g-1) in goat milk powder samples. In general, the determination of trace elements by ICP OES is only possible using larger amounts of sample, depending on the element and its content in the sample. The use of infrared radiation to accomplish the digestion of larger masses of samples is an alternative to using only laboratory microwave oven cavity.